WorldWideScience

Sample records for aryl chlorides bromides

  1. Homocoupling of Aryl Bromides Catalyzed by Nickel Chloride in Pyridine

    Institute of Scientific and Technical Information of China (English)

    TAO, Xiao-Chun; ZHOU, Wei; ZHANG, Yue-Ping; DAI, Chun-ya; SHEN, Dong; HUANG, Mei

    2006-01-01

    Pyridine was used as a solvent for homocoupling of aryl bromides catalyzed by nickel chloride/triarylphosphine in the presence of zinc and recycled easily. Triphenylphosphine was the best ligand for nickel in this coupling reaction.

  2. Highly efficient synthesis of phenols by copper-catalyzed hydroxylation of aryl iodides, bromides, and chlorides.

    Science.gov (United States)

    Yang, Kai; Li, Zheng; Wang, Zhaoyang; Yao, Zhiyi; Jiang, Sheng

    2011-08-19

    8-Hydroxyquinolin-N-oxide was found to be a very efficient ligand for the copper-catalyzed hydroxylation of aryl iodides, aryl bromides, or aryl chlorides under mild reaction conditions. This methodology provides a direct transformation of aryl halides to phenols and to alkyl aryl ethers. The inexpensive catalytic system showed great functional group tolerance and excellent selectivity. © 2011 American Chemical Society

  3. Ammonium Chloride Promoted Palladium-Catalyzed Ullmann Coupling of Aryl Bromide

    Institute of Scientific and Technical Information of China (English)

    李金恒; 梁云; 刘文杰; 唐石; 谢叶香

    2004-01-01

    In water, ammonium chloride was found to promote palladium-catalyzed Ullmann coupling reactions of aryl bromides. In the presence of Pd/C, zinc, NH4Cl, and water, coupling of various aryl bromides was carried out smoothly to afford the corresponding homocoupling products in moderate yields.

  4. Palladium-catalyzed conversion of aryl and vinyl triflates to bromides and chlorides.

    Science.gov (United States)

    Shen, Xiaoqiang; Hyde, Alan M; Buchwald, Stephen L

    2010-10-13

    The palladium-catalyzed conversion of aryl and vinyl triflates to aryl and vinyl halides (bromides and chlorides) has been developed using dialkylbiaryl phosphine ligands. A variety of aryl, heteroaryl, and vinyl halides can be prepared via this method in good to excellent yields.

  5. An improved palladium-catalyzed conversion of aryl and vinyl triflates to bromides and chlorides.

    Science.gov (United States)

    Pan, Jun; Wang, Xinyan; Zhang, Yong; Buchwald, Stephen L

    2011-09-16

    A facile Pd-catalyzed conversion of aryl and vinyl triflates to aryl and vinyl halides (bromides and chlorides) is described. This method allows convenient access to a variety of aryl, heteroaryl, and vinyl halides in good to excellent yields and with greatly simplified conditions relative to our previous report. © 2011 American Chemical Society

  6. Efficient palladium-catalyzed coupling reactions of aryl bromides and chlorides with phenols.

    Science.gov (United States)

    Hu, Tongjie; Schulz, Thomas; Torborg, Christian; Chen, Xiaorong; Wang, Jun; Beller, Matthias; Huang, Jun

    2009-12-21

    A convenient and general palladium-catalyzed coupling reaction of aryl bromides and chlorides with phenols was developed. Various functional groups such as nitriles, aldehydes, ketones and esters are well tolerated and the corresponding products are obtained in good to excellent yield.

  7. Pd-catalyzed decarboxylative cross coupling of potassium polyfluorobenzoates with aryl bromides, chlorides, and triflates.

    Science.gov (United States)

    Shang, Rui; Xu, Qing; Jiang, Yuan-Ye; Wang, Yan; Liu, Lei

    2010-03-05

    Pd-catalyzed decarboxylative cross coupling of potassium polyfluorobenzoates with aryl bromides, chlorides, and triflates is achieved by using diglyme as the solvent. The reaction is useful for synthesis of polyfluorobiaryls from readily accessible and nonvolatile polyfluorobenzoate salts. Unlike the Cu-catalyzed decarboxylation cross coupling where oxidative addition is the rate-limiting step, in the Pd-catalyzed version decarboxylation is the rate-limiting step.

  8. Replacing conventional carbon nucleophiles with electrophiles: nickel-catalyzed reductive alkylation of aryl bromides and chlorides.

    Science.gov (United States)

    Everson, Daniel A; Jones, Brittany A; Weix, Daniel J

    2012-04-11

    A general method is presented for the synthesis of alkylated arenes by the chemoselective combination of two electrophilic carbons. Under the optimized conditions, a variety of aryl and vinyl bromides are reductively coupled with alkyl bromides in high yields. Under similar conditions, activated aryl chlorides can also be coupled with bromoalkanes. The protocols are highly functional-group tolerant (-OH, -NHTs, -OAc, -OTs, -OTf, -COMe, -NHBoc, -NHCbz, -CN, -SO(2)Me), and the reactions are assembled on the benchtop with no special precautions to exclude air or moisture. The reaction displays different chemoselectivity than conventional cross-coupling reactions, such as the Suzuki-Miyaura, Stille, and Hiyama-Denmark reactions. Substrates bearing both an electrophilic and nucleophilic carbon result in selective coupling at the electrophilic carbon (R-X) and no reaction at the nucleophilic carbon (R-[M]) for organoboron (-Bpin), organotin (-SnMe(3)), and organosilicon (-SiMe(2)OH) containing organic halides (X-R-[M]). A Hammett study showed a linear correlation of σ and σ(-) parameters with the relative rate of reaction of substituted aryl bromides with bromoalkanes. The small ρ values for these correlations (1.2-1.7) indicate that oxidative addition of the bromoarene is not the turnover-frequency determining step. The rate of reaction has a positive dependence on the concentration of alkyl bromide and catalyst, no dependence upon the amount of zinc (reducing agent), and an inverse dependence upon aryl halide concentration. These results and studies with an organic reductant (TDAE) argue against the intermediacy of organozinc reagents. © 2012 American Chemical Society

  9. New air-stable planar chiral ferrocenyl monophosphine ligands: Suzuki cross-coupling of aryl chlorides and bromides

    DEFF Research Database (Denmark)

    Jensen, Jakob Feldthusen; Johannsen, Mogens

    2003-01-01

    GraphicA novel class of planar chiral electron-rich monophosphine ligands has been developed. The modular design allows a short and efficient synthesis of an array of aryl-ferrocenyl derivatives carrying the donating bis(dicyclohexyl)phosphino moiety. These new ligands have successfully been appl...... applied in the palladium-catalyzed Suzuki cross-coupling of activated as well as nonactivated aryl chlorides at room temperature. The asymmetric coupling of an aryl bromide and an aryl boronic acid was also tested, giving ees up to 54%....

  10. Palladium-catalyzed coupling of ammonia with aryl chlorides, bromides, iodides, and sulfonates: a general method for the preparation of primary arylamines.

    Science.gov (United States)

    Vo, Giang D; Hartwig, John F

    2009-08-12

    We report that the complex generated from Pd[P(o-tol)(3)](2) and the alkylbisphosphine CyPF-t-Bu is a highly active and selective catalyst for the coupling of ammonia with aryl chlorides, bromides, iodides, and sulfonates. The couplings of ammonia with this catalyst conducted with a solution of ammonia in dioxane form primary arylamines from a variety of aryl electrophiles in high yields. Catalyst loadings as low as 0.1 mol % were sufficient for reactions of many aryl chlorides and bromides. In the presence of this catalyst, aryl sulfonates also coupled with ammonia for the first time in high yields. A comparison of reactions in the presence of this catalyst versus those in the presence of existing copper and palladium systems revealed a complementary, if not broader, substrate scope. The utility of this method to generate amides, imides, and carbamates is illustrated by a one-pot synthesis of a small library of these carbonyl compounds from aryl bromides and chlorides, ammonia, and acid chlorides or anhydrides. Mechanistic studies show that reactions conducted with the combination of Pd[P(o-tol)(3)](2) and CyPF-t-Bu as catalyst occur with faster rates and higher yields than those conducted with CyPF-t-Bu and palladiun(II) as catalyst precursors because of the low concentration of active catalyst that is generated from the combination of palladium(II), ammonia, and base.

  11. A general, practical palladium-catalyzed cyanation of (hetero)aryl chlorides and bromides.

    Science.gov (United States)

    Senecal, Todd D; Shu, Wei; Buchwald, Stephen L

    2013-09-16

    Playing it safe: The nontoxic cyanide source K4 [Fe(CN)6]·3H2O can be used for the cyanation of (hetero)aryl halides. The application of palladacycle catalysts prevents poisoning during catalyst formation, thereby allowing for low catalyst loadings, fast reaction times, and wide heterocyclic substrate scope. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  12. Nickel-catalyzed cross-coupling of functionalized difluoromethyl bromides and chlorides with aryl boronic acids: a general method for difluoroalkylated arenes.

    Science.gov (United States)

    Xiao, Yu-Lan; Guo, Wen-Hao; He, Guo-Zhen; Pan, Qiang; Zhang, Xingang

    2014-09-08

    Transition-metal-catalyzed difluoroalkylation of aromatics remains challenging despite the importance of difluoroalkylated arenes in medicinal chemistry. Herein, the first successful example of nickel-catalyzed difluoroalkylation of aryl boronic acids is described. The reaction allows access to a variety of functionalized difluoromethyl bromides and chlorides, and paves the way to highly cost-efficient synthesis of a wide range of difluoroalkylated arenes. The notable features of this protocol are its high generality, excellent functional-group compatibility, low-cost nickel-catalyst, and practicality for gram-scale production, thus providing a facile method for applications in drug discovery and development. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  13. Rhodium(NHC)-catalyzed O-arylation of aryl bromides.

    Science.gov (United States)

    Kim, Hyun Jin; Kim, Min; Chang, Sukbok

    2011-05-06

    The first example of the rhodium-catalyzed O-arylation of aryl bromides is reported. While the right combination of rhodium species and N-heterocyclic carbene (NHC) offered an effective catalytic system enabling the arylation to proceed, the choice of NHC was determined to be most important. The developed O-arylation protocol has a wide range of substrate scope, high functional group tolerance, and flexibility allowing a complementary route to either N- or O-arylation depending on the choice of NHC.

  14. New air-stable planar chiral ferrocenyl monophosphine ligands: Suzuki cross-coupling of aryl chlorides and bromides

    DEFF Research Database (Denmark)

    Jensen, Jakob Feldthusen; Johannsen, Mogens

    2003-01-01

    GraphicA novel class of planar chiral electron-rich monophosphine ligands has been developed. The modular design allows a short and efficient synthesis of an array of aryl-ferrocenyl derivatives carrying the donating bis(dicyclohexyl)phosphino moiety. These new ligands have successfully been...

  15. Palladium-catalyzed cross-coupling of cyclopropylmagnesium bromide with aryl bromides mediated by zinc halide additives.

    Science.gov (United States)

    Shu, Chutian; Sidhu, Kanwar; Zhang, Li; Wang, Xiao-Jun; Krishnamurthy, Dhileepkumar; Senanayake, Chris H

    2010-10-01

    The key Pd-catalyzed cross-coupling of aryl bromides or triflates and cyclopropylmagnesium bromide in the presence of substoichiometric amounts of zinc bromide produces cyclopropyl arenes in good to excellent yields. The cross-coupling of other alkyl, cycloalkyl, and aryl Grignard reagents with aryl bromides under the same conditions gives the corresponding substituted arenes in good yields.

  16. Miyaura Borylations of Aryl Bromides in Water at Room Temperature

    OpenAIRE

    Lipshutz, Bruce H.; Moser, Ralph; Voigtritter, Karl R.

    2010-01-01

    New technology for palladium-catalyzed cross-couplings between B2pin2 and aryl bromides leading to arylboronates is described. Micellar catalysis serves to enable borylations to take place in water as the only medium at ambient temperatures.

  17. Direct acylation of aryl bromides with aldehydes by palladium catalysis.

    Science.gov (United States)

    Ruan, Jiwu; Saidi, Ourida; Iggo, Jonathan A; Xiao, Jianliang

    2008-08-13

    A new protocol for the direct acylation of aryl bromides with aldehydes is established. It appears to involve palladium-amine cooperative catalysis, affording synthetically important alkyl aryl ketones in moderate to excellent yields in a straightforward manner, and broadening the scope of metal-catalyzed coupling reactions.

  18. Pd-catalyzed carbonylative α-arylation of aryl bromides: scope and mechanistic studies.

    Science.gov (United States)

    Nielsen, Dennis U; Lescot, Camille; Gøgsig, Thomas M; Lindhardt, Anders T; Skrydstrup, Troels

    2013-12-23

    Reaction conditions for the three-component synthesis of aryl 1,3-diketones are reported applying the palladium-catalyzed carbonylative α-arylation of ketones with aryl bromides. The optimal conditions were found by using a catalytic system derived from [Pd(dba)2] (dba=dibenzylideneacetone) as the palladium source and 1,3-bis(diphenylphosphino)propane (DPPP) as the bidentate ligand. These transformations were run in the two-chamber reactor, COware, applying only 1.5 equivalents of carbon monoxide generated from the CO-releasing compound, 9-methylfluorene-9-carbonyl chloride (COgen). The methodology proved adaptable to a wide variety of aryl and heteroaryl bromides leading to a diverse range of aryl 1,3-diketones. A mechanistic investigation of this transformation relying on 31P and 13C NMR spectroscopy was undertaken to determine the possible catalytic pathway. Our results revealed that the combination of [Pd(dba)2] and DPPP was only reactive towards 4-bromoanisole in the presence of the sodium enolate of propiophenone suggesting that a [Pd(dppp)(enolate)] anion was initially generated before the oxidative-addition step. Subsequent CO insertion into an [Pd(Ar)(dppp)(enolate)] species provided the 1,3-diketone. These results indicate that a catalytic cycle, different from the classical carbonylation mechanism proposed by Heck, is operating. To investigate the effect of the dba ligand, the Pd0 precursor, [Pd(η3-1-PhC3H4)(η5-C5H5)], was examined. In the presence of DPPP, and in contrast to [Pd(dba)2], its oxidative addition with 4-bromoanisole occurred smoothly providing the [PdBr(Ar)(dppp)] complex. After treatment with CO, the acyl complex [Pd(CO)Br(Ar)(dppp)] was generated, however, its treatment with the sodium enolate led exclusively to the acylated enol in high yield. Nevertheless, the carbonylative α-arylation of 4-bromoanisole with either catalytic or stoichiometric [Pd(η3-1-PhC3H4)(η5-C5H5)] over a short reaction time, led to the 1,3-diketone product

  19. Palladium-catalyzed silylation of aryl chlorides with hexamethyldisilane.

    Science.gov (United States)

    McNeill, Eric; Barder, Timothy E; Buchwald, Stephen L

    2007-09-13

    A method for the palladium-catalyzed silylation of aryl chlorides has been developed. The method affords desired product in good yield, is tolerant of a variety of functional groups, and provides access to a wide variety of aryltrimethylsilanes from commercially available aryl chlorides. Additionally, a one-pot procedure that converts aryl chlorides into aryl iodides has been developed.

  20. Synthesis of dimethyl aryl acylsulfonium bromides from aryl methyl ketones in a DMSO-HBr system.

    Science.gov (United States)

    Cao, Zhiling; Shi, Dahua; Qu, Yingying; Tao, Chuanzhou; Liu, Weiwei; Yao, Guowei

    2013-12-16

    A new, simplified method for the synthesis of dimethyl aryl acylsulfonium salts has been developed. A series of dimethyl aryl acylsulfonium bromides were prepared by the reaction of aryl methyl ketones with hydrobromic acid and dimethylsulfoxide (DMSO). This sulfonium salt confirms that bromine production and the bromination reaction take place in the DMSO-HBr oxidation system. What's more, it is also a key intermediate for the synthesis of arylglyoxals.

  1. Synthesis of Dimethyl Aryl Acylsulfonium Bromides from Aryl Methyl Ketones in a DMSO-HBr System

    Directory of Open Access Journals (Sweden)

    Zhiling Cao

    2013-12-01

    Full Text Available A new, simplified method for the synthesis of dimethyl aryl acylsulfonium salts has been developed. A series of dimethyl aryl acylsulfonium bromides were prepared by the reaction of aryl methyl ketones with hydrobromic acid and dimethylsulfoxide (DMSO. This sulfonium salt confirms that bromine production and the bromination reaction take place in the DMSO-HBr oxidation system. What’s more, it is also a key intermediate for the synthesis of arylglyoxals.

  2. Pd-catalyzed nucleophilic fluorination of aryl bromides.

    Science.gov (United States)

    Lee, Hong Geun; Milner, Phillip J; Buchwald, Stephen L

    2014-03-12

    On the basis of mechanism-driven reaction design, a Pd-catalyzed nucleophilic fluorination of aryl bromides and iodides has been developed. The method exhibits a broad substrate scope, especially with respect to nitrogen-containing heteroaryl bromides, and proceeds with minimal formation of the corresponding reduction products. A facilitated ligand modification process was shown to be critical to the success of the reaction.

  3. Reductive cross-coupling of nonaromatic, heterocyclic bromides with aryl and heteroaryl bromides.

    Science.gov (United States)

    Molander, Gary A; Traister, Kaitlin M; O'Neill, Brian T

    2014-06-20

    Reductive cross-coupling allows the direct C-C bond formation between two organic halides without the need for preformation of an organometallic reagent. A method has been developed for the reductive cross-coupling of nonaromatic, heterocyclic bromides with aryl or heteroaryl bromides. The developed conditions use an air-stable Ni(II) source in the presence of a diamine ligand and a metal reductant to allow late-stage incorporation of saturated heterocyclic rings onto aryl halides in a functional-group tolerant manner.

  4. DBU-Promoted Trifluoromethylation of Aryl Iodides with Difluoromethyltriphenylphosphonium Bromide

    Institute of Scientific and Technical Information of China (English)

    Yun Wei; Liuying Yu; Jinhong Lin; Xing Zheng; Jichang Xiao

    2016-01-01

    DBU-promoted trifluoromethylation of aryl iodides with difluoromethyltriphenylphosphonium bromide (DFPB) in the presence of copper source is described.In this transformation,DBU not only acts as base to deprotonate the difluoromethyl group in DFPB to generate difluoromethylene phosphonium ylide Ph3P+CF2,but also converts the difluorocarbene generated from ylide Ph3P+CF2 into trifluoromethyl anion,finally resulting in the trifluoromethylation of aryl iodides.The reactions proceeded smoothly to afford expected products in moderate to good yields.

  5. Direct palladium-catalyzed C-3 arylation of free (NH)-indoles with aryl bromides under ligandless conditions.

    Science.gov (United States)

    Bellina, Fabio; Benelli, Francesca; Rossi, Renzo

    2008-07-18

    A new method for the efficient, practical, and highly regioselective direct palladium-catalyzed C-3 arylation of free (NH)-indole and its electron-rich 1-unsubstituted derivatives under ligandless conditions is described. The reactions, which are run outside a glovebox without purification of solvent and reagents, involve treatment of free (NH)-indoles with activated, unactivated, and deactivated aryl bromides in refluxing toluene in the presence of K2CO3 as the base and a catalyst system consisting of a combination of Pd(OAc)2 and benzyl(tributyl)ammonium chloride. The experimental results are consistent with a catalytic cycle based on an electrophilic palladation pathway at the 3-position of 1-indolyl potassium salts.

  6. Direct palladium-catalyzed arylations of aryl bromides with 2/9-substituted pyrimido[5,4-b]indolizines.

    Science.gov (United States)

    Jiang, Min; Li, Ting; Meng, Linghua; Yang, Chunhao; Xie, Yuyuan; Ding, Jian

    2009-01-01

    C-5 arylated 2/9-substituted pyrimido[5,4-b]indolizines were synthesized via palladium-catalyzed direct arylation. A variety of substituents on both pyrimido[5,4-b]indolizines and aryl/heteroaryl bromides are tolerated, providing rapid access to substituted pyrimido[5,4-b]indolizines in good to excellent yields.

  7. Visible-Light-Promoted Nickel- and Organic-Dye-Cocatalyzed Formylation Reaction of Aryl Halides and Triflates and Vinyl Bromides with Diethoxyacetic Acid as a Formyl Equivalent.

    Science.gov (United States)

    Huang, He; Li, Xiangmin; Yu, Chenguang; Zhang, Yueteng; Mariano, Patrick S; Wang, Wei

    2017-02-01

    A simple formylation reaction of aryl halides, aryl triflates, and vinyl bromides under synergistic nickel- and organic-dye-mediated photoredox catalysis is reported. Distinct from widely used palladium-catalyzed formylation processes, this reaction proceeds by a two-step mechanistic sequence involving initial in situ generation of the diethoxymethyl radical from diethoxyacetic acid by a 4CzIPN-mediated photoredox reaction. The formyl-radical equivalent then undergoes nickel-catalyzed substitution reactions with aryl halides and triflates and vinyl bromides to form the corresponding aldehyde products. Significantly, besides aryl bromides, less reactive aryl chlorides and triflates and vinyl halides serve as effective substrates for this process. Since the mild conditions involved in this reaction tolerate a plethora of functional groups, the process can be applied to the efficient preparation of diverse aromatic aldehydes. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  8. Multimetallic catalysed cross-coupling of aryl bromides with aryl triflates.

    Science.gov (United States)

    Ackerman, Laura K G; Lovell, Matthew M; Weix, Daniel J

    2015-08-27

    The advent of transition-metal catalysed strategies for forming new carbon-carbon bonds has revolutionized the field of organic chemistry, enabling the efficient synthesis of ligands, materials, and biologically active molecules. In cases where a single metal fails to promote a selective or efficient transformation, the synergistic cooperation of two distinct catalysts--multimetallic catalysis--can be used instead. Many important reactions rely on multimetallic catalysis, such as the Wacker oxidation of olefins and the Sonogashira coupling of alkynes with aryl halides, but this approach has largely been limited to the use of metals with distinct reactivities, with only one metal catalyst undergoing oxidative addition. Here, we demonstrate that cooperativity between two group 10 metal catalysts--(bipyridine)nickel and (1,3-bis(diphenylphosphino)propane)palladium--enables a general cross-Ullmann reaction (the cross-coupling of two different aryl electrophiles). Our method couples aryl bromides with aryl triflates directly, eliminating the use of arylmetal reagents and avoiding the challenge of differentiating between multiple carbon-hydrogen bonds that is required for direct arylation methods. Selectivity can be achieved without an excess of either substrate and originates from the orthogonal reactivity of the two catalysts and the relative stability of the two arylmetal intermediates. While (1,3-bis(diphenylphosphino)propane)palladium reacts preferentially with aryl triflates to afford a persistent intermediate, (bipyridine)nickel reacts preferentially with aryl bromides to form a transient, reactive intermediate. Although each catalyst forms less than 5 per cent cross-coupled product in isolation, together they are able to achieve a yield of up to 94 per cent. Our results reveal a new method for the synthesis of biaryls, heteroaryls, and dienes, as well as a general mechanism for the selective transfer of ligands between two metal catalysts. We anticipate that this

  9. Multimetallic catalysed cross-coupling of aryl bromides with aryl triflates

    Science.gov (United States)

    Ackerman, Laura K. G.; Lovell, Matthew M.; Weix, Daniel J.

    2015-08-01

    The advent of transition-metal catalysed strategies for forming new carbon-carbon bonds has revolutionized the field of organic chemistry, enabling the efficient synthesis of ligands, materials, and biologically active molecules. In cases where a single metal fails to promote a selective or efficient transformation, the synergistic cooperation of two distinct catalysts--multimetallic catalysis--can be used instead. Many important reactions rely on multimetallic catalysis, such as the Wacker oxidation of olefins and the Sonogashira coupling of alkynes with aryl halides, but this approach has largely been limited to the use of metals with distinct reactivities, with only one metal catalyst undergoing oxidative addition. Here, we demonstrate that cooperativity between two group 10 metal catalysts--(bipyridine)nickel and (1,3-bis(diphenylphosphino)propane)palladium--enables a general cross-Ullmann reaction (the cross-coupling of two different aryl electrophiles). Our method couples aryl bromides with aryl triflates directly, eliminating the use of arylmetal reagents and avoiding the challenge of differentiating between multiple carbon-hydrogen bonds that is required for direct arylation methods. Selectivity can be achieved without an excess of either substrate and originates from the orthogonal reactivity of the two catalysts and the relative stability of the two arylmetal intermediates. While (1,3-bis(diphenylphosphino)propane)palladium reacts preferentially with aryl triflates to afford a persistent intermediate, (bipyridine)nickel reacts preferentially with aryl bromides to form a transient, reactive intermediate. Although each catalyst forms less than 5 per cent cross-coupled product in isolation, together they are able to achieve a yield of up to 94 per cent. Our results reveal a new method for the synthesis of biaryls, heteroaryls, and dienes, as well as a general mechanism for the selective transfer of ligands between two metal catalysts. We anticipate that this

  10. Copper-catalysed N-arylation of arylsulfonamides with aryl bromides and aryl iodides using KF/Al2O3

    Indian Academy of Sciences (India)

    Rahman Hosseinzadeh; Mahmood Tajbakhsh; Maryam Mohadjerani; Mohammad Alikarami

    2010-03-01

    An efficient synthesis of -arylsulfonamides with a variety of aryl bromides, aryl iodides and heteroaryl bromides using KF/Al2O3 as a suitable base, CuI as an inexpensive catalyst and ,'-dimethylethylenediamine (,'-DMEDA) as an effective ligand is described.

  11. Efficient catalyst for the Suzuki-Miyaura coupling of potassium aryl trifluoroborates with aryl chlorides.

    Science.gov (United States)

    Barder, Timothy E; Buchwald, Stephen L

    2004-08-05

    Palladium-catalyzed Suzuki-Miyaura cross-coupling reactions of aryl- and heteroaryl chlorides with potassium aryl- and heteroaryltrifluoroborates have been accomplished with the supporting ligand S-Phos in good to excellent yield. Hindered biaryls and substrates containing a variety of functional groups can be prepared. Suzuki-Miyaura couplings of a 3-pyridyl boron-based nucleophile with aryl- and heteroaryl chlorides proceed in good to very good yield. [reaction: see text

  12. Silver-catalyzed cross-coupling reactions of alkyl bromides with alkyl or aryl Grignard reagents

    OpenAIRE

    Someya, Hidenori; Yorimitsu, Hideki; Oshima, Koichiro

    2009-01-01

    reatment of secondary or tertiary alkyl bromides with alkyl Grignard reagents in the presence of catalytic amounts of silver bromide and potassium fluoride in CH2Cl2 afforded the corresponding cross-coupling products in reasonable yields. Moreover, silver showed catalytic activity for the cross-coupling reactions of alkyl bromides with aryl Grignard reagents.

  13. Copper/N,N-Dimethylglycine Catalyzed Goldberg Reactions Between Aryl Bromides and Amides, Aryl Iodides and Secondary Acyclic Amides

    Directory of Open Access Journals (Sweden)

    Liqin Jiang

    2014-08-01

    Full Text Available An efficient and general copper-catalyzed Goldberg reaction at 90–110 °C between aryl bromides and amides providing the desired products in good to excellent yields has been developed using N,N-dimethylglycine as the ligand. The reaction is tolerant toward a wide range of amides and a variety of functional group substituted aryl bromides. In addition, hindered, unreactive aromatic and aliphatic secondary acyclic amides, known to be poor nucleophiles, are efficiently coupled with aryl iodides through this simple and cheap copper/N,N-dimethylglycine catalytic system.

  14. Hindered aryl bromides for regioselective palladium-catalysed direct arylation at less favourable C5-carbon of 3-substituted thiophenes

    Directory of Open Access Journals (Sweden)

    Rongwei Jin

    2014-05-01

    Full Text Available The use of the congested aryl bromide 2-bromo-1,3-dichlorobenzene as coupling partner allows to modify the regioselectivity of the arylation of 3-substituted thiophene derivatives in favour of carbon C5. The coupling of this aryl bromide with a variety of 3-substituted thiophenes gave in all cases the desired 5-arylation products in moderate to good yields using only 0.5 mol % of a phosphine-free and air-stable palladium catalyst. Then, from these 5-arylthiophenes, a second palladium-catalysed C–H bond functionalization at C2 of the thiophene ring allows the synthesis of 2,5-diarylthiophenes with two different aryl units.

  15. Chloride, bromide and iodide scintillators with europium

    Science.gov (United States)

    Zhuravleva, Mariya; Yang, Kan

    2016-09-27

    A halide scintillator material is disclosed where the halide may comprise chloride, bromide or iodide. The material is single-crystalline and has a composition of the general formula ABX.sub.3 where A is an alkali, B is an alkali earth and X is a halide which general composition was investigated. In particular, crystals of the formula ACa.sub.1-yEu.sub.yI.sub.3 where A=K, Rb and Cs were formed as well as crystals of the formula CsA.sub.1-yEu.sub.yX.sub.3 (where A=Ca, Sr, Ba, or a combination thereof and X=Cl, Br or I or a combination thereof) with divalent Europium doping where 0.ltoreq.y.ltoreq.1, and more particularly Eu doping has been studied at one to ten mol %. The disclosed scintillator materials are suitable for making scintillation detectors used in applications such as medical imaging and homeland security.

  16. Multimetallic Catalysis Enabled Cross-Coupling of Aryl Bromides with Aryl Triflates

    Science.gov (United States)

    Ackerman, Laura K.G.; Lovell, Matthew M.

    2015-01-01

    Transition metal-catalyzed strategies for the formation of new C-C bonds have revolutionized the field of organic chemistry, enabling the efficient synthesis of ligands, materials, and biologically active molecules.1–3 In cases where a single metal fails to promote a selective or efficient transformation, the synergistic cooperation4 of two distinct catalysts – multimetallic catalysis – can be employed instead. Many important reactions rely on multimetallic catalysis,5 including the Wacker oxidation of olefins6–8 and the Sonogashira coupling of alkynes with aryl halides.9–10 However, the application of this strategy, even in recently developed methods11, has largely been limited to the use of metals with distinct reactivities, with only one metal catalyst undergoing an oxidative addition.12 In this manuscript, we demonstrate that cooperativity between two d10 metal catalysts, (bipyridine)nickel and (1,3-bis(diphenylphosphino)propane)palladium, enables a general cross-Ullman reaction.13–15 Our method couples aryl bromides with aryl triflates directly, eliminating the use of arylmetal reagents and avoiding the challenge of differentiating between multiple C–H bonds that is required for many C–H activation methods.16–17 The selectivity does not require an excess of either substrate and originates from the orthogonal activity of the two catalysts and the relative stability of the two arylmetal intermediates. While (dppp)Pd reacts preferentially with aryl triflates to afford a persistent intermediate, (bpy)Ni reacts preferentially with aryl bromides to form a transient, reactive intermediate. Although each catalyst forms less than 5% cross product in isolation, together they are able to achieve up to 94% yield. Our results reveal a new, general method for the synthesis of biaryls, heteroaryls, and dienes, as well as a new mechanism for selective transmetalation between two catalysts. We anticipate that this reaction will simplify the synthesis of

  17. Aminomethylations via Cross-Coupling of Potassium Organotrifluoroborates with Aryl Bromides

    Science.gov (United States)

    Sandrock, Deidre L.

    2008-01-01

    The Suzuki-Miyaura cross-coupling reaction of N,N-dialkylaminomethyltrifluoroborates with aryl halides allows the construction of an aminomethyl aryl linkage through a disconnection based on dissonant reactivity patterns. A variety of these aminomethyltrifluoroborate substrates were prepared in good to excellent yields and then shown to cross-couple with equal facility to both electron-rich and electron-poor aryl halides as well as to a variety of heteroaromatic bromides. PMID:17367156

  18. Well-Defined Copper(I) Fluoroalkoxide Complexes for Trifluoroethoxylation of Aryl and Heteroaryl Bromides

    KAUST Repository

    Huang, Ronglu

    2015-03-17

    © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim. Copper(I) fluoroalkoxide complexes bearing dinitrogen ligands were synthesized and the structure and reactivity of the complexes toward trifluoroethoxylation, pentafluoropropoxylation, and tetrafluoropropoxylation of aryl and heteroaryl bromides were investigated. Efficiency drive: A series of copper(I) fluoroalkoxide complexes bearing N,N ligands have been prepared and structurally characterized. These well-defined complexes serve as efficient reagents for the fluoroalkoxylation of aryl and heteroaryl bromides to produce a wide range of trifluoroethyl, pentafluoropropyl, and tetrafluoropropyl (hetero)aryl ethers in good to excellent yields.

  19. Pd/Cu-catalyzed C-H arylation of 1,3,4-thiadiazoles with (hetero)aryl iodides, bromides, and triflates.

    Science.gov (United States)

    Vachhani, Dipak D; Sharma, Abhishek; Van der Eycken, Erik

    2012-10-05

    The direct C-H arylation of 1,3,4-thiadiazoles with a wide range of (hetero)aryl iodides, bromides, and triflates is described using a Pd/Cu-catalyzed protocol. The methodology is compatible with substrates possessing electron-donating or electron-withdrawing substituents and also tolerates sterically hindered aryl halides. The utility of the developed protocol is demonstrated by a one-pot C-H arylation-Suzuki coupling sequence.

  20. The copper catalysed reaction of sodium methoxide with aryl bromides. A mechanistic study leading to a facile synthesis of anisole derivatives

    NARCIS (Netherlands)

    Koten, G. van; Aalten, H.L.; Grove, D.M.; Kuilman, T.; Piekstra, O.G.; Hulshof, L.A.; Sheldon, R.A.

    1989-01-01

    The copper catalysed reaction of unactivated aryl bromides with sodium methoxide has been investigated by studying a number of parameters (copper catalyst, cosolvent, concentration and relative ratio of the reactants, additives and aryl bromide substituents) which influence this reaction. The

  1. A general, efficient, and functional-group-tolerant catalyst system for the palladium-catalyzed thioetherification of aryl bromides and iodides.

    Science.gov (United States)

    Fernández-Rodríguez, Manuel A; Hartwig, John F

    2009-02-20

    The cross-coupling reaction of aryl bromides and iodides with aliphatic and aromatic thiols catalyzed by palladium complexes of the bisphosphine ligand CyPF-tBu (1) is reported. Reactions occur in excellent yields, broad scope, high tolerance of functional groups, and with turnover numbers that exceed those of previous catalysts by 2 or 3 orders of magnitude. These couplings of bromo- and iodoarenes are more efficient than the corresponding reactions of chloroarenes and could be conducted with less catalyst loading and/or milder reaction conditions. Consequently, limitations regarding scope and functional group tolerance previously reported in the coupling of aryl chlorides are now overcome.

  2. Mild Pd-catalyzed aminocarbonylation of (hetero)aryl bromides with a palladacycle precatalyst.

    Science.gov (United States)

    Friis, Stig D; Skrydstrup, Troels; Buchwald, Stephen L

    2014-08-15

    A palladacyclic precatalyst is employed to cleanly generate a highly active XantPhos-ligated Pd-catalyst. Its use in low temperature aminocarbonylations of (hetero)aryl bromides provides access to a range of challenging products in good to excellent yields with low catalyst loading and only a slight excess of CO. Some products are unattainable by traditional carbonylative coupling.

  3. Microwave-Enhanced Cross-Coupling Reactions Involving Alkynyltrifluoroborates with Aryl Bromides

    Directory of Open Access Journals (Sweden)

    George W. Kabalka

    2013-01-01

    Full Text Available Palladium-catalyzed alkynylation has emerged as one of the most reliable methods for the synthesis of alkynes which are often used in natural product syntheses and material science. An efficient method for coupling alkynyltrifluoroborates with various aryl bromides in the presence of a palladium catalyst has been developed using microwave irradiation. The microwave reactions are rapid and efficient.

  4. Palladium-catalyzed carbonylative synthesis of quinazolinones from 2-aminobenzamide and aryl bromides.

    Science.gov (United States)

    Wu, Xiao-Feng; He, Lin; Neumann, Helfried; Beller, Matthias

    2013-09-16

    C from CO! A straightforward procedure for the carbonylative synthesis of quinazolinones from readily available 2-aminobenzamide and aryl bromides has been developed. In the presence of a palladium catalyst, various quinazolinones were produced in moderate to excellent yields. Remarkably, no chromatography was needed for purification (see scheme).

  5. Palladium-catalyzed carbonylation reaction of aryl bromides with 2-hydroxyacetophenones to form flavones.

    Science.gov (United States)

    Wu, Xiao-Feng; Neumann, Helfried; Beller, Matthias

    2012-10-01

    Flavone of the month: a general and efficient method for the palladium-catalyzed carbonylative synthesis of flavones has been developed. Starting from aryl bromides and 2-hydroxyacetophenones, the corresponding flavones have been isolated in good yields. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  6. Microwave-enhanced cross-coupling reactions involving alkynyltrifluoroborates with aryl bromides.

    Science.gov (United States)

    Coltuclu, Vitali; Dadush, Eric; Naravane, Abhijit; Kabalka, George W

    2013-01-29

    Palladium-catalyzed alkynylation has emerged as one of the most reliable methods for the synthesis of alkynes which are often used in natural product syntheses and material science. An efficient method for coupling alkynyltrifluoroborates with various aryl bromides in the presence of a palladium catalyst has been developed using microwave irradiation. The microwave reactions are rapid and efficient.

  7. Palladium-catalyzed carbonylative sonogashira coupling of aryl bromides using near stoichiometric carbon monoxide

    DEFF Research Database (Denmark)

    Neumann, Karoline T.; Laursen, Simon R.; Lindhardt, Anders T.

    2014-01-01

    A general procedure for the palladium-catalyzed carbonylative Sonogashira coupling of aryl bromides is reported, using near stoichiometric amounts of carbon monoxide. The method allows a broad substrate scope in moderate to excellent yields. The formed alkynone motive serves as a platform...

  8. Palladium-Catalyzed Carbonylation of Aryl Bromides with N-Substituted Cyanamides

    DEFF Research Database (Denmark)

    Lian, Zhong; Friis, Stig D.; Lindhardt, Anders T.;

    2014-01-01

    The palladium(0)-catalyzed three-component coupling reaction of aryl bromides, carbon monoxide, and N-alkyl cyan­amides has been developed employing a two-chamber system with ex situ generation of carbon monoxide from a silacarboxylic acid. The reactions proceeded well and were complete with a re...

  9. Aminoarenethiolate-Copper(I)-Catalyzed Amination of Aryl Bromides

    NARCIS (Netherlands)

    Jerphagnon, Thomas; Klink, Gerard P.M. van; Vries, Johannes G. de; Koten, Gerard van

    2005-01-01

    Aminoarenethiolate-copper(I) complexes are known to be efficient catalysts for carbon-carbon bond formation. Here, we show the first examples that these thiolate-copper(I) complexes are efficient for carbon-nitrogen bond formation reactions as well. N-Arylation of benzylamine and imidazole with

  10. Aminoarenethiolate-Copper(I)-Catalyzed Amination of Aryl Bromides

    NARCIS (Netherlands)

    Jerphagnon, Thomas; Klink, Gerard P.M. van; Vries, Johannes G. de; Koten, Gerard van

    2005-01-01

    Aminoarenethiolate-copper(I) complexes are known to be efficient catalysts for carbon-carbon bond formation. Here, we show the first examples that these thiolate-copper(I) complexes are efficient for carbon-nitrogen bond formation reactions as well. N-Arylation of benzylamine and imidazole with brom

  11. Viscosity and density of some lower alkyl chlorides and bromides

    Energy Technology Data Exchange (ETDEWEB)

    Rutherford, W.M.

    1988-07-01

    A high-pressure capillary viscometer, used previously to measure the viscosity of methyl chloride was rebuilt to eliminate the first-order dependence of the measured viscosity on the value assumed for the density of the fluid being investigated. At the same time, the system was arranged so that part of the apparatus could be used to measure density by a volumetric displacement technique. Viscosity and density were measured for ethyl chloride, 1-chloropropane, 1-chlorobutane, methyl bromide, ethyl bromide, and 1-bromopropane. The temperature and pressure ranges of the experiments were 20-150 /sup 0/C and 0.27-6.99 MPa, respectively. The accuracy of the viscosity measurements was estimated to be +-1% and of the density measurements, +-0.2%.

  12. Reusable and Ligand-Free Palladium-Catalyzed Suzuki- Miyaura Cross-Couplings of Aryl Halides with Arylboronic Acids in Tetra-n-butylammonium Bromide

    Institute of Scientific and Technical Information of China (English)

    XIE,Ye-Xiang; WANG,Jian; LI,Jin-Heng; LIANG,Yun

    2008-01-01

    Ligand-free and reusable palladium-catalyzed Suzuki-Miyaura cross-coupling reaction performed in TBAB (tetra-n-butylammonium bromide) was presented. It was found that the amount of water affected these reactions. Excellent results were obtained when there was w= 1% of water in TBAB. In the presence of 3 mol% of Pd(Oac)2 and 1.5 g of TBAB (containing w= 1% of water), a number of aryl halides were coupled with arylboronic acids smoothly in moderate to excellent yields. Moreover, the Pd(Oac)2/TBAB system among the couplings of aryl bro-mides and activated chlorides could be recovered and reused three times without a loss of catalytic efficiency.

  13. Palladium-catalyzed carbonylation reactions of aryl bromides at atmospheric pressure: a general system based on Xantphos.

    Science.gov (United States)

    Martinelli, Joseph R; Watson, Donald A; Freckmann, Dominique M M; Barder, Timothy E; Buchwald, Stephen L

    2008-09-19

    A method for the Pd-catalyzed carbonylation of aryl bromides has been developed using Xantphos as the ligand. This method is effective for the direct synthesis of Weinreb amides, primary and secondary benzamides, and methyl esters from the corresponding aryl bromides at atmospheric pressure. In addition, a putative catalytic intermediate, (Xanphos)Pd(Br)benzoyl, was prepared and an X-ray crystal structure was obtained revealing an unusual cis-coordination mode of Xantphos in this palladium-acyl complex.

  14. Different Performance of Two Isomeric Phosphinobiphenyl Amidosulfonates in Pd-Catalyzed Cyanation of Aryl Bromides

    Directory of Open Access Journals (Sweden)

    Jiří Schulz

    2016-11-01

    Full Text Available A hydrophilic phosphinobiphenyl amidosulfonate, 2′-(dicyclohexylphosphino-2- {[(sulfonatomethylamino]carbonyl}[1,1′-biphenyl], triethylammonium salt (L2, was prepared and, together with its isomer bearing the polar amido-sulfonate tag in the position 4 of the biphenyl scaffold (compound L1, evaluated as a supporting ligand in Pd-catalyzed cyanation of aryl bromides using K4[Fe(CN6] as the non-toxic cyanide source. The less sterically demanding ligand L1 was found to form more active catalysts than the newly prepared compound L2. A catalyst formed in situ from palladium(II acetate and L1 efficiently mediated cyanation of aryl bromides bearing electron-donating substituents but failed in the analogous reactions with electron-poor substrates.

  15. A convenient catalyst system for microwave accelerated cross-coupling of a range of aryl boronic acids with aryl chlorides

    Directory of Open Access Journals (Sweden)

    Milton Edward J

    2007-05-01

    Full Text Available Abstract A convenient microwave accelerated cross-coupling procedure between aryl chlorides with a range of boronic acids has been developed. An explanation for the low reactivity of highly fluorinated boronic acids in Suzuki coupling is provided.

  16. C-N Coupling of nitrogen nucleophiles with aryl and heteroaryl bromides using aminoarenethiolato-copper(I) (pre-)catalyst

    NARCIS (Netherlands)

    Sperotto, Elena; Klink, Gerard P.M. van; Vries, Johannes G. de; Koten, Gerard van

    2010-01-01

    The activity of a library of 2-aminoarenethiolato-copper(I) (CuSAr) (pre-)catalyst was explored in the arylation reaction of amines and N-containing heterocycles with aryl and heteroaryl bromides, respectively. These CuSAr pre-catalysts are thermally stable, are soluble in common organic solvents

  17. Nickel-mediated radioiodination of aryl and heteroaryl bromides: rapid synthesis of tracers for SPECT imaging.

    Science.gov (United States)

    Cant, Alastair A; Champion, Sue; Bhalla, Rajiv; Pimlott, Sally L; Sutherland, Andrew

    2013-07-22

    Rapid and efficient radioiodination of aryl and heteroaryl bromides has been achieved using a nickel(0)-mediated halogen-exchange reaction. This transformation gives direct access to [(123)I]- and [(125)I]-imaging agents for single photon emission computed tomography (SPECT), such as 5-[(123)I]-A85380 (see scheme, Boc = tert-butyloxycarbonyl, cod = 1,5-cyclooctadiene, TFA = trifluoroacetic acid). Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  18. Copper(I)-catalyzed aryl bromides to form intermolecular and intramolecular carbon-oxygen bonds.

    Science.gov (United States)

    Niu, Jiajia; Guo, Pengran; Kang, Juntao; Li, Zhigang; Xu, Jingwei; Hu, Shaojing

    2009-07-17

    A highly efficient Cu-catalyzed C-O bond-forming reaction of alcohol and aryl bromides has been developed. This transformation was realized through the use of copper(I) iodide as a catalyst, 8-hydroxyquinoline as a ligand, and K(3)PO(4) as a base. A variety of functionalized substrates were found to react under these reaction conditions to provide products in good to excellent yields.

  19. Practical synthesis of aryl-2-methyl-3-butyn-2-ols from aryl bromides via conventional and decarboxylative copper-free Sonogashira coupling reactions

    Directory of Open Access Journals (Sweden)

    Andrea Caporale

    2014-02-01

    Full Text Available Two efficient protocols for the palladium-catalyzed synthesis of aryl-2-methyl-3-butyn-2-ols from aryl bromides in the absence of copper were developed. A simple catalytic system consisting of Pd(OAc2 and P(p-tol3 using DBU as the base and THF as the solvent was found to be highly effective for the coupling reaction of 2-methyl-3-butyn-2-ol (4 with a wide range of aryl bromides in good to excellent yields. Analogously, the synthesis of aryl-2-methyl-3-butyn-2-ols was performed also through the decarboxylative coupling reaction of 4-hydroxy-4-methyl-2-pentynoic acid with aryl bromides, using a catalyst containing Pd(OAc2 in combination with SPhos or XPhos in the presence of tetra-n-butylammonium fluoride (TBAF as the base and THF as the solvent. Therefore, new efficient approaches to the synthesis of terminal acetylenes from widely available aryl bromides rather than expensive iodides and using 4 or propiolic acid rather than TMS-acetylene as inexpensive alkyne sources are described.

  20. An efficient method for the preparation of tertiary esters by palladium-catalyzed alkoxycarbonylation of aryl bromides.

    Science.gov (United States)

    Xin, Zhuo; Gøgsig, Thomas M; Lindhardt, Anders T; Skrydstrup, Troels

    2012-01-06

    The palladium-catalyzed alkoxycarbonylation of aryl bromides is described for the efficient preparation of tertiary esters. The protocol proved compatible with a wide variety of functionalized (hetero)aromatic bromides, as well as several different sterically hindered tertiary alcohols, affording the alkoxycarbonylated products in high yields. Finally, the formation of aromatic trityl esters is discussed. © 2011 American Chemical Society

  1. Oxidative addition of aryl chlorides to monoligated palladium(0): A DFT-SCRF study

    DEFF Research Database (Denmark)

    Ahlquist, Mårten Sten Gösta; Norrby, Per-Ola

    2007-01-01

    Oxidative addition of aryl chlorides to palladium has been investigated by hybrid density functional theory methods (B3LYP), including a continuum model describing the solvent implicitly. A series of para-substituted aryl chlorides were studied to see the influence of electronic effects on the re...

  2. A Fluorinated Ligand Enables Room-Temperature and Regioselective Pd-Catalyzed Fluorination of Aryl Triflates and Bromides.

    Science.gov (United States)

    Sather, Aaron C; Lee, Hong Geun; De La Rosa, Valentina Y; Yang, Yang; Müller, Peter; Buchwald, Stephen L

    2015-10-21

    A new biaryl monophosphine ligand (AlPhos, L1) allows for the room-temperature Pd-catalyzed fluorination of a variety of activated (hetero)aryl triflates. Furthermore, aryl triflates and bromides that are prone to give mixtures of regioisomeric aryl fluorides with Pd-catalysis can now be converted to the desired aryl fluorides with high regioselectivity. Analysis of the solid-state structures of several Pd(II) complexes, as well as density functional theory (DFT) calculations, shed light on the origin of the enhanced reactivity observed with L1.

  3. Palladium-catalyzed microwave-assisted direct arylation of imidazo[2,1-b]thiazoles with aryl bromides: synthesis and mechanistic study.

    Science.gov (United States)

    Zhu, Yi-Shuo; Shi, Benyi; Fang, Ran; Wang, Xiaoxuan; Jing, Huanwang

    2014-08-14

    A palladium-catalyzed direct C-H arylation of various imidazo[2,1-b]thiazoles with a range of aryl bromides under microwave irradiation is described. 6-Phenyl substituted imidazo[2,1-b]thiazoles could be regioselectively C-5 arylated using the developed protocol. The utility of this method enables the representative coupling product to be achieved by a sequential one-pot reaction. Density functional theory (DFT) calculations show that this arylation proceeds via a concerted metalation-deprotonation (CMD) pathway, which is in agreement with our experimental results. This work provides a convenient access to a variety of biologically active imidazo[2,1-b]thiazole derivatives. Also, it enriches the mechanism study of site-selective C-H arylation in fused heterocycles, and offers a valuable guide to design highly efficient catalytic systems for the preparation of similar compounds.

  4. An Efficient and General Method for Formylation of Aryl Bromides with CO2 and Poly(methylhydrosiloxane).

    Science.gov (United States)

    Yu, Bo; Yang, Zhenzhen; Zhao, Yanfei; Hao, Leiduan; Zhang, Hongye; Gao, Xiang; Han, Buxing; Liu, Zhimin

    2016-01-18

    The formylation of aryl halides with CO2 to generate aryl aldehydes is challenging. Herein, we report a novel synthesis of aryl aldehydes by formylation of aryl bromides with CO2 and a waste silane, poly(methylhydrosiloxane) (PMHS). It has been discovered that a simple combination of 1,3-bis(diphenyphosphino)propane (DPPP)-chelated Pd catalyst, Pd(DPPP)Cl2 , with 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU) is able to effectively catalyze the reaction, leading to aryl aldehydes in moderate to excellent yields, and without any by-products in most cases. Moreover, this route could be extended to the formylation of aryl iodides with high efficiency. This approach is simple, less costly, and environmentally friendly, and also widens the applications of CO2 to form value-added chemicals by the construction of new C-C bonds.

  5. Palladium-Catalyzed Carbonylation Reactions of Aryl Bromides at Atmospheric Pressure: A General System Based on Xantphos

    OpenAIRE

    Martinelli, Joseph R.; Watson, Donald A.; Freckmann, Dominique M. M.; Barder, Timothy E.; Buchwald, Stephen L.

    2008-01-01

    A method for the Pd-catalyzed carbonylation of aryl bromides has been developed using Xantphos as the ligand. This method is effective for the direct synthesis of Weinreb amides, 1° and 2° benzamides and methyl esters from the corresponding aryl bromides at atmospheric pressure. In addition, a putative catalytic intermediate, (Xanphos)Pd(Br)benzoyl, was prepared and an X-ray crystal structure was obtained revealing an unusual cis-coordination mode of Xantphos in this palladium-acyl complex.

  6. Chloride, bromide and iodide scintillators with europium doping

    Science.gov (United States)

    Zhuravleva, Mariya; Yang, Kan

    2014-08-26

    A halide scintillator material is disclosed where the halide may comprise chloride, bromide or iodide. The material is single-crystalline and has a composition of the general formula ABX.sub.3 where A is an alkali, B is an alkali earth and X is a halide which general composition was investigated. In particular, crystals of the formula ACa.sub.1-yEu.sub.yI.sub.3 where A=K, Rb and Cs were formed as well as crystals of the formula CsA.sub.1-yEu.sub.yX.sub.3 (where A=Ca, Sr, Ba, or a combination thereof and X=Cl, Br or I or a combination thereof) with divalent Europium doping where 0.ltoreq.y.ltoreq.1, and more particularly Eu doping has been studied at one to ten mol %. The disclosed scintillator materials are suitable for making scintillation detectors used in applications such as medical imaging and homeland security.

  7. Aryl Radical Geometry Determines Nanographene Formation on Au(111)

    NARCIS (Netherlands)

    Jacobse, Peter H.; van den Hoogenband, Adrianus; Moret, Marc Etienne; Klein Gebbink, Robertus J M; Swart, Ingmar

    2016-01-01

    The Ullmann coupling has been used extensively as a synthetic tool for the formation of C−C bonds on surfaces. Thus far, most syntheses made use of aryl bromides or aryl iodides. We investigated the applicability of an aryl chloride in the bottom-up assembly of graphene nanoribbons. Specifically, th

  8. Efficient, regioselective palladium-catalyzed tandem Heck-isomerization reaction of aryl bromides and non-allylic benzyl alcohols.

    Science.gov (United States)

    Crawley, Matthew L; Phipps, Kristin M; Goljer, Igor; Mehlmann, John F; Lundquist, Joseph T; Ullrich, John W; Yang, Cuijian; Mahaney, Paige E

    2009-03-05

    An efficient and mild method to couple aryl bromides and activated non-allylic alcohols in a Heck reaction with tandem isomerization to selectively afford high yields of 1,5-diarylalkan-1-ones has been developed. Mechanistic insight was gained through NMR studies of products derived from deuterium-labeled intermediates.

  9. C-H activation dependent Pd-catalyzed carbonylative coupling of (hetero)aryl bromides and polyfluoroarenes.

    Science.gov (United States)

    Lian, Zhong; Friis, Stig D; Skrydstrup, Troels

    2015-02-04

    The carbonylative coupling of aryl and heteroaryl bromides with polyfluoroarenes via palladium-catalyzed C-H activation is presented. This transformation proceeds efficiently at moderate reaction temperatures and does not require strong base or reactive intermediates. A near stoichiometric amount of CO is sufficient and the methodology can thus be easily expanded to include the preparation of [(13)C]-acyl labeled benzopolyfluorophenones.

  10. tBuLi-Mediated One-Pot Direct Highly Selective Cross-Coupling of Two Distinct Aryl Bromides

    NARCIS (Netherlands)

    Vila, Carlos; Cembellin, Sara; Hornillos, Valentin; Giannerini, Massimo; Fananas-Mastral, Martin; Feringa, Ben L.

    2015-01-01

    A Pd-catalyzed direct cross-coupling of two distinct aryl bromides mediated by tBuLi is described. The use of [Pd-PEPPSI-IPr] or [Pd-PEPPSI-IPent] as catalyst allows for the efficient one-pot synthesis of unsymmetrical biaryls at room temperature. The key for this selective cross-coupling is the use

  11. N-heterocyclic carbene-assisted, bis(phosphine)nickel-catalyzed cross-couplings of diarylborinic acids with aryl chlorides, tosylates, and sulfamates.

    Science.gov (United States)

    Ke, Haihua; Chen, Xiaofeng; Zou, Gang

    2014-08-01

    Efficient bis(phosphine)nickel-catalyzed cross-couplings of diarylborinic acids with aryl chlorides, tosylates, and sulfamates have been effected with an assistance of N-heterocyclic carbene (NHC) generated in situ from N,N'-dialkylimidazoliums, e.g., N-butyl-N'-methylimidazolium bromide ([Bmim]Br), in toluene using K3PO4·3H2O as base. In contrast to bis(NHC)nickel-catalyzed conventional Suzuki coupling of arylboronic acids, mono(NHC)bis(phosphine)nickel species generated in situ from Ni(PPh3)2Cl2/[Bmim]Br displayed high catalytic activities in the cross-couplings of diarylborinic acids. The structural influences from diarylborinic acids were found to be rather small, while electronic factors from aryl chlorides, tosylates, and sulfamates affected the couplings remarkably. The couplings of electronically activated aryl chlorides, tosylates, and sulfamates could be efficiently effected with 1.5 mol % NiCl2(PPh3)2/[Bmim]Br as catalyst precursor to give the biaryl products in excellent yields, while 3-5 mol % loadings had to be used for the couplings of non- and deactivated ones. A small ortho-substitutent on the aromatic ring of aryl chlorides, tosylates, and sulfamates was tolerable. Applicability of the nickel-catalyzed cross-couplings in practical synthesis of fine chemicals has been demonstrated in process development for a third-generation topical retinoid, Adapalene.

  12. Suzuki Reaction of Aryl Bromides Using a Phosphine-Free Magnetic Nanoparticle-Supported Palladium Catalyst

    Institute of Scientific and Technical Information of China (English)

    Nghia T. BUI; Trung B. DANG; Ha V. LE; Nam T. S. PHAN

    2011-01-01

    A palladium catalyst immobilized on superparaganetic nanoparticles was prepared with a palladium loading of 0.30 mmol/g.The catalyst was characterized using X-ray diffraction,scanning electron microscopy,transmission electron microscopy,vibrating sample magnetometry,thermogravimetric analysis,Fourier transform infrared,atomic absorption spectrophotometry,and nitrogen adsorption.The immobilized palladium catalyst was an efficient catalyst without added phosphine ligands for the Suzuki cross-coupling reaction of several aryl bromides with phenylboronic acid.The recovery of catalyst was simply by magnetic decantation in the presence of a magnet.The immobilized palladium catalyst can be reused many times without significant degradation in catalytic activity.No leaching of active palladium species into the reaction solution was detected.

  13. A General Palladium-Catalyzed Hiyama Cross-Coupling Reaction of Aryl and Heteroaryl Chlorides.

    Science.gov (United States)

    Yuen, On Ying; So, Chau Ming; Man, Ho Wing; Kwong, Fuk Yee

    2016-05-01

    A general palladium-catalyzed Hiyama cross-coupling reaction of aryl and heteroaryl chlorides with aryl and heteroaryl trialkoxysilanes by a Pd(OAc)2 /L2 catalytic system is presented. A newly developed water addition protocol can dramatically improve the product yields. The conjugation of the Pd/L2 system and the water addition protocol can efficiently catalyze a broad range of electron-rich, -neutral, -deficient, and sterically hindered aryl chlorides and heteroaryl chlorides with excellent yields within three hours and the catalyst loading can be down to 0.05 mol % Pd for the first time. Hiyama coupling of heteroaryl chlorides with heteroaryl silanes is also reported for the first time. The reaction can be easily scaled up 200 times (100 mmol) without any degasification and purification of reactants; this facilitates the practical application in routine synthesis.

  14. Ligand-free palladium catalysed Heck reaction of methyl 2-acetamido acrylate and aryl bromides as key step in the synthesis of enantiopure substituted phenylalanines

    NARCIS (Netherlands)

    Willans, Charlotte E.; Mulders, Jan M.C.A.; Vries, Johannes G. de; Vries, André H.M. de

    2003-01-01

    A range of substituted aryl bromides were coupled with methyl 2-acetamido acrylate using ligand-free palladium catalysis. Subsequently asymmetric hydrogenation with Rh/MonoPhos yielded substituted phenylalanines in high enantioselectivities (e.e. 92-99%).

  15. Photoinduced C-C Cross-Coupling of Aryl Chlorides and Inert Arenes

    Directory of Open Access Journals (Sweden)

    Lele Wang

    2016-01-01

    Full Text Available Here we report a facile, efficient, and catalyst-free method to realize C-C cross-coupling of aryl chlorides and inert arenes under UV light irradiation. The aryl radical upon homolytic cleavage of C-Cl bond initiated the nucleophilic substitution reaction with inert arenes to give biaryl products. This mild reaction mode can also be applied to other synthetic reactions, such as the construction of C-N bonds and trifluoromethylated compounds.

