Yamazawa H, Nakajima N, Wakamura S, Arakaki N, Yamamoto M, Ando T
Graduate School of Bio-Applications and Systems Engineering, Tokyo University of Agriculture and Technology, Koganei, Japan.
J Chem Ecol. 2001 Nov;27(11):2153-67. doi: 10.1023/a:1012255201380.
All stereoisomers of three diepoxyalkenes derived from (3Z,6Z,9Z)-trienes with a C21, C19, or C18 straight chain, lymantriid sex pheromones and their candidates, were synthesized by MCPBA oxidation of optically active epoxyalkadienes. Their chromatographic behaviors were examined with GC and LC equipped with achiral and chiral columns. Detailed inspection of the mass spectra of these epoxides indicated the following diagnostic ions for determining the chemical structures: m/z 128, 167, M-87 and M-85 for (Z)-cis-3,4-cis-6,7-diepoxy-9-enes; m/z 111, M-125 and M-69 for (Z)-cis-6,7-cis-9,10-diepoxy-3-enes; and m/z M-125 and M-139 for (Z)-cis-3,4-cis-9,10-diepoxy-6-enes. Mass chromatographic analysis that monitored these fragment ions revealed the existence of a new pheromonal compound with a C21 chain in an extract from virgin females of a lymantriid species, Perina nuda F. The three diepoxyalkenes were converted into the corresponding DMDS adducts, which showed characteristic ions from fragmentation between the two thiomethyl groups, reflecting the position of an original double bond.
通过光学活性环氧链二烯的间氯过氧苯甲酸（MCPBA）氧化反应，合成了三种衍生自具有C21、C19或C18直链的（3Z,6Z,9Z）-三烯、舞毒蛾性信息素及其候选物的二环氧烯烃所有立体异构体。使用配备有非手性柱和手性柱的气相色谱（GC）和液相色谱（LC）对它们的色谱行为进行了研究。对这些环氧化合物质谱的详细检查表明，以下诊断离子可用于确定化学结构：对于（Z）-顺式-3,4-顺式-6,7-二环氧-9-烯，m/z 128、167、M - 87和M - 85；对于（Z）-顺式-6,7-顺式-9,10-二环氧-3-烯，m/z 111、M - 125和M - 69；对于（Z）-顺式-3,4-顺式-9,10-二环氧-6-烯，m/z M - 125和M - 139。监测这些碎片离子的质量色谱分析表明，在舞毒蛾科一种昆虫——柳毒蛾（Perina nuda F.）未交配雌虫的提取物中存在一种具有C21链的新信息素化合物。这三种二环氧烯烃被转化为相应的二甲基二硫（DMDS）加合物，其显示出两个硫甲基之间断裂产生的特征离子，反映了原始双键的位置。
