Male-specific tetraene and triene hydrocarbons ofCarpophilus hemipterus: Structure and pheromonal activity

Abstract

Males ofCarpophilus hemipterus (L.), the dried-fruit beetle, (Coleoptera: Nitidulidae) were found to emit nine all-E tetraene and one all-E triene hydrocarbons in addition to two pheromonally active tetraenes that had been reported previously. The previously known compounds are (2E,4E,6E,8E)-3,5,7-trimethyl-2,4,6,8-decatetraene(1) and (2E,4E,6E,8E)-3, 5,7-trimethyl-2,4,6,8-undecatetraene(2). The new tetraenes were all related to structure1 by having one additional carbon at either one or two of the following four locations: at carbon 1 of the chain, at carbon 10 of the chain, at the 5-alkyl branch, or at the 7-alkyl branch. (Structure 2 also fits within this pattern.) The triene inC. hemipterus is (2E,4E,6E)-5-ethyl-3-methyl-2, 4,6-nonatriene. Also identified from volatile collections from the beetles were the 2Z and 4Z isomers of1. All structures were proven by synthesis, with NMR and mass spectral data for the compounds provided. Two of the newly discovered compounds, (2E,4E,6E,8E)-7-ethyl-3,5-dimethyl-2,4,6,8-decatetraene and (2E,4E,6E,8E)-7-ethyl-3,5-dimethyl-2,4,6,8-undecatetraene, were quite active in the wind-tunnel bioassay, but others, such as (2E,4E,6E,8E)-5-ethyl-3,7-dimethyl-2,4,6,8-decatetraene and (2E,4E,6E,8E)-4,6,8-trimethyl-2,4,6,8-undecatetraene were not. Structureactivity relationships are explored among the natural compounds and additional, synthetic analogs, which were never detected from the beetles. Some of these analogs, such as (2E,4E,6E,8E)-3,5-dimethyl-7-propyl-2,4,6,8-undecatetraene, were quite active in the bioassay. The biosynthesis of the beetle-derived compounds is discussed. A single biosynthetic scheme that lacks complete enzyme specificity at four specific steps could account for the entire series of compounds found in the beetles and their relative proportions. The definition of “pheromone” is discussed in relation to these hydrocarbons.