  16. Cu(OAc)2/Pyrimidines-Catalyzed Cross-coupling Reactions of Aryl Iodides and Activated Aryl Bromides with Alkynes under Aerobic, Solvent-free and Palladium-free Conditions

    Institute of Scientific and Technical Information of China (English)

    XIE Ye-Xiang; DENG Chen-Liang; PI Shao-Feng; LI Jin-Heng; YIN Du-Lin

    2006-01-01

    Excellent results have been achieved in the Cu(OAc)2-catalyzed Sonogashira cross-couplings of aryl iodides and activated aryl bromides utilizing TBAF (tetrabutylammonium fluoride) as the base and 4,6-dimethoxypyrimidin-2-amine as the ligand. It is noteworthy that the reaction is conducted under aerobic, solvent-free and palladium-free conditions.

  17. Palladium-catalyzed heck coupling reaction of aryl bromides in aqueous media using tetrahydropyrimidinium salts as carbene ligands.

    Science.gov (United States)

    Yaşar, Sedat; Ozcan, Emine Ozge; Gürbüz, Nevin; Cetinkaya, Bekir; Ozdemir, Ismail

    2010-01-28

    An efficient and stereoselective catalytic system for the Heck cross coupling reaction using novel 1,3-dialkyl-3,4,5,6-tetrahydropyrimidinium salts (1, LHX) and Pd(OAc)2 loading has been reported. The palladium complexes derived from the salts 1a-f prepared in situ exhibit good catalytic activity in the Heck coupling reaction of aryl bromides under mild conditions.

  18. Sonogashira coupling reaction of homopropargyl ether with aryl bromides and synthesis of 2,5-disubstituted 3-bromofurans

    Institute of Scientific and Technical Information of China (English)

    2009-01-01

    This paper presents Sonogashira coupling reaction of aryl bromides with protected homopropargyl alcohols such as tert-butyldimethyl(1-phenylbut-3-ynyloxy)silane and tert-butyldimethyl(1-(2,4-dichlorophenyl)but-3-ynyloxy)silane in piperidine catalyzed by PdCl2/PPh3 without copper(Ⅰ). The coupling products, disubstituted acetylene, are obtained in good or excellent yields. These products can be further used for the synthesis of 2,5-disubstituted 3-bromofurans.

  19. Palladium-Catalyzed Heck Coupling Reaction of Aryl Bromides in Aqueous Media Using Tetrahydropyrimidinium Salts as Carbene Ligands

    Directory of Open Access Journals (Sweden)

    İsmail Özdemir

    2010-01-01

    Full Text Available An efficient and stereoselective catalytic system for the Heck cross coupling reaction using novel 1,3-dialkyl-3,4,5,6-tetrahydropyrimidinium salts (1, LHX and Pd(OAc2 loading has been reported. The palladium complexes derived from the salts 1a-f prepared in situ exhibit good catalytic activity in the Heck coupling reaction of aryl bromides under mild conditions.

  20. Palladium-catalyzed carbonylative coupling of (2-azaaryl)methyl anion equivalents with (hetero)aryl bromides.

    Science.gov (United States)

    Jusseau, Xavier; Yin, Hongfei; Lindhardt, Anders T; Skrydstrup, Troels

    2014-11-24

    Conditions for the palladium-catalyzed coupling of (2-pyridyl)acetones with aryl bromides have been developed. Followed by an acid-promoted deacetylation step, the desired 1-(het)aryl-2-(2-pyridyl)ethanones were obtained in good to excellent yields with high functional group tolerance. Test reactions revealed that both the addition of MgCl2 and a specifically positioned heteroatom in the heteroaromatic ring were crucial for product formation indicating the importance of a chelated intermediate in the reaction mechanism. The reaction conditions proved suitable for a number of 5- and 6-membered heteroaromatic starting materials affording all products in good yields. The utility of the obtained 1-(het)aryl-2-(2-pyridyl)ethanones was demonstrated by the straightforward synthesis of several multiaromatic derivatives in only few additional steps. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  1. Palladium-catalyzed carbonylative α-arylation of 2-oxindoles with (hetero)aryl bromides: efficient and complementary approach to 3-acyl-2-oxindoles.

    Science.gov (United States)

    Lian, Zhong; Friis, Stig D; Skrydstrup, Troels

    2014-09-01

    An efficient Pd-catalyzed carbonylative α-arylation of 2-oxindoles with aryl and heteroaryl bromides for the one-step synthesis of 3-acyl-2-oxindoles has been developed. This reaction proceeds efficiently under mild conditions and is complementary to the more common oxindole forming reactions. The transformation only requires a mild base and provides good to excellent yields even with heteroaromatic substrates. Employing a near stoichiometric amount of (13) COgen, the methodology was easily extended to [(13) C] acyl labeling. The general applicability of the reaction conditions was demonstrated in the synthesis of a structure related to the pharmaceutically active 3-acyl-2-oxindoles, tenidap. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  2. Synthesis of zwitterionic palladium complexes and their application as catalysts in cross-coupling reactions of aryl, heteroaryl and benzyl bromides with organoboron reagents in neat water.

    Science.gov (United States)

    Ramakrishna, V; Dastagiri Reddy, N

    2017-07-04

    N-(3-Chloro-2-quinoxalinyl)-N'-arylimidazolium salts (aryl = 2,6-diisopropylphenyl [HL1Cl]Cl, aryl = mesityl [HL2Cl]Cl) have been synthesized by treating 2,3-dichloroquinoxaline with the corresponding N'-arylimidazole in neat water. Facile reactions of these imidazolium salts with Pd(PPh3)4 and Pd2(dba)3/PPh3 (dba = dibenzyledene acetone) at 50 °C have afforded zwitterionic palladium(ii) complexes [Pd(HL1)(PPh3)Cl2] (I) and [Pd(HL2)(PPh3)Cl2] (II) in excellent yields. I and II have been tested for their ability to catalyze Suzuki-Miyaura cross coupling (SMC) reactions in neat water/K2CO3 and are found to be highly active for carrying out these reactions between aryl bromides and organoboron reagents. Furthermore, the scope of the catalyst I was also examined by employing (hetero)aryl bromides, hydrophilic aryl bromides, benzyl bromides and various organoboron reagents. More than 80 aryl/benzyl bromide-arylboronic acid combinations were screened in neat water/K2CO3 and it was found that I was a versatile catalyst, which produced biaryls/diarylmethanes in excellent yields. A TON of 82 000 was achieved by using I. Studies on the mechanism have also been carried out to investigate the involvement of carbene complexes in the catalytic path. Poison tests and a two-phase test were also conducted and the results are reported.

  3. Bromide, Chloride, and Sulfate Concentrations, and Specific Conductance, Lake Texoma, Texas and Oklahoma, 2007-08

    Science.gov (United States)

    Baldys, Stanley

    2009-01-01

    The U.S. Geological Survey, in cooperation with the City of Dallas Water Utilities Division, collected water-quality data from 11 sites on Lake Texoma, a reservoir on the Texas-Oklahoma border, during April 2007-September 2008. At 10 of the sites, physical properties (depth, specific conductance, pH, temperature, dissolved oxygen, and alkalinity) were measured and samples were collected for analysis of selected dissolved constituents (bromide, calcium, magnesium, potassium, sodium, carbonate, bicarbonate, chloride, and sulfate); at one site, only physical properties were measured. The primary constituent of interest was bromide. Bromate can form when ozone is used to disinfect raw water containing bromide, and bromate is a suspected human carcinogen. Chloride and sulfate were of secondary interest. Only the analytical results for bromide, chloride, sulfate, and measured specific conductance are discussed in this report. Median dissolved bromide concentrations ranged from 0.28 to 0.60 milligrams per liter. The largest median dissolved bromide concentration (0.60 milligram per liter at site 11) was from the Red River arm of Lake Texoma. Dissolved bromide concentrations generally were larger in the Red River arm of Lake Texoma than in the Washita arm of the lake. Median dissolved chloride concentrations were largest in the Red River arm of Lake Texoma at site 11 (431 milligrams per liter) and smallest at site 8 (122 milligrams per liter) in the Washita arm. At site 11 in the Red River arm, the mean and median chloride concentrations exceeded the secondary maximum contaminant level of 300 milligrams per liter for chloride established by the 'Texas Surface Water Quality Standards' for surface-water bodies designated for the public water supply use. Median dissolved sulfate concentrations ranged from 182 milligrams per liter at site 4 in the Big Mineral arm to 246 milligrams per liter at site 11 in the Red River arm. None of the mean or median sulfate concentrations

  4. Dielectric relaxation losses in lead chloride and lead bromide: Localized dipoles

    NARCIS (Netherlands)

    Brom, W.E. van den; Volger, J.

    1974-01-01

    A further analysis of previous reported measurements of dielectric relaxation losses in lead chloride and lead bromide crystals shows that the dipoles may occupy several energetically different positions, giving rise to localization of the dipoles and anomalous behaviour of the susceptibility. This

  5. The influence of ipratropium bromide and sodium cromoglycate on benzalkonium chloride-induced bronchoconstriction in asthma.

    Science.gov (United States)

    Miszkiel, K A; Beasley, R; Holgate, S T

    1988-01-01

    1. Benzalkonium chloride, an antibacterial preservative that is added to nebuliser solutions, has been shown to cause bronchoconstriction when inhaled by asthmatic subjects. 2. To investigate the potential role of reflex and mast cell-dependent mechanisms in the pathogenesis of bronchoconstriction produced by benzalkonium chloride we examined the effects of ipratropium bromide and sodium cromoglycate on this response in both concentration-response and time-course studies in nine asthmatic subjects. 3. Pretreatment with inhaled ipratropium bromide (1 mg) and sodium cromoglycate (40 mg) displaced the benzalkonium chloride concentration-response curves to the right by a mean 2.2 fold and 3.1 fold respectively. 4. Ipratropium bromide and sodium cromoglycate markedly attenuated the airway response to benzalkonium chloride throughout the 45 min time course period, inhibiting the overall response by 56% and 78% respectively. 5. We conclude that benzalkonium chloride provokes bronchoconstriction in asthmatic subjects through a combination of mast cell activation and stimulation of peripheral and central neural pathways. PMID:2972308

  6. Sonogashira couplin8 reaction of homoproparsyl ether with aryl bromides and synthesis of 2,5-disubstituted 3-bromofurans

    Institute of Scientific and Technical Information of China (English)

    WANG Xin; LIU LingYan; CHANG WeiXing; LI Jing

    2009-01-01

    This paper presents Sonogashira coupling reaction of aryl bromides with protected homopropargyl alcohols such as tert-butyldimethyl(1-phenylbut-3-ynyloxy)silane and tert-butyldimethyl(1-(2,4-dichlorophenyl)but-3-ynyloxy)silane in piperidine catalyzed by PdCl2/PPh3 without copper(Ⅰ).The coupling products,disubstituted acetylene,are obtained in good or excellent yields.These products can be further used for the synthesis of 2,5-disubstituted 3-bromofurans.

  7. Mild synthesis of N'-aryl-N,N-dimethylformamidinium chloride by Vilsmeier-Haack reagent

    Institute of Scientific and Technical Information of China (English)

    Ge Meng; Yao Wu Sha; Rui Zhang; Nan Bai

    2011-01-01

    Formamidine derivatives could be used as the building blocks for substituted heterocyclic compounds with various biological activities. N'-Aryl-N,N-dimethylformamidinium chlorides have been synthesized in high yields by reaction of aromatic primary amines with Vilsmeier-Haack reagent at room temperature. The structures of all the new compounds were identified by ESI-MS, IR and NMR spectra. The steric structures of some of these compounds were clarified by X-ray single crystal analysis.

  8. Theoretical studies on N-O or N-N bond formation from aryl azide catalyzed by iron(II) bromide complex.

    Science.gov (United States)

    Li, Juan; Zhang, Qi; Zhou, Lixin

    2012-03-02

    DFT calculations have been carried out to study the reaction mechanism on N-O or N-N bond formation from aryl azide catalyzed by iron(II) bromide complex. A favorable reaction pathway is proposed to account for the construction of the core structure of 2H-indazoles or 2,1-benzisoxazoles.

  9. Rapid synthesis of an electron-deficient t-BuPHOX ligand: cross-coupling of aryl bromides with secondary phosphine oxides

    KAUST Repository

    McDougal, Nolan T.

    2010-10-01

    Herein an efficient and direct copper-catalyzed coupling of oxazoline-containing aryl bromides with electron-deficient secondary phosphine oxides is reported. The resulting tertiary phosphine oxides can be reduced to prepare a range of PHOX ligands. The presented strategy is a useful alternative to known methods for constructing PHOX derivatives.

  10. Nickel-catalyzed cross-coupling reactions of benzylic zinc reagents with aromatic bromides, chlorides and tosylates.

    Science.gov (United States)

    Schade, Matthias A; Metzger, Albrecht; Hug, Stephan; Knochel, Paul

    2008-07-14

    Benzylic zinc reagents prepared by direct insertion of zinc to benzylic chlorides in the presence of LiCl undergo smooth cross-coupling reactions with aromatic chlorides, bromides and tosylates using Ni(acac)(2) and PPh(3) as a catalyst system.

  11. Palladium Catalyzed Suzuki Cross-coupling Reaction in Molten Tetra-n-butylammonium Bromide

    Institute of Scientific and Technical Information of China (English)

    ZOU, Yue(邹岳); WANG, Quan-Rui(王全瑞); TAO, Feng-Gang(陶凤岗); DING, Zong-Biao(丁宗彪)

    2004-01-01

    A practical procedure for palladium catalyzed Suzuki cross-coupling reaction of arylboronic acids with aryl halides, including aryl chlorides in molten tetra-n-butylammonium bromide (TBAB) was developed. The reaction exhibits high efficiency and functional group tolerance. The recovery of the catalyst and molten n-Bu4NBr was also investigated.

  12. Comparative characteristics of copper, copper chloride, and copper bromide vapor lasers

    Energy Technology Data Exchange (ETDEWEB)

    Kazarian, M.A.; Petrash, G.G.; Trofimov, A.N.

    1980-03-01

    The paper reports the results of a comparative study of copper and copper halide vapor lasers emitting in a repetitively-pulsed regime. Copper chloride and copper bromide vapor lasers are found to have identical lasing characteristics under any excitation conditions. These characteristics are different from those of a copper vapor laser. An average lasing power of 13 W has been obtained for all lasers studied for an efficiency of 1%. It is shown that the choice of a laser will largely depend on the laser design suitability for a specific application.

  13. Mixed micelles of benzyldimethyltetradecylammonium chloride with tetradecyltrimethylammonium and tetradecyltriphenylphosphonium bromides: a head group contribution.

    Science.gov (United States)

    Bakshi, Mandeep Singh; Kaur, Ishpinder; Sood, Rohit; Singh, Jasmeet; Singh, Kulbir; Sachar, Shweta; Singh, Kanwar Jit; Kaur, Gurinder

    2004-03-01

    Mixed micelle formation by tetradecyltrimethylammonium (TTAB) and tetradecyltriphenylphosphonium bromides (TTPB) with benzyldimethyltetradecylammonium chloride (BTDACl) was studied with the help of conductivity and Kraft point measurements. The BTDACl + TTAB mixtures showed synergistic interactions whereas those of BTDACl + TTPB indicated weak antagonistic behavior. From Kraft temperature measurements, the enthalpy of fusion (H(1)(0)) from solid hydrated BTDACl to the liquid state in the presence of TTAB or TTPB was computed. It was found that DeltaH(1)(0) was much more positive for BTDACl + TTPB than for BTDACl + TTAB mixtures.

  14. Generation, spectroscopy, and structure of cyanoformyl chloride and cyanoformyl bromide, XC(O)CN.

    Science.gov (United States)

    Pasinszki, Tibor; Vass, Gábor; Klapstein, Dieter; Westwood, Nicholas P C

    2012-04-01

    Cyanoformyl chloride and cyanoformyl bromide, XC(O)CN (X = Cl and Br), have been investigated in the gas phase by UV photoelectron and mid-infrared spectroscopies. The ground-state geometries of the neutral molecules have been obtained from quantum-chemical calculations at the B3LYP and CCSD(T) levels using the aug-cc-pVTZ basis set. The individual spectroscopies provide a detailed investigation into the vibrational and electronic character of the molecules and are supported by quantum-chemical calculations. The results are compared to data for structurally and chemically related molecules.

  15. Determination of the heat capacities of Lithium/BCX (bromide chloride in thionyl chloride) batteries

    Science.gov (United States)

    Kubow, Stephen A.; Takeuchi, Kenneth J.; Takeuchi, Esther S.

    1989-12-01

    Heat capacities of twelve different Lithium/BCX (BrCl in thionyl chloride) batteries in sizes AA, C, D, and DD were determined. Procedures and measurement results are reported. The procedure allowed simple, reproducible, and precise determinations of heat capacities of industrially important Lithium/BCX cells, without interfering with performance of the cells. Use of aluminum standards allowed the accuracy of the measurements to be maintained. The measured heat capacities were within 5 percent of calculated heat capacity values.

  16. COMPARISION OF ROCURONIUM BROMIDE AND SUXAMETHONIUM CHLORIDE FOR USE DURING RAPID SEQUENCE INDUCTION OF ANAESTHESIA

    Directory of Open Access Journals (Sweden)

    Sarita

    2015-12-01

    Full Text Available AIM To evaluate the quality of intubating conditions with Suxamethonium chloride and Rocuronium bromide for rapid sequence induction intubation and to observe the correlation between the intubating conditions and the response to single twitch stimulation. MATERIALS AND METHODS The present study, entitled “Comparison of Rocuronium bromide and Suxamethonium chloride for use during rapid sequence induction of anaesthesia was done in 50 adult patients divided into two groups and were randomly allocated Group-I: IV Rocuronium 0.9mg/kg and Group-II: IV Suxamethonium 1mg/kg. Laryngoscopy was attempted at 60 sec. and assessment of quality of intubating conditions was performed by using a Viby Mogensen Scale. Neuromuscular monitor was used to observe the correlation between the intubating conditions and the adductor pollicis response to single twitch ulnar nerve stimulation. RESULTS Intubating conditions were excellent (Score 15 in 88% of cases in Group-I whereas vocal cord position was intermediate (10- 14 in 12% of cases, in Group-II all cases could be intubated at 60 sec. (Score 15 in 100% cases. The onset of maximal blockade at adductor pollicis was found to correlate well with satisfactory intubating conditions in Group-II (Sch whereas in 20% of patients in Group-I had single twitch response (though diminished at the time of intubation. CONCLUSION Rocuronium bromide in dose of 0.9mg/kg provided neuromuscular blockade with a fast onset time and good to excellent intubating conditions at 60 sec. resembling those of Suxamethonium.

  17. Enhancement of neighbouring-group participation in Cu0-promoted cross-coupling gem-difluoromethylenation of aryl/alkenyl halides with 1,3-azolic difluoromethyl bromides.

    Science.gov (United States)

    Jiang, Haizhen; Lu, Wenjun; Yang, Kun; Ma, Guobin; Xu, Minjun; Li, Jian; Yao, Jianhua; Wan, Wen; Deng, Hongmei; Wu, Shaoxiong; Zhu, Shizheng; Hao, Jian

    2014-08-04

    A copper(0)-promoted direct reductive gem-difluoromethylenation of unactivated aryl or alkenyl halides with benzo-1,3-azolic (oxa-, thia- or aza-) difluoromethyl bromides or 2-bromodifluoromethyl-1,3-oxazoline has been developed for the construction of pharmaceutically important gem-difluoromethylene-linked twin molecules. The unique π-conjugated aryl-fused 1,3-azolic moiety in difluoromethyl bromide substrates could stabilise the reaction intermediates, which promotes the reactivities, providing facile access to the cross-coupling products in good to excellent yields, and allowing significant functional group tolerance. The reaction exhibits an enhanced neighbouring-group-participation effect. This method could provide a new strategy for the construction of gem-difluoromethylene-linked identical or nonidentical twin drugs through further functionalisation of 1,3-azolic skeletons. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  18. Catalytic activity of some oxime-based Pd(II-complexes in Suzuki coupling of aryl and heteroaryl bromides in water

    Directory of Open Access Journals (Sweden)

    Kamal M. Dawood

    2017-05-01

    Full Text Available The catalytic activity of four Pd(II-complexes of benzoazole-oximes was extensively studied in Suzuki–Miyaura C–C cross coupling reactions in water, as an eco-friendly green solvent, under both thermal heating as well as microwave irradiation conditions. The cross-coupling reactions included different activated and deactivated aryl- or heteroaryl-bromides with several arylboronic acids. The protected oxime-complexes were found to be more efficient than the free ones.

  19. Pd-catalyzed amidation of aryl chlorides using monodentate biaryl phosphine ligands: a kinetic, computational, and synthetic investigation.

    Science.gov (United States)

    Ikawa, Takashi; Barder, Timothy E; Biscoe, Mark R; Buchwald, Stephen L

    2007-10-31

    We present results on the amidation of aryl halides and sulfonates utilizing a monodentate biaryl phosphine-Pd catalyst. Our results are in accord with a previous report that suggests that the formation of kappa(2)-amidate complexes is deleterious to the effectiveness of a catalyst for this transformation and that their formation can be prevented by the use of appropriate bidentate ligands. We now provide data that suggest that the use of certain monodentate ligands can also prevent the formation of the kappa(2)-amidate complexes and thereby generate more stable catalysts for the amination of aryl chlorides. Furthermore, computational studies shed light on the importance of the key feature(s) of the biaryl phosphines (a methyl group ortho to the phosphorus center) that enable the coupling to occur. The use of ligands that possess a methyl group ortho to the phosphorus center allows a variety of aryl and heteroaryl chlorides with various amides to be coupled in high yield.

  20. General method for the preparation of active esters by palladium-catalyzed alkoxycarbonylation of aryl bromides.

    Science.gov (United States)

    de Almeida, Angelina M; Andersen, Thomas L; Lindhardt, Anders T; de Almeida, Mauro V; Skrydstrup, Troels

    2015-02-06

    A useful method was developed for the synthesis of active esters by palladium-catalyzed alkoxycarbonylation of (hetero)aromatic bromides. The protocol was general for a range of oxygen nucleophiles including N-hydroxysuccinimide (NHS), pentafluorophenol (PFP), hexafluoroisopropyl alcohol (HFP), 4-nitrophenol, and N-hydroxyphthalimide. A high functional group tolerance was displayed, and several active esters were prepared with good to excellent isolated yields. The protocol was extended to access an important synthetic precursor to the HIV-protease inhibitor, saquinavir, by formation of an NHS ester followed by acyl substitution.

  1. Amination of electron deficient aryl chlorides promoted by nano sized Mg(OH)2 under transition metals free condition

    Institute of Scientific and Technical Information of China (English)

    Zhi Hao Cui; Zi Hui Meng; Yan Qing Mi; Peng Wang; Qi Wang; Lin Man Zhao; Ke Jian Cui; Fang Yu; Zhi Bin Xu

    2012-01-01

    This paper presents the amination reactions of electron deficient aryl chlorides promoted by Mg(OH)2 without transition metals.Only using stoichiometric amount of nano sized Mg(OH)2,good to moderate isolated yields could be achieved in N-methylpyrrolidone (NMP) after 24 h at 150 ℃.

  2. A highly versatile catalyst system for the cross-coupling of aryl chlorides and amines.

    Science.gov (United States)

    Lundgren, Rylan J; Sappong-Kumankumah, Antonia; Stradiotto, Mark

    2010-02-08

    The syntheses of 2-(di-tert-butylphosphino)-N,N-dimethylaniline (L1, 71%) and 2-(di-1-adamantylphosphino)-N,N-dimethylaniline (L2, 74 %), and their application in Buchwald-Hartwig amination, are reported. In combination with [Pd(allyl)Cl](2) or [Pd(cinnamyl)Cl](2), these structurally simple and air-stable P,N ligands enable the cross-coupling of aryl and heteroaryl chlorides, including those bearing as substituents enolizable ketones, ethers, esters, carboxylic acids, phenols, alcohols, olefins, amides, and halogens, to a diverse range of amine and related substrates that includes primary alkyl- and arylamines, cyclic and acyclic secondary amines, N-H imines, hydrazones, lithium amide, and ammonia. In many cases, the reactions can be performed at low catalyst loadings (0.5-0.02 mol % Pd) with excellent functional group tolerance and chemoselectivity. Examples of cross-coupling reactions involving 1,4-bromochlorobenzene and iodobenzene are also reported. Under similar conditions, inferior catalytic performance was achieved when using Pd(OAc)(2), PdCl(2), [PdCl(2)(cod)] (cod = 1,5-cyclooctadiene), [PdCl(2)(MeCN)(2)], or [Pd(2)(dba)(3)] (dba = dibenzylideneacetone) in combination with L1 or L2, or by use of [Pd(allyl)Cl](2) or [Pd(cinnamyl)Cl](2) with variants of L1 and L2 bearing less basic or less sterically demanding substituents on phosphorus or lacking an ortho-dimethylamino fragment. Given current limitations associated with established ligand classes with regard to maintaining high activity across the diverse possible range of C-N coupling applications, L1 and L2 represent unusually versatile ligand systems for the cross-coupling of aryl chlorides and amines.

  3. A new one-pot synthesis of 1,2,4-oxadiazoles from aryl nitriles, hydroxylamine and crotonoyl chloride

    Indian Academy of Sciences (India)

    Masoumeh Zakeri; Majid M Heravi; Ebrahim Abouzari-Lotf

    2013-07-01

    The reaction of aryl nitriles with hydroxylamine using acetic acid as a catalyst followed by subsequent addition of crotonoyl chloride to the intermediate amidoxime represents a straightforward one-pot access to new 1,2,4-oxadiazole synthesis under mild conditions. The course of the reaction was found to be high yielding and all new compounds were well characterized by nuclear magnetic resonance (NMR), mass spectrometry (MS) and elemental analysis.

  4. Association of defects in lead chloride and lead bromide: Ionic conductivity and dielectric loss measurements

    NARCIS (Netherlands)

    Brom, W.E. van den; Schoonman, J.; Wit, J.H.W. de

    The ionic conductivity data of pure and doped lead bromide without associated defects are used in order to explain the anomalous conductivity behaviour of copper (I) bromide and lead oxide-doped lead-bromide crystals. In these crystals precipitated dopant and associated defects are present. The

  5. Association of defects in lead chloride and lead bromide: Ionic conductivity and dielectric loss measurements

    NARCIS (Netherlands)

    Brom, W.E. van den; Schoonman, J.; Wit, J.H.W. de

    1972-01-01

    The ionic conductivity data of pure and doped lead bromide without associated defects are used in order to explain the anomalous conductivity behaviour of copper (I) bromide and lead oxide-doped lead-bromide crystals. In these crystals precipitated dopant and associated defects are present. The asso

  6. Efficient Pd-catalyzed allene synthesis from alkynes and aryl bromides through an intramolecular base-assisted deprotonation (iBAD) mechanism.

    Science.gov (United States)

    Nella, Natalie; Parker, Evelyne; Hitce, Julien; Larini, Paolo; Jazzar, Rodolphe; Baudoin, Olivier

    2014-10-06

    An optimized ligand-controlled palladium-catalyzed allene synthesis starting from alkynes and aryl bromides giving rise to allene products in a simple and direct manner is described. The methodology is performed in an inter- and intramolecular fashion with unprecedented scope and excellent yields. Based on mechanistic investigations and on DFT calculations, the role played by the carboxylic additive (i.e., PivOH) in controlling the selectivity of the reaction is discussed, allowing us to propose an intramolecular base-assisted deprotonation (iBAD) mechanism for this process. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  7. Methyl chloride and methyl bromide emissions from baking: an unrecognized anthropogenic source.

    Science.gov (United States)

    Thornton, Brett F; Horst, Axel; Carrizo, Daniel; Holmstrand, Henry

    2016-05-01

    Methyl chloride and methyl bromide (CH3Cl and CH3Br) are the largest natural sources of chlorine and bromine, respectively, to the stratosphere, where they contribute to ozone depletion. We report the anthropogenic production of CH3Cl and CH3Br during breadbaking, and suggest this production is an abiotic process involving the methyl ester functional groups in pectin and lignin structural polymers of plant cells. Wide variations in baking styles allow only rough estimates of this flux of methyl halides on a global basis. A simple model suggests that CH3Br emissions from breadbaking likely peaked circa 1990 at approximately 200tonnes per year (about 0.3% of industrial production), prior to restrictions on the dough conditioner potassium bromate. In contrast, CH3Cl emissions from breadbaking may be of similar magnitude as acknowledged present-day CH3Cl industrial emissions. Because the mechanisms involve functional groups and compounds widely found in plant materials, this type of methyl halide production may occur in other cooking techniques as well. Copyright © 2016 Elsevier B.V. All rights reserved.

  8. Binding of dyes to hydroxyapatite treated with cetylpyridinium chloride or cetrimonium bromide.

    Science.gov (United States)

    Jensen, J E

    1978-03-01

    The effect of cetylpyridinium chloride (CPC) and cetrimonium bromide (CTAB) on the adsorption of some acidic food dyes to hydroxyapatite was studied. The dyes investigated were brilliant blue (FD&C Blue No. 1), tartrazine (FD&C Yellow No. 5), sunset yellow (FD&C Yellow No. 6) and amaranth (FD&C Red No. 2). The apatite had adsorbed 9.2 mumol CPC per g dry weight. The adsorbed CPC was in equilibrium with a free concentration of 20 microgram/ml (58 micrometer). The adsorption of CPC and CTAB to the apatite was followed by an increased ability of the crystals to bind the dyes. The dyes were very firmly adsorbed and were not released during a series of washings. Untreated apatite showed only a minor affinity for the dyes. The adsorbed dyes were easily washed out. CPC and CTAB showed the smae specific ability to increase the binding capacity of the apatite. The results are discussed and related to the formation of stains on the teeth in persons using quaternary ammonium compounds for mouthrinsing. A mechanism explaining the production of stains is proposed.

  9. Troponate/Aminotroponate Ruthenium-Arene Complexes: Synthesis, Structure, and Ligand-Tuned Mechanistic Pathway for Direct C-H Bond Arylation with Aryl Chlorides in Water.

    Science.gov (United States)

    Dwivedi, Ambikesh D; Binnani, Chinky; Tyagi, Deepika; Rawat, Kuber S; Li, Pei-Zhou; Zhao, Yanli; Mobin, Shaikh M; Pathak, Biswarup; Singh, Sanjay K

    2016-07-05

    A series of water-soluble troponate/aminotroponate ruthenium(II)-arene complexes were synthesized, where O,O and N,O chelating troponate/aminotroponate ligands stabilized the piano-stool mononuclear ruthenium-arene complexes. Structural identities for two of the representating complexes were also established by single-crystal X-ray diffraction studies. These newly synthesized troponate/aminotroponate ruthenium-arene complexes enable efficient C-H bond arylation of arylpyridine in water. The unique structure-activity relationship in these complexes is the key to achieve efficient direct C-H bond arylation of arylpyridine. Moreover, the steric bulkiness of the carboxylate additives systematically directs the selectivity toward mono- versus diarylation of arylpyridines. Detailed mechanistic studies were performed using mass-spectral studies including identification of several key cyclometalated intermediates. These studies provided strong support for an initial cycloruthenation driven by carbonate-assisted deprotonation of 2-phenylpyridine, where the relative strength of η(6)-arene and the troponate/aminotroponate ligand drives the formation of cyclometalated 2-phenylpyridine Ru-arene species, [(η(6)-arene)Ru(κ(2)-C,N-phenylpyridine) (OH2)](+) by elimination of troponate/aminotroponate ligands and retaining η(6)-arene, while cyclometalated 2-phenylpyridine Ru-troponate/aminotroponate species [(κ (2)-troponate/aminotroponate)Ru(κ(2)-C,N-phenylpyridine)(OH2)2] was generated by decoordination of η(6)-arene ring during initial C-H bond activation of 2-phenylpyridine. Along with the experimental mass-spectral evidence, density functional theory calculation also supports the formation of such species for these complexes. Subsequently, these cycloruthenated products activate aryl chloride by facile oxidative addition to generate C-H arylated products.

  10. Evidence for the interaction between (t)BuOK and 1,10-phenanthroline to form the 1,10-phenanthroline radical anion: a key step for the activation of aryl bromides by electron transfer.

    Science.gov (United States)

    Yi, Hong; Jutand, Anny; Lei, Aiwen

    2015-01-11

    Electron paramagnetic resonance and electrochemistry are used to evidence the interaction between 1,10-phenanthroline (Phen) and KO(t)Bu to form the 1,10-phenanthroline radical anion, Phen˙(-), and the (t)BuO˙ radical via an inner-sphere electron transfer. In addition, electrochemistry is also used to explain the formation of aryl radicals from aryl bromides via outer-sphere electron transfer from the key intermediate Phen˙(-).

  11. Reactivity of Aryl Halides for Reductive Dehalogenation in (Seawater Using Polymer-Supported Terpyridine Palladium Catalyst

    Directory of Open Access Journals (Sweden)

    Toshimasa Suzuka

    2015-05-01

    Full Text Available A polymer-supported terpyridine palladium complex was prepared. The complex was found to promote hydrodechlorination of aryl chlorides with potassium formate in seawater. Generally, reductive cleavage of aryl chlorides using transition metal catalysts is more difficult than that of aryl bromides and iodides (reactivity: I > Br > Cl; however, the results obtained did not follow the general trend. Therefore, we investigated the reaction inhibition agents and found a method to remove these inhibitors. The polymeric catalysts showed high catalytic activity and high reusability for transfer reduction in seawater.

  12. A Well-Defined {[(PhCH2O2P(CH32CHNCH(CH32]2PdCl2} Complex Catalyzed Hiyama Coupling of Aryl Bromides with Arylsilanes

    Directory of Open Access Journals (Sweden)

    Mengping Guo

    2016-07-01

    Full Text Available A palladium (II complex {[(PhCH2O2P(CH32CHNCH(CH32]2PdCl2} catalyzed Hiyama cross-coupling reaction between aryl bromides and arylsilanes has been developed. The substituted biaryls were produced in moderate to high yields, regardless of electron-withdrawing or electron-donating.

  13. Simple, Efficient Protocols for the Pd-Catalyzed Cross-Coupling Reaction of Aryl Chlorides and Dimethylamine

    Science.gov (United States)

    Lee, Brian K.; Biscoe, Mark R.; Buchwald, Stephen L.

    2011-01-01

    Simple and efficient procedures for the Pd-catalyzed cross-coupling reaction of aryl chlorides and dimethylamine are described. At room temperature with a strong base, t-BuXPhos is employed as the supporting ligand; at 110 °C with a weak base, XPhos is employed as the supporting ligand. In each of these cases, commercially available solutions constitute the source of the dimethylamine, and recently disclosed precatalysts constitute the source of the ligand and Pd. This work further expands the utility of these precatalysts in reactions that benefit from an easily activated source of L1Pd(0). PMID:21818164

  14. Tetradentate N2O2 Chelated Palladium(II Complexes: Synthesis, Characterization, and Catalytic Activity towards Mizoroki-Heck Reaction of Aryl Bromides

    Directory of Open Access Journals (Sweden)

    Siti Kamilah Che Soh

    2013-01-01

    Full Text Available Four air and moisture-stable palladium(II-Schiff base complexes, N,N′-bis(α-methylsalicylidenepropane-1,3-diamine palladium(II (2a, N,N′-bis(4-methyl-α-methylsalicylidenepropane-1,3-diamine palladium(II (2b, N,N′-bis(3,5-di-tert-butylsalicylidenepropane-1,3-diamine palladium(II (2c, and N,N′-bis(4-methoxy-salicylidenepropane-1,3-diamine palladium(II (2d, have been successfully synthesised and characterised by CHN elemental analyses and conventional spectroscopic methods. These complexes were investigated as catalysts in the phosphine-free Mizoroki-Heck cross-coupling reactions of aryl bromides with methyl acrylate.

  15. Organozinc Chemistry Enabled by Micellar Catalysis. Palladium-Catalyzed Cross-Couplings between Alkyl and Aryl Bromides in Water at Room Temperature.

    Science.gov (United States)

    Duplais, Christophe; Krasovskiy, Arkady; Lipshutz, Bruce H

    2011-11-28

    Negishi-like cross-couplings between (functionalized) alkyl and aryl bromides are described. Despite the fact that organozinc reagents are intolerant of water, their formation as well as their use in an aqueous micellar environment is discussed herein. Each component of this complex series of events leading up to C-C bond formation has an important role which has been determined insofar as the type of zinc, amine ligand, surfactant, and palladium catalyst are concerned. In particular, the nature of the surfactant has been found to be crucial in order to obtain synthetically useful results involving highly reactive, moisture-sensitive organometallics. Neither organic solvent nor heat is required for these cross-couplings to occur; just add water.

  16. Trifluoromethylthiolation of aryl iodides and bromides enabled by a bench-stable and easy-to-recover dinuclear palladium(I) catalyst.

    Science.gov (United States)

    Yin, Guoyin; Kalvet, Indrek; Schoenebeck, Franziska

    2015-06-01

    While palladium catalysis is ubiquitous in modern chemical research, the recovery of the active transition-metal complex under routine laboratory applications is frequently challenging. Described herein is the concept of alternative cross-coupling cycles with a more robust (air-, moisture-, and thermally-stable) dinuclear Pd(I) complex, thus avoiding the handling of sensitive Pd(0) species or ligands. Highly efficient C-SCF3 coupling of a range of aryl iodides and bromides was achieved, and the recovery of the Pd(I) complex was accomplished via simple open-atmosphere column chromatography. Kinetic and computational data support the feasibility of dinuclear Pd(I) catalysis. A novel SCF3-bridged Pd(I) dimer was isolated, characterized by X-ray crystallography, and verified to be a competent catalytic intermediate.

  17. Synthesis and in vitro antifungal activities of new 2-aryl-6,7-methylenedioxy-3,4-dihydroisoquinolin-2-ium bromides.

    Science.gov (United States)

    Yang, Xinjuan; Yao, Yao; Qin, Yuyan; Hou, Zhe; Yang, Rui; Miao, Fang; Zhou, Le

    2013-01-01

    2-Aryl-3,4-dihydroisoquinolin-2-iums might be considered as a class of simple analogues of natural quaternary benzo[c]phenanthridine alkaloids. In this paper, 26 new 2-aryl-6,7-methylenedioxy-3,4-dihydroisoquinolin-2-ium bromides with various substituents in N-aromatic ring were synthesized from commercially available 1,3-benzodioxole in good to excellent yields. All the compounds were elucidated by MS, high resolution (HR)-MS, IR, (1)H- and (13)C-NMR analysis, and evaluated for antifungal activities in vitro against Alternaria alternate, Curvularia lunata and Fusarium oxysporum sp. niveum at 50 µg/mL. Most of the compounds showed higher activities against all the test fungi than their natural model compounds sanguinarine and chelerythrine. For A. alternate and Curvularia lunata, most of them were also more active than thiabendazole, a commercial fungicide standard. The structure-activity relationship indicated that the substituent in N-aromatic ring and its position had significant effect on the activity. The general trend was that halogen atoms and CF3 remarkably enhanced the activity while CH3 and OCH3 decreased the activity. Generally, o-substituted isomers were more active than m- and p-substituted isomer. The present results suggest that the title compounds are potential for the development of new isoquinoline antimicrobial agents.

  18. A well-defined (POCOP)Rh catalyst for the coupling of aryl halides with thiols.

    Science.gov (United States)

    Timpa, Samuel D; Pell, Christopher J; Ozerov, Oleg V

    2014-10-22

    This article describes a well-defined pincer-Rh catalyst for C-S cross-coupling reactions. (POCOP)Rh(H)(Cl) serves as an active precatalyst for the coupling of aryl chlorides and bromides with aryl and alkyl thiols under reasonable conditions (3% mol cat., 110 °C, 2-24 h, >90% yield). For select substrates, >90% yields were obtained with catalyst loading as low as 0.1%. Key mechanistic intermediates have been isolated and fully characterized, including (POCOP)Rh(Ph)(SPh) (6a) and (POCOP)Rh(SPh2) (6b). The aryl/bis(phosphinite) (POCOP)Rh system has been shown to favor aryl thiolate reductive elimination at elevated temperatures and in some cases at room temperature, compared with the analogous diarylamido/bis(phosphine) (PNP)Rh pincer system. Concerted reductive elimination has been studied with 6a directly and in the presence of aryl bromide and aryl chloride traps. This investigation demonstrates a clear rate dependence on aryl chloride concentration during catalysis, a dependence that is absent when using aryl bromides. The rate of catalysis is dramatically reduced or brought to zero for ortho-tolyl halides, which can be traced to slower C-S coupling and slower carbon-halogen oxidative addition for ortho-substituted aryls. The influence of the sterics in the thiol component is less straightforward. The S-H oxidative addition product (POCOP)Rh(H)(SPh) (16) has been fully characterized and its reactivity has been examined, resulting in the isolation of the sodium-thiolate adduct (POCOP)Rh(NaSPh) (19). The solid-state structure of 19 shows Na interactions not only with sulfur, but also with a neighboring Rh and the chelating aryl carbon of the pincer framework. The reactivity of 16 and 19 indicates that these potential side products should not hinder catalysis.

  19. An expedient Pd/DBU mediated cyanation of aryl/heteroaryl bromides with K4[Fe(CN)6].

    Science.gov (United States)

    Zhang, Dengyou; Sun, Haifeng; Zhang, Lei; Zhou, Yu; Li, Chunpu; Jiang, Hualiang; Chen, Kaixian; Liu, Hong

    2012-03-18

    A practical Pd(PPh(3))(4)/DBU catalytic system for the synthesis of pharmaceutically relevant aminopyridine nitrile intermediates, as well as a variety of other aryl nitriles using non-toxic K(4)[Fe(CN)(6)] has been developed. The key features of our new protocol for cyanation lie in that the reaction can be carried out with readily available Pd(PPh(3))(4) under mild and green conditions, even without the assistance of other ligands.

  20. A General Method for Nucleophilic Aromatic Substitution of Aryl Fluorides and Chlorides with Dimethylamine using Hydroxide-Assisted Decomposition of N,N-Dimethylforamide.

    Science.gov (United States)

    Garcia, Juana; Sorrentino, Jacob; Diller, Emily J; Chapman, Daniel; Woydziak, Zachary R

    A practical and convenient procedure for the nucleophilic aromatic substitution of aryl fluorides and chlorides with dimethylamine was developed using a hydroxide assisted, thermal decomposition of N,N-dimethylforamide. These conditions are tolerant of nitro, nitrile, aldehyde, ketone, and amide groups but will undergo acyl substitution to form amides for methyl esters and acyl chlorides. Isolated yields of the products range from 44 - 98%, with the majority being greater than 70% for seventeen examples.

  1. Design, Synthesis, and Validation of an Effective, Reusable Silicon-Based Transfer Agent for Room-Temperature Pd-Catalyzed Cross-Coupling Reactions of Aryl and Heteroaryl Chlorides with Readily Available Aryl Lithium Reagents.

    Science.gov (United States)

    Martinez-Solorio, Dionicio; Melillo, Bruno; Sanchez, Luis; Liang, Yong; Lam, Erwin; Houk, K N; Smith, Amos B

    2016-02-17

    A reusable silicon-based transfer agent (1) has been designed, synthesized, and validated for effective room-temperature palladium-catalyzed cross-coupling reactions (CCRs) of aryl and heteroaryl chlorides with readily accessible aryl lithium reagents. The crystalline, bench-stable siloxane transfer agent (1) is easily prepared via a one-step protocol. Importantly, this "green" CCR protocol circumvents prefunctionalization, isolation of organometallic cross-coupling partners, and/or stoichiometric waste aside from LiCl. DFT calculations support a σ-bond metathesis mechanism during transmetalation and lead to insights on the importance of the CF3 groups.

  2. Suzuki-Miyaura cross-coupling of potassium dioxolanylethyltrifluoroborate and aryl/heteroaryl chlorides.

    Science.gov (United States)

    Fleury-Brégeot, Nicolas; Oehlrich, Daniel; Rombouts, Frederik; Molander, Gary A

    2013-04-01

    A robust and efficient protocol for the introduction of the dioxolanylethyl moiety onto various aryl and heteroaryl halides has been developed, providing cross-coupling yields up to 93%. Copper-catalyzed borylation of 2-(2-bromoethyl)-1,3-dioxolane with bis(pinacolato)diboron followed by treatment with potassium bifluoride provides the key organotrifluoroborate reagent.

  3. Apparent and partial molar volumes of long-chain alkyldimethylbenzylammonium chlorides and bromides in aqueous solutions at T=15 deg. C and T=25 deg. C[Alkyldimethylbenzylammonium chlorides; Alkyldimethylbenzylammonium bromides; Micellization; Density; Apparent molar volumes

    Energy Technology Data Exchange (ETDEWEB)

    Gonzalez-Perez, A.; Ruso, J.M.; Nimo, J.; Rodriguez, J.R. E-mail: fmjulio@usc.es

    2003-12-01

    Density measurements of dodecyl- (C{sub 12}DBACl), tetradecyl- (C{sub 14}DBACl), hexadecyldimethylbenzylammonium chloride (C{sub 16}DBACl) and of decyl- (C{sub 10}DBABr) and dodecyldimethylbenzylammonium bromide (C{sub 12}DBABr) in aqueous solutions at T=15 deg. C and T=25 deg. C have been carried out. From these results, apparent and partial molar volumes were calculated. Positive deviations from the Debye-Hueckel limiting law provide evidence for limited association at concentrations below the critical micelle concentration. The change of the apparent molar volume upon micellization was calculated. The relevant parameters have been presented in function of the alkyl chain length. Apparent molar volumes of the present compounds in the micellar phase, V{sub phi}{sup m}, and the change upon micellization, {delta}V{sub phi}{sup m}, have been discussed in terms of temperature and type of counterion.

  4. Blue-Green Color Tunable Solution Processable Organolead Chloride-Bromide Mixed Halide Perovskites for Optoelectronic Applications.

    Science.gov (United States)

    Sadhanala, Aditya; Ahmad, Shahab; Zhao, Baodan; Giesbrecht, Nadja; Pearce, Phoebe M; Deschler, Felix; Hoye, Robert L Z; Gödel, Karl C; Bein, Thomas; Docampo, Pablo; Dutton, Siân E; De Volder, Michael F L; Friend, Richard H

    2015-09-09

    Solution-processed organo-lead halide perovskites are produced with sharp, color-pure electroluminescence that can be tuned from blue to green region of visible spectrum (425-570 nm). This was accomplished by controlling the halide composition of CH3NH3Pb(BrxCl1-x)3 [0 ≤ x ≤ 1] perovskites. The bandgap and lattice parameters change monotonically with composition. The films possess remarkably sharp band edges and a clean bandgap, with a single optically active phase. These chloride-bromide perovskites can potentially be used in optoelectronic devices like solar cells and light emitting diodes (LEDs). Here we demonstrate high color-purity, tunable LEDs with narrow emission full width at half maxima (FWHM) and low turn on voltages using thin-films of these perovskite materials, including a blue CH3NH3PbCl3 perovskite LED with a narrow emission FWHM of 5 nm.

  5. Synthesis of 2-aryl-3,4-dihydroisoquinolin-2-ium bromides and their in vitro acaricidal activity against Psoroptes cuniculi.

    Science.gov (United States)

    Ma, Yan-Ni; Yang, Xin-Juan; Pan, Le; Hou, Zhe; Geng, Hui-Ling; Song, Xiao-Ping; Zhou, Le; Miao, Fang

    2013-01-01

    By employing sanguinarine, a natural active quaternary isoquinoline alkaloid, as a model molecule, a series of structurally simple quaternary 2-aryl-3,4-dihydroisoquinolin-2-ium compounds were designed and synthesized and evaluated for in vitro acaricidal activity against P. cuniculi. A new approach towards the title compounds was developed with isochroman as starting material. The results showed that 22 of 24 tested compounds displayed the activity in varying degrees at 0.4 mg/mL. Fourteen compounds were significantly more effective than ivermectin, a standard acaricide, and 6-methoxy dihydrosanguinarine, a derivative of sanguinarine (p<0.05). And their comprehensive relative activity was 1.4 to 16.5 times than that of ivermectin and 1.5 to 18.8 times than that of 6-methoxy dihydrosanguinarine. The structure-activity relationship indicated that the introduction of a substituent to N-benzene ring, especially halogen atom and trifluoromethyl group, led to great improvement of the activity. The position of fluorine atom, methyl group and hydroxyl group made very significant effects on the activity. It was concluded that 2-aryl-3,4-dihydroisoquinolin-2-iums are very promising candidates for the development of new isoquinoline acaricidal agents.

  6. Far-infrared laser action in vinyl chloride, vinyl bromide, and vinyl fluoride optically pumped by a CW N2O laser

    Science.gov (United States)

    Gastaud, C.; Redon, M.; Belland, P.; Fourrier, M.

    1984-06-01

    This paper reports the first use of a N2O laser for optically pumping vinyl halides, to obtain new cw submillimeter laser lines. Eighteen far-infrared (FIR) emissions have been observed in vinyl chloride, twenty five in vinyl bromide and thirty eight in vinyl flouride.

  7. Multicomponent, solvent-free synthesis of 12-aryl-8,9,10,12-tetrahydrobenzo[]-xanthen-11-one derivatives catalysed by cyanuric chloride

    Indian Academy of Sciences (India)

    Zhan-Hui Zhang; Peng Zhang; Shu-Hong Yang; Hong-Juan Wang; Jia Deng

    2010-05-01

    An efficient and direct protocol for the preparation of 12-aryl-8,9,10,12-tetrahydro-benzo[] xanthen-11-one derivatives employing a three-component one-pot reaction of aryl aldehydes, 2-naphthol and cyclic 1,3-dicarbonyl compounds in the presence of a catalytic amount of cyanuric chloride (2,4,6-trichloro-1,3,5-triazine, TCT) under solvent-free conditions is described. The desired products are obtained in high yields with short reaction times.

  8. Exchange equilibria between bicarbonate, carbonate, chloride and bromide on dowex 1 x 8.

    Science.gov (United States)

    Lundström, U; Olin, A

    1984-07-01

    The exchange reaction 2R(+)HCO(3)(2-) + CO(3)(2-) right harpoon over left harpoon R(2)(+) CO(3)(2-) + 2HCO(3)(2-) has been studied on Dowex 1 x 8 in the presence of bicarbonate solution in equilibrium with atmospheric carbon dioxide (open system). The experiments showed, as theory predicts, that the composition of the resin phase is independent of the concentration of the bicarbonate solution. The mole fraction of carbonate at equilibrium is about 0.4 and the equilibrium constant is 0.15M at 20 degrees . With this value of the constant, the composition of the ion-exchanger for various bicarbonate concentrations has been calculated for a closed system. At [HCO(3)(-)] Chromatographie enrichment of bromide from fresh water.

  9. Chloride and bromide sources in water: Quantitative model use and uncertainty

    Science.gov (United States)

    Horner, Kyle N.; Short, Michael A.; McPhail, D. C.

    2017-06-01

    Dissolved chloride is a commonly used geochemical tracer in hydrological studies. Assumptions underlying many chloride-based tracer methods do not hold where processes such as halide-bearing mineral dissolution, fluid mixing, or diffusion modify dissolved Cl- concentrations. Failure to identify, quantify, or correct such processes can introduce significant uncertainty to chloride-based tracer calculations. Mass balance or isotopic techniques offer a means to address this uncertainty, however, concurrent evaporation or transpiration can complicate corrections. In this study Cl/Br ratios are used to derive equations that can be used to correct a solution's total dissolved Cl- and Br- concentration for inputs from mineral dissolution and/or binary mixing. We demonstrate the equations' applicability to waters modified by evapotranspiration. The equations can be used to quickly determine the maximum proportion of dissolved Cl- and Br- from each end-member, providing no halide-bearing minerals have precipitated and the Cl/Br ratio of each end member is known. This allows rapid evaluation of halite dissolution or binary mixing contributions to total dissolved Cl- and Br-. Equation sensitivity to heterogeneity and analytical uncertainty is demonstrated through bench-top experiments simulating halite dissolution and variable degrees of evapotranspiration, as commonly occur in arid environments. The predictions agree with the experimental results to within 6% and typically much less, with the sensitivity of the predicted results varying as a function of end-member compositions and analytical uncertainty. Finally, we present a case-study illustrating how the equations presented here can be used to quantify Cl- and Br- sources and sinks in surface water and groundwater and how the equations can be applied to constrain uncertainty in chloride-based tracer calculations.

  10. Palladium-meta-terarylphosphine catalyst for the Mizoroki-Heck reaction of (hetero)aryl bromides and functional olefins.

    Science.gov (United States)

    Tay, Daniel Weiliang; Jong, Howard; Lim, Yee Hwee; Wu, Wenqin; Chew, Xinying; Robins, Edward G; Johannes, Charles W

    2015-04-17

    The evolutionary meta-terarylphosphine ligand architecture of Cy*Phine was recently shown to be a key feature that imposed outstanding performance in palladium-catalyzed copper-free Sonogashira applications. Herein, the Pd-Cy*Phine combination has similarly proven to be a powerful catalyst system for the Mizoroki-Heck reaction. Using high-throughput screening (HTS) methodology, DMF and NaHCO3 were rapidly identified as the most effective solvent and base pair for the cross-coupling catalysis of challenging and industrially valuable substrates including highly electron-rich heteroaryl bromides and unactivated olefins. Unprotected functional groups were well tolerated using low catalyst loadings, and the simple protocol produced excellent yields (up to 99%) with unprecedented substrate diversity. The Pd-Cy*Phine system broadly outperformed many state-of-the-art commercial alternatives, which demonstrated its potential as a next-generation cross-coupling catalyst.

  11. Survey on fluoride, bromide and chloride contents in public drinking water supplies in Sicily (Italy).

    Science.gov (United States)

    D'Alessandro, Walter; Bellomo, Sergio; Parello, Francesco; Brusca, Lorenzo; Longo, Manfredi

    2008-10-01

    Six hundred and sixty-seven water samples were collected from public drinking water supplies in Sicily and analysed for electric conductivity and for their Cl(-), Br(-) and F(-) contents. The samples were, as far as possible, collected evenly over the entire territory with an average sampling density of about one sample for every 7,600 inhabitants. The contents of Cl(-) and Br(-), ranging between 5.53 and 1,302 mg/l and between <0.025 and 4.76 mg/l respectively, correlated well with the electric conductivity, a parameter used as a proxy for water salinity. The highest values were found both along the NW and SE coasts, which we attributed to seawater contamination, and in the central part of Sicily, which we attributed to evaporitic rock dissolution. The fluoride concentrations ranged from 0.023 to 3.28 mg/l, while the highest values (only three exceeding the maximum admissible concentration of 1.5 mg/l) generally correlated either with the presence in the area of crystalline (volcanic or metamorphic) or evaporitic rocks or with contamination from hydrothermal activity. Apart from these limited cases of exceeding F(-) levels, the waters of public drinking water supplies in Sicily can be considered safe for human consumption for the analysed parameters. Some limited concern could arise from the intake of bromide-rich waters (about 3% exceeding 1 mg/l) because of the potential formation of dangerous disinfection by-products.

  12. The direct arylation of benzoxazoles with aryl bromides cocatalyzed by Pd(OAc)2 and CuI%Pd(OAc)2/CuI共催化杂环C—H键与芳基溴的直接芳基化反应研究

    Institute of Scientific and Technical Information of China (English)

    颜雪明; 肖新荣; 谭倪

    2012-01-01

    研究开发了一个实用高效的Pd(OAc)2/Cul共催化体系,只需在1% Pd(OAc)2,10% CuI,0.5 mol PPh3配 体存在下,苯并唑类杂环与各种芳基溴的直接芳基化反应就能够在温和的反应条件下顺利进行,并得到良好的收率.%A practical,efficient Pd(OAc)2/CuI cocatalytic system has been developed. With only 1% Pd(OAc)2,10% CuI,and 0. 5 mol of inexpensive PPh3 as ligand,the direct arylation of benzoxazoles with aryl bromides could be performed smoothly in mild condition, affording the desired arylated benzoxazoles in good yields.

  13. Utility of N-aryl 2-aroylhydrazono-propanehydrazonoyl chlorides as precursors for synthesis of new functionalized 1,3,4-thiadiazoles with potential antimicrobial activity

    Directory of Open Access Journals (Sweden)

    Abdou O. Abdelhamid

    2015-11-01

    Full Text Available Starting from N-aryl 2-aroylhydrazono-propanehydrazonoyl chlorides, a series of new functionalized 1,3,4-thiadiazoles were prepared. The structures of the compounds prepared were confirmed by both elemental and spectral analyses as well as by alternate synthesis. The mechanisms of the studied reactions are outlined. The antimicrobial activities of the compounds prepared were screened and the results showed that most of such compounds exhibit considerable activities.

  14. Sol-gel Transition of Methylcellulose Solution in the Coexistence of Hexadecyltrimethylammonium Bromide and Sodium Chloride

    Institute of Scientific and Technical Information of China (English)

    Shah Zhou; Hai-yang Yang; Yong-jun Xie; Hua-zhen Li; Guang-ming Liu

    2011-01-01

    The sol-gel transition of methylcellulose (MC) solution in the presence of NaCl and hexadecyltrimethylammonium bromide (HTAB),together with MC/NaCl solution in the presence of HTAB and MC/HATB solution in the presence of NaCl,was investigated by the rheological measurements.It has been found that the sol-gel transition temperature of MC solution decreases linearly with the concentration of NaCl in solution but increases linearly with the concentration of HTAB in solution,respectively.However,the sol-gel transition temperature of MC/NaCl solution in the presence of HTAB keeps the same value,independent of the concentration of HTAB in solution.On the other hand,the sol-gel transition temperature of MC/HTAB solution decreases linearly with the concentration of NaCl in solution.The experimental results suggest that,for MC/NaCl solution in the presence of HTAB,the saltinduced spherical micelles of HTAB should have formed in bulk solution.For MC solution in the absence of NaCl,no spherical micelles have been formed in bulk solution,though the concentration of HTAB in our experiment is almost one order of magnitude higher than the critical micelle concentration of HTAB in polymer-free solution.In fact,due to adsorption of HTAB on MC chains,the realconcentration of HTAB in bulk solution,is much less than the apparent concentration of HTAB dissolved in MC solution.

  15. Evaluation of the effect of tetraethylammonium bromide and chloride on the growth and development of terrestrial plants.

    Science.gov (United States)

    Pawłowska, Barbara; Biczak, Robert

    2016-04-01

    Quaternary ammonium salts (QAS), which also include ionic liquids, constitute a vast group of chemical compounds that are increasingly common in the commercial use. This situation may lead to the contamination of the natural environment and may constitute a potential threat to all its elements, including terrestrial higher plants. This paper presents the effect of tetraethylammonium chloride [TEA][Cl] and tetraethylammonium bromide [TEA][Br] on the growth and development of spring barley and common radish. The applied QAS were characterized with phytotoxicity dependent on the concentration of compound and characteristics of the study plants. Spring barley turned out to be highly susceptible plant to the analyzed compounds, which was confirmed by % inhibition of length of plants, root length and fresh weight of plants and by calculated values for EC50, NOEC as well as LOEC. On the contrary, a common radish revealed the resistance to QAS used in the study; although, phytotoxic symptoms were still observed when high concentrations of dry weight of soil were applied (1000, 3000 and 5000 mg/kg). The applied QAS caused oxidative stress symptoms, mainly in spring barley seedlings, which were manifested by decreased assimilation of pigments content, increased hydrogen peroxide (H2O2) and malondialdehyde (MDA) content in plant cells and with a changed activity of superoxide dismutase (SOD), catalase (CAT) and peroxidase (POD).

