1-碘乙基异丙基碳酸酯的合成

探讨了以甲苯为反应介质 ,以四丁基溴化铵作相转移催化剂 ,由 1 氯乙基异丙基碳酸酯合成 1 碘乙基异丙基碳酸酯的工艺条件。     

相转移催化合成N,N-二乙基苯胺工艺研究

针对目前常压相转移催化法合成N,N-二乙基苯胺工艺中催化剂无法实现分离的问题,开展了非均相固体相转移催化剂催化合成N,N-二乙基苯胺工艺研究。以苯胺、溴乙烷为原料,氢氧化钠作为缚酸剂,在磷钼钒杂多酸季铵盐催化剂催化合成了N,N-二乙基苯胺,实现了固体非均相相转移催化剂的工艺路线,及催化剂的快速分离。利用单因素试验法对N,N-二乙基苯胺合成工艺进行了优化,得到最佳工艺条件为:反应温度为54℃,n(苯胺)∶n(溴乙烷)=1∶2.4,催化剂用量分别为1.6g,反应时间为5.5h,氢氧化钠用量为0.55 mol,氢氧化钠浓度为35%,收率达到82.8%。     

相转移催化合成肉桂酸

以苄基三乙基氯化铵为相转移催化剂,K2CO3为催化剂,通过Pinker反应合成了肉桂酸。在回流条件下,以苄基三乙基氯化铵为相转移催化剂时,n(苯甲醛)∶n(乙酸酐)∶n(碳酸钾)∶n(苄基三乙基氯化铵)=1∶3∶1∶0.03,回流90min,肉桂酸的产率可达到78.5%。     

四乙基氢氧化铵相转移催化合成N,N-二乙基苯胺的研究

以苯胺和溴乙烷为原料 ,用四乙基氢氧化铵作相转移催化剂 ,在常压下合成N ,N 二乙基苯胺。研究了各反应因素对目的产物收率的影响 ,并提出了优惠工艺条件。     

N,N—二乙基苯胺的相转移催化合成

使用一种相转移催化剂可在常压下由苯胺和溴乙烷合成N,N-二乙基苯胺。研究了使用四丁基氯化铵(TBAC)作相转移催化剂制备N,N-二乙基苯胺的最佳条件。     

利用季铵盐催化剂提高地亚农收率

以嘧啶醇和O，O-二乙基硫代磷酰氯（简称氯化物）为原料，在相转移催化剂作用下合成地亚农，考察了影响反应的因素。结果表明；选用苄基基乙基氯化铵做相转移催化剂，0.1mol嘧啶醇用1.0g催化剂，溶剂选用甲苯，嘧啶醇和氯化物的物质的量比为1：1.1，收率可以达到94%。     

聚乙二醇相转移催化合成乙基愈创木酚

研究了以邻苯二酚、氯乙烷为原料，在加压和相转移催化剂存在的条件下合成乙基愈创木酚的工艺条件，讨论了反应物的配比、反应温度、时间、催化剂和碱对反应收率的影响。     

相转移催化法合成N-乙基咔唑的研究

以咔唑和溴乙烷为原料,在季铵盐相转移催化剂的条件下合成了N-乙基咔唑,考察了温度、催化剂种类、催化剂用量以及投料比等因素对N-乙基咔唑收率的影响,确定了最佳的催化剂及工艺条件。结果表明,四丁基溴化铵具有最佳的催化活性,在适宜反应条件下,N-乙基咔唑的收率可达97%。     

四丁基溴化铵催化合成N,N—二乙基苯胺优化工艺条件的研究

研究了以四丁基溴化铵作相转移催化剂各种反应因素对Ｎ，Ｎ－二乙基苯胺产率的影响，提出了常压四丁基溴化铵催化合成Ｎ，Ｎ－二乙基苯胺的最佳工艺条件。     

乙基香兰素的相转移催化合成

报道了应用相转移催化技术合成中间体邻乙氧基苯酚及最终产物乙基香兰素,考察了反应温度、时间、物料配比等因素对合成的影响,确定了最佳反应条件,邻乙氧基苯酚反应的最佳温度60℃;合成乙基香兰素最佳温度55～60℃。研究结果显示聚乙二醇作为相转移催化剂合成邻乙氧基苯酚,四丁基溴化胺相转移催化合成乙基香兰素,其结果均优于以往报道,邻乙氧基苯酚最高收率可达75.5%,乙基香兰素最高收率可达70%。     

