Aphrodisiac Pheromones from the Wings of the Small Cabbage White and Large Cabbage White Butterflies, Pieris rapae and Pieris brassicae

Abstract

The small and large cabbage butterflies, Pieris rapae and P. brassicae, are found worldwide and are of considerable economic importance. The composition of the male scent-producing organs present on the wings was investigated. More than 120 components were identified, but only a small portion proved to be male specific. Major components were the known beetle pheromone ferrulactone (1) in P. rapae and its previously unknown larger analogue, brassicalactone (2), in P. brassicae. The latter carries an additional isoprene unit and is closely related to 1. Other components present in larger amounts on male relative to female wings were hexahydrofarnesylacetone (18) and phytol (23). Brassicalactone (2) was fully characterized by synthesis of its various diastereomers by using ring-closing metathesis. A similar approach to ferrulactone (1) failed, presumably because of its smaller ring size. Instead, this compound was synthesized by using a modified literature procedure. The biological activity of the compounds in the extract was tested by coupled gas chromatographic-electroantennographic (GC-EAD) analysis, which showed that both macrolides and the other major components of the wings can be detected by the antennae of the conspecific female butterflies. Other detectable compounds included several alkanes, which are typical constituents of the butterfly cuticula, derivatives of phytol (23) and long-chain secondary alcohols. Finally, bioassays with males showed that the mixture of 1 (P. rapae) or 2 (P. brassicae) together with 18 and 23 applied to freshly eclosed males increased mating success compared to untreated males. Therefore, the two macrolides 1 and 2 are aphrodisiac pheromone components of male small and large cabbage white butterflies, respectively.

Timing of Male Sex Pheromone Biosynthesis in a Butterfly – Different Dynamics under Direct or Diapause Development

“…In the genus Pieris, the male sex pheromone is known for both Pieris brassicae, P. rapae (Yildizhan et al, 2009), and P. napi (Andersson et al, 2007). The green-veined white butterfly, P. napi, is a well-documented model organism for evolutionary studies, and is one of the few butterfly species (see Nieberding et al, 2008) where both behavioral (e.g., and chemical (Andersson et al, 2000(Andersson et al, , 2007 background information is available on male sex pheromones.…”

The Biosynthesis of Hexahydrofarnesylacetone in the Butterfly Pieris brassicae

“…A retroaldol-fragmentation of the hydroxycarbonyl compounds 6 or 7 follows that releases hexahydrofarnesylacetone and acetaldehyde or acetate. The intermediate 4 can be found as a trace component in the male wing extracts (Yildizhan et al, 2009). Alternatively, a direct oxidative cleavage of the double bond of 1 is possible, but the dioxygenase enzymes capable of doing this usually act on aromatic systems.…”

“…These authors also established the absolute configuration of insect-derived 1 for the first time. We have found that Pieris butterflies use 1 as a component of the aphrodisiac pheromone of the males (Yildizhan et al, 2009). Hexahydrofarnesylacetone is a known degradation product of (E)-phytol (3), a diterpene alcohol that occurs as a side chain of chlorophyll a in all plants.…”

Females of the Bumblebee Parasite, Aphomia sociella, Excite Males Using a Courtship Pheromone

“…In other Galleriinae, males often use TMPD-ol for communication: this compound is a component of the male sex pheromone of the African sugarcane borer Eldana saccharina (Burger et al, 1985(Burger et al, , 1993 and Tirathaba mundella (Sasaerila et al 2003) (Lepidoptera: Pyralidae: Galleriinae). TMPD-ol is also part of the maleproduced aphrodisiac pheromone of the small and large cabbage white butterflies Pieris rapae and Pieris brasicae (Yildizhan et al 2009), and the African butterfly, Bicyclus anynana (Nieberding et al, 2008). E-Phytol [(E)-3,7,11,15-tetramethyl-2-hexadecen-l-ol], a compound related to TMPDol, a constituent in the male-produced wing gland sex pheromone in a related species, Ephestia elutella (Lepidoptera: Pyralidae; Phycitinae; Phelan et al, 1986).…”