  16. Niobium(v) chloride and imidazolium bromides as efficient dual catalyst systems for the cycloaddition of carbon dioxide and propylene oxide

    KAUST Repository

    Wilhelm, Michael E.

    2014-02-19

    The application of niobium(v) chloride and several imidazolium bromides as catalyst systems for the cycloaddition of propylene oxide (PO) with carbon dioxide to propylene carbonate (PC) is reported. A set of 31 different imidazolium bromides has been synthesized with varying substituents at all five imidazolium ring atoms, of which 17 have not been reported before. The impact of different substitution patterns (steric and electronic changes and solubility in PO) at the imidazolium ring on the catalytic activity was investigated. The optimisation of the catalyst structure allows for the valorisation of carbon dioxide under mild reaction conditions with high reaction rates in very good yield and selectivity for PC. This journal is © the Partner Organisations 2014.

  17. Niobium(v) chloride and imidazolium bromides as efficient dual catalyst systems for the cycloaddition of carbon dioxide and propylene oxide

    KAUST Repository

    Wilhelm, Michael E.

    2014-01-01

    The application of niobium(v) chloride and several imidazolium bromides as catalyst systems for the cycloaddition of propylene oxide (PO) with carbon dioxide to propylene carbonate (PC) is reported. A set of 31 different imidazolium bromides has been synthesized with varying substituents at all five imidazolium ring atoms, of which 17 have not been reported before. The impact of different substitution patterns (steric and electronic changes and solubility in PO) at the imidazolium ring on the catalytic activity was investigated. The optimisation of the catalyst structure allows for the valorisation of carbon dioxide under mild reaction conditions with high reaction rates in very good yield and selectivity for PC. This journal is © the Partner Organisations 2014.

  18. Highly efficient palladium precatalysts of homoscorpionate bispyrazolyl ligands for the more challenging Suzuki-Miyaura cross-coupling of aryl chlorides.

    Science.gov (United States)

    John, Alex; Shaikh, Mobin M; Butcher, Ray J; Ghosh, Prasenjit

    2010-08-21

    Highly efficient palladium precatalysts {[RN{-(CH(2))(n)-pz(3,5-Me)(2)}(2)]PdCl(2)}(m) [m = n = 1; R = 2,6-Me(2)C(6)H(3) (1), 2,4,6-Me(3)C(6)H(2) (2), CH(2)Ph (3) and m = n = 2; R = CH(2)Ph (4)] of a series of homoscorpionate bispyrazolyl ligands for the Suzuki-Miyaura cross-coupling of the more challenging aryl chloride substrates are reported. In particular, the palladium 1-4 precatalysts carried out the Suzuki-Miyaura cross-coupling of a wide variety of aryl chloride substrates bearing electron withdrawing, electron donating and heteroaryl substituents. Remarkably enough, the molecular structure determination of the 1-4 precatalysts by X-ray diffraction studies revealed the presence of anagostic [C-H...Pd] type interactions in the mononuclear 1-3 complexes of methylene bridged bispyrazolyl ligands whereas the ethylene bridged analog 4 yielded an interesting dimeric 20-membered macrometallacyclic complex devoid of any such interaction.

  19. Halogen-bonding for visual chloride ion sensing: a case study using supramolecular poly(aryl ether) dendritic organogel systems.

    Science.gov (United States)

    Liu, Zhi-Xiong; Sun, Yihua; Feng, Yu; Chen, Hui; He, Yan-Mei; Fan, Qing-Hua

    2016-02-07

    A convenient and straightforward method for the visual recognition of chloride ion has been established through a chloride-responsive dendritic organogel. The specificity was largely attributed to the higher binding affinity of the dendritic gelator for chloride compared with other anions through halogen bonding interactions.

  20. Room-Temperature Palladium-Catalyzed Direct 2-Arylation of Benzoxazoles with Aryl and Heteroaryl Bromides†

    Science.gov (United States)

    Gao, Feng; Kim, Byeong-Seon; Walsh, Patrick J.

    2014-01-01

    An efficient room-temperature palladium-catalyzed direct 2-arylation of benzoxazoles with aryl bromides is presented. The Pd(OAc)2/NiXantphos-based catalyst enables the introduction of various aryl and heteroaryl groups, via a deprotonative cross-coupling process (DCCP) in good to excellent yields (75–99%). PMID:25078988

  1. Palladium-catalyzed oxidative Heck-type alkylation/aryl migration/desulfonylation between alkenes with α-carbonyl alkyl bromides.

    Science.gov (United States)

    Fan, Jian-Hong; Yang, Ji; Song, Ren-Jie; Li, Jin-Heng

    2015-02-20

    A new Pd(II)-catalyzed alkene oxidative difunctionalization initiated by Heck insertion has been developed for the selective synthesis of acyclic and cyclic all-carbon quaternary stereocenters, which achieves an oxidative Heck-type alkylation, aryl migration, and desulfonylation sequence and represents a different input from those previously used Heck coupling in synthesis is reported.

  2. Homogeneous catalysts supported on soluble polymers: biphasic Suzuki-Miyaura coupling of aryl chlorides using phase-tagged palladium-phosphine catalysts.

    Science.gov (United States)

    an der Heiden, Markus; Plenio, Herbert

    2004-04-02

    The Suzuki-Miyaura coupling of aryl chlorides and PhB(OH)(2) under biphasic conditions (DMSO/heptane) can be performed in almost quantitative yields over several cycles by means of polymeric Pd catalysts with soluble polyethylene glycol phase tags. Three sterically demanding and electron-rich phosphines 1-CH(2)Br,4-CH(2)P(1-Ad)(2)-C(6)H(4), and 2-PCy(2),2'-OH-biphenyl, and 2-PtBu(2),2'-OH-biphenyl were covalently bonded to 2000 Dalton MeOPEG-OH. The catalysts, which were formed in situ from Na(2)[PdCl(4)], the respective polymeric phosphine, KF/K(3)PO(4), and PhB(OH)(2), efficiently couple aryl chlorides at 80 degrees C at 0.5 mol % loading, resulting in a >90 % yield of the respective biphenyl derivatives. The use of polar phase tags allows the efficient recovery of palladium-phosphine catalysts by simple phase separation of the catalyst-containing DMSO solution and the product-containing n-heptane phase. The high activity (TOF) of the catalyst remains almost constant over more than five reaction cycles, which involve the catalytic reaction, separation of the product phase from the catalyst phase, and addition of new reactants to initiate the next cycle. The Buchwald type biphenyl phosphines form the most active Pd catalysts, which are 1.3-2.8 times more active than catalysts derived from diadamantyl-benzylphosphine, but appear to be less robust in the recycling experiments. There is no apparent leaching of the catalyst into the heptane solution (<0.05 %), as evidenced by spectrophotometric measurements, and contamination of the product with Pd is avoided.

  3. Palladium-Catalyzed Arylation of Fluoroalkylamines

    Science.gov (United States)

    Brusoe, Andrew T.; Hartwig, John F.

    2015-01-01

    We report the synthesis of fluorinated anilines by palladium-catalyzed coupling of fluoroalkylamines with aryl bromides and aryl chlorides. The products of these reactions are valuable because anilines typically require the presence of an electron-withdrawing substituent on nitrogen to suppress aerobic or metabolic oxidation, and the fluoroalkyl groups have steric properties and polarity distinct from those of more common electron-withdrawing amide and sulfonamide units. The fluoroalkylaniline products are unstable under typical conditions for C–N coupling reactions (heat and strong base). However, the reactions conducted with the weaker base KOPh, which has rarely been used in cross-coupling to form C–N bonds, occurred in high yield in the presence of a catalyst derived from commercially available AdBippyPhos and [Pd(allyl)Cl]2. Under these conditions, the reactions occur with low catalyst loadings (<0.50 mol % for most substrates) and tolerate the presence of various functional groups that react with the strong bases that are typically used in Pd-catalyzed C–N cross-coupling reactions of aryl halides. The resting state of the catalyst is the phenoxide complex, (BippyPhosPd(Ar)OPh); due to the electron-withdrawing property of the fluoroalkyl substituent, the turnover-limiting step of the reaction is reductive elimination to form the C–N bond. PMID:26065341

  4. A general and efficient copper catalyst for the amidation of aryl halides.

    Science.gov (United States)

    Klapars, Artis; Huang, Xiaohua; Buchwald, Stephen L

    2002-06-26

    An experimentally simple and inexpensive catalyst system was developed for the amidation of aryl halides by using 0.2-10 mol % of CuI, 5-20 mol % of a 1,2-diamine ligand, and K(3)PO(4), K(2)CO(3), or Cs(2)CO(3) as base. Catalyst systems based on N,N'-dimethylethylenediamine or trans-N,N'-dimethyl-1,2-cyclohexanediamine were found to be the most active even though several other 1,2-diamine ligands could be used in the easiest cases. Aryl iodides, bromides, and in some cases even aryl chlorides can be efficiently amidated. A variety of functional groups are tolerated in the reaction, including many that are not compatible with Pd-catalyzed amidation or amination methodology.

  5. C–H arylation of unsubstituted furan and thiophene with acceptor bromides: access to donor–acceptor–donor-type building blocks for organic electronics.

    Science.gov (United States)

    Matsidik, Rukiya; Martin, Johannes; Schmidt, Simon; Obermayer, Johannes; Lombeck, Florian; Nübling, Fritz; Komber, Hartmut; Fazzi, Daniele; Sommer, Michael

    2015-01-16

    Pd-catalyzed direct arylation (DA) reaction conditions have been established for unsubstituted furan (Fu) and thiophene (Th) with three popular acceptor building blocks to be used in materials for organic electronics, namely 4,7-dibromo-2,1,3-benzothiadiazole (BTBr2), N,N′-dialkylated 2,6-dibromonaphthalene-1,4,5,8-bis(dicarboximide) (NDIBr2), and 1,4-dibromotetrafluorobenzene (F4Br2). Reactions with BTBr2, F4Br2, and NDIBr2 require different solvents to obtain high yields. The use of dimethylacetamide (DMAc) is essential for the successful coupling of BTBr2 and F4Br2, but detrimental for NDIBr2, as the electron-deficient NDI core is prone to nucleophilic core substitution in DMAc as solvent but not in toluene. NDIFu2 is much more planar compared to NDITh2, resulting in an enhanced charge-transfer character, which makes it an interesting building block for conjugated systems designed for organic electronics. This study highlights direct arylation as a simple and inexpensive method to construct a series of important donor–acceptor–donor building blocks to be further used for the preparation of a variety of conjugated materials.

  6. Simple synthesis of P(Cbz-alt-TBT) and PCDTBT by combining direct arylation with suzuki polycondensation of heteroaryl chlorides.

    Science.gov (United States)

    Lombeck, Florian; Matsidik, Rukiya; Komber, Hartmut; Sommer, Michael

    2015-01-01

    Direct arylation (DA) of 2-chlorothiophene and 2-chloro-3-hexylthiophene with 4,7-dibromo-2,1,3-benzothiadiazole is used to synthesize 4,7-bis(5-chloro-2-thienyl)-2,1,3-benzothiadiazole (TBTCl2) and 4,7-bis(5-chloro-4-hexyl-2-thienyl)-2,1,3-benzothiadiazole (DH-TBTCl2) in one step. Suitable conditions of the Suzuki polycondensations (SPC) of TBTCl2 and DH-TBTCl2 with the carbazole comonomer CbzPBE2 are established, furnishing PCDTBT and P(Cbz-alt-TBT) with high molecular weight and yield. Compared with control samples made from the corresponding dibromides, high-temperature NMR and UV-vis spectroscopy indicate similar properties for PCDTBT but an increased content of Cbz-Cbz homocouplings for P(Cbz-alt-TBT).

  7. [Studies on local anesthetics. Part 183: micellization and thermodynamic parameters of heptacainium chloride in the solution of potassium bromide].

    Science.gov (United States)

    Andriamainty, F; Cizmárik, J; Malík, I; Horvat, S

    2008-06-01

    The critical micellar concentration (CMC) of the local anaesthetic agent heptacainium chloride in the solution of KBr was determined by the spectrophotometric method in the UV region of the spectrum at the temperature range of t = 20-40 degrees C and pH = 4.5-5.0. The dependence of CMC on the temperature T turned out forming the U-shape with the minimum at the temperature of t = 25 degrees C. The parabolic dependence of CMC on the temperature T was drawn by the fitting of the values using the polynomial function and the so-called power law equation. The CMC dependence on the temperature T was fitted by the second degree polynomial function. The obtained parabolic equations were applied to the "phase separation model", so the following thermodynamic parameters could be calculated: standard Gibbs free energy (deltaG), enthalpy (deltaH degrees), and entropy (deltaS degrees). The thermodynamic parameters were further used to determine the so-called entropy-enthalpy compensation of the systems under study. The compensation temperature was in the following range: (301 +/- 1-303 +/- 3)K. Then the temperature dependence of the enthalpy (deltaH degrees) and entropy (-TdeltaS degrees) contributions to the standard Gibbs free energy (deltaG degrees) for all prepared concentrations of the compound were calculated.

  8. MAPbI2.9-xBrxCl0.1 hybrid halide perovskites: Shedding light on the effect of chloride and bromide ions on structural and photoluminescence properties

    Science.gov (United States)

    Atourki, Lahoucine; Vega, Erika; Marí, Bernabé; Mollar, Miguel; Ait Ahsaine, Hassan; Bouabid, Khalid; Ihlal, Ahmed

    2016-12-01

    The optical and structural properties of CH3NH3PbI3 can be adjusted by introducing other extrinsic ions such as chloride and bromide. In this work, mixed bromide iodide lead perovskites with a 10% fraction of chloride were prepared from methylamine, lead nitrate and the corresponding hydro acid (X = I, Br, Cl). The effect of bromide and chloride incorporation on different properties of perovskite thin film was investigated. The Pawley fit method indicates the formation of the iodide halide MAPbI3 Pm-3 m cubic phase for x = 0 and the tetragonal P4/mmm phase for x ≥ 0.3. All deposited films showed a strong absorbance in the UV-vis range. The band gap values were estimated from absorbance measurements. It was found that the onset of the absorption edge for MAPbI2.9-xBrxCl0.1 thin film perovskites ranges between 1.60 and 1.80 eV. Moreover, it was found that both Cl and Br affect the PL emission of the mixed halide lead perovskite, the MAPbI2.9-xBrxCl0.1 films displayed intermediate values from 730 nm (MAPbI2.2Br0.7Cl0.1) to 770 nm (MAPbI2.6Br0.3Cl0.1).

  9. Palladium-Catalyzed α-Arylation of Zinc Enolates of Esters: Reaction Conditions and Substrate Scope

    Science.gov (United States)

    Hama, Takuo; Ge, Shaozhong; Hartwig, John F.

    2013-01-01

    The intermolecular α-arylation of esters by palladium-catalyzed coupling of aryl bromides with zinc enolates of esters is reported. Reactions of three different types of zinc enolates have been developed. α-Arylation of esters occurs in high yields with isolated Reformatsky reagents, with Reformatsky reagents generated from α-bromo esters and activated zinc, and with zinc enolates generated by quenching lithium enolates of esters with zinc chloride. The use of zinc enolates, instead of alkali metal enolates, greatly expands the scope of the arylation of esters. The reactions occur at room temperature or at 70 °C with bromoarenes containing cyano, nitro, ester, keto, fluoro, enolizable hydrogen, hydroxyl or amino functionality and with bromopyridines. The scope of esters encompasses acyclic acetates, propionates, and isobutyrates, α-alkoxyesters, and lactones. The arylation of zinc enolates of esters was conducted with catalysts bearing the hindered pentaphenylferrocenyl di-tert-butylphosphine (Q-phos) or the highly reactive dimeric Pd(I) complex {[P(t-Bu)3]PdBr}2. PMID:23931445

  10. Palladium-catalyzed α-arylation of zinc enolates of esters: reaction conditions and substrate scope.

    Science.gov (United States)

    Hama, Takuo; Ge, Shaozhong; Hartwig, John F

    2013-09-06

    The intermolecular α-arylation of esters by palladium-catalyzed coupling of aryl bromides with zinc enolates of esters is reported. Reactions of three different types of zinc enolates have been developed. α-Arylation of esters occurs in high yields with isolated Reformatsky reagents, with Reformatsky reagents generated from α-bromo esters and activated zinc, and with zinc enolates generated by quenching alkali metal enolates of esters with zinc chloride. The use of zinc enolates, instead of alkali metal enolates, greatly expands the scope of the arylation of esters. The reactions occur at room temperature or at 70 °C with bromoarenes containing cyano, nitro, ester, keto, fluoro, enolizable hydrogen, hydroxyl, or amino functionality and with bromopyridines. The scope of esters encompasses acyclic acetates, propionates, and isobutyrates, α-alkoxyesters, and lactones. The arylation of zinc enolates of esters was conducted with catalysts bearing the hindered pentaphenylferrocenyl di-tert-butylphosphine (Q-phos) or the highly reactive dimeric Pd(I) complex {[P(t-Bu)3]PdBr}2.

  11. Determination of bromide, chloride, fluoride, nitrate and sulphate by ion chromatography: comparisons of methodologies for rainfall, cloud water and river waters at the Plynlimon catchments of mid-Wales

    Directory of Open Access Journals (Sweden)

    2007-01-01

    Full Text Available The results of determination of bromide, chloride, fluoride, nitrate and sulphate using ion chromatography (IC are compared with those obtained by colorimetric and inductively coupled plasma optical emission spectroscopy (ICPOES for rainfall, cloud water and stream waters in the Plynlimon experimental catchments of mid-Wales. For bromide, the concentrations determined by IC are lower than those for the colorimetric method used; the colorimetric method probably determined bromide plus organo-bromine compounds. It is suggested that the values determined by the colorimetric method be termed dissolved labile bromine (DLBr. The study shows that sulphate is the overriding form of sulphur in the waters. For chloride and nitrate, measurements by both methods approach a 1:1 relationship that is barely statistically significantly different from unity. For fluoride, the IC method gives lower values than the colorimetric, especially for the stream waters. However, the colorimetric method determines total fluorine so that a difference is to be expected (for example, fluoride strongly complexes with aluminium that is present, especially in the streamwater.

  12. Development of a palladium-catalyzed α-arylation of cyclopropyl nitriles.

    Science.gov (United States)

    McCabe Dunn, Jamie M; Kuethe, Jeffrey T; Orr, Robert K; Tudge, Matthew; Campeau, Louis-Charles

    2014-12-19

    1,1-Disubstituted aryl cyclopropyl nitriles are useful moieties in biologically active compounds and provide access to a range of cyclopropyl derivatives. Herein, we describe the development of a palladium-catalyzed α-arylation of cyclopropyl, cyclobutyl, and cyclopentyl nitriles that affords these functional groups in one step from a variety of aryl bromides in good to excellent yields. Furthermore, we demonstrate the transformation of aryl cyclopropyl nitriles into aryl trifluoromethyl cyclopropanes.

  13. Lewis acidic (choline chloride.3ZnCl2) ionic liquid: A green and recyclable catalyst for the one-pot synthesis of 4-((3-indolyl)(aryl)methyl)-N,N-dimethylanilines under solvent-free conditions

    Indian Academy of Sciences (India)

    Rahim Hekmatshoar; Farnoush Mousavizadeh; Reyhaneh Rahnamafar

    2013-09-01

    A green and convenient procedure for the one-pot multicomponent synthesis of 4-((3-indolyl)(aryl)methyl)-N,N-dimethylanilines using (choline chloride.3ZnCl2) ionic liquid as catalyst, at 100°C and under solvent-free condition is described. Utilizing environmentally benign reagents, elimination of organic solvents, enhanced rates, reusability and moisture stability of the catalyst are the remarkable features observed in the reported reaction system. The catalyst was recycled up to four times with no noticeable drop in activity.

  14. A Palladium Catalyst System for the Efficient Cross-Coupling Reaction of Aryl Bromides and Chlorides with Phenylboronic Acid: Synthesis and Biological Activity Evaluation

    Directory of Open Access Journals (Sweden)

    Boubakri Lamia

    2017-03-01

    Full Text Available New benzimidazolium salts 1a–c and their palladium bis-N-heterocyclic carbene complexes 2a–c and palladium PEPPSI-type complexes 3a–c were designed, synthesized and structurally characterized by NMR (1H and 13C, IR, DART-TOF mass spectrometry and elemental analysis. Then these complexes 2–3 were employed in the Suzuki-Miyaura cross-coupling reaction of substituted arenes with phenylboronic acid under mild conditions in toluene and DMF/H2O (1/1 to afford functionalized biaryl derivatives in good to excellent yields. The antibacterial activity of palladium bis-N-heterocyclic carbene complexes 2a–c and palladium PEPPSI-type complexes 3a–c was measured by disc diffusion method against Gram positive and Gram negative bacteria. Compounds 2a, 2c and 3a–c exhibited potential antibacterial activity against four bacterial species among the five used indicator cells. The product 2b inhibits the growth of the all five tested microorganisms. Moreover, the antioxidant activity determination of these complexes 2–3, using 2.2-diphenyl-1-picrylhydrazyl (DPPH as a reagent, showed that compounds 2a–c and 3b possess DPPH antiradical activity. The higher antioxidant activity was obtained from the product 2b which has radical scavenging activity comparable to that of the two used positive controls (gallic acid “GA“ and tutylatedhydroxytoluene “BHT“. Investigation of the anti-acetylcholinesterase activity of the studied complexes showed that compounds 2b, 3a, and 3b exhibited moderate activity at 100 μg/mL and product 2b is the most active.

  15. A Palladium Catalyst System for the Efficient Cross-Coupling Reaction of Aryl Bromides and Chlorides with Phenylboronic Acid: Synthesis and Biological Activity Evaluation.

    Science.gov (United States)

    Lamia, Boubakri; Chakchouk-Mtibaa, Ahlem; Hallouma, Bilel; Mansour, Lamjed; Mellouli, Lotfi; Özdemir, Ismail; Yaşar, Sedat; Hamdi, Naceur

    2017-03-07

    New benzimidazolium salts 1a-c and their palladium bis-N-heterocyclic carbene complexes 2a-c and palladium PEPPSI-type complexes 3a-c were designed, synthesized and structurally characterized by NMR (1H and 13C), IR, DART-TOF mass spectrometry and elemental analysis. Then these complexes 2-3 were employed in the Suzuki-Miyaura cross-coupling reaction of substituted arenes with phenylboronic acid under mild conditions in toluene and DMF/H2O (1/1) to afford functionalized biaryl derivatives in good to excellent yields. The antibacterial activity of palladium bis-N-heterocyclic carbene complexes 2a-c and palladium PEPPSI-type complexes 3a-c was measured by disc diffusion method against Gram positive and Gram negative bacteria. Compounds 2a, 2c and 3a-c exhibited potential antibacterial activity against four bacterial species among the five used indicator cells. The product 2b inhibits the growth of the all five tested microorganisms. Moreover, the antioxidant activity determination of these complexes 2-3, using 2.2-diphenyl-1-picrylhydrazyl (DPPH) as a reagent, showed that compounds 2a-c and 3b possess DPPH antiradical activity. The higher antioxidant activity was obtained from the product 2b which has radical scavenging activity comparable to that of the two used positive controls (gallic acid "GA" and tutylatedhydroxytoluene "BHT"). Investigation of the anti-acetylcholinesterase activity of the studied complexes showed that compounds 2b, 3a, and 3b exhibited moderate activity at 100 μg/mL and product 2b is the most active.

  16. Synthesis of β-arylated alkylamides via Pd-catalyzed one-pot installation of a directing group and C(sp3)–H arylation

    Science.gov (United States)

    Zhang, Yi; Cao, Xiaoji; Wan, Jie-Ping

    2016-01-01

    Summary The synthesis of β-arylated alkylamides via alkyl C–H bond arylation has been realized by means of direct one-pot reactions of acyl chlorides, aryl iodides and 8-aminoquinoline. Depending on the structure of the starting materials, both single and double β-arylated alkylamides could be accessed. PMID:27340500

  17. Influence of the anions on the N-cationic benzethonium salts in the solid state and solution: Chloride, bromide, hydroxide and citrate hydrates

    Energy Technology Data Exchange (ETDEWEB)

    Paradies, Henrich H., E-mail: hparadies@aol.com, E-mail: hparadies@jacobs-university.de [The University of Salford, Joule Physics Laboratory, Faculty of Science, Engineering and Environment, Manchester M5 4 WT (United Kingdom); Jacobs University Bremen, Life Sciences and Chemistry Department, Campus Ring 1, D-28759 Bremen (Germany); Reichelt, Hendrik [The University of Salford, Joule Physics Laboratory, Faculty of Science, Engineering and Environment, Manchester M5 4 WT (United Kingdom)

    2016-06-15

    The crystal structures of the hydrated cationic surfactant benzethonium (Bzth) chloride, bromide, hydroxide, and citrate have been determined by X-ray diffraction analysis and compared with their structures in solution well above their critical micelle concentration. The differences in the nature of the various anions of the four Bzth-X materials lead to unique anion environments and 3-D molecular arrangements. The water molecule in the monoclinic Bzth-Cl or Bzth-Br forms is hydrogen bonded to the halides and particularly to the hydrogens of the methoxy groups of the Bzth moiety notwithstanding the weak Brønsted acidity of the methoxy hydrogens. The citrate strongly interacts with the hydrogens of the methoxy group forming an embedded anionic spherical cluster of a radius of 2.6 Å. The Bzth-OH crystallizes in a hexagonal lattice with two water molecules and reveals free water molecules forming hydrogen bonded channels through the Bzth-OH crystal along the c-axis. The distances between the cationic nitrogen and the halides are 4.04 Å and 4.20 Å, significantly longer than expected for typical van der Waals distances of 3.30 Å. The structures show weakly interacting, alternating apolar and polar layers, which run parallel to the crystallographic a-b planes or a-c planes. The Bzth-X salts were also examined in aqueous solution containing 20% (v/v) ethanol and 1.0 % (v/v) glycerol well above their critical micelle concentration by small-angle X-ray scattering (SAXS) and wide-angle X-ray scattering (WAXS). The [1,1,1] planes for the Bzth Cl or Br, the [0,0,2] and [1,1,0] planes for the Bzth-citrate, the [2,-1,0] planes and the [0,0,1] planes for the Bzth-OH found in the crystalline phase were also present in the solution phase, accordingly, the preservation of these phases are a strong indication of periodicity in the solution phase.

  18. Degradation of methyl bromide and methyl chloride in soil microcosms: Use of stable C isotope fractionation and stable isotope probing to identify reactions and the responsible microorganisms

    Science.gov (United States)

    Miller, L.G.; Warner, K.L.; Baesman, S.M.; Oremland, R.S.; McDonald, I.R.; Radajewski, S.; Murrell, J.C.

    2004-01-01

    Bacteria in soil microcosm experiments oxidized elevated levels of methyl chloride (MeCl) and methyl bromide (MeBr), the former compound more rapidly than the latter. MeBr was also removed by chemical reactions while MeCl was not. Chemical degradation dominated the early removal of MeBr and accounted for more than half of its total loss. Fractionation of stable carbon isotopes during chemical degradation of MeBr resulted in a kinetic isotope effect (KIE) of 59 ?? 7???. Soil bacterial oxidation dominated the later removal of MeBr and MeCl and was characterized by different KIEs for each compound. The KIE for MeBr oxidation was 69 ?? 9??? and the KIE for MeCl oxidation was 49 ?? 3???. Stable isotope probing revealed that different populations of soil bacteria assimilated added 13C-labeled MeBr and MeCl. The identity of the active MeBr and MeCl degrading bacteria in soil was determined by analysis of 16S rRNA gene sequences amplified from 13C-DNA fractions, which identified a number of sequences from organisms not previously thought to be involved in methyl halide degradation. These included Burkholderia , the major clone type in the 13C-MeBr fraction, and Rhodobacter, Lysobacter and Nocardioides the major clone types in the 13C-MeCl fraction. None of the 16S rRNA gene sequences for methyl halide oxidizing bacteria currently in culture (including Aminobacter strain IMB-1 isolated from fumigated soil) were identified. Functional gene clone types closely related to Aminobacter spp. were identified in libraries containing the sequences for the cmuA gene, which codes for the enzyme known to catalyze the initial step in the oxidation of MeBr and MeCl. The cmuA gene was limited to members of the alpha-Proteobacteria whereas the greater diversity demonstrated by the 16S rRNA gene may indicate that other enzymes catalyze methyl halide oxidation in different groups of bacteria. Copyright ?? 2004 Elsevier Ltd.

  19. Benzalkonium chloride (BAC) and dimethyldioctadecyl-ammonium bromide (DDAB), two common quaternary ammonium compounds, cause genotoxic effects in mammalian and plant cells at environmentally relevant concentrations.

    Science.gov (United States)

    Ferk, F; Misík, M; Hoelzl, C; Uhl, M; Fuerhacker, M; Grillitsch, B; Parzefall, W; Nersesyan, A; Micieta, K; Grummt, T; Ehrlich, V; Knasmüller, S

    2007-11-01

    Quaternary ammonium compounds (QACs) are cationic surfactants that are widely used as disinfectants. In the present study, we tested two important representatives, namely, benzalkonium chloride (BAC) and dimethyldioctadecyl-ammonium bromide (DDAB) in four genotoxicity tests, namely, in the Salmonella/microsome assay with strains TA 98, TA 100 and TA 102, in the single-cell gel electrophoresis (SCGE) assay with primary rat hepatocytes and in micronucleus (MN) assays with peripheral human lymphocytes and with root tip cells of Vicia faba. In the bacterial experiments, consistently negative results were obtained in the dose range between 0.001 and 110 microg per plate in the presence and absence of metabolic activation while significant induction of DNA migration was detected in the liver cells. With BAC, a moderate but significant effect was found with an exposure concentration of 1.0 mg/l while DDAB caused damage at lower doses (0.3 mg/l). The effects were not altered when the nuclei were treated with formamidopyridine glycosylase, indicating that they are not due to formation of oxidized purines. The MN assays with blood cells were carried out under identical conditions to the SCGE experiments and a significant increase was seen at the highest dose levels (BAC: 1.0 and 3.0 mg/l; DDAB: 1 mg/l). Both compounds also caused significant induction of MN as well as inhibition of cell division in plant cells, the lowest effective levels were 1.0 and 10 mg/l for DDAB and BAC, respectively. Our findings show that both chemicals induce moderate but significant genotoxic effects in eukaryotic cells at concentrations which are found in wastewaters and indicate that their release into the environment may cause genetic damage in exposed organisms. Furthermore, the direct contact of humans to QAC-containing detergents and pharmaceuticals that contain substantially higher concentrations than those which were required to cause effects in eukaryotic cells in the present study should

  20. Aclidinium Bromide

    DEFF Research Database (Denmark)

    Ulrik, Charlotte Suppli

    2012-01-01

    Long-acting bronchodilators are the mainstay of pharmacological treatment for patients with chronic obstructive pulmonary disease (COPD). The aim of this review is to provide an overview of the clinical studies evaluating the safety and efficacy of inhaled aclidinium bromide, a novel long...

  1. 吡啶氮桥联三唑卡宾反应性质及其Pd(Ⅱ)-配合物催化杂芳环与芳基溴的α-烷基化反应研究%Study on Reactivity of Pyrido-annulated Triazol-3-ylidenes and Its Application of Pd(Ⅱ)Complex in α-Arylation of Caffeines with Aryl Bromide

    Institute of Scientific and Technical Information of China (English)

    马亚军; 严彪; 郭政科; 赵明涛; 韩海飞; 程芬芬; 葛靖国; 王金龙; 张岗虎

    2011-01-01

    The triazolium carbene 2 and the pyrido-annulated triazolium carbene enetetramine 4 were synthesized from the pyrido-annulated triazolium salt 1 by deproton under strong base NaH and weak base K2CO3.The reaction performances of the carbene 2 and its enetetramine 4 with electrophilic reagents had also been studied, and the X-ray single-crystal analysis of the product N-ehthyl-N-(pyridine-1-yl)formohy-drazide 3 was studied.Reaction condition effect was tested.The Pd(Ⅱ) complex of the triazolium carbene 2 turned out to be a powerful catalyst in direct α-arylation of caffeines with aryl bromide, which was comparable with or even superior to other well-established triazolylidenes already in the literature.%报道了吡啶氮桥联的双环三唑鎓盐1在NaH,K2CO3为碱的条件下脱去质子,分别形成三唑卡宾2和吡啶氮桥联三唑卡宾二聚体4,研究了2和4与亲电试剂的反应性质,2与水的反应产物Ⅳ-乙基-N'-吡啶基甲醛肼3经单晶衍射结构分析.考察了配体1的卡宾-Pd(Ⅱ)配合物催化咖啡因与芳基溴的α-芳基化反应,在优化催化反应条件下,比较了不同三唑鎓盐之间的催化活性.结果表明,三唑鎓盐1表现出优良的催化活性.

  2. Visible Light Mediated Photoredox Catalytic Arylation Reactions.

    Science.gov (United States)

    Ghosh, Indrajit; Marzo, Leyre; Das, Amrita; Shaikh, Rizwan; König, Burkhard

    2016-08-16

    Introducing aryl- and heteroaryl moieties into molecular scaffolds are often key steps in the syntheses of natural products, drugs, or functional materials. A variety of cross-coupling methods have been well established, mainly using transition metal mediated reactions between prefunctionalized substrates and arenes or C-H arylations with functionalization in only one coupling partner. Although highly developed, one drawback of the established sp2-sp2 arylations is the required transition metal catalyst, often in combination with specific ligands and additives. Therefore, photoredox mediated arylation methods have been developed as alternative over the past decade. We begin our survey with visible light photo-Meerwein arylation reactions, which allow C-H arylation of heteroarenes, enones, alkenes, and alkynes with organic dyes, such as eosin Y, as the photocatalyst. A good number of examples from different groups illustrate the broad application of the reaction in synthetic transformations. While initially only photo-Meerwein arylation-elimination processes were reported, the reaction was later extended to photo-Meerwein arylation-addition reactions giving access to the photoinduced three component synthesis of amides and esters from alkenes, aryl diazonium salts, nitriles or formamides, respectively. Other substrates with redox-active leaving groups have been explored in photocatalyzed arylation reactions, such as diaryliodonium and triarylsulfonium salts, and arylsulfonyl chlorides. We discus some examples with their scope and limitations. The scope of arylation reagents for photoredox reactions was extended to aryl halides. The challenge here is the extremely negative reduction potential of aryl halides in the initial electron transfer step compared to, e.g., aryl diazonium or diaryliodonium salts. In order to reach reduction potentials over -2.0 V vs SCE two consecutive photoinduced electron transfer steps were used. The intermediary formed colored radical

  3. Copper-diamine-catalyzed N-arylation of pyrroles, pyrazoles, indazoles, imidazoles, and triazoles.

    Science.gov (United States)

    Antilla, Jon C; Baskin, Jeremy M; Barder, Timothy E; Buchwald, Stephen L

    2004-08-20

    This paper details the copper-catalyzed N-arylation of pi-excessive nitrogen heterocycles. The coupling of either aryl iodides or aryl bromides with common nitrogen heterocycles (pyrroles, pyrazoles, indazoles, imidazoles, and triazoles) was successfully performed in good yield with catalysts derived from diamine ligands and CuI. General conditions were found that tolerate functional groups such as aldehydes, ketones, alcohols, primary amines, and nitriles on the aryl halide or heterocycle. Hindered aryl halides or heterocycles were also found to be suitable substrates using the conditions reported herein. Copyright 2004 American Chemical Society

  4. Pd-NHC-Catalyzed Alkynylation of General Aryl Sulfides with Alkynyl Grignard Reagents.

    Science.gov (United States)

    Baralle, Alexandre; Yorimitsu, Hideki; Osuka, Atsuhiro

    2016-07-25

    Cross-coupling reactions of unactivated aryl sulfides with alkynylmagnesium chloride have been invented to afford 1-aryl-1-alkynes with the aid of a palladium/N-heterocyclic carbene complex. This reaction has by far the widest scope of all transformations utilizing aryl sulfides and alkynes, while known cross-coupling alkynylations of aryl-sulfur electrophiles require activated azaaryl sulfides, thiolactams, or arenesulfonyl chlorides. The alkynylation of aryl sulfides is compatible with typical protecting functional groups. The alkynylation is applied to the synthesis of benzofuran-based fluorescent molecules by taking advantage of characteristic organosulfur chemistry.

  5. Bromide, Chloride, and Sulfate Concentrations and Loads at U.S. Geological Survey Streamflow-Gaging Stations 07331600 Red River at Denison Dam, 07335500 Red River at Arthur City, and 07336820 Red River near DeKalb, Texas, 2007-09

    Science.gov (United States)

    Baldys, Stanley; Churchill, Christopher J.; Mobley, Craig A.; Coffman, David K.

    2010-01-01

    The U.S. Geological Survey, in cooperation with the City of Dallas Water Utilities Division, did a study to characterize bromide, chloride, and sulfate concentrations and loads at three U.S. Geological Survey streamflow-gaging stations on the reach of the Red River from Denison Dam, which impounds Lake Texoma, to the U.S. Highway 259 bridge near DeKalb, Texas. Bromide, chloride, and sulfate concentrations and loads were computed for streamflow-gaging stations on the study reach of the Red River. Continuous streamflow and specific conductance data and discrete samples for bromide, chloride, sulfate, and specific conductance were collected at three main-stem streamflow-gaging stations on the Red River: 07331600 Red River at Denison Dam near Denison, Texas (Denison Dam gage), 07335500 Red River at Arthur City, Texas (Arthur City gage), and 07336820 Red River near DeKalb, Texas (DeKalb gage). At each of these streamflow-gaging stations, discrete water-quality data were collected during January 2007-February 2009; continuous water-quality data were collected during March 2007-February 2009. Two periods of high flow resulted from floods during the study; floods during June-July 2007 resulted in elevated flow during June-September 2007 and smaller floods during March-April 2008 resulted in elevated flow during March-April 2008. Bromide, chloride, and sulfate concentrations in samples collected at the three gages decreased downstream. Median bromide concentrations ranged from 0.32 milligram per liter at the Denison Dam gage to 0.19 milligram per liter at the DeKalb gage. Median chloride concentrations ranged from 176 milligrams per liter at the Denison Dam gage to 108 milligrams per liter at the DeKalb gage, less than the 300-milligrams per liter secondary maximum contaminant level established by the Texas Commission on Environmental Quality. Median sulfate concentrations ranged from 213 milligrams per liter at the Denison Dam gage to 117 milligrams per liter at the De

  6. Palladium-catalyzed regioselective arylation of imidazo[1,2-a]pyrimidine.

    Science.gov (United States)

    Li, Wenjie; Nelson, Dorian P; Jensen, Mark S; Hoerrner, R Scott; Javadi, Gary J; Cai, Dongwei; Larsen, Robert D

    2003-12-11

    Imidazo[1,2-a]pyrimidine can be arylated at the 3-position with aryl bromides in the presence of base and a catalytic amount of palladium. This provides an efficient one-step synthesis of 3-arylimidazo[1,2-a]pyrimidines from the unsubstituted heterocycle. [reaction: see text

  7. Unusual selectivity-determining factors in the phosphine-free Heck arylation of allyl ethers

    DEFF Research Database (Denmark)

    Ambrogio, I.; Fabrizi, G.; Cacchi, S.

    2008-01-01

    The Heck reaction of aryl iodides and bromides with allyl ethers has been investigated. Using phosphinefree Pd(OAc)(2) in DNIF at 90 degrees C in the presence of Bu4NOAc, the reaction gave cinnamyl derivatives, usually in good to high yields, with a wide range of aryl halides. The reaction tolera...

  8. Room temperature N-arylation of amino acids and peptides using copper(I) and β-diketone.

    Science.gov (United States)

    Sharma, Krishna K; Sharma, Swagat; Kudwal, Anurag; Jain, Rahul

    2015-04-28

    A mild and efficient method for the N-arylation of zwitterionic amino acids, amino acid esters and peptides is described. The procedure provides the first room temperature synthesis of N-arylated amino acids and peptides using CuI as a catalyst, diketone as a ligand, and aryl iodides as coupling partners. The method is equally applicable for using relatively inexpensive aryl bromides as coupling partners at 80 °C. Using this procedure, electronically and sterically diverse aryl halides, containing reactive functional groups were efficiently coupled in good to excellent yields.

  9. Automated determination of bromide in waters by ion chromatography with an amperometric detector

    Science.gov (United States)

    Pyen, G.S.; Erdmann, D.E.

    1983-01-01

    An automated ion chromatograph, including a program controller, an automatic sampler, an integrator, and an amperometric detector, was used to develop a procedure for the determination of bromide in rain water and many ground waters. Approximately 10 min is required to obtain a chromatogram. The detection limit for bromide is 0.01 mg l-1 and the relative standard deivation is <5% for bromide concentrations between 0.05 and 0.5 mg l-1. Chloride interferes if the chloride-to-bromide ratio is greater than 1 000:1 for a range of 0.01-0.1 mg l-1 bromide; similarly, chloride interferes in the 0.1-1.0 mg l-1 range if the ratio is greater than 5 000:1. In the latter case, a maximum of 2 000 mg l-1 of chloride can be tolerated. Recoveries of known concentrations of bromide added to several samples, ranged from 97 to 110%. ?? 1983.

  10. Regiocontroled Pd-catalysed C5-arylation of 3-substituted thiophene derivatives using a bromo-substituent as blocking group

    Directory of Open Access Journals (Sweden)

    Mariem Brahim

    2016-10-01

    Full Text Available The use of a bromo-substituent as blocking group at the C2-position of 3-substituted thiophenes allows the regioselective introduction of aryl substituents at C5-position via Pd-catalysed direct arylation. With 1 mol % of a phosphine-free Pd catalyst, KOAc as the base and DMA as the solvent and various electron-deficient aryl bromides as aryl sources, C5-(heteroarylated thiophenes were synthesized in moderate to high yields, without cleavage of the thienyl C–Br bond. Moreover, sequential direct thienyl C5-arylation followed by Pd-catalysed direct arylation or Suzuki coupling at the C2-position allows to prepare 2,5-di(heteroarylated thiophenes bearing two different (heteroaryl units in only two steps. This method provides a “green” access to arylated thiophene derivatives as it reduces the number of steps to prepare these compounds and also the formation of wastes.

  11. Atom-efficient coupling reaction of aryl bromideswith sodium tetraphenylborate catalyzed by reusable Pd/C in water under focused microwave irradiation

    Institute of Scientific and Technical Information of China (English)

    Lin Bai

    2009-01-01

    A rapid and heterogeneous Pal/C-catalyzed atom-efficient phenylation of aryl bromides by sodium tetraphenylborate takes place under focused microwave irradiation in water.The palladium catalyst can be easily recovered and reused.

  12. Pd-NHC-Catalyzed Direct Arylation of 1,4-Disubstituted 1,2,3-Triazoles with Aryl Halides

    Institute of Scientific and Technical Information of China (English)

    何涛; 王敏; 李品华; 王磊

    2012-01-01

    A highly efficient method for the synthesis of unsymmetrical multi-substituted 1,2,3-triazoles via a direct Pd-NHC system catalyzed C(5)-arylation of 1,4-disubstituted triazoles, which are readily accessible via "click" chemistry has been developed. It is important to note that C--H bond functionalizations of 1,2,3-triazoles with a variety of differently substituted aryl iodides and bromides as electrophiles can be conveniently achieved through this catalytic system at significantly milder reaction temperatures of 100 ℃ under air.

  13. 2,6-Dimethylpyridinium bromide

    Directory of Open Access Journals (Sweden)

    Salim F. Haddad

    2012-10-01

    Full Text Available The asymmetric unit of the title salt, C7H10N+·Br−, comprises two 2,6-dimethylpyridinium cations and two bromide anions. One cation and one anion are situated in general positions, while the other cation and the other anion lie on a crystallographic mirror plane parallel to (010. Each pair of ions interact via N—H...Br and C—H...Br hydrogen bonding, generating motifs depending on the cation and anion involved. Thus, the cation and the anion on the mirror plane generate infinite chains along the c axis, while the other ionic pair leads to sheets parallel to the ac plane. In the overall crystal packing, both motifs alternate along the b axis, with a single layer of the chain motif sandwiched between two double layers of the sheet motif. The sheets and chains are further connected via aryl π–π interactions [centroid–centroid distances = 3.690 (2 and 3.714 (2 Å], giving a three-dimensional network.

  14. Solid miscibility of common-anion lithium and sodium halides. Experimental determination of the region of demixing in lithium bromide + sodium bromide

    NARCIS (Netherlands)

    Oonk, H.A.J.; Wijk, H.J. van; Doornhof, D.

    1984-01-01

    The region of demixing of solid lithium bromide + sodium bromide mixtures has been measured by X-ray diffraction. The critical temperature of mixing corresponding to a thermodynamic fit of the experimental data is 513 K. Estimates are given of the regions of demixing in solid lithium chloride + sodi

  15. Palladium-catalyzed α-arylation of benzylic phosphine oxides.

    Science.gov (United States)

    Montel, Sonia; Jia, Tiezheng; Walsh, Patrick J

    2014-01-03

    A novel approach to prepare diarylmethyl phosphine oxides from benzyl phosphine oxides via deprotonative cross-coupling processes (DCCP) is reported. The optimization of the reaction was guided by High-Throughput Experimentation (HTE) techniques. The Pd(OAc)2/Xantphos-based catalyst enabled the reaction between benzyl diphenyl or dicyclohexyl phosphine oxide derivatives and aryl bromides in good to excellent yields (51-91%).

  16. Synthesis and properties of poly(sulfone-arylate) copolymers

    NARCIS (Netherlands)

    Stephen, Ranimol; Gibon, Cécile M.; Weber, Martin; Gaymans, Reinoud J.

    2009-01-01

    Poly(sulfone-arylate) was synthesized in a reaction between dihydroxy polysulfone prepolymers and either diphenyl terephthalate or terephthaloyl chloride. The dihydroxy polysulfone prepolymers had molecular weights of 2000 and 4000 g/mol. The polymerization with diphenyl terephthalate was carried ou

  17. Synthesis of aryl phosphates based on pyrimidine and triazine scaffolds.

    Science.gov (United States)

    Courme, Caroline; Gresh, Nohad; Vidal, Michel; Lenoir, Christine; Garbay, Christiane; Florent, Jean-Claude; Bertounesque, Emmanuel

    2010-01-01

    The syntheses of the triazinyl-based bis-aryl phosphates 2 and 3, and of the aminopyrimidyl-based aryl phosphate 4 are described. Each compound contains a diaryl ether-phosphate structural motif. The synthetic route to bis-aryl phosphates 2 and 3 consisted in two nucleophilic substitution reactions with amines from cyanuric chloride, followed by a Suzuki coupling with the resulting 2,4-diamino-6-chloro-1,3,5-triazine derivative 12 to introduce the diaryl ether functionality. Aryl phosphate 4 was obtained via condensation of aryl guanidine 34 with aryloxyphenyl butenone 31. These de novo-designed aryl phosphates were evaluated as potential inhibitors of the Grb2-SH2 domain using an ELISA assay. The water-soluble sodium salt 26 of 3 gave an IC(50) value in the high micromolar range. Molecular modeling studies were subsequently performed upon modifying the 1,3,5-trisubstituted triazine scaffold of 3. Non-phosphate derivatives encompassing cyclopropane, pyrrole, keto-acid, and IZD fragments were thus step-wise designed and their Grb2-SH2 complexes were modeled by molecular dynamics. Some derivatives gave rise to an enriched pattern of H-bonds and cation-pi interactions with Grb2-SH2.

  18. Efficient Catalyst One-Pot Synthesis of 7-(Aryl-10,10-dimethyl-10,11-dihydrochromeno[4,3-b]chromene-6,8(7H,9H-dione Derivatives Complemented by Antibacterial Activity

    Directory of Open Access Journals (Sweden)

    Yasameen K. Al-Majedy

    2016-01-01

    Full Text Available The problem of bacteria resistance to many known agents has inspired scientists and researchers to discover novel efficient antibacterial drugs. Three rapid, clean, and highly efficient methods were developed for one-pot synthesis of 7-(aryl-10,10-dimethyl-10,11-dihydrochromeno[4,3-b]chromene-6,8(7H,9H-dione derivatives. Three components are condensed in the synthesis, 4-hydroxycoumarin, 5,5-dimethyl-1,3-cyclohexanedione, and aromatic aldehydes, using tetrabutylammonium bromide (TBAB, diammonium hydrogen phosphate (DAHP, or ferric chloride (FeCl3, respectively. Each method has different reaction mechanisms according to the catalyst. The present methods have advantages, including one-pot synthesis, excellent yields, short reaction times, and easy isolation of product. All catalysts utilized in our study could be reused several times without losing their catalytic efficiency. All synthesized compounds were fully characterized and evaluated for their antibacterial activity.

  19. Efficient synthesis of π-conjugated molecules incorporating fluorinated phenylene units through palladium-catalyzed iterative C(sp2–H bond arylations

    Directory of Open Access Journals (Sweden)

    Fatiha Abdelmalek

    2015-10-01

    Full Text Available We report herein a two or three step synthesis of fluorinated π-conjugated oligomers through iterative C–H bond arylations. Palladium-catalyzed desulfitative arylation of heteroarenes allowed in a first step the synthesis of fluoroaryl-heteroarene units in high yields. Then, the next steps involve direct arylation with aryl bromides catalyzed by PdCl(C3H5(dppb to afford triad or tetrad heteroaromatic compounds via regioselective activation of C(sp2–H bonds.

  20. Selective oxidation of bromide in wastewater brines from hydraulic fracturing.

    Science.gov (United States)

    Sun, Mei; Lowry, Gregory V; Gregory, Kelvin B

    2013-07-01

    Brines generated from oil and natural gas production, including flowback water and produced water from hydraulic fracturing of shale gas, may contain elevated concentrations of bromide (~1 g/L). Bromide is a broad concern due to the potential for forming brominated disinfection byproducts (DBPs) during drinking water treatment. Conventional treatment processes for bromide removal is costly and not specific. Selective bromide removal is technically challenging due to the presence of other ions in the brine, especially chloride as high as 30-200 g/L. This study evaluates the ability of solid graphite electrodes to selectively oxidize bromide to bromine in flowback water and produced water from a shale gas operation in Southwestern PA. The bromine can then be outgassed from the solution and recovered, as a process well understood in the bromine industry. This study revealed that bromide may be selectively and rapidly removed from oil and gas brines (~10 h(-1) m(-2) for produced water and ~60 h(-1) m(-2) for flowback water). The electrolysis occurs with a current efficiency between 60 and 90%, and the estimated energy cost is ~6 kJ/g Br. These data are similar to those for the chlor-alkali process that is commonly used for chlorine gas and sodium hydroxide production. The results demonstrate that bromide may be selectively removed from oil and gas brines to create an opportunity for environmental protection and resource recovery.

  1. Relation between chloride exchange diffusion and a conductive chloride pathway across the isolated skin of the toad (Bufo bufo)

    DEFF Research Database (Denmark)

    Kristensen, P; Larsen, Erik Hviid

    1978-01-01

    Substitution of chloride in the outside bathing medium of the toad skin with bromide, iodide, nitrate and sulphate leads to a reduction in the apparent exchange diffusion of chloride across this tissue, and also to a reduction of the chloride current recorded during hyperpolarization. A series of...

  2. Peripheral arylation of subporphyrazines.

    Science.gov (United States)

    Higashino, Tomohiro; Rodríguez-Morgade, M Salomé; Osuka, Atsuhiro; Torres, Tomás

    2013-07-29

    Peripherally hexaarylated subporphyrazines (SubPzs) have been prepared through a Pd-catalyzed, CuTC-mediated coupling of a hexaethylsulfanylated subporphyrazine with arylboronic acids. The introduced aryl substituents strongly influence the electronic properties of the subporphyrazine through effective conjugative interaction. Aryl rings endowed with π-electron-donating groups at the para positions produce a remarkable perturbation of the electron density of the SubPz macrocycle. This is reflected through significant redshifts of the SubPz CT and Q-bands, together with increase of the molar absorptivity of the former, with respect to those exhibited by the hexaphenyl-SubPz 2 a. Moreover, the trend in the first SubPz reduction potentials correlates with the Hammett constants (σp ) corresponding to the para substituents of the aryl. The domed, extended SubPz π-system self-assembles in the solid state to form a dimeric capsule that houses a solvent molecule.

  3. Crystal structure and Hirshfeld surface analysis of 1-carboxy-2-(3,4-dihydroxyphenylethan-1-aminium chloride 2-ammonio-3-(3,4-dihydroxyphenylpropanoate: a new polymorph of l-dopa HCl and isotypic with its bromide counterpart

    Directory of Open Access Journals (Sweden)

    Perumal Kathiravan

    2016-11-01

    Full Text Available The title molecular salt, C9H12NO4+·Cl−·C9H11NO4, is isotypic with that of the bromide counterpart [Kathiravan et al. (2016. Acta Cryst. E72, 1544–1548]. The title salt is a second monoclinic polymorph of the l-dopa HCl structure reported earlier in the monoclinic space group P21 [Jandacek & Earle (1971. Acta Cryst. B27, 841–845; Mostad & Rømming (1974. Acta Chemica Scand. B28, 1161–1168]. In the title compound, monoclinic space group I2, one of the dopa molecules has a positive charge with a protonated α-amino group and the α-carboxylic acid group uncharged, while the second dopa molecule has a neutral charge, the α-amino group is protonated and the α-carboxylic acid is deprotonated. In the previously reported form, a single dopa molecule is observed in which the α-amino group is protonated and the α-carboxylic acid group is uncharged. The invariant and variations of various types of intermolecular interactions present in these two forms of dopa HCl structures are discussed with the aid of two-dimensional fingerprint plots.

  4. The inhibition effect of 2,3,7,8-tetrachlorinated dibenzo-p-dioxin-induced aryl hydrocarbon receptor activation in human hepatoma cells with the treatment of cadmium chloride

    Energy Technology Data Exchange (ETDEWEB)

    Chao, How-Ran [Department of Environmental Science and Engineering, National Pingtung University of Science and Technology, Neipu, Pingtung 912, Taiwan (China); Emerging Compounds Research Center, National Pingtung University of Science and Technology, Neipu, Pingtung 912, Taiwan (China); Tsou, Tsui-Chun [Division of Environmental Health and Occupational Medicine, National Health Research Institutes, Zhunan, Miaoli 350, Taiwan (China); Chen, Hung-Ta [Sustainable Environment Research Center, National Cheng Kung University, Tainan 701, Taiwan (China); Chang, Eddy Essen; Tsai, Feng-Yuan [Division of Environmental Health and Occupational Medicine, National Health Research Institutes, Zhunan, Miaoli 350, Taiwan (China); Lin, Ding-Yan [Department of Environmental Science and Engineering, National Pingtung University of Science and Technology, Neipu, Pingtung 912, Taiwan (China); Chen, Fu-An [Graduate Institute of Pharmaceutical Science, Department of Pharmacy, Tajen University, Yan-Pu, Pingtung 907, Taiwan (China); Wang, Ya-Fen, E-mail: yfwang@cycu.edu.tw [Department of Bioenvironmental Engineering, Chung Yuan Christian University, Chungli, Taoyuan 320, Taiwan (China); R and D Center of Membrane Technology, Chung Yuan Christian University, Chungli 320, Taiwan (China)

    2009-10-15

    Polychlorinated dibenzo-p-dioxins (PCDDs) and dibenzofurans (PCDFs), considered as endocrine disruptors, tend to accumulate in fatty tissues. Dioxin-responsive element chemical activated luciferase gene expression assay (DRE-luciferase assay) has been recognized as a semi-quantitative method for screening dioxins for its fast and low-cost as compared with HRGC/HRMS. However, some problems with the bioassay, including specificity, detection variation resulted from different cleanup strategies, and uncertainty of false-negative or false-positive results, remain to be overcome. Cadmium is a prevalent environmental contaminant around the world. This study was aimed to examine the effects of cadmium on the 2,3,7,8-tetrachlorodibenzo-p-dioxin (TCDD)-induced activation of aryl hydrocarbon receptor (AhR)-mediated gene expression in human hepatoma cells (Huh7-DRE-Luc cells and Huh7 cells). Ethoxyresorufin-O-deethylase (EROD) and DRE-luciferase assay were employed to determine the enzyme activity of cytochrome P450 1A1 (CYP1A1) and activation of AhR, respectively. The results showed that Cd{sup 2+} levels significantly inhibited the induction of TCDD-induced CYP1A1 and DRE luciferase activation in hepatoma cells. The 50% inhibited concentrations (IC{sub 50}) of CdCl{sub 2} were 0.414 {mu}M (95% confidence interval (C.I.): 0.230-0.602 {mu}M) in Huh7-DRE-Luc cells and 23.2 {mu}M (95% C.I.: 21.7-25.4 {mu}M) in Huh7 cells. Accordingly, prevention of interference with non-dioxin-like compounds in a DRE-luciferase assay is of great importance in an extensive cleanup procedure.

  5. Amination Reactions of Aryl Halides with Nitrogen-Containing Reagents Catalyzed by Cul in Ionic Liquid

    Institute of Scientific and Technical Information of China (English)

    YAN,Jin-Can; ZHOU,Li; WANG,Lei

    2008-01-01

    CuI-catalyzed coupling reactions of aryl iodides and electron-deficient aryl bromides with nitrogen-containing reagents, such as imidazole, benzimidazole, aliphatic primary and secondary amines, aniline, primary and secondary amides, in ionic liquid were developed. The reaction conditions involved the use of[Bmim][BF4] as the solvent,potassium phosphate as the base, and CuI as the catalyst. The CuI and[Bmim][BF4] could be recovered and recycled for five consecutive trials without significant loss of their activity.

  6. One-pot four-component synthesis of 2-aryl-3,3-dihaloacrylonitriles using potassium hexacyanoferrate(II) as environmentally benign cyanide source

    OpenAIRE

    Zhao,Zhouxing; Li, Zheng

    2011-01-01

    An efficient route to one-pot four-component reactions of aroyl chlorides, potassium hexacyanoferrate(II), triphenylphosphine and carbon tetrahalides to synthesize 2-aryl-3,3-dichloroacrylonitriles and 2-aryl-3,3-dibromoacrylonitriles was described. This protocol has advantages of use of non-toxic cyanide source, high yield and simple work-up procedure.

  7. One-pot four-component synthesis of 2-aryl-3,3-dihaloacrylonitriles using potassium hexacyanoferrate(II) as environmentally benign cyanide source

    Energy Technology Data Exchange (ETDEWEB)

    Zhao, Zhouxing; Li, Zheng, E-mail: lizheng@nwnu.edu.c [Northwest Normal Univ., Lanzhou, Gansu (China). Key Lab. of Polymer Materials of Gansu Province

    2011-07-01

    An efficient route to one-pot four-component reactions of aroyl chlorides, potassium hexacyanoferrate(II), triphenylphosphine and carbon tetrahalides to synthesize 2-aryl-3,3-dichloroacrylonitriles and 2-aryl-3,3-dibromoacrylonitriles was described. This protocol has advantages of use of non-toxic cyanide source, high yield and simple work-up procedure. (author)

  8. Synthesis of 2,3-epoxy-1-phenyl-3-aryl-1-propanone by combination of phase transfer catalyst and ultrasound irradiation

    Directory of Open Access Journals (Sweden)

    Ji-Tai Li

    2009-03-01

    Full Text Available Seven 2,3-epoxy-1-phenyl-3-aryl-1-propanones were synthesized via epoxidation of thecorresponding 1-phenyl-3-aryl-2-propen-1-ones with 30% aqueous hydrogen peroxide in 74-99% yields usingbenzyldimethyltetradecylammonium chloride as phase transfer catalyst under ultrasound irradiation.

