1. We studied the effects of flash photolysis on the novel enantiomeric cardiac inotropes EMD 57033 (a calcium sensitizer) and EMD 57439 (a phosphodiesterase III inhibitor) in rat isolated ventricular...Full Text Available
Room-temperature phosphorescence (RTP) has generated considerable interest over the past several years. Several materials have been used to induce RTP from a variety of compounds. However, there is still a need to test additional materials and experimental conditions for RTP so the maximum sensitivity and selectivity can be obtained. In this work, three solid surfaces and several experimental conditions were tested for RTP of nitrogen heterocycles and aromatic amines. Nitrogen heterocycles and aromatic amines are an important class of compounds as shown by work in areas such as environmental research and coal liquefaction research. 18 references.
Mutation assay with Salmonella typhimurium enabled us to detect various types of mutagens in cooked foods. A series of mutagenic heterocyclic amines has been isolated and identified in broiled fish...Full Text Available
A Pd(0)-catalyzed intramolecular Heck-type reaction of oxime ether has been developed, providing convenient access to heterocyclic oximes. PMID:21964259
Plants often synthesize secondary metabolites that are enantiomers. Enantiomers can cause very different physiological responses. Ammodendrine (1) and anabasine (2) are teratogens that can cause congenital malformations in livestock and enantiomeric forms of each have been found in Lupinus spp. an...
Polynuclear aromatic sulphur heterocycles (PASHs) were isolated from a coal extract by two-step separation method using silica gel column chromatography and ligand exchanges thin layer chromatography (PdCl{sub 2}/SiO{sub 2}). The subfraction was examined by capillary column gas chromatography with flame ionization detector and flame photometric detector and gas chromatography - mass spectrometry. Identification was accomplished by comparison of chromatographic retention indices and mass spectra of compounds with those reported in the literature. It was found that the principal structures of the sulphur-containing fraction of Guiding coal extract have 3-4 aromatic rings. Dibenzothiophene, C{sub 1} - C{sub 3} alkylated dibenzothiophenes, benzonaphthothiophene and its alkylated derivatives were the main compounds. Only a few other polynuclear sulfur heterocycles were detected. No benzothiophene and its derivatives were presented. 8 refs., 2 figs., ...
The purpose of work is systematical studying of benzo (B) of thiophene-1,1-dioxides and their 2,3-di-hydro derivatives behaviour in the reactions of electrophflic, radical, nucleophilic nitration, reduction of nitro group, embodiment of synthesis of N-amino derivatives, investigation of sulfur containing hetero-cyclic compounds, including of residues of some steroids
Heterocyclic amines such as 2-amino-3-methylimidazo [4,5-f] quinoline (IQ) and 2-amino-3,8-dimethylimidazo [4,5-f] quinoxaline (MeIQx) are dietary carcinogens generated when meats are cooked...Full Text Available
A novel, one-pot, multicomponent synthesis of 4-arylidene-3-methyl-1-(4-arylthiazol-2-yl)-1H-pyrazol-5(4H)-ones is described using phenacyl bromides, thiosemicarbazide, ethylacetoacetate, and aryl aldehydes. This synthesis involves simultaneous formation of two heterocycles like thiazole and pyrazolone along with condensation of active methylene group by aldehydes via Knoevenagel reaction. The methodology is mild, efficient, and high yielding. GRAPHICAL ABSTRACT[image omitted
Racemic and enantiomerically pure b-amino-a-trifluoromethyl alcohols were obtained via sequential nucleophilic trifluoromethylation of selected a-imino ketones, derived from arylglyoxals, and subsequent removal of the MeO or Ph(Me)CH substituent, respectively, located at the N-atom. The obtained products, containing a primary amino group, were used for the synthesis of imidazole N-oxides bearing a trifluoromethyl group as a part of the N(1)-alkyl chain. Imidazole N-oxides with an electron-withdrawing ester group at C(4) underwent spontaneous isomerization under the reaction conditions, and the corresponding imidazol-2-ones derivatives were isolated as final products.
