文献类型：期刊文献

中文题名：α-蒎烯合成杀虫增效剂的研究

英文题名：STUDY ON SYNTHESIS OF SYNERGIST OF INSECTICIDE FROM αPINENE

作者：周永红[1] 王延[1] 宋湛谦[1]

第一作者：周永红

机构：[1]中国林业科学研究院林产化学工业研究所

年份：1998

卷号：18

期号：1

起止页码：1-11

中文期刊名：林产化学与工业

外文期刊名：CHEMISTRY AND INDUSTRY OF FOREST PRODUCTS

收录：CSTPCD;;Scopus;北大核心:【北大核心1996】；CSCD:【CSCD_E2011_2012】；

基金：国家科委专用化学品资助

语种：中文

中文关键词：α-蒎烯;杀虫增效剂;相转移催化;松节油;蒎烯

外文关键词：αPinene; Synergist of insecticide; Phase transfer catalysis

分类号：TQ453.9

摘要：松节油的主要成分α蒎烯经异构同时与马来酸酐发生ＤｉｅｌｓＡｌｄｅｒ反应，生成１异丙基４甲基二环［２，２，２］５辛烯２，３二羧酸酐（ＴＭ）。研究影响反应的主要因素：加料顺序、催化剂和助催化剂用量、原料配比、反应时间和反应温度等，得出比较适宜的反应条件。产物ＴＭ收率在９０％以上，纯度在８５％以上。常压下，ＴＭ和氨气反应，合成１异丙基４甲基二环［２，２，２］５辛烯２，３二甲酰亚胺（ＴＭＩ）。以四丁基溴化铵（ＴＢＡＢ）为催化剂，由ＴＭＩ和１溴２乙基己烷固液相转移催化合成杀虫增效剂Ａ１：Ｎ（２乙基）己基１异丙基４甲基二环［２，２，２］５辛烯２，３二甲酰亚胺，收率为８０２％。这一合成方法未见文献报道。讨论影响ＴＭＩ的相转移催化Ｎ烷基化反应的因素：催化剂品种和用量、催化方式、搅拌速度、反应温度和反应时间等。利用ＩＲ、ＭＳ和１ＨＮＭＲ分析对合成产物及中间体进行结构鉴定。通过毒理学试验，Ａ１增效剂急性毒性试验，口服ＬＤ５０＞１００００ｍｇ／ｋｇ，经皮下ＬＤ５０＞５０００ｍｇ／ｋｇ，属微毒类化学物，对人畜无害。应用试验证明：Ａ１对拟除虫菊酯、氨基甲酸酯和有机磷杀虫?
Synergist A1 was synthesized from turpentine which is abundant in China. The study may give a new kind of synergist for pesticide industry and provides a new pathway for utilization of Chinese turpentine.1Isopropyl4methyl bicyclo oct5ene2,3dicarboxylic anhydride (TM) was prepared via isomerization of αpinene and DielsAlder reaction with maleic anhydride in the presence of catalyst and cocatalyst. Then, the synthesis of 1isopropyl4methyl bicyclo oct5ene2,3dicarboximide (TMI) was performed by reaction of TM with ammonium under atmospheric pressure. TMI was reacted with 1bromo2ethylhexane, with tetrabutyl ammonium (TBAB) as phase transfer catalyst, to produce N(2ethyl) hexyl1isopropyl4methyl bicyclo oct5ene2,3dicarboximide (A1). The synthesis method of A1 with phase transfer catalysis (PTC) has not been reported in the literatures. Influences of charge sequence, molar ratio of raw materials, amounts and kinds of catalyst and cocatalyst, reaction time and temperature on the synthesis of TM were studied. The optimum conditions were obtained. Factors effecting Nalkylation reaction of TMI with PTC, such as kinds and amounts of catalyst, mode of catalysis, stirring speed, reaction temperature and time, were also investigated. The results show that TBAB is an ideal solidliquid phase transfer catalyst. TLC was used to purify the products obtained. The structure of the products were identified by IR,MS and 1HNMR. The acute oral toxicity LD50>10000mg/kg and the acute dermal toxicity LD50>5000mg/kg prove that synergist A1 is nontoxic to human and animals. The synergistic tests show that synergist A1 has the synergism toward pyrethroids, carbamates and organic phosphorate insecticides and that it corresponds to piperonyl butoxide (S1).