Polymerization by phase transfer catalysis

Summary Polycarbonates and polythiocarbonates from phosgene and thiophosgene respectively, were synthesized from diphenols with chlorinated aromatic side groups under phase transfer conditions using several quaternary ammonium and phosphonium salts and dichloromethane as solvent. Polymers were characterized by IR and ¹H NMR, and the molecular weights estimated by viscosity measurements. The influence of the catalysts and the structure of the diphenols were studied.for part 9, see ref. 9     

Polymerization by phase transfer catalysis

Summary The hydrolysis of bisphenol A polythiocarbonate is studied under phase transfer conditions, and occurs principally in the organic phase, influenced by the catalysts according to their structure.For part 6, see the preceding paper     

Polymerization by phase transfer catalysis

Summary Polyethers from 1,4-bis(chloromethylene)-2,5-dimethoxybenzene and 4,4-biphenol were obtained by phase transfer catalysis, using different catalysts and solvents. The molecular weights and yields were determined, showing a solvent effect and a influence of the catalysts used.     

Polymerization by phase transfer catalysis

Summary Poly(amido-carbonate)s and poly(amido-thiocarbonate)s derived from 1,6-bis(4-hydroxyphenyl-carbamoyl)-hexamethylene I and 1,4-bis(4-hydroxyphenyl-carbamoyl)-phenylene II, and phosgene or thiophosgene, have been synthesized by a phase transfer catalysis process, which was ineffective for polymers derived from monomer I because the best results were obtained without catalyst, but was effective for those derived from monomer II obtaining higher yields when the catalysts were used. The ineffectivity was attributed to a hydrolytic process of the polymeric chains in the reaction media.     

Polymerization by phase transfer catalysis

Summary Polycarbonates, polythiocarbonates, and polyesters from 1,1,3-trimethyl-3-(4-hydroxy-phenyl)-4-indanol were synthesized using phase transfer conditions. THe effects of several catalysts and reactions times were evaluated by the yields and inherent viscosities. Phase transfer catalysis was not an efficient technique due to the rigid structure of the diphenol with the indanic group. The results were compared with that obtained with a diphenol having the same number of carbon atoms but forming an aliphatic side chain.For part 12, see ref. 7     

邻烯丙氧基苯酚的相转移催化合成

以邻苯二酚与氯丙烯为原料，氢氧化钠为碱，十六烷基三甲基溴化铵为相转移催化剂（PTC），在适量还原剂Na2S2O4存在下，经Williamson醚化反应合成邻烯丙氧基苯酚，产率最高可达86.67%。最佳合成条件；邻苯二酚；氯丙烯；氢氧化钠=1.6:1：1；还原剂用量为7%，氢氧化钠的质量分数为33%（浓度），反应温度65-70℃，反应时间2.5h，此法革除了有机溶剂，改善了产品的色泽，缩短了反应时间，提高了收率。     

三唑磷的相转移催化合成

研究了相转移催化合成三唑磷的方法,采用复合催化剂,原料易得,反应条件温和,产率较高。经过大量试验,选择的较佳合成条件：反应温度为20℃～35℃,pH为7～8,催化剂为四丁基溴化铵（TBAB）＋4-二甲基氨基吡啶（DMAP）,每种0．04g／mol,溶剂为二氯甲烷1300ml／mol。三唑磷收率为90．2％。     

相转移催化合成二元羟乙氧基苯

用相转移催化的方法合成了二元羟乙氧基苯。提高了产品产率，缩短了反应时间。     

Preparation of diphenyl acetonitrile by phase transfer catalysis

Preparation of diphenyl acetonitrile has been investigated by the reaction of diphenyl methyl bromide with aqueous sodium cyanide, using quaternary ammonium salts as phase transfer catalysts. The effect of catalyst, temperature, catalyst loading, and reactant concentration on the conversion of diphenyl methyl bromide to diphenyl acetonitrile has been studied. Suitable process conditions have been established for the production of diphenyl acetonitrile.     

相转移催化合成蔗糖油酸酯

以蔗糖和油酸酯为原料应用相转移催化剂(PTC)与碱性催化剂结合，合成蔗糖油酸酯，考察了反应时间、反应温度和催化剂用量对蔗糖油酸酯产率的影响，得出反应时间为4h，反应温度为100℃～110℃、催化剂聚乙二醇400(PEG-400)为油酸甲酯摩尔数的8％～10％，蔗糖油酸酯的产率达80％以上，单酯质量分数可以达到50％。     

Chemical transformation of PVC by phase transfer catalysis

Summary Suspension type PVC was reacted with sodium phenoxide in presence of different quaternary ammonium halides in THF or THF/water mixtures. The competition elimination vs. substitution of chlorine atoms depends on the homogeneity of the system, i.e. the more homogeneous the reaction mixture the less substituted the polymer.Dedicated to the 60th anniversary of Prof. Otto Vogl     