Acetohydroxyacid synthase (AHAS; EC 2.2.1.6) is the first enzyme in the biosynthetic pathway of the branched-chain amino acids. It catalyzes the conversion of two molecules of pyruvate into 2-acetolactate or one molecule of pyruvate and one molecule of 2-ketobutyrate into 2-aceto-2-hydroxybutyrate. AHAS requires the cofactors thiamine diphosphate (ThDP), Mg{sup 2+} and FAD for activity. The herbicides that target this enzyme are effective in protecting a broad range of crops from weed species. However, resistance in the field is now a serious problem worldwide. To address this, two new sulfonylureas, monosulfuron and monosulfuron ester, have been developed as commercial herbicides in China. These molecules differ from the traditional sulfonylureas in that the heterocyclic ring attached to the nitrogen atom of the sulfonylurea bridge is monosubstituted rather than disubstituted. The structures of these compounds in complex with the catalytic subunit of Arabidopsis ...
The authors studied the resolution of racemic glycidol through esterification with butyric acid catalyzed by porcine pancreatic lipase in organic media. A screening of seven solvents (log P values between 0.49 and 3.0, P being the n-octanol-water partition coefficient of the solvent) showed that neither log P nor the logarithm of the molar solubility of water in the solvent provides good correlations between enantioselectivity and the properties of the organic media. Chloroform was one of the best solvents as regards the enantiometic purity (e.p.) of the ester produced. In this solvent, the optimum temperature for the reaction was determined to be 35C. The enzyme exhibited maximum activity at a water content of 13 [plus minus] 2% (w/w). The enantiomeric purity obtained was 83 [plus minus] 2% of (S)-glycidol butyrate and did not depend on the alcohol concentration or the enzyme water content for values of these parameters up to 200 mM and 25% (w/w), respectively. ...
One salt and two Cu(II) complexes (H2hsm)(ox), 1, [Cu(hsm)(ox)], 2, and [Cu(hsm)(ox)H2O], 3, have been synthesized and X-ray characterized (hsm is histamine and ox2? is the oxalate dianion). Starting from the prochiral tetracoordinated complex 2, pentacoordinated complex 3 crystallizes as a racemic mixture of the enantiomeric ? and ? isomers, in space group P21/c. In all cases, the side chain of the hsm group is gauche, allowing the formation of strong hydrogen bonds in the salt 1, and to chelate the metal center in complexes 2 and 3. The combination hsm/ox seems to favor the formation of 2D supramolecular structures (planes or wavy planes), through efficient networks of N?H???O hydrogen bonds. Cell parameters: 1, P21/c, a?=?6.260 (2) ?, b?=?11.500 (4) ?, c?=?12.525 (4) ?, ??=?104.047 (17)...
The enantiomeric separations of three pesticides fipronil (asymmetric nitrogen), isocarbophos (asymmetric phosphorus) and carfentrazone-ethyl (asymmetric carbon) were studied on cellulose-tri(3,5-dimethylphenylcarbamate) chiral stationary phase using high-performance liquid chromatography under normal phase. The mobile phase was n-hexane with alcohols including ethanol, n-propanol, iso-propanol, n-butanol and iso-butanol as polar modifiers. The flow rate was 1.0 mL/min with UV detection at 280, 225 and 230 nm for fipronil, isocarbophos and carfentrazone-ethyl respectively. The influence of the modifiers and their volume content and temperature from 0 to 50 degrees C on the separations was investigated. The chiral stationary phase showed excellent stereoselectivity for the two enantiomers of fipronil and isocarbophos and certain chiral recognition for carfentrazone-ethyl. Iso-propanol was more suitable for the chiral separation of isocarbophos and ...
A series of NHC silver(I), mercury(II) and palladium(II) complexes, [(1,3-diethylbimy)6Ag4I3]I (2), [(1-benzyl-3-picolylbimy)Ag2Br2]n (3), [(1-benzyl-3-picolylbimy)HgI(CH2CN)]2 (4), {[(1-picolyl-3-npropylbimy)2Hg][Hg2I6]}n (5) and [(1,3-dipicolylbimy)PdCl]Cl (6), as well as one anionic complex [1,3-diethylbimidazolium]2[HgI4] (1) (bimy=benzimidazol-2-ylidene), have been prepared and characterized. Interestingly, a wind wheel-like Ag4I3 arrangement in 2 is formed, 1D polymeric chain containing 12-membered macrometallocycles and quadrangle Ag2Br2 units in 3 is generated, and the a-carbon atom of deprotonated acetonitrile ([CH2CN]-) in 4 participates in coordination with mercury(II) atom. In the crystal packings of complexes 1-6, 2D supramolecular layers or 3D supramolecular architectures are...
