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.

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.

The most biologically active enantiomer of trimedlure, a synthetic lure attractive to male Mediterranean fruit flies, is the 1S,2S,4R enantiomer of isomer C, the fert-butyl ester of ris-4-chloro-trans-2-methylcyclohexanecarboxylic acid. We also determined that the 1R,2R,5S enantiomer of isomer A is significantly more attractive than its optical antipode. Essential differences in the current synthetic work that are critical to possible commercialization of this preparation are detailed herein.

Prompted by growing agricultural and industrial interest in the chemistry of lipaases for a great variety of reactions, and the usefulness of glycerol derivatives in characterizing lipase activity, we devised syntheses of 1,2- and 1,3-diakylglycerol diethers and their esters. Configurational analyses of the diethers has been accomplished by derivatizing them to form diastereomers that are separable by gas chromatography. The alternative methods employed for determining the configuration of triglycerides and related glycerol derivatives are reviewed briefly with reference to the stereoselectivity of their lipase catalyzed reactions.

AbstractThe regioisomeric chiral methyloctanoic acids (R)‐(VIII), (R)‐(XIV), and (R)‐(XVII) are prepared via optical resolution of the 2‐methylated carboxylic acids (±)‐(III).

ChemInformVolume 19, Issue 28 Reviews ChemInform Abstract: Enzymes for Chiral Synthesis. P. E. SONNET, P. E. SONNET Agric. Res. Serv., US Dep. Agric., Philadelphia, PA 19118, USASearch for more papers by this author P. E. SONNET, P. E. SONNET Agric. Res. Serv., US Dep. Agric., Philadelphia, PA 19118, USASearch for more papers by this author First published: July 12, 1988 https://doi.org/10.1002/chin.198828303Read the full textAboutPDF ToolsRequest permissionExport citationAdd to favoritesTrack citation ShareShare Give accessShare full text accessShare full-text accessPlease review our Terms and Conditions of Use and check box below to share full-text version of article.I have read and accept the Wiley Online Library Terms and Conditions of UseShareable LinkUse the link below to share a full-text version of this article with your friends and colleagues. Learn more.Copy URL Share a linkShare onFacebookTwitterLinked InRedditWechat No abstract is available for this article. Volume19, Issue28July 12, 1988 RelatedInformation

The responses ofMicroplitis croceipes (Cresson) andMicroplitis demolitor Wilkinson to theR andS stereoisomers of the kairomone 13-meth-ylhentriacontane were evaluated. Singly and in combination at 5, 50-, and 500-ng dosage levels each were tested. There was a linear dosage response by both species to the three dosages. Furthermore, there was no difference between responses to the two stereoisomers or their combination by either species at any dosage level. The effects of the two stereoisomers were fully interchangeable and additive. This is the first report of parasitoid responses to stereoisomers of a kairomone.

ChemInformVolume 19, Issue 32 Reviews ChemInform Abstract: Enzymatic Processes for Pheromone Synthesis P. E. SONNET, P. E. SONNET Animal Biomat. Unit, East Reg. Res. Center, Agric. Res. Serv., US Dep. Agric., Wyndmoor, PA 19118, USASearch for more papers by this author P. E. SONNET, P. E. SONNET Animal Biomat. Unit, East Reg. Res. Center, Agric. Res. Serv., US Dep. Agric., Wyndmoor, PA 19118, USASearch for more papers by this author First published: August 9, 1988 https://doi.org/10.1002/chin.198832360Read the full textAboutPDF ToolsRequest permissionExport citationAdd to favoritesTrack citation ShareShare Give accessShare full text accessShare full-text accessPlease review our Terms and Conditions of Use and check box below to share full-text version of article.I have read and accept the Wiley Online Library Terms and Conditions of UseShareable LinkUse the link below to share a full-text version of this article with your friends and colleagues. Learn more.Copy URL Share a linkShare onFacebookTwitterLinkedInRedditWechat No abstract is available for this article. Volume19, Issue32August 9, 1988 RelatedInformation

AbstractHydroxyethylated amides such as (VII), which are good wetting agents, are prepared as mixtures from amides such as (VIII) and ethylene oxide under basic catalysis.

The synthesis of the enantiomeric 14-methyl-1-octadecenes in >99% EE is described. Enantiomeric 2-methyl-1-hexanols were intermediates in the synthesis. The 1-alkene had been previously identified as the sex pheromone of the peach leafminer moth. Several closely related structures that have δ12 unsaturation are also described.

