Journal of Chemical Ecology

, Volume 9, Issue 5, pp 551–560 | Cite as

Improved preparations of alkyne nitriles, acetates, and alcohols

Application to the synthesis of the sex pheromone components of the Douglas fir tussock moth and peach fruit moth
  • Philip E. Sonnet
Article

Abstract

One-pot conversions of terminai alkynes to cyanoethylated and cyanopropylated alkynes are described. Reactions of these nitriles with Grignard reagents produced alkynones, the reductions of which gave alkenones. The described routes provide 3-step syntheses of several insect sex or stimulatory pheromones, namely, those of the peach fruit moth (Carposina niponensis Walsingham), Douglas fir tussock moth (Orgyia pseudotsugata [McDunnough]), and housefly (Musca domestica L.). Additionally, potentially useful one-pot processes for the preparation of hydroxyalkylated and acetoxyalkylated alkynes are reported.

Key words

Synthesis nitriles acetates alcohols esters pheromone attractant sex pheromone Douglas fir tussock moth Orgyia pseudotsugata peach fruit moth Carposina niponensis 

Preview

Unable to display preview. Download preview PDF.

Unable to display preview. Download preview PDF.

References

  1. Cahiez, G., Alexakis, A., andNormant, J.F. 1980. Simple stereospecific synthesis of the insect sex pheromones ofCossus cossus, Eupoecilia ambiguella andOrgyia pseudotsugata.Tetrahedron Lett. 21:1433–1436.Google Scholar
  2. Fetizon, M., andLazare, C. 1978. A rapid and convenient synthesis of the sex pheromone of the Douglas fir LepidopteraOrgyia pseudotsugata.J. Chem. Soc., Perkin I 1978:842–844.Google Scholar
  3. Heath, R.R., Jordan, J.R., Sonnet, P.E., andTumlinson, J.H. 1979. Potential for the separation of insect pheromones by gas chromatography on columns coated with cholesteryl cinnamate, a liquid-crystal phase.J. HRC & CC 2:712–714.Google Scholar
  4. Henrick, C.A. 1977. The synthesis of insect sex pheromones.Tetrahedron 33(15):1845–1890.Google Scholar
  5. Kocienski, P.J., andCernigliaro, G.J. 1976. A synthesis of (Z)-6-heneicosen-11-one. The sex pheromone of the Douglas fir tussock moth.J. Org. Chem. 41(17):2927–2928.PubMedGoogle Scholar
  6. Kondo, K., andMurahashi, S. 1979. Selective transformation of organoboranes to Grignard reagents by using pentane-1,5-di-(magnesium bromide). Syntheses of the pheromones of southern army worm moth and Douglas fir tussock moth.Tetrahedron Lett. 14:1237–1240.Google Scholar
  7. Litchfield, C., Harlow, R.D., Isbell, A.F., andReiser, R. 1965.cis-trans Isomerization of oleic acid with HNO2.J. Am. Oil Chem. Soc. 42(2):73–78.Google Scholar
  8. Liu, M., Zeng, X., andYan, Z. 1981. Synthesis of the sex pheromones of the peach fruit moth, (Z)-7-eicosen-11-one and (Z)-7-nonadecen-11-one.Huaxue Xuebo 39(5):475–480.Chem. Abstr. 1982 (96): 103911.Google Scholar
  9. Mori, K., Uchida, M., andMatsui, M. 1977. Synthesis of aliphatic insect pheromones from alicyclic materials. (Z)-6-Heneicosen-11-one and (Z)-8-dodecenyl acetate.Tetrahedron 33(4):385–387.Google Scholar
  10. Mozingo, R. 1955. Palladium catalysts.Org. Synth. Coll. 3:685–690.Google Scholar
  11. Naoshima, Y., Kawakubo, M., Wakabayashi, S., andHayashi, S. 1981. Synthesis of (Z)-7-eicosen-11-one and (Z)-7-nonadecen-11-one, the sex pheromone of peach fruit moth.Agric. Boil. Chem. 45(2):439–442.Google Scholar
  12. Normant, H. 1967. Hexamethylphosphoramide.Angew. Chem. Int. Ed. 6:1045–1067.Google Scholar
  13. San Filippo, J., Jr., Chern, C., andValentine, J.S. 1975. The reaction of Superoxide with alkyl halides and tosylates.J. Org. Chem. 40(11):1678–1680.Google Scholar
  14. Smith, R.G., Daterman, G.E., andDaves, G.D., Jr. 1975a. Douglas fir tussock moth: Sex pheromone identification and synthesis.Science 188:63–64.PubMedGoogle Scholar
  15. Smith, R.G., Daves, G.D., Jr., andDatehman, G.E. 1975b. Synthesis of (Z)-6-heneicosen-11-one. Douglas fir tussock moth sex attractant.J. Org. Chem. 40(11):1593–1595.Google Scholar
  16. Smith, W.N., andKuehne, E.D. 1973. Synthetic reactions of propynyllithium and propynylsodium.J. Org. Chem. 38(20):3588–3591.Google Scholar
  17. Tamada, S., Mori, K., andMatsui, M. 1978. Simple synthesis of (Z)-7-eicosen-11-one and (Z)-7-nonadecen-11-one, the pheromone of peach fruit moth.Agric. Biol. Chem. 42(1):191–192.Google Scholar
  18. Tamaki, Y., Honma, K., andKawasaki, K. 1977. Sex pheromone of the peach fruit moth,Carpesina niponensis Walsingham (Lepidoptera: Carposinidae): Isolation, identification and synthesis.Appl. Entomol. Zool. 12(l):60–68.Google Scholar
  19. Uebel, E.G., Schwarz, M., Lusby, W.R., Miller, R.W., andSonnet, P.E. 1978. Cuticular non-hydrocarbons of the female house fly and their evaluation as mating stimulants.Lloydia 41(l):63–67.Google