相转移催化技术在有机合成中的应用

概述了相转移催化剂的相转移催化原理，相转移催化剂的种类；并以此为基础讨论了相转移催化剂在有机合成及药物合成中的应用。     

KINETIC STUDY OF SYNTHESIZING DIALKOXYMETHANE USING 4-(TRIALKYLAMMONIUM) PROPANSULTANS AS NEW PHASE-TRANSFER CATALYSTS

In this work, sulfobetaine (4-(trialkylammonium) propansultan (TAAPS)) was first developed as a new phase-transfer catalyst for synthesizing dialkoxymethane. The addition reaction of 1,3-propane sultone (PS) and trialkylamines (TAA) was successfully carried out to synthesize sulfobetaines in a homogeneous organic solution. In this work, for the first time, five different TAAPSs, which possess high reactivity, stability, selectivity, and performance, were employed as phase-transfer catalysis to synthesize dialkoxymethane. The reaction of alcohol and dibromomethane in a highly alkaline solution of KOH/organic solvent two-phase medium to produce dialkoxymethane was carried out under phase-transfer catalysis using 4-(trialkylammonium) propansultan as the catalyst. From the experimental observation, a rational reaction mechanism using this new phase-transfer catalyst was proposed. Kinetics of the reaction are studied in detail.     

KINETIC STUDY OF SYNTHESIZING DIALKOXYMETHANE USING 4-(TRIALKYLAMMONIUM) PROPANSULTANS AS NEW PHASE-TRANSFER CATALYSTS

In this work, sulfobetaine (4-(trialkylammonium) propansultan (TAAPS)) was first developed as a new phase-transfer catalyst for synthesizing dialkoxymethane. The addition reaction of 1,3-propane sultone (PS) and trialkylamines (TAA) was successfully carried out to synthesize sulfobetaines in a homogeneous organic solution. In this work, for the first time, five different TAAPSs, which possess high reactivity, stability, selectivity, and performance, were employed as phase-transfer catalysis to synthesize dialkoxymethane. The reaction of alcohol and dibromomethane in a highly alkaline solution of KOH/organic solvent two-phase medium to produce dialkoxymethane was carried out under phase-transfer catalysis using 4-(trialkylammonium) propansultan as the catalyst. From the experimental observation, a rational reaction mechanism using this new phase-transfer catalyst was proposed. Kinetics of the reaction are studied in detail.     

水/有机两相温控相转移催化新进展

综述了水/有机两相"温控相转移催化"的原理,在此基础上设计、合成了以非离子型水溶性膦配体和两性双吡啶配体,并与过渡金属络合制备出温控相转移催化剂。综述了其在水/有机两相CO还原,烯烃加氢和Heck反应中的应用效果。     

Synthetic opportunities of gas-liquid phase-transfer catalysis

A concise survey of gas-liquid phase-transfer catalysis is reported, showing the main features of the method, and, in particular, discussing the influence of the temperature and pressure, catalyst selection and nature of the solid bed on the outcome of the reaction. Some new results concerning the malonate synthesis and the halide-exchange on hydrocarbons are reported: the former shows that the monoalkylated ester can be selectively obtained by using the polyethyleneglycol “Carbowax 6000” as a catalyst adsorbed over potassium carbonate, whilst the latter refers to a true catalytic process, which can proceed indefinitely without renewing the catalytic bed. The influence of the catalyst percentage on the reaction equilibrium is also discussed. The advantages and the problems of gas-liquid phase-transfer catalysis are reviewed, together with its analogies to classic phase-transfer catalysis and gas chromatography.     

