title: Synthesis and characterization of hexadecadienyl compounds with a conjugated diene system, sex pheromone of the persimmon fruit moth and related compounds.
abstract: Hexadecadien-1-ol and the derivatives (acetate and aldehyde) with a conjugated diene system have recently been identified from a pheromone gland extract of the persimmon fruit moth (Stathmopoda masinissa), a pest insect of persimmon fruits distributed in East Asia. The alcohol and acetate showed their base peaks at m/z 79 in a GC-MS analysis by electron impact ionization, but the aldehyde produced a unique base peak at m/z 84, suggesting a 4,6-diene structure. To confirm this inference, four geometrical isomers of each 4,6-hexadecadienyl compound were synthesized by two different routes in which one of two double bonds was furnished in a highly stereoselective manner. Separation of the two isomers synthesized together by each route was facilely accomplished by preparative HPLC. Their mass spectra coincided well with those of natural components, indicating that they were available for use as authentic standards for determining the configuration of the natural pheromone. Furthermore, other hexadecadienyl compounds, including the conjugated diene system between the 3- and 10-positions, were synthesized to accumulate the spectral data of pheromone candidates. 5,7-Hexadecadienal interestingly showed the base peak at m/z 80; meanwhile, the base peaks of its alcohol and acetate were detected at m/z 79 like the corresponding 4,6-dienes. The base peaks of all 6,8-, 7,9-, and 8,10-dienes universally appeared at m/z 67 like 9,11-, 10,12-, and 13,15-dienes, the spectra of which have already been published. Although 3,5-hexadecadienal was not prepared, base peaks at m/z 67 and 79 were recorded for the alcohol and acetate, respectively.
authors.affiliation: Graduate School of Bio-Applications and Systems Engineering (BASE), Tokyo University of Agriculture and Technology, Koganei, Tokyo 184-8588, Japan.
authors.forename: Takanobu
authors.initials: T
authors.lastname: Nishida
authors.forename: Van Le
authors.initials: VL
authors.lastname: Vang
authors.forename: Hiroyuki
authors.initials: H
authors.lastname: Yamazawa
authors.forename: Ryuji
authors.initials: R
authors.lastname: Yoshida
authors.forename: Hideshi
authors.initials: H
authors.lastname: Naka
authors.forename: Koji
authors.initials: K
authors.lastname: Tsuchida
authors.forename: Tetsu
authors.initials: T
authors.lastname: Ando
mesh_terms: D000085:Acetates; D000438:Alcohols; D000447:Aldehydes; D000466:Alkadienes / Q000138:chemical synthesis* / Q000494:pharmacology; D000473:Alkanes; D000818:Animals; D029788:Diospyros; D006841:Hydrocarbons, Aromatic / Q000138:chemical synthesis / Q000494:pharmacology; D009682:Magnetic Resonance Spectroscopy; D008297:Male; D013058:Mass Spectrometry; D009036:Moths; D012724:Sex Attractants / Q000737:chemistry*; D013237:Stereoisomerism
chemical_list: D000085:Acetates; D000438:Alcohols; D000447:Aldehydes; D000466:Alkadienes; D000473:Alkanes; D006841:Hydrocarbons, Aromatic; D012724:Sex Attractants; C007932:n-hexadecane