  9. Pd/C-Catalyzed Carbonylative Esterification of Aryl Halides with Alcohols by Using Oxiranes as CO Sources.

    Science.gov (United States)

    Min, Byul-Hana; Kim, Dong-Su; Park, Hyo-Soon; Jun, Chul-Ho

    2016-04-25

    A carbonylative esterification reaction between aryl bromides and alcohols, promoted by Pd/C and NaF in the presence of oxiranes, has been developed. In this process, oxiranes serve as sources of carbon monoxide by their conversion to aldehydes through a palladium-promoted Meinwald rearrangement pathway. Intramolecular versions of this process serve as methods for the synthesis of lactones and phthalimides.

  10. Eco-friendly synthesis of 2-substituted benzothiazoles catalyzed by cetyltrimethyl ammonium bromide (CTAB) in water

    OpenAIRE

    Yang, Xiao-Liang; Xu, Chun-Mei; Lin,Shao-Miao; Chen,Jiu-Xi; Ding,Jin-Chang; Wu,Hua-Yue; Su,Wei-Ke

    2010-01-01

    A series of 2-substituted benzothiazoles have been synthesized by the condensation of 2-aminothiophenol with aldehydes (RCHO: R = Alkyl, Aryl, Heteroaryl, 2-Arylformyl) in the presence of a catalytic amount of cetyltrimethyl ammonium bromide (CTAB) "on water" by a one-pot procedure without additional organic solvents and oxidants. Thereinto, 2-alkylbenzothiazoles were synthesized in high yields and 2-arylformylbenzothiazoles were obtained from the condensation of 2-aminothiophenol with arylfo...

  11. Nickel-catalyzed cross-electrophile coupling of 2-chloropyridines with alkyl bromides.

    Science.gov (United States)

    Everson, Daniel A; Buonomo, Joseph A; Weix, Daniel J

    2014-01-01

    The synthesis of 2-alkylated pyridines by the nickel-catalyzed cross-coupling of two different electrophiles, 2-chloropyridines with alkyl bromides, is described. Compared to our previously published conditions for aryl halides, this method uses the different, more rigid bathophenanthroline ligand and is conducted at high concentration in DMF solvent. The method displays promising functional group compatibility and the conditions are orthogonal to the Stille coupling.

  12. Direct N9-arylation of purines with aryl halides

    DEFF Research Database (Denmark)

    Larsen, Anders Foller; Ulven, Trond

    2014-01-01

    An efficient method for N-arylation of purines is reported. The N-arylation is catalysed by Cu(i) and 4,7-bis(2-hydroxyethylamino)-1,10-phenanthroline (BHPhen) in aqueous DMF or ethanol. The reaction generally proceeds with high selectivity for the N(9)-position....

  13. Rhodium catalyzed arylation of diazo compounds with aryl boronic acids.

    Science.gov (United States)

    Ghorai, Jayanta; Anbarasan, Pazhamalai

    2015-04-03

    A general and efficient synthesis of diarylacetate, a diarylmethine derivative, was accomplished through rhodium catalyzed direct arylation of diazo compounds with arylboronic acids. The reaction tolerates various boronic acid derivatives and functional groups. Notably, chemoselective arylation of diazo compounds over other electrophiles were demonstrated. The efficacy of the developed methodology is shown by the expeditious synthesis of the core structure of diclofensine.

  14. Rh(I)-Catalyzed Arylation of Heterocycles via C-H Bond Activation: Expanded Scope Through Mechanistic Insight

    Energy Technology Data Exchange (ETDEWEB)

    Lewis, Jared; Berman, Ashley; Bergman, Robert; Ellman, Jonathan

    2007-07-18

    A practical, functional group tolerant method for the Rh-catalyzed direct arylation of a variety of pharmaceutically important azoles with aryl bromides is described. Many of the successful azole and aryl bromide coupling partners are not compatible with methods for the direct arylation of heterocycles using Pd(0) or Cu(I) catalysts. The readily prepared, low molecular weight ligand, Z-1-tert-butyl-2,3,6,7-tetrahydrophosphepine, which coordinates to Rh in a bidentate P-olefin fashion to provide a highly active yet thermally stable arylation catalyst, is essential to the success of this method. By using the tetrafluoroborate salt of the corresponding phosphonium, the reactions can be assembled outside of a glove box without purification of reagents or solvent. The reactions are also conducted in THF or dioxane, which greatly simplifies product isolation relative to most other methods for direct arylation of azoles employing high-boiling amide solvents. The reactions are performed with heating in a microwave reactor to obtain excellent product yields in two hours.

  15. Rapacuronium bromide (Organon Teknika).

    Science.gov (United States)

    Plowman, A N

    1999-07-01

    Organon Teknika's rapacuronium bromide (Org-9487), the 16-N-allyl, 17-beta-propionate analog of vecuronium bromide, is in phase III clinical trials in the US and Europe for potential use as an anesthetic. It is a steroidal neuromuscular blocking drug characterized by low potency, rapid rate of block development and short time course of neuromuscular blocking action as compared with other non-depolarizing compounds [170210,221422]. A multicenter, randomized, assessor-blind, placebo-controlled, dose-finding study in patients undergoing tracheal intubation showed that the drug produced a dose dependent neuromuscular block. Doses of 1.5 to 2 mg/kg allowed rapid intubation and short duration of action [273336]. Another study showed that the drug does not cause cardiovascular side-effects [273336]. A meeting was held in Europe on 8 February 1999 to brief company employees on the registration and release of rapacuronium [319211] for which the company anticipates a launch in late 1999 [320706]. Organon estimates that the market value of Org-9487 is between dollar 100 m and dollar 250 m a year, each for Europe and the US [221422].

  16. Efficient loading of primary alcohols onto a solid phase using a trityl bromide linker

    DEFF Research Database (Denmark)

    Crestey, François; Ottesen, Lars Korsgaard; Jaroszewski, Jerzy Witold

    2008-01-01

    The Letter describes an improved, rapid and mild strategy for the loading of primary alcohols onto a polystyrene trityl resin via a highly reactive trityl bromide linker. This protocol facilitates an efficient resin loading even of acid-sensitive or heat-labile alcohols, which otherwise require...... of a sensitive alcohol containing an activated aziridine functionality, the use of the trityl bromide linker proved superior to a recently described silver triflate-assisted trityl chloride resin-based procedure....

  17. Methylnaltrexone bromide methanol monosolvate

    Directory of Open Access Journals (Sweden)

    Xinbo Zhou

    2012-03-01

    Full Text Available In the title compound [systematic name: (4R,4aS,7aR,12bS-3-cyclopropylmethyl-4a,9-hydroxy-7-oxo-2,3,4,4a,5,6,7,7a-octahydro-1H-4,12-methanobenzofuro[3,2-e]isoquinolin-3-ium bromide methanol monosolvate], C21H26NO4+·Br−·CH3OH, two of the three six-membered rings adopt chair conformations while the third, which contains a C=C double bond, adopts an approximate half-boat conformation. The 2,3-dihydrofuran ring adopts an envelope conformation. In the crystal, the components are linked by O—H...O and O—H...Br hydrogen bonds. The absolute stereochemistry was inferred from one of the starting materials.

  18. Iron bromide vapor laser

    Science.gov (United States)

    Sukhanov, V. B.; Shiyanov, D. V.; Trigub, M. V.; Dimaki, V. A.; Evtushenko, G. S.

    2016-03-01

    We have studied the characteristics of a pulsed gas-discharge laser on iron bromide vapor generating radiation with a wavelength of 452.9 nm at a pulse repetition frequency (PRF) of 5-30 kHz. The maximum output power amounted to 10 mW at a PRF within 5-15 kHz for a voltage of 20-25 kV applied to electrodes of the discharge tube. Addition of HBr to the medium produced leveling of the radial profile of emission. Initial weak lasing at a wavelength of 868.9 nm was observed for the first time, which ceased with buildup of the main 452.9-nm line.

  19. Nucleophilic addition of benzimidazoles to alkynyl bromides/palladium-catalyzed intramolecular C-H vinylation: synthesis of benzo[4,5]imidazo[2,1-a]isoquinolines.

    Science.gov (United States)

    Peng, Jinsong; Shang, Guoning; Chen, Chunxia; Miao, Zhongshuo; Li, Bin

    2013-02-01

    An efficient "one-pot" route for the synthesis of benzo[4,5]imidazo[2,1-a] isoquinolines has been developed via nucleophilic addition of 2-aryl benzimidazoles to alkynyl bromides and subsequent palladium-catalyzed intramolecular C-H vinylation.

  20. Aryl substitution of pentacenes

    Directory of Open Access Journals (Sweden)

    Andreas R. Waterloo

    2014-07-01

    Full Text Available A series of 11 new pentacene derivatives has been synthesized, with unsymmetrical substitution based on a trialkylsilylethynyl group at the 6-position and various aryl groups appended to the 13-position. The electronic and physical properties of the new pentacene chromophores have been analyzed by UV–vis spectroscopy (solution and thin films, thermoanalytical methods (DSC and TGA, cyclic voltammetry, as well as X-ray crystallography (for 8 derivatives. X-ray crystallography has been specifically used to study the influence of unsymmetrical substitution on the solid-state packing of the pentacene derivatives. The obtained results add to our ability to better predict substitution patterns that might be helpful for designing new semiconductors for use in solid-state devices.

  1. Intensification of sonochemical degradation of malachite green by bromide ions.

    Science.gov (United States)

    Moumeni, Ouarda; Hamdaoui, Oualid

    2012-05-01

    Sonochemical oxidation has been investigated as a viable advanced oxidation process (AOP) for the destruction of various pollutants in water. Ultrasonic irradiation generates ()OH radicals that can recombine, react with other gaseous species present in the cavity, or diffuse out of the bubble into the bulk liquid medium where they are able to react with solute molecules. The extent of degradation of an organic dye such as malachite green (MG) is limited by the quantity of hydroxyl radicals diffused from cavitation bubbles. In this work, the effect of bromide ions on sonolytic degradation of MG was investigated. The obtained results clearly demonstrated the considerable enhancement of sonochemical destruction of MG in the presence of bromide. No significant differences were observed in the presence of chloride and sulfate, excluding the salting-out effect. Positive effect of bromide ions, which increases with increasing bromide level and decreasing MG concentration, is due to the generation of dibromine radical anion (Br(2)(-)) formed by reaction of Br(-) with ()OH radicals followed by rapid complexation with another anion. The generated Br(2)(-) radicals, reactive but less than ()OH, are likely able to migrate far from the cavitation bubbles towards the solution bulk and are suitable for degradation of an organic dye such as MG. Additionally, Br(2)(-) radicals undergo radical-radical recombination at a lesser extent than hydroxyl radicals and would be more available than ()OH for substrate degradation, both at the bubble surface and in the solution bulk. This effect compensates for the lower reactivity of Br(2)(-) compared to ()OH toward organic substrate. Addition of bromide to natural and sea waters induces a slight positive effect on MG degradation. In the absence of bromide, ultrasonic treatment for the removal of MG was promoted in complex matrices such as natural and sea waters.

  2. Synthesis of Novel 3-Aryl Isoindolinone Derivatives

    Institute of Scientific and Technical Information of China (English)

    HU Chen-ming; ZHENG Lian-you; PEI Ya-zhong; BAI Xu

    2013-01-01

    A library of novel 3-aryl isoindolinone derivatives with aromatic amino acid derivative fragments was designed and synthesized.Two synthetic routes were employed to construct 3-aryl isoindolinone ring system for different amino acid derivatives.

  3. Microwave assisted synthesis and biological activity of 3-aryl-furo[3,2-c]coumarins

    Directory of Open Access Journals (Sweden)

    Ankit R. Kaneria

    2017-02-01

    Full Text Available The synthesis of various 3-aryl-furo[3,2-c]coumarins 4a–l has been carried out by employing two different methodologies under microwave irradiation condition. In the first method different 3-aryl-furo[3,2-c]coumarins 4a–l have been synthesized by reacting various 4-hydroxy coumarins 1a–d with appropriate 2-aryl-1-nitro ethenes 2a–c under Nef reaction condition, while in the second method the same target compounds have been synthesized by reacting various 4-hydroxy coumarins 1a–d with appropriate aroylmethyl bromides 3a–c under Feist–Benary reaction condition. All the synthesized compounds were characterized by elemental analysis and IR, 1H NMR, 13C NMR, DEPT-90 spectral analysis. All the synthesized compounds 4a–l were screened for their antimicrobial activity.

  4. Eco-friendly solvents for palladium-catalyzed desulfitative C-H bond arylation of heteroarenes.

    Science.gov (United States)

    Hfaiedh, Anoir; Yuan, Kedong; Ben Ammar, Hamed; Ben Hassine, Bechir; Soulé, Jean-François; Doucet, Henri

    2015-05-22

    Herein, we report the Pd-catalyzed regioselective direct arylation of heteroarenes in which benzenesulfonyl chlorides are used as coupling partners through a desulfitative cross-coupling that can be performed in diethyl carbonate (DEC) or cyclopentyl methyl ether (CPME) as green and renewable solvents or even in neat conditions instead of dioxane or dimethylacetamide (DMA). Under these solvent conditions, the reaction proceeds with a wide range of heteroarenes. C2- or C5-arylated products were obtained with furan and pyrrole derivatives. Benzofuran was also arylated regioselectively at the C2-position, whereas the reaction proceeds selectively at the C3- or C4-positions if thiophenes and benzothiophenes are used. Moreover, in some cases, especially with 1-methylindole, solvent-free conditions afforded better regioselectivities and/or yields than the reaction performed in the presence of solvents. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  5. Silica-Supported Arsine Palladium(0) Complex: a Highly Active and Stereoselective Catalyst for Arylation of Butyl Acrylate and Acrylamide

    Institute of Scientific and Technical Information of China (English)

    蔡明中; 赵红; 胡文英

    2005-01-01

    A silica-supported arsine palladium(O) complex has been prepared from y-chloropropyltriethoxysilane via immobilization on fumed silica, followed by reaction with potassium diphenylarsenide and palladium chloride, and then reduction with hydrazine hydrate. The complex has been characterized by X-ray photoelectron spectroscopy (XPS) and it is a highly active and stereoselective catalyst for arylation of butyl acrylate and acrylamide with aryl halides, affording a variety of tram-butyl cinnamates and trans-cinnamamides in high yields.

  6. Evaluation of the influence of base and alkyl bromide on synthesis of pyrazinoic acid esters through fatorial design

    Directory of Open Access Journals (Sweden)

    João Paulo dos Santos Fernandes

    2009-01-01

    Full Text Available Pyrazinoic acid esters have been synthesized as prodrugs of pyrazinoic acid. In the literature, its preparation is reported through the reaction of pyrazinoyl chloride with alcohols and the reaction with DCC/DMAP. In this work, it is reported a 2² factorial design to evaluate the preparation of these esters through the substitution of alkyl bromides with carboxylate anion. The controlled factors were alkyl chain length of bromides (ethyl and hexyl and the used base (triethylamine and DBU. Results revealed that the used base used has significant effect on yield, and alkyl bromide used has neither significant influence, nor its interaction effect with base.

  7. Bromide in some coastal and oceanic waters of India

    Digital Repository Service at National Institute of Oceanography (India)

    DeSouza, F.P.; Dalal, V.N.K.

    Bromide concentration and bromide/chlorinity ratio are estimated in coastal waters of Goa, Minicoy Lagoon, Western Arabian Sea and Western Bay of Bengal. The influence of precipitation and river runoff on bromide and bromide/chlorinity ratio...

  8. Amine and Titanium (IV Chloride, Boron (III Chloride or Zirconium (IV Chloride-Promoted Baylis-Hillman Reactions

    Directory of Open Access Journals (Sweden)

    Shi-Cong Cui

    2001-10-01

    Full Text Available The Baylis-Hillman reactions of various aryl aldehydes with methyl vinyl ketone at temperatures below -20oC using Lewis acids such as titanium (IV chloride, boron (III chloride or zirconium (IV chloride in the presence of a catalytic amount of selected amines used as a Lewis bases afford the chlorinated compounds 1 as the major product in very high yields. Acrylonitrile can also undergo the same reaction to give the corresponding chlorinated product in moderate yield. A plausible reaction mechanism is proposed. However, if the reaction was carried out at room temperature (ca. 20oC, then the Z-configuration of the elimination product 3, derived from 1, was formed as the major product.

  9. Eco-friendly synthesis of 2-substituted benzothiazoles catalyzed by cetyltrimethyl ammonium bromide (CTAB) in water

    Energy Technology Data Exchange (ETDEWEB)

    Yang, Xiao-Liang; Xu, Chun-Mei; Lin, Shao-Miao; Chen, Jiu-Xi; Ding, Jin-Chang; Wu, Hua-Yue [Wenzhou University (China). College of Chemistry and Materials Engineering; Su, Wei-Ke [Zhejiang University of Technology, Hangzhou (China). College of Pharmaceutical Sciences. Zhejiang Key Laboratory of Pharmaceutical Engineering

    2010-07-01

    A series of 2-substituted benzothiazoles have been synthesized by the condensation of 2-aminothiophenol with aldehydes (RCHO: R = Alkyl, Aryl, Heteroaryl, 2-Arylformyl) in the presence of a catalytic amount of cetyltrimethyl ammonium bromide (CTAB) 'on water' by a one-pot procedure without additional organic solvents and oxidants. Thereinto, 2-alkylbenzothiazoles were synthesized in high yields and 2-arylformylbenzothiazoles were obtained from the condensation of 2-aminothiophenol with arylformyl aldehydes for the first time using the present protocol. (author)

  10. Strontium and bromide as tracers in X-ray microanalysis of biological tissue

    Energy Technology Data Exchange (ETDEWEB)

    Wroblewski, J.; Sagstroem, S.M.; Mulders, H.; Roomans, G.M. (Karolinska Institutet, Stockholm (Sweden))

    1989-09-01

    Since energy dispersive X-ray microanalysis cannot distinguish between isotopes of the same element, alternative methods have to be used to get information similar to that obtained in experiments with radioactive tracers. In the present study, strontium was used as a tracer for calcium, and bromide as a tracer for chloride. Rats were injected with strontium chloride in vivo, and the uptake of strontium in the acinar cells of the submandibular gland was studied. Eventually a Sr/Ca ratio of 0.3 was reached. In some animals, secretion of mucus had been elicited by stimulation with isoproterenol 4 h prior to injection of strontium chloride. Exchange of calcium for strontium was enhanced by prior injection with isoproterenol. In a second experiment, rats were injected with sodium bromide, and the uptake of bromide by the submandibular acinar cells was followed in time, both in pilocarpine-stimulated and unstimulated glands. Under the experimental conditions, bromide was rapidly taken up by the cells, and the cellular Br/Cl ratio was close to that found in serum. Submandibular glands take up Br somewhat faster than other tissues (liver, heart muscle, skeletal muscle). The uptake of Br in pancreatic acinar cells was studied in vitro. These experiments showed a 1:1 ratio (molar) exchange of Cl for Br.

  11. Clean and fast cross-coupling of aryl halides in one-pot

    Directory of Open Access Journals (Sweden)

    Valerica Pandarus

    2014-04-01

    Full Text Available Unsymmetrically coupled biaryls are synthesized in high yield starting from different aryl bromides and bis(pinacolatodiboron by carrying out the Miyaura borylation reaction followed by the Suzuki–Miyaura reaction in the same reaction pot over 1–2 mol % SiliaCat DPP-Pd. The SiliaCat DPP-Pd catalyst is air-stable and the method does not require the use of inert conditions. The use of non-toxic isopropanol or 2-butanol as reaction solvent further adds to the environmental benefits of this new green synthetic methodology.

  12. Determination of Water Soluble Fluoride, Chloride, Bromide and Nitrate in Iron Ores by Supersonic Extraction-Ion Chromatography%超声提取-离子色谱法测定铁矿石中水溶性氟氯溴及硝酸根

    Institute of Scientific and Technical Information of China (English)

    胡德新; 马德起; 安鹏升; 王振坤; 王虹; 李权斌; 谷松海; 魏红兵

    2012-01-01

    An ion chromatography method with ultrasonic extraction has been developed to simultaneously determine the water solubility of fluoride, chloride, bromide and nitrate in iron ores. The sample solution was extracted ultrasonically and precipitation separation was carried out by centrifugation. The clarified solution was passed through IC-RP, IC-Na and a 0.22 pjn filter membrane. The anions were separated and data were collected by using AS-19 type anion separation column and ASRS 300-4 mm self-electric chemistry suppressor with the 25.00 mmol/L NaOH as eluent. The organic matter in the sample solution was absorbed by IC-RP column and the heavy metal ions were replaced by IC-Na column, which is the same cation as that in eluent. Based on the study of the extraction efficiency for water solubility anions, the extraction time was 30 min. In order to eliminate the effect of a negative peak from water, a certain amount of eluent was added into the standard and sample solutions to make the conductivity in each solution match each other. Under optimal conditions, the detection limits of F- , Cl- , Br~ and NO3~ were 2.1, 3.5, 2.5 and 2.0 |Xg/g, respectively. The linear correlation was good for the work curve, and the linearly dependent coefficient was greater than 0. 999. The accuracy and precision of this method was verified by iron ore standard material GBW 07218a and the results were consistent with certified values. The RSD (? = 10) was less than 5% and recovery rates with interior standard were 96% - 104%. The results for the actual samples were consistent with those obtained by ion selective electrode method. The method has the benefits of applying to a wide linear range, is simple and has rapid and high efficiency, making it suitable for routine lab inspection work.%铁矿石样品经超声提取、离心机分离沉淀后,分别通过IC-RP柱、IC-Na柱及0.22 μm微孔过滤膜过滤,25.00 mmol/L NaOH溶液作为淋洗液,利用AS-19型阴离子分离柱和ASRS 300

  13. n-Dodecylammonium bromide monohydrate

    Directory of Open Access Journals (Sweden)

    Wenyan Dan

    2010-04-01

    Full Text Available In the title compound, C12H28N+·Br−·H2O, the ionic pairs formed by n-dodecylammonium cations and bromide anions are arranged into thick layers; these layers are linked in a nearly perpendicular fashion [the angle between the layers is 85.84 (5°] by hydrogen-bonding interactions involving the water molecules. The methylene part of the alkyl chain in the cation adopts an all-trans conformation. In the crystal structure, molecules are linked by intermolecular N—H...Br, O—H...Br and N—H...O hydrogen bonds.

  14. Conversion of Alcohols to Bromides by Trimethylsilane and lithium Bromide in Acetone

    Institute of Scientific and Technical Information of China (English)

    Wei Feng; Zhang Xiao-xia; Zhang Qing; Wang Ji-yu; Chen Dai-mo

    2004-01-01

    Conversion of alcohols to alkyl bromides is one of the most frequently used functional group transformation reactions. Phosphorus tribromide is one of the most popular classical reagents.Triphenylphosphine has been used in combination with bromine,carbon tetrabromide,N-halo imides and other bromide compounds as a mild reagents for the preparation of alkyl bromides.More reacently, halotrimethylsilanes were found to be useful for halogenation of alcohols. George A.Olah successfully converted alcohols to bromides with chlorotrimethylsilane/lithium bromide in acetonitrile. But in our research, we found that we got no bromides but methylation products when we planed to convered our substances to bromides according to Gerge's method. We did some experiments, and we found that when the substituent group in the 2-N was donor group,we got the methylation products,but when it was acceptor group,the bromide could be got.(Scheme 1).Then we did some experiments with several other solvents, we found excitedly that when the solvent was acetone ,the bromides could be got even the substituent group was donor.(Scheme 2).When we changed the substances to normal alcohols ,such as ethyl alcohol,benzyl alcohol,isopropyl alcohol and 3,4-dimethoxy benzyl alcohol,we also got the bromides.In conclusion, we found a simple method to convert alcohols to bromides with trimethylsilane/li thium bromide in acetone,which was better than Geroge's method.

  15. Chloride transference during electrochemical chloride extraction process

    Institute of Scientific and Technical Information of China (English)

    2010-01-01

    Chemical titration method and lab-made chloride probes were jointly adopted to investigate the effects of water-to-cement (W/C) ratio and the impressed current density on chloride transport for cement-based materials during electrochemical chloride extraction (ECE) process.The dissolution of bound chlorides and the effect of current density on dissolution were analyzed.The variations of chloride concentration at different depths and the chloride transference process were monitored.Test results show that W/C ratios adopted have slight influence on chloride extraction,while chloride extraction efficiency is mainly determined by the impressed current density.During ECE process a portion of bound chloride ions dissolved and the amount of bound chlorides released is directly proportional to current density.

  16. Crystal structure and Hirshfeld surface analysis of 1-carboxy-2-(3,4-dihydroxyphenyl)ethan-1-aminium chloride 2-ammonio-3-(3,4-dihydroxyphenyl)propanoate: a new polymorph of l-dopa HCl and isotypic with its bromide counterpart

    OpenAIRE

    Perumal Kathiravan; Thangavelu Balakrishnan; Perumal Venkatesan; Kandasamy Ramamurthi; María Judith Percino; Subbiah Thamotharan

    2016-01-01

    The title molecular salt, C9H12NO4+·Cl−·C9H11NO4, is isotypic with that of the bromide counterpart [Kathiravan et al. (2016). Acta Cryst. E72, 1544–1548]. The title salt is a second monoclinic polymorph of the l-dopa HCl structure reported earlier in the monoclinic space group P21 [Jandacek & Earle (1971). Acta Cryst. B27, 841–845; Mostad & Rømming (1974). Acta Chemica Scand. B28, 1161–1168]. In the title compound, monoclinic space group I2, one of the dopa molecules has a positive charge wit...

  17. Crystal structure and Hirshfeld surface analysis of 1-carb­oxy-2-(3,4-di­hydroxy­phen­yl)ethan-1-aminium chloride 2-ammonio-3-(3,4-di­hydroxy­phen­yl)propano­ate: a new polymorph of l-dopa HCl and isotypic with its bromide counterpart

    OpenAIRE

    Kathiravan, Perumal; Balakrishnan, Thangavelu; Venkatesan, Perumal; Ramamurthi, Kandasamy; Percino, María Judith; Thamotharan, Subbiah

    2016-01-01

    The title mol­ecular salt, C9H12NO4 +·Cl−·C9H11NO4, is isotypic with that of the bromide counterpart [Kathiravan et al. (2016 ▸). Acta Cryst. E72, 1544–1548]. The title salt is a second monoclinic polymorph of the l-dopa HCl structure reported earlier in the monoclinic space group P21 [Jandacek & Earle (1971 ▸). Acta Cryst. B27, 841–845; Mostad & Rømming (1974 ▸). Acta Chemica Scand. B28, 1161–1168]. In the title compound, monoclinic space group I2, one of the dopa mol­ecules has a positive c...

  18. Palladium-catalyzed carbonylative Sonogashira coupling of aryl bromides via tert-butyl isocyanide insertion.

    Science.gov (United States)

    Tang, Ting; Fei, Xiang-Dong; Ge, Zhi-Yuan; Chen, Zhong; Zhu, Yong-Ming; Ji, Shun-Jun

    2013-04-05

    A simple and efficient palladium-catalyzed carbonylative Sonogashira coupling via tert-butyl isocyanide insertion has been developed, which demonstrates the utility of isocyanides in intermolecular C-C bond construction. This methodology provides a novel pathway for the synthesis of alkynyl imines which can undergo simple silica gel catalyzed hydrolysis to afford alkynones. The approach is tolerant of a wide range of substrates and applicable to library synthesis.

  19. Pd-catalyzed intermolecular amidation of aryl halides: the discovery that xantphos can be trans-chelating in a palladium complex.

    Science.gov (United States)

    Yin, Jingjun; Buchwald, Stephen L

    2002-05-29

    A general method for the intermolecular coupling of aryl halides and amides using a Xantphos/Pd catalyst is described. This system displays good functional group compatibility, and the desired C-N bond forming process proceeds in good to excellent yields with 1-4 mol % of the Pd catalyst. Additionally, the arylation of sulfonamides, oxazolidinones, and ureas is reported. The efficiency of these transformations was found to be highly dependent on reaction concentrations and catalyst loadings. A Pd complex resulting from oxidative addition of 4-bromobenzonitrile, (Xantphos)Pd(4-cyanophenyl)(Br) (II), was prepared in one step from Xantphos, Pd(2)(dba)(3), and the aryl bromide. Complex II proved to be an active catalyst for the coupling between 4-bromobenzonitrile and benzamide. X-ray crystallographic analysis of II revealed a rare trans-chelating bisphosphine-Pd(II) structure with a large bite angle of 150.7 degrees.

  20. Pharmacological studies on otilonium bromide.

    Science.gov (United States)

    Giachetti, A

    1991-11-01

    Otilonium bromide (OB) is a quaternary ammonium compound characterized by a long aliphatic chain. Its chemical properties are responsible for both a poor penetration in CNS and a prolonged binding to cell membranes. OB is a spasmolytic agent which acts by modifying Ca++ fluxes from extra and intracellular sites. It has been documented that iv administration (10 mg/kg) of OB causes a marked reduction of colonic motility lasting from 2 to 3 hours, whereas an inhibition of upper GI motor activity is present only at higher dosages. In conclusion, OB seems to exert its activity mainly on distal GI tract, and its spasmolytic effect may be due to its ability to inhibit Ca++ fluxes and to a direct action of the drug on the contractile proteins of the smooth muscle.

  1. Synthesis, Characterization and Biological Activities of N-Acyl-3-(3-pyridyl)-5-aryl-pyrazoles

    Institute of Scientific and Technical Information of China (English)

    KANG Yan-fang; WANG Dun-jia; XU Ben-po; WEI Xian-hong; ZHENG Jing

    2013-01-01

    Ten novel N-acyl-3-(3-pyridyl)-5-aryl-pyrazoles were synthesized by Claisen condensation of the aryl methyl ketones with ethyl nicotinate,the cyclization with hydrazine hydrate and the N-acylation with acyl chloride in turn.The structures of all the compounds synthesized were confirmed by means of Fourier transform infrared(FTIR),1H NMR,mass spectroscopy and elemental analysis.The biological activities of the title compounds were examined by disc diffusion method against Escherichia coli,Staphylococcus aureus,Pyricularia oryzae and Rhizoctnia solani.All the N-acyl-3-(3-pyridyl)-5-aryl-pyrazoles exhibited a certain degree of antibacterial and antifungal activities.Comparatively,compounds 3c and 3d exhibited much significant antibacterial and antifungal activities than the other pyrazole derivatives.

  2. Pyrolysis of Aryl Sulfonate Esters in the Absence of Solvent: E1 or E2? A Puzzle for the Organic Laboratory

    Science.gov (United States)

    Nash, John J.; Leininger, Marnie A.; Keyes, Kurt

    2008-01-01

    The aryl sulfonate ester, menthyl N-acetylsulfanilate, is synthesized from N-acetylsulfanilyl chloride and menthol in pyridine, then pyrolyzed (thermally decomposed) at reduced pressure. The volatile (elimination) products of the reaction are analyzed using gas chromatography, and the resulting product distribution is used to determine whether the…

  3. Pyrolysis of Aryl Sulfonate Esters in the Absence of Solvent: E1 or E2? A Puzzle for the Organic Laboratory

    Science.gov (United States)

    Nash, John J.; Leininger, Marnie A.; Keyes, Kurt

    2008-01-01

    The aryl sulfonate ester, menthyl N-acetylsulfanilate, is synthesized from N-acetylsulfanilyl chloride and menthol in pyridine, then pyrolyzed (thermally decomposed) at reduced pressure. The volatile (elimination) products of the reaction are analyzed using gas chromatography, and the resulting product distribution is used to determine whether the…

  4. Tribenzylammonium chloride

    Directory of Open Access Journals (Sweden)

    Waly Diallo

    2014-05-01

    Full Text Available Single crystals of the title salt, C21H21NH+·Cl−, were isolated as a side product from the reaction involving [(C6H5CH23NH]2[HPO4] and Sn(CH33Cl in ethanol. Both the cation and the anion are situated on a threefold rotation axis. The central N atom in the cation has a slightly distorted tetrahedral environment, with angles ranging from 107.7 to 111.16 (10°. In the crystal, the tribenzylammonium cations and chloride anions are linked through N—H...Cl and C—H...Cl hydrogen bonds, leading to the formation of infinite chains along [001]. The crystal studied was a merohedral twin.

  5. Covalently Cross-Linked Sulfone Polybenzimidazole Membranes with Poly(Vinylbenzyl Chloride) for Fuel Cell Applications

    DEFF Research Database (Denmark)

    Yang, Jingshuai; Aili, David; Li, Qingfeng;

    2013-01-01

    Covalently cross-linked polymer membranes were fabricated from poly(aryl sulfone benzimidazole) (SO(2) PBI) and poly(vinylbenzyl chloride) (PVBCl) as electrolytes for high-temperature proton-exchange-membrane fuel cells. The cross-linking imparted organo insolubility and chemical stability against...

  6. Catalytic asymmetric synthesis of secondary nitriles via stereoconvergent Negishi arylations and alkenylations of racemic α-bromonitriles.

    Science.gov (United States)

    Choi, Junwon; Fu, Gregory C

    2012-06-06

    The first method for the stereoconvergent cross-coupling of racemic α-halonitriles is described, specifically, nickel-catalyzed Negishi arylations and alkenylations that furnish an array of enantioenriched α-arylnitriles and allylic nitriles, respectively. Noteworthy features of this investigation include: the highly enantioselective synthesis of α-alkyl-α-aryl nitriles that bear secondary α-alkyl substituents; the first examples of the use of alkenylzinc reagents in stereoconvergent Negishi reactions of alkyl electrophiles; demonstration of the utility of a new family of ligands for asymmetric Negishi cross-couplings (a bidentate bis(oxazoline), rather than a tridentate pybox); in the case of arylzinc reagents, carbon-carbon bond formation at a remarkably low temperature (-78 °C), the lowest reported to date for an enantioselective cross-coupling of an alkyl electrophile; a mechanistic dichotomy between Negishi reactions of an unactivated versus an activated secondary alkyl bromide.

  7. Chloride binding site of neurotransmitter sodium symporters.

    Science.gov (United States)

    Kantcheva, Adriana K; Quick, Matthias; Shi, Lei; Winther, Anne-Marie Lund; Stolzenberg, Sebastian; Weinstein, Harel; Javitch, Jonathan A; Nissen, Poul

    2013-05-21

    Neurotransmitter:sodium symporters (NSSs) play a critical role in signaling by reuptake of neurotransmitters. Eukaryotic NSSs are chloride-dependent, whereas prokaryotic NSS homologs like LeuT are chloride-independent but contain an acidic residue (Glu290 in LeuT) at a site where eukaryotic NSSs have a serine. The LeuT-E290S mutant displays chloride-dependent activity. We show that, in LeuT-E290S cocrystallized with bromide or chloride, the anion is coordinated by side chain hydroxyls from Tyr47, Ser290, and Thr254 and the side chain amide of Gln250. The bound anion and the nearby sodium ion in the Na1 site organize a connection between their coordinating residues and the extracellular gate of LeuT through a continuous H-bond network. The specific insights from the structures, combined with results from substrate binding studies and molecular dynamics simulations, reveal an anion-dependent occlusion mechanism for NSS and shed light on the functional role of chloride binding.

  8. The first barium tin(II) bromide fluoride

    Science.gov (United States)

    Dénès, Georges; Merazig, Hocine; Muntasar, Abdualhafeed; Porterfield, Robyn

    2014-04-01

    In an effort to prepare barium tin(II) bromide fluorides for the first time, possibly similar to the chloride fluorides obtained earlier in our laboratory, precipitation reactions were carried out by mixing aqueous solutions of SnF2 and of BaBr2.2H2O. In contrast with the chloride fluoride system, a single powdered phase was obtained throughout the SnF2 - BaBr2 system, with the yield being maximum at X ≈ 0.25, where X is the molar fraction of barium bromide in the reaction mixture. Phase identification with the JCPDS database failed to produce a match, confirming that a new phase had been produced. The exact chemical composition of the new compound has not been obtained yet. Based on the X value for the maximum yield, the Sn/Ba ratio is likely to be 3/1 or 2/1. The Mössbauer spectrum at ambient conditions shows that bonding to tin(II) is covalent, therefore with the tin lone pair being stereoactive. The Mössbauer parameters ( δ = 3.68 mm/s, Δ = 0.99 mm/s) are similar to those of SnBrF and of Sn2BrF5, thereby showing that tin is bonded to both fluorine and bromine. The larger isomer shift and lower quadrupole splitting than in tin(II) fluorides show that the stereoactivity of the tin lone pair is lower than in the fluorides. The Mössbauer parameters fit well the linear correlation of the quadrupole splitting versus the isomer shift" that has been shown to be present in other series of tin(II) compounds. The linear decrease on this correlation shows that the contribution of non-spherical orbitals ( p and d) to the lone pair is a much larger contributor to the quadrupole splitting than lattice distortions. The structure is likely made of Ba2+ cations and tin(II) fluoride bromide polyatomic anions, with covalent bonding withinthe anions.

  9. Palladium-catalysed ortho arylation of acetanilides

    Indian Academy of Sciences (India)

    Guo-zhen zhang; Cheng-Qun Chen; Xin-Hua Feng; Guo-Sheng Huang

    2010-03-01

    The palladium-catalysed direct arylation of acetanilides by using C-H activation methodology has been demonstrated. Several acetanilides were coupled with aryl iodides in the presence of 10 mol% of Pd(OAc)2, 1.0 equiv of Cu(OTf)2, and 0.6 equiv of Ag2O to afford the corresponding products in moderate to excellent yields. The results showed that the amount of Ag2O was important for this protocol.

  10. Isotachophoretic separation of cetyltrimethylammonium bromide.

    Science.gov (United States)

    Praus, Petr

    2005-01-15

    Capillary isotachophoresis (ITP), equipped with the conductivity detection, was tested for the separation of cetyltrimethylamonium (CTMA) bromide. To prevent adsorption of CTMA to the capillary walls, several neutral polymers and ethanol were added into the leading electrolytes. Unlike polymer additives, the CTMA free monomers and micelles, created as a result of the isotachophoretic concentration effect, were recognised in the presence of ethanol from 10 to 25% (v/v). At 30% of ethanol, only a single zone of CTMA monomer was registered because the micellization process did not take place under this condition. Employing an ITP apparatus in the column-coupling configuration, the operational system with 30% of ethanol was tested for the determination of CTMA in hair conditioners. The achieved detection limits were about 0.02mM. Both model solutions and real samples of hair conditioners were analysed with the precision about R.S.D. = 3%. One analysis in the column-coupled system takes circa 15min.

  11. Growth and characterization of lead bromide crystals

    Science.gov (United States)

    Singh, N. B.; Gottlieb, M.; Henningsen, T.; Hopkins, R. H.; Mazelsky, R.; Glicksman, M. E.; Coriell, S. R.; Santoro, G. J.; Duval, W. M. B.

    1992-01-01

    Lead(II) bromide was purified by a combination of directional freezing and zone-refining methods. Differential thermal analysis of the lead bromide showed that a destructive phase transformation occurs below the melting temperature. This transformation causes extensive cracking, making it very difficult to grow a large single crystal. Energy of phase transformation for pure lead bromide was determined to be 24.67 cal/g. To circumvent this limitation, crystals were doped by silver bromide which decreased the energy of phase transformation. The addition of silver helped in achieving the size, but enhanced the inhomogeneity in the crystal. The acoustic attenuation constant was almost identical for the pure and doped (below 3000 ppm) crystals.

  12. A novel 4-aminoantipyrine-Pd(II complex catalyzes Suzuki–Miyaura cross-coupling reactions of aryl halides

    Directory of Open Access Journals (Sweden)

    Claudia A. Contreras-Celedón

    2014-12-01

    Full Text Available A simple and efficient catalytic system based on a Pd complex of 4-aminoantipyrine, 4-AAP–Pd(II, was found to be highly active for Suzuki–Miyaura cross-coupling of aryl iodides and bromides with phenylboronic acids under mild reaction conditions. Good to excellent product yields from the cross-coupling reaction can be achieved when the reaction is carried out in ethanol, in the open air, using low loading of 4-AAP–Pd(II as a precatalyst, and in the presence of aqueous K2CO3 as the base. A variety of functional groups are tolerated.

  13. Rapid Synthesis of Glycosyl Bromides by Ultrasound Irradiation

    Institute of Scientific and Technical Information of China (English)

    ZHAO Jin-zhong; ZHANG Xue-qin; WU Xin; XING Ze-bing; YUE Ai-qin; SHAO Hua-wu

    2013-01-01

    A convenient and environmentally friendly reactor for the synthesis of glycosyl bromides via ultrasound irradiation was designed.Peracetylated glycosyl bromides were synthesized from free saccharides by means of a one-pot method.Benzoylated and 6-subsituted glycosyl bromides were prepared from protected saccharides.The glycosyl bromides were obtained in isolated yields of 83% to 96%.

  14. Ascertaining the suitability of aryl sulfonyl fluorides for [18F]radiochemistry applications: a systematic investigation using microfluidics.

    Science.gov (United States)

    Matesic, Lidia; Wyatt, Naomi A; Fraser, Benjamin H; Roberts, Maxine P; Pham, Tien Q; Greguric, Ivan

    2013-11-15

    Optimization of [(18)F]radiolabeling conditions and subsequent stability analysis in mobile phase, PBS buffer, and rat serum of 12 aryl sulfonyl chloride precursors with various substituents (electron-withdrawing groups, electron-donating groups, increased steric bulk, heterocyclic) were performed using an Advion NanoTek Microfluidic Synthesis System. A comparison of radiochemical yields and reaction times for a microfluidics device versus a conventional reaction vessel is reported. [(18)F]Radiolabeling of sulfonyl chlorides in the presence of competing nucleophiles, H-bond donors, and water was also assessed and demonstrated the versatility and potential utility of [(18)F]sulfonyl fluorides as synthons for indirect radiolabeling.

  15. CuI-catalyzed Synthesis of Aryl Thiocyanates from Aryl Iodides

    Institute of Scientific and Technical Information of China (English)

    Ye Feng WANG; Yuan ZHOU; Jia Rui WANG; Lei LIU; Qing Xiang GUO

    2006-01-01

    An operationally simple and inexpensive catalyst system was developed for the cross coupling of potassium thiocyanate with aryl iodides by using CuI as catalyst, 1, 10-phenanthroline as ligand, and tetraethylammonium iodide as activator. The procedure is applicable for the synthesis of diverse aryl thiocyanates without any exotic, poisonous reagents.

  16. One-pot, two-step, microwave-assisted palladium-catalyzed conversion of aryl alcohols to aryl fluorides via aryl nonaflates.

    Science.gov (United States)

    Wannberg, Johan; Wallinder, Charlotta; Ünlüsoy, Meltem; Sköld, Christian; Larhed, Mats

    2013-04-19

    A convenient procedure for converting aryl alcohols to aryl fluorides via aryl nonafluorobutylsulfonates (ArONf) is presented. Moderate to good one-pot, two-step yields were achieved by this nonaflation and microwave-assisted, palladium-catalyzed fluorination sequence. The reductive elimination step was investigated by DFT calculations to compare fluorination with chlorination, proving a larger thermodynamic driving force for the aryl fluoride product. Finally, a key aryl fluoride intermediate for the synthesis of a potent HCV NS3 protease inhibitor was smoothly prepared with the novel protocol.

  17. Crystal structure and Hirshfeld surface analysis of 1-carb­oxy-2-(3,4-di­hydroxy­phen­yl)ethan-1-aminium chloride 2-ammonio-3-(3,4-di­hydroxy­phen­yl)propano­ate: a new polymorph of l-dopa HCl and isotypic with its bromide counterpart

    Science.gov (United States)

    Kathiravan, Perumal; Balakrishnan, Thangavelu; Venkatesan, Perumal; Ramamurthi, Kandasamy; Percino, María Judith; Thamotharan, Subbiah

    2016-01-01

    The title mol­ecular salt, C9H12NO4 +·Cl−·C9H11NO4, is isotypic with that of the bromide counterpart [Kathiravan et al. (2016 ▸). Acta Cryst. E72, 1544–1548]. The title salt is a second monoclinic polymorph of the l-dopa HCl structure reported earlier in the monoclinic space group P21 [Jandacek & Earle (1971 ▸). Acta Cryst. B27, 841–845; Mostad & Rømming (1974 ▸). Acta Chemica Scand. B28, 1161–1168]. In the title compound, monoclinic space group I2, one of the dopa mol­ecules has a positive charge with a protonated α-amino group and the α-carb­oxy­lic acid group uncharged, while the second dopa mol­ecule has a neutral charge, the α-amino group is protonated and the α-carb­oxy­lic acid is deprotonated. In the previously reported form, a single dopa mol­ecule is observed in which the α-amino group is protonated and the α-carb­oxy­lic acid group is uncharged. The invariant and variations of various types of inter­molecular inter­actions present in these two forms of dopa HCl structures are discussed with the aid of two-dimensional fingerprint plots. PMID:27840723

  18. Crystal structure and Hirshfeld surface analysis of 1-carb-oxy-2-(3,4-di-hydroxy-phen-yl)ethan-1-aminium chloride 2-ammonio-3-(3,4-di-hydroxy-phen-yl)propano-ate: a new polymorph of l-dopa HCl and isotypic with its bromide counterpart.

    Science.gov (United States)

    Kathiravan, Perumal; Balakrishnan, Thangavelu; Venkatesan, Perumal; Ramamurthi, Kandasamy; Percino, María Judith; Thamotharan, Subbiah

    2016-11-01

    The title mol-ecular salt, C9H12NO4(+)·Cl(-)·C9H11NO4, is isotypic with that of the bromide counterpart [Kathiravan et al. (2016 ▸). Acta Cryst. E72, 1544-1548]. The title salt is a second monoclinic polymorph of the l-dopa HCl structure reported earlier in the monoclinic space group P21 [Jandacek & Earle (1971 ▸). Acta Cryst. B27, 841-845; Mostad & Rømming (1974 ▸). Acta Chemica Scand. B28, 1161-1168]. In the title compound, monoclinic space group I2, one of the dopa mol-ecules has a positive charge with a protonated α-amino group and the α-carb-oxy-lic acid group uncharged, while the second dopa mol-ecule has a neutral charge, the α-amino group is protonated and the α-carb-oxy-lic acid is deprotonated. In the previously reported form, a single dopa mol-ecule is observed in which the α-amino group is protonated and the α-carb-oxy-lic acid group is uncharged. The invariant and variations of various types of inter-molecular inter-actions present in these two forms of dopa HCl structures are discussed with the aid of two-dimensional fingerprint plots.

  19. Synthesis of N-benzoyl-N'-aryl selenoureas under PTC

    Institute of Scientific and Technical Information of China (English)

    WANG Hai; LIN Qi; ZHANG You-ming; WEI Tai-bao

    2004-01-01

    Recently many syntheses of selenium-containing compounds have been reported and studied, in which compounds selenoureas are used as the precursors for the syntheses of selenium-nitrogen heterocyclic compounds and their activities have received increasing attentions.Herein, we report the facile preparation of N-benzoyl-N'-aryl selenourea derivatives using potassium selenocyanate.In this typical procedure, Benzoyl chloride 1 was treated with potassium selenocyanate in CH2C12 under the condition of solid-liquid phase transfer catalysis using polyethylene glycal-400 as the catalyst to give the corresponding benzoyl isoselenocyanate 2. This compound did not need to be isolated and reacted with aromatic amine affording the N-benzoyl-N'-aryl selenourea derivatives 3.The reaction is described as:All the experiments were carried out under the condition of solid-liquid phase transfer catalysis using polyethylene glycal-400 as the catalyst and room temperature. And the structure was determined by IR, 1H NMR and 13C NMR. Selected data for N-benzoyl-N'-(4-fluoro)-selenourea:IR(KBr) 3426, 3274, 1672,1234,1155(C=Se); 1HMR(500MHz, DMSO) δ 12.85 (1H,S),11.86(1H,S), 7.27(2H,d,J=2.15), 7.98(2H,s,J=l.15), 7.30(2H,d,J=2.05), 7.56(2H.t,J=6.50),7.67(1H,t,J=6.20); 13C NMR(500MHz, DMSO)δ 181,168(C=Se),135,133, 132,115, 128.3, 128.8,161, 129.

  20. [Pharmacology of the bronchospasmolytic oxitropium bromide].

    Science.gov (United States)

    Bauer, V R

    1985-01-01

    The anticholinergic substance (8r)-6 beta, 7 beta-epoxy-8-ethyl-3 alpha-[(-)-tropoyloxyl]-1 alpha H, 5 alpha H-tropanium bromide (oxitropium bromide, Ba 253 BR, Ventilat) is a competitive antagonist of acetylcholine. In vitro, it is many times as effective as atropine. In vivo, oxitropium bromide, following i.v. administration, is also more effective than atropine. Due to its quaternary structure, a central anticholinergic effect cannot be demonstrated. Furthermore, poor enteral resorption is to be expected. Locally administered, as an aqueous aerosol, the effect of the substance is distinctly greater than that of atropine, both in potency and duration of action. This is also true when administered by metered-dose inhaler compared with ipratropium bromide. As, following aerosol administration, the margin between major effect and the most sensitive side-effect is in the ratio 1 : 100, side-effects are unlikely even with marked inhalational overdosage. Oxitropium bromide can be described, therefore, as a preparation free of side-effects which represents in prophylactic use in many cases of obstructive airway disease, an alternative to beta-mimetics and xanthine derivatives.

  1. Biological processes for the production of aryl sulfates

    DEFF Research Database (Denmark)

    2016-01-01

    The present invention generally relates to the field of biotechnology as it applies to the production of aryl sulfates using polypeptides or recombinant cells comprising said polypeptides. More particularly, the present invention pertains to polypeptides having aryl sulfotransferase activity......, recombinant host cells expressing same and processes for the production of aryl sulfates employing these polypeptides or recombinant host cells....

  2. Palladium catalyzed C3-arylation of 4-hydroxy-2-pyridones.

    Science.gov (United States)

    Anagnostaki, Elissavet E; Fotiadou, Anna D; Demertzidou, Vera; Zografos, Alexandros L

    2014-07-01

    The direct arylation of N-substituted-4-hydroxy-2-pyridones with aryl boronic acids has been achieved under palladium catalysis. The mild reaction conditions applied in this method and the use of a conventional catalytic system offer an attractive protocol for the efficient synthesis of a variety of 3-arylated products.

  3. Efficient Synthesis of Functionalized Benzimidazoles and Perimidines: Ytterbium Chloride Catalyzed CmC Bond Cleavage%Efficient Synthesis of Functionalized Benzimidazoles and Perimidines: Ytterbium Chloride Catalyzed CmC Bond Cleavage

    Institute of Scientific and Technical Information of China (English)

    Cai, Lijian; Ji, Xiaofeng; Yao, Zhigang; Xu, Fan; Shen, Qi

    2011-01-01

    An efficient method is developed for the synthesis of functionalized benzimidazoles and perimidines by the condensation of aryl diamines with β-carbonyl compounds catalyzed by ytterbium chloride. The reactions give good yields under mild conditions. A mechanism involving a lanthanide activated C--C bond cleavage is proposed.

  4. Heterogeneous Palladium Chloride Catalyzed Ligand-free Suzuki-Miyaura Coupling Reactions at Ambient Temperature

    Institute of Scientific and Technical Information of China (English)

    WANG Min; WANG Lei

    2008-01-01

    A mild and efficient ligand-free Suzuki-Miyaura coupling reaction catalyzed by heterogeneous palladium chloride was developed at room temperature in a short reaction time under air atmosphere.Various phenyl iodides,bromides and activated chlorides were coupled with sodium tetraphenylborate or phenylboronic acids efficiently to afford the corresponding cross-coupled products in good to excellent yields.Furthermore,the catalyst could be recycled up to four times without loss of its activity.

  5. Electronic structure and tautomerism of aryl ketones

    Energy Technology Data Exchange (ETDEWEB)

    Novak, Igor, E-mail: inovak@csu.edu.au [Charles Sturt University, POB 883, Orange, NSW 2800 (Australia); Klasinc, Leo, E-mail: klasinc@irb.hr [Physical Chemistry Department, Ruđer Bošković Institute, HR-10002 Zagreb (Croatia); Šket, Boris, E-mail: Boris.Sket@fkkt.uni-lj.si [Faculty of Chemistry and Chemical Technology, University of Ljubljana, SI-1000 (Slovenia); McGlynn, S.P., E-mail: sean.mcglynn@chemgate.chem.lsu.edu [Louisiana State University, Baton Rouge, LA 70803 (United States)

    2015-07-15

    Graphical abstract: Photoelectron spectroscopy, tautomerism. - Highlights: • UV photoelectron spectroscopy of aryl ketones. • The relative stability of tautomers and their electronic structures. • The factors influencing tautomerism. - Abstract: The electronic structures of several aryl ketones (AK) and their α-halo derivatives have been studied by UV photoelectron spectroscopy (UPS). The relative stabilities of keto–enol tautomers have been determined using high-level ab initio calculations and the results were used in the analysis of UPS spectra. The main features of electronic structure and tautomerism of the AK derivatives are discussed.

  6. [The clinical pharmacological profile of pinaverium bromide].

    Science.gov (United States)

    Guslandi, M

    1994-04-01

    Pinaverium bromide is a locally acting spasmolytic agent of the digestive tract. Its mechanism of action relies upon inhibition of calcium ion entrance into smooth muscle cells (calcium-antagonist effect). In humans pinaverium facilitates gastric emptying and decreases intestinal transit time in patients with constipation. Pinaverium is very effective in improving symptoms of irritable bowel syndrome (abdominal pain, gas, diarrhea or constipation). In this respect the drug proved to be significantly superior to placebo, at least as effective as trimebutine and on the whole more active than otilonium and prifinium bromide, being always extremely well tolerated.

  7. Palladium nanoparticle anchored polyphosphazene nanotubes: preparation and catalytic activity on aryl coupling reactions

    Indian Academy of Sciences (India)

    V Devi; A Ashok Kumar; S Sankar; K Dinakaran

    2015-06-01

    Highly accessible-supported palladium (Pd) nanoparticles anchored polyphosphazene (PPZ) nanotubes (NTs) having average diameter of 120 nm were synthesized rapidly at room temperature and homogeneously decorated with Pd nanoparticles. The resultant PPZ–Pd nanocomposites were morphologically and structurally characterized by means of transmission electron microscope equipped with energy-dispersive X-ray spectroscopy and X-ray diffraction analysis. Characterization results showed that the Pd nanoparticles with good dispersibility could be well anchored onto the surfaces of the PPZ NTs. The PPZ–Pd NTs show enhanced catalytic activity for the Suzuki coupling of aryl bromides with arylboronic acid. In addition, these PPZ–Pd NTs show excellent behaviour as reusable catalysts of the Suzuki and Heck coupling reactions.

  8. Dynamic fluorescence quenching of quinine sulfate dication by chloride ion in ionic and neutral micellar environments

    Science.gov (United States)

    Joshi, Sunita; Varma Y, Tej Varma; Pant, Debi D.

    2014-04-01

    Fluorescence quenching of Quinine sulfate dication (QSD) by chloride-ion (Cl-) in micellar environments of anionic, sodium dodecyl sulfate (SDS), cationic, cetyltrimethylammonium bromide (CTAB) and neutral, triton X-100 (TX-100) in aqueous phase has been investigated by time-resolved and steady- state fluorescence measurements. The quenching follows linear Stern-Volmer relation in micellar solutions and is dynamic in nature.

  9. Synthesis, Characterization, Anti-Inflammatory and in Vitro Antimicrobial Activity of Some Novel Alkyl/Aryl Substituted Tertiary Alcohols

    Directory of Open Access Journals (Sweden)

    Rafiuzzaman SaeedulHaq

    2011-12-01

    Full Text Available The synthesis of some novel alkyl/aryl substituted tertiary alcohols was accomplished in two steps. The synthetic route involves preparation of Grignard reagents by treating alkyl/aryl bromides with magnesium turnings in dry ether. Then substituted chalcones were reacted with the Grignard reagents to afford alkyl/aryl substituted tertiary alcohols 1-10. The structures of the synthesized compounds were assigned on the basis of FT-IR, 1H-NMR, 13C-NMR and mass spectroscopic data. The in vivo anti-inflammatory activity of the synthesized compounds was evaluated using the carrageenan-induced hind paw edema method and was compared with that of ibuprofen. Some of the newly synthesized compounds showed promising anti-inflammatory activity. The tertiary alcohols 1-10 were also screened for antibacterial activity against ten bacterial strains using seven Gram-positive and three Gram-negative bacteria and for antifungal activity against Aspergillus Flavus, Aspergillus Niger and Aspergillus pterus. Tertiary alcohols 1-10 were found to exhibit good to excellent antimicrobial activities compared to levofloxacin and fluconazole used as standard drugs.

  10. Crystal structures of five 1-alkyl-4-aryl-1,2,4-triazol-1-ium halide salts

    Directory of Open Access Journals (Sweden)

    Marites A. Guino-o

    2015-06-01

    Full Text Available The asymmetric units for the salts 4-(4-fluorophenyl-1-isopropyl-1,2,4-triazol-1-ium iodide, C11H13FN3+·I−, (1, 1-isopropyl-4-(4-methylphenyl-1,2,4-triazol-1-ium iodide, C12H16N3+·I−, (2, 1-isopropyl-4-phenyl-1,2,4-triazol-1-ium iodide, C11H14N3+·I−, (3, and 1-methyl-4-phenyl-1,2,4-triazol-1-ium iodide, C9H10N3+·I−, (4, contain one cation and one iodide ion, whereas in 1-benzyl-4-phenyl-1,2,4-triazol-1-ium bromide monohydrate, C15H14N3+·Br−·H2O, (5, there is an additional single water molecule. There is a predominant C—H...X(halide interaction for all salts, resulting in a two-dimensional extended sheet network between the triazolium cation and the halide ions. For salts with para-substitution on the aryl ring, there is an additional π–anion interaction between a triazolium carbon and iodide displayed by the layers. For salts without the para-substitution on the aryl ring, the π–π interactions are between the triazolium and aryl rings. The melting points of these salts agree with the predicted substituent inductive effects.

  11. Electrical polarization of lead bromide crystals. I

    NARCIS (Netherlands)

    Schoonman, A.; Macke, A.J.H.

    1972-01-01

    An attempt was made to measure electronic conductivity in lead bromide in equilibrium with lead, since experimental data on the cell −Pb/PbBr2/C+ in the literature are not consistent with existing theories. Combination of our results with published data for bromine-induced hole conduction in lead br

  12. Electrical polarization of lead bromide crystals. I

    NARCIS (Netherlands)

    Schoonman, A.; Macke, A.J.H.

    An attempt was made to measure electronic conductivity in lead bromide in equilibrium with lead, since experimental data on the cell −Pb/PbBr2/C+ in the literature are not consistent with existing theories. Combination of our results with published data for bromine-induced hole conduction in lead

  13. A comparison of the action of otilonium bromide and pinaverium bromide: study conducted under clinical control.

    Science.gov (United States)

    Defrance, P; Casini, A

    1991-11-01

    We studied 40 patients with irritable bowel syndrome (IBS) which received in a simple-blind fashion otilonium and pinaverium bromide (15 days each drug). During each 15-day period we evaluated: number of pain episodes, intensity of pain, number of bowel movements, side effects. Otilonium bromide, (OB), compared with pinaverium bromide was able to significantly (p less than 0.05) reduce the number of pain attacks, whereas no significant differences were found between the 2 groups as regards the other parameters. The occurrence of side effects was similar in the two treatment courses. We can conclude that the two types of treatment were similarly useful in IBS, although OB seems more effective than pinaverium bromide.

