Syntheses of (Z,E)-5,7-Dodecadienol and (E,Z)-10,12-Hexadecadienol, Lepidoptera Pheromone Components, via Zinc Reduction of Enyne Precursors. Test of Pheromone Efficacy against the Siberian Moth

• Published in: Journal of agricultural and food chemistry 2002-10, Vol.50 (22), p.6366-6370
• Main Authors: Khrimian, Ashot, Klun, Jerome A, Hijji, Yousef, Baranchikov, Yuri N, Pet'ko, Vladimir M, Mastro, Victor C, Kramer, Matthew H
• Format: Article
• Language: English
• Subjects: Animals; Copper; Isomerism; Moths - physiology; Oxidation-Reduction; Pest Control, Biological; Sex Attractants - biosynthesis; Sex Attractants - pharmacology; Zinc - metabolism
• ISSN: 0021-8561; 1520-5118
• DOI: 10.1021/jf020472s

Efficient syntheses of (Z,E)-5,7-dodecadienol, a pheromone component of the Siberian moth, Dendrolimus superans sibiricus, and (E,Z)-10,12-hexadecadienol, a pheromone component of various Lepidoptera pheromones, were accomplished by cis reduction of the corresponding enynols with activated zinc. The most energetic reagent was zinc galvanized with copper and silver (Zn/Cu/Ag) that achieved rapid and high-yield reduction in methanol−water. The stereoselectivity of semi-hydrogenation was ≥98%. A process whereby zinc dust was continuously activated throughout the reduction with an acid was also satisfactory (95−98% cis). Field evaluation of the 1:1 mixture of (Z,E)-5,7-dodecadienol and (Z,E)-5,7-dodecadienal with the Siberian moth in Russia showed that the rubber septa pretreated with compound and stored at −80 °C were as effective as freshly treated septa. Moth responses to septa aged in open air indicated that lure effectiveness declined significantly after 2 weeks of aging. Thus, if rubber septa are used as pheromone dispensers in Siberian moth traps monitoring, they should be replaced biweekly with fresh septa for optimal trap effectiveness. Keywords: (Z,E)-5,7-Dodecadienol; Siberian moth; Dendrolimus superans sibiricus; (E,Z)-10,12-hexadecadienol; pheromone; zinc reduction