Frontalin Asian elephant pheromone

Abstract A relatively small number of mammalian pheromones has been identified, in contrast to a plethora of known insect pheromones, but two remarkable Asian elephant/insect pheromonal linkages have been elucidated, namely, (Z)-7-dodecen-1-yl acetate and frontalin. In addition, behavioral bioassays have demonstrated the presence of a chemical signal in the urine of female African elephants around the time of ovulation. Our search for possible ovulatory pheromones in the headspace over female African elephant urine has revealed for the first time the presence of a number of known insect pheromones. This search has been facilitated by the use of a powerful new analytical technique, automated solid phase dynamic extraction (SPDE)/GC-MS, as well as by novel macros for enhanced and rapid comparison of multiple mass spectral data files from Agilent ChemStation . This chapter will focus on our methodologies and results, as well as on a comparison of SPDE and the more established techniques of solid phase microextraction (SPME) and stir bar sorptive extraction (SBSE). 

First identified in Asian elephants during a headspace analysis of volatiles collected from secretions of the musth temporal gland of adult males,156 frontalin (52) is a bicyclic ketal, which is structurally reminiscent of the male mouse priming pheromone component 3,4-dehydro-ara-brevicomin (37). Frontalin (52), Z-7-dodecen-l-yl acetate (51), was already known because of its chemosensory role in the insect world it is an aggregation pheromone in bark beetles.157 Interestingly, the ratio of the two enantiomers of frontalin (52) changes with age and stage of musth and elicits different behavioral responses.158... 

Examples include the alkylated 2,8-dioxabicyclo[3.2.1]octane (aro-brevicomin, 54), 6,8-dioxabicyclo[3.2.1]-octanes (frontalin, 55, and multistriatin, 56), and the 2,9-dioxabicyclo[3.3.1]nonane (57). Brevicomin, frontalin, and multistriatin are important components of the male or female pheromones of several bark beetle species. More recently, several hydroxylated 6,8-dioxabicyclo[3.2.1]octanes, including 58-60, have been identified from the mountain pine beetle, Dendroctonusponderosae Interestingly, frontalin (55) also represents an important component of the Asian elephant s male pheromone (Figure 20). ... 

---