  14. 21 CFR 522.275 - N-Butylscopolammonium bromide.

    Science.gov (United States)

    2010-04-01

    ... 21 Food and Drugs 6 2010-04-01 2010-04-01 false N-Butylscopolammonium bromide. 522.275 Section 522....275 N-Butylscopolammonium bromide. (a) Specifications. Each milliliter of solution contains 20 milligrams (mg) N-butylscopolammonium bromide. (b) Sponsor. See No. 000010 in § 510.600(c) of this chapter...

  15. Branching out at C-2 of septanosides. Synthesis of 2-deoxy-2-C-alkyl/aryl septanosides from a bromo-oxepine

    Directory of Open Access Journals (Sweden)

    Supriya Dey

    2012-04-01

    Full Text Available This paper deals with the synthesis of 2-deoxy-2-C-alkyl/aryl septanosides. A range of such septanoside derivatives was synthesized by using a common bromo-oxepine intermediate, involving C–C bond forming organometallic reactions. Unsaturated, seven-membered septanoside vinyl bromides or bromo-oxepines, obtained through a ring expansion methodology of the cyclopropane derivatives of oxyglycals, displayed a good reactivity towards several acceptor moieties in C–C bond forming Heck, Suzuki and Sonogashira coupling reactions, thus affording 2-deoxy-2-C-alkyl/aryl septanosides. Whereas Heck and Sonogashira coupling reactions afforded 2-deoxy-2-C-alkenyl and -alkynyl derivatives, respectively, the Suzuki reaction afforded 2-deoxy-2-C-aryl septanosides. Deprotection and reduction of the 2-deoxy-2-alkenyl derivative afforded the corresponding 2-deoxy-2-C-alkyl septanoside free of protecting groups. The present study illustrates the reactivity of bromo-oxepine in the synthesis of hitherto unknown septanosides, branching out at C-2, through C–C bond formation with alkyl and aryl substituents.

  16. Synthesis of Aryl Allyl Ether in the Recyclable Ionic Liquid [bmim]PF6

    Institute of Scientific and Technical Information of China (English)

    Zhou Mei-Yun; Li Yi-Qun; Xu Xin-Ming

    2004-01-01

    Ionic liquids, especially imidazonium salts, have recently gained recognition as possible environmentally benign alternative chemical process solvents. This is mainly due to their nonvolatile nature, insolubility in some solvents as well as their ability to dissolve a wide range of organic and inorganic materials, allowing the ionic liquids easy recovery and recycling. Examples of their application in organic reactions have been summarized in a number of recent review articles.1Aryl allyl ether is very useful intermediate in organic synthesis. The Williamson reaction is a well knows method for the preparation ethers. However, the reaction of alkylating agents with the phenoxide ions was conventionally carried out in the organic solvents. The usual solvents for this type of reaction are DCM, 2 DMSO, 3 DMF, 4 CH3CN5 etc. With the current desire to avoid the use of organic molecular solvents in organic synthesis, we decide to investigate the use of the ionic liquid for the alternative solvent for the Williamson reaction to prepare the aryl allyl ethers. The ionic liquid employed here was the moisture stable 1-butyl-3-methylimidazolium hexafluorophosphate [bmim]PF6.6 The ionic liquid is non-volatile, thermally stable, and depending on the anion, can present low immiscible with water,alkanes and dialky ethers. We have now found that aryl allyl ethers can have been obtained from various phenols and allyl bromide in the presence of potassium hydroxide in [bmim]PF6 as a replacement for classical organic solvents in the ambient temperature. The results are shown in Scheme 1.The reaction were carried out by simple mixing the phenolwith the ally bromide and potassium hydroxide in [bmim]PF6 and stirred at room temperature for 4h. The results are summarized in Table 1.In conclusion, Williamson reaction can be successfully conducted in ionic liquid [bmim]PF6 with a number of advantages: the procedure is simple, the reaction condition is mild and the yields are excellent

  17. 40 CFR 180.123 - Inorganic bromide residues resulting from fumigation with methyl bromide; tolerances for residues.

    Science.gov (United States)

    2010-07-01

    ... on dog food, resulting from fumigation with methyl bromide. (ii) 125 parts per million for residues... PESTICIDE CHEMICAL RESIDUES IN FOOD Specific Tolerances § 180.123 Inorganic bromide residues resulting from... residues of inorganic bromides (calculated as Br) in or on the following food commodities which have been...

  18. Direct no-carrier-added {sup 18}F-labelling of arenes via nucleophilic substitution on aryl(2-thienyl)iodonium salts

    Energy Technology Data Exchange (ETDEWEB)

    Ross, T.L.

    2006-01-15

    For in vivo imaging of molecular processes via positron emission tomography (PET) radiotracers of high specific activity are demanded. In case of the most commonly used positron emitter fluorine-18, this is only achievable with no-carrier-added [{sup 18}F]fluoride, which implies nucleophilic methods of {sup 18}F-substitution. Whereas electron deficient aromatic groups can be labelled in one step using no-carrier-added [{sup 18}F]fluoride, electron rich {sup 18}F-labelled aromatic molecules are only available by multi-step radiosyntheses or carrier-added electrophilic reactions. Here, diaryliodonium salts represent an alternative, since they have been proven as potent precursor for a direct nucleophilic {sup 18}F-introduction into aromatic molecules. Furthermore, as known from non-radioactive studies, the highly electron rich 2-thienyliodonium leaving group leads to a high regioselectivity in nucleophilic substitution reactions. Consequently, a direct nucleophilic no-carrier-added {sup 18}F-labelling of electron rich arenes via aryl(2-thienyl)iodonium precursors was developed in this work. The applicability of direct nucleophilic {sup 18}F-labelling was examined in a systematic study on eighteen aryl(2-thienyl)iodonium salts. As electron rich precursors the ortho-, meta- and para-methoxyphenyl(2-thienyl)iodonium bromides, iodides, tosylates and triflates were synthesised. In addition, para-substituted (R=BnO, CH{sub 3}, H, Cl, Br, I) aryl(2-thienyl)iodonium bromides were prepared as precursors with a systematically varying electron density. As first approach, the general reaction conditions of the nucleophilic {sup 18}F-substitution procedure were optimised. The best conditions for direct nucleophilic no-carrier-added {sup 18}F-labelling via aryl(2-thienyl)iodonium salts were found with dimethylformamide as solvent, a reaction temperature of 130{+-}3 C and 25 mmol/l as concentration of the precursor. (orig.)

  19. Synthesis and In Vitro Antimicrobial, Anthelmintic and Insecticidal Activities Study of 4(4'-Bromophenyl-6-substituted-aryl-1-acetyl pyrimidine-2-thiols

    Directory of Open Access Journals (Sweden)

    Rita Bamnela

    2010-01-01

    Full Text Available A new series of 4(4'-bromophenyl-6-substituted aryl-1-acetyl pyrimidine-2-thiol derivatives were synthesized by heating chalcones with thiourea, in the presence of ethanolic potassium hydroxide, followed by treatment with acetyl chloride. The structure of the compounds was characterized by IR and H1 NMR spectral study and elemental analysis. The compounds were screened for their antimicrobial, anthelmintic and insecticidal activities. All the compounds exhibited significant to moderate biological activities.

  20. DFT-Based Explanation of the Effect of Simple Anionic Ligands on the Regioselectivity of the Heck Arylation of Acrolein Acetals

    DEFF Research Database (Denmark)

    Henriksen, Signe Teuber; Tanner, David Ackland; Cacchi, Sandro

    2009-01-01

    The Heck arylation of acrolein acetal has been studied computationally and compared to the corresponding reaction with allyl ethers. The reaction can be controlled to give either cinnamaldehydes or arylpropanoic esters by addition of different coordinating anions, acetate, or chloride. The comput...... reaction conditions. The difference between the two substrate classes could be rationalized in terms of relative hydride donating power of the two substrates....

  1. C(aryl-O Bond Formation from Aryl Methanesulfonates via Consecutive Deprotection and SNAr Reactions with Aryl Halides in an Ionic Liquid

    Directory of Open Access Journals (Sweden)

    Yang Chen

    2007-04-01

    Full Text Available An efficient K3PO4-mediated synthesis of unsymmetrical diaryl ethers using the ionic liquid [Bmim]BF4 (1-butyl-3-methylimidazolium tetrafluoroborate as solvent has been developed. The procedure involves consecutive deprotection of aryl methane-sulfonates and a nucleophilic aromatic substitution (SNAr with activated aryl halides.

  2. Nitroethylation of vinyl triflates and bromides.

    Science.gov (United States)

    Padilla-Salinas, Rosaura; Walvoord, Ryan R; Tcyrulnikov, Sergei; Kozlowski, Marisa C

    2013-08-02

    A two-carbon homologation of vinyl triflates and bromides for the synthesis of homoallylic nitro products is described. This palladium-catalyzed double coupling of nitromethane exploits the anion stabilizing and leaving group properties of nitromethane, generating the homo allyl nitro products via a tandem cross-coupling/π-allylation sequence. The resultant process provides a mild and convenient entry to nitroethylated products, which are versatile precursors to β,γ-unsaturated carbonyls, homoallylic amines, and nitrile oxides.

  3. Propantheline bromide is effective against dog drooling

    DEFF Research Database (Denmark)

    Gyldenløve, Mette; Thyssen, Jacob P

    2015-01-01

    Hyperhidrosis is a common condition characterized by extensive sweat secretion. Systemic treatment with anticholinergics might prove effective, but patients often suffer from side effects, e.g. dryness of the mouth. We present a clinical case of severe polydipsia in a six-month-old puppy who had ...... accidentally consumed 50 tablets of propantheline bromide 15 mg. Afterwards the puppy suffered from severe polydipsia, which cleared without treatment after three days....

  4. Chloride ingress prediction

    DEFF Research Database (Denmark)

    Frederiksen, Jens Mejer; Geiker, Mette Rica

    2008-01-01

    Prediction of chloride ingress into concrete is an important part of durability design of reinforced concrete structures exposed to chloride containing environment. This paper presents experimentally based design parameters for Portland cement concretes with and without silica fume and fly ash...... in marine atmospheric and submersed South Scandinavian environment. The design parameters are based on sequential measurements of 86 chloride profiles taken over ten years from 13 different types of concrete. The design parameters provide the input for an analytical model for chloride profiles as function...

  5. Palladium-Catalyzed Synthesis of N-Aryl Carbamates

    Science.gov (United States)

    Vinogradova, Ekaterina V.; Park, Nathaniel H.; Fors, Brett P.; Buchwald, Stephen L.

    2013-01-01

    An efficient synthesis of aryl carbamates was achieved by introducing alcohols into the reaction of palladium-catalyzed cross-coupling of ArX (X = Cl, OTf) with sodium cyanate. The use of aryl triflates as electrophilic components in this transformation allowed for an expanded substrate scope for direct synthesis of aryl isocyanates. This methodology provides direct access to major carbamate protecting groups, S-thiocarbamates, and diisocyanate precursors to polyurethane materials. PMID:23441814

  6. Reverse osmosis membrane composition, structure and performance modification by bisulphite, iron(III), bromide and chlorite exposure.

    Science.gov (United States)

    Ferrer, O; Gibert, O; Cortina, J L

    2016-10-15

    Reverse osmosis (RO) membrane exposure to bisulphite, chlorite, bromide and iron(III) was assessed in terms of membrane composition, structure and performance. Membrane composition was determined by Rutherford backscattering spectrometry (RBS) and membrane performance was assessed by water and chloride permeation, using a modified version of the solution-diffusion model. Iron(III) dosage in presence of bisulphite led to an autooxidation of the latter, probably generating free radicals which damaged the membrane. It comprised a significant raise in chloride passage (chloride permeation coefficient increased 5.3-5.1 fold compared to the virgin membrane under the conditions studied) rapidly. No major differences in terms of water permeability and membrane composition were observed. Nevertheless, an increase in the size of the network pores, and a raise in the fraction of aggregate pores of the polyamide (PA) layer were identified, but no amide bond cleavage was observed. These structural changes were therefore, in accordance with the transport properties observed.

  7. Carbonate polymers containing ethenyl aryl moieties

    OpenAIRE

    1993-01-01

    There are disclosed carbonate polymers having ethenyl aryl moieties. Such carbonate polymers are prepared from one or more multi-hydric compounds and have an average degree of polymerization of at least about 1 based on multi-hydric compound. These polymers, including blends thereof, can be easily processed and shaped into various forms and structures according to the known techniques. During or subsequent to the processing, the polymers can be crosslinked, by exposure to heat or radiation, f...

  8. Antibacterial sesquiterpene aryl esters from Armillaria mellea.

    Science.gov (United States)

    Donnelly, D M; Abe, F; Coveney, D; Fukuda, N; O'Reilly, J; Polonsky, J; Prangé, T

    1985-01-01

    Investigation of the mycelial extract of Armillaria mellea led to the isolation of the known melleolide (2a) and two new sesquiterpene aryl eters, 4-O-methylmelleolide (2b) and judeol (1c). Their structures were deduced from spectral data and that of (2b) confirmed by X-ray analysis. The new esters (1c) and (2b) showed strong antibacterial activity against gram-positive bacteria.

  9. Fluoroalkylation of aryl ether perfluorocyclobutyl polymers

    OpenAIRE

    Ligon, Clark; Ameduri, Bruno; Boutevin, Bernard; Smith, Dennis

    2008-01-01

    International audience; Post functionalization of aryl ether perfluorocyclobutyl (PFCB) polymers with fluoroalkyl side chains was accomplished with Umemoto's FITS reagents. The fluoroalkylated PFCB polymers (20 % functionalized) showed increases in both hydrophobicity and oleophobicity. Static contact angle for hexadecane was increased after fluoroalkylation from 0° to greater than 30° for the two PFCB polymers tested. Increased oil repellency makes these materials potential candidates for va...

  10. NEW TRENDS IN ARYL HYDROCARBON RECEPTOR BIOLOGY

    OpenAIRE

    Fernández-Salguero, Pedro M.; Sonia eMulero-Navarro

    2016-01-01

    Traditionally considered as a critical intermediate in the toxic and carcinogenic response to dioxin (2,3,7,8-tetrachlorodibenzo-p-dioxin, TCDD), the Aryl hydrocarbon/Dioxin receptor (AhR) has proven to be also an important regulator of cell physiology and organ homeostasis. AhR has become an interesting and actual area of research mainly boosted by a significant number of recent studies analyzing its contribution to the proper functioning of the immune, hepatic, cardiovascular, vascular and ...

  11. New Trends in Aryl Hydrocarbon Receptor Biology

    OpenAIRE

    Mulero-navarro, Sonia; Fernandez-Salguero, Pedro M.

    2016-01-01

    Traditionally considered as a critical intermediate in the toxic and carcinogenic response to dioxin (2,3,7,8-tetrachlorodibenzo-p-dioxin, TCDD), the Aryl hydrocarbon/Dioxin receptor (AhR) has proven to be also an important regulator of cell physiology and organ homeostasis. AhR has become an interesting and actual area of research mainly boosted by a significant number of recent studies analyzing its contribution to the proper functioning of the immune, hepatic, cardiovascular, vascular and ...

  12. Chloride/bromide and chloride/fluoride ratios of domestic sewage effluents and associated contaminated ground water

    Energy Technology Data Exchange (ETDEWEB)

    Vengosh, A.; Pankratov, I. [Hydrological Service, Jerusalem (Israel)

    1998-09-01

    To establish geochemical tools for tracing the origin of ground water contamination, the authors examined the variations of Cl/Br and Cl/F (weight) ratios in (1) domestic waste water from the Dan Region Sewage Reclamation Project and from reservoirs in the central coast of Israel; (2) associated contaminated ground water; and (3) pristine ground water from the Mediterranean coastal aquifer of Israel. The data show that supply water, anthropogenic NaCl and fluoridation control the Cl/Br and Cl/F ratios of domestic waste water, and conventional sewage treatment does not affect the anthropogenic inorganic signals. The Cl/Br ratios of ground water contaminated with sewage effluent reflect conservative mixing proportions of sewage and regional ground water components. Sensitivity tests demonstrate that it is possible to detect and distinguish sewage contamination from marine ratios after a sewage contribution of 5 to 15% is mixed with regional ground water. Mixing with Br-enriched fresh water however, would reduce this sensitivity. Since the high Cl/Br signal of sewage effluents is distinguishable from other anthropogenic sources with low Cl/Br ratios and from natural contamination sources, Cl/Br ratios can therefore be a useful inorganic tracer for identification of the origin of contaminated ground water. The Cl/F ratios of sewage-contaminated ground water were higher than those in the original sewage effluent, which suggests retention of fluoride into the aquifer solid phase.

  13. WITTIG REACTION APPROACH FOR THE SYNTHESIS OF 7-METHOXY-2-[4- ALKYL/ARYL]-L-BENZOFURAN-5-CARBOXALDEHYDE Wittig-Reaktion Ansatz für die Synthese von 7-Methoxy-2-[4 - ALKYL / ARYL]-L-BENZOFURAN-5-CARBOXALDEHYDE

    Directory of Open Access Journals (Sweden)

    Bapu R Thorata, Dyneshwar Shelke, Ramdas Atram and Ramesh Yamgar

    2013-07-01

    Full Text Available Vanillin undergoes sequence of reaction forming phosphonium salt through dimethyaminomethyl derivative (Mannich reaction. The synthesis of phosphonium salt can be achieved by sequence of three steps which was condense with series of aliphatic/aromatic acid chlorides by refluxing in toluene in presence of triethylamine (Wittig reaction as key step resulting 7-methoxy-2-alkyl/aryl-l-benzofuran-5-carboxaldehyde. The crude product was purified by using column chromatography and characterized by FTIR, NMR and Mass spectroscopy.

  14. IBS and the role of otilonium bromide.

    Science.gov (United States)

    Boeckxstaens, Guy; Corazziari, Enrico S; Mearin, Fermín; Tack, Jan

    2013-03-01

    Awareness of the seriousness of irritable bowel disorder (IBS) remains low among clinicians. In this review, we summarize the current knowledge of IBS and highlight the major personal, economic, and social burden of the disease, and the importance of adequate treatment of what is still often viewed as a trivial disorder. In fact, IBS is a major reason for referral. It is crucial that the varied pathophysiologies of this complex heterogeneous disease are understood in order to be able to treat both the presenting symptoms (pain, bloating, flatulence, abnormal defecation, diarrhea, constipation) and the underlying disorder effectively. Low-grade inflammatory and immune activation has been observed, but the precise triggers and mechanisms, and the relevance to symptom generation, remain to be established. IBS patients require different treatment strategies according to the pattern, severity, frequency, and symptoms. While initial therapy traditionally targets the most bothersome symptom, long-term therapy aims at maintaining symptom control and preventing recurrence. In addition to dietary/lifestyle interventions and psychosocial strategies, a wide range of pharmacologic therapies are approved for use in IBS depending on the symptoms reported. Musculotropic spasmolytics, which act directly on intestinal smooth muscle contractility, such as otilonium bromide, are effective, particularly in the relief of abdominal pain and bloating, and are well tolerated in IBS. THE OBIS TRIAL: The recent large placebo-controlled Otilonium Bromide in Irritable Bowel Syndrome study demonstrated the superiority of otilonium bromide versus placebo not only in the reduction of pain and bloating, but also in protection from relapse due to the long-lasting effect.

  15. Europium-doped barium bromide iodide

    Energy Technology Data Exchange (ETDEWEB)

    Gundiah, Gautam; Hanrahan, Stephen M.; Hollander, Fredrick J.; Bourret-Courchesne, Edith D.

    2009-10-21

    Single crystals of Ba0.96Eu0.04BrI (barium europium bromide iodide) were grown by the Bridgman technique. The title compound adopts the ordered PbCl2 structure [Braekken (1932). Z. Kristallogr. 83, 222-282]. All atoms occupy the fourfold special positions (4c, site symmetry m) of the space group Pnma with a statistical distribution of Ba and Eu. They lie on the mirror planes, perpendicular to the b axis at y = +-0.25. Each cation is coordinated by nine anions in a tricapped trigonal prismatic arrangement.

  16. Selective copper catalysed aromatic N-arylation in water

    DEFF Research Database (Denmark)

    Engel-Andreasen, Jens; Shimpukade, Bharat; Ulven, Trond.

    2013-01-01

    4,7-Dipyrrolidinyl-1,10-phenanthroline (DPPhen) was identified as an efficient ligand for copper catalyzed selective arom. N-arylation in water. N-Arylation of indoles, imidazoles and purines proceeds with moderate to excellent yields and complete selectivity over aliph. amines. Aq. medium...

  17. Palladium-Catalyzed alpha-Arylation of Tetramic Acids

    DEFF Research Database (Denmark)

    Storgaard, Morten; Dorwald, F. Z.; Peschke, B.;

    2009-01-01

    A mild, racemization-free, palladium-Catalyzed alpha-arylation of tetramic acids (2,4-pyrrolidinediones) has been developed. Various amino acid-derived tetramic acids were cleanly arylated by treatment with 2 mol % of Pd(OAc)(2), 4 mol % of a sterically demanding biaryl phosphine, 2.3 equiv of K2CO...

  18. EFFICACY OF HYOSCINE BUTYL BROMIDE SUPPOSITORY FOR POSTOPERATIVE PAIN RELIEF

    National Research Council Canada - National Science Library

    Soniya C. Alphonse; Acka Priya Varghese

    2017-01-01

    .... MATERIALS AND METHODS The study is a prospective randomized controlled study conducted at a tertiary care hospital to study the effect of Hyoscine Butyl Bromide Suppositories for postoperative...

  19. Catalytic Effect of Cetyltrimethylammonium Bromide on the Oxidation of Triethylene glycol by Chloramine-T in Acidic Medium

    Directory of Open Access Journals (Sweden)

    Vandana Sharma

    2008-01-01

    Full Text Available The kinetics and mechanism of cetyltrimethylammonium bromide catalyzed oxidation of triethylene glycol [2,2'-ethylene diqxybis(ethanol] by chloramine-T in acidic acid medium have been investigated. The reaction is first order dependence on chloramine-T and fractional order for triethylene glycol with excess concentration of other reactants. The catalytic effect due to cetyletrimethylammonium bromide has been studied. The small salt effect and increase in the reaction rate with increasing dielectric constant suggest the involvement of neutral molecule in the rate-determining step. The addition of p-toluene sulfonamide retards the reaction rate. The effect of chloride ion on the reaction also studied. The effect of temperature on the reaction has been investigated in the temperature range 313-333K and thermodynamic parameters were calculated from the Arrhenious plot. A tentative mechanism consistent with the experimental results has been proposed.

  20. Effects of chloride and silver ions on gold nanorod formation

    Science.gov (United States)

    Ock Park, Jin; Cho, So-Hye; Jeong, Dae-Yong; Kong, Young-Min; Lee, Seung Yong

    2015-01-01

    The ability to tune the longitudinal localized surface plasmon resonance of gold nanorods (AuNRs) via simple modification of their aspect ratio is a large contributing factor to their widespread use across multiple fields. An understanding of the synthesis conditions that affect the aspect ratio and yield of AuNRs is therefore of utmost importance. From this perspective, we take a systematic approach in investigating the effect of the following conditions on the seed-mediated formation of AuNRs: the addition of chloride or silver ions, and the use of a hexadecyltrimethylammonium bromide (CTAB) source with different levels of effectiveness on controlling the shape of growing AuNRs.

  1. SYNTHESIS OF BIOLOGICALLY ACTIVE 2-CHLORO-N-ALKYL/ARYL ACETAMIDE DERIVATIVES

    Directory of Open Access Journals (Sweden)

    S.A.Katke

    2011-07-01

    Full Text Available Medicinal chemistry plays an important role in development of drug for cure; maintain and improved health of human being. It is also equally important to design chemical entities for prevent the growth of micro-organism, which come in contact with human being in day-to-day life. We have synthesized 2-chloro-N-alkyl/aryl Acetamide derivatives with an aim as new bioactive agent, which can be used as anti microbial agents such as herbicides, antifungal, disinfectant. The present study involves the synthesis, purification and characterization of various N-substituted chloroacetamide derivatives. The chloroacetyl chloride treated with various aliphatic and aromatic amines at room temperature with stirring for few hours with monitoring reaction by thin layer chromatography gave 2-chloro-N-alkyl/aryl Acetamide as solid compounds. We checked the melting point of synthesized compounds with an open ended capillary tube method. The spectral techniques like Infra red and GC-MS have been used for characterization and establishment of structure of synthesized compounds. The antimicrobial screening of the synthesized chloroacetamides have shown excellent antibacterial and antifungalactivity.

  2. Copper-catalyzed aerobic oxidative cleavage of C-C bonds in epoxides leading to aryl nitriles and aryl aldehydes.

    Science.gov (United States)

    Gu, Lijun; Jin, Cheng

    2015-04-18

    Novel copper-catalyzed aerobic synthesis of aryl nitriles and aldehydes from epoxides via C-C single bond cleavage has been discovered. This reaction provides a practical method toward the synthesis of aryl nitriles and aldehydes, which are versatile intermediates and building blocks in organic synthesis.

  3. N-Arylation of azaheterocycles with aryl and heteroaryl halides catalyzed by iminodiacetic acid resin-chelated copper complex

    Institute of Scientific and Technical Information of China (English)

    2010-01-01

    Iminodiacetic acid resin-chelated copper(Ⅱ) complex is effective in cross-coupling reactions between azaheterocycles and aryl or heteroaryl halides,providing N-arylated products in good to excellent yields.The copper catalyst is air stable and can be readily recovered and reused with minimal loss of activity for three runs.

  4. Lithium Sulfuryl Chloride Battery.

    Science.gov (United States)

    Primary batteries , Electrochemistry, Ionic current, Electrolytes, Cathodes(Electrolytic cell), Anodes(Electrolytic cell), Thionyl chloride ...Phosphorus compounds, Electrical conductivity, Calibration, Solutions(Mixtures), Electrical resistance, Performance tests, Solvents, Lithium compounds

  5. C- versus O-Arylation of an Enol-Lactone Using Potassium tert-butoxide

    Directory of Open Access Journals (Sweden)

    El Moktar Essassi

    2003-05-01

    Full Text Available Abstract: The use of potassium tert-butoxide as the base in arylation reactions of an enollactone with a series of benzyl halides was explored. Our work demonstrates that the ratio of C-arylation to O-arylation varies with the substitution pattern of the aryl halide.

  6. A combined solid-state NMR and X-ray crystallography study of the bromide ion environments in triphenylphosphonium bromides.

    Science.gov (United States)

    Burgess, Kevin M N; Korobkov, Ilia; Bryce, David L

    2012-04-27

    Multinuclear ((31)P and (79/81)Br), multifield (9.4, 11.75, and 21.1 T) solid-state nuclear magnetic resonance experiments are performed for seven phosphonium bromides bearing the triphenylphosphonium cation, a molecular scaffold found in many applications in chemistry. This is undertaken to fully characterise their bromine electric field gradient (EFG) tensors, as well as the chemical shift (CS) tensors of both the halogen and the phosphorus nuclei, providing a rare and novel insight into the local electronic environments surrounding them. New crystal structures, obtained from single-crystal X-ray diffraction, are reported for six compounds to aid in the interpretation of the NMR data. Among them is a new structure of BrPPh(4), because the previously reported one was inconsistent with our magnetic resonance data, thereby demonstrating how NMR data of non-standard nuclei can correct or improve X-ray diffraction data. Our results indicate that, despite sizable quadrupolar interactions, (79/81)Br magnetic resonance spectroscopy is a powerful characterisation tool that allows for the differentiation between chemically similar bromine sites, as shown through the range in the characteristic NMR parameters. (35/37)Cl solid-state NMR data, obtained for an analogous phosphonium chloride sample, provide insight into the relationship between unit cell volume, nuclear quadrupolar coupling constants, and Sternheimer antishielding factors. The experimental findings are complemented by gauge-including projector-augmented wave (GIPAW) DFT calculations, which substantiate our experimentally determined strong dependence of the largest component of the bromine CS tensor, δ(11), on the shortest Br-P distance in the crystal structure, a finding that has possible application in the field of NMR crystallography. This trend is explained in terms of Ramsey's theory on paramagnetic shielding. Overall, this work demonstrates how careful NMR studies of underexploited exotic nuclides, such

  7. Chloride in Groundwater and Surface Water in Areas Underlain by the Glacial Aquifer System, Northern United States

    Science.gov (United States)

    Mullaney, John R.; Lorenz, David L.; Arntson, Alan D.

    2009-01-01

    A study of chloride in groundwater and surface water was conducted for the glacial aquifer system of the northern United States in forested, agricultural, and urban areas by analyzing data collected for the National Water-Quality Assessment Program from 1991 to 2004. Groundwater-quality data from a sampling of 1,329 wells in 19 states were analyzed. Chloride concentrations were greater than the secondary maximum contaminant level established by the U.S. Environmental Protection Agency of 250 milligrams per liter in 2.5 percent of samples from 797 shallow monitoring wells and in 1.7 percent of samples from 532 drinking-water supply wells. Water samples from shallow monitoring wells in urban areas had the largest concentration of chloride, followed by water samples from agricultural and forested areas (medians of 46, 12, and 2.9 milligrams per liter, respectively). An analysis of chloride:bromide ratios, by mass, and chloride concentrations compared to binary mixing curves for dilute groundwater, halite, sewage and animal waste, potassium chloride fertilizer, basin brines, seawater, and landfill leachate in samples from monitoring wells indicated multiple sources of chloride in samples from wells in urban areas and agricultural areas. Water from shallow monitoring wells in urban areas had the largest chloride:bromide ratio, and samples with chloride:bromide ratios greater than 1,000 and chloride concentrations greater than 100 milligrams per liter were dominated by halite; however, the samples commonly contained mixtures that indicated input from sewage or animal waste. Chloride:bromide ratios were significantly larger in samples from public-supply drinking-water wells than from private drinking-water wells, and ratios were significantly larger in all drinking-water wells in eastern and central regions of the glacial aquifer system than in west-central and western regions of the glacial aquifer system. Surface-water-quality data collected regularly during varying

  8. Interferences in automated phenol red method for determination of bromide in water

    Science.gov (United States)

    Basel, C.L.; Defreese, J.D.; Whittemore, D.O.

    1982-01-01

    The phenol red method for the determination of bromide in water has been automated by segmented flow analysis. Samples can be analyzed at a rate of 20 samples/h with a method detection limit, defined, as the concentration giving a signal about three times the standard deviation of replicate anaiyte determinations in reagent water, of 10 ??g/L. Samples studied include oil-field brines, halite solution brines, ground-waters contaminated with these brines, and fresh groundwaters. Chloride and bicarbonate cause significant positive interferences at levels as low as 100 mg/L and 50 mg/L, respectively. Ammonia gives a negative interference that is important at levels as low as 0.05 mg/L. An ionic strength buffer is used to suppress a positive ionic strength interference, correction curves are used to compensate for the chloride interference, the bicarbonate interference is minimized by acidification, and the ammonia interference is eliminated by its removal by ion exchange. Reaction product studies are used to suggest a plausible mode of chloride interference. ?? 1982 American Chemical Society.

  9. Palladium-phosphinous acid complexes catalyzed Suzuki cross-coupling reaction of heteroaryl bromides with phenylboronic acid in water/alcoholic solvents

    Institute of Scientific and Technical Information of China (English)

    Ben Li; Cuiping Wang; Guang Chen; Zhiqiang Zhang

    2013-01-01

    Highly active,air-stable and water-soluble palladium-phosphinous acid complexes have been applied to Suzuki cross-coupling reaction of heteroaryl bromides under mild conditions in water/alcoholic solvents.Suzuki cross-coupling reaction of heteroaryl bromides with phenylboronic acid occurred efficiently using palladium phosphinous acid complexes (POPd) and phase transfer catalyst (tetrabutylammonium bromide and polyethylene glycol) in water/ethanol mixture,water/propanol mixture and neat water respectively,the corresponding yields of cross-coupling heteroaryl-aryls were satisfied.The tert-butyl substituted ligand di-tert-butylphosphino in combination with POPd was found to be more active than the same family derived catalysts dipalladium complexes POPdl and POPd2,and other two kinds of Pd-catalysts Pd(PPh3)4 and Pd2(dba)3.The mechanism of Suzuki cross-coupling reaction between heteroaryl bromides and phenylboronic acid in water was proposed with respect to the key role of phase transfer catalyst on the transmetallation step.Compared with other solid phase transfer catalysts,TBAB was tested as the ideal one.The alkalinity of base and the molar proportion between POPd and TBAB were investigated in water and alcoholic solvents.Notably,in the presence of TBAB adding alcoholic solvents into water enhanced the yields of target products.However in terms of the liquid phase transfer catalyst of PEGs,mixing water into PEGs could slightly decrease the yields with respect to the water free PEGs bulk phase,which was probably due to the homogenous liquid conditions in pure PEGs and weak interactions between PEGs and heteroaryl bromide molecules in water depending on their molecular chain lengths.

  10. Palladium-phosphinous acid complexes catalyzed Suzuki cross-coupling reaction of heteroaryl bromides with phenylboronic acid in water/alcoholic solvents.

    Science.gov (United States)

    Li, Ben; Wang, Cuiping; Chen, Guang; Zhang, Zhiqiang

    2013-06-01

    Highly active, air-stable and water-soluble palladium-phosphinous acid complexes have been applied to Suzuki cross-coupling reaction of heteroaryl bromides under mild conditions in water/alcoholic solvents. Suzuki cross-coupling reaction of heteroaryl bromides with phenylboronic acid occurred efficiently using palladium phosphinous acid complexes (POPd) and phase transfer catalyst (tetrabutylammonium bromide and polyethylene glycol) in water/ethanol mixture, water/propanol mixture and neat water respectively, the corresponding yields of cross-coupling heteroaryl-aryls were satisfied. The tert-butyl substituted ligand di-tert-butylphosphino in combination with POPd was found to be more active than the same family derived catalysts dipalladium complexes POPd1 and POPd2, and other two kinds of Pd-catalysts Pd(PPh3)4 and Pd2(dba)3. The mechanism of Suzuki cross-coupling reaction between heteroaryl bromides and phenylboronic acid in water was proposed with respect to the key role of phase transfer catalyst on the transmetallation step. Compared with other solid phase transfer catalysts, TBAB was tested as the ideal one. The alkalinity of base and the molar proportion between POPd and TBAB were investigated in water and alcoholic solvents. Notably, in the presence of TBAB adding alcoholic solvents into water enhanced the yields of target products. However in terms of the liquid phase transfer catalyst of PEGs, mixing water into PEGs could slightly decrease the yields with respect to the water free PEGs bulk phase, which was probably due to the homogenous liquid conditions in pure PEGs and weak interactions between PEGs and heteroaryl bromide molecules in water depending on their molecular chain lengths.

  11. Continental-scale variation in chloride/bromide ratios of wet deposition.

    Science.gov (United States)

    Short, M A; de Caritat, P; McPhail, D C

    2017-01-01

    Chlorine and bromine play crucial roles in atmospheric element cycles and are important environmental tracers in catchment investigations, so understanding their distribution at the Earth's near-surface is imperative for deciphering their behaviour. This study presents the first continental-scale analysis of Cl(-) and Br(-) concentrations of wet deposition, based on six and half years of weekly samples collected across North America. A recently developed imputation algorithm was applied to estimate the high proportion of censored Br(-) values, as well as the other eight analytes, based on the multivariate relationships of nine analytes. The results are consistent with previous studies that have found that the concentrations of these two ions in wet deposition, and the Cl(-)/Br(-) ratios of wet deposition decrease with distance inland. Close to the coast, Cl(-)/Br(-) ratios of wet deposition are similar to the ratio found in seawater (~288 by mass), rapidly decrease to approximately a third of the seawater ratio at ~200km inland, and then decrease at a much lesser rate to reach mass-ratios of 20 to 10 at ~1500km inland, following a logarithmic regression. The Niagara Falls and the Great Salt Lake are identified as localised sources of atmospheric solutes based on elevated Cl(-)/Br(-) ratios of wet deposition at proximal sites. Our observations provide further confidence in the findings presented in previous studies that have shown that Cl(-)/Br(-) ratios systematically decrease with increasing distance from the coast, despite the potential confounding impact of other processes, such as weather patterns, chemical behaviour and anthropogenic activity. Our results provide improved estimates of Cl(-)/Br(-) ratios of wet deposition source water in the absence of site-specific data.

  12. A general and efficient palladium-catalyzed carbonylative synthesis of 2-aryloxazolines and 2-aryloxazines from aryl bromides.

    Science.gov (United States)

    Wu, Xiao-Feng; Neumann, Helfried; Neumann, Stephan; Beller, Matthias

    2012-10-22

    Oxazoline is OK! A general and efficient method for the synthesis of oxazolines has been developed. This allowed the preparation of 27 five-membered-ring heterocycles and 11 six-membered-ring heterocycles in moderate to good yields. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  13. Protecting group-free, selective cross-coupling of alkyltrifluoroborates with borylated aryl bromides via photoredox/nickel dual catalysis.

    Science.gov (United States)

    Yamashita, Yohei; Tellis, John C; Molander, Gary A

    2015-09-29

    Orthogonal reactivity modes offer substantial opportunities for rapid construction of complex small molecules. However, most strategies for imparting orthogonality to cross-coupling reactions rely on differential protection of reactive sites, greatly reducing both atom and step economies. Reported here is a strategy for orthogonal cross-coupling wherein a mechanistically distinct activation mode for transmetalation of sp(3)-hybridized organoboron reagents enables C-C bond formation in the presence of various protected and unprotected sp(2)-hybridized organoborons. This manifold has the potential for broad application, because orthogonality is inherent to the activation mode itself. The diversification potential of this platform is shown in the rapid elaboration of a trifunctional lynchpin through various transition metal-catalyzed processes without nonproductive deprotection or functional group manipulation steps.

  14. Conduction bands and invariant energy gaps in alkali bromides

    NARCIS (Netherlands)

    Boer, P.K. de; Groot, R.A. de

    1998-01-01

    Electronic structure calculations of the alkali bromides LiBr, NaBr, KBr, RbBr and CsBr are reported. It is shown that the conduction band has primarily bromine character. The size of the band gaps of bromides and alkali halides in general is reinterpreted.

  15. Antioxidant Functions of the Aryl Hydrocarbon Receptor

    Directory of Open Access Journals (Sweden)

    Cornelia Dietrich

    2016-01-01

    Full Text Available The aryl hydrocarbon receptor (AhR is a transcription factor belonging to the basic helix-loop-helix/PER-ARNT-SIM family. It is activated by a variety of ligands, such as environmental contaminants like polycyclic aromatic hydrocarbons or dioxins, but also by naturally occurring compounds and endogenous ligands. Binding of the ligand leads to dimerization of the AhR with aryl hydrocarbon receptor nuclear translocator (ARNT and transcriptional activation of several xenobiotic phase I and phase II metabolizing enzymes. It is generally accepted that the toxic responses of polycyclic aromatic hydrocarbons, dioxins, and structurally related compounds are mediated by activation of the AhR. A multitude of studies indicate that the AhR operates beyond xenobiotic metabolism and exerts pleiotropic functions. Increasing evidence points to a protective role of the AhR against carcinogenesis and oxidative stress. Herein, I will highlight data demonstrating a causal role of the AhR in the antioxidant response and present novel findings on potential AhR-mediated antioxidative mechanisms.

  16. Design, synthesis and in vitro cytotoxicity studies of novel β-carbolinium bromides.

    Science.gov (United States)

    Venkataramana Reddy, P O; Mishra, Shriprada; Tantak, Mukund P; Nikhil, Kumar; Sadana, Rachna; Shah, Kavita; Kumar, Dalip

    2017-03-15

    A series of novel β-carbolinium bromides has been synthesized from easily accessible β-carbolines and 1-aryl-2-bromoethanones. The newly synthesized compounds were evaluated for their in vitro anticancer activity. Among the synthesized derivatives, compounds 16l, 16o and 16s exhibited potent anticancer activity with IC50 values of <10μM against tested cancer cell lines. The most potent analogue 16l was broadly active against all the tested cancer cell lines (IC50=3.16-7.93μM). In order to test the mechanism of cell death, we exposed castration resistant prostate cancer cell line (C4-2) to compounds 16l and 16s, which resulted in increased levels of cleaved PARP1 and AO/EB staining, indicating that β-carbolinium salts induce apoptosis in these cells. Additionally, the most potent β-carbolines 16l and 16s were found to inhibit tubulin polymerization. Copyright © 2017 Elsevier Ltd. All rights reserved.

  17. Anti-proliferative and apoptotic effects of the derivatives from 4-aryl-4H-chromene family on human leukemia K562 cells.

    Science.gov (United States)

    Aryapour, Hassan; Mahdavi, Majid; Mohebbi, Seyed Reza; Zali, Mohammad Reza; Foroumadi, Alireza

    2012-09-01

    Previous studies suggest that 4-aryl-4H-chromenes are potent apoptosis-inducing agents in various cancer cell lines. In this study, anti-proliferative and apoptotic effects of the derivatives from 4-aryl-4H-chromene family were investigated in the human leukemia K562 cells using [3-(4,5)-dimethyl-2-thiazolyl]-2,5-diphenyl-2H-tetrazolium bromide (MTT) growth inhibition assay. 3-NC was more active among these compounds with IC₅₀ of 65 nM and was selected for further studies. Apoptosis, as the mechanism of cell death, was investigated morphologically by Hoechst 33258 staining, cell surface expression assay of phosphatidylserine by Annexin V/PI technique, caspase-3 activation assay, as well as the formation of DNA ladder. The K562 cells underwent apoptosis upon a single dose (at IC₅₀ value) of the compound, and also increased caspase-3 activity by more than 2.3-fold, following a 72 h treatment. Caspase-9 was also activated which could be detected 48 hours post-treatment. Furthermore, Western blot analysis revealed that the treatment with the compound down-regulated the expression of certain IAP protein, including survivin. These data further suggest that these derivatives from 4-aryl-4H-chromene may provide a novel therapeutic approach for the treatment of leukemia.

  18. Kinetic spectrophotometric determination of bromide in clidinium-c drug

    Institute of Scientific and Technical Information of China (English)

    Ali Sheibani; M. Reza Shishehbore; Zahra Tavakolian Ardakani

    2011-01-01

    A simple, rapid and sensitive method has been described for the determination of the trace amounts of bromide. The method is based on the catalytic effect of bromide ion on the oxidation of methylene blue by bromate in sulfuric acid media. The reaction is monitored spectrophotometrically by measuring the decrease in the absorbance of methylene blue at 665 nm. Bromide was determined in the range of 0.05-1.90 μg/mL with the detection limit of 0.03 μg/mL. The relative standard deviations of five replicate determinations of 0.20 and 10.0 μg/mL of bromide were 2.4% and 1.8%, respectively. The influence of potential interfering ions and substances was studied. The method is applied to the analysis of bromide in clidinium-c tablet as a real sample.

  19. Irritable bowel syndrome: focus on otilonium bromide.

    Science.gov (United States)

    Boeckxstaens, Guy; Clavé, Pere; Corazziari, Enrico S; Tack, Jan

    2014-02-01

    Irritable bowel syndrome is a prevalent and chronic disorder, characterized by recurrent abdominal pain/discomfort, bloating and altered bowel habits. This condition affects an estimated 10-15% of the population worldwide and impacts heavily on a patient's daily life and ability to work, as well as healthcare resource utilization. Drug therapy aimed at correcting the primary symptoms of diarrhea/constipation/bloating may have little effect on abdominal pain, which results from visceral hypersensitivity. Smooth muscle relaxants or antispasmodics decrease the tone and contractility of intestinal smooth muscle, effectively managing abdominal pain. Otilonium bromide has been widely used worldwide and has been found to be safe and well tolerated, and superior to placebo for the reduction of symptoms and the prevention of symptom relapse in patients with irritable bowel syndrome.

  20. Receptor binding profile of Otilonium bromide.

    Science.gov (United States)

    Evangelista, S; Giachetti, A; Chapelain, B; Neliat, G; Maggi, C A

    1998-08-01

    The interaction of Otilonium bromide (OB) with binding sites for 63 different receptors and ion channels in appropriate preparations has been investigated. Experiments were also performed in rat colon, the preferred tissue for OB 'in vivo' uptake after oral administration. Among the receptors investigated OB binds with sub microM affinity to muscarinic M1, M2, M4, M5 and PAF receptors and with microM affinity to the diltiazem binding site on L type Ca2+ channels. In the rat colon OB shows competitive interaction with the verapamil binding site on L type Ca2+ channels and with muscarinic M2 receptors with IC50 of 1020 and 1220 nM, respectively. These findings provide a molecular rationale to explain the spasmolytic action exerted by OB on intestinal smooth muscle. In particular, a combination of antimuscarinic and Ca2+ channel blocker properties seems to best account for the action of this compound.

  1. Variable selectivity of the Hitachi chemistry analyzer chloride ion-selective electrode toward interfering ions.

    Science.gov (United States)

    Wang, T; Diamandis, E P; Lane, A; Baines, A D

    1994-02-01

    Chloride measurements by ion-selective electrodes are vulnerable to interference by anions such as iodide, thiocyanate, nitrate, and bromide. We have found that the degree of interference of these anions on the Hitachi chemistry analyzer chloride electrode varies from electrode to electrode and this variation can even occur within the same lot of membrane. This variation is not dependent upon the length of time the cartridge has been in the analyzer because no correlation existed between the usage time and the electrode response to interfering ions. Neither is this variation due to the deterioration of the electrode because all electrodes tested had calibration slopes within the manufacturer's specification. Our study, however, showed that even after repeated exposure to a plasma sample containing 2 mM thiocyanate, the chloride electrode was still able to accurately measure the chloride in plasma without thiocyanate, thus confirming that a carryover effect does not exist from a previous thiocyanate-containing sample.

  2. Development of a Method for the N-Arylation of Amino Acid Esters with Aryl Triflates

    Science.gov (United States)

    2016-01-01

    A general method for the N-arylation of amino acid esters with aryl triflates is described. Both α- and β-amino acid esters, including methyl, tert-butyl, and benzyl esters, are viable substrates. Reaction optimization was carried out by design of experiment (DOE) analysis using JMP software. The mild reaction conditions, which use t-BuBrettPhos Pd G3 or G4 precatalyst, result in minimal racemization of the amino acid ester. This method is the first synthetic application of the t-BuBrettPhos Pd G4 precatalyst. Mechanistic studies show that the observed erosion in enantiomeric excess is due to racemization of the amino acid ester starting material and not of the product. PMID:27498618

  3. Influence of Functionality on Direct Arylation of Model Systems as a Route Toward Fluorinated Copolymers via Direct Arylation Polymerization (DArP)

    DEFF Research Database (Denmark)

    Livi, Francesco; Gobalasingham, Nemal S.; Bundgaard, Eva

    2015-01-01

    A screening of direct arylation conditions on amodel small molecule system is carried out to develop suitableconditions for the direct arylation polymerization (DArP) of fluorinatedcopolymers, which are incompatible with conditionspreviously utilized successfully for nonfluorinated systems...

  4. Strain IMB-1, a novel bacterium for the removal of methyl bromide in fumigated agricultural soils

    Science.gov (United States)

    Connell, Hancock T.L.; Costello, A.M.; Lidstrom, M.E.; Oremland, R.S.

    1998-01-01

    A facultatively methylotrophic bacterium, strain IMB-1, that has been isolated from agricultural soil grows on methyl bromide (MeBr), methyl iodide, methyl chloride, and methylated amines, as well as on glucose, pyruvate, or acetate. Phylogenetic analysis of its 16S rRNA gene sequence indicates that strain IMB-1 classes in the alpha subgroup of the class Proteobacteria and is closely related to members of the genus Rhizobium. The ability of strain IMB-1 to oxidize MeBr to CO2 is constitutive in cells regardless of the growth substrate. Addition of cell suspensions of strain IMB-1 to soils greatly accelerates the oxidation of MeBr, as does pretreatment of soils with low concentrations of methyl iodide. These results suggest that soil treatment strategies can be devised whereby bacteria can effectively consume MeBr during field fumigations, which would diminish or eliminate the outward flux of MeBr to the atmosphere.

  5. Synthesis of 3-fluoro-3-aryl oxindoles: Direct enantioselective α arylation of amides

    KAUST Repository

    Wu, Linglin

    2012-02-06

    Modus operandi: Catalytic access to the title compounds through a new asymmetric α-arylation protocol is reported (see scheme). These products are formed in good yields and excellent enantioselectivities by using a new and easily synthesized chiral N-heterocyclic carbene (NHC) ligand. Advanced DFT calculations reveal the properties of the NHC ligand and the mode of operation of the catalyst. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  6. Perturbations at the chloride site during the photosynthetic oxygen-evolving cycle.

    Science.gov (United States)

    Cooper, Ian B; Barry, Bridgette A

    2007-06-01

    Photosystem II (PSII) catalyzes the oxidation of water to O2 at the manganese-containing, oxygen-evolving complex (OEC). Photoexcitation of PSII results in the oxidation of the OEC; four sequential oxidation reactions are required for the generation and release of molecular oxygen. Therefore, with flash illumination, the OEC cycles among five Sn states. Chloride depletion inhibits O2 evolution. However, the binding site of chloride in the OEC is not known, and the role of chloride in oxygen evolution has not as yet been elucidated. We have employed reaction-induced FT-IR spectroscopy and selective flash excitation, which cycles PSII samples through the S state transitions. On the time scale employed, these FT-IR difference spectra reflect long-lived structural changes in the OEC. Bromide substitution supports oxygen evolution and was used to identify vibrational bands arising from structural changes at the chloride-binding site. Contributions to the vibrational spectrum from bromide-sensitive bands were observed on each flash. Sulfate treatment led to an elimination of oxygen evolution activity and of the FT-IR spectra assigned to the S3 to S0 (third flash) and S0 to S1 transitions (fourth flash). However, sulfate treatment changed, but did not eliminate, the FT-IR spectra obtained with the first and second flashes. Solvent isotope exchange in chloride-exchanged samples suggests flash-dependent structural changes, which alter protein dynamics during the S state cycle.

  7. The unexpected influence of aryl substituents in N-aryl-3-oxobutanamides on the behavior of their multicomponent reactions with 5-amino-3-methylisoxazole and salicylaldehyde

    Directory of Open Access Journals (Sweden)

    Volodymyr V. Tkachenko

    2014-12-01

    Full Text Available The switchable three-component reactions of 5-amino-3-methylisoxazole, salicylaldehyde and N-aryl-3-oxobutanamides under different conditions were studied and discussed. The unexpected influence of the aryl substituent in N-aryl-3-oxobutanamides on the behavior of the reaction was discovered. The key influence of ultrasonication and Lewis acid catalysts led to an established protocol to selectively obtain two or three types of heterocyclic scaffolds depending on the substituent in the N-aryl moiety.

  8. The electrochemical reduction of 1,4-dichloroazoethanes: Reductive elimination of chloride to form aryl azines

    Energy Technology Data Exchange (ETDEWEB)

    Sauro, Vittorio A.; Magri, David C.; Pitters, Jason L. [Department of Chemistry, University of Western Ontario, London, ON, N6A 5B7 (Canada); Workentin, Mark S., E-mail: mworkent@uwo.c [Department of Chemistry, University of Western Ontario, London, ON, N6A 5B7 (Canada)

    2010-08-01

    Graphical abstract: -- Abstract: A series of 1,4-dichloroazoethanes (1-X/Y, X and Y = 4-NO{sub 2}, 4-CN, 4-CH{sub 3} or 4-H) were studied in N,N-dimethylformamide using cyclic voltammetry, constant potential sweep voltammetry (CPSW) and constant potential electrolysis. The voltammograms of 1-X/Y exhibit an irreversible two-electron wave corresponding to dissociative electron transfer (DET) reduction of the carbon-chlorine bond resulting in formation of the azines 2-X/Y in quantitative yield. Additional redox waves correspond to the reversible reduction of the azines to the 2-X/Y{center_dot}{sup -} radical anion and 2-X/Y{sup 2-} dianion consecutively, with the exception of 1-NO{sub 2}/NO{sub 2} where both NO{sub 2} groups are reduced simultaneously in a two-electron reversible wave. Thermodynamic and kinetic parameters were determined from CPSW: the standard reduction potentials (E{sup o}) vary between -0.7 and -1.3 V versus SCE as a function of electron-withdrawing substituent; the heterogeneous rate constants (k{sub het}) are consistent with a slow heterogeneous electron transfer with values ranging from 10{sup -3} to 10{sup -5} cm s{sup -1}; the transfer coefficients ({alpha}) for 1-NO{sub 2}/NO{sub 2} and 1-NO{sub 2}/H are greater than 0.5, indicative of a stepwise DET mechanism for the C-Cl bond cleavage while the remaining 1-X/Y compounds have {alpha} values between 0.35 and 0.5, and the intrinsic barriers are all significantly lower than predicted for a concerted DET, thereby also suggesting a stepwise DET mechanism.

  9. New Synthesis and Antiparasitic Activity of Model 5-Aryl-1-methyl-4-nitroimidazoles

    Directory of Open Access Journals (Sweden)

    Mustafa M. El-Abadelah

    2009-07-01

    Full Text Available A number of 5-aryl-1-methyl-4-nitroimidazoles 5a-f have been synthesized in good yields by the Suzuki coupling reaction between 5-chloro-1-methyl-4-nitroimidazole (3 and arylboronic acids 4a-f, aided by dichlorobis-(triphenylphosphinepalladium(II, K2CO3, and tetrabutylammonium bromide in water at 70-80 °C. Compounds 5a-f were characterized by elemental analysis, NMR and MS spectral data. On the basis of in vitro screening data, 5-(3-chlorophenyl-1-methyl-4-nitro-1H-imidazole (5fexhibited potent lethal activity against Entamoeba histolytica and Giardia intestinalis with IC50 = 1.47 µM/mL, a value lower by a factor of two than that of the standard drug, metronidazole. The boosted activity of 5f was not accompanied by any increased cytotoxicity.The rest of the series also exhibited potent antiparasitic activity with IC50 valuesin the 1.72-4.43 µM/mL range. The cytotoxicity of the derivatives 5c and 5e was increased compared to the precursor compound, metronidazole, although they remain non-cytotoxic at concentrations much higher than the antiparasitic concentration of the two derivatives.

  10. chloride mass balance

    African Journals Online (AJOL)

    Agadaga

    1Geology Department, Faculty of Sciences and Techniques, University ... characterization of groundwater, rainfall and the unsaturated zone were also carried out using a .... 2008 in collaboration with the Senegal National Meteorological .... [Cl]sm is estimated as average chloride concentration in ..... sands of Australia.

  11. Chloride ingress prediction

    DEFF Research Database (Denmark)

    Frederiksen, Jens Mejer; Geiker, Mette Rica

    2008-01-01

    and time, and where both the surface chloride concentration and the diffusion coefficient are allowed to vary in time; the Mejlbro-Poulsen model is the general solution to Fick’s 2nd law. The paper also presents conversion formulas for the four decisive but rather abstract parameters to parameters, which...

  12. Selective oxidation of alcohols with alkali metal bromides as bromide catalysts: experimental study of the reaction mechanism.

    Science.gov (United States)

    Moriyama, Katsuhiko; Takemura, Misato; Togo, Hideo

    2014-07-03

    A bromide-catalyzed oxidation of alcohols was developed which proceeded in the presence of an alkali metal bromide and an oxidant under mild conditions. The reaction involved an organic-molecule-free oxidation using KBr and Oxone and a Brønsted acid assisted oxidation using KBr and aqueous H2O2 solution to provide a broad range of carbonyl compounds in high yields. Moreover, the bromide-catalyzed oxidation of primary alcohols enabled the divergent synthesis of carboxylic acids and aldehydes under both reaction conditions in the presence of TEMPO. A possible catalytic mechanism was suggested on the basis of various mechanistic studies.

  13. A new convenient access to highly functionalized ()-2-arylvinyl bromides

    Indian Academy of Sciences (India)

    Yubo Jiang; Chunxiang Kuang

    2009-11-01

    Highly functionalized ()-2-arylvinyl bromides were prepared in high yields through a new convenient access by acylation of ()-4-(2-bromovinyl)phenol with fatty and aromatic acids at room temperature using dicyclohexyl carbodiimide (DCC) and dimethylaminopyridine (DMAP).

  14. Methyl Bromide Commodity Fumigation Buffer Zone Lookup Tables

    Science.gov (United States)

    Product labels for methyl bromide used in commodity and structural fumigation include requirements for buffer zones around treated areas. The information on this page will allow you to find the appropriate buffer zone for your planned application.

  15. Disinfection byproduct regulatory compliance surrogates and bromide-associated risk.

    Science.gov (United States)

    Kolb, Chelsea; Francis, Royce A; VanBriesen, Jeanne M

    2017-08-01

    Natural and anthropogenic factors can alter bromide concentrations in drinking water sources. Increasing source water bromide concentrations increases the formation and alters the speciation of disinfection byproducts (DBPs) formed during drinking water treatment. Brominated DBPs are more toxic than their chlorinated analogs, and thus have a greater impact on human health. However, DBPs are regulated based on the mass sum of DBPs within a given class (e.g., trihalomethanes and haloacetic acids), not based on species-specific risk or extent of bromine incorporation. The regulated surrogate measures are intended to protect against not only the species they directly represent, but also against unregulated DBPs that are not routinely measured. Surrogates that do not incorporate effects of increasing bromide may not adequately capture human health risk associated with drinking water when source water bromide is elevated. The present study analyzes trihalomethanes (THMs), measured as TTHM, with varying source water bromide concentrations, and assesses its correlation with brominated THM, TTHM risk and species-specific THM concentrations and associated risk. Alternative potential surrogates are evaluated to assess their ability to capture THM risk under different source water bromide concentration conditions. The results of the present study indicate that TTHM does not adequately capture risk of the regulated species when source water bromide concentrations are elevated, and thus would also likely be an inadequate surrogate for many unregulated brominated species. Alternative surrogate measures, including THM3 and the bromodichloromethane concentration, are more robust surrogates for species-specific THM risk at varying source water bromide concentrations. Copyright © 2017. Published by Elsevier B.V.

  16. Direct oxidative arylation of aryl C - H bonds with aryl boronic acids via pd catalysis directed by the N,N-dimethylaminomethyl group.

    Science.gov (United States)

    Zhang, Ji-Cheng; Shi, Jiang-Ling; Wang, Bi-Qin; Hu, Ping; Zhao, Ke-Qing; Shi, Zhang-Jie

    2015-04-01

    Biaryl skeletons were directly constructed via palladium-catalyzed ortho-arylation of N,N-dimethyl benzylamine with aryl boronic acids with high efficiency and high regioselectivity under open-flask conditions. The N,N-dimethylaminomethyl group was first applied as a directing group in such an oxidative coupling. Various substrates proved to be efficient coupling partners, furnishing the corresponding ortho-monoarylated or -diarylated arenes in moderate to good yields under mild conditions. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  17. Pharmacology of the anticholinergic bronchospasmolytic agent flutropium bromide.

