树脂固载的β—酮砜的烷基化反应

Samuelsson等由季铵盐、碱和β-酮砜化合物制得相应的β-酮砜阴离子季铵盐,可直接用于烷基化反应。此法较经典方法虽有条件温和,产率较高的优点,但分离麻烦,季铵盐用量大且不能回收.聚合物负载的季铵盐作为相转移催化剂和反应底物的载体,已用于含活泼亚甲基化合物的烷基化反应.本文用离子交换法制得了大孔季铵盐离子固载的β-酮砜阴离子试剂,探索了这种试剂的烷基化反应条件,制得了一系列β-酮砜化合物的衍生物。     

强碱离子交换树脂支载的反应 Ⅲ.硝基乙酸乙酯的烷基化反应研究

用凝胶和大孔强碱离子交换树脂(OH~-或CO_3~(2-))一型)作为碱性试剂通过固载化或直接反应的方法研究了硝基乙酸乙酯用溴化物烷基化制备取代的硝基乙酸乙酯的过程。结果表明,在季铵型树脂存在下,用溴化物进行烷基化时可得到C-和O-烷基化的硝基乙酸乙酯;降低反应温度,缩短反应时间,有利于制得C-烷基化的产物。用树脂固载的硝基乙酸乙酯季铵盐可得到较高产率C-烷基化产物。     

聚苯乙烯支载聚氧乙烯季铵盐的合成及催化性能

本文合成了共聚苯乙烯-二乙烯基苯支载四聚乙二醇季铵盐以及共聚苯乙烯-二乙烯基苯支载聚乙二醇辛基苯基季铵盐, 并对它们在1-溴辛烷与碘化钾反应中的催化活性进行了研究。     

交联聚丙烯酸固载化氧化β-环糊精的合成及其对尿素的吸附性能

大孔交联聚丙烯酸树脂(D151和D152)用氯化亚砜转化为酰氯后,通过成酯反应固载β-环糊精,再进一步用高碘酸钠氧化,合成出具有环状多醛结构的交联聚丙烯酸固载化氧化β-环糊精。系统研究了反应条件对β-环糊精固载化反应的影响,发现摩尔投料比(—COC1/β-CD)为1.5—1/1、温度80℃、时间24 h为最佳固载反应条件。探讨交联聚丙烯酸固载化氧化β-环糊精对尿素的吸附性能,阐明了吸附时间、溶液中尿素浓度、及介质pH值等对吸附量的影响。在尿素浓度130 mg/dL、吸附时间4h、介质pH 7、温度25℃时,交联聚丙烯酸固载化氧化β-环糊精对尿素呈现出最大吸附量82.13 mg/g。     

相转移催化不对称碳烷化研究—光学活性的二氢吲哚酮类衍生物的合成

本文报道了手性季铵盐1-7催化溴代烷与1,3-二甲基-5-甲氧基-2-二氢吲哚酮(8)的不对称3-C烷化反应, 并通过研究不同的催化剂结构、溶剂、温度及溴代烷结构对产物光学活性的影响, 讨论了不对称诱导机理.     

季铵化β-环糊精聚合物的制备及其对相转移反应的催化作用研究

本文采用羟基活化的方法对β-环糊精树脂进行活化,之后通过一步反应引入季铵基功能基团制得了一类新型的β-环糊精聚合物.考察了反应体系NaOH浓度、反应温度、反应时间、加料顺序及体系溶剂种类对树脂活化程度的影响.结果表明此种制备方法简便易行,用此方法可合成出多种季铵盐型β-环糊精树脂.对这类新型树脂的相转移催化性能的研究表明,树脂对硫氰酸苄酯具有较好的催化性能,催化量的树脂即可使产率显著提高.     