相转移催化法合成邻硝基茴香醚

论述了以相转移催化剂催化合成邻硝基茴香醚的新方法。在相转移催化剂存在下，于常压、回流温度下滴加浓碱合成了邻硝基茴香醚，产品收率达85%。探讨了催化剂类型、用量、碱的浓度、反应时间等对应的影响，确定了最佳工艺条件。     

由碳酸二甲酯合成芳香醚的绿色工艺

综述了酚类化合物与碳酸二甲酯(DMC)甲基化反应合成芳香醚的绿色工艺。气相连续流动法和液相间歇法是2种有效的由DMC合成芳香醚的方法。在气液相转移催化和液固相转移催化的条件下,酚与DMC甲基化反应的产率和选择性均很高。酚与DMC甲基化反应的均相催化剂一般选择叔胺、叔膦、季铵盐及Schiff碱等有机碱,多相催化剂为碱金属碳酸盐、沸石、氧化铝及附载有金属盐的氧化铝和煅烧的Mg-Al水滑石。     

ANALYSIS OF FACTORS AFFECTING THE SYNTHESIS OF ALLYL PHENYL ETHER BY TRI-LIQUID-PHASE CATALYSIS

In order to improve the selectivity of allyl phenyl ether (ROPh), the main product, in the etherification of allyl bromide (RBr) and sodium phenolate (NaOPh) with tetra-n-butylammonium bromide (QBr) as a phase-transfer catalyst, the technique of tri-liquid-phase phase-transfer catalysis, instead of the liquid-liquid one, was employed. The reaction was performed in a batch reactor, and the factors affecting the conversion and selectivity were investigated. The possibility of reusing the phase-transfer catalyst was also evaluated. Experimental results indicate that the addition of a small amount of Na₂CO₃ will benefit the formation of a third liquid phase and enhances both the conversion of RBr and the overall yield of ROPh. Both the conversion and the overall yield are maximal when the mole fraction of QBr in the mixture of NaOPh and QBr is about 0.3. A high reaction temperature enhances the conversion and the overall yield. Under optimal conditions, complete conversion and near 100% yield can be obtained within 10 minutes. Although the reaction rate by the tri-liquid-phase catalysis is slightly lower than that observed with the same amount of catalyst by conventional liquid-liquid phase-transfer catalysis, the selectivity of ROPh is higher and the catalyst can be easily reused by the reuse of the third liquid phase without any loss of its catalytic activity in the former case. Because the reuse of catalyst was found to be feasible, the production of ROPh with a continuous-flow reactor becomes possible.     

相转移催化研究新进展概述

通过对相转移催化与超声波技术,微波技术联用的研究,以及相转移催化氧化脱除汽油中含硫化合物的研究,阐述了相转移催化技术研究的新进展。     

ANALYSIS OF FACTORS AFFECTING THE SYNTHESIS OF ALLYL PHENYL ETHER BY TRI-LIQUID-PHASE CATALYSIS

In order to improve the selectivity of allyl phenyl ether (ROPh), the main product, in the etherification of allyl bromide (RBr) and sodium phenolate (NaOPh) with tetra-n-butylammonium bromide (QBr) as a phase-transfer catalyst, the technique of tri-liquid-phase phase-transfer catalysis, instead of the liquid-liquid one, was employed. The reaction was performed in a batch reactor, and the factors affecting the conversion and selectivity were investigated. The possibility of reusing the phase-transfer catalyst was also evaluated. Experimental results indicate that the addition of a small amount of Na₂CO₃ will benefit the formation of a third liquid phase and enhances both the conversion of RBr and the overall yield of ROPh. Both the conversion and the overall yield are maximal when the mole fraction of QBr in the mixture of NaOPh and QBr is about 0.3. A high reaction temperature enhances the conversion and the overall yield. Under optimal conditions, complete conversion and near 100% yield can be obtained within 10 minutes. Although the reaction rate by the tri-liquid-phase catalysis is slightly lower than that observed with the same amount of catalyst by conventional liquid-liquid phase-transfer catalysis, the selectivity of ROPh is higher and the catalyst can be easily reused by the reuse of the third liquid phase without any loss of its catalytic activity in the former case. Because the reuse of catalyst was found to be feasible, the production of ROPh with a continuous-flow reactor becomes possible.