易溶性铜酞菁磺酸酯的合成及其凝聚性能

将酞菁氯磺化,然后与含有羟基的化合物反应,合成了铜酞菁磺酸苯酯、铜酞菁磺酸邻甲基苯酯、铜酞菁磺酸萘酯和铜酞菁磺酸 4 乙基萘酯,并测定了产物在不同溶剂中的溶解度、凝聚性能及红外光谱.这类铜酞菁衍生物的酯溶性很好.     

P,P,P',P'-四氯联苯二膦的合成

芳环的二氯膦化产物是有机合成中的重要中间体,广泛应用于不对称合成领域制备手性膦配体,紫外光固化领域合成膦酰氧光引发剂等。文献报道的芳环二氯膦化方法有如下几种：(1)由芳基溴制备格氏试剂或由芳基溴直接锂化,然后与三氯化膦反应。(2)由芳基溴经格氏试剂或直接锂化,然后与二(二乙胺基)氯化膦反应,最     

微波辐射法合成丙二酸甲(乙)烷酯

丙二酸甲(乙)烷酯类是一些药物和天然产物合成的中间体,一般由丙二酸二甲(乙)酯经部分水解得到丙二酸单甲(乙)酯钠盐,再通过酸化、酰氯化和酯化反应制得[1],该方法路线较长、酰氯化反应会产生有毒尾气。羧酸(包括烷酸和芳酸)酯可由其盐和卤代烃直接反应制得[2-4],而且可利用无溶剂相转移催化的条件进一步加速反应和提高产率。微波技术用于有机合成[5-7]具有操作简便、产率高和速度快等优点。我们参考文献[2-4]方法,应用微波技术合成了标题化合物。1　实验部分1 1　仪器ＢｒｕｋｅｒＤＰＸ 300ＦＴ ＮＭＲ型核磁光谱仪,ＴＭＳ为内标;ＩＲ…     

基于复合氯化剂CuCl_2·5/3NaCl·5/2Al_2O_3的1-氯-2-芳基乙炔的合成

直接使用CuCl2氯化芳基乙炔的反应通常存在着选择性差(有取代氯化和多种加成氯化的产物生成)、副产物多和分离困难等问题.描述了一种复合氯化剂(CuCl2·无机盐·载体)的制备以及基于该氯化剂取代氯化芳基乙炔的有效方法.首先通过一系列对比实验获得了CuCl2、载体和无机盐添加物的最佳配比.在此基础上考察了溶剂、复合氯化剂用量、反应温度诸因素对取代氯化反应的影响,提出了最佳反应条件:复合氯化剂为CuCl2·5/3Na Cl·5/2Al2O3,芳基乙炔与氯化剂的物质的量比为1∶3,溶剂为CH2Cl2,反应温度为35℃.在优化条件下,高产率(72%~99%)地合成了一系列1-氯-2-芳基乙炔目标产物1a~1n,并对这些化合物进行了表征.该方法反应条件温和、产率高、选择性好,并且适用于芳环上带有各种基团的底物.     

硅亲电试剂参与碳硅交叉偶联反应研究进展

有机硅化合物因其特殊的性质而广泛应用于合成化学、材料、药物和农药化学等领域.有机硅化合物通常由亲核取代、烯烃硅氢化和碳氢键直接硅化等方法制备.近年来,通过交叉偶联构建碳硅键合成有机硅烷取得突破性进展,引起合成化学领域研究者的广泛关注和兴趣,成为有机硅化合物合成研究热点.主要从硅亲电试剂参与的Heck反应、Negishi...     

