P. E. Sonnet

Sex pheromone of the stable flyl: Isolation and preliminary identification of compounds that induce mating strike behavior

Cuticular rinses of the female stable fly,Stomoxys calcitrans (L.), contained saturated and unsaturated hydrocarbons that incited the male fly to attempt couplation. These compounds present in GLC trappings of the saturated hydrocarbon fraction showing highest biological activity were mono- and dimethyl-substituted hentria- and tritriacontanes. Active trappings from the unsaturated hydrocarbon fraction contained (Z)-9-hentriacontene, (Z)-9-tritriacontene, and methyl-branched hentria- and tritriacontenes.

Sex pheromone of the face fly,Musca autumnalis De Geer (Diptera: Muscidae)

Components of a sex pheromone that cause male face flies to strike at females were found to be the straight-chain monoalkenes (Z)-14-nonacosene, (Z)-13-nonacosene, and (Z)-13-heptacosene. Although these compounds were found in the extracts of both sexes, extracts from sexually mature males contained a much higher proportion of nonacosane and heptacosane, which attenuated the activity of the active monoalkenes. The monoalkenes were readily synthesized by a Wittig reaction modified by the use of hexamethylphosphoric triamide as a cosolvent with tetrahydrofuran to produce a product containing 94–96% (Z) isomer.

Identification of a female-produced sex pheromone of the western corn rootworm

A sex pheromone has been isolated and identified from virgin females of the western corn rootworm (WCR),Diabrotica virgifera virgifera LeConte. The synthesized compound, racemic 8-methyl-2-decanol propanoate, was equal in attraction to the natural pheromone when tested in the field as a trap bait against three taxa ofDiabrotica known to respond to pheromone extracts from female WCR. Five taxa (D. virgifera virgifera; D. virgifera zeae Krysan and Smith, Mexican corn rootworm;D. longicornis barberi Smith and Lawrence, northern corn rootworm;D. longicornis longicornis (Say); andD. porracea Harold) were attracted to traps baited with 8-methyl-2-decanol propanoate. The response of male northern corn rootworms (NCR) in the field peaked at a relatively low concentration of 8-methyl-2-decanol propanoate and then was severely reduced at the higher concentrations tested. Conversely, the response of male WCR in the field continued to increase up to the highest dose tested.

Mating-stimulant pheromone and cuticular lipid constituents of the little house fly,Fannia canicularis (L.)

Chromatograms of the cuticular lipids washed from recently emerged female and maleFannia canicularis (L.) flies were nearly identical, but by the time the flies were 5 days old, the cuticular components of the two sexes differed considerably. A monoolefin which constituted 66% of the cuticular lipid from 5-day-old females stimulated a copulatory response from males and was identified as (Z)-9-pentacosene. The cuticular lipid of the same age males contained only 1% of this compound. Although all the major constituents of the cuticular lipid from mature females were hydrocarbons, 27% of the lipid washed from 5-day-old males was a nonhydrocarbon material that was represented by a single GLC peak. This material was identified as heneicosan-8-ol acetate.

Identification of a female-produced sex pheromone from the Southern corn rootworm, Diabrotica undecimpunctata howardi Barber

A sex pheromone has been isolated and identified from virgin females of the southern corn rootworm (SCR),Diabrotica undecimpunctata howardi Barber. The synthesized compound, 10-methyl-2-tridecanone was shown to be attractive to males of the SCR, and also to males ofD. u. undecimpunctata Mannerheim, the western spotted cucumber beetle (WSCB), and ofD. u. duodecimnotata in Mexico. Males of both the SCR and the WSCB strongly preferred theR over theS enantiomer. The resolved enantiomers were not tested againstD. u. duodecimnotata.