Journal Article Attraction of Harrisina americana and Acoloithus falsarius Males (Lepidoptera: Zygaenidae) to (R)-(−)-2-butyl-(Z)-7-tetradecenoate Get access P. J. Landolt, P. J. Landolt Insect Attractants, Behavior, and Basic Biology Research Laboratory, Agricultural Research Service, U.S. Department of Agriculture, Gainesville, Florida 32604 Search for other works by this author on: Oxford Academic PubMed Google Scholar R. R. Heath, R. R. Heath Insect Attractants, Behavior, and Basic Biology Research Laboratory, Agricultural Research Service, U.S. Department of Agriculture, Gainesville, Florida 32604 Search for other works by this author on: Oxford Academic PubMed Google Scholar P. E. Sonnet, P. E. Sonnet 2 Insect Attractants, Behavior, and Basic Biology Research Laboratory, Agricultural Research Service, U.S. Department of Agriculture, Gainesville, Florida 32604 2Chemical Modifications Group, ARS-USDA, Wyndemere, PA 19118. Search for other works by this author on: Oxford Academic PubMed Google Scholar K. Matsumoto K. Matsumoto 3 Insect Attractants, Behavior, and Basic Biology Research Laboratory, Agricultural Research Service, U.S. Department of Agriculture, Gainesville, Florida 32604 3Biocommunications Chemistry Research Unit, ARS-USDA, Berkeley, CA 94710. Search for other works by this author on: Oxford Academic PubMed Google Scholar Environmental Entomology, Volume 15, Issue 4, 1 August 1986, Pages 959–962, https://doi.org/10.1093/ee/15.4.959 Published: 01 August 1986 Article history Received: 08 November 1985 Accepted: 02 May 1986 Published: 01 August 1986

The four stereoisomers of 8-methyl-2-decyl-propanoate (MDP) were tested in the field for attractiveness to Diabrotica longicornis (Say) and D. lemniscata LeConte. Males of both species were attracted to the (2S,8R) isomer, and D. lemniscata was weakly attracted to the (2R,8R) isomer. Tests of the response of D. longicornis to combinations of isomers revealed that the (2R,8R) isomer significantly reduced catch at traps baited with (2S,8R); the other two isomers were without detectable effect. Sex pheromones were collected from virgin female D. virgifera virgifera LeConte and D. longicornis. When used as bait in traps in the presence of males of D. v. virgifera and D. longicornis, the material from D. v. virgifera attracted only conspecific males; that from D. longicornis attracted males of both species. According to electroantennographic monitoring of gas chromatographic effluent with D. longicornis males, a substance obtained from the extracts of filter papers that had been contaminated with secretions from virgin female D. longicornis had retention times coincident with MDP on four gas chromatographic liquid phases.

A sex pheromone of the sweetpotato weevil,Cylas formicarius elegantulus (Summers), was obtained from collections of volatiles from virgin females, and pheromone was isolated by means of liquid and gas chromatography. The purification procedure was monitored by quantitative laboratory and field bioassays and the compound was identified as (Z)-3-dodecen-1-ol (E)-2-butenoate by means of spectroscopic and microchemical methods. Synthesis, followed by laboratory and field bioassays, showed that the biological activity of the synthetic material was qualitatively and quantitatively indistinguishable from that of the purified natural product.

The four stereoisomers of 8-methyl-2-decyl propanoate were tested in South Dakota for attractiveness to the northern corn rootworm,Diabrotica barberi Smith and Lawrence (NCR). Only the 2R,8R configuration was attractive to the NCR. Inhibition of the NCR response to 2R,8R occurred when either the 2S,8R or 2S,8S isomers were components of the pheromone source. The 2R,8S configuration elicited no behavioral activity in the NCR.

AbstractEinen interessanten Sexuallockstoff für die mediterrane Fruchtfliege Ceratitis capitata stellt das synthetische Lockstoff‐Gemisch Trimedlure dar, als des‐ " sen wesentliche Inhaltsstoffe die isomeren tert.‐Butylester (I) und (II) erkannt wurden.

The preparations and resolutions of a series of aryl substituted diastereomeric alkenes is described using bonded non-polar and cholesteric liquid crystal columns, the latter operated in its mesophase. Separations of diastereomers were notably greater using the more more aligned cholesteric phase. Elution orders of the diastereomers are determined by asymmetric synthesis, and is discussed in terms of molecular size and shape. The greatest diastereomer resolutions are achieved in this study when one of the asymmetric centers bears a 1- or 2-naphthyl group. Hence, it is suggested that a resolved 2-(1′- or 2′-naphthyl)propyl phosphonium salt could be useful as a derivatizing agent via Wittig condensations with chiral aldehydes. That is to say, the resulting diastereomeric alkenes would likely be separable allowing both the assignment of aldehyde absolute configuration by means of elution order and configurational purity by means of diastereomer ratio.

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.