二苄基锡双氨荒酸酯的合成

由二苄基二氯化锡与氨荒酸盐反应，合成了１０个新的二苄基锡双氨荒酯化合物，利用元素分析，ＩＲ和＾１ＮＮＭＲ表征了这些化合物的结构。     

气相色谱-质谱法同时测定聚氯乙烯塑料制品中的10种有机锡化合物

采用气相色谱-质谱法(GC-MS)同时快速有效地测定了聚氯乙烯（PVC）塑料制品中的二丁基氯化锡、单丁基氯化锡、三乙基氯化锡、三苯基氯化锡、三丁基氯化锡、三丙基氯化锡、二苯基氯化锡、四丁基锡、二辛基氯化锡和单苯基氯化锡等10种有机锡化合物。使用四氢呋喃溶解PVC样品,甲醇沉淀样品中的聚合物,超声萃取其中的有机锡化合物,将提取液衍生化后用正己烷萃取,采用GC-MS总离子流和选择离子进行定性定量测定。对衍生化时间、衍生化pH值、衍生化试剂用量、沉淀试剂用量等样品前处理条件进行了优化,并进行了线性关系、回收率、精密度等考察。结果表明,方法的线性范围为0.5～50 mg/L,线性相关系数为0.9978～0.9997。10种有机锡化合物的回收率及相对标准偏差(n=9)分别为84.23%～109.1%和4.24%～10.75%。所建立的方法能很好地应用于PVC塑料制品中有机锡化合物的检测。     

酯交换反应合成酯基三氯化锡及其配合物

本文首次利用β-甲氧羰(或β-丁氧羰)乙基三氯化锡和醇的酯交换反应合成了一系列相应的β-烷基羰乙基三氯化锡, 并以此合成了它们与2, 2'-联吡啶、1, 10-菲罗啉、4, 7-二苯基-1, 10-菲罗啉的配合物。通过元素分析、摩尔电导、IR、UV、^1H NMR等对上述化合物进行了表征, 提出了β-烷氧羰乙基三氯化锡分子内Lewis酸催化的酯交换反应机理。     

用二氧化硫脲合成4-甲基-4′-氨基二苯醚的研究

4甲基4′氨基二苯醚是合成农药、染(颜)料、医药的重要中间体.传统的制备方法是由4 甲基4′硝基化合物(简称硝基物)在盐酸存在下用二氯化锡还原得到[1] ,该方法工艺成熟、产品质量好,但产率低,污染严重.陈其亮等报道了由硝基物催化加氢的方法[2],但存在设备投资大,操作繁锁等缺点.二氧化硫脲(Thiourea dioxide ,简称TD)是一种非常优良的还原剂,已广泛应用于有机合成的许多方面[3,4],但应用于标题化合物的制备未见报道,本文对此进行了研究,收到较好效果.合成路线如下:     

三苯基锗烯或炔基膦酸衍生物的合成

由三苯基氯化猪与烯或炔基膦酸盐反应,合成了８种新的三苯基锗烯基或炔基膦酸衍生物,利用元素分析,ＩＲ和ＨＮＭＲ表征了这些化合物的结构     

Chlorosulfonyl styrene–divinylbenzene copolymer characteristics as a function of chlorosulfonation and chlorination reaction parameters

Chlorosulfonyl substituted styrene–divinylbenzene copolymer is a highly reactive intermediate used in organic synthesis. It is obtained in three steps: (1) the polymeric support in the form of spherical beads is prepared by free radical polymerization of styrene; (2) the divinylbenzene mixture and the aromatic styrene groups of the obtained copolymer are sulfonated with chlorosulfonic acid in dichloroethane and (3) this is followed by chlorination of the sulfonyl groups with PCl₅/POCl₃ mixture. Chemical analysis shows that chlorosulfonation leads to both sulfonyl and chlorosulfonyl products in which content and ratio vary as a function of reaction parameters: maximum total group content of 5.1 meq/g is reached after 3 hr reaction, at 40°C with styrene to a chlorosulfonic acid molar ratio of 12.4:1. In the chlorination reaction, sulfonyl to chlorosulfonyl conversion is also observed to vary as a function of time and chlorinating mixture composition: 99.6 mol% conversion degree is attained after 2 hr reaction with styrene/PCl₅/POCl₃ in a molar ratio of 1:4:23. © 1997 John Wiley & Sons, Ltd.     