    Science.gov (United States)

    Bauer, R; Fügner, A

    1986-09-01

    The anticholinergic agent (8r)-8-(2-fluoroethyl)-3 alpha-hydroxy-1 alpha H,tropanium bromide benzilic acid ester (flutropium bromide, Ba 598 BR) is a classic competitive antagonist of acetylcholine. In in vitro experiments it is more effective than atropine. In addition there are indications, that flutropium bromide may interfere with the anaphylactic reaction in a certain dose range in vitro. In in vivo experiments for the characterization of the anticholinergic properties flutropium bromide is also somewhat more effective than atropine after parenteral administration. Because of its quaternary structure no central anticholinergic effect is detectable. Furthermore, a poor enteral absorption is to be expected; this can be concluded from the low relative effectiveness after oral administration. After systemic administration, flutropium bromide is only slightly more effective than atropine. The duration of action is longer. After local administration as an aerosol it is superior to atropine with regard to both effectiveness and duration of action. Since in aerosol administration the ratio of the main effect to the most sensitive side effects, inhibition of salivary secretion, is 1:100, no side effects are to be expected even after high inhalational overdoses. Flutropium bromide can therefore be described as a preparation which is free of side effects. When used prophylactically it represents a therapeutic alternative to beta-mimetics and xanthine derivatives for most cases of obstructive airway diseases.

  18. Metastable fragmentation of silver bromide clusters

    Energy Technology Data Exchange (ETDEWEB)

    L' Hermite, J.M.; Rabilloud, F.; Marcou, L.; Labastie, P. [Lab. CAR/IRSAMC, Univ. Paul Sabatier, Toulouse (France)

    2001-06-01

    The abundance spectra and the fragmentation channels of silver bromide clusters have been measured and analyzed. The most abundant species are Ag{sub n}Br{sub n} {sub -} {sub 1}{sup +} and Ag {sub n}Br {sub n} {sub +} {sub 1}{sup -} and Ag {sub 14}Br {sub 13}{sup +} is a magic number, revealing their ionic nature. However, some features depart from what is generally observed for alkali-halide ionic clusters. From a certain size, Ag {sub n}Br {sub n} {sub -} {sub 1}{sup +} is no more the main series, and Ag {sub n}Br {sub n} {sub -} {sub 2,} {sub 3}{sup +} series become almost as important. The fast fragmentation induced by a UV laser makes the cations lose more bromine than silver ions and lead to more silver-rich clusters. Negative ions mass spectra contain also species with more silver atoms than required by stoichiometry. We have investigated the metastable fragmentation of the cations using a new experimental method. The large majority of the cations release mainly a neutral Ag {sub 3}Br {sub 3} cluster. These decay channels are in full agreement with our recent ab initio DFT calculations, which show that Ag {sup +}-Ag {sup +} repulsion is reduced due to a globally attractive interaction of their d orbitals. This effect leads to a particularly stable trimer (AgBr) {sub 3} and to quasi-planar cyclic structures of (AgBr) {sub n} clusters up to n = 6. We have shown that these two features may be extended to other silver halides, to silver hydroxides (AgOH) {sub n}, and to cuprous halide compounds. (orig.)

  19. Advanced hybrid fluoropolymers from the cycloaddition of aryl trifluorovinyl ethers

    Science.gov (United States)

    Ligon, S. Clark, Jr.

    This dissertation discusses the synthesis of aryl trifluorovinyl ethers and their cycloaddition polymerization to give perfluorocyclobutyl (PFCB) polymers. To explore the stereochemistry of these polymers, simple monomfunctional aryl trifluorovinyl ethers were dimerized and the resultant cis and trans isomers were separated. Differences in structure help to improve understanding of the amorphous nature of the bulk PFCB polymeric material. To apply this knowledge, crown ether containing perfluorocyclobutyl (PFCB) polymers were synthesized for use in lithium ion battery applications. While poor solubility has hindered further development of these materials, slight modifications to structure may provide a solution. Also described is a fluorinated aryl vinyl ether and its attempted copolymerization with chlorotrifluoroethylene. While this copolymerization did not yield the desired materials, novel semifluorinated phenol precursors have been utilized in reactions with carboxylic acids to give polyesters and most recently with phosgene like species to give polycarbonates. Next, PFCB polymers were post functionalized with fluoroalkyl tethers to improve oleophobicity and hydrophobicity without decreasing thermal stability or optical clarity. In addition, various silica nanostructures were functionalized with aryl trifluorovinyl ethers. This includes the reaction of aryl silanes to give trifluorovinyl ether functional POSS and their polymerization to provide PFCB hybrid materials. Silane coupling agents were also used to functionalize colloidal silica and fumed silica nanoparticles. These procedures allow excellent dispersion of the silica nanoparticles throughout the fluoropolymer matrix. Finally, the reaction of aryl trifluorovinyl ether with nonfluorinated alkenes and alkynes was explored. In these reactions, the fluorinated olefin adds with the hydrocarbon olefin to give semifluorinated cyclobutanes (SFCB) and with the alkyne to give semifluorinated cyclobutene. The

  20. Copper and amine free Sonogashira cross-coupling reaction catalyzed by efficient diphosphane-palladium catalyst

    Institute of Scientific and Technical Information of China (English)

    Ting He; Lei Lei Wu; Xing Li Fu; Hai Yan Fu; Hua Chen; Rui Xiang Li

    2011-01-01

    The commercially available diphosphane ligand MeO-BIPHEP was first investigated in the palladium-catalyzed Sonogashira reaction in the absence of copper and amine. The coupling of various aryl bromides and aryl chlorides with phenylacetylene gave moderate to excellent yields.

  1. Synthesis of functional aromatic multisulfonyl chlorides and their masked precursors.

    Science.gov (United States)

    Percec, V; Bera, T K; De, B B; Sanai, Y; Smith, J; Holerca, M N; Barboiu, B; Grubbs, R B; Fréchet, J M

    2001-03-23

    The synthesis of functional aromatic bis(sulfonyl chlorides) containing an acetophenone and two sulfonyl chloride groups, i.e., 3,5-bis[4-(chlorosulfonyl)phenyl]-1-acetophenone (16), 3,5-bis(chlorosulfonyl)-1-acetophenone (17), and 3,5-bis(4-(chlorosulfonyl)phenyloxy)-1-acetophenone (18) via a sequence of reactions, involving in the last step the quantitative oxidative chlorination of S-(aryl)- N,N'-diethylthiocarbamate, alkyl- or benzyl thiophenyl groups as masked nonreactive precursors to sulfonyl chlorides is described. A related sequence of reactions was used for the synthesis of the aromatic trisulfonyl chloride 1,1,1-tris(4-chlorosulfonylphenyl)ethane (24). 4-(Chlorosulfonyl)phenoxyacetic acid, 2,2-bis[[[4-(chlorosulfonyl)phenoxyacetyl]oxy]methyl]-1,3-propanediyl ester (27), 5,11,17,23-tetrakis(chlorosulfonyl)-25,26,27,28-tetrakis(ethoxycarbonylmethoxy)calix[4]arene (38), 5,11,17,23,29,35-hexakis(chlorosulfonyl)-37,38,39,40,41,42-hexakis(ethoxycarbonylmethoxy)calix[6]arene (39), 5,11,17,23,29,35,41,47-octakis(chlorosulfonyl)-49,50,51,52,53,54,55,56-octakis(ethoxycarbonylmethoxy)calix[8]arene (40), 5,11,17,23-tetrakis(tert-butyl)-25,26,27,28-tetrakis(chlorosulfonyl phenoxyacetoxy)calix[4]arene (44), 5,11,17,23,29,35-hexakis(tert-butyl)-37,38,39,40,41,42-hexakis(chlorosulfonylphenoxyacetoxy)calix[6]arene (45), and 5,11,17,23,29,35,41,47-octakis(tert-butyl)-49,40,51,52,53,54,55,56-octakis(chlorosulfonylphenoxyacetoxy)calix[8]arene (46) were synthesized by two different multistep reaction procedures, the last step of both methods consisting of the chlorosulfonation of compounds containing suitable activated aromatic positions. 2,4,6-Tris(chlorosulfonyl)aniline (47) was obtained by the chlorosulfonation of aniline. The conformation of two series of multisulfonyl chlorides i.e., 38, 39, 40 and 44, 45, 46, was investigated by (1)H NMR spectroscopy. The masked nonreactive precursor states of the functional aromatic multisulfonyl chlorides and the aromatic

  2. Benzalkonium Chloride and Glaucoma

    OpenAIRE

    Rasmussen, Carol A.; Kaufman, Paul L.; Kiland, Julie A.

    2014-01-01

    Glaucoma patients routinely take multiple medications, with multiple daily doses, for years or even decades. Benzalkonium chloride (BAK) is the most common preservative in glaucoma medications. BAK has been detected in the trabecular meshwork (TM), corneal endothelium, lens, and retina after topical drop installation and may accumulate in those tissues. There is evidence that BAK causes corneal and conjunctival toxicity, including cell loss, disruption of tight junctions, apoptosis and preapo...

  3. Assessment of Ethidium bromide and Ethidium monoazide bromide removal from aqueous matrices by adsorption on cupric oxide nanoparticles.

    Science.gov (United States)

    Fakhri, Ali

    2014-06-01

    The present study was undertaken to develop an effective adsorbent and to study the adsorption of Ethidium bromide and Ethidium monoazide bromide from aqueous solution using the CuO nanoparticles. The characteristics of CuO nanoparticles were determined and found to have a surface area 89.59m(2)/g. Operational parameters such as pH, contact time and adsorbent concentration, initial concentration and temperature were also studied. The amount of removal increases with the increase in pH from one to seven and reaches the maximum when the pH is nine. Adsorption data fitted well with the Langmuir, Freundlich and Florry-Huggins models. The results show that the best fit was achieved with the Langmuir isotherm equation with maximum adsorption capacities of 0.868 and 0.662mg/g for Ethidium bromide and Ethidium monoazide bromide, respectively. The adsorption process was found to follow pseudo-second-order kinetics. The calculated thermodynamic parameters, namely ΔG, ΔH and ΔS showed that adsorption of Ethidium bromide and Ethidium monoazide bromide was spontaneous and endothermic under examined conditions.

  4. Preparation of 5-acyl- and 5-aryl-substituted 1-(benzyloxy)pyrazoles via directed ortho-lithiation/transmetalation and palladium catalyzed cross- coupling

    DEFF Research Database (Denmark)

    Kristensen, Jesper Langgaard; Begtrup, M.; Vedsø, P.

    1998-01-01

    Palladium(0) catalyzed cross-coupling of 1-(benzyloxy)pyrazol-5-ylzinc halides 3a,b, prepared by transmetalation of 1-(benzyloxy)-5-lithiopyrazole (2), with acyl chlorides produced 5 acyl-1-(benzyloxy)pyrazoles 4a-d in high yields. Similar coupling of the pyrazol-5-ylzinc halide with amino-, hydr......-, hydroxy- , methoxy-, fluoro-, nitro-, or formyl-substituted iodobenzene gave the corresponding 5-aryl-1-(benzyloxy)pyrazoles 5a-f, while coupling with iodothiophene, iodopyrazole or bromopyridine provided the corresponding 1- (benzyloxy)-5-heteroarylpyrazoles 6a-c....

  5. Preparation of 5-acyl- and 5-aryl-substituted 1-(benzyloxy)pyrazoles via directed ortho-lithiation/transmetalation and palladium catalyzed cross- coupling

    DEFF Research Database (Denmark)

    Kristensen, Jesper Langgaard; Begtrup, M.; Vedsø, P.

    1998-01-01

    Palladium(0) catalyzed cross-coupling of 1-(benzyloxy)pyrazol-5-ylzinc halides 3a,b, prepared by transmetalation of 1-(benzyloxy)-5-lithiopyrazole (2), with acyl chlorides produced 5 acyl-1-(benzyloxy)pyrazoles 4a-d in high yields. Similar coupling of the pyrazol-5-ylzinc halide with amino......-, hydroxy- , methoxy-, fluoro-, nitro-, or formyl-substituted iodobenzene gave the corresponding 5-aryl-1-(benzyloxy)pyrazoles 5a-f, while coupling with iodothiophene, iodopyrazole or bromopyridine provided the corresponding 1- (benzyloxy)-5-heteroarylpyrazoles 6a-c....

  6. Microwave-Promoted Rapid Synthesis of 1-Aryl-1, 2, 3-Triazoles

    Institute of Scientific and Technical Information of China (English)

    2001-01-01

    Aryl azides and a-keto phosphorus ylides were reacted within 4~10 minutes with silica gel support, under microwave irridiation to afford corresponding l-aryl-l, 2, 3-triazoles in moderate to good yields.

  7. Substituent effects on the nitrogen-15 and carbon-13 shieldings of some N-arylguanidinium chlorides

    OpenAIRE

    Botto, Robert E.; Schwartz, Joseph H.; Roberts, John D.

    1980-01-01

    The 13C and 15N chemical shifts of five N-arylguanidinium chlorides carrying polar substituents, ranging in character from 4-methoxy to 4-nitro groups, have been determined by NMR spectroscopy at the natural-abundance level of 13C and 15N in dimethyl sulfoxide solution. Comparison of the 13C shifts of these salts with those of monosubstituted benzenes shows that the guanidinium group induces an average downfield shift of -5.8 ppm of the resonance of the aryl carbon to which it is attached (C1...

  8. Synthesis and fungicidal activity of aryl carbamic acid-5-aryl-2-furanmethyl ester.

    Science.gov (United States)

    Li, Ying; Li, Bao-Ju; Ling, Yun; Miao, Hong-Jian; Shi, Yan-Xia; Yang, Xin-Ling

    2010-03-10

    Chitin, a major structural component of insect cuticle and fungus cell wall but absent in plants and vertebrates, is regarded as a safe and selective target for pest control agents. Chitin synthesis inhibitors (CSIs) have been well-known as insect growth regulators (IGRs) but rarely found as fungicides in agriculture. To find novel CSIs with good activity, benzoylphenylurea, a typical kind of CSIs, was chosen as the lead compound and 26 novel aryl carbamic acid-5-aryl-2-furanmethyl esters were designed by converting the urea linkages of benzoylphenylureas to carbamic acid esters and changing the aniline parts into furanmethyl groups. The title compounds were synthesized and their structures confirmed by IR, (1)H NMR, and elemental analysis. Preliminary insecticidal and fungicidal bioassays were carried out. The results indicated that the title compounds had no insecticidal effect on Culex pipiens pallens and Plutella xylostella Linnaeus , but most compounds exhibited good fungicidal activities against Corynespora cassiicola , Thanatephorus cucumeris , Botrytis cinerea , and Fusarium oxysporum . In particular, compounds V-4, V-6, V-7, and V-8 showed better activities against the four strains than those of the commercialized fungicides. The morphologic result suggested that compound V-21 had disturbed the cell wall formation of C. cassiicola. The results indicated that modification on the urea linkage of benzoylphenylurea was an effective way to discover new candidates for fungicides.

  9. Control of Reactivity and Regioselectivity for On-Surface Dehydrogenative Aryl-Aryl Bond Formation.

    Science.gov (United States)

    Kocić, Nemanja; Liu, Xunshan; Chen, Songjie; Decurtins, Silvio; Krejčí, Ondřej; Jelínek, Pavel; Repp, Jascha; Liu, Shi-Xia

    2016-05-04

    Regioselectivity is of fundamental importance in chemical synthesis. Although many concepts for site-selective reactions are well established for solution chemistry, it is not a priori clear whether they can easily be transferred to reactions taking place on a metal surface. A metal will fix the chemical potential of the electrons and perturb the electronic states of the reactants because of hybridization. Additionally, techniques to characterize chemical reactions in solution are generally not applicable to on-surface reactions. Only recent developments in resolving chemical structures by atomic force microscopy (AFM) and scanning tunneling microscopy (STM) paved the way for identifying individual reaction products on surfaces. Here we exploit a combined STM/AFM technique to demonstrate the on-surface formation of complex molecular architectures built up from a heteroaromatic precursor, the tetracyclic pyrazino[2,3-f][4,7]phenanthroline (pap) molecule. Selective intermolecular aryl-aryl coupling via dehydrogenative C-H activation occurs on Au(111) upon thermal annealing under ultrahigh vacuum (UHV) conditions. A full atomistic description of the different reaction products based on an unambiguous discrimination between pyrazine and pyridine moieties is presented. Our work not only elucidates that ortho-hydrogen atoms of the pyrazine rings are preferentially activated over their pyridine equivalents, but also sheds new light onto the participation of substrate atoms in metal-organic coordination bonding during covalent C-C bond formation.

  10. Synthesis of Macrocyclic Ionophore for the Development of Highly Selective Chloride Sensor

    Directory of Open Access Journals (Sweden)

    Sameena Mehtab

    2015-03-01

    Full Text Available The macrocyclic ligands 3,8,12,17-tetramethyl-2,18,9,11-bipyridyl-1,4,7,10,13,16-hexaazacyclooctadecanetetrahydro bromide has been synthesized and explored as suitable ionophores for chloride selective membrane sensors. It displays Nernstian behavior (59.2 mV decade-1 across the range of 4.1 × 10-8 to 1.0 × 10-2 M. The detection limit of the electrode is ~ 15 nM and the response time and life times are 14 s and eight weeks respectively over a wide pH range (3.5 - 9.5. Interference from other anions is very low and it can be used as indicator electrode in the potentiometric titration of chloride ions and to determine chloride in agricultural soil water samples.

  11. Decarboxylative Aminomethylation of Aryl- and Vinylsulfonates through Combined Nickel- and Photoredox-Catalyzed Cross-Coupling

    KAUST Repository

    Fan, Lulu

    2016-09-23

    A mild approach for the decarboxylative aminomethylation of aryl sulfonates by the combination of photoredox and nickel catalysis through C−O bond cleavage is described for the first time. A wide range of aryl triflates as well as aryl mesylates, tosylates and alkenyl triflates afford the corresponding products in good to excellent yields.

  12. Ruthenium(II)-Catalyzed C-C Arylations and Alkylations: Decarbamoylative C-C Functionalizations.

    Science.gov (United States)

    Moselage, Marc; Li, Jie; Kramm, Frederik; Ackermann, Lutz

    2017-04-05

    Ruthenium(II)biscarboxylate catalysis enabled selective C-C functionalizations by means of decarbamoylative C-C arylations. The versatility of the ruthenium(II) catalysis was reflected by widely applicable C-C arylations and C-C alkylations of aryl amides, as well as acids with modifiable pyrazoles, through facile organometallic C-C activation.

  13. Mechanisms and origins of switchable chemoselectivity of Ni-catalyzed C(aryl)-O and C(acyl)-O activation of aryl esters with phosphine ligands.

    Science.gov (United States)

    Hong, Xin; Liang, Yong; Houk, K N

    2014-02-05

    Many experiments have shown that nickel with monodentate phosphine ligands favors the C(aryl)-O activation over the C(acyl)-O activation for aryl esters. However, Itami and co-workers recently discovered that nickel with bidentate phosphine ligands can selectively activate the C(acyl)-O bond of aryl esters of aromatic carboxylic acids. The chemoselectivity with bidentate phosphine ligands can be switched back to C(aryl)-O activation when aryl pivalates are employed. To understand the mechanisms and origins of this switchable chemoselectivity, density functional theory (DFT) calculations have been conducted. For aryl esters, nickel with bidentate phosphine ligands cleaves C(acyl)-O and C(aryl)-O bonds via three-centered transition states. The C(acyl)-O activation is more favorable due to the lower bond dissociation energy (BDE) of C(acyl)-O bond, which translates into a lower transition-state distortion energy. However, when monodentate phosphine ligands are used, a vacant coordination site on nickel creates an extra Ni-O bond in the five-centered C(aryl)-O cleavage transition state. The additional interaction energy between the catalyst and substrate makes C(aryl)-O activation favorable. In the case of aryl pivalates, nickel with bidentate phosphine ligands still favors the C(acyl)-O activation over the C(aryl)-O activation at the cleavage step. However, the subsequent decarbonylation generates a very unstable tBu-Ni(II) intermediate, and this unfavorable step greatly increases the overall barrier for generating the C(acyl)-O activation products. Instead, the subsequent C-H activation of azoles and C-C coupling in the C(aryl)-O activation pathway are much easier, leading to the observed C(aryl)-O activation products.

  14. NIR photoluminescence of bismuth-doped CsCdBr{sub 3} – The first ternary bromide phase with a univalent bismuth impurity center

    Energy Technology Data Exchange (ETDEWEB)

    Romanov, Alexey N., E-mail: alexey.romanov@list.ru [N.N. Semenov Institute of Chemical Physics, Russian Academy of Sciences, 4 Kosygina Street, 119991 (Russian Federation); Veber, Alexander A. [Universität Erlangen-Nürnberg, Lehrstuhl für Glas und Keramik, Martensstraße 5, 91058 Erlangen (Germany); Vtyurina, Daria N. [N.N. Semenov Institute of Chemical Physics, Russian Academy of Sciences, 4 Kosygina Street, 119991 (Russian Federation); Kouznetsov, Mikhail S.; Zaramenskikh, Ksenia S.; Lisitsky, Igor S. [State Scientific-Research and Design Institute of Rare-Metal Industry “Giredmet” JSC, 5-1 B.Tolmachevsky Lane, 119017 Moscow (Russian Federation); Fattakhova, Zukhra T.; Haula, Elena V. [N.N. Semenov Institute of Chemical Physics, Russian Academy of Sciences, 4 Kosygina Street, 119991 (Russian Federation); Loiko, Pavel A.; Yumashev, Konstantin V. [Center for Optical Materials and Technologies, Belarusian National Technical University, 65/17 Nezavisimosti Avenue, 220013 Minsk (Belarus); Korchak, Vladimir N. [N.N. Semenov Institute of Chemical Physics, Russian Academy of Sciences, 4 Kosygina Street, 119991 (Russian Federation)

    2015-11-15

    Single crystals of ternary bromide phase CsCdBr{sub 3} doped with univalent bismuth cations are prepared for the first time by the Bridgman method. Bi{sup +} impurity center emits a broadband long-lived near-infrared photoluminescence with a maximum at ~1053 nm. The characteristics of this photoluminescence and its relations with the energy spectrum of Bi{sup +} impurity center are discussed. A comparison of Bi{sup +} photoluminescence in CsCdBr{sub 3} and ternary chlorides (studied previously) is performed. - Highlights: • Single crystals of Bi{sup +}-doped ternary bromide CsCdBr{sub 3} were prepared. • Broadband NIR photoluminescence was observed from Bi{sup +}-doped CsCdBr{sub 3}. • Single optical center is responsible for NIR emission in Bi{sup +}-doped CsCdBr{sub 3}.

  15. Reconciling Experiment and Theory in the Use of Aryl-Extended Calix[4]pyrrole Receptors for the Experimental Quantification of Chloride–π Interactions in Solution

    Directory of Open Access Journals (Sweden)

    Antonio Bauzá

    2015-04-01

    Full Text Available In this manuscript we consider from a theoretical point of view the recently reported experimental quantification of anion–π interactions (the attractive force between electron deficient aromatic rings and anions in solution using aryl extended calix[4]pyrrole receptors as model systems. Experimentally, two series of calix[4]pyrrole receptors functionalized, respectively, with two and four aryl rings at the meso positions, were used to assess the strength of chloride–π interactions in acetonitrile solution. As a result of these studies the contribution of each individual chloride–π interaction was quantified to be very small (<1 kcal/mol. This result is in contrast with the values derived from most theoretical calculations. Herein we report a theoretical study using high-level density functional theory (DFT calculations that provides a plausible explanation for the observed disagreement between theory and experiment. The study reveals the existence of molecular interactions between solvent molecules and the aromatic walls of the receptors that strongly modulate the chloride–π interaction. In addition, the obtained theoretical results also suggest that the chloride-calix[4]pyrrole complex used as reference to dissect experimentally the contribution of the chloride–π interactions to the total binding energy for both the two and four-wall aryl-extended calix[4]pyrrole model systems is probably not ideal.

  16. Oxomemazine hydro-chloride.

    Science.gov (United States)

    Siddegowda, M S; Butcher, Ray J; Akkurt, Mehmet; Yathirajan, H S; Ramesh, A R

    2011-08-01

    IN THE TITLE COMPOUND [SYSTEMATIC NAME: 3-(5,5-dioxo-phen-othia-zin-10-yl)-N,N,2-trimethyl-propanaminium chloride], C(18)H(23)N(2)O(2)S(+)·Cl(-), the dihedral angle between the two outer aromatic rings of the phenothia-zine unit is 30.5 (2)°. In the crystal, the components are linked by N-H⋯Cl and C-H⋯Cl hydrogen bonds and C-H⋯π inter-actions.

  17. Poly(vinyl chloride)-supported Pd(II) complex as an efficient catalyst for Heck and Cu-free Sonogashira reactions under aerobic conditions

    Institute of Scientific and Technical Information of China (English)

    Mohammad Bakherad; Ali Keivanloo; Shahrzad Samangooei

    2014-01-01

    A novel poly(vinyl chloride)-supported Pd complex was found to be a highly active catalyst for the Heck and Sonogashira reactions of aryl halides under aerobic conditions. The complex is thermally stable, and can be easily recovered and reused. The catalyst was recycled for the Heck and So-nogashira reactions for five runs without appreciable loss of its catalytic activity, and with negligible metal leaching.

  18. Aryl diazonium salts new coupling agents and surface science

    CERN Document Server

    Chehimi, Mohamed Mehdi

    2012-01-01

    Diazonium compounds are employed as a new class of coupling agents to link polymers, biomacromolecules, and other species (e. g. metallic nanoparticles) to the surface of materials. The resulting high performance materials show improved chemical and physical properties and find widespread applications. The advantage of aryl diazonium salts compared to other surface modifiers lies in their ease of preparation, rapid (electro)reduction, large choice of reactive functional groups, and strong aryl-surface covalent bonding.This unique book summarizes the current knowledge of the surface and

  19. Clinical potential of aclidinium bromide in chronic obstructive pulmonary disease

    Directory of Open Access Journals (Sweden)

    Zhong J

    2014-06-01

    Full Text Available Jun Zhong, Michael Roth Pneumology and Pulmonary Cell Research, Department of Biomedicine and Internal Medicine, University Hospital Basel, Basel, Switzerland Abstract: Chronic obstructive pulmonary disease (COPD is increasing worldwide and is predicted to become the third most frequent cause of death by 2030. Muscarinic receptor antagonists, alone or in combination with long-acting ß2-agonists, are frequently used for COPD therapy. Aclidinium bromide is a novel muscarinic receptor antagonist, and clinical studies indicate that its metabolism is more rapid than that of other muscarinic receptor inhibitors, so systemic side effects are expected to occur less frequently. Aclidinium bromide is well tolerated, and when compared with other muscarinic receptor antagonists, the drug achieves better control of lung function, especially night-time symptoms in COPD patients. This review summarizes the safety profile and side effects reported by recent clinical studies using aclidinium bromide alone. Keywords: aclidinium, tiotropium, side effects, clinical safety

  20. Water- Lithium Bromide-γ- Butyrolactone Absorption Refrigerating Machine

    Science.gov (United States)

    Iyoki, Shigeki; Uemura, Tadashi

    This investigation was carried out in order to find corrosion inhibitors which would be effective in controlling the corrosion for the water-lithium bromide-γ-butyrolactone (20 moles water/1 mole γ-butyrolactone) absorption refrigerating machine. The experiments were carried out on continuous boiling test, intermittent boiling test and galvanic corrosion test with the use of organic inhibitors and inorganic inhibitors in γ-butyrolactone aqueous solution of lithium bromide. The metals used in these corrosion tests were mainly SS 41 and copper. From these experimental results, the most suitable corrosion inhibitors for SS 41 and copper in γ-butyrolactone aqueous solution of lithium bromide Were recognized to be benzotriazole, tolyltriazole and lithium molybdate.

  1. Study of y-irradiated benzothiazole-doped polyvinyl chloride by positron annihilation

    Energy Technology Data Exchange (ETDEWEB)

    Misheva, M. [Faculty of Physics, Sofia Univ. (Bulgaria); Djourelov, N. [Inst. of Nuclear Research and Nuclear Energy, Sofia (Bulgaria); Sertova, N.; Petkov, I.; Deligeorgiev, T. [Faculty of Chemistry, Sofia Univ. (Bulgaria)

    2001-07-01

    Poly(vinyl chloride) (PVC) films containing different (0 / 4) weight percentage of 2-aryl substituted benzothiazole (BT) are studied by positron lifetime and Doppler broadening of annihilation line measurements. The effects of gamma-irradiation dose and of BT contents on positron annihilation parameters are studied. The positron lifetimes and intensities depend on irradiation dose only for BT-doped films. The ortho-positronium intensities for pure and doped PVC decrease with dose increasing in a similar way. The influence of doping is significant only at first doping with 0.125 wt% BT and is weak afterwards. Some of the observed changes of the parameters are explained by the protonation of BT and its conversion into [BTH{sup +}.Cl{sup -}] complexes by the interaction with hydrogen chloride - a product of PVC photodegradation. (orig.)

  2. Pseudoephedrine-Directed Asymmetric α-Arylation of α-Amino Acid Derivatives.

    Science.gov (United States)

    Atkinson, Rachel C; Fernández-Nieto, Fernando; Mas Roselló, Josep; Clayden, Jonathan

    2015-07-27

    Available α-amino acids undergo arylation at their α position in an enantioselective manner on treatment with base of N'-aryl urea derivatives ligated to pseudoephedrine as a chiral auxiliary. In situ silylation and enolization induces diastereoselective migration of the N'-aryl group to the α position of the amino acid, followed by ring closure to a hydantoin with concomitant explulsion of the recyclable auxiliary. The hydrolysis of the hydantoin products provides derivatives of quaternary amino acids. The arylation avoids the use of heavy-metal additives, and is successful with a range of amino acids and with aryl rings of varying electronic character.

  3. Derivatives of aryl-4-guanidinomethylbenzoate and N-aryl-4-guanidinomethylbenzamide as new antibacterial agents: synthesis and bioactivity

    Institute of Scientific and Technical Information of China (English)

    Wen-yuan YU; Li-xia YANG; Jian-shu XIE; Ling ZHOU; Xue-yuan JIANG; De-xu ZHU; Mutsumi MURAMATSU; Ming-wei WANG

    2008-01-01

    Aim: The aim of the present study was to design, synthesize, and evaluate novel antibacterial agents, derivatives of aryl-4-guanidinomethylbenzoate and N-aryl-4-guanidinomethylbenzamide. Methods: A total of 44 derivatives of aryl-4-guanidin-omethylbenzoate (series A) and N-aryl-4-guanidinomethylbenzamide (series B) were synthesized and their antibacterial activities were assessed in vitro against a variety of Gram-positive and Gram-negative bacteria by an agar dilution method. Results: Twelve compounds showed potent bactericidal effects against a panel of Gram-positive germs, including methicillin-resistant Staphylococcus aureus (MRSA), vancomycin-resistant enterococci (VRE), vancomycin-intermediate Sta-phylococcus aureus (VISA), and methicillin-resistant coagulase-negative staphy-lococci (MRCNS), with minimum inhibitory concentrations (MIC) ranging be-tween 0.5 and 8 μg/mL, which were comparable to the MIC values of several marketed antibiotics. They exhibited weak or no activity on the Gram-negative bacteria tested. In addition, these compounds displayed high inhibitory activities towards oligopeptidase B of bacterial origin. Conclusion: In comparison with the previ-ously reported MIC values of several known antibiotics, the derivatives of aryl-4-guanidinomethylbenzoate and N-aryl-4-guanidinomethylbenzamide showed com-parable in vitro bactericidal activities against VRE and VISA as linezolid. Their growth inhibitory effects on MRSA were similar to vancomycin, but were less potent than linezolid and vancomycin against MRCNS. This class of compounds may have the potential to be developed into narrow spectrum antibacterial agents against certain drug-resistant strains of bacteria.

  4. Glycosylation with Disarmed Glycosyl Bromides Promoted by Iodonium Ions

    DEFF Research Database (Denmark)

    Lanz, Gyrithe; Madsen, Robert

    2016-01-01

    Iodonium ions have been developed for activating glycosyl bromides in the coupling to glycosyl acceptors. The iodonium ions are generated from N-iodosuccinimide and a protic acid such as camphorsulfonic acid or triflic acid, where the latter gives the most reactive promoter system. The couplings...... occur with the release of iodine monobromide, and the best results are obtained with benzoylated glycosyl donors and acceptors. In this way, disarmed glycosyl bromides can serve as glycosyl donors without the use of heavy-metal salts....

  5. Preparation and characterization of rosin glycerin ester and its bromide

    Institute of Scientific and Technical Information of China (English)

    Yu Caili; Zhang Faai

    2006-01-01

    Rosin glycerin ester and its bromide were prepared from natural renewable rosin,glycerin and liquid bromine which were first subjected to an esterification reaction,followed by an addition reaction.Their structures were characterized by an infrared(IR)spectrum and their thermal resistance was conducted with thermal gravity(TG)and differential scanning calorimetry(DSC).It showed that the bromide in the rosin glycerin ester decomposed faster than the ester;hence it may be used as fire-resistant material.

  6. The speciation of aqueous zinc(II) bromide solutions to 500 °C and 900 MPa determined using Raman spectroscopy

    Science.gov (United States)

    Mibe, Kenji; Chou, I-Ming; Anderson, Alan J.; Mayanovic, Robert A.; Bassett, William A.

    2009-01-01

    A Raman spectral study was carried out on 3 solutions of varying concentration and bromide/zinc ratios. Spectra were collected at 11 different temperature-pressure conditions ranging from ambient to 500????C-0.9??GPa. Raman band assignments for zinc(II) bromide species reported in previous studies were used to determine the relative concentrations of ZnBr42-, ZnBr3-, ZnBr2, and ZnBr+ species at various temperatures and pressures. Our results are in close agreement with X-ray absorption spectroscopic (XAS) data, and confirm that the tetrabromo zinc(II) complex, ZnBr42-, is the predominant species up to 500????C in solutions having high Zn concentrations (1??m) and high bromide/zinc molar ratios ([Br]/[Zn] = 8). In agreement with previous solubility and Raman spectroscopic experiments, our measurements indicate that species with a lower number of halide ligands and charge are favored with increasing temperature in dilute solutions, and solutions with low bromide/zinc ratios ([Br]/[Zn] Raman technique provides an independent experimental means of evaluating the quality of XAS analyses of data obtained from high temperature disordered systems. The combination of these two techniques provides complementary data on speciation and the structure of zinc(II) bromide complexes. The preponderance of the ZnBr42- species in highly saline brines at high temperature is consistent with the predominance of ZnCl42- in chloride-rich brines reported in previous XAS studies. Knowledge of Zn complexing in metal-rich highly saline brines is important for numerical models of ore deposition in high temperature systems such as skarns and porphyry-type deposits. ?? 2008 Elsevier B.V.

  7. Synthesis of C-aryl Glycosides Catalyzed by CuI/TMEDA%CuI/TMEDA催化合成芳基葡萄糖碳苷化合物

    Institute of Scientific and Technical Information of China (English)

    毛泽伟; 饶高雄

    2016-01-01

    C-aryl glycosides(2a~2c) were stereoselectively synthesized by substitution reaction of 2, 3,4,6-tetra-O-acetyl-α-D-glucopyranosyl bromide and aryl Grignard reagents, using THF as the solvent and CuI/TMEDA as the catalyst.The structures were confirmed by 1 H NMR and 13 C NMR.Under the optimized reaction conditions(THF as the solvent, 10%CuI and 10%TMEDA as the catalyst, and the reac-tion temperature was 0℃), the yields of 2a~2c were 58%~71%andα/βwere 1/6.5~1/7.1.%以THF为溶剂,CuI/TMEDA为催化剂,四乙酰溴代葡萄糖与芳基溴化镁经取代反应合成了芳基葡萄糖碳苷(2a~2c),其结构经1H NMR和13C NMR确证。在最佳反应条件(THF为溶剂,10%CuI和10%TMEDA为催化剂,于0℃反应至终点)下,2a~2c的收率为58%~71%,α/β为1/6.5~1/7.1。

  8. 3,4-trans-4-Aryl-3-(1-pyridinio)-1,2,3,4-tetrahydropyridine-6-thiolates--new group of potential cardiotonic drugs.

    Science.gov (United States)

    Krauze, A; Vītoliņa, R; Garaliene, V; Sīle, L; Klusa, V; Duburs, G

    2005-11-01

    3,4-trans-4-Aryl-3-(1-pyridinio)-1,2,3,4-tetrahydropyridine-6-thiolates 6-11 were prepared by a Michael reaction of N-acetonylpyridinium chloride with 3-aryl-2-cyanothioacrylamides or by a one-pot three-carbon condensation of N-acetonylpyridinium chloride, aromatic aldehyde and 2-cyanothioacetamide, and their cardiotonic properties were studied. 3,4-trans-5-cyano-2-hydroxy-2-methyl-4-(3-nitrophenyl)-3-(1-pyridinio)-1,2,3,4-tetrahydropyridine-6-thiolate 8 was considered as a lead compound in this series since it in vitro experiments (spontaneously beating rat atria) showed a cardiotonic activity similar to that of milrinone 2, however compound 8 induced activity at lover concentrations and without influence on chronotropic action of the heart. Unlike milrinone 2, thiolate 8 in vivo experiments (anaesthetized rats) did not influence blood pressure and heart rate. The acute toxicity of compound 8 was more than 10 times lower than that of milrinone 2.

  9. Aryl tetrahydropyridine inhibitors of farnesyltransferase: glycine, phenylalanine and histidine derivatives.

    Science.gov (United States)

    Gwaltney, Stephen L; O'Connor, Stephen J; Nelson, Lissa T J; Sullivan, Gerard M; Imade, Hovis; Wang, Weibo; Hasvold, Lisa; Li, Qun; Cohen, Jerome; Gu, Wen-Zhen; Tahir, Stephen K; Bauch, Joy; Marsh, Kennan; Ng, Shi-Chung; Frost, David J; Zhang, Haiying; Muchmore, Steve; Jakob, Clarissa G; Stoll, Vincent; Hutchins, Charles; Rosenberg, Saul H; Sham, Hing L

    2003-04-07

    Inhibitors of farnesyltransferase are effective against a variety of tumors in mouse models of cancer. Clinical trials to evaluate these agents in humans are ongoing. In our effort to develop new farnesyltransferase inhibitors, we have discovered a series of aryl tetrahydropyridines that incorporate substituted glycine, phenylalanine and histidine residues. The design, synthesis, SAR and biological properties of these compounds will be discussed.

  10. Kinetic Resolution of Aryl Alkenylcarbinols Catalyzed by Fc-PIP

    Institute of Scientific and Technical Information of China (English)

    胡斌; 孟萌; 姜山山; 邓卫平

    2012-01-01

    An effective kinetic resolution of a variety of aryl alkenylcarbinols catalyzed by nonenzymatic acyl transfer catalyst Fe-PIP was developed, affording corresponding unreacted alcohols in good to excellent ee value up to 99% and with selectivity factors up to 24.

  11. Rh-Catalyzed arylation of fluorinated ketones with arylboronic acids.

    Science.gov (United States)

    Dobson, Luca S; Pattison, Graham

    2016-09-25

    The Rh-catalyzed arylation of fluorinated ketones with boronic acids is reported. This efficient process allows access to fluorinated alcohols in high yields under mild conditions. Competition experiments suggest that difluoromethyl ketones are more reactive than trifluoromethyl ketones in this process, despite their decreased electronic activation, an effect we postulate to be steric in origin.

  12. Oxidative electrochemical aryl C-C coupling of spiropyrans

    NARCIS (Netherlands)

    Ivashenko, Oleksii; van Herpt, Jochem T.; Rudolf, Petra; Feringa, Ben L.; Browne, Wesley R.

    2013-01-01

    The isolation and definitive assignment of the species formed upon electrochemical oxidation of nitro-spiropyran (SP) is reported. The oxidative aryl C-C coupling at the indoline moiety of the SP radical cation to form covalent dimers of the ring-closed SP form is demonstrated. The coupling is block

  13. Iron-Mediated Direct Arylation of Unactivated Arenes in Air

    NARCIS (Netherlands)

    Huang, Yuxing; Moret, Marc-Etienne; Klein Gebbink, Bert

    2014-01-01

    Biaryls are a common motif in both natural and synthetic chemicals. Several methods have recently been reported for the preparation of these compounds using direct arylation catalyzed by iron, other base metals, or transition-metal-free systems. To date, these methods have all required inert and/or

  14. Amberlyst-15 catalyzed synthesis of alkyl/aryl/heterocyclic phosphonates

    Institute of Scientific and Technical Information of China (English)

    U.M. Rao Kunda; V.N. Reddy Mudumala; C.S. Reddy Gangireddy; B.R. Nemallapudi; K.N. Sandip; S.R. Cirandur

    2011-01-01

    A novel and efficient procedure for the synthesis of alkyl phosphonates through one pot condensation of alkyl halide and tri-alkyl/aryl phosphite in the presence of Amberlyst-15 as catalyst under solvent free conditions was applied. It demonstrated several advantages such as good yields of products, simple operation, convenient separation and inexpensive catalyst.

  15. Nickel-catalyzed monofluoromethylation of aryl boronic acids.

    Science.gov (United States)

    Su, Yi-Ming; Feng, Guang-Shou; Wang, Zhen-Yu; Lan, Quan; Wang, Xi-Sheng

    2015-05-11

    Aryl boronic acids can be monofluoromethylated under nickel catalysis. The utility of this method is demonstrated by the monofluoromethylation of a borylated and acyl-protected derivative of the statin drug ezetimibe. Mechanistic investigations indicate that a fluoromethyl radical is involved in the Ni(I)/Ni(III) catalytic cycle. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  16. Chloride on the Move

    KAUST Repository

    Li, Bo

    2017-01-09

    Chloride (Cl−) is an essential plant nutrient but under saline conditions it can accumulate to toxic levels in leaves; limiting this accumulation improves the salt tolerance of some crops. The rate-limiting step for this process – the transfer of Cl− from root symplast to xylem apoplast, which can antagonize delivery of the macronutrient nitrate (NO3−) to shoots – is regulated by abscisic acid (ABA) and is multigenic. Until recently the molecular mechanisms underpinning this salt-tolerance trait were poorly defined. We discuss here how recent advances highlight the role of newly identified transport proteins, some that directly transfer Cl− into the xylem, and others that act on endomembranes in ‘gatekeeper’ cell types in the root stele to control root-to-shoot delivery of Cl−.

  17. Benzalkonium chloride and glaucoma.

    Science.gov (United States)

    Rasmussen, Carol A; Kaufman, Paul L; Kiland, Julie A

    2014-01-01

    Glaucoma patients routinely take multiple medications, with multiple daily doses, for years or even decades. Benzalkonium chloride (BAK) is the most common preservative in glaucoma medications. BAK has been detected in the trabecular meshwork (TM), corneal endothelium, lens, and retina after topical drop installation and may accumulate in those tissues. There is evidence that BAK causes corneal and conjunctival toxicity, including cell loss, disruption of tight junctions, apoptosis and preapoptosis, cytoskeleton changes, and immunoinflammatory reactions. These same effects have been reported in cultured human TM cells exposed to concentrations of BAK found in common glaucoma drugs and in the TM of primary open-angle glaucoma donor eyes. It is possible that a relationship exists between chronic exposure to BAK and glaucoma. The hypothesis that BAK causes/worsens glaucoma is being tested experimentally in an animal model that closely reflects human physiology.

  18. Een ionchromatografische methode voor de simultane bepaling van nitriet, bromide en sulfiet in water

    NARCIS (Netherlands)

    Beld WA van den; Cleven RFMJ; LAC

    1996-01-01

    Betreft resultaten van een onderzoek naar het ontwikkelen van een geautomatiseerde ionchromatografische methode voor de bepaling van nitriet, bromide en sulfiet. Het onderzoek heeft geresulteerd in een betrouwbare, selectieve en gevoelige methode voor de simultane bepaling van nitriet, bromide e

  19. 77 FR 20752 - Methyl Bromide; Proposed Pesticide Tolerance

    Science.gov (United States)

    2012-04-06

    ... necessary to prevent the introduction of a plant pest into the United States or the dissemination of a plant... partition into organic vs. aqueous environments, and is therefore commonly used to predict the likelihood...). See the February 22, 2002, Residue Chemistry Chapter for the methyl bromide RED available in...

  20. On the existence of ‘L-alanine cadmium bromide'

    Science.gov (United States)

    Srinivasan, Bikshandarkoil R.

    2013-12-01

    It is argued that the recently reported nonlinear optical crystal L-alanine cadmium bromide, grown by slow solvent evaporation method at room temperature [P. Ilayabarathi, J. Chandrasekaran, Spectrochim. Acta 96A (2012) 684-689] is the well-known L-alanine crystal. The isolation of L-alanine crystal is explained due to fractional crystallization.

  1. On the existence of 'L-alanine cadmium bromide'.

    Science.gov (United States)

    Srinivasan, Bikshandarkoil R

    2013-12-01

    It is argued that the recently reported nonlinear optical crystal L-alanine cadmium bromide, grown by slow solvent evaporation method at room temperature [P. Ilayabarathi, J. Chandrasekaran, Spectrochim. Acta 96A (2012) 684-689] is the well-known L-alanine crystal. The isolation of L-alanine crystal is explained due to fractional crystallization.

  2. Preozonation of bromide-bearing source water in south China

    Institute of Scientific and Technical Information of China (English)

    2006-01-01

    The effectiveness of preozonation was evaluated on treating a bromide-bearing dam source water in south China through batch-scale experiments. Preozonation at ozone doses of 0.5-1.0 mg/L (at ozone consumption base) enhanced total organic carbon(TOC) removal through coagulation, and resulted in an almost linear reduction of ultraviolet absorbance at 254 nm (UV254). The removals of TOC (after coagulation) and UV254 at the ozone dose of 1.0 mg/L were 36% and 70%, respectively. Preozonation at an ozone dose between 0.5 and 1.0 mg/L resulted in the removal of disinfection byproducts formation potential (DBFP) including trihalomethane formation potential (THMFP) and haloacetic acid formation potential (HAAFP) for about 50%. The removals of THMFP and HAAFP decreased with the further increase of ozone dose. Ozonation of bromide-bearing water (bromide concentration,34 μg/L) produced a bromate concentration under the detection limit(2 μg/L) at ozone doses < 1.5 mg/L. However, bromate >10 μg/L could be produced when the bromide concentration was increased to 96 μg/L.

  3. Chloride ion-aided self-assembly of pseudoclathrochelate metal tris-pyrazoloximates.

    Science.gov (United States)

    Varzatskii, Oleg A; Penkova, Larysa V; Kats, Svitlana V; Dolganov, Alexander V; Vologzhanina, Anna V; Pavlov, Alexander A; Novikov, Valentin V; Bogomyakov, Artem S; Nemykin, Victor N; Voloshin, Yan Z

    2014-03-17

    Chloride ion-aided one-pot template self-assembly of a mixed pyrazoloxime ligand with phenylboronic acid on a corresponding metal(II) ion as a matrix afforded the first boron-capped zinc, cobalt, iron, and manganese pseudoclathrochelate tris-pyrazoloximates. The presence of a pseudocross-linking hydrogen-bonded chloride ion is critical for their formation, as the same chloride-capped complexes were isolated even in the presence of large excesses of bromide and iodide ions. As revealed by X-ray diffraction, all complexes are capped with a chloride ion via three N-H···Cl hydrogen bonds that stabilize their pseudomacrobicyclic frameworks. The MN6 coordination polyhedra possess a distorted trigonal prismatic geometry, with the distortion angles φ between their nonequivalent N3 bases of approximately 0°. Temperature dependences of the effective magnetic moment for the paramagnetic complexes showed the encapsulated metal(II) ions to be in a high-spin state in the temperature range of 2-300 K. In the case of the iron(II) pseudoclathrochelate, density functional theory (DFT) and time-dependent DFT calculations were used to assess its spin state as well as the (57)Fe Mössbauer and UV-vis-NIR parameters. Cyclic voltammetry studies performed for these pseudomacrobicyclic complexes showed them to undergo irreversible or quasi-reversible metal-localized oxidations and reductions. As no changes are observed in the presence of a substantial excess of bromide ion, no anion-exchange reaction occurs, and thus the pseudoclathrochelates have a high affinity toward chloride anions in solution.

  4. T-type Ca(2+) channel modulation by otilonium bromide.

    Science.gov (United States)

    Strege, Peter R; Sha, Lei; Beyder, Arthur; Bernard, Cheryl E; Perez-Reyes, Edward; Evangelista, Stefano; Gibbons, Simon J; Szurszewski, Joseph H; Farrugia, Gianrico

    2010-05-01

    Antispasmodics are used clinically to treat a variety of gastrointestinal disorders by inhibition of smooth muscle contraction. The main pathway for smooth muscle Ca(2+) entry is through L-type channels; however, there is increasing evidence that T-type Ca(2+) channels also play a role in regulating contractility. Otilonium bromide, an antispasmodic, has previously been shown to inhibit L-type Ca(2+) channels and colonic contractile activity. The objective of this study was to determine whether otilonium bromide also inhibits T-type Ca(2+) channels. Whole cell currents were recorded by patch-clamp technique from HEK293 cells transfected with cDNAs encoding the T-type Ca(2+) channels, Ca(V)3.1 (alpha1G), Ca(V)3.2 (alpha1H), or Ca(V)3.3 (alpha1I) alpha subunits. Extracellular solution was exchanged with otilonium bromide (10(-8) to 10(-5) M). Otilonium bromide reversibly blocked all T-type Ca(2+) channels with a significantly greater affinity for Ca(V)3.3 than Ca(V)3.1 or Ca(V)3.2. Additionally, the drug slowed inactivation in Ca(V)3.1 and Ca(V)3.3. Inhibition of T-type Ca(2+) channels may contribute to inhibition of contractility by otilonium bromide. This may represent a new mechanism of action for antispasmodics and may contribute to the observed increased clinical effectiveness of antispasmodics compared with selective L-type Ca(2+) channel blockers.

  5. T-type Ca2+ channel modulation by otilonium bromide

    Science.gov (United States)

    Strege, Peter R.; Sha, Lei; Beyder, Arthur; Bernard, Cheryl E.; Perez-Reyes, Edward; Evangelista, Stefano; Gibbons, Simon J.; Szurszewski, Joseph H.

    2010-01-01

    Antispasmodics are used clinically to treat a variety of gastrointestinal disorders by inhibition of smooth muscle contraction. The main pathway for smooth muscle Ca2+ entry is through L-type channels; however, there is increasing evidence that T-type Ca2+ channels also play a role in regulating contractility. Otilonium bromide, an antispasmodic, has previously been shown to inhibit L-type Ca2+ channels and colonic contractile activity. The objective of this study was to determine whether otilonium bromide also inhibits T-type Ca2+ channels. Whole cell currents were recorded by patch-clamp technique from HEK293 cells transfected with cDNAs encoding the T-type Ca2+ channels, CaV3.1 (α1G), CaV3.2 (α1H), or CaV3.3 (α1I) alpha subunits. Extracellular solution was exchanged with otilonium bromide (10−8 to 10−5 M). Otilonium bromide reversibly blocked all T-type Ca2+ channels with a significantly greater affinity for CaV3.3 than CaV3.1 or CaV3.2. Additionally, the drug slowed inactivation in CaV3.1 and CaV3.3. Inhibition of T-type Ca2+ channels may contribute to inhibition of contractility by otilonium bromide. This may represent a new mechanism of action for antispasmodics and may contribute to the observed increased clinical effectiveness of antispasmodics compared with selective L-type Ca2+ channel blockers. PMID:20203058

  6. 40 CFR 180.519 - Bromide ion and residual bromine; tolerances for residues.

    Science.gov (United States)

    2010-07-01

    ... 40 Protection of Environment 23 2010-07-01 2010-07-01 false Bromide ion and residual bromine... Tolerances § 180.519 Bromide ion and residual bromine; tolerances for residues. (a) General. The food additives, bromide ion and residual bromine, may be present in water, potable in accordance with...

  7. Uptake of ozone to mixed sodium bromide/ citric acid solutions

    Science.gov (United States)

    Lee, Ming-Tao; Steimle, Emilie; Bartels-Rausch, Thorsten; Kato, Shunsuke; Lampimäki, Markus; Brown, Matthew; van Bokhoven, Jeroen; Nolting, Frithjof; Kleibert, Armin; Türler, Andreas; Ammann, Markus

    2013-04-01

    Sea-salt solution - air interfaces play an important role in the chemistry of the marine boundary layer. The reaction of ozone (O3) with bromide is of interest in the context of formation of photolabile halogens (Br2, BrCl) in the marine boundary layer. Recent experiments have suggested that the bromide oxidation rate is related to the surface concentration of bromide [1] and inversely related to the gas phase concentration of O3, an indication for a precursor mediated reaction at the surface [2]. So far, the effect of organics (such as those occurring at the ocean surface or in marine aerosols) on the reaction of O3 with bromide aerosols has not been studied yet. In our study we investigate the uptake kinetics of O3 to a mixed solution of sodium bromide (NaBr) and citric acid (CA), which represents highly oxidized organic compounds present in the environment, with a well-established coated wall flow tube technique, which leads to exposure of the film to O3 allowing the heterogeneous reactions to take place and the loss of O3 being measured. The results indicate that the uptake of O3 to the films with the higher bromide concentrations (0.34M and 4M) is independent of the gas phase concentration and roughly consistent with uptake limited by reaction in the bulk. For the lower bromide concentration (84mM), however, we observe a trend of the uptake coefficient to decrease with increasing O3 concentration, indicating an increasing importance of a surface reaction. In an attempt to constrain the kinetic data, we employed X-ray photoelectron spectroscopy (XPS) to get insight into the surface composition of the aqueous solution - air interface. Previous XPS studies have shown that halide ion concentrations are enhanced at the aqueous solution air interface [3-4], which likely promotes the surface reactions of bromide or iodide with O3. A first XPS study of ternary solutions of KI with butanol indicated the importance of specific interactions of the cation with the alcohol

  8. Synthesis, characterization and antibacterial properties of dihydroxy quaternary ammonium salts with long chain alkyl bromides.

    Science.gov (United States)

    Liu, Wen-Shuai; Wang, Chun-Hua; Sun, Ju-Feng; Hou, Gui-Ge; Wang, Yu-Peng; Qu, Rong-Jun

    2015-01-01

    Five N-methyl-N-R-N,N-bis(2-hydroxyethyl) ammonium bromides (R = -benzyl (chloride, BNQAS), -dodecyl (C12QAS), -tetradecyl (C14QAS), -hexadecyl (C16QAS), -octadecyl (C18QAS)) were prepared based on N-methyldiethanolamine (MDEA) and halohydrocarbon. Five QAS were characterized by FTIR, NMR, and MS. BNQAS, C12QAS, C14QAS, and C16QAS were confirmed by X-ray single-crystal diffraction. Their antibacterial properties indicated good antibacterial abilities against E. coli, S. aureus, B. subtilis, especially C12QAS with the best antibacterial ability (100% to E. coli, 95.65% to S. aureus, and 91.41% to B. subtilis). In addition, C12QAS also displayed the best antifungal activities than BNQAS and C18QAS against Cytospora mandshurica, Botryosphaeria ribis, Physalospora piricola, and Glomerella cingulata with the ratio of full marks. The strategy provides a facile way to design and develop new types of antibacterial drugs for application in preventing the fruit rot, especially apple. © 2014 John Wiley & Sons A/S.

  9. Removal of nitrate from aqueous solution using cetylpyridinium bromide (CPB) modified zeolite as adsorbent

    Energy Technology Data Exchange (ETDEWEB)

    Zhan Yanhui [State Key Laboratory of Pollution Control and Resource Reuse, Tongji University, Shanghai 200092 (China); Lin Jianwei, E-mail: jwlin@shou.edu.cn [College of Marine Science, Shanghai Ocean University, No. 999 Hucheng Huan Road, Pudong District, Shanghai 201306 (China); Zhu Zhiliang [State Key Laboratory of Pollution Control and Resource Reuse, Tongji University, Shanghai 200092 (China)

    2011-02-28

    Surfactant modified zeolites (SMZ) with different coverage types were prepared by loading the cetylpyridinium bromide (CPB) onto the surface of the natural zeolites. The adsorption behavior of nitrate on SMZ was investigated. Natural zeolite and SMZ with monolayer CPB coverage were inefficient for the removal of nitrate from aqueous solution. However, SMZ with patchy bilayer or bilayer CPB coverage was efficient in nitrate removal, and the nitrate adsorption capacity of SMZ increased with its CPB loading. For typical SMZ with bilayer CPB coverage, the nitrate adsorption process was well described by the pseudo-second-order kinetic model, and the experimental isotherm data fitted well with the Langmuir, Freundlich and Dubinin-Redushkevich isotherm models. Thermodynamic parameters such as Gibbs free energy change, enthalpy change and entropy change were calculated and the results showed that the adsorption of nitrate on SMZ was spontaneous and exothermic in nature. The presence of competing anions such as chloride, sulfate and bicarbonate ions slightly reduced the nitrate adsorption efficiency. Anionic exchange and electrostatic interaction were proven to be the main mechanisms that govern the adsorption of nitrate on SMZ.

  10. Removal of nitrate from aqueous solution using cetylpyridinium bromide (CPB) modified zeolite as adsorbent.

    Science.gov (United States)

    Zhan, Yanhui; Lin, Jianwei; Zhu, Zhiliang

    2011-02-28

    Surfactant modified zeolites (SMZ) with different coverage types were prepared by loading the cetylpyridinium bromide (CPB) onto the surface of the natural zeolites. The adsorption behavior of nitrate on SMZ was investigated. Natural zeolite and SMZ with monolayer CPB coverage were inefficient for the removal of nitrate from aqueous solution. However, SMZ with patchy bilayer or bilayer CPB coverage was efficient in nitrate removal, and the nitrate adsorption capacity of SMZ increased with its CPB loading. For typical SMZ with bilayer CPB coverage, the nitrate adsorption process was well described by the pseudo-second-order kinetic model, and the experimental isotherm data fitted well with the Langmuir, Freundlich and Dubinin-Redushkevich isotherm models. Thermodynamic parameters such as Gibbs free energy change, enthalpy change and entropy change were calculated and the results showed that the adsorption of nitrate on SMZ was spontaneous and exothermic in nature. The presence of competing anions such as chloride, sulfate and bicarbonate ions slightly reduced the nitrate adsorption efficiency. Anionic exchange and electrostatic interaction were proven to be the main mechanisms that govern the adsorption of nitrate on SMZ.

  11. A universal procedure for the [¹⁸F]trifluoromethylation of aryl iodides and aryl boronic acids with highly improved specific activity.

    Science.gov (United States)

    van der Born, Dion; Sewing, Claudia; Herscheid, J Koos D M; Windhorst, Albert D; Orru, Romano V A; Vugts, Danielle J

    2014-10-06

    Herein, we describe a valuable method for the introduction of the [(18)F]CF3 group into arenes with highly improved specific activity by the reaction of [(18)F]trifluoromethane with aryl iodides or aryl boronic acids. This [(18)F]trifluoromethylation reaction is the first to be described in which the [(18)F]CF3 products are generated in actual trace amounts and can therefore effectively be used as PET tracers. The method shows broad scope with respect to possible aryl iodide and aryl boronic acid substrates, as well as good to excellent conversion. In particular, the [(18)F]trifluoromethylation of boronic acids was found to outperform [(18)F]trifluoromethylation reactions of halogenated aryl precursors with regard to conversion, reaction conditions, and kinetics. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  12. Synthesis and Crystal Structures of Azolo[b]1,3,4-Thiadiazinium Bromides

    Directory of Open Access Journals (Sweden)

    Gerhard Laus

    2014-12-01

    Full Text Available Three azolo[b]1,3,4-thiadiazinium bromides were prepared from the respective N-amino-N'-methylazolethiones and phenacyl bromide, and their crystal structures were determined. 6-Phenyl-1-methylimidazo[2,1-b]1,3,4-thiadiazinium bromide (1 crystallized as methanol solvate (P21/n, 6-phenyl-1-methyl-1,2,4-triazolo[3,4-b]1,3,4-thiadiazinium bromide (2 as hemi-ethanol solvate (P21/n, and 6-phenyl-1-methyl-1,2,4-triazolo[3,2-b]1,3,4-thiadiazinium bromide (3 solvent-free (P21/c. Interionic contacts were identified.

