Identification and Synthesis of (Z,Z)-8,11-Heptadecadienyl Formate and (Z)-8-Heptadecenyl Formate: Unsaturated Aliphatic Formates Found in the Unidentified Astigmatid Mite, Sancassania sp. Sasagawa (Acari: Acaridae).

Abstract

We identified two aliphatic formates, (Z,Z)-8,11-heptadecadienyl formate and (Z)-8-heptadecenyl formate in the opisthonotal gland secretions of an unidentified acarid species, namely Sancassania sp. Sasagawa. Both compounds were isolated using silica gel column chromatography and the structures were elucidated by 1H-NMR and GC/FT-IR. Further information on the double bond positions was obtained by GC-MS analysis of the corresponding dimethyl disulfide derivatives. Based on the estimated structures of the two formates and using linoleic and oleic acids as the respective starting materials, a simple four-step synthesis was achieved via Barton decarboxylation as the key step. The aliphatic formates identified in acarids thus far are neryl formate ((Z)-3,7-dimethylocta-2,6-dienyl formate) and lardolure (1,3,5,7-tetramethyldecyl formate), and both have been reported to have pheromone functions. The biological function of the two formates isolated in this study is currently being investigated. Although we can speculate that the two compounds were biosynthesized from linoleic and oleic acid, there is a possibility that the synthetic processes featured a novel chain shortening and formic acid esterification mechanism.