Synthesis and Chemical Characterization of Hydrocarbons with a 6,9,11-, 3,6,9,11-, or 1,3,6,9-Polyene System, Pheromone Candidates in Lepidoptera
Synthesis and Chemical Characterization of Hydrocarbons with a 6,9,11-, 3,6,9,11-, or 1,3,6,9-Polyene System, Pheromone Candidates in Lepidoptera
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鳞翅目信息素候选物 6,9,11-、3,6,9,11- 或 1,3,6,9- 多烯系统碳氢化合物的合成和化学表征
DOI：
10.1007/s10886-008-9461-z
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发表时间：
2008
影响因子：
2.3
通讯作者：
T. Ando
中科院分区：
文献类型：
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作者：
Masanobu Yamamoto;Rei Yamakawa;Toshiya Oga;Yousuke Takei;Masakatsu Kinjo;T. Ando
鳞翅目昆虫II型性信息素主要由6，9-二烯、3，6，9-三烯及其环氧衍生物组成，它们是高等鳞翅目某些科昆虫以亚油酸和亚麻酸为原料生物合成的。为了进一步研究这一主题的结构修饰，我们合成了带有C17-C21链的多不饱和烃，其中包括一个额外的双键。利用Wittig反应，以具有合适碳链的(E)-2-烯烃为原料合成了(Z，Z，E)-6，9，11-三烯和(Z，E)-3，6，9，11-四烯，并以3-己烷-1，6-二醇为原料合成了(Z，Z，Z)-1，3，6，9-四烯。用气相色谱-质谱仪(GC-MS)对每一种合成的多烯进行了分析，其化学结构经~1H和~(13)C核磁共振确证，发现了一些反映双键位置的特征碎片离子，即6，9，11-三烯的m/z79、110、163和M-85，3，6，9，11-四烯的m/z79、108和M-82，以及1，3，6，9-四烯的m/z79、91、106和M-54。由于用有限数量的天然信息素通过化学衍生法很难确定不饱和位置，因此在真实样品中发现的这些诊断离子将有助于识别信息素提取物中的碳氢化合物。此外，我们在日本的森林中进行了这些多烯类的野外筛选试验，并记录了东京的4种蝗虫和伊里奥莫特群岛的1种夜蛾的引诱作用。
Lepidopteran Type II sex pheromones are mainly composed of 6,9-dienes, 3,6,9-trienes, and their epoxy derivatives, which are biosynthesized from linoleic and linolenic acids by the species in some families of higher Lepidoptera. To investigate further structural modifications on this theme, we synthesized polyunsaturated hydrocarbons with a C17–C21chain, which included an extra double bond. Using the Wittig reaction, (Z,Z,E)-6,9,11-trienes and (Z,Z,Z,E)-3,6,9,11-tetraenes were synthesized from (E)-2-alkenals with appropriate carbon chains, and (Z,Z,Z)-1,3,6,9-tetraenes were synthesized from 3-hexyn-1,6-diol. The gas chromatography-mass spectrometry (GC-MS) analysis of each synthetic polyene, whose chemical structure was confirmed by1H NMR and13C NMR, revealed some characteristic fragment ions reflecting the positions of the double bonds, i.e.,m/z79, 110, 163, and M-85 of the 6,9,11-trienes,m/z79, 108, and M-82 of the 3,6,9,11-tetraenes, andm/z79, 91, 106, and M-54 of the 1,3,6,9-tetraenes. Because the determination of the unsaturated positions is difficult to accomplish by chemical derivatization with a limited amount of natural pheromones, these diagnostic ions found in authentic samples would help identify the hydrocarbons in a pheromone extract. Furthermore, we carried out field screening tests of these polyenes in forests in Japan, and documented the attraction of four geometrid species in Tokyo and one noctuid species in the Iriomote Islands.
石垣和冲绳草丛蛾 Orgyia postica 品系中性信息素及相关化合物的鉴定
DOI：
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发表时间：
2005
期刊：
Biosci.Biotechnol.Biochem 69(5)
影响因子：
--
作者：
S.Wakamura;N.Arakaki;M.Yamamoto;S.Hiradate;H.Yasui;K.Kinjo;T.Yasuda;T.Ando
通讯作者：
T.Ando