  13. Synthesis and Thermal Crosslinking Behavior of Poly(aryl ether ketone)s Containing 1,4-Naphthalene Moieties

    Institute of Scientific and Technical Information of China (English)

    NIU Ya-ming; ZHANG Yun-he; CHEN Xing-bo; WANG Gui-bin; JIANG Zhen-hua

    2005-01-01

    A new monomer, 1,4-bis(4-fluorobenzoyl) naphthalene(compound 2) was synthesized via a two-step reaction. 1,4-Naphthalenedicarboxylic acid chloride(compound 1) was prepared by using the acyl chlorization reaction of 1,4-naphthalenedicarboxylic acid with thionyl chloride. The Friedel-Crafts acylation of compound 1 with fluorobenzene afforded compound 2 in a 80% yield. The polycondensation of compound 2 with various bisphenols in tetramethylene sulfone(TMS) in the presence of excess potassium carbonate as a condensation reagent was carried out at 210 ℃ to quantitatively afford the corresponding poly(aryl ether ketone)s(compounds 3_8) containing 1,4-naphthalene moieties. Thermal analyses showed that the polymers have Tg values ranging from 496 to 500 K and are thermally stable in air with initial mass loss above 500 ℃. These novel polymers exhibited an excellent solubility in organic solvents including NMP, DMAc, and chloroform, etc. In addition, the glass transition temperatures of these polymers increased and the polymers became insoluble in chloroform after treated at 260 ℃, indicating the occurrence of a thermal crosslinking reaction.

  14. Palladium-catalyzed direct arylation and cyclization of o-iodobiaryls to a library of tetraphenylenes

    Science.gov (United States)

    Zhu, Chendan; Zhao, Yue; Wang, Di; Sun, Wei-Yin; Shi, Zhuangzhi

    2016-09-01

    Aryl–aryl bond formation constitutes one of the most important subjects in organic synthesis. The recent developments in direct arylation reactions forming aryl–aryl bond have emerged as very attractive alternatives to traditional cross-coupling reactions. Here, we describe a general palladium-catalyzed direct arylation and cyclization of o-iodobiaryls to build a library of tetraphenylenes. This transformation represents one of the very few examples of C-H activation process that involves simultaneous formation of two aryl–aryl bonds. Oxygen plays a vital role by ensuring high reactivity, with air as the promoter furnished the best results. We anticipate this ligand-free and aerobic catalytic system will simplify the synthesis of tetraphenylenes as many of the reported methods involve use of preformed organometallic reagents and will lead to the discovery of highly efficient new direct arylation process.

  15. Studies Update Vinyl Chloride Hazards.

    Science.gov (United States)

    Rawls, Rebecca

    1980-01-01

    Extensive study affirms that vinyl chloride is a potent animal carcinogen. Epidemiological studies show elevated rates of human cancers in association with extended contact with the compound. (Author/RE)

  16. Parameters Affecting Hydrogen Chloride Measurements

    Science.gov (United States)

    1993-06-01

    contain sea salt, which is hygroscopic because of the magnesium chloride present, or ammonium bisulfate , which mostly comes from sulfur pollution and is...boosters release hydrogen chloride as a combustion product, and hydrazines or nitric acid can be spilled from liquid fuel motors. Monitoring the...solubility constant, and the second is the acid ionization constant. From experimental work, the product of the two constants is well established (Reference

  17. Diversification of indoles via microwave-assisted ligand-free copper-catalyzed N-arylation

    Energy Technology Data Exchange (ETDEWEB)

    Kwon, Jae Kwan; Lee, Jin Hee; Kim, Tae Sung; Yum, Eul Kgun [Dept. of Chemistry, Chu ngnam National University, Daejon (Korea, Republic of); Park, Jee Jung [Western Seoul Center Korea Basic Science Institute, Seoul (Korea, Republic of)

    2016-12-15

    A simple, efficient Cu{sub 2}O catalyst system under microwave irradiation was developed for N-arylation of various indoles without ligands and additives. Diverse N-heteroarylated indoles were prepared by coupling indoles with various heteroaryl halides within 1 h. The selective reactivity of bromoindole with aryl iodide provided N-aryl bromoindoles, which could be useful intermediates for palladium-catalyzed Heck and Suzuki coupling reactions.

  18. Nickel-catalyzed cross-coupling of aryl phosphates with arylboronic acids.

    Science.gov (United States)

    Chen, Hu; Huang, Zhongbin; Hu, Xiaoming; Tang, Guo; Xu, Pengxiang; Zhao, Yufen; Cheng, Chien-Hong

    2011-04-01

    The Suzuki-Miyaura cross-coupling of aryl phosphates using Ni(PCy(3))(2)Cl(2) as an inexpensive, bench-stable catalyst is described. Broad substrate scope and high efficiency are demonstrated by the syntheses of more than 40 biaryls and by constructing complex organic molecules. The poor reactivity of aryl phosphates relative to aryl halides is successfully employed to construct polyarenes by selective cross-coupling using Pd and Ni catalysts.

  19. Cul/8-Hydroxyquinalidine Promoted N-Arylation of Indole and Azoles

    Institute of Scientific and Technical Information of China (English)

    杨新业; 邢辉; 张烨; 赖宜生; 张奕华; 蒋咏文; 马大为

    2012-01-01

    An efficient catalytic system of CuI/8-hydroxyquinalidine was developed for the coupling of aryl iodides and indole as well as some azoles. The reaction could be carried out at 90 ~C under the condition of relatively low cata- lyst loading, affording various N-arylindoles and N-aryl azoles in good yields. The functionalized and hindered aryl iodides were suitable substrates for this transformation.

  20. Chloride channels in stroke

    Institute of Scientific and Technical Information of China (English)

    Ya-ping ZHANG; Hao ZHANG; Dayue Darrel DUAN

    2013-01-01

    Vascular remodeling of cerebral arterioles,including proliferation,migration,and apoptosis of vascular smooth muscle cells (VSMCs),is the major cause of changes in the cross-sectional area and diameter of the arteries and sudden interruption of blood flow or hemorrhage in the brain,ie,stroke.Accumulating evidence strongly supports an important role for chloride (Clˉ) channels in vascular remodeling and stroke.At least three Clˉ channel genes are expressed in VSMCs:1) the TMEM16A (or Ano1),which may encode the calcium-activated Clˉ channels (CACCs); 2) the CLC-3 Clˉ channel and Clˉ/H+ antiporter,which is closely related to the volume-regulated Clˉ channels (VRCCs); and 3) the cystic fibrosis transmembrane conductance regulator (CFTR),which encodes the PKA-and PKC-activated Clˉ channels.Activation of the CACCs by agonist-induced increase in intracellular Ca2+ causes membrane depolarization,vasoconstriction,and inhibition of VSMC proliferation.Activation of VRCCs by cell volume increase or membrane stretch promotes the production of reactive oxygen species,induces proliferation and inhibits apoptosis of VSMCs.Activation of CFTR inhibits oxidative stress and may prevent the development of hypertension.In addition,Clˉ current mediated by gammaaminobutyric acid (GABA) receptor has also been implicated a role in ischemic neuron death.This review focuses on the functional roles of Clˉ channels in the development of stroke and provides a perspective on the future directions for research and the potential to develop Clˉ channels as new targets for the prevention and treatment of stroke.

  1. Comparison of Heat and Bromide as Ground Water Tracers Near Streams

    Science.gov (United States)

    Constantz, J.; Cox, M.H.; Su, G.W.

    2003-01-01

    Heat and bromide were compared as tracers for examining stream/ground water exchanges along the middle reaches of the Santa Clara River, California, during a 10-hour surface water sodium bromide injection test. Three cross sections that comprise six shallow (sodium bromide injection test. Vertical, one-dimensional simulations of bromide concentrations in the sediments yielded a good match to the observed bromide concentrations, without adjustment of any model parameters except solute dispersivities. This indicates that, for the spatial and temporal scales examined on the Santa Clara River, the use of heat and bromide as tracers provide comparable information with respect to apparent hydraulic conductivities and fluxes for sediments near streams. In other settings, caution should be used due to differences in the nature of conservative (bromide) versus nonconservative (heat) tracers, particularly when preferential flowpaths are present.

  2. Menthone aryl acid hydrazones: a new class of anticonvulsants.

    Science.gov (United States)

    Jain, Jainendra; Kumar, Y; Sinha, Reema; Kumar, Rajeev; Stables, James

    2011-01-01

    A series of ten compounds (Compounds J(1)-J(10)) of (±) 3-menthone aryl acid hydrazone was synthesized and characterized by thin layer chromatography and spectral analysis. Synthesized compounds were evaluated for anticonvulsant activity after intraperitoneal (i.p) administration to mice by maximal electroshock (MES) and subcutaneous pentylenetetrazole (scPTZ) induced seizure method and minimal clonic seizure test. Minimal motor impairment was also determined for these compounds. Results obtained showed that four compounds out of ten afforded significant protection in the minimal clonic seizure screen at 6 Hz. Compound J(6), 4-Chloro-N-(2-isopropyl-5-methylcyclohexylidene) benzohydrazide was found to be the most active compound with MES ED(50) of 16.1 mg/kg and protective index (pI) of greater than 20, indicating that (±) 3-menthone aryl acid hydrazone possesses better and safer anticonvulsant properties than other reported menthone derivatives viz. menthone Schiff bases, menthone semicarbazides and thiosemicarbazides.

  3. New 1-Aryl-3-Substituted Propanol Derivatives as Antimalarial Agents

    Directory of Open Access Journals (Sweden)

    Antonio Monge

    2009-10-01

    Full Text Available This paper describes the synthesis and in vitro antimalarial activity against a P. falciparum 3D7 strain of some new 1-aryl-3-substituted propanol derivatives. Twelve of the tested compounds showed an IC50 lower than 1 μM. These compounds were also tested for cytotoxicity in murine J774 macrophages. The most active compounds were evaluated for in vivo activity against P. berghei in a 4-day suppressive test. Compound 12 inhibited more than 50% of parasite growth at a dose of 50 mg/kg/day. In addition, an FBIT test was performed to measure the ability to inhibit ferriprotoporphyrin biocrystallization. This data indicates that 1-aryl-3-substituted propanol derivatives hold promise as a new therapeutic option for the treatment of malaria.

  4. Study of ferroelectric characteristics of diisopropylammonium bromide films

    Science.gov (United States)

    Thirmal, C.; Biswas, P. P.; Shin, Y. J.; Noh, T. W.; Giridharan, N. V.; Venimadhav, A.; Murugavel, P.

    2016-09-01

    Organic molecular ferroelectrics are highly desirable due to their numerous advantages. In the present work, a thick film of diisopropylammonium bromide organic molecular ferroelectric is fabricated on the ITO/glass substrate. The grown film shows preferential orientation along the c-axis with a ferroelectric transition at 419 K. The piezoresponse force microscopic measurements are done in a dual ac resonance tracking mode for its switching characteristics. The amplitude and phase images of the oppositely written domain patterns exhibit a clear contrast with 180° phase difference. The dynamical spectroscopic studies reveal a butterfly loop in amplitude and hysteretic character of the phase which are the expected characteristics features of ferroelectrics. In addition, the macroscopic polarization versus electric field hysteresis gives an additional proof for ferroelectric character of the film with the maximum polarization of 3.5 μC/cm2. Overall, we have successfully fabricated diisopropylammonium bromide organic films and demonstrated its room temperature ferroelectric characteristics.

  5. A novel and robust conditioning lesion induced by ethidium bromide.

    Science.gov (United States)

    Hollis, Edmund R; Ishiko, Nao; Tolentino, Kristine; Doherty, Ernest; Rodriguez, Maria J; Calcutt, Nigel A; Zou, Yimin

    2015-03-01

    Molecular and cellular mechanisms underlying the peripheral conditioning lesion remain unsolved. We show here that injection of a chemical demyelinating agent, ethidium bromide, into the sciatic nerve induces a similar set of regeneration-associated genes and promotes a 2.7-fold greater extent of sensory axon regeneration in the spinal cord than sciatic nerve crush. We found that more severe peripheral demyelination correlates with more severe functional and electrophysiological deficits, but more robust central regeneration. Ethidium bromide injection does not activate macrophages at the demyelinated sciatic nerve site, as observed after nerve crush, but briefly activates macrophages in the dorsal root ganglion. This study provides a new method for investigating the underlying mechanisms of the conditioning response and suggests that loss of the peripheral myelin may be a major signal to change the intrinsic growth state of adult sensory neurons and promote regeneration.

  6. Aluminium Electroplating on Steel from a Fused Bromide Electrolyte

    Energy Technology Data Exchange (ETDEWEB)

    Prabhat Tripathy; Laura Wurth; Eric Dufek; Toni Y. Gutknecht; Natalie Gese; Paula Hahn; Steven Frank; Guy Fredrickson; J Stephen Herring

    2014-08-01

    A quaternary bromide bath (LiBr-KBr-CsBr-AlBr3) was used to electro-coat aluminium on steel substrates. The electrolyte was prepared by the addition of AlBr3 into the eutectic LiBr-KBr-CsBr melt. A smooth, thick, adherent and shiny aluminium coating could be obtained with 80 wt.% AlBr3 in the ternary melt. The SEM photographs of the coated surfaces suggest the formation of thick and dense coatings with good aluminium coverage. Both salt immersion and open circuit potential measurement suggest that the coatings did display good corrosion-resistance behavior. Annealing of the coated surfaces, prior to corrosion tests, suggested the robustness of the metallic aluminium coating in preventing the corrosion of the steel surfaces. Studies also indicated that the quaternary bromide plating bath can potentially provide a better aluminium coating on both ferrous and non-ferrous metals, including complex surfaces/geometries.

  7. Preparation of ethyl magnesium bromide for regiospecific analysis of triacylglycerols.

    Science.gov (United States)

    Ando, Yasuhiro; Tomita, Yuki; Haba, Yusuke

    2008-01-01

    This paper presents a procedure for preparation of a Grignard reagent, ethyl magnesium bromide, used for partial deacylation of triacylglycerols (TAG) in their regiospecific analysis. Magnesium turnings were reacted with ethereal solution of bromoethane in a screw-capped test tube to synthesize 2 mL of 1 M ethyl magnesium bromide. Continuously stirred with a vortex mixer, the reaction smoothly proceeded at room temperature. Regiospecific analysis of 1,3-distearoyl-2-oleoylglycerol using this product showed that fatty acid compositions of the sn-1(3) and sn-2 positions were contaminated by less than 2 mol% of fatty acids migrated from isomeric positions. The analyses of lard and cod liver/mackerel oil TAG showed typical distribution patterns of 16:0, 22:5n-3 and 22:6n-3 in pig and fish depot TAG. These results confirmed the view that the freshly prepared reagent is usable for regiospecific analysis of TAG.

  8. 21 CFR 184.1138 - Ammonium chloride.

    Science.gov (United States)

    2010-04-01

    ... 21 Food and Drugs 3 2010-04-01 2009-04-01 true Ammonium chloride. 184.1138 Section 184.1138 Food... Specific Substances Affirmed as GRAS § 184.1138 Ammonium chloride. (a) Ammonium chloride (NH4Cl, CAS Reg. No. 12125-02-9) is produced by the reaction of sodium chloride and an ammonium salt in solution....

  9. Antibacterial Activity of Cetyltrimethylammonium Bromide Modified Silver-Bentonite

    OpenAIRE

    Nik Malek Nik Ahmad Nizam; Azalisa Wan Nur; Yieh Lin Clara Chong

    2016-01-01

    Organo-Ag-bentonite was prepared by the attachment of cationic surfactant cetyltrimethylammonium bromide on silver(A)g-exchanged bentonite. The prepared samples were characterized by X-ray diffraction (XRD), Fourier transform infrared (FTIR) spectroscopy and energy dispersive X-ray (EDX) analysis and antibacterial assay was performed against Escherichia coli in different percentage of saline solutions through minimum inhibition concentration (MIC) method. Organo-Ag-bentonite showed higher ant...

  10. Transformation of bromide in thermo activated persulfate oxidation processes.

    Science.gov (United States)

    Lu, Junhe; Wu, Jinwei; Ji, Yuefei; Kong, Deyang

    2015-07-01

    Sulfate radicals ( [Formula: see text] ) are applied to degrade various organic pollutants. Due to its high oxidative potential, [Formula: see text] is presumed to be able to transform bromide to reactive bromine species that can react with natural organic matter subsequently to form brominated products including brominated disinfection by-products (Br-DBPs). This research was designed to investigate the transformation of bromide in thermo activated persulfate oxidation process in the presence of humic acid (HA). Significant formation of bromoform and bromoacetic acids was verified. Their formation was attributed to the reactions of HA and reactive bromine species including Br·, [Formula: see text] HOBr(-), and free bromine resulted from the oxidation of bromide by [Formula: see text] . Yields of Br-DBPs increased monotonically at persulfate concentration of 1.0 mM and working temperature of 70 °C. However, the time-depended formation exhibited an increasing and the decreasing profile when persulfate was 5.0 mM, suggesting further degradation of organic bromine. HPLC/ICP-MS analysis demonstrated that the organic bromine was eventually transformed to bromate at this condition. Thus, a transformation scheme was proposed in which the bromine could be recycled multiple times between inorganic bromide and organic bromine before being finally transformed to bromate. This is the first study that reveals the comprehensive transformation map of bromine in [Formula: see text] based reaction systems, which should be taken into consideration when such technologies are used to eliminate contamination in real practice.

  11. A Lithium Bromide Absorption Chiller with Cold Storage

    Science.gov (United States)

    2011-01-15

    TO R A G E A LITHIUM BROMIDE ABSORPTION CHILLER WITH COLD STORAGE William Gerstler, et al, General Electric Global Research UNCLASSIFIED UNLIMITED...Research ABSTRACT A LiBr-based absorption chiller can use waste heat or solar energy to produce useful space cooling for small buildings...However, operating this absorption chiller at high ambient tem- peratures may result in performance degradation, crystallization in the absorber, and

  12. COMPARISON OF DROTAVERINE HYDROCHLORIDE AND VALETHAMATE BROMIDE ON CERVICAL DILATATION

    OpenAIRE

    Mallika Selvaraj; Sumathi

    2016-01-01

    AIM To compare the two drugs drotaverine hydrochloride and valethamate bromide and their effects on cervical dilatation and labour duration. METHODOLOGY It is a prospective study undertaken at Government Rajaji Hospital on 150 randomly selected primigravidae patients. RESULTS The duration of active phase of first stage of labour was significantly reduced (p value 0.003), rate of cervical dilatation was higher (p value 0.0001) with drotaverine hydrochloride. CONCLUS...

  13. Antileishmanial, antimicrobial and antifungal activities of some new aryl azomethines.

    Science.gov (United States)

    Al-Kahraman, Yasser M S A; Madkour, Hassan M F; Ali, Dildar; Yasinzai, Masoom

    2010-01-28

    A series of eighteen azomethines has been synthesized by the reaction of appropriate primary aromatic amines with aryl and/or heteroaryl carboxaldehydes. The synthesized azomethines have been evaluated for their in vitro antileishmanial, antibacterial and antifungal activities. The results revealed some antifungal activity of most of the synthesized compounds, whereas the antileishmaniasis activity results highlighted that all synthesized azomethines inhibited parasite growth and most of them showed highly potent action towards Leishmania major promastigotes. No remarkable bactericidal activities were observed.

  14. Palladium- (and nickel-) catalyzed vinylation of aryl halides†

    OpenAIRE

    DENMARK, SCOTT E.; Butler, Christopher R.

    2008-01-01

    Functionalized styrenes are extremely useful building blocks for organic synthesis and for functional polymers. One of the most general syntheses of styrenes involves the combination of an aryl halide with a vinyl organometallic reagent under catalysis by palladium or nickel complexes. This Feature Article provides the first comprehensive summary of the vinylation methods currently available along with a critical comparison of the efficiency, cost and scope of the methods.

  15. Occurrence, Distribution, Sources, and Trends of Elevated Chloride Concentrations in the Mississippi River Valley Alluvial Aquifer in Southeastern Arkansas

    Science.gov (United States)

    Kresse, Timothy M.; Clark, Brian R.

    2008-01-01

    underlies the alluvial aquifer, indicate that leakage from the river and upward flow of saline water in underlying aquifers are not likely sources for the saline water in the alluvial aquifer in Area I. A good comparison was noted for chloride concentrations in Area I and surface geomorphology. In the majority of cases, elevated chloride concentrations occurred in backswamp deposits, with low concentrations (less than 50 milligrams per liter) in areas of active or abandoned channel deposits. The fine-grained, clay-rich deposits associated with backswamp areas likely restrict recharge, induce increased ratios between evapotranspiration and recharge, and experience minimal flushing of salts concentrated during evapotranspiration. In Area II, chloride isoconcentration maps of the underlying upper Claiborne aquifer, in addition to samples from wells completed in the middle and lower Claiborne aquifers, showed a similar chloride distribution to that of the alluvial aquifer with decreasing chloride concentrations to the east of the zone of elevated chloride concentrations, which suggests a deeper source of saline water that affects Tertiary and Quaternary aquifer systems. Mixing curves developed from bromide/chloride ratios in water samples from the alluvial aquifer, Tertiary aquifers, and samples of brine water from the Jurrasic Smackover Formation additionally discounted upward flow of saline water from underlying Tertiary formations as a potential mechanism for salinity in the alluvial aquifer in Area II. A review of information on oil exploration wells in Chicot County revealed that most of these wells were drilled from 1960 to 1980, after the elevated chloride concentrations were detected in the early 1950s. The elongated nature of the zone of elevated chloride concentrations in Area II suggests a line source or linear conduit connection with the source. Maps of a fractured limestone in the Smackover Formation in Arkansas, Mississippi, and Louisiana for purpose

  16. Synthesis and characterization of 5-heteroarylsulfanyl-4-aryl-1,2,3-selena/thiadiazoles

    Indian Academy of Sciences (India)

    Ramaiyan Manikannan; Masilamani Shanmugaraja; Seetharaman Manojveer; Shanmugam Muthusubramanian

    2012-03-01

    Synthesis and spectral characterization of 2-methyl-5-[(4-aryl-1,2,3-selenadiazol-5-yl)sulfanyl]-1,3,4-thiadiazoles, 5-[4-aryl-1,2,3-selenadiazol-5-yl]sulfanyl-1-phenyl-1-1,2,3,4-tetraazoles, 4-aryl-5-[(5-methyl-1,3,4-thiadiazol-2-yl)sulfanyl]-1,2,3-thiadiazole and 5-[4-aryl-1,2,3-thiadiazol-5-yl]sulfanyl-1-phenyl-1-1,2,3,4-tetraazole have been reported.

  17. Synthesis of novel aryl(heteroaryl)sulfonyl ureas of possible biological interest.

    Science.gov (United States)

    Saczewski, Franciszek; Kuchnio, Anna; Samsel, Monika; Łobocka, Marta; Kiedrowska, Agnieszka; Lisewska, Karolina; Saczewski, Jarosław; Gdaniec, Maria; Bednarski, Patrick J

    2010-02-26

    The course of reaction of aryl and heteroaryl sulfonamides with diphenylcarbonate (DPC) and 4-dimethylaminopyridine (DMAP) was found to depend on the pKa of the sulfonamide used. Aryl sulfonamides with pKa approximately 10 gave 4-dimethylamino-pyridinium arylsulfonyl-carbamoylides, while the more acidic heteroaryl sulfonamides (pKa approximately 8) furnished 4-dimethylaminopyridinium heteroarylsulfonyl carbamates. Both the carbamoylides and carbamate salts reacted with aliphatic and aromatic amines with the formation of appropriate aryl(heteroaryl)sulfonyl ureas, and therefore, can be regarded as safe and stable substitutes of the hazardous and difficult to handle aryl(heteroaryl)sulfonyl isocyanates.

  18. Synthesis of Novel Aryl(heteroarylsulfonyl Ureas of Possible Biological Interest

    Directory of Open Access Journals (Sweden)

    Maria Gdaniec

    2010-02-01

    Full Text Available The course of reaction of aryl and heteroaryl sulfonamides with diphenylcarbonate (DPC and 4-dimethylaminopyridine (DMAP was found to depend on the pKa of the sulfonamide used. Aryl sulfonamides with pKa ~ 10 gave 4-dimethylamino-pyridinium arylsulfonyl-carbamoylides, while the more acidic heteroaryl sulfonamides (pKa ~ 8 furnished 4-dimethylaminopyridinium heteroarylsulfonyl carbamates. Both the carbamoylides and carbamate salts reacted with aliphatic and aromatic amines with the formation of appropriate aryl(heteroarylsulfonyl ureas, and therefore, can be regarded as safe and stable substitutes of the hazardous and difficult to handle aryl(heteroarylsulfonyl isocyanates.

  19. Water-solubilization of alkyloxo(methoxo)porphyrinatoantimony bromides.

    Science.gov (United States)

    Matsumoto, Jin; Tanimura, Shin-ichiro; Shiragami, Tsutomu; Yasuda, Masahide

    2009-11-14

    In order to develop water-soluble porphyrins, alkyloxo(methoxo)porphyrinatoantimony bromides (alkyl = hexyl (1a), decyl (1b), dodecyl (1c), tetradecyl (1d), octadecyl (1e)) were prepared. 1 had more than 1 mmol dm(-3) of solubility in water. From the dependence of the half-width of the bands in the absorption spectra and surface tension on the concentration of 1, it was estimated that 1b-d were present as aggregates in concentrations higher than 10 micromol dm(-3). From the NMR analysis in D(2)O, it was deduced that the alkyloxo ligands of 1 were arranged alternately in the aggregates. The diameter of the aggregates of 1 in water was determined to be around 100 nm by the dynamic light scattering method. Since the solubilities of di(methoxo)tetraphenylporphyrinatoantimony bromide and 5-(4'-decyloxyphenyl)-10,15,20-triphenylporphyrinato(dimethoxo)antimony(v) bromide were low, it was calculated that the long alkyl axial ligands were requisite for the high solubility in water.

  20. Conservative tracer bromide inhibits pesticide mineralisation in soil.

    Science.gov (United States)

    Bech, Tina B; Rosenbom, Annette E; Sørensen, Sebastian R; Jacobsen, Carsten S

    2017-03-01

    Bromide is a conservative tracer that is often applied with non-conservative solutes such as pesticides to estimate their retardation in the soil. It has been applied in concentrations of up to 250 g Br L(-1), levels at which the growth of single-celled organisms can be inhibited. Bromide applications may therefore affect the biodegradation of non-conservative solutes in soil. The present study investigated the effect of potassium bromide (KBr) on the mineralisation of three pesticides - glyphosate, MCPA and metribuzin - in four agricultural A-horizon soils. KBr was added to soil microcosms at concentrations of 0, 0.5, 2.5 and 5 g Br(-) L(-1) in the soil solution. The study concluded that KBr had a negative effect on pesticide mineralisation. The inhibitory effect varied depending on the KBr concentration, the type of pesticide and the type of soil. Furthermore, 16 S amplicon sequencing revealed that the KBr treatment generally reduced the abundance of bacteroidetes and proteobacteria on both an RNA and DNA level. Therefore, in order to reduce the effect of KBr on the soil bacterial community and consequently also on xenobiotic degradation, it is recommended that KBr be applied in a concentration that does not exceed 0.5 g Br(-) L(-1) in the soil water.

  1. Structural, vibrational and theoretical studies of L-histidine bromide

    Science.gov (United States)

    Ahmed, A. Ben; Feki, H.; Abid, Y.; Boughzala, H.; Mlayah, A.

    2008-10-01

    This paper presents the results of our calculations of the geometric parameters, vibrational spectra and hyperpolarizability of a non linear optical material, L-histidine bromide. Due to the lack of sufficiently precise information on the geometric structure available in literature, theoretical calculations were preceded by re-determination of the crystal X-ray structure. Single crystals of L-histidine bromide have been grown by slow evaporation of an aqueous solution at room temperature. The compound crystallizes in the non-Centro symmetric space group P2 12 12 1 of the orthorhombic system. Raman spectra have been recorded in the range [200-3500 cm -1]. All observed vibrational bands have been discussed and assigned to normal mode or to combinations and overtones on the basis of our calculations. The optimized geometric bond lengths and bond angles obtained by using HF and DFT (B3LYP and BLYP) show good agreement with the experimental data. Comparison between the measured and the calculated vibrational frequencies indicate that B3LYP is superior to the scaled HF approach for molecular vibrational problems. To investigate microscopic second order non linear optical properties of L-histidine bromide, the electric dipole μ, the polarizability α and the hyperpolarizability β were computed using DFT//B3LYP/6-31G(d) method. According to our calculations, the title compound exhibits non-zero β value revealing microscopic second order NLO behaviour.

  2. Oral teratogenicity studies of methyl bromide in rats and rabbits.

    Science.gov (United States)

    Kaneda, M; Hojo, H; Teramoto, S; Maita, K

    1998-05-01

    Teratogenicity studies of methyl bromide, a widely used fumigant, were conducted in rats and rabbits. Methyl bromide was dissolved in corn oil and administered orally to groups of 24 copulated female Crj:CD (SD) rats at dose levels of 0 (corn oil), 3, 10 or 30 mg/kg/day on days 6-15 of gestation and to groups of 18 artificially inseminated female Kbl:JW rabbits at 0, 1, 3 or 10 mg/kg/day on days 6-18 of gestation. Maternal rats and rabbits were euthanized on respective days 20 and 27 of gestation. Foetuses were examined for survival, growth and teratological alterations. Maternal toxicity was evident in the high-dose groups for both species. In these groups, maternal body weight gains and food consumption were significantly decreased during the dosing and post-dosing periods. Necropsy of maternal rats also revealed erosive lesions in the stomach and the surrounding organs. However, no treatment-related adverse effects were found in foetuses of the treated groups for both rat and rabbit studies. These results led to the conclusion that methyl bromide was not foetotoxic or teratogenic to rat and rabbit foetuses up to dose levels of 30 and 10 mg/kg/day, respectively, at which maternal toxicity was evident for both species.

  3. 46 CFR 151.50-34 - Vinyl chloride (vinyl chloride monomer).

    Science.gov (United States)

    2010-10-01

    ... 46 Shipping 5 2010-10-01 2010-10-01 false Vinyl chloride (vinyl chloride monomer). 151.50-34... chloride (vinyl chloride monomer). (a) Copper, aluminum, magnesium, mercury, silver, and their alloys shall... equipment that may come in contact with vinyl chloride liquid or vapor. (b) Valves, flanges, and...

  4. 40 CFR 61.65 - Emission standard for ethylene dichloride, vinyl chloride and polyvinyl chloride plants.

    Science.gov (United States)

    2010-07-01

    ... dichloride, vinyl chloride and polyvinyl chloride plants. 61.65 Section 61.65 Protection of Environment... AIR POLLUTANTS National Emission Standard for Vinyl Chloride § 61.65 Emission standard for ethylene dichloride, vinyl chloride and polyvinyl chloride plants. An owner or operator of an ethylene...

  5. 含芳酯侧基聚芳醚酮的合成与性能%SYNTHESIS AND PROPERTIES OF POLY(ARYL ETHER KETONE) S CONTAINING PENDANT ARYL ESTER GROUPS

    Institute of Scientific and Technical Information of China (English)

    宋琤; 余雯雯; 钟鸣; 祝志芳; 易志群; 宋才生

    2011-01-01

    以偏苯三甲酸酐酰氯(TMAc),对苯二甲酰氯(TPC),1,4-二(4-苯氧基苯甲酰基)苯(p-EKKE)为单体,采用亲电溶液共缩聚,通过改变TMAc、TPC的摩尔比,制备了系列含羧基侧基的聚芳醚酮树脂(PEK-A).在对甲苯磺酸催化下与苯酚进行酯化反应合成了系列主链带芳酯侧基的聚芳醚酮树脂(PEK-COO-Ar).用红外光谱(FTIR),广角X射线衍射(WAXD),热失重(TGA),示差量热扫描(DSC)等技术对聚合物的结构和性能进行表征,考察了聚合物的溶解性能.结果表明,随着主链中芳酯侧基比例的增加,聚合物的Tg提高(195~219℃),而Tm降低.当TPC/TMAc摩尔比小于1∶1时,树脂呈非晶态结构.当TPC/TMAc摩尔比为50/50和60/40时,树脂经等温结晶后,具有优良的机械力学性能.%A series of novel poly (aryl ether ketone)s containing pendant aryl ester groups (PEK-COO-Ar)were prepared from poly( aryl ether ketone)s containing pendant carboxyl acid groups (PEK-A) and phenol in the presence of 1,1,2,2-tetrachloroethane and by using p-toluenesulfonic acid as a catalyst. The PEK-A was synthesized from trimellitic anhydride chloride ( TMAc ), terephthaloyl chloride ( TPC ) and 1,4-bis ( 4-phenoxybenzoyl) benzene (p-EKKE) by low temperature solution poly-condensation. By changing the molar ratio of TMAc and TPC a series of PEK-A polymers were prepared. The PEK-COO-Ars were characterized by Fourier transform infrared spectroscopy ( FTIR ) , wide-angle X-ray diffraction ( WAXD ) , thermal gravimetric analysis (TGA) and differential scanning calorimetry (DSC). The results showed that the glass transition temperature (Ts ) of the PEK-COO-Ar was in the range of 195 ~ 219℃ and the decomposition temperature (Td) at 5% weight loss was from 416℃ to 447℃ and the melting temperature (Tm) was between 325℃ and 345℃. The Ts of the PEK-COO-Ar increased by increasing the mole ratio of aryl ester groups in the polymer,while the Td deceased. The polymers were readily

  6. CHLORIDE WASHER PERFORMACE TESTING

    Energy Technology Data Exchange (ETDEWEB)

    Coughlin, J; David Best, D; Robert Pierce, R

    2007-11-30

    Testing was performed to determine the chloride (Cl-) removal capabilities of the Savannah River National Laboratory (SRNL) designed and built Cl- washing equipment intended for HB-Line installation. The equipment to be deployed was tested using a cerium oxide (CeO2) based simulant in place of the 3013 plutonium oxide (PuO2) material. Two different simulant mixtures were included in this testing -- one having higher Cl- content than the other. The higher Cl- simulant was based on K-Area Interim Surveillance Inspection Program (KIS) material with Cl- content approximately equal to 70,000 ppm. The lower Cl- level simulant was comparable to KIS material containing approximately 8,000-ppm Cl- content. The performance testing results indicate that the washer is capable of reducing the Cl- content of both surrogates to below 200 ppm with three 1/2-liter washes of 0.1M sodium hydroxide (NaOH) solution. Larger wash volumes were used with similar results - all of the prescribed test parameters consistently reduced the Cl- content of the surrogate to a value below 200 ppm Cl- in the final washed surrogate material. The washer uses a 20-micron filter to retain the surrogate solids. Tests showed that 0.16-0.41% of the insoluble fraction of the starting mass passed through the 20-micron filter. The solids retention performance indicates that the fissile masses passing through the 20-micron filter should not exceed the waste acceptance criteria for discard in grout to TRU waste. It is recommended that additional testing be pursued for further verification and optimization purposes. It is likely that wash volumes smaller than those tested could still reduce the Cl- values to acceptable levels. Along with reduced wash volumes, reuse of the third wash volume (in the next run processed) should be tested as a wash solution minimization plan. A 67% reduction in the number of grouted paint pails could be realized if wash solution minimization testing returned acceptable results.

  7. On the distribution of bromide and bromide/chlorinity ratios in the waters of the Arabian sea off central Indian coast

    Digital Repository Service at National Institute of Oceanography (India)

    DeSouza, F.P.; SenGupta, R.

    Water samples from surface to 2000 m depth at two stations in the Arabian Sea collected during the 82nd cruise of R V Gaveshani in November, 1980 were analysed for bromide. The average bromide concentration was 0.068 g/kg plus or minus 0...

  8. Aquifer Recharge Estimation through Atmospheric Chloride Mass Balance at Las Cañadas Caldera, Tenerife, Canary Islands, Spain

    Directory of Open Access Journals (Sweden)

    Rayco Marrero-Diaz

    2015-05-01

    Full Text Available The atmospheric chloride mass balance (CMB method was used to estimate net aquifer recharge in Las Cañadas Caldera, an endorheic summit aquifer area about 2000 m a.s.l. with negligible surface runoff, which hosts the largest freshwater reserve in Tenerife Island, Canary Islands, Spain. The wet hydrological year 2005–2006 was selected to compare yearly atmospheric chloride bulk deposition and average chloride content in recharge water just above the water table, both deduced from periodical sampling. The potential contribution of chloride to groundwater from endogenous HCl gas may invalidate the CMB method. The chloride-to-bromide molar ratio was an efficient tracer used to select recharge water samples having atmospheric origin of chloride. Yearly net aquifer recharge was 631 mm year−1, i.e., 69% of yearly precipitation. This result is in agreement with potential aquifer recharge estimated through an independent lumped-parameter rainfall-runoff model operated by the Insular Water Council of Tenerife. This paper illustrates basic procedures and routines to use the CMB method for aquifer recharge in active volcanic oceanic islands having sparse-data coverage and groundwater receiving contribution of endogenous halides.

  9. Synthesis and Structural Characterization of 1-[2-(5-Nitro-1H-indol-2-ylphenyl]methylpyridinium Chloride

    Directory of Open Access Journals (Sweden)

    John B. Bremner

    2011-09-01

    Full Text Available In the course of studies on hybrid antibacterials incorporating 2-aryl-5-nitro-1H-indole moieties as potential bacterial NorA efflux pump inhibitors, the compound 1-[2-(5-nitro-1H-indol-2-ylphenyl]methylpyridinium chloride (2 was synthesized and structurally characterized. This pyridinium chloride salt crystallized in the monoclinic space group P21/c with the following unit cell dimensions: a 10.274(3 Å, b 13.101(4 Å, c 13.439(4 Å, b 107.702(7°, V 1723.2(9 Å3, Z (f.u. = 4; R1 = 0.048, and wR2 = 0.13. Of interest in the single crystal X-ray structure is the (intramolecular disposition of the pyridinium plane over the indole heterocyclic residue [interplanar dihedral angle 17.91(4°].

  10. Synthesis of 2- and 2,3-substituted pyrazolo[1,5-a]pyridines: scope and mechanistic considerations of a domino direct alkynylation and cyclization of N-iminopyridinium ylides using alkenyl bromides, alkenyl iodides, and alkynes.

    Science.gov (United States)

    Mousseau, James J; Bull, James A; Ladd, Carolyn L; Fortier, Angélique; Sustac Roman, Daniela; Charette, André B

    2011-10-21

    Direct functionalization and tandem processes have both received considerable recent interest due to their cost and time efficiency. Herein we report the synthesis of difficult to obtain 2-substituted pyrazolo[1,5-a]pyridines through a tandem palladium-catalyzed/silver-mediated elimination/direct functionalization/cyclization reaction involving N-benzoyliminopyridinium ylides. As such, these biologically important molecules are prepared in an efficient, high-yielding manner, only requiring a two-step sequence from pyridine. Aryl-substituted alkenyl bromides and iodides are effective ylide coupling partners. Mechanistic studies led to the use of terminal alkynes, which extended the scope of the reaction to include alkyl substitution on the unsaturated reactive site. The optimization, scope, and mechanistic considerations of the process are discussed.

  11. Electrochemical Chloride extraction using external electrodes?

    DEFF Research Database (Denmark)

    Ottosen, Lisbeth M.; Pedersen, Anne Juul

    2006-01-01

    Electrochemical methods for the removal of chloride from concrete have been developed and the methods are primarily designed for situations where corrosion has started due to an increased chloride concentration in the vicinity of the reinforcement. In these methods the reinforcement is used...... as the cathode. However, some unwanted side effects can occur, including alkali-silica reaction and in some cases hydrogen embrittlement. It is also suggested also to use electrochemical chloride extraction in a preventive way in constructions where chloride induced corrosion is likely to be a problem after...... a period of time, i.e. remove the chlorides before the chloride front reaches the reinforcement. If the chlorides are removed from outer few centimetres from the surface, the chloride will not reach the reinforcement and cause damage. By using the electrochemical chloride removal in this preventive way...

  12. Bromination of Aromatic Compounds by Residual Bromide in Sodium Chloride Matrix Modifier Salt During Heated Headspace GC/MS Analysis

    Science.gov (United States)

    Analytical artifacts attributed to the bromination of toluene, xylenes, and trimethylbenzenes were found during the heated headspace gas chromatography/mass spectrometry (GC/MS) analysis of aqueous samples. The aqueous samples were produced from Fenton-like chemical oxidation rea...

  13. Aryl Ketone Synthesis via Tandem Orthoplatinated Triarylphosphite-Catalyzed Addition Reactions of Arylboronic Acids with Aldehydes Followed by Oxidation

    Science.gov (United States)

    Liao, Yuan-Xi; Hu, Qiao-Sheng

    2010-01-01

    Tandem orthoplatinated triarylphosphite-catalyzed addition reactions of arylboronic acids with aldehydes followed by oxidation to yield aryl ketones is described. 3-Pentanone was identified as a suitable oxidant for the tandem aryl ketone formation reaction. By using microwave energy, aryl ketones were obtained in high yields with the catalyst loading as low as 0.01%. PMID:20849092

  14. Lubiprostone: a chloride channel activator.

    Science.gov (United States)

    Lacy, Brian E; Levy, L Campbell

    2007-04-01

    In January 2006 the Food and Drug Administration approved lubiprostone for the treatment of chronic constipation in men and women aged 18 and over. Lubiprostone is categorized as a prostone, a bicyclic fatty acid metabolite of prostaglandin E1. Lubiprostone activates a specific chloride channel (ClC-2) in the gastrointestinal (GI) tract to enhance intestinal fluid secretion, which increases GI transit and improves symptoms of constipation. This article reviews the role of chloride channels in the GI tract, describes the structure, function, and pharmacokinetics of lubiprostone, and discusses clinically important data on this new medication.

  15. Modular approach to novel chiral aryl-ferrocenyl phosphines by Suzuki cross-coupling

    DEFF Research Database (Denmark)

    Jensen, Jakob Feldthusen; Søtofte, Inger; Sorensen, H.O.;

    2002-01-01

    Two novel planar chiral and atropisomeric P,N and P,O aryl-ferrocenyl ligand systems have been developed. The strategy is short and involves a new synthetic approach to aryl-ferrocenyl compounds via a Suzuki cross-coupling procedure. The modular design can easily give access to variety of chiral ...

  16. Copper-catalyzed aerobic oxidative synthesis of aryl nitriles from benzylic alcohols and aqueous ammonia.

    Science.gov (United States)

    Tao, Chuanzhou; Liu, Feng; Zhu, Youmin; Liu, Weiwei; Cao, Zhiling

    2013-05-28

    Copper-catalyzed direct conversion of benzylic alcohols to aryl nitriles was realized using NH3(aq.) as the nitrogen source, O2 as the oxidant and TEMPO as the co-catalyst. Furthermore, copper-catalyzed one-pot synthesis of primary aryl amides from alcohols was also achieved.

  17. Catalytic membrane-installed microchannel reactors for one-second allylic arylation.

    Science.gov (United States)

    Yamada, Yoichi M A; Watanabe, Toshihiro; Torii, Kaoru; Uozumi, Yasuhiro

    2009-10-07

    A variety of catalytic membranes of palladium-complexes with linear polymer ligands were prepared inside a microchannel reactor via coordinative and ionic molecular convolution to provide catalytic membrane-installed microdevices, which were applied to the instantaneous allylic arylation reaction of allylic esters and aryl boron reagents under microflow conditions to afford the corresponding coupling products within 1 second of residence time.

  18. Synthesis of 3-cyano-4-aryl-5-ethoxycarbonyl-6-methyl-3,4-dihydropyridine-2-thiones

    Energy Technology Data Exchange (ETDEWEB)

    Krauze, A.A.; Liepin' sh, E.E.; Pelcher, Yu.E.; Kalme, Z.A.; Dipan, I.V.; Dubur, G.Ya.

    1985-12-01

    The condensation of ethyl arylidenacetoacetate with cyanothioacetamide and of arylidenecyanothioacetamides with ethyl acetoacetate or of arylidenecyanothioacetamides with ethyl ..beta..-aminocrotonate gave 3-cyano-4-aryl-5-ethoxycarbonyl-6-methyl-3,4-dihydropyridine-2-thiones. PMR spectroscopy showed that the 3-cyano-4-aryl-3,4-dihydro-pyridine-2-thiones are formed as a mixture of cis and trans isomers.

  19. Unprecedentedly mild direct Pd-catalyzed arylation of oxazolo[4,5-b]pyridine

    DEFF Research Database (Denmark)

    Zhuravlev, Fedor

    2006-01-01

    Pd-catalyzed C-2 arylation of oxazolo[4,5-b]pyridine proceeds efficiently at 30 degrees C and tolerates a variety of aryl halides, including derivatized amino acids for which no racemization was observed during the reaction. Experimental evidence for facile deprotonation of oxazolo[4,5-b]pyridine...

  20. Chelation in Metal Intoxication XLVI:Synthesis of Some α-Mercapto-β-Substituted Aryl Acrylic Acids and Their In vitro Cadmium Chelating Ability

    Institute of Scientific and Technical Information of China (English)

    MADHUMITA CHATTERJEE; VINOD K. DWIVEDI; KIRTI KHANDEKAR; SUSHIL K. TANDON

    2004-01-01

    Objective To synthesize some new α-mercapto-β-substituted aryl acrylic acids, characterize them and investigate their in vitro cadmium chelating ability. Methods Six α-mercapto-β-substituted aryl acrylic acids were prepared by the alkaline hydrolysis of 5-(aryl methylene)rhodanines, obtained from the condensation of substituted aldehydes and rhodanine following the reported procedure. The new compounds were characterized by elemental analysis, infrared (IR) and nuclear magnetic resonance (NMR) spectroscopy. The liver and kidney from cadmium chloride pre-administered rats were homogenized and their nuclear mitochondrial fraction (NMF) and supernatant cytosol fraction (SCF) were separated. A measured volume of each fraction was dialyzed separately using "dialysis sack" against buffered-KCl medium containing a compound in the final concentration of 1×10-3 mol/L for 3 h at 37℃C. The whole content of "sack" was subjected to cadmiumestimation following digestion with conc. Nitric acid was detected using flame atomic absorption spectrometer. Results The in vitro screening showed that α-mercapto-β-(p-methoxyphenyl)acrylic acid (compound 2) and α-mercapto-β-(m-methoxy, p-hydroxyphenyl) acrylic acid (compound 4) were more effective than α-mercapto-β-thienyl acrylic acid (compound 1) and α-mercapto-β-(p-dimethylaminophenyl) acrylic acid (compound 3) in mobilizing cadmium as their dialyzable chelates. The presence of a methoxy group on the phenyl moiety (compounds 2 and 4) increases the metal chelating ability of mercapto acrylic acids. Conclusions Compounds 2 and 4 seem to have accessibility to the cellular system and capability of chelating-out the intracellularly bound cadmium.

  1. EFFICACY OF HYOSCINE BUTYL BROMIDE SUPPOSITORY FOR POSTOPERATIVE PAIN RELIEF

    Directory of Open Access Journals (Sweden)

    Soniya C. Alphonse

    2017-07-01

    Full Text Available BACKGROUND Caesarean Section is on the rise all over the world. Women undergoing Caesarean section often wish to be awake post operatively and to avoid excessive medications affecting interactions with the new born infant. Multimodal pain therapy has been advocated for postoperative pain management after caesarean section. MATERIALS AND METHODS The study is a prospective randomized controlled study conducted at a tertiary care hospital to study the effect of Hyoscine Butyl Bromide Suppositories for postoperative analgesia following elective repeat caesarean section. The study included sixty patients divided into two groups- Group1 (study group were given Hyoscine Butyl Bromide Suppository (10 mg along with Injection. Tramadol 50 mg IM and Group II (control group were given Injection Tramadol IM only at the end of surgery. Pain score of the patient assessed at 1 hr, 2 hrs, 6hrs and 24 hrs post operatively. The total no of doses of injection tramadol needed in 24 hrs and the interval between 1st and 2nd dose of tramadol was also noted. The adverse effects of the drug and additional advantages of the drug if any were also assessed. RESULTS There was no statistically significant difference in pain score during the assessment intervals between the two groups. There was no difference in the number of doses of tramadol needed in the first 24 hrs. The mean interval between the 1st and 2nd dose of tramadol was found to be 7.6538 hours for group 1 patients and 6.9130 for group patients which was found to be statistically significant. There was no statistically significant side effects/ additional advantages for the drugs. CONCLUSION Concurrent administration of Hyoscine Butyl Bromide Suppository (10 mg and injection Tramadol 50 mg IM offers a longer postoperative analgesia without any increased adverse effects.

  2. Interaction between gaseous ozone and crystalline potassium bromide

    Science.gov (United States)

    Levanov, A. V.; Maksimov, I. B.; Isaikina, O. Ya.; Antipenko, E. E.; Lunin, V. V.

    2016-07-01

    The formation of nonvolatile products of the oxidation of a bromide ion during the interaction between gaseous ozone and powdered crystalline KBr is studied. It is found that potassium bromate KBrO3 is the main product of the reaction. The influence of major experimental factors (the duration of ozonation, the concentration of ozone, the humidity of the initial gas, and the temperature) on the rate of formation of bromate is studied. The effective constants of the formation of bromate during the interaction between O3 and Br- in a heterogeneous gas-solid body system and in a homogeneous aqueous solution are compared.

  3. Suicide by intravenous injection of rocuronium-bromide: Case report

    Directory of Open Access Journals (Sweden)

    Nikolić Slobodan

    2005-01-01

    Full Text Available Suicides by intravenous injection of an overdose of medicaments are uncommon. In this paper, we present the case of a suicide by rocuronium-bromide injection in combination with an oral overdose of metoprolol. Unfortunately, in Belgrade, there is no toxicological laboratory capable of detecting rocuronium. The interpretation of autopsy and toxicological data in this case was made difficult due to the extreme putrefaction of the body of the deceased. So, by forensic investigation, the case was solved indirectly, through circumstantial evidence: an empty ampoule of rocuronium found near the body, as well as a plastic syringe and cloth-bandage found in the left hand of the deceased.

  4. COMPARISON OF DROTAVERINE HYDROCHLORIDE AND VALETHAMATE BROMIDE ON CERVICAL DILATATION

    Directory of Open Access Journals (Sweden)

    Mallika Selvaraj

    2016-06-01

    Full Text Available AIM To compare the two drugs drotaverine hydrochloride and valethamate bromide and their effects on cervical dilatation and labour duration. METHODOLOGY It is a prospective study undertaken at Government Rajaji Hospital on 150 randomly selected primigravidae patients. RESULTS The duration of active phase of first stage of labour was significantly reduced (p value 0.003, rate of cervical dilatation was higher (p value 0.0001 with drotaverine hydrochloride. CONCLUSION Drotaverine hydrochloride is a safe, potent and effective drug to be used in the active phase of labour.

  5. A practical comparison of Copper Bromide Laser for the treatment of vascular lesions.

    Science.gov (United States)

    Lee, SunWoo; Lee, TaeBum; Kim, HoYoun; Kim, JungSoo; Eun, HyeJun; Kim, RyunKyung

    2013-01-01

    The recent rapid growth in demand for aesthetic non-invasive laser treatments such as unwanted skin rejuvenation, removal of age-related vascular blemishes has led to a boom in the medical devices to treat these conditions. Among diverse laser for skin treatment, copper bromide laser is a very effective, safe, and well tolerated treatment for facial telangiectasia at various energy levels and the most important thing of the copper bromide laser device is that the stability of the energy. However there is no evidence about effective copper bromide laser's energy level for the treatment of vascular lesions. We compared energy stability and treatment performance between two energy levels in 2 W and 8 W which commonly use in laser treatment for the vascular lesions. 8 W copper bromide laser was more stable compared than 2 W copper bromide laser. Also, 8 W copper bromide laser was effectively superior to 2 W copper bromide laser in treatment of vascular legion. Consequently, 8 W copper bromide laser treatment for vascular lesion might be more suitable than 2 W copper bromide laser.

  6. Transient neuromyopathy after bromide intoxication in a dog with idiopathic epilepsy

    Directory of Open Access Journals (Sweden)

    Steinmetz Sonja

    2012-12-01

    Full Text Available Abstract A seven-year old Australian Shepherd, suffering from idiopathic epilepsy under treatment with phenobarbitone and potassium bromide, was presented with generalised lower motor neuron signs. Electrophysiology and muscle-nerve biopsies revealed a neuromyopathy. The serum bromide concentration was increased more than two-fold above the upper reference value. Clinical signs disappeared after applying diuretics and reducing the potassium bromide dose rate. This is the first case report describing electrophysiological and histopathological findings associated with bromide induced lower motor neuron dysfunction in a dog.

  7. Chloride : The queen of electrolytes?

    NARCIS (Netherlands)

    Berend, Kenrick; van Hulsteijn, Leonard Hendrik; Gans, Rijk O. B.

    2012-01-01

    Background: Channelopathies, defined as diseases that are caused by mutations in genes encoding ion channels, are associated with a wide variety of symptoms and have been documented extensively over the past decade. In contrast, despite the important role of chloride in serum, textbooks in general d

  8. 1,5-Diaminotetrazolium chloride

    Directory of Open Access Journals (Sweden)

    Ling-Qiao Meng

    2010-04-01

    Full Text Available The title compound, CH5N6+·Cl−, crystallized with two indepedent 1,5-diaminotetrazolium cations and two independent chloride anions in the asymmetric unit. In the crystal, there are a number of N—H...Cl hydrogen-bonding interactions, which generate a three-dimensional network.

  9. [Headspace GC/MS analysis of residual vinyl chloride and vinylidene chloride in polyvinyl chloride and polyvinylidene chloride products].

    Science.gov (United States)

    Ohno, Hiroyuki; Mutsuga, Motoh; Kawamura, Yoko; Suzuki, Masako; Aoyama, Taiki

    2005-02-01

    A headspace GC/MS analysis method for the simultaneous determination of residual vinyl chloride (VC) and vinylidene chloride (VDC) in polyvinyl chloride (PVC) and polyvinylidene chloride (PVDC) products was developed. A test sample was swelled overnight with N,N-dimethylacetamide in a sealed vial. The vial was incubated for 1 hour at 90 degrees C, then the headspace gas was analyzed by GC/MS using a PLOT capillary column. The recoveries from spiked PVC and PVDC samples were 90.0-112.3% for VC and 85.2-108.3% for VDC. The determination limits were 0.01 microg/g for VC and 0.06/microg/g for VDC, respectively. By this method, VC was detected in two PVC water supply pipes at the levels of 0.61 and 0.01 microg/g. On the other hand, VC and VDC were not detected in any of the food container-packages or toys tested.

  10. Degradation of β-Aryl Ether Bonds in Transgenic Plants

    DEFF Research Database (Denmark)

    Mnich, Ewelina

    of the monolignols coniferyl alcohol, p-coumaryl alcohol and sinapyl alcohol which during radical-mediated oxidative coupling bind together forming different linkage types. Lignin is the main obstacle in biofuel production as it forms a mechanical barrier limiting accessibility for polysaccharide hydrolyzing enzymes...... system to degrade lignin. An important step in this degradation is cleavage of the most abundant lignin linkage type, β-aryl ether. It is cleaved in a three step reaction catalyzed by a dehydrogenase, a glutathione S-transferase and a glutathione lyase. Due to the nature of the enzymatic reactions...

  11. Antileishmanial, Antimicrobial and Antifungal Activities of Some New Aryl Azomethines

    Directory of Open Access Journals (Sweden)

    Masoom Yasinzai

    2010-01-01

    Full Text Available A series of eighteen azomethines has been synthesized by the reaction of appropriate primary aromatic amines with aryl and/or heteroaryl carboxaldehydes. The synthesized azomethines have been evaluated for their in vitro antileishmanial, antibacterial and antifungal activities. The results revealed some antifungal activity of most of the synthesized compounds, whereas the antileishmaniasis activity results highlighted that all synthesized azomethines inhibited parasite growth and most of them showed highly potent action towards Leishmania major promastigotes. No remarkable bactericidal activities were observed.

  12. Role of the Aryl Hydrocarbon Receptor in Colon Neoplasia

    Directory of Open Access Journals (Sweden)

    Guofeng Xie

    2015-07-01

    Full Text Available For both men and women, colorectal cancer (CRC is the second leading cause of cancer death in the United States, primarily as a consequence of limited therapies for metastatic disease. The aryl hydrocarbon receptor (AhR is a ligand-dependent transcription factor with diverse functions in detoxification of xenobiotics, inflammatory responses, and tissue homeostasis. Emerging evidence indicates that AhR also plays an important role in regulating intestinal cell proliferation and tumorigenesis. Here, we review both the pro- and anti-carcinogenic properties of AhR signaling and its potential role as a therapeutic target in CRC.

  13. Catalytic arylation methods from the academic lab to industrial processes

    CERN Document Server

    Burke, Anthony J

    2014-01-01

    A current view of the challenging field of catalytic arylation reactions. Clearly structured, the chapters in this one-stop resource are arranged according to the reaction type, and focus on novel, efficient and sustainable processes, rather than the well-known and established cross-coupling methods.The entire contents are written by two authors with academic and industrial expertise to ensure consistent coverage of the latest developments in the field, as well as industrial applications, such as C-H activation, iron and gold-catalyzed coupling reactions, cycloadditions or novel methodologies

  14. Aryl- and heteroaryl-substituted phenylalanines as AMPA receptor ligands

    DEFF Research Database (Denmark)

    Szymańska, Ewa; Chałupnik, Paulina; Johansen, Tommy Nørskov

    2017-01-01

    in radioligand binding assays at native rat ionotropic glutamate receptors. The most interesting compound in this series, (RS)-2-amino-3-(3'-hydroxy-5-(1H-pyrazol-4-yl)-[1,1'-biphenyl]-3-yl)propanoic acid 7e, showed the binding affinity of 4.6 µM for native AMPA receptors and almost 5-fold lower affinity...... with molecular modeling confirmed that aryl/heteroaryl-substituted phenylalanine analogues effectively bind to AMPA receptors with low micromolar affinity and high selectivity over native NMDA and kainate receptors. These properties make 7e a promising lead for the further development of new AMPA receptor...

  15. Role of the Aryl Hydrocarbon Receptor in Colon Neoplasia

    Energy Technology Data Exchange (ETDEWEB)

    Xie, Guofeng, E-mail: gxie@medicine.umaryland.edu; Raufman, Jean-Pierre [Division of Gastroenterology and Hepatology, Veterans Administration Maryland Health Care System, University of Maryland School of Medicine, Baltimore, MD 21201 (United States)

    2015-07-31

    For both men and women, colorectal cancer (CRC) is the second leading cause of cancer death in the United States, primarily as a consequence of limited therapies for metastatic disease. The aryl hydrocarbon receptor (AhR) is a ligand-dependent transcription factor with diverse functions in detoxification of xenobiotics, inflammatory responses, and tissue homeostasis. Emerging evidence indicates that AhR also plays an important role in regulating intestinal cell proliferation and tumorigenesis. Here, we review both the pro- and anti-carcinogenic properties of AhR signaling and its potential role as a therapeutic target in CRC.

  16. Copper-catalyzed arylation of alkyl halides with arylaluminum reagents

    Directory of Open Access Journals (Sweden)

    Bijay Shrestha

    2015-12-01

    Full Text Available We report a Cu-catalyzed coupling between triarylaluminum reagents and alkyl halides to form arylalkanes. The reaction proceeds in the presence of N,N,N’,N’-tetramethyl-o-phenylenediamine (NN-1 as a ligand in combination with CuI as a catalyst. This catalyst system enables the coupling of primary alkyl iodides and bromides with electron-neutral and electron-rich triarylaluminum reagents and affords the cross-coupled products in good to excellent yields.

  17. 21 CFR 173.375 - Cetylpyridinium chloride.

    Science.gov (United States)

    2010-04-01

    ... CONSUMPTION Specific Usage Additives § 173.375 Cetylpyridinium chloride. Cetylpyridinium chloride (CAS Reg. No... Nutrition's Library, Food and Drug Administration, 5100 Paint Branch Pkwy., College Park, MD 20740, or...

  18. The in vitro and in vivo profile of aclidinium bromide in comparison with glycopyrronium bromide.

    Science.gov (United States)

    Gavaldà, Amadeu; Ramos, Israel; Carcasona, Carla; Calama, Elena; Otal, Raquel; Montero, José Luis; Sentellas, Sonia; Aparici, Monica; Vilella, Dolors; Alberti, Joan; Beleta, Jorge; Miralpeix, Montserrat

    2014-08-01

    This study characterised the in vitro and in vivo profiles of two novel long-acting muscarinic antagonists, aclidinium bromide and glycopyrronium bromide, using tiotropium bromide and ipratropium bromide as comparators. All four antagonists had high affinity for the five muscarinic receptor sub-types (M1-M5); aclidinium had comparable affinity to tiotropium but higher affinity than glycopyrronium and ipratropium for all receptors. Glycopyrronium dissociated faster from recombinant M3 receptors than aclidinium and tiotropium but more slowly than ipratropium; all four compounds dissociated more rapidly from M2 receptors than from M3 receptors. In vitro, aclidinium, glycopyrronium and tiotropium had a long duration of action at native M3 receptors (>8 h versus 42 min for ipratropium). In vivo, all compounds were equi-potent at reversing acetylcholine-induced bronchoconstriction. Aclidinium, glycopyrronium and ipratropium had a faster onset of bronchodilator action than tiotropium. Aclidinium had a longer duration of action than glycopyronnium (time to 50% recovery of effect [t½ offset] = 29 h and 13 h, respectively); these compare with a t½ offset of 64 h and 8 h for tiotropium and ipratropium, respectively. Aclidinium was less potent than glycopyrronium and tiotropium at inhibiting salivation in conscious rats (dose required to produce half-maximal effect [ED50] = 38, 0.74 and 0.88 μg/kg, respectively) and was more rapidly hydrolysed in rat, guinea pig and human plasma compared with glycopyrronium or tiotropium. These results indicate that while aclidinium and glycopyrronium are both potent antagonists at muscarinic receptors with similar kinetic selectivity for M3 receptors versus M2, aclidinium has a longer dissociation half-life at M3 receptors and a longer duration of bronchodilator action in vivo than glycopyrronium. The rapid plasma hydrolysis of aclidinium, coupled to its kinetic selectivity, may confer a reduced propensity for systemic

  19. Octahedral Rotation Preferences in Perovskite Iodides and Bromides.

    Science.gov (United States)

    Young, Joshua; Rondinelli, James M

    2016-03-03

    Phase transitions in ABX3 perovskites are often accompanied by rigid rotations of the corner-connected BX6 octahedral network. Although the mechanisms for the preferred rotation patterns of perovskite oxides are fairly well recognized, the same cannot be said of halide variants (i.e., X = Cl, Br, or I), several of which undergo an unusual displacive transition to a tetragonal phase exhibiting in-phase rotations about one axis (a(0)a(0)c(+) in Glazer notation). To discern the chemical factors stabilizing this unique phase, we investigated a series of 12 perovskite bromides and iodides using density functional theory calculations and compared them with similar oxides. We find that in-phase tilting provides a better arrangement of the larger bromide and iodide anions, which minimizes the electrostatic interactions, improves the bond valence of the A-site cations, and enhances the covalency between the A-site metal and Br(-) or I(-) ions. The opposite effect is present in the oxides, with out-of-phase tilting maximizing these factors.

  20. Development of copper bromide laser master oscillator power amplifier system

    Indian Academy of Sciences (India)

    G N Tiwari; R K Mishra; R Khare; S V Nakhe

    2014-02-01

    Development of master oscillator power amplifier (MOPA) system of copper bromide laser (CBL) operating at 110 W average power is reported. The spectral distribution of power at green (510.6 nm) and yellow (578.2 nm) components in the output of a copper bromide laser is studied as a function of operating parameters. The electrical input power was varied from 2.6 to 4.3 kW, the pulse repetition frequency (PRF) was changed from 16 to 19 kHz, and the pressure of the buffer gas (neon) was kept fixed at 20 mbar. When the electrical input power was increased to 4.3 kW from 2.6 kW, the tube-wall temperature also increased to 488°C from 426°C but the ratio of the green to yellow power decreased to 1.53 from 3.73. The ratio of green to yellow power decreased to 1.53 from 1.63 when the PRF of the laser was increased to 19 kHz from 16 kHz. These observations are explained in terms of electron temperature, energy levels of transitions, and voltage and current waveforms across the laser head.

  1. Progress of Carbonation in Chloride Contaminated Concretes

    OpenAIRE

    Wang, Yaocheng; Basheer, P. A.M.; Nanukuttan, S; Bai, Y.

    2016-01-01

    Concretes used in marine environment are generally under the cyclic effect of CO2 and chloride ions (Cl-). To date, the influence of carbonation on ingress of chloride ions in concretes has been widely studied; in comparison, study on the influence of Cl- on the progress of carbonation is limited. During the study, concretes were exposed to independent and combined mechanisms of carbonation and chloride ingress regimes. Profiles of apparent pH and chloride concentration were used to indicate ...

  2. Microbial reductive dehalogenation of vinyl chloride

    Energy Technology Data Exchange (ETDEWEB)

    Spormann, Alfred M [Stanford, CA; Muller, Jochen A [Baltimore, MD; Rosner, Bettina M [Berlin, DE; Von Abendroth, Gregory [Mannheim, DE; Meshulam-Simon, Galit [Los Angeles, CA; McCarty, Perry L [Stanford, CA

    2014-02-11

    Compositions and methods are provided that relate to the bioremediation of chlorinated ethenes, particularly the bioremediation of vinyl chloride by Dehalococcoides-like organisms. An isolated strain of bacteria, Dehalococcoides sp. strain VS, that metabolizes vinyl chloride is provided; the genetic sequence of the enzyme responsible for vinyl chloride dehalogenation; methods of assessing the capability of endogenous organisms at an environmental site to metabolize vinyl chloride; and a method of using the strains of the invention for bioremediation.

  3. Cystic Fibrosis (CF): Chloride Sweat Test

    Science.gov (United States)

    ... Old Feeding Your 1- to 2-Year-Old Cystic Fibrosis (CF) Chloride Sweat Test KidsHealth > For Parents > Cystic Fibrosis (CF) Chloride Sweat Test Print A A A ... It Is A chloride sweat test helps diagnose cystic fibrosis (CF) , an inherited disorder that makes kids sick ...

  4. 21 CFR 184.1426 - Magnesium chloride.

    Science.gov (United States)

    2010-04-01

    ... mineral bischofite. It is prepared by dissolving magnesium oxide, hydroxide, or carbonate in aqueous... 21 Food and Drugs 3 2010-04-01 2009-04-01 true Magnesium chloride. 184.1426 Section 184.1426 Food... Specific Substances Affirmed as GRAS § 184.1426 Magnesium chloride. (a) Magnesium chloride (MgC12·6H2O,...

  5. 75 FR 33824 - Barium Chloride From China

    Science.gov (United States)

    2010-06-15

    ... COMMISSION Barium Chloride From China Determination On the basis of the record\\1\\ developed in the subject... order on barium chloride from China would be likely to lead to continuation or recurrence of material... Barium Chloride from China: Investigation No. 731-TA-149 (Third Review). By order of the...

  6. 75 FR 19657 - Barium Chloride From China

    Science.gov (United States)

    2010-04-15

    ... COMMISSION Barium Chloride From China AGENCY: United States International Trade Commission. ACTION: Notice of... chloride from China. SUMMARY: The Commission hereby gives notice that it will proceed with a full review... revocation of the antidumping duty order on barium chloride from China would be likely to lead...

  7. 21 CFR 172.180 - Stannous chloride.

    Science.gov (United States)

    2010-04-01

    ... Preservatives § 172.180 Stannous chloride. The food additive stannous chloride may be safely used for color... 21 Food and Drugs 3 2010-04-01 2009-04-01 true Stannous chloride. 172.180 Section 172.180 Food and Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF HEALTH AND HUMAN SERVICES (CONTINUED) FOOD FOR...

  8. 21 CFR 582.5446 - Manganese chloride.

    Science.gov (United States)

    2010-04-01

    ... 21 Food and Drugs 6 2010-04-01 2010-04-01 false Manganese chloride. 582.5446 Section 582.5446 Food and Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF HEALTH AND HUMAN SERVICES (CONTINUED) ANIMAL... Supplements 1 § 582.5446 Manganese chloride. (a) Product. Manganese chloride. (b) Conditions of use....

  9. Catalytic enantioselective arylations: boron to zinc exchange as a powerful tool for the generation of transferable aryl groups

    Energy Technology Data Exchange (ETDEWEB)

    Paixao, Marcio W. [Universidade de Sao Paulo (USP), SP (Brazil). Inst. de Quimica]. E-mail: marelloweber@gmail.com; Braga, Antonio L. [Universidade Federal de Santa Maria (UFSM), RS (Brazil). Dept. de Quimica]. E-mail: albraga@quimica.ufsm.br; Luedtke, Diogo S. [Universidade de Sao Paulo (USP), SP (Brazil). Faculdade de Ciencias Farmaceuticas]. E-mail: dsludtke@usp.br

    2008-07-01

    The transmetalation between boron and zinc is of great importance for application in organic synthesis, since it allows the formation of new carbon-carbon bonds between organometallic units and electrophiles. The direct arylation of aldehydes or more scarcely ketones, in a catalytic, enantioselective manner using chiral catalysts has been described recently. The enantiomerically enriched diarylmethanols obtained in these reactions are valuable precursors for important bioactive molecules. This review provides a synopsis of this ever-growing field and highlights some of the challenges that still remain. (author)

  10. Absence of aryl hydrocarbon hydroxylase (AHH) in three marine bivalves

    Energy Technology Data Exchange (ETDEWEB)

    Vandermeulen, J.H. (Bedford Inst. of Oceanography, Dartmouth, Nova Scotia); Penrose, W.R.

    1978-05-01

    Bivalves exposed to short-term (4 d) and long-term (6 yr) oil pollution were assayed for aryl hydrocarbon hydroxylase (AHH) and N-demethylase activity. Short-term induction studies were carried out on Mya arenaria, Mytilus edulis, and Ostrea edulis incubated in aqueous extracts of Kuwait crude oil or Bunker C (fuel) oil. For the chronic-induction studies Mya arenaria and Mytilus edulis were collected from oiled clam beds (Arrow Bunker C) in Chedabucto Bay, Nova Scotia. None of the bivalves showed any basal or petroleum-hydrocarbon-induced aryl hydrocarbon hydroxylase or N-demethylase activity, as shown by their inability to metabolize benzopyrene or imipramine. In contrast, oil-free control trout and trout taken from a polluted lake readily metabolized both these compounds. The inability of these bivalves to degrade petroleum aromatic hydrocarbons and the tendency of these compounds to accumulate in their tissues present an opportunity for transfer of unaltered hydrocarbons into the food chain.

  11. Steric Effects in the Reaction of Aryl Radicals on Surfaces

    Energy Technology Data Exchange (ETDEWEB)

    Combellas, Catherine [CNRS-ESPCI; Jiang, Deen [ORNL; Kanoufi, Frederic [CNRS-ESPCI; Pinson, Jean [Alchimer; Podvorica, Fetah [University of Prishtina, Kosovo

    2009-01-01

    Steric effects are investigated in the reaction of aryl radicals with surfaces. The electrochemical reduction of 2-, 3-, 4-methyl, 2-methoxy, 2-ethyl, 2,6-, 2,4-, and 3,5-dimethyl, 4-tert-butyl, 3,5-bis-tert-butyl benzenediazonium, 3,5-bis(trifluoromethyl), and pentafluoro benzenediazonium tetrafluoroborates is examined in acetonitrile solutions. It leads to the formation of grafted layers only if the steric hindrance at the 2- or 2,6-position(s) is small. When the 3,5-positions are crowded with tert-butyl groups, the growth of the organic layer is limited by steric effects and a monolayer is formed. The efficiency of the grafting process is assessed by cyclic voltammetry, X-ray photoelectron spectroscopy, infrared, and ellipsometry. These experiments, together with density functional computations of bonding energies of substituted phenyl groups on a copper surface, are discussed in terms of the reactivity of aryl radicals in the electrografting reaction and in the growth of the polyaryl layer.

  12. Aryl Diazonium Chemistry for the Surface Functionalization of Glassy Biosensors.

    Science.gov (United States)

    Zheng, Wei; van den Hurk, Remko; Cao, Yong; Du, Rongbing; Sun, Xuejun; Wang, Yiyu; McDermott, Mark T; Evoy, Stephane

    2016-03-14

    Nanostring resonator and fiber-optics-based biosensors are of interest as they offer high sensitivity, real-time measurements and the ability to integrate with electronics. However, these devices are somewhat impaired by issues related to surface modification. Both nanostring resonators and photonic sensors employ glassy materials, which are incompatible with electrochemistry. A surface chemistry approach providing strong and stable adhesion to glassy surfaces is thus required. In this work, a diazonium salt induced aryl film grafting process is employed to modify a novel SiCN glassy material. Sandwich rabbit IgG binding assays are performed on the diazonium treated SiCN surfaces. Fluorescently labelled anti-rabbit IgG and anti-rabbit IgG conjugated gold nanoparticles were used as markers to demonstrate the absorption of anti-rabbit IgG and therefore verify the successful grafting of the aryl film. The results of the experiments support the effectiveness of diazonium chemistry for the surface functionalization of SiCN surfaces. This method is applicable to other types of glassy materials and potentially can be expanded to various nanomechanical and optical biosensors.

  13. Aryl Diazonium Chemistry for the Surface Functionalization of Glassy Biosensors

    Science.gov (United States)

    Zheng, Wei; van den Hurk, Remko; Cao, Yong; Du, Rongbing; Sun, Xuejun; Wang, Yiyu; McDermott, Mark T.; Evoy, Stephane

    2016-01-01

    Nanostring resonator and fiber-optics-based biosensors are of interest as they offer high sensitivity, real-time measurements and the ability to integrate with electronics. However, these devices are somewhat impaired by issues related to surface modification. Both nanostring resonators and photonic sensors employ glassy materials, which are incompatible with electrochemistry. A surface chemistry approach providing strong and stable adhesion to glassy surfaces is thus required. In this work, a diazonium salt induced aryl film grafting process is employed to modify a novel SiCN glassy material. Sandwich rabbit IgG binding assays are performed on the diazonium treated SiCN surfaces. Fluorescently labelled anti-rabbit IgG and anti-rabbit IgG conjugated gold nanoparticles were used as markers to demonstrate the absorption of anti-rabbit IgG and therefore verify the successful grafting of the aryl film. The results of the experiments support the effectiveness of diazonium chemistry for the surface functionalization of SiCN surfaces. This method is applicable to other types of glassy materials and potentially can be expanded to various nanomechanical and optical biosensors. PMID:26985910

  14. Possible intermediates of Cu(phen)-catalyzed C-O cross-coupling of phenol with an aryl bromide by in situ ESI-MS and EPR studies.

    Science.gov (United States)

    Chen, Hong-Jie; Hsu, I-Jui; Tseng, Mei-Chun; Shyu, Shin-Guang

    2014-08-07

    The C-O coupling reaction between 2,4-dimethylphenol and 4-bromotoluene catalyzed by the CuI/K2CO3/phen system can be inhibited by the radical scavenger cumene. Complexes [Cu(i)(phen)(1-(2,4-dimethylphenoxy)-4-methylbenzene)](+) (denoted as A), {H[Cu(i)(phen)(2,4-dimethylphenoxy)]}(+) and [Cu(i)(2,4-dimethylphenoxy)2](-) (denoted as B) were observed by in situ electrospray ionization mass spectrometry (ESI-MS) analysis of the copper(i)-catalyzed C-O coupling reaction under the catalytic reaction conditions indicating that they could be intermediates in the reaction. The in situ EPR study of the reaction solution detected the Cu(ii) species with a fitted g value of 2.188. A catalytic cycle with a single electron transfer (SET) step was proposed based on these observations.

  15. A COMPARATIVE CLINICAL EVALUATION OF INTUBATING CONDITIONS AND HAEMODYNAMIC EFFECTS AFTER ADMINISTRATION OF SUCCINYL CHOLINE & ROCURONIUM BROMIDE

    Directory of Open Access Journals (Sweden)

    Abhishek

    2015-04-01

    Full Text Available BACKGROUND: Rapid and safe endotracheal intubation is of paramount importance in practice of general anesthesia . Succinylcholine chloride , a depolarizing muscl e relaxant due to its quick onset of action and excellent intubating conditions has remained a muscle relaxant of choice . Rocuronium was proved to be safe alternative to Succinylcholine for endotracheal intubation . AIMS : Study was conducted to evaluate & c ompare the onset time , clinical duration and intubating condition of Succinylcholine and Rocuronium Bromide and Haemodynamic changes caused by these agents . METHODS & MATERIALS : 80 patients were randomly divided into two groups . Group - 1 , Succinylcholine ( 1 . 5mg/kg and group - 2 Rocuronium Bromide ( 0 . 6mg/kg . After 60 sec of administration of muscle relaxant , intubating conditions were judged according to scoring system by Cooper et al . 1 Onset time and duration of action was noted . Hemodynamic parameters ( H eart rate , Systolic Blood Pressure , Diastolic Blood Pressure , Mean Atrial pressure and SPO 2 were monitored before intubation , during intubation and just after intubation at 1 , 2 and 5 minutes . RESULTS : The mean onset time and duration of action was signi ficantly longer for Rocuronium ( 95 . 15±9 . 47 seconds than Succinylcholine ( 59 . 80±14 . 30 seconds and Rocuronium ( 42 . 60±13 . 15 minutes than Succinylcholine ( 5 . 10±2 . 35 minutes . Intubating conditions was excellent in 35 ( 87% and good in 5 ( 12 . 5% patients in su ccinylcholine whereas , in Rocuronium produced excellent intubation in only 23 ( 57 . 5% patients and good intubation in 14 ( 35% patients . The heart rate increased significantly after induction ( maximum at 1 minute with both Rocuronium ( 98 . 75±15 . 53 and Succi nylcholine ( 112 . 75±15 . 89 . But it gradually declined towards normal and change in heart rate with either drug was not significant at 5 minutes . The mean blood pressure increased significantly after induction

  16. Vapour pressures, densities, and viscosities of the (water + lithium bromide + potassium acetate) system and (water + lithium bromide + sodium lactate) system

    Energy Technology Data Exchange (ETDEWEB)

    Lucas, Antonio de [Department of Chemical Engineering, University of Castilla - La Mancha, Avda. de Camilo Jose Cela s/n, 13004 Ciudad Real (Spain); Donate, Marina [Department of Chemical Engineering, University of Castilla - La Mancha, Avda. de Camilo Jose Cela s/n, 13004 Ciudad Real (Spain); Rodriguez, Juan F. [Department of Chemical Engineering, University of Castilla - La Mancha, Avda. de Camilo Jose Cela s/n, 13004 Ciudad Real (Spain)]. E-mail: juan.rromero@uclm.es

    2006-02-15

    Measurements of thermophysical properties (vapour pressure, density, and viscosity) of the (water + lithium bromide + potassium acetate) system LiBr:CH{sub 3}COOK = 2:1 by mass ratio and the (water + lithium bromide + sodium lactate) system LiBr:CH{sub 3}CH(OH)COONa = 2:1 by mass ratio were measured. The system, a possible new working fluid for absorption heat pump, consists of absorbent (LiBr + CH{sub 3}COOK) or (LiBr + CH{sub 3}CH(OH)COONa) and refrigerant H{sub 2}O. The vapour pressures were measured in the ranges of temperature and absorbent concentration from T = (293.15 to 333.15) K and from mass fraction 0.20 to 0.50, densities and viscosities were measured from T = (293.15 to 323.15) K and from mass fraction 0.20 to 0.40. The experimental data were correlated with an Antoine-type equation. Densities and viscosities were measured in the same range of temperature and absorbent concentration as that of the vapour pressure. Regression equations for densities and viscosities were obtained with a minimum mean square error criterion.

  17. Preparation of semisynthetic (+)-tubocurarine chloride.

    Science.gov (United States)

    Naghaway, J; Soine, T O

    1979-05-01

    Semisynthetic (+)-tubocurarine chloride (II) was prepared by monoquaternization of (+)-tubocurine. The method involved treating (+)-tubocurine with a 0.5 M equivalent of hydrochloric acid prior to quaternization with methyl iodide, followed by neutralization and iodide-chloride ion-exchange. Column chromatography and crystallization procedures were utilized for pure semisynthetic II preparation. The neuromuscular junction blocking activities of the semisynthetic and commercial II were determined by the in vivo cat hypoglossal nerve-tongue muscle preparation. No delectable differences among physical constants, spectral data, and neuromuscular junction blocking activities were noted between the commercial product and the semisynthetic II. This result substantiates the chemical and biological data for the well-accepted new formula for II. The unexplained M + n14 mass spectral peaks shown by the curare-type bases are characteristic of the molecular species rather than a result of contaminants.

  18. SYNTHESIS AND CATALYTIC PROPERTIES OF HYDROPHOBICALLY MODIFIED POLY(ALKYLMETHYLDIALLYLAMMONIUM BROMIDES)

    NARCIS (Netherlands)

    YANG, YJ; ENGBERTS, JBFN

    1991-01-01

    A series of hydrophobically modified homo- and copolymers of the poly(alkylmethyldiallylammonium bromide) type has been prepared by free-radical cyclo(co)polymerization of alkylmethyldiallylammonium bromide monomers in aqueous solution. Depending on the length of the alkyl side chain (varied between

  19. Effects of Inhalation or Incubation of Oxitropium Bromide on Diaphragm Muscle Contractility in Mice

    Directory of Open Access Journals (Sweden)

    Chiyohiko Shindoh

    2011-01-01

    Conclusions: We speculate that the increment of muscle contractility with the inhalation of oxitropium bromide was induced by the antagonization of musucarinic acetylcholine receptors (mAChR. In addition, the changes of fatigue resistance provoked by oxitropium bromide, which also is speculated to antagonize mAChR, may be beneficial in the treatment of patients with COPD.

  20. Pancreatitis associated with potassium bromide/phenobarbital combination therapy in epileptic dogs.

    OpenAIRE

    Gaskill, C L; Cribb, A E

    2000-01-01

    In a retrospective study, at least 10% of dogs receiving potassium bromide/phenobarbital combination therapy, compared with 0.3% of dogs receiving phenobarbital monotherapy, had probable pancreatitis. Pancreatitis may be a more frequent and more serious adverse effect of potassium bromide/phenobarbital combination therapy than has been reported previously.

  1. A study of bromide in the Mandovi-Zuari river system of Goa

    Digital Repository Service at National Institute of Oceanography (India)

    DeSouza, F.P.; Dalal, V.N.K.

    concentrations were computed. The variation of bromide with chlorinity was linear indicating the purely conservative character of bromide and its seawater origin. Seawater ranged between 1 and 3% in monsoon, 76 and 91% in post-monsoon and 92 and 97% in pre...

  2. Acrolein as Potential Alternative to Methyl Bromide in California-Grown Calla Lilies

    Science.gov (United States)

    Cut flower and ornamental bulb industries rely heavily on a methyl bromide/chloropicrin (MB/Pic) mixture as a key pest management tool. The loss of methyl bromide (MB) will seriously affect the cut flower and bulb industry, and in the future, will require growers to use alternative fumigants. Theref...

  3. SYNTHESIS AND CATALYTIC PROPERTIES OF HYDROPHOBICALLY MODIFIED POLY(ALKYLMETHYLDIALLYLAMMONIUM BROMIDES)

    NARCIS (Netherlands)

    YANG, YJ; ENGBERTS, JBFN

    1991-01-01

    A series of hydrophobically modified homo- and copolymers of the poly(alkylmethyldiallylammonium bromide) type has been prepared by free-radical cyclo(co)polymerization of alkylmethyldiallylammonium bromide monomers in aqueous solution. Depending on the length of the alkyl side chain (varied between

  4. Destruction of methyl bromide sorbed to activated carbon by thiosulfate and electrolysis

    Science.gov (United States)

    Methyl bromide is widely used as a fumigant for post-harvest and quarantine uses at port facilities due to the low treatment times required, but it is vented to the atmosphere after its use. Due to the potential contributions of methyl bromide to stratospheric ozone depletion, technologies for the c...

  5. Zinc--bromide secondary cell. [C anode, C or Zr cathode with ion exchange diaphragm between

    Energy Technology Data Exchange (ETDEWEB)

    Leddy, J.J.; Gritzner, G.

    1975-12-30

    A zinc-bromine secondary cell is divided into two compartments by an ion exchange diaphragm. The electrolyte system includes an essentially bromide-ion-free, aqueous solution containing a zinc ion as an anolyte and a bromide ion containing catholyte. A method of operating the cell is disclosed. 2 figures, 2 tables. (auth)

  6. Oxomemazine hydro­chloride

    OpenAIRE

    Siddegowda, M. S.; Butcher, Ray J.; Mehmet Akkurt; Yathirajan, H.S.; Ramesh, A. R.

    2011-01-01

    In the title compound [systematic name: 3-(5,5-dioxophenothiazin-10-yl)-N,N,2-trimethylpropanaminium chloride], C18H23N2O2S+·Cl−, the dihedral angle between the two outer aromatic rings of the phenothiazine unit is 30.5 (2)°. In the crystal, the components are linked by N—H...Cl and C—H...Cl hydrogen bonds and C—H...π interactions.

  7. Shock compression of polyvinyl chloride

    Science.gov (United States)

    Neogi, Anupam; Mitra, Nilanjan

    2016-04-01

    This study presents shock compression simulation of atactic polyvinyl chloride (PVC) using ab-initio and classical molecular dynamics. The manuscript also identifies the limits of applicability of classical molecular dynamics based shock compression simulation for PVC. The mechanism of bond dissociation under shock loading and its progression is demonstrated in this manuscript using the density functional theory based molecular dynamics simulations. The rate of dissociation of different bonds at different shock velocities is also presented in this manuscript.

  8. Regioselective synthesis and biological studies of novel 1-aryl-3, 5-bis (het) aryl pyrazole derivatives as potential antiproliferative agents.

    Science.gov (United States)

    Ananda, Hanumappa; Sharath Kumar, Kothanahally S; Nishana, Mayilaadumveettil; Hegde, Mahesh; Srivastava, Mrinal; Byregowda, Raghava; Choudhary, Bibha; Raghavan, Sathees C; Rangappa, Kanchugarakoppal S

    2017-02-01

    Pyrazole moiety represents an important category of heterocyclic compound in pharmaceutical and medicinal chemistry. The novel 1-aryl-3, 5-bis (het) aryl pyrazole derivatives were synthesized with complementary regioselectivity. The chemical structures were confirmed by IR, (1)H NMR, (13)C NMR, and mass spectral analysis. The chemical entities were screened in various cancer cell lines to assess their cell viability activity. Results showed that the compound 3-(1-(4-bromophenyl)-5-phenyl-1H-pyrazol-3-yl) pyridine (5d) possessed maximum cytotoxic effect against breast cancer and leukemic cells. The cytotoxicity was confirmed by live-dead cell assay and cell cycle analysis. Mitochondrial membrane potential, Annexin V-FITC staining, DNA fragmentation, Hoechst staining, and western blot assays revealed the ability of compound 5d to induce cell death by activating apoptosis in cancer cells. Thus, the present study demonstrates that compound 5d could be an attractive chemical entity for the development of small molecule inhibitors for treatment of leukemia and breast cancer.

  9. Salt, chloride, bleach, and innate host defense.

    Science.gov (United States)

    Wang, Guoshun; Nauseef, William M

    2015-08-01

    Salt provides 2 life-essential elements: sodium and chlorine. Chloride, the ionic form of chlorine, derived exclusively from dietary absorption and constituting the most abundant anion in the human body, plays critical roles in many vital physiologic functions, from fluid retention and secretion to osmotic maintenance and pH balance. However, an often overlooked role of chloride is its function in innate host defense against infection. Chloride serves as a substrate for the generation of the potent microbicide chlorine bleach by stimulated neutrophils and also contributes to regulation of ionic homeostasis for optimal antimicrobial activity within phagosomes. An inadequate supply of chloride to phagocytes and their phagosomes, such as in CF disease and other chloride channel disorders, severely compromises host defense against infection. We provide an overview of the roles that chloride plays in normal innate immunity, highlighting specific links between defective chloride channel function and failures in host defense.

  10. Salt, chloride, bleach, and innate host defense

    Science.gov (United States)

    Wang, Guoshun; Nauseef, William M.

    2015-01-01

    Salt provides 2 life-essential elements: sodium and chlorine. Chloride, the ionic form of chlorine, derived exclusively from dietary absorption and constituting the most abundant anion in the human body, plays critical roles in many vital physiologic functions, from fluid retention and secretion to osmotic maintenance and pH balance. However, an often overlooked role of chloride is its function in innate host defense against infection. Chloride serves as a substrate for the generation of the potent microbicide chlorine bleach by stimulated neutrophils and also contributes to regulation of ionic homeostasis for optimal antimicrobial activity within phagosomes. An inadequate supply of chloride to phagocytes and their phagosomes, such as in CF disease and other chloride channel disorders, severely compromises host defense against infection. We provide an overview of the roles that chloride plays in normal innate immunity, highlighting specific links between defective chloride channel function and failures in host defense. PMID:26048979

  11. Developing chloride resisting concrete using PFA

    Energy Technology Data Exchange (ETDEWEB)

    Dhir, R.K.; El-Mohr, M.A.K.; Dyer, T.D. [Univ. of Dundee (United Kingdom). Dept. of Civil Engineering

    1997-11-01

    PFA concrete mixes were designed to optimize resistance to chloride ingress. Chloride binding capacity, intrinsic permeability and their concomitant influence on the coefficient of chloride diffusion have been investigated. PFA replacements up to 67% and exposure concentrations of 0.1, 0.5, 1.0 and 5.0 mole/liter were used. Chloride binding capacity was found to increase with increasing PFA replacement up to 50% and to then decline. It increased with chloride exposure concentration as well as water/binder ratio. The coefficient of chloride diffusion of concrete samples was found to be dependent on both the intrinsic permeability of the concrete and the ability of its cement matrix to bind chlorides.

  12. An advantageous route to oxcarbazepine (trileptal) based on palladium-catalyzed arylations free of transmetallating agents.

    Science.gov (United States)

    Carril, Mónica; SanMartin, Raul; Churruca, Fátima; Tellitu, Imanol; Domínguez, Esther

    2005-10-27

    [reaction: see text] A new route to oxcarbazepine (Trileptal), the most widely prescribed antiepileptic drug, starting from commercially available 2'-aminoacetophenone and 1,2-dibromobenzene, is reported. The sequentially accomplished key steps are palladium-catalyzed intermolecular alpha-arylation of ketone enolates and intramolecular N-arylation reactions. After several experiments to establish the best conditions for both arylation processes, the target oxcarbazepine is obtained in a satisfactory overall yield, minimizing the number of steps and employing scalable catalytic procedures developed in partially aqueous media.

  13. One-pot synthesis of aryl sulfones from organometallic reagents and iodonium salts.

    Science.gov (United States)

    Margraf, Natalie; Manolikakes, Georg

    2015-03-06

    A transition-metal-free arylation of lithium, magnesium, and zinc sulfinates with diaryliodonium salts is described. The sulfinic acid salts were prepared from the reaction of the corresponding organometallic reagents and sulfur dioxide. Combination of the three single steps (preparation of the organometallic compound, sulfinate formation, and arylation) leads to a one-pot sequence for the synthesis of aryl sulfones from simple starting materials. The chemoselectivity of unsymmetrical diaryliodonium salts has been investigated. Potential and limitations of this method will be discussed.

  14. Suzuki-Miyaura cross-coupling reactions of aryl tellurides with potassium aryltrifluoroborate salts.

    Science.gov (United States)

    Cella, Rodrigo; Cunha, Rodrigo L O R; Reis, Ana E S; Pimenta, Daniel C; Klitzke, Clécio F; Stefani, Hélio A

    2006-01-06

    [reaction: see text] Palladium(0)-catalyzed cross-coupling between potassium aryltrifluoroborate salts and aryl tellurides proceeds readily to afford the desired biaryls in good to excellent yield. The reaction seems to be unaffected by the presence of electron-withdrawing or electron-donating substituents in both the potassium aryltrifluoroborate salts and aryl tellurides partners. Biaryls containing a variety of functional groups can be prepared. A chemoselectivity study was also carried out using aryl tellurides bearing halogen atoms in the same compound. In addition, this new version of the Suzuki-Miyaura cross-coupling reaction was monitored by electrospray ionization mass spectrometry where some reaction intermediates were detected and analyzed.

  15. Fluorination of aryl boronic acids using acetyl hypofluorite made directly from diluted fluorine.

    Science.gov (United States)

    Vints, Inna; Gatenyo, Julia; Rozen, Shlomo

    2013-12-06

    Aryl boronic acids or pinacol esters containing EDG were converted in good yields and fast reactions to the corresponding aryl fluorides using the readily obtainable solutions of AcOF. In reactions with aryl boronic acids containing EWG at the para position, there are two competing forces: one directing the fluorination to take place ortho to the boronic acid and the other, toward an ipso substitution. With EWG meta to the boronic acid, substitution ipso to the boron moiety takes place in good yields.

  16. Microwave-assisted synthesis of α-aryl malonates: Key intermediates for the

    Directory of Open Access Journals (Sweden)

    Mohamed A. Ibrahim

    2016-11-01

    Full Text Available We disclose a new microwave-assisted protocol for the effective α-arylation of diethyl malonate. The coupling of aryl halides with diethyl malonate proceeds smoothly in short reaction time in the presence of a catalytic amount of Cu(OTf2, 2-picolinic acid and Cs2CO3 in toluene using microwave irradiation. The resulting α-aryl malonates are then used as key intermediates for synthesis of variety of heterocyclic compounds, including benzodiazepines, isoquinolines and pyrrolopyridine scaffolds.

  17. Antibacterial Activity of Cetyltrimethylammonium Bromide Modified Silver-Bentonite

    Directory of Open Access Journals (Sweden)

    Nik Malek Nik Ahmad Nizam

    2016-01-01

    Full Text Available Organo-Ag-bentonite was prepared by the attachment of cationic surfactant cetyltrimethylammonium bromide on silver(Ag-exchanged bentonite. The prepared samples were characterized by X-ray diffraction (XRD, Fourier transform infrared (FTIR spectroscopy and energy dispersive X-ray (EDX analysis and antibacterial assay was performed against Escherichia coli in different percentage of saline solutions through minimum inhibition concentration (MIC method. Organo-Ag-bentonite showed higher antibacterial activity than organo-bentonite and Ag-bentonite especially in saline solution suggesting that the precipitation of AgCl in the presence of Ag-bentonite in saline solution could be avoided by the attachment of cationic surfactant on Ag-bentonite surfaces, hence increased their antibacterial activity.

  18. Design and Fabrication of Externally heated Copper Bromide Laser

    Directory of Open Access Journals (Sweden)

    J.P. Dudeja

    1993-04-01

    Full Text Available An externally-heated, longitudinally-discharged, low-repetition-rate copper bromide laser, was designed and fabricated. The green-coloured wavelength at 5106 A from this laser can be used for underwater ranging and detection of submerged objects. Several new changes in the design of discharge tube, heating technique, buffer-gas-flow sub-system and electrical circuit have been conceived and incorporated advantageously in our system. Various parameters, for example, the type of buffer gas and its flow rate, mixture of gases, temperature of the discharge tube, delay between dissociation and excitation pulses, dissociation and excitation energies, and various resonator configurations are being optimised to get the maximum output power/energy from the laser system.

  19. Solvent effects in the reaction between piperazine and benzyl bromide

    Indian Academy of Sciences (India)

    S Ranga Reddy; P Manikyamba

    2007-11-01

    The reaction between piperazine and benzyl bromide was studied conductometrically and the second order rate constants were computed. These rate constants determined in 12 different protic and aprotic solvents indicate that the rate of the reaction is influenced by electrophilicity (), hydrogen bond donor ability () and dipolarity/polarizability (*) of the solvent. The LSER derived from the statistical analysis indicates that the transition state is more solvated than the reactants due to hydrogen bond donation and polarizability of the solvent while the reactant is more solvated than the transition state due to electrophilicity of the solvent. Study of the reaction in methanol, dimethyl formamide mixtures suggests that the rate is maximum when dipolar interactions between the two solvents are maximum.

  20. Xanthine Biosensor Based on Didodecyldimethylammonium Bromide Modified Pyrolytic Graphite Electrode

    Institute of Scientific and Technical Information of China (English)

    TANG,Ji-Lin(唐纪琳); HAN,Xiao-Jun(韩晓军); HUANG,Wei-Min(黄卫民); WANG,Er-Kang(汪尔康)

    2002-01-01

    The vesicle of didodecyldimethylammonium bromide (DDAB)which contained tetrathiafulvalene (TTF) was mixed with xanthine oxidase, and the mixture was cast on the pyrolytic graphite electrode. The lipid films were used to supply a biological environment resembling biomembrane on the surface of the electrode. TTF was used as a mediator because of its high electron-transfer efficiency. A novel xanthine biosensor based on cast DDAB film was developed. The effects of pH and operating potential were explored for optimum analytical performance by using the amperometric method. The response time of the biosensor was less than 10 s. The detection limit of the biosensor was 3.2 × 10-7 mol/L and the liner range was from 4 × 10-7 mol/L to 2.4 × 10-6 mol/L.

  1. Mechanism of the Deaquation of Aquopentaaminocobalt(Ⅲ) Bromide

    Institute of Scientific and Technical Information of China (English)

    MA,Li-Dun(马礼敦); CHENG,Guang-Hui(程广辉); WU,Hong-Xiang(吴宏翔); LIN,Han-Yi(林涵毅); SHEN,Xiao-Liang(沈孝良); SHI,Guo-Shun(施国顺)

    2002-01-01

    There are two theories, SN1 and SN2, for the mechanism of the deaquation of aquopentaamincobalt(Ⅲ) bromide (AAC-B).Both of the theories are supported by some experimental and calculated data. But there are not any experiments to determine directly the structure of the intermediates at different reaction time. In this paper the structures of the intermediates at different reaction time in deaquation-anation of AACB were de-termined by extended X-ray absorption fine structure (EXAFS)and the reaction process wes studied by the combination of Xray powder diffraction and EXAFS. It was demonstrated that the deaquation-anation of AACB obeys the SN2 theory.

  2. Mechanism of the Deaquation of Aquopentaaminocobalt(Ⅲ)Bromide

    Institute of Scientific and Technical Information of China (English)

    MA,Li-Dun; CHENG,Guang-Hui; 等

    2002-01-01

    There are two theories,SN1 and SN2, for the mechanism of the deaquation of aquopentaamincobalt(Ⅲ) bromide(AAC-B). Both of the theories are supported by some experimental and calculated data. But there are not any experiments to determine directly the structure of the intermediates at dififferent reaction time.In this paper the structures of the intermediates at different reaction time in deaquation-anation of AACB were determined by extended X-ray absorption fine structure (EXAFS) and the reaction process was studied by the combination of X-ray powder diffraction and EXAFS.It was demonstrated that the deaquation-anation of AACB obeys the SN2 theory.

  3. Classifying the Basic Parameters of Ultraviolet Copper Bromide Laser

    Science.gov (United States)

    Gocheva-Ilieva, S. G.; Iliev, I. P.; Temelkov, K. A.; Vuchkov, N. K.; Sabotinov, N. V.

    2009-10-01

    The performance of deep ultraviolet copper bromide lasers is of great importance because of their applications in medicine, microbiology, high-precision processing of new materials, high-resolution laser lithography in microelectronics, high-density optical recording of information, laser-induced fluorescence in plasma and wide-gap semiconductors and more. In this paper we present a statistical study on the classification of 12 basic lasing parameters, by using different agglomerative methods of cluster analysis. The results are based on a big amount of experimental data for UV Cu+ Ne-CuBr laser with wavelengths 248.6 nm, 252.9 nm, 260.0 nm and 270.3 nm, obtained in Georgi Nadjakov Institute of Solid State Physics, Bulgarian Academy of Sciences. The relevant influence of parameters on laser generation is also evaluated. The results are applicable in computer modeling and planning the experiments and further laser development with improved output characteristics.

  4. Oral bioavailability and enterohepatic recirculation of otilonium bromide in rats.

    Science.gov (United States)

    Shin, Beom Soo; Kim, Jung Jun; Kim, John; Hu, Sul Ki; Kim, Hyoung Jun; Hong, Seok Hyun; Kim, Han Kyung; Lee, Hye Suk; Yoo, Sun Dong

    2008-01-01

    This study was conducted to examine the oral bioavailability and the possibility of enterohepatic recirculation of otilonium bromide in rats. A sensitive LC/MS/MS assay (LLOQ 0.5 ng/mL) was developed for the determination of otilonium and applied to i.v. and oral administration studies in bile duct cannulated (BDC) and non-BDC rats. After i.v. injection to BDC rats (1 mg/ kg as otilonium), average t(1/2), CL, Vz and AUC were 7.9 +/- 1.9 h, 8.7 +/- 3.1 mL/min/kg, 5.7 +/- 1.4 L/kg and 2,088 +/- 676 ng h/mL, respectively, and these values were comparable to those found in non-BDC rats. The percentages of i.v. dose excreted unchanged in bile and urine in BDC rats were 11.6 +/- 3.0 and 3.1 +/- 0.7%, respectively. Upon oral administration to non-BDC rats (20 mg/kg as otilonium), t(1/2), Cmax, Tmax and AUC were 6.4 +/- 1.3 h, 182.8 +/- 44.6 ng/mL, 1.9 +/- 1.6 h and 579 +/- 113 ng h/mL, respectively. The absolute oral bioavailability was low (1.1%), while the drug was preferentially distributed to gastrointestinal tissues. A secondary peak was observed in the serum concentration-time profiles in non-BDC rats following both i.v. and oral administration, indicating that otilonium bromide was subject to enterohepatic recirculation.

  5. Comparative mobility of sulfonamides and bromide tracer in three soils

    Science.gov (United States)

    Kurwadkar, S.T.; Adams, C.D.; Meyer, M.T.; Kolpin, D.W.

    2011-01-01

    In animal agriculture, sulfonamides are one of the routinely used groups of antimicrobials for therapeutic and sub-therapeutic purposes. It is observed that, the animals when administered the antimicrobials, often do not completely metabolize them; and excrete the partially metabolized forms into the environment. Due to the continued use of antimicrobials and disposal of untreated waste, widespread occurrence of partially metabolized antimicrobials in aquatic and terrestrial environments has been reported in various scientific journals. In this research, the mobility of two sulfonamides - sulfamethazine (SMN), sulfathiazole (STZ) and a conservative bromide tracer was investigated in three soils collected from regions in the United States with large number of concentrated animal-feed operations. Results of a series of column studies indicate that the mobility of these two sulfonamides was dependent on pH, soil charge density, and contact time. At low pH and high charge density, substantial retention of sulfonamides was observed in all three soils investigated, due to the increased fraction of cationic and neutral forms of the sulfonamides. Conversely, enhanced mobility was observed at high pH, where the sulfonamides are predominantly in the anionic form. The results indicate that when both SMN and STZ are predominantly in anionic forms, their mobility approximates the mobility of a conservative bromide tracer. This observation is consistent for the mobility of both SMN and STZ individually, and also in the presence of several other antimicrobials in all three soils investigated. Higher contact time indicates lower mobility due to increased interaction with soil material. ?? 2011.

  6. Novel Fluorinated Phosphorus–Sulfur Heteroatom Compounds: Synthesis and Characterization of Ferrocenyl- and Aryl-Phosphonofluorodithioic Salts, Adducts, and Esters

    Directory of Open Access Journals (Sweden)

    Guoxiong Hua

    2015-07-01

    Full Text Available A series of novel ferrocenyl- and aryl-phosphonofluorodithioic salts, adducts, and esters has been prepared. The reaction of 2,4-diferrocenyl-1,3,2,4-diathiadiphosphetane 2,4-disulfide {[FcP(μ-SS]2, FcLR} with dry KF or tetrabutylammonium fluoride (TBAF led to the corresponding potassium and tetrabutylammonium salts of ferrocenyldithiofluorophosphinic acids. Treating potassium ferrocenyldithiofluorophosphinic acid with an equimolar amount of tetraphenylphosphonium chloride readily yielded the corresponding organic adducts, and with mono- and di-halogenated alkanes generated a series of the corresponding esters of ferrocenylphosphonofluoridodithioates. Similarly, using 1,3-epithionaphtho[1,8-cd][1,2,6] oxadiphosphinine 1,3-disulfide or Belleau’s Reagent in place of FcLR resulted in the corresponding novel salts, adducts, and ester derivatives. All new compounds have been characterized by means of multi-NMR (1H, 13C, 31P, 19F spectroscopy and accurate mass measurement in conjunction with single crystal X-ray crystallography of four structures.

  7. Hydrolysis of cupric chloride in aqueous ammoniacal ammonium chloride solutions

    Directory of Open Access Journals (Sweden)

    Limpo, J. L.

    1995-06-01

    Full Text Available Cupric solubility in the CuCl2-NH4Cl-NH3-H2O system for chloride concentrations lower than 4 molal in the temperature range 25-60 °C was studied. The experimental results show that for chloride concentration between 3.0 and 1.0 molal the cupric solubility is determined by the solubility of the cupric hydroxychloride Cu(OH1.5Cl0.5. For a chloride concentration value of 4.0 molal, there are two cupric compounds, the hydroxychloride Cu(OH1.5Cl0.5 or the diammine chloride Cu(NH32Cl2, on which the solubility of Cu(II depends, according to the temperature and the value of the ratio [NH3]Total/[Cu]Total.

    Se estudia la solubilidad del Cu(II en el sistema CuCl2-NH4Cl-NH3-H2O para concentraciones de cloruro inferiores a 4 molal en el intervalo de temperaturas 25-60 °C. Los resultados experimentales muestran que, para concentraciones de cloruros comprendidas entre 3,0 y 1,0 molal, la solubilidad cúprica viene determinada por la solubilidad del hidroxicloruro cúprico, Cu(OH1.5Cl0.5. Para concentraciones de cloruro 4,0 molal, existen dos compuestos cúpricos, el hidroxicloruro, Cu(OH1.5Cl0.5 o el cloruro de diamina, Cu(NH32Cl2, de los que, de acuerdo con la temperatura y con el valor de la relación [NH3]Total/[Cu]Total depende la solubilidad del Cu(II.

  8. X-ray Crystal Structure, Raman Spectroscopy and Ab Initio Density Functional Theory Calculations on 1,1,3,3-Tetramethylguanidinium Bromide

    DEFF Research Database (Denmark)

    Berg, Rolf W.; Riisager, Anders; Nguyen van Buu, Olivier

    2010-01-01

    = 104.31(3)°, Z = 2, based on 11769 reflections, measured from θ = 2.71-28.00° on a small colorless needle crystal. Raman and IR spectra are presented and assigned. When heated, both the chloride and the bromide salts form vapor phases. The Raman spectra of the vapors are surprisingly alike, showing......, for example, a characteristic strong band at 2229 cm-1. This band was interpreted by some of us to show that the [tmgH]Cl gas phase should consist of monomeric ion pair “molecules” held together by a single N-H+ · · · Cl- hydrogen bond, the stretching vibration of which should be causing the band, based on ab...

  9. Critical pitting temperature for Type 254 SMO stainless steel in chloride solutions

    Energy Technology Data Exchange (ETDEWEB)

    Abd El Meguid, E.A. [Department of Electrochemistry and Corrosion, National Research Centre, Dokki, Cairo (Egypt)]. E-mail: eameguid_nrc@yahoo.com; Abd El Latif, A.A. [Department of Electrochemistry and Corrosion, National Research Centre, Dokki, Cairo (Egypt)

    2007-02-15

    The variation with time of the open circuit potential of high molybdenum containing stainless steel (Type 254 SMO) was measured in 4% sodium chloride solution in the temperatures range 30-100 deg. C. The plot of steady state potentials as function of temperature showed an inflection at 50 deg. C, attributed to the decrease of oxygen solubility in test solution above 50 deg. C. Potentiodynamic cycling anodic polarization technique was used to determine the critical pitting potential (E {sub pit}) and the critical protection potential (E {sub prot}) of the steel in 4-30% NaCl solutions at temperatures between 30 and 100 deg. C. By plotting the two values versus solution temperature, the corresponding critical pitting (CPT) and the critical protection (CPrT) temperatures were determined. Both parameters decreased with increasing chloride content. Above the CPT, E {sub pit} and E {sub prot} decreased linearly with log[Cl{sup -}]. The addition of bromide ions to the solution shifted both E {sub pit} and E {sub prot} towards positive values. In 4% NaCl, E {sub pit} increased linearly with pH in the range 1-10. The combined effect of chloride ion concentration and pH on the morphology of the pits was examined by scanning electron microscopy (SEM) following potentiodynamic cycling anodic polarization.

  10. Study on the Synthetic Technology of 4-Nitrobenzyl Bromide%对硝基溴苄的合成工艺研究

    Institute of Scientific and Technical Information of China (English)

    叶彬彬; 王玲燕; 谢菊冲; 何文杰; 徐丹萍

    2014-01-01

    A new method of preparation 4 -nitrobenzyl bromide was developed using p -nitrotoluene as raw material, NBS as bromination agent and AIBN as initiator , with the optimum solvent methylene chloride , reaction temperature 50 ℃, reaction time 8 h, and the yield was up to 85%.The method of the basis of traditional process of bromine bromine preparation hydrobromide improved agent bromide.This process route had the characteristics of a low production cost , simple operation , short reaction time , easy industrial production and environmentally friendly.%以对硝基甲苯作为原料,针对传统的溴素制备氢溴酸上溴工艺,改进溴化剂,引入N-溴代丁二酰亚胺( NBS )作为溴化剂,偶氮二异丁腈( AIBN)作为引发剂,二氯甲烷作为最佳反应溶剂,50℃反应8 h,反应收率≥85%。该工艺路线具有生产成本低、操作简便、反应时间短、适合工业化生产以及符合环保要求等特点。

  11. Aryl hydrocarbon mono-oxygenase activity in human lymphocytes

    Energy Technology Data Exchange (ETDEWEB)

    Griffin, G.D.; Schuresko, D.D.

    1981-06-01

    Aryl hydrocarbon mono-oxygenase (AHM), an enzyme of key importance in metabolism of xenobiotic chemicals such as polynuclear aromatic hydrocarbons (PNA), is present in human lymphocytes. Studies investing the relation of activity of AHM in human lymphocytes to parameters such as disease state, PNA exposure, in vitro mitogen stimulation, etc. have been summarized in this report. Some studies have demonstrated increased AHM activity in lymphocytes from cigarette smokers (compared to nonsmokers), and in lung cancer patients when compared to appropriate control groups. These observations are confused by extreme variability in human lymphocyte AHM activities, such variability arising from factors such as genetic variation in AHM activity, variation in in vitro culture conditions which affect AHM activity, and the problematical relationship of common AHM assays to actual PNA metabolism taking place in lymphocytes. If some of the foregoing problems can be adequately addressed, lymphocyte AHM activity could hold the promise of being a useful biomarker system for human PNA exposure.

  12. Novel aryl carbamate derivatives of metronidazole as potential antiamoebic agents.

    Science.gov (United States)

    Hayat, Faisal; Wahedi, Hussain Mustatab; Park, Seonghyeok; Tariq, Saba; Azam, Amir; Shin, Dongyun

    2016-01-01

    A series of novel aryl carbamate derivatives of metronidazole (MNZ) were designed, synthesized, and screened for antiamoebic activity. As compared to MNZ, most of the derivatives exhibited moderate to excellent activity against the HM1:IMSS strain of Entamoeba histolytica. Compounds 7, 14, 16, 19, and 21 exhibited the most promising antiamoebic activity with IC50 values of 0.24, 0.08, 0.26, 0.26, and 0.15 μM, respectively, compared to that of MNZ (1.78 μM). Moreover, from the toxicological studies of these compounds on human melanocytes, the melan-a cell line revealed that the potent compounds are nontoxic at concentrations ranging from 2.5 to 50 μM.

  13. Fluorescence characteristics of aryl boronic acid derivate (PBA)

    Science.gov (United States)

    Patil, S. S.; Muddapur, G. V.; Patil, N. R.; Melavanki, R. M.; Kusanur, R. A.

    2015-03-01

    The absorption and fluorescence spectra of newly synthesized aryl boronic acid derivative namely Phenyl boronic acid (PBA) have been recorded in various solvents of different polarities. The ground state dipole moment of PBA was obtained from quantum chemical calculations. Solvatochromic correlations were used to estimate the ground state (μg) and excited state (μe) dipole moments. The excited state dipole moments are observed to be greater than the ground state dipole moments. Further, the ground and excited state dipole moments are not parallel but subtend by an angle of 70°. The changes in dipole moment (Δμ) were calculated both from solvatochromic shift method and microscopic solvent polarity parameter (ETN), and the values are compared. Solvent effects on the absorption and fluorescence spectra were quantified using Reichardt's and bulk solvent polarity parameters were complemented by the results of the Kamlet-Taft treatment.

  14. Aryl Polyphosphonates: Useful Halogen-Free Flame Retardants for Polymers

    Directory of Open Access Journals (Sweden)

    Li Chen

    2010-10-01

    Full Text Available Aryl polyphosphonates (ArPPN have been demonstrated to function in wide applications as flame retardants for different polymer materials, including thermosets, polycarbonate, polyesters and polyamides, particularly due to their satisfactory thermal stability compared to aliphatic flame retardants, and to their desirable flow behavior observed during the processing of polymeric materials. This paper provides a brief overview of the main developments in ArPPN and their derivatives for flame-retarding polymeric materials, primarily based on the authors’ research work and the literature published over the last two decades. The synthetic chemistry of these compounds is discussed along with their thermal stabilities and flame-retardant properties. The possible mechanisms of ArPPN and their derivatives containing hetero elements, which exhibit a synergistic effect with phosphorus, are also discussed.

  15. A Direct Transformation of Aryl Aldehydes to Benzyl Iodides Via Reductive Iodination

    Energy Technology Data Exchange (ETDEWEB)

    Ruso, Jayaraman Sembian; Rajendiran, Nagappan; Kumaran, Rajendran Senthil [Univ. of Madras, Chennai (India)

    2014-02-15

    A facile transformation of aryl aldehydes to benzyl iodides through one-pot reductive iodination is reported. This protocol displays remarkable functional group tolerance and the title compound was obtained in good to excellent yield.

  16. Microwave Assisted Solvent Free Synthesis of Azomethines from Aryl Aldehydes on Melamin Formaldehyde as Solid Support

    Directory of Open Access Journals (Sweden)

    Ramin Rezaei

    2011-01-01

    Full Text Available Various aryl aldehydes underwent prompt one pot conversion into the corresponding azomethines in high yields by reacting with hydroxylamine hydrochloride supported on melamine formaldehyde under microwave irradiation.

  17. Recent Advancements and Biological Activities of Aryl Propionic Acid Derivatives: (A Review

    Directory of Open Access Journals (Sweden)

    Harshita Dhall

    2016-08-01

    Full Text Available The aryl propionic acid derivatives belong to an important class of NSAIDs (Non Steroidal Anti-inflammatory Drugs. Ibuprofen, chemically called 2-(4-isobutyl phenyl propionic acid, is a well known NSAID. Aryl propionic acid derivatives possesses a wide range of biological activities including anti-bacterial, anti-convulsant, anti-cancer, analgesic and anti-inflammatory activities. Apart from very potent compounds in the field of analgesics and antipyrectics as Ibuprofen, Oxaprozin, Ketoprofen, Fenoprofen; aryl propionic acid derivatives plays important role to treat other ailments also. Through this review, an attempt has been made to emphasize on recent work done and recent advancements in arena of aryl propionic acid derivatives in view of medicinal chemistry.

  18. Thermal properties of polyfurfuryl alcohol absorbed/adsorbed on arylated soy protein films

    CSIR Research Space (South Africa)

    Kumar, R

    2012-02-01

    Full Text Available backbone through arylation is revealed from Fourier transform infrared study. Thermal studies of SPI, SPI-PFA and SPIPFA-Ar were carried out by thermogravimetric analysis, differential scanning calorimetry and dynamic mechanical thermal analysis...

  19. Synthesis and application of chiral N,N′-dialkylated cyclohexanediamine for asymmetric hydrogenation of aryl ketones

    Institute of Scientific and Technical Information of China (English)

    Meng Lin Ma; Chuan Hong Ren; Ya Jing Lv; Hua Chen; Xian Jun Li

    2011-01-01

    Chiral N,N′-dialkylated cyclohexanediamine derived ligands have been synthesized and used in the asymmetric hydrogenation of aryl ketones. Optically active alcohols with up to 90% enantiomeric excess were obtained in high yields.

  20. Genetic expression of aryl hydrocarbon hydroxylase activity in the mouse.

    Science.gov (United States)

    Nebert, D W; Robinson, J R; Niwa, A; Kumaki, K; Poland, A P

    1975-04-01

    Monooxygenases require NADPH and molecular oxygen during the metabolism of numerous endogenous hydrophobic substrates and carcinogenic and toxic exogenous chemicals. The complexity of these membrane-bound multicomponent drug-metabolizing enzyme systems is reviewed. What "aryl hydrocarbon (benzo[a]pyrene) hydroxylase activity" actually represents is reviewed and discussed. At least two forms of the hydroxylase activity exist and we suggest that they are associated with different molecular species of membrane-bound CO-binding hemoprotein (i.e., they are associated with different enzyme active-sties). At least two, and probably more than two, nonlinked loci are responsible for the genetic expression of new cytochrome P1450 formation and aryl hydrocarbon hydroxylase induction--and the stimulation of 10 other monooxygenase "activities"--in the mouse treated with certain aromatic hydrocarbons. The individual variability of hydroxylase activity in an inbred and in a random-bred strain of micr is illustrated. The basal hydroxylase activity appears to be inherited differently from the aromatic hydrocarbon-inducible hydroxylase activity. The potent inducer 2,3,7,8-tetrachlorodibenzo-p-dioxin can stimulate increases in these hepatic monooxygenase activities and p1450 formation in so-called "nonresponsive" mice, whereas inducers such as beta-naphthoflavone and 3-methylcholanthrene cannot. Thus, the genetically "nonresponsive" micr apparently possess the structural and regulatory genes necessary for expression of these inducible monooxygenase activities and associated new formation of cytochrome P1450. We suggest that a mutation has occurred in the "nonresponsive" inbred strains that results in production of an inducer-binding receptor having a diminished affinity for aromatic hydrocarbons.