含羧甲磺酰基水暂溶性分散染料的研究──几个中间体及染料的合成

用氯磺化法或硫醚氧化法结合成出８个中间体，并以其作为重氮组分，合成出１０个新的含羧甲磺酰基水暂溶性分散染料。     

Anodic chlorination of aromatic compounds in acetic acid part II

The anodic chlorination of aromatic compounds in anhydrous acetic acid has been further investigated. Evidence has been found for two different methods of electrochemical chlorination, in the systems Cl₂/aromatic compounds and Cl^?/aromatic compounds. These methods were also compared with the uncatalyzed chemical chlorination reaction. The yields of monochlorinated products and the related isometric distributions were taken into account. Since the isomeric distributions are equal with chemical and electrochemical chlorination methods, the formation of the same intermediate was proposed for both.     

Synthesis of functional aromatic multisulfonyl chlorides and their masked precursors

The synthesis of functional aromatic bis(sulfonyl chlorides) containing an acetophenone and two sulfonyl chloride groups, i.e., 3,5-bis[4-(chlorosulfonyl)phenyl]-1-acetophenone (16), 3,5-bis(chlorosulfonyl)-1-acetophenone (17), and 3,5-bis(4-(chlorosulfonyl)phenyloxy)-1-acetophenone (18) via a sequence of reactions, involving in the last step the quantitative oxidative chlorination of S-(aryl)- N,N'-diethylthiocarbamate, alkyl- or benzyl thiophenyl groups as masked nonreactive precursors to sulfonyl chlorides is described. A related sequence of reactions was used for the synthesis of the aromatic trisulfonyl chloride 1,1,1-tris(4-chlorosulfonylphenyl)ethane (24). 4-(Chlorosulfonyl)phenoxyacetic acid, 2,2-bis[[[4-(chlorosulfonyl)phenoxyacetyl]oxy]methyl]-1,3-propanediyl ester (27), 5,11,17,23-tetrakis(chlorosulfonyl)-25,26,27,28-tetrakis(ethoxycarbonylmethoxy)calix[4]arene (38), 5,11,17,23,29,35-hexakis(chlorosulfonyl)-37,38,39,40,41,42-hexakis(ethoxycarbonylmethoxy)calix[6]arene (39), 5,11,17,23,29,35,41,47-octakis(chlorosulfonyl)-49,50,51,52,53,54,55,56-octakis(ethoxycarbonylmethoxy)calix[8]arene (40), 5,11,17,23-tetrakis(tert-butyl)-25,26,27,28-tetrakis(chlorosulfonyl phenoxyacetoxy)calix[4]arene (44), 5,11,17,23,29,35-hexakis(tert-butyl)-37,38,39,40,41,42-hexakis(chlorosulfonylphenoxyacetoxy)calix[6]arene (45), and 5,11,17,23,29,35,41,47-octakis(tert-butyl)-49,40,51,52,53,54,55,56-octakis(chlorosulfonylphenoxyacetoxy)calix[8]arene (46) were synthesized by two different multistep reaction procedures, the last step of both methods consisting of the chlorosulfonation of compounds containing suitable activated aromatic positions. 2,4,6-Tris(chlorosulfonyl)aniline (47) was obtained by the chlorosulfonation of aniline. The conformation of two series of multisulfonyl chlorides i.e., 38, 39, 40 and 44, 45, 46, was investigated by (1)H NMR spectroscopy. The masked nonreactive precursor states of the functional aromatic multisulfonyl chlorides and the aromatic multisulfonyl chlorides reported here represent the main starting building blocks required in a new synthetic strategy elaborated for the preparation of dendritic and other complex organic molecules.     

Chlorosulfonation of 2-arylimidazoles

The chlorosulfonation of 2-arylimidazoles was investigated; the resulting sulfonyl chloride derivatives were isolated and characterized as the corresponding sulfonamides. When the 2-aryl substituent was 3,4-dichlorophenyl or 3-pyridyl, chlorosulfonation occurred only on the imidazole ring. The chlorosulfonation of 2-(4-chlorophenyl)imidazole was temperature dependent, yielding either a mono or disulfonamide after treatment with ammonia. The structure of this disulfon-amide was determined from pmr spectra to be 2-(4-chloro-3-sulfamoyl)-4(5)sulfamoylimidazole.     

