USDA-ARS, Invasive Insect Biocontrol and Behavior Laboratory, Beltsville Agricultural Research Center, Building 007, Room 301, 10300 Baltimore Avenue, Beltsville, Maryland 20705, USA.
J Agric Food Chem. 2010 Feb 10;58(3):1828-33. doi: 10.1021/jf903468c.
The winter moth, Operophtera brumata (Lepidoptera: Geometridae), is an early-season defoliator that attacks a wide variety of hardwoods and, in some cases, conifers. The insect is native to Europe but has become established in at least three areas of North America including southeastern New England. The female-produced sex attractant pheromone of the winter moth was identified as (3Z,6Z,9Z)-1,3,6,9-nonadecatetraene (1), which also attracts a native congener, the Bruce spanworm, Operophtera bruceata . Dissection, or (for certainty) DNA molecular testing, is required to differentiate between males of the two species. Thus, a trapping method that is selective for winter moth would be desirable. A geometric isomer of the pheromone, (3E,6Z,9Z)-1,3,6,9-nonadecatetraene (2), can reportedly inhibit attraction of Bruce spanworm to traps without affecting winter moth catch, but use of the pheromone and inhibitor together has not been optimized, nor has the synthesis of the inhibitor. This paper presents two new syntheses of the inhibitor (3E,6Z,9Z)-1,3,6,9-nonadecatetraene based on the intermediate (3Z,6Z)-3,6-hexadecadien-1-ol (4), which has also been utilized in the synthesis of the pheromone. The syntheses combine traditional acetylenic chemistry and Wittig olefination reactions. In one approach, 2 was synthesized in 80% purity (20% being pheromone 1), and in the second, tetraene 2 of 96% purity (and free of 1) was produced in 25% overall yield from dienol 4. The last method benefitted from a refined TEMPO-mediated PhI(OAc)(2) oxidation of 4 and a two-carbon homologation of the corresponding aldehyde 7.
冬尺蠖（Operophtera brumata）（鳞翅目：尺蛾科）是一种早春的食叶昆虫，它以多种硬木为食，在某些情况下还会以针叶树为食。该昆虫原产于欧洲，但已在北美至少三个地区（包括新英格兰东南部）建立了种群。冬尺蠖雌蛾产生的性信息素诱芯被鉴定为（3Z，6Z，9Z）-1，3，6，9-十九碳四烯（1），它还吸引了一种本地近缘种，布鲁斯尺蠖（Operophtera bruceata）。要区分这两个物种的雄蛾，需要进行解剖，或者（为了确定）进行 DNA 分子测试。因此，需要一种选择性捕捉冬尺蠖的方法。性信息素的一种几何异构体，（3E，6Z，9Z）-1，3，6，9-十九碳四烯（2），据报道可以抑制布鲁斯尺蠖对诱捕器的吸引力，而不影响对冬尺蠖的捕捉，但该信息素和抑制剂的联合使用尚未得到优化，抑制剂的合成也没有得到优化。本文提出了两种基于中间体（3Z，6Z）-3，6-十六碳二烯-1-醇（4）的新的抑制剂（3E，6Z，9Z）-1，3，6，9-十九碳四烯的合成方法，该中间体也用于合成性信息素。这些合成方法结合了传统的炔烃化学和维蒂希烯烃化反应。在一种方法中，2 的纯度为 80%（20%为 1），而在另一种方法中，从二烯醇 4 中以 25%的总收率得到了纯度为 96%（且不含 1）的四烯 2。最后一种方法得益于 TEMPO 介导的 PhI(OAc)2 氧化 4 的改进和相应醛 7 的两碳同系化。
