Propionates and Acetates of Chiral Secondary Alcohols: Novel Sex Pheromone Components Produced by a Lichen Moth Barsine expressa (Arctiidae: Lithosiinae)
Propionates and Acetates of Chiral Secondary Alcohols: Novel Sex Pheromone Components Produced by a Lichen Moth Barsine expressa (Arctiidae: Lithosiinae)
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DOI：
10.1007/s10886-012-0225-4
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发表时间：
2013-01-01
影响因子：
2.3
通讯作者：
Ando, Tetsu
中科院分区：
文献类型：
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作者：
Fujii, Toru;Yamakawa, Rei;Ando, Tetsu
女性的地衣蛾，Barsine expressa（Arctiidae，Lithosiinae），居住在日本西表岛，被捕获的黑光灯陷阱，和信息素腺体提取物进行了分析，气相色谱（GC）与触角电位（EAG）检测器，并通过GC与质谱联用。雌性产生了几个EAG活性酯，和一个主要成分的质谱表明的混合物由丙酸衍生自C-17饱和仲醇，这是不可分割的毛细管GC柱。除了这些主要成分外，信息素腺体还包括C-17醇的两种乙酸酯衍生物，以及C-16和C-15醇的其他丙酸酯。用K2 CO 3处理粗提取物，得到具有C-6-或C-7-链部分的C-17醇的1：1混合物。这两种醇通过甲磺酰化和随后的LiAlD 4还原均匀地转化为单氘代正十七烷。这一结果揭示了直链结构的C-17醇与酰基位于7-或8-位。在西表岛的现场试验表明，合成酯具有行为活性。通过格氏偶联反应合成了7-丙氧基十七烷和8-丙氧基十七烷的外消旋体，它们的1：1混合物吸引雄蛾。此外，通过使用水解动力学拆分与Jacobsen的催化剂对映选择性合成的醇的丙酸酯进行了评价。只有用具有相同S-构型的两种酯的混合物作为诱饵的陷阱显著地吸引了B。expressa男性。在东京地区，丙酸混合物吸引了一个密切相关的物种，Barsine aberrans aberrans。
Females of a lichen moth, Barsine expressa (Arctiidae, Lithosiinae), which inhabit Iriomote Island in Japan, were captured by a black-light trap, and the pheromone gland extract was analyzed by gas chromatography (GC) with an electroantennographic (EAG) detector, and by GC coupled with mass spectrometry. The females produced several EAG-active esters, and the mass spectrum of a major component indicated the mixture consists of propionates derived from C-17-saturated secondary alcohols, which were inseparable on the capillary GC column. In addition to these main components, the pheromone glands included two acetate derivatives of C-17 alcohols, and other propionates of C-16 and C-15 alcohols. The crude extract was treated with K2CO3, and a 1:1 mixture of C-17 alcohols with a C-6- or C-7-chain moiety was obtained. The two alcohols were uniformly converted into monodeuterated n-heptadecane by mesylation and succeeding LiAlD4 reduction. This result revealed a straight-chain structure of the C-17 alcohols with the acyl groups located at the 7- or 8-position. Field tests on Iriomote Island showed that the synthetic esters were behaviorally active. A 1:1 mixture of racemic 7-propioxyheptadecane and 8-propioxyheptadecane, which were prepared from the secondary alcohols synthesized by a Grignard coupling reaction, attracted male moths. Furthermore, propionates of the alcohols synthesized enantioselectively by using a hydrolytic kinetic resolution with Jacobsen's catalyst were evaluated. Only the traps baited with a mixture of the two esters with the same S-configuration significantly attracted B. expressa males. In the Tokyo area, the propionate mixture attracted a closely related species, Barsine aberrans aberrans.