利用相转移催化法合成Reissert化合物

喹啉、异喹啉等杂环化合物与酰卤、氰化钠(或钾)生成的加成产物为Reissert化合物,例如N-苯甲酰基-1,2-二氢喹啉腈(1)、N-苯甲酰基-1,2-二氢异喹啉腈(2)。由于它们的氰基可转换成羧酸或醛,又可经负碳离子在杂环上引入侧链,因此Reissert化合物是重要的合成中间体[1]。     

利用相转移催化法合成Reissert化合物

隆批、异隆琳等杂环化合物与酸卤、氰化钠（或钾）生成的加成产物为Reissert化合物,例如N一苯甲酷基一l,2一二氢喷淋睛（l）、N一苯甲酸基一1,2一二氢异座咐睛（2）。由于它们的氰基可转换成核酸或难,又可经负碳离子在杂环上弓外侧链,因此Reissert化合物是重要的合成中间体［’j。Reissert化合物的制备通常采用二氯甲烷一水体系作反应溶剂;苯甲酸氯需要过量,溶在二氯甲烷中向混悬着喷淋的氰化钢水溶液中搞加;反应过程中要猛烈搅拌;氰化钠有时采用2次加料方法L’我们在合成中药青风藤中的有效成分青藤定碱的过程中利用澳代四丁基…     

相转移催化合成苯甲酸苄酯

苯甲酸苄酯是白色结晶或无色粘稠液体 ,可用作麝香的溶剂 ,香精的定香剂 ,也用于配制百日咳药、气喘药等。传统的合成方法是用苯甲酸甲酯与过量的苄醇在浓硫酸的作用下发生酯交换反应 ,也有用苯甲酸钠与苄氯作用 ,但产率不理想。作者直接以苯甲酸和苄氯为原料 ,通过使用相转移催化剂 ,能获得较为满意的产率。1　反应原理COOH +CH2 Cl TBAB- Na OH- H2 O1 0 4～ 1 0 6℃ ,3hCOOCH22　苯甲酸苄酯的制备向装有电动搅拌、回流冷凝管、温度计及滴液漏斗的 50 0 m L四颈瓶中 ,加入 1 5.2 5g( 0 .1 2 5mol)苯甲酸、5g( 0 .1 2 5mol)氢氧化…     

相转移催化合成乙酸异戊酯

以冰乙酸和异戊醇为原料,用浓硫酸和四丁基氯化铵混合物催化合成乙酸异戊酯。探讨了原料配比、催化剂用量及反应时间等对合成乙酸异戊酯产率的影响。结果表明,合成较佳工艺条件:异戊醇18 mL、冰乙酸25 mL、浓硫酸1.5 g、四丁基氯化铵0.25 mL,保温回流1 h。乙酸异戊酯平均产率为89.6%。     

Polymerization by phase transfer catalysis. 15. Polyesters from tetrachloroterephthalic acid and related diacids with bisphenol A

Chlorinated polyesters were synthesized from the following acid di-chlorides: 2,3,5,6-tetrachloro-1,4-terephthaloyl ( I ), 2,3,5,6-tetrachloro-1,4-phenylenediacetyl ( II ), and 2,3,5,6-tetrachloro-1,4-phenylenedi(oxyacetyl) ( III ), and bisphenol A, under phase transfer conditions, using several ammonium and phosphonium salts as catalysts and a biphasic CH₂Cl₂/NaOH system. The influence of the nature of the catalysts and the reaction times were evaluated by the yields and ηinh of the polyesters. The reactivity of the monomers was I < II < III , due to the smaller influence of the tetrachlorinated ring when there is a spacer group between the aromatic ring and the acid chloride group.     

Functional polymers and sequential copolymers by phase transfer catalysis

Summary Poly(epichlorohydrin) (PECH) containing pendant mesogenic units separated from the polymer main chain through spacers of zero to ten methylene units were synthesized and characterized. The synthetic pathway used for the chemical modification of PECH involved the phase transfer catalyzed etherification and esterification of the chloromethyl groups with sodium 4-methoxy-4-biphenoxide and potassium -(4-methoxy-4-oxybiphenyl)alkanoates. All the resulting polymers, including that with no spacer, present thermotropic liquid crystalline mesomorphism.Part 29 in this series: C. Pugh and V. Percec, Polym. Bull., preceding paper     

Functional polymers and sequential copolymers by phase transfer catalysis

Summary Two new synthetic methods for the preparation of functional polymers containing 2-oxazoline pendant groups are presented. The first one consists on the phase transfer catalyzed etherification of 2-(p-hydroxyphenyl)-2-oxazoline with a mixture of m- and p-chloromethylstyrene to provide, after separation, m- and p-vinylbenzyl ethers of 2-(p-hydroxyphenyl)-2-oxazoline. Both monomers can be polymerized by a radical mechanism to provide polystyrene containing 2-oxazoline pendant groups. The second method represents a phase transfer catalyzed etherification of a poly(2,6-dimethyl-1,4-phenylene oxide) containing pendant bromomethyl groups with 2-(p-hydroxyphenyl)-2-oxazoline. Incomplete etherification of the bromobenzyl groups in this case, leads to the first example of a functional polymer containing not only cationically polymerizable heterocycles, but also their own cationic initiator as pendant groups.