氢型丝光沸石催化β─蒎烯高选择性水合反应的研究

本文研究了季铵盐辅助氢型丝光沸石催化β-蒎烯选择性水合反应，季铵盐的结构及用量对该反应生成单环产物的选择性具有显著的影响。选择适当的季铵盐，通过该水合反应一步合成得到α-松油醇，产率53．6％，并且产物的光学活性能够得到较好的保持。     

应用亲核性离子交换树脂(PhS型)制备苯硫醚

用强碱性离子交换树脂(OH型)与PhSH反应,得到一种离子交换树脂支载的PhS试剂,它与卤代物和α,β-不饱和醛酮很容易反应,得到相应的苯硫醚,产率较高或中等。     

β-环糊精季铵化的吡啶类离子液体的合成与表征

通过单-6-碘-β-环糊精(mono-6-I-β-CD)与吡啶反应合成吡啶衍生的β-环糊精碘化季铵盐作为中间体,将其与无机银盐(AgBF4,AgPF6)经过阴离子交换合成了两种新型的β-环糊精季铵化的吡啶类离子液体,并通过1HNMR,IR和MS对它们的结构进行了表征.     

乳化剂对聚硅氧烷乳液稳定性的影响

研究了乳化剂烷基酚聚氧乙烯醚(OP)、烷基聚氧乙烯醚和烷基季铵盐对聚硅氧烷乳液聚合的影响。采用复合乳化剂可以提高乳液稳定性。结果表明：①在以D4、N-β-氨乙基-γ-氨丙基甲基二甲氧基硅烷为原料的乳液聚合中。当非离子型乳化剂烷基聚氧乙烯醚和离子型乳化剂烷基季铵盐复合使用时,二者性能互补,产生协同效应,可使聚合物乳液具有很大的稳定性。②在实验选定的乳化剂中,非离子型烷基聚氧乙烯醚乳化剂用量为80mL(含量为0．05g／mL)、离子型烷基季铵盐乳化剂为60mL(浓度为0．05g／mL)时。其乳液的电解质稳定性、pH稳定性、冻融高温稳定性和离心稳定性等较好。     

Hydrolysis of epoxides and aziridines catalyzed by polymer-supported quarternary ammonium bisulfate

Macroporous resin （D201）-supported quartemary ammonium bisulfate （D201-HSO4） was prepared and effectively used in catalyzing the hydrolysis of epoxides or aziridines under mild and non-metal conditions to give the corresponding 1,2-diols and β-amino alcohols in high yields. The catalyst was facilely prepared and recyclable.     

Quaternary ammonium salt gemini surfactants containing perfluoroalkyl tails catalyzed one-pot Mannich reactions in aqueous media

A newly prepared quaternary ammonium salt (QAS) gemini fluorosurfactants efficiently catalyze one-pot Mannich reactions of aldehydes, amines and ketones in aqueous media at ambient temperature to afford corresponding β-aminocarbonyl compounds in good to excellent yields. In addition, the gemini fluorosurfactant catalysts were recovered and reused for three times with little loss of their catalytic activities.     

Catalytic investigations of calix[4]arene scaffold based phase transfer catalyst

Calix[4]arene scaffold based quaternary ammonium salts as multi-site phase transfer catalysts were prepared and their catalytic activities were investigated for Darzens condensation, O/N-alkylation reactions and ethyl benzene oxidation. These calix[4]arene based multi-site phase transfer catalysts showed significant high catalytic activity as compared to single-site phase transfer catalysts.     