The synthesis of (3-{sup 15}N)-labeled adenine has been reported by several groups. Each of these syntheses followed essentially the same route, in which the {sup 15}N is introduced by nitration of 4-bromoimidazole under forcing conditions using ({sup 15}N)-HNO{sub 3}. The authors have devised an alternate route which uses an azo coupling reaction for introduction of the {sup 15}N and proceeds through the intermediacy of (5-{sup 15}N)-labeled 5-aminoimidazole-4-carboxamide (AICA). An unrelated route to the (5-{sup 15}N)-labeled 5-amino-imidazole ribonucleoside (AIRs) was recently reported. AICA is a versatile precursor, which is most commonly used for entry into the guanine or isoguanine families, although it is usually used as the AICA-riboside rather than the heterocycle itself. The authors have found that AICA also can be used for the adenine family by cyclization to hypoxanthine using diethoxymethyl acetate in DMF at reflux. Although these conditions are more ...
In order to establish coal NOx preventive measures, discussions were given on formation of N2 in the fixed-bed pyrolysis of low rank coals and the mechanisms thereof. Chinese ZN coal and German RB coal were used for the discussions. Both coals do not produce N2 at 600{degree}C, and the main product is volatile nitrogen. Conversion into N2 does not depend on heating rates, but increases linearly with increasing temperature, and reaches 65% to 70% at 1200{degree}C. In contrast, char nitrogen decreases linearly with the temperature. More specifically, these phenomena suggest that the char nitrogen or its precursor is the major supply source of N2. When mineral substances are removed by using hydrochloric acid, their catalytic action is lost, and conversion into N2 decreases remarkably. Iron existing in ion-exchanged condition in low-rank coal is reduced and finely diffused into metallic iron particles. The particles react with heterocyclic nitrogen compounds and turn ...
Chiral auxiliaries are promising emerging tools for the asymmetric synthesis of octahedral metal complexes. We recently introduced chiral salicyloxazolines as coordinating bidentate chiral ligands which provide excellent control over the metal-centered configuration in the course of ligand substitution reactions and can be removed afterward in an acid-induced fashion under complete retention of configuration (J. Am. Chem. Soc. 2009, 131, 9602-9603). Here reported is our detailed investigation of this sequence of reactions, affording virtually enantiopure ruthenium polypyridyl complexes. The control of the metal-centered chirality by the coordinated chiral salicyloxazolinate ligand was evaluated as a function of reaction conditions, the employed bidentate 2,2'-bipyridine and 1,10-phenanthroline ligands, and the substituent at the asymmetric 5-position of the oxazoline heterocycle. Most striking was the strong influence of the reaction solvent, with aprotic solvents ...
A preliminary chemical characterization is presented of phosphate-free aminolipids isolation from Chlorobium limicola f. thiosulfatophilum. The lipid contains no phosphorus, glycerol, sugar, ornithine, or lysine. Ultraviolet absorption and fluorescence spectra indicate that the amino moiety of the lipid is an aromatic heterocyclic compound. Infrared spectra indicate that the lipid is a secondary or tertiary amide, and gas chromatograhic analysis of the hydrolyzed lipid shows that for each 1100 g of lipid, 1 mol of myristic acid (C/sub 14:0/) is linked in an amide bond. Acid hydrolysis of the lipid yields two fluorescent substances, A (ninhydrine positive) and B (negative), in addition to myristic acid. Proton nuclear magnetic resonance (NMR) studies indicate that substance A contains a butyl groups attached to a conjugated ring carbon, two equivalent ethyl groups attached to one or two nitrogen atoms, and two downfield protons (8.4 ppm), perhaps attached to a ring ...