Production of poly(chlorosulfostyrene) by synthesis in a gel

Synthesis in a gel as a method for the preparation of poly(chlorosulfostyrene) by treating polystyrene with chlorosulfonic acid was proposed, which makes it possible to obtain a polymer with a total degree of functionalization of sulfo and chlorosulfo groups up to 1.0. The possibility of regulating the degree of chlorosulfonation in the range from 50 to 100% was shown. The composition and structure of the products of polymer-analogous transformations were characterized by elemental analysis, FTIR spectroscopy, and thermogravimetry with IR identification of the decomposition products. Chlorosulfonation in the gel makes it possible to achieve a high degree of functionalization even at lower temperatures, at room temperature, and at less time than compared with known methods.     

Short and Efficient Synthesis of Thiol Group Functionalized Crown Ethers

A synthesis of thiol group functionalized crown ethers is reported. The reaction is accomplished by the direct chlorosulfonation of simple crown ethers with chlorosulfonic acid and the reduction of the sulfonyl chloride moiety with LiAlH₄ in two steps. This new process is simple to operate, and it generates high‐purity mercaptobenzocrowns with excellent yields.     

Chlorosulfonation of 2-acylthiophenes: an examination on the reaction regiochemistry

Chlorosulfonation of thenoyltrifluoroacetone with neat chlorosulfuric acid was found to give a 25:75 mixture of 3- and 2-chlorosulfonated thenoyltrifluoroacetone isomers in 33% overall yield. The use of dichloromethane as solvent for the chlorosulfonation reaction gave only the 2-chlorosulfonated isomer in 45% yield. On the contrary, the reaction of 2-acetylthiophene with neat chlorosulfuric acid gave only the 3-chlorosulfonated-5-acetylthiophene in 35% yield. The identity of these chlorosulfonated compounds was unambiguously established by NMR techniques and confirmed by the crystal structure determination of the 2-chlorosulfonated isomer.     

Pyrrolidine Carboxaldehyde Hydrohalide Catalyzed Halogenations of Aliphatic Aldehydes

Efficient methods for the direct chlorination or bromination of aliphatic aldehydes to their corresponding α,α-dihalo aldehydes in high yield and purity are unknown. Many approaches have suffered from one or more of the following, formation of byproducts, aldol condensations incomplete conversions and losses through tedious workup procedures. Early investigations have shown that the vapor phase chlorination of aliphatic ketones has produced good yields of 2-chloro ketones,⁽¹⁾ while the vapor phase chlorination of aliphatic aldehydes has resulted in the formation of acid chlorides.⁽²⁾ One of the first successful acid catalyzed chlorinations of propionaldehyde was reported by Dick⁽³⁾ who obtained 50–60% yields of 2,2-dichloropropionaldehyde accompanied by aldol condensations and polyhalogenated trioxanes. The reaction was carried out in standardized aqueous mineral acid solutions and the product was isolated by means of a laborious azeotropic distillation. The use of sulfuryl chloride in the presence of a catalytic amount of diphenyl sulfide for the chlorination of aldehydes was shown by Dalman⁽⁴⁾ to give 60–70% yields of 2-chloro and 2,2-dichlorinated aldehydes. Clean separations i.e. products free of sulfuryl chloride could only be obtained by distillation with a spinning band column at high reflux ratios.     

氯磺化聚乙烯结构和性能研究Ⅰ.氯磺化反应及其对晶体结构的影响

氯磺化聚乙烯水解后是一种性能特异的离子交换膜。本文研究了低密度及高密度聚乙烯中空纤维氯磺化反应时间与交换容量之间的关系,并用红外光谱及广角X射线衍射法测定了氯磺化反应对聚乙烯晶体结构的影响。结果表明,氯磺化反应主要发生在聚乙烯的非晶区,最大交换容量及反应速度均与非晶区含量有关。反应对晶粒表面也有一定程度的侵蚀作用,随着交换容量的增加,结晶度下降,晶粒度减小。低密度及高密度聚乙烯的变化趋势相似,但前者比后者变化更显著。