相转移催化在高分子化合物合成中的应用

 综述了相转移催化用于高分子化合物合成的主要研究进展．介绍了季铵盐类及冠醚类相转移催化剂在高聚物的亲核取代反应、阴离子开环聚合反应及自由基聚合反应中的应用．重点总结了亲核取代反应中聚苯乙烯类化合物的功能化及化学修饰，包括合成路线、反应机理、温度以及催化剂和溶剂的种类与用量等因素对反应的影响．冠醚类化合物的催化效果略优于季铵盐类化合物，而后者的成本低、毒性小、应用更广泛，其催化的反应应作为今后研究的重点，以期将相转移催化技术尽早用于工业化生产．     

1-Alkyl-4-dialkylaminopyridinium Halides as Phase-Transfer Catalysts in Dichlorocarbene Reactions

Summary.  A series of 1-alkyl-4-dialkylaminopyridinium halides derived from 4-dimethylamino- and 4-morpholinopyridines were synthesized and tested as phase-transfer catalysts in three typical reactions of dichlorocarbene: dehydration of benzamide, N-formylation of diphenylamine, and dichlorocyclopropanation of styrene. The catalytic performance of the above compounds was found comparable or higher than that of conventional quaternary ammonium catalysts. The influence of catalyst structure on the reactivity was evaluated. Received June 27, 2001. Accepted (revised) September 25, 2001     

1-Alkyl-4-dialkylaminopyridinium Halides as Phase-Transfer Catalysts in Dichlorocarbene Reactions

 A series of 1-alkyl-4-dialkylaminopyridinium halides derived from 4-dimethylamino- and 4-morpholinopyridines were synthesized and tested as phase-transfer catalysts in three typical reactions of dichlorocarbene: dehydration of benzamide, N-formylation of diphenylamine, and dichlorocyclopropanation of styrene. The catalytic performance of the above compounds was found comparable or higher than that of conventional quaternary ammonium catalysts. The influence of catalyst structure on the reactivity was evaluated.     

Direct organocatalytic hydroalkoxylation of α,β-unsaturated ketones

The direct addition of a variety of alcohols to in situ activated olefins was observed in the presence of mild bifunctional amine/acid catalysts. Unlike existing methods, the reactions proceed at room temperature and in the absence of transition metals. The use of simple commercially available catalysts, amines and acids makes this an attractive method for the preparation of β-alkoxy ketones, which are prevalent targets and intermediates in organic synthesis.     

Addition of kinetic boron enolates generated from β-alkoxy methyl ketones to aldehydes. Density functional theory calculations on the transition structures

Herein we report that good to excellent levels of 1,5-anti stereoinduction are obtained in boron enolate aldol reactions of 1,2-syn β-alkoxy methyl ketones with achiral aldehydes, when the β-alkoxy protecting group is part of a benzylidene acetal. We have also investigated the effects of the ligands on boron, the α-, β-, and γ-substituents and the β-alkoxy protecting group on the boron enolates, using density functional theory (B3LYP) and Møller-Plesset perturbation theory (MP2) calculations.     

Highly Regio- and Stereoselective Synthesis of β-Halohydrins from Epoxides Catalyzed with Ceric Ammonium Nitrate

Ce(IV) as ceric ammonium nitrate can effectively catalyze ring opening of epoxides with halides under very mild conditions and easy procedure to give the corresponding β-chloro-and β-bromohydrins in excellent yields. The reactions occur with both substituted and unsubstituted quaternary ammonium halides and with high regio- and stereoselectivity. The reaction of optically active styrene oxide with chloride ion was found to be highly stereospecific and afforded the corresponding β-halohydrin in 96% ee.     

β-/γ-环糊精与Gemini草酸酯季铵盐的相互作用

本文对新合成的双子草酸酯季铵盐表面活性剂以表面张力法测定了25～45℃范围内的临界胶束浓度(0.6698～0.6099mmol·L-1),并计算了胶束形成的相关热力学参数ΔGm0、ΔHm0、ΔSm0.对其与β-,γ-环糊精(β-,γ-CD)的包结作用进行了研究.β-环糊精与双子草酸酯季铵盐表面活性剂的主客体包结物包结比主要为2:1.实验结果表明,环糊精对双子草酸酯季铵盐的胶束化有显著影响.由于双子草酸酯季铵盐的水链被环糊精的空腔包裹,削弱了其胶束生成的能力,使溶液的表面张力随环糊精浓度的增加而大大增加.