United States Patent (19) 11 Patent Number: 4,563,348 Soderstrom et al. 45 Date of Patent: Jan. 7, 1986 54) SEC-BUTYL (Z)-7-TETRADECENOATE AND lytic Type B and Non-Proteolytic Types E and F of ITS USE AS A SEX ATTRACTANT FOR THE Clostridium botulinum, Chem. Abstracts, vol. 72, No. GRAPELEAF SKELETONIZER 10025n, 1970. 75 Inventors: Edwin L. Soderstrom, Fresno; M. M. Barnes, D. W. Robinson and A. G. Forkes, "At William F. Haddon, Larkspur; Joel tractants for Moths of the Western Grape Leaf Skele Myerson, Belmont, all of Calif. tonizer,' Journal of Economic Entomology, vol. 47, pp. 58-63, (1954). 73) Assignee: The United States of America as David G. Sullivan, "Characterization of the Western represented by the Secretary of Grapeleaf Skeletonizer,' (Harrisina brillians, B & Agriculture, Washington, D.C. McD.; Family Zygaenidae) Pheromone(s), 1975, (un (21) Appl. No.: 462,491 published). (22 Filed: Jan. 31, 1983 Primary Examiner-Thomas A. Waltz 51) Int. Cl."...................... A01N 25/00; C11B 11/00; Attorney, Agent, or Firm-M. Howard Silverstein; C11B 1/OO David G. McConnell; Margaret A. Connor 52 U.S. C. ................................... 424/84; 260/405.5; 260/410.9 R; 514/549 57) ABSTRACT 58) Field of Search ............... 424/312, 84; 260/405.5, A pheromonal compound produced by the western 260/410.9 R, 410.9 D; 514/549 grapeleaf skeletonizer has been identified as sec-butyl 56) References Cited (Z)-7-tetradecenoate. The synthetically-prepared com PUBLICATIONS pound demonstrates activity toward both the western Francke et al., Isopropyl Esters of Carboxylic Acids-A grapeleaf skeletonizer, Harrisina brillians Barnes and New Class of Insect Pheromones, Chem. Abstracts, vol. McDunnough and the grapeleaf skeletonizer, Harrisina 91, No. 207727s, 1979. americana (Guerin). By attracting adult moths to field Batchelor et al., Occurence of Cis-7-Tetradecenoic traps, this compound offers a useful tool in monitoring Acid in the Envelop Phospholipids of Escherichia coli and control of this pest. K12, Chem. Abs., vol. 79, No. 892.12x, 1973. Kimble et al., Comparison of the Fatty Acids of Proteo 13 Claims, No Drawings 4,563,348 1 2 grapeleaf skeletonizer (GLS), Harrisina americana SEC-BUTYL (Z)-7-TETRADECENOATE AND ITS (Guerin). USE ASA SEX ATTRACTANT FOR THE Our invention provides means for detection of the GRAPELEAF SKELETONZER skeletonizer and provides potential for population con trol and population density estimation of this pest. Its BACKGROUND OF THE INVENTION usefulness in eliciting a behavioral response when ap 1. Field of the Invention plied to a locus of skeletonizer males suggests the fol This invention relates to a novel compound useful as lowing economic applications of the attractant: (1) the a sex attractant for the grapeleaf skeletonizer, Harrisina detecting of infestation outbreaks; (2) the monitoring of species (Lepidoptera: Zygaenidae). The invention re O existing adult populations in order to predict infestation lates further to use of this compound in combination levels the following year for scheduling of treatment with or integration with other insect control agents with larval insecticides and (3) the control of reproduc such as insecticides, parasites, predators and pathogens tion in adult populations either by direct disruption of to simultaneously attract and combat the skeletonizer. mating through confusing or inhibitory properties, or 2. Description of the Prior Art 15 by attracting a demographically significant portion of Insects of the group known as the grapeleaf skeleton the male population for subsequent destruction or steril izer, Harrisina species (Lepidoptera: Zygaenidae) are ization. pests of vineyards, backyard grapevines, wild grapes as In accordance with this discovery, it is an object of well as some ornamental plants such as Virginia creeper the invention to identify for the first time a sex phero and Boston ivy and occasionally, fruit trees. In addition 20 mone from a representative of the genus Harrisina, and to defloliating grapevines and feeding on the fruit, the more particularly from the species brillians. skeletonizer has urticating setae which can produce skin A further object of the invention is to produce sec welts on vineyard workers. butyl (Z)-7-tetradecenoate as a synthetic counterpart of In California, the western grapeleaf skeletonizer the natural WLGS sex pheromone and as a sex attrac (WGLS), Harrisina brillians Barnes and McDunnough, 25 tant for use in attracting other species of the grapeleaf poses a threat to commercial grape production. For skeletonizer. years chemical pesticide sprays used to control other Another object of the invention is to utilize sec-butyl insects have controlled the skeletonizer in commercial (Z)-7-tetradecanoate as a detection, monitoring or con vineyards, but the intensive use of conventional chemi trol agent for the grapeleaf skeletonizer. cals may ultimately present hazards to man and the 30 A further object is to provide a grapeleaf