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Nieves Gonzlez Carlos Elvira Julio San Romn 《Journal of polymer science. Part A, Polymer chemistry》2003,41(3):395-407
This article deals with the synthesis of hydrophilic methacrylic monomers derived from ethyl pyrrolidone [2‐ethyl‐(2‐pyrrolidone) methacrylate (EPM)] and ethyl pyrrolidine [2‐ethyl‐(2‐pyrrolidine) methacrylate (EPyM)] and their respective homopolymers. For the determination of their reactivity in radical copolymerization reactions, both monomers were copolymerized with methyl methacrylate (MMA), the reactivity ratios being calculated by the application of linear and nonlinear mathematical methods. EPM and MMA had ratios of rEPM = 1.11 and rMMA = 0.76, and this indicated that EPM with MMA had a higher reactivity in radical copolymerization processes than vinyl pyrrolidone (VP; rVP = 0.005 and rMMA = 4.7). EPyM and MMA had reactivity ratios of rEPyM = 1.31 and rMMA = 0.92, and this implied, as for the EPM–MMA copolymers, a tendency to form random or Bernoullian copolymers. The glass‐transition temperatures of the prepared copolymers were determined by differential scanning calorimetry (DSC) and were found to adjust to the Fox equation. Total‐conversion copolymers were prepared, and their behavior in aqueous media was found to be dependent on the copolymer composition. The swelling kinetics of the copolymers followed water transport mechanism case II, which is the most desirable kinetic behavior for a swelling controlled‐release material. Finally, the different states of water in the hydrogels—nonfreezing water, freezing bound water, and unbound freezing water—were determined by DSC and found to be dependent on the hydrophilic and hydrophobic units of the copolymers. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 395–407, 2003 相似文献
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A series of ethyl(phenyl) 6-amino-2,3,6-trideoxy--D-glucopyranosides (amino=piperidino (Pip), pyrrolidino (Pyr), azetidino (Az), Bu2N) have been prepared from tri-O-acetyl-D-glucal to obtain catalysts for asymmetric synthesis and the starting compounds for the syntheses of other bidentate ligands.Published in Khimiya Geterotsiklicheskikh Soedinenii, No. 1, pp. 45–52, January, 2000. 相似文献
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Wang J Li H Lou B Zu L Guo H Wang W 《Chemistry (Weinheim an der Bergstrasse, Germany)》2006,12(16):4321-4332
Chiral (S)-pyrrolidine trifluoromethanesulfonamide has been shown to serve as an effective catalyst for direct Michael addition reactions of aldehydes and ketones with nitroolefins. A wide range of aldehydes and ketones as Michael donors and nitroolefins as acceptors participate in the process, which proceeds with high levels of enantioselectivity (up to 99 % ee) and diastereoselectivity (up to 50:1 d.r.). The methodology has been employed successfully in an efficient synthesis of the potent H(3) agonist Sch 50917. In addition, a practical three-step procedure for the preparation of (S)-pyrrolidine trifluoromethanesulfonamide has been developed. The high levels of stereochemical control attending Michael addition reactions catalyzed by this pyrrolidine sulfonamide, have been investigated by using ab initio and density functional methods. Transition state structures for the rate-limiting C--C bond-forming step, corresponding to re- and si-face addition to the reactive conformation of the key enamine intermediates have been calculated. Analysis of these structures indicates that hydrogen bonding plays an important role in catalysis and that the energy barrier for si-face attack in reactions of aldehydes to form 2R,3S products is lower than that for the re-face attack leading to 2S,3R products. In contrast, the energy barrier for re-face addition is lower than that for si-face addition in reactions of ketones. The computational results, which are in good agreement with the experimental observations, are discussed in the context of the stereochemical course of these Michael addition reactions. 相似文献
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Jing Chao DONG Run Tao LI* Tie Ming CHENG* Department of Bioorganic Chemistry School of Pharmaceutical Sciences Peking University Beijing 《中国化学快报》2001,(12)
Since Daly reported the structure of epibatidine and its potent analgesic activity in 19921, study on the synthesis of epibatidine and its derivatives and relationships between the structure and activity of epibatidine has received much attention2. During the course of our research for the synthesis of epibatidine derivatives, N-boc-2, 5-bis(trimethylsilyl)pyrrolidine 4 was used as the key intermediate to construct the skeleton of epibatidine via the 1, 3-dipolar cycloaddition (Scheme 1). Ac… 相似文献
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Dongping Wang Mei Wang Xiuna Wang Rong Zhang Jia Ma Licheng Sun 《Journal of molecular catalysis. A, Chemical》2007,270(1-2):278-283
Chiral (pyrrolidine salen)Mn(III) complexes 1 with an N-benzoyl group and 2 with an N-isonicotinoyl group as well as the corresponding N-methyl (3) and N-benzyl (4) pyridinium salts of 2 were synthesized. The catalytic properties of 1–4 and 2 with excess CH3I were explored to figure out the influence of the internal pyridinium salt in the catalyst on asymmetric epoxidation of substituted chromenes with NaClO/PPNO as an oxidant system in the aqueous/organic biphasic medium. The (pyrrolidine salen)Mn(III) complexes with an internal pyridinium salt, either formed in situ or isolated, displayed higher activities than analogous complexes 1, 2 and Jacobsen's catalyst in the aforementioned reaction, with comparable high yields and ee values. The acceleration of the reaction rate is attributed to the phase transfer capability of the built-in pyridinium salt of the (salen)Mn(III) catalyst. The effect of the internal pyridinium salt on the epoxidation of substituted chromenes is similar to that of the external pyridinium salts and ammonium halides. 相似文献
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Franklin A. Davis Bin Yang Jianghe Deng Yongzhong Wu Yulian Zhang Ashwin Rao 《Phosphorus, sulfur, and silicon and the related elements》2013,188(5-6):1109-1117
Abstract Sulfinimine-derived polyfunctionalized chiral building blocks, often prepared in one pot, provide efficient access, with a minimum of chemical manipulation, to enantiopure, multifunctional amine derivatives including piperidines and pyrrolidines. 相似文献
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The first example of pyrrolidine‐based room‐temperature chiral ionic liquids using 2‐aminobutanol as chiral auxiliary is described. 相似文献
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近年来,由有机配体保护的原子精确金属团簇在合成方面已取得了重要进展,其独特的原子结构对一些化学反应产生独特的催化效果.原子精确的团簇催化剂明显不同于纳米颗粒催化剂和单原子催化剂,是一种关联均相和多相的、原子数目确定、尺寸均一、结构精确的新型催化剂.从原子尺度上精确构筑团簇催化剂,探究亚纳米尺度的微观结构对催化性能的影响... 相似文献