Syntheses of Alarm Pheromone Analogues of the Mold Mite,Tyrophagus putrescentiae,and Their Biological Activities

Against the mold mite, Tyrophagus putrescentiae, 3,7-dimethyl-(Z)-2-octenyl formate (II) is the most active compound as an alarm pheromone besides the natural pheromone, neryl formate (I), and this activity is equal to I (1-10 ppm). In order to elucidate the structural requisites for inducing alarm pheromone activity, a total of 16 analogues of I were prepared by modifying the structure of II. For preparation of 3-methyl- and 3-ethyl-(Z)-2-alkenyl formates, the Wittig reaction of ethoxy- or methoxy-carbonylmethylene triphenyl phosphorane with 2-alkanone or 3-alkanone was used. The reaction with 2-alkanone gave a mixture of (Z)-2-alkenoate (ca. 40%) and (E)-2-alkenoate (ca. 60%) in an average 60% yield. The reaction with 3-alkanone gave a mixture of (Z)-2-alkenoate (56%) and (E)-2-alkenonate (44%).

Alarm pheromone activities were demonstrated on 14 compounds of (Z)-2-alkenyl formates. The presence of the (Z)-allylic primary alcohol formate moiety in a molecule was clarified as the key to induce pheromone activity, and no necessity for an acyclic monoterpene carbon skeleton was demonstrated.