文献类型：期刊文献

中文题名：间／对混合二乙炔基苯的合成

英文题名：Synthesis of m/p-Diethynylbenzene

作者：蔡良珍[1];裘海啸[1];王洪太[2];杨苗[2];沈永嘉[1]

机构：[1]华东理工大学精细化工研究所结构可控先进功能材料及其制备教育部重点实验室,上海200237;[2]胶州市精细化工有限公司,山东青岛266300

年份：2008

卷号：22

期号：4

起止页码：630

中文期刊名：高校化学工程学报

外文期刊名：Journal of Chemical Engineering of Chinese Universities

收录：CSTPCD;;EI(收录号：20083711540635);Scopus;北大核心:【北大核心2004】；CSCD:【CSCD2011_2012】；

语种：中文

中文关键词：二乙烯基苯;溴化;二(α,β-二溴乙基)苯;二乙炔基苯

外文关键词：divinylbenzene; bromination; bis-（α，β-dibromoethyl）-benzene; diethynylbenzene

摘要：混合二乙炔基苯在药物合成,液晶材料,航天航空材料等方面具有十分重要的用途,因而较大规模地合成二乙炔基苯受到广泛的关注。今从工业级二乙烯基苯(含间二乙烯基苯59.5%,对二乙烯基苯21.8%,间乙基苯乙烯11.3%,对乙基苯乙烯7.4%)出发,经溴化加成反应得到二(α,β-二溴乙基)苯(或相应的溴化物),冷却后分离出部分对二(α,β-二溴乙基)苯,残余物经减压蒸馏分离出沸点小于160℃/1～2mmHg的间/对乙基-α,β-二溴乙基苯,使间/对二(α,β-二溴乙基)苯的含量达到98%以上。后者在乙醇钠/乙醇介质中脱去溴化氢,经纯化处理后得到含量98%的间/对混合二乙炔基苯。讨论了影响各步反应及分离的因素,给出了较佳的反应参数,使用上述条件实现了50kg/批规模的生产。
m/p-Diethynylbenzene is one of the key intermediates for the pharmaceutical synthesis and production of liquid-crystal materials, aeronautics and astronautics materials. Therefore, how to carry out its large scale production is deeply concerned. A new process capable of producing m/p-diethynylbenzene in large scale was proposed. Bis-（α,β-dibromoethyl）-benzene together with corresponding bromides could be synthesized by bromination of commercial divinylbenzene consisted of 1,3-divinylbenzene （59.5%）, 1,4-divinylbenzene （21.8%）, 1,3-ethyl styrene （11.3%） and 1,4-ethyl styrene （7.4%）. The most of 1,4-bis-（α,β-dibromoethyl）-benzenes were isolated from the bromides by cooling; and majority of ethyl-（α,β-dibromoethyl）-benzenes could be distilled off at 160℃/1-2 mmHg. The residue which contents m/p-bis-（α,β-dibromoethyl）-benzene as high as 98% （GC） was treated with sodium ethoxide in ethanol to afford m/p-diethynylbenzene, and after further distillation under reduced pressure, the m/p-diethynylbenzene content can be as high as 98%. The factors of affecting the reactions and separations were discussed; and the optimized operation parameters were given. According to the process proposed, m/p-diethynylbenzene can be produced with the scale of 50 kg/batch.