Sample records for butyrolactam

  1. Hg/Pt-catalyzed conversion of bromo alkynamines/alkynols to saturated and unsaturated γ-butyrolactams/lactones via intramolecular electrophilic cyclization. (United States)

    Kiran Kumar, Yalla; Ranjith Kumar, Gadi; Sridhar Reddy, Maddi


    Convenient and general Hg(ii)/Pt(iv) catalyzed syntheses of γ-butyrolactams and α,β-unsaturated γ-butyrolactones/lactams are described via intramolecular electrophilic cyclizations of bromoalkynes with tosylamino and hydroxyl tethers. The reaction features the use of wet solvents, the exclusion of any base and additive, mild conditions and practical yields. We also synthesised few chiral lactams through this pathway. Additionally, it is shown that the NHTs group distanced further from the homopropargylic position assists regioselective bromoalkyne hydration to yield useful α-bromoketones. Furthermore, Boc protected bromo homo propargyl amines undergo 6-endo-dig cyclization through Boc oxygen to give bromomethylene substituted oxazinones. PMID:26647118

  2. Physicochemical properties of low viscous lactam based ionic liquids

    International Nuclear Information System (INIS)

    Graphical abstract: Remarkably low viscosities of butyrolactam acetate and caprolactam acetate: experimental values (symbols) and VTF equation fitting (solid lines). - Highlights: • Caprolactam and butyrolactam based novel six ionic liquids have been synthesized. • Density, viscosity and speed of sound of lactam based ionic liquids have been measured. • Remarkably low viscosity has been observed for studied lactum based ionic liquids. • Effects of alkyl chain length on anion, geometry of cation and temperature upon studied properties have been discussed. - Abstract: Lactam based ionic liquids were synthesized by an atom economization process between a lactam such as caprolactam or butyrolactam with a Brønsted acid such as formic acid, acetic acid or hexanoic acid. The density, speed of sound and viscosity were measured at atmospheric pressure and as a function of temperature from T = (293.15 to 333.15) K. The experimental density and viscosity values were fitted with linear and Vogel–Tamman–Fulcher (VTF) equations, respectively and found to be fitting well within the experimental error. Thermodynamically important derived properties such as the coefficient of thermal expansion (α) and isentropic compressibility (βs) were calculated from the experimental density and speed of sound values. Lattice potential energy (UPOT) has been calculated to understand the strength of ionic interaction between the ions and the standard entropy (So) has been estimated to assess the disorder within the fluids. The remarkably low values of viscosity of ionic liquids studied are discussed on the basis of activation energy estimated from the Arrhenius equation. Furthermore, the effect of alkyl chain length on the anion, geometry of the cation and temperature has been analysed for the properties studied

  3. Diverse Natural Products from Dichlorocyclobutanones: An Evolutionary Tale. (United States)

    Deprés, Jean-Pierre; Delair, Philippe; Poisson, Jean-François; Kanazawa, Alice; Greene, Andrew E


    11-Nor PGE2 was prepared in our laboratory several years ago and used to obtain the corresponding ring-expanded γ-butyrolactam, γ-butyrolactone, and cyclopentanone derivatives. The conversion of a cyclobutanone into a cyclopentanone had relatively little precedent and merited further study. It was soon found that the presence of a single chlorine adjacent to the carbonyl not only greatly accelerated the reaction with ethereal diazomethane, but also substantially enhanced its regioselectivity; not surprisingly, a second chlorine further increased both. The confluence of this finding and the discovery by Krepski and Hassner that the presence of phosphorus oxychloride significantly improved the Zn-mediated dehalogenation procedure for the preparation of α,α-dichlorocyclobutanones from olefins provided the starting point for decades' worth of exciting adventures in natural product synthesis. A wide variety of naturally occurring 5-membered carbocycles (e.g., hirsutanes, cuparenones, bakkanes, guaianolides, azulenes) could thus be prepared by using dichloroketene-olefin cycloaddition, followed by regioselective one-carbon ring expansion with diazomethane. Importantly, it was also found that natural γ-butyrolactones (e.g., β-oxygenated γ-butyrolactones, lactone fatty acids) could be secured through regioselective Baeyer-Villiger oxidation of cycloadducts with m-CPBA and that naturally occurring γ-butyrolactam derivatives (e.g., amino acids, pyrrolidines, pyrrolizidines, indolizidines) could be efficiently obtained by regioselective Beckmann ring expansion of the adducts with O-(mesitylenesulfonyl)hydroxylamine (Tamura's reagent). These 5-membered carbocycles, γ-butyrolactones, and γ-butyrolactam derivatives were generally secured in enantiopure form through the use of either intrinsically chiral olefins or olefins bearing Stericol, a highly effective chiral auxiliary developed specifically for this "three-atom olefin annelation" approach. In addition

  4. Synthesis and biological evaluation of piperlongumine derivatives as potent anti-inflammatory agents. (United States)

    Seo, Young Hwa; Kim, Jin-Kyung; Jun, Jong-Gab


    Piperlongumine (PL) and its derivatives were synthesized by the direct reaction between acid chloride of 3,4,5-trimethoxycinnamic acid and various amides/lactams. Later their anti-inflammatory effects were evaluated in lipopolysaccharide (LPS)-induced RAW-264.7 macrophages. Of the piperlogs prepared in this study, the maximum (91%) inhibitory activity was observed with PL (IC50=3 μM) but showed cytotoxicity whereas compound 3 (IC50=6 μM) which possess α,β-unsaturated γ-butyrolactam moiety offered good level (65%) of activity with no cytotoxicity. This study revealed that amide/lactam moiety connected to cinnamoyl group with minimum 3 carbon chain length and α,β-unsaturation is fruitful to show potent anti-inflammatory activity. PMID:25453809