Low-calorie triglyceride synthesis by lipase-catalyzed esterification of monoglycerides

Monoglycerides of erucic acid (C22:1, Δ13), prepared by conventional methods, were reacted with caprylic acid (octanoic acid, C8.0) by using lipases as catalysts with the intention of synthesizing a triglyceride that contains two molecules of caprylic acid and one molecule of erucic acid (caprucin). The reaction was carried out by mixing lipase powder, a small quantity of water, and the reactants in a temperature-controlled stirred batch reactor. Organic solvents or emulsifying agents were not required. When the nonspecific lipase fromPseudomonas cepacia was used, a yield of approximately 37% caprucin was obtained, together with a complex mixture of di- and triglycerides that resulted from the random transesterification of the erucic acid. The fatty acid-specific lipase fromGeotrichum candidum promoted minimal transesterification of erucic acid and resulted in a yield of 75% caprucin and approximately 10% interesterification products. Lipase fromCandida rugosa exhibited a similar, although less pronounced, specificity to that fromG. candidum and promoted more transesterification of erucic acid. Optimum conditions forG. candidum lipase were at 50°C and an initial water content of 5.5%. After the reaction, erucic acid was converted to behenic acid by hydrogenation, thereby converting caprucin into caprenin, a commercially available low-calorie triglyceride.

Regioselective analysis of triacylglycerols by lipase hydrolysis

A modified procedure for the regiospecific analysis of triacylglycerols (TAG) with a 1,3-specific lipase is described. After partial lipase hydrolysis of the triacylglycerol, the released free fatty acids (FFA) and 1,2(2,3)-diacylglycerols (DAG) were isolated by thin-layer chromatography (TLC) and converted to fatty acid methyl esters (FAME). The FAME were analyzed by gas-liquid chromatography (GLC). The 1,3-specific lipases used in this study included supported preparations from strains ofMucor miehei andRhizopus oryzae. The method also was applied to the regiospecific analyses of tung nut and Chinese melon seed oil triacyglycerols, both of which contain high proportions of α-elaeostearic acid. The TAG composition of the oils was substantiated in parallel analysis of the oils by highperformance liquid chromatography with chemical ionization mass spectrometric detection of intact TAG.

Response ofDiabrotica virgifera virgifera, D. v. Zeae, andD. porracea to stereoisomers of 8-methyl-2-decyl propanoate

The four stereoisomers of 8-methyl-2-decyl propanoate were tested in the United States and Mexico for attractiveness toDiabrotica virgifera virgifera LeConte, the western corn rootworm,D. v. zeae Krysan and Smith, the Mexican corn rootworm, andD. porracea Harold. Males ofD. v. virgifera andD. v. zeae responded strongly to the (2R,8R)-isomer and secondarily to (2S,8R), whileD. ponacea responded exclusively to the (2S,8R)-isomer. The (2S,8S)- and (2R,8S)-isomers were inactive in all tests. Synergism or inhibition was not detected when various mixtures of the isomers were tested withD. v. virgifera. These phenomena were not tested withD. v. zeae andD. ponacea.

Reactions of dioxiranes with selected oleochemicals

Reaction of fatty acids with dimethyldioxirane in acetone produces ketoacids in 9–12% yields in which the ketone carbonyl is distributed along the fatty chain. The n-1 position appears to be preferred. Lactones of hydroxy fatty acids are oxidized by this reagent, but in low yields, to the corresponding ketoacids. Biphasic epoxidations with methylethyldioxirane in 2-butanone were conducted with methyl oleate and methyl ricinoleate to give the corresponding expoxides in high yield, and olive oil and tallow were cleanly epoxidized by this procedure as well.

Sex pheromone of the stable fly

The cuticular alkenes of the female stable fly,Stomoxys calcitrans (L), which were responsible for inducing male fly copulatory behavior are (Z)-9-hentriacontene, (Z)-9-tritriacontene, 13-methyl-1-hen-triacontene and 13-methyl-1-tritriacontene. The identifications of the branched alkenes and the synthesis of these four compounds are described. Bioassays indicate that these materials in combination with previously described methyl branched alkanes are more active than the individual components.