skeletonizer environment. Furthermore, intensive use of insecticides attractant for use with insecticides, biological control to control other insect pests has frequently resulted in agents and the like to attract and combat the skeleton the survival of insecticide-resistant insect populations izer. that can no longer be treated effectively, thus methods 35 Other objects and advantages of the invention will be of pest control which offer an alternative to the conven evident from the following description where in parts tional use of insecticides are needed. Although at pres and percentages are by weight. ent in California infestations of the skeletonizer are in DETAILED DESCRIPTION OF THE backyard plantings or wild grapes that are not treated INVENTION adequately with insecticides, a major escalation of the 40 economic effect of this insect could occur if it becomes Sec-butyl (Z)-7-tetradecenoate was identified by resistant to insecticides and invades commercial vine chemical, spectroscopic and chromatographic tech yards. niques as the major component of volatiles emitted by The continued search for alternatives to the wide WGLS female moths. This compound produced wing spread application of insecticides has led to the investi 45 flutter, hair pencil display and dancing in male WGLS gation of sex attractants as potential agents for use in moths in laboratory tests and was highly attractive to integrated pest management. A number of economically WGLS males in field tests as shown in Examples 3-5 important insects are currently monitored and at least below. It has also been shown to be an attractant for partially controlled by use of their own specific sex grapeleaf skeletonizer (GLS), Harrisina americana pheromone. In the case of the grapeleaf skeletonizer, 50 (Guerin) males. Its ability to attract GLS males as well although Barnes et al., Journal of Economic Entomology, as WGLS males suggest that its biosynthesis is not lim Volume 47, pp 58-63 (1954), reported that male western ited to the WGLS species and that it may be a sex at grapeleaf skeletonizer moths were attracted to extracts tractant of the United States Harrisina species, Harrisina of WGLS females, the lack of identification and com coracina (Clemens) as well as grapeleaf skeletonizers mercial availability of a skeletonizer pheromone has 55 found outside the United States. precluded application of this technology to the treat Three other compounds were identified in the vola ment of this pest. tiles emitted by WGLS female moths-isopropyl (Z)-7- tetradecenoate, sec-butyl decanoate and sec-butyl SUMMARY OF THE INVENTION dodecanoate. Secondary butyl or isopropyl unsaturated We have now for the the first time obtained in pure or 60 esters have never before been reported from the volatile substantially pure form the major female-produced sex complex of a lepidopteran species, thus our identifica pheromone of the western grapeleaf skeletonizer. This tion has resulted in the discovery of a new structural new compound, identified as sec-butyl (Z)-7-tet class of insect volatiles. Both sec-B (Z)-7-T and isopro radecenoate (sec-B (Z)-7-T) has been isolated from pyl (Z)-7-tetradecenoate are novel compounds. females of the western grapeleaf skeletonizer (WGLS), 65 Field tests of sec-B (Z)-7-T versus an equal amount of Harrisina brillians Barnes and McDunnough and has sec-B (Z)-7-T contained in a mixture of the other three also been successfully synthesized. It is an effective insect volatiles in the ratio found in the natural extract attractant for WGLS males as well as males of the showed that sec-B (Z)-7-T alone has the same attract 4,563,348 3 4. ancy as the mixture, suggesting that it is the only phero The attractant may also be used to control the skele mone component. tonizer by confusion of males, thus preventing mating. The sec butyl (Z)-7-tetradecenoate compound of this For example, one technique is to permeate the atmo invention is characterized by the following structural sphere with the pheromone to prevent the males of the formula: p species from orienting to and inseminating the females. Other uses of the attractant will be obvious to those in CH3 O the art. EXAMPLES O The following examples are intended only to further It is apparent therefrom that the compound may exist as illustrate the invention and are not intended to limit the either of two stereoconfigurations by virtue of the chi scope of the invention which is defined by the claims. ral center denoted by the *. The amount of R- or S EXAMPLE 1. enantiomer in the natural isolate is not known, however tests of the synthetically produced RS-compound show 15 Isolation and Identification of Volatiles From Female that it is very highly attractive to WGLS males (100 ug Western Grapeleaf Skeletonizers of a crude synthetic preparation had the attractancy of The volatiles from female western grapeleaf skeleton about four female moths as described in detail in Exam izers were collected by two methods.