| Title: | "Improved synthesis of (3E,6Z,9Z)-1,3,6,9-nonadecatetraene, attraction inhibitor of bruce spanworm, Operophtera bruceata, to pheromone traps for monitoring winter moth, Operophtera brumata" |
| Author(s): | Khrimian A; Lance DR; Mastro VC; Elkinton JS; |
| Address: | "USDA-ARS, Invasive Insect Biocontrol and Behavior Laboratory, Beltsville Agricultural Research Center, Building 007, Room 301, 10300 Baltimore Avenue, Beltsville, Maryland 20705, USA. ashot.khrimian@ars.usda.gov" |
| ISSN/ISBN: | 1520-5118 (Electronic) 0021-8561 (Linking) |
| Abstract: | "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" |
| Keywords: | "Animals Female *Insect Control Isomerism Male Moths/drug effects/*physiology Polyenes/*chemical synthesis/chemistry/pharmacology Sex Attractants/*antagonists & inhibitors/chemical synthesis/chemistry/pharmacology Sexual Behavior, Animal/drug effects;" |
| Notes: | "MedlineKhrimian, Ashot Lance, David R Mastro, Victor C Elkinton, Joseph S eng 2010/01/01 J Agric Food Chem. 2010 Feb 10; 58(3):1828-33. doi: 10.1021/jf903468c" |