  5. Crystal Structure and Properties of the Carboxylic Acid Derivatives of Schizonpeta mulifida (L.) Briq.

    Institute of Scientific and Technical Information of China (English)

    LIU,Ju-Tao; YU,Ji-Cheng; JIANG,Hui-Ming; ZHANG,Li-Ying; ZHAO,Xiao-Jing; FAN,Sheng-Di


    The chemical constituents of the carboxylic acid derivatives from the ear of Schizonepeta were investigated,1H and 13C NMR chemical shifts of the carboxylic acid derivatives were accurately assigned.Two carboxylic acid derivative constituents were separated by a silica gel column.The structures were elucidated by the physical and chemical properties,IR,1H NMR,13C NMR,MALDI-TDF-MS and X-ray single crystal diffractometry.They were identified as 3-imino-N-(a-imidoethylamino)butyrolactam and neononane tetracid,respectively.The antitumoral activity on liver tumor ceils SMMC-7721 was determined in vitro.The experimental results showed that the former was better than the latter,and with increasing the concentration of the former the inhibitory activity was increased.

  6. A general strategy for the catalytic, highly enantio- and diastereoselective synthesis of indolizidine-based alkaloids. (United States)

    Abels, Falko; Lindemann, Chris; Schneider, Christoph


    Sixteen indolizidine-based alkaloids (IBAs) that were isolated as poison constituents of the skin of frogs were synthesized in a highly flexible and stereoselective manner. As a key step, a three-component, organocatalytic, highly enantio- and diastereoselective vinylogous Mukaiyama-Mannich reaction was employed furnishing optically highly enriched butyrolactams as central intermediates on a multigram scale. The attached six-membered ring was constructed through cyclization of the pendant enoate moiety onto the pyrrolidine ring. The absolute configuration of the bridgehead chiral center and the adjacent 8-position was established in the initial vinylogous Mannich reaction, whereas the 3- and 5-substituents were introduced through organometallic addition at a late stage of the synthesis with full stereochemical control from the substrate. With this strategy, simple as well as even more complex alkaloids were accessible in good overall yields as single stereoisomers. These syntheses also served to establish the absolute and relative configuration of those IBAs that had never been synthesized before. PMID:24436076


    Institute of Scientific and Technical Information of China (English)

    褚奇; 罗平亚; 苏俊霖; 冯俊雄


    采用自由基聚合方法,以丙烯酰胺(AM)、2丙烯酰胺基2甲基丙磺酸(AMPS)、N乙烯基吡咯烷酮(NVP)和N-(3-三乙氧基甲硅氧烷基)丙基丙烯酰胺(APTS)为原料制备了有机硅耐温降滤失剂AM/AMPS/NVP/APTS.使用FT-IR光谱表征了分子结构,评价了其钻井液性能.结果表明,随着AM/AMPS/NVP/APTS质量分数的升高,180℃老化16 h后的淡水钻井液的常温中压滤失量(FLAPI)和高温高压滤失量(FLHTHP)随之减小.当AM/AMPS/NVP/APTS的质量分数为0.6%时,即可将FLAPI维持在9.2 mL,FLHTHP维持在14.2 mL.加入1.0% AM/AMPS/NVP/APTS的淡水钻井液老化后的滤失量,随着温度的升高(150~220℃)而增大(FLAPI:7.8~19.8 mL;FLHTHP:13.5~56.7 mL),抗温可达200℃.通过测定淡水钻井液中有机硅共聚物的颗粒粒度、吸附量和Zeta电位,分析了该有机硅降滤失剂的作用机理.%An organosilicon temperature-resistant fluid loss additive (AM/AMPS/NVP/APTS) was synthesized with acrylamide (AM), 2-acrylamido 2-methyl propane sulfuric acid (AMPS), N-Vinyl-butyrolactam (NVP) and acrylamidypropyl tris(triethylsiloxy)silane(APTS) as raw materials by free-radical polymerization. The structure of the polymer was researched by Fourier transform-infrared spectroscopy (FT-IR), and the properties of drilling fluids of the polymer were evaluated in laboratory. The results show that with the addition of AM/AMPS/NVP/APTS, the American Petroleum Institute filtrate volume (FLAPI) and High-temperature and High-pressure filtrate volume (FLhthp) of fresh water based drilling fluid decreased gradually after being aged at 180 °C for 16 h. FLAPI remained stable at 9. 2 mL, and FLHTHP remained stable at 14. 2 mL while AM/AMPS/NVP/APTS concentration was 0. 6%. With 1. 0% AM/AMPS/NVP/APTS added, FLAPI increased from 7. 8 mL to 19. 8 mL, and FLhthp increased from 13. 5 mL to 56. 7 mL with the aging temperature increasing from 150 ℃ to 220 V. The thermal resistance of AM/AMPS/NVP/APTS was