光学活性仲丁威的合成和生物活性  

Synthesis and bioactivity studies on optically active fenobucarb

作　　者：唐子龙[1] 许栋梁[1] 刘汉文[1] 欧晓明[2] 陈卫文[1] 张超逸[1] 

机构地区：[1]湖南科技大学化学化工学院理论化学与分子模拟省部共建教育部重点实验室,湖南湘潭411201 [2]湖南化工研究院国家农药创制工程技术研究中心,长沙410007

出　　处：《华中师范大学学报（自然科学版）》2009年第4期593-597,604,共6页Journal of Central China Normal University：Natural Sciences

基　　金：教育部留学回国人员科研启动基金项目([2007]1108);湖南省自然科学基金项目(06JJ50016);湖南省教育厅科研项目(07C288)

摘　　要：主要研究了光学活性仲丁威的合成方法及其生物活性.在DCC和DMAP的作用下,N-苄氧甲酰基-L-苯丙氨酸和邻仲丁基苯酚发生缩合反应生成了N-苄氧甲酰基-L-苯丙氨酸-(2-仲丁基苯)酯,将N-苄氧甲酰基-L-苯丙氨酸-(2-仲丁基苯)酯通过重结晶拆分得到两个光学活性非对映体,再分别水解得到两个光学活性邻仲丁基苯酚,然后将两个光学活性邻仲丁基苯酚分别与甲基异氰酸酯反应得到两个光学活性仲丁威.用~1H NMR,^(13)C NMR,MS和IR对中间体及目标化合物的结构进行了表征.对合成的光学活性仲丁威进行了初步的生物活性测试,结果表明光学活性仲丁威(+)-7(22.3%ee)和(-)-8(13.8%ee)对稻黑尾叶蝉的毒力比外消旋体仲丁威小.This paper mainly studied the synthesis and bioactivity of optically active carbamate insecticide fenobucarb. Firstly, N-benzyloxycarbonyl-L-phenylalanine 2-sec-butylphenyl ester 2 was synthesized by condensation reaction of N-benzyloxycarbonyl-L- phenylalanine with racemic 2-sec-butylphenol in the presence of DCC and DMAP. Then, two diastereomers of 2 were resolved by recrystallizion, and hydrolyzed to afford the two optically active 2-sec-butylphenols, respectively. The two optically active 2-sec-butylphenols reacted with methyl isocyanate yielding the corresponding optically active （＋）-fenobucarb （22.3 %ee） and （-）-fenobucarb（13.8 % ee）. The target products and intermediates were characterized by 1H NMR, lac NMR and IR. A preliminary bioactivi- ty test of optically active （＋）-fenobucarb and （-）-fenobucarb was then investigated, and the results showed that their activity against Nephotettix cincticeps was （±）-fenobucarb〉（-）-fenobuearb （13.8 % ee）and（＋）-fenobuearb （22.3 %ee）.

关 键 词：不对称合成 光学活性邻仲丁基苯酚 光学活性仲丁威 生物活性 

分 类 号：O623.6[理学—有机化学]