A new series of heteroleptic cyclometalated platinum(II) complexes Pt-1a-f was synthesized, employing 2-arylpyridine (or 1-arylisoquinoline) (HC{sup L}AMDAN-1) and 1,3-bis(3,4-dibutoxyphenyl)propane-1,3-dione (HO{sup L}AMDAO-1) for cyclometalation and as ancillary ligands, respectively, and photoluminescent properties were investigated. Focusing on red-shifted phosphorescence, C{sup L}AMDAN ligands containing pi-extended aromatics and electron-rich heterocycles were examined. All obtained complexes exhibited photoluminescence at ambient temperature, and the emission maxima ranged from green (lambda{sub PL}=518 nm) to far red (lambda{sub PL}=708 nm). The large Stokes shifts of more than 100 nm and sub-microsecond or microsecond emission lifetimes revealed that these complexes are phosphorescent emissive. The quantum yield of Pt-1 ranged from 0.02 to 0.59 at ambient temperature and decreased as the emission maximum was red-shifted. In comparison with the reference ...
The 1,3-dipolar cyclo addition reactions between benzyl azide and the alpha,beta-unsaturated lactones crotonolactone, alpha-methylenebutyrolactone and Beta-angelica lactone have been performed. The best yields of cycloadducts were obtained by working without solvent, at 60 degree centigree in a sealed tube under nitrogen atmosphere. (3aRS,6aSR)-1-Benzyl-3 a, 4,6,6a-tetrahydro-1H-furo[3,4-d]-1,2,3-triazol-4-one and 3-benzyl-7-oxa-1,2,3-triazaspiro[4.4] non-1-en-6-one have been isolated in 36% and 78% yield from the reactions of the two first lactones respectively. The second product is the first example of this heterocyclic system. The reaction with Beta-angelica lactone yielded the primary cycloadducts (3aR,S,6RS,6aSR)-and (3aRS,6SR,6aSR)-1-benzyl-3a,4,6,6a-tetrahydro-6-methyl-1H-furo[3,4-d]-1,1,3-triazol-4-one and the nitrogen elimination product 4-benzylamino-5-methyl 1-2(5H)-furanone in 44%, 11%, and 7% yield respectively. 26 refs.
Ternary copper(II) complexes [Cu(L1)B](ClO4) (1, 2) and [Cu(L2)B](ClO4) (3, 4), where HL1 and HL2 are tridentate NSO- and ONO-donor Schiff bases and B is a heterocyclic base, viz. dipyrido[3,2-d:2',3'-f]quinoxaline (dpq, 1 and 3) or dipyrido[3,2-a:2',3'-c]phenazine (dppz, 2 and 4), were prepared and their DNA binding and photoinduced DNA cleavage activity studied. Complex 1, structurally characterized by single-crystal X-ray crystallography, shows an axially elongated square-pyramidal (4 + 1) coordination geometry in which the monoanionic L1 binds at the equatorial plane. The NN-donor dpq ligand exhibits an axial-equatorial binding mode. The complexes display good binding propensity to calf thymus DNA, giving a relative order 2 (NSO-dppz) > 4 (ONO-dppz) > 1 (NSO-dpq) > 3 (ONO-dpq). They cleave supercoiled pUC19 DNA to its nicked circular form when treated with 3-mercaptopropionic acid (MPA) by formation of hydroxyl radicals as the cleavage active species ...
The rate of the oxygen-exchange reaction in an aqueous solution of a heterocyclic oxygen compound, 2,4,6-trimethylpyrylium perchlorate, was quantitated. The /sup 18/O isotope effect in /sup 13/C NMR spectroscopy affords a direct, continuous, and relatively simple analysis of the reaction and was used to obtain data on the incorporation of /sup 18/O from solvent H/sub 2//sup 18/O into the pyrylium salt. Due to the low solubility of this salt in aqueous solutions, 2,4,6-trimethyl(2-/sup 13/C)pyrylium perchlorate and 2,4,6-trimethyl(2,6-/sup 13/C/sub 2/)pyrylium perchlorate were synthesized to facilitate the acquisition of the data on an NTC-200 spectrometer operating at 50.31 MHz. Upon incorporation of /sup 18/O into the pyrylium salt, the /sup 13/C NMR signal of the directly bonded carbon atom is shifted upfield 0.038 ppm. A /sup 13/C isotope effect is also detected in the doubly /sup 13/C-enriched pyrylium salt where the /sup 13/C NMR signal for /sup 13/C-O-/sup ...