相转移催化合成氯菊酯的研究.pdf

相转移催化合成氯菊酯研究中文摘要相转移催化合成氯菊酯研究专业:化学生物学硕士生:黄创锋指导老师:古练权教授鄢明教授中文摘要从贲亭酸甲酯出发合成了3,3一二甲基一4,6,6,(2)。深入研究了在相转移催化剂的存在下,于水一有机两相反应介质中从四氯酯(3,,6,6,)(2)N各氯菊酸甲酯[2,(2,2一二氯乙烯基)环丙烷羧酸甲酯1(3)的方法。检验了多种常用的相转移催化剂(如季铵盐、聚乙二醇、冠醚等)和不同的碱对反应的影响。发现反应能够获得预期的氯菊酸甲酯。与目前采用的于有机溶剂中用醇钠作碱的反应方法相比,使用相转移催化法能够显著减少有机溶剂的用量,降低对环境的污染,并且能够使用廉价的氢氧化钠等无机碱代替醇钠。然而使用相转移催化法获得的反应产率较使用纯有机溶剂法更低。此外也研究了从手性的(.).sparteine制得的季铵盐催化的反应,获得了产物氯菊酸甲酯。从制备的氯菊酸甲酯出发,通过水解、成酰氯、与间苯氧基苄醇反应等后续步骤,合成了菊酯类农药氯菊酯『2,2一二甲基一3一(2,2一二氯乙烯基)环丙烷羧酸一间苯氧苄醇酯](5)。本论文的研究对于发展更清洁、有效、对环境友好的合成菊酯类农药的新路线有较高的参考价值,在此基础上,通过使用手性相转移催化剂, 将能够发展制备光学活性的菊酯类农药的新路线。关键词:相转移催化、拟除虫菊酯、氯菊酯、合成 Synthesis ofPermethrin under Phase Transfer Catalysis Synthesis ofPermethrin under Phase Transfer Catalysis Major:Chemical Biology Name:Chuangfeng Huang Supervisor:Professor Lianquan Gu ProfessorMing Yan Abstract Methyl4,6,6,6·tetrachloro一3,3一dimcthylhexanoate(2)was prepared frommethyl 3,3一dimethylpent-4-enoate(1)in good ording tothereported the anic diphase system,the synthesis of methyl 3一(2,2一dichloro— vinyl)一2,2一dimethylcyclopropanecarboxylate(3)from methyl 4,6,6,6一tetracbloro一3,3一 dimethylhexanoate(2)was studied indetailusingphase seriesof frequently used phase transfercatalysts(quaternaryammonium,polyethylene glycol, crown etheretc.)were examined influence ofselected bases on thechemical yield was expected product,methyl 3一(2,2一dichlorovinyl)一2,2一dimethylcyclopropanecarboxylate(3),was obtained with phase paring with present synthetic procedure ofmethyl 3一(2,2-dichlorovinyl)-2,2·dimethylcyclopropanecarboxylate 0) using sodium methoxide anic solvents,the phase transfercatalyticprocedure could provide following advantages:use offewamount anicsolvents,small detrimental effect on theenvironment and use ofcheap anic bases such assodium hydroxide or potassium hydroxide instead ofsodium thechemical yield under phase transfer catalysis was lower than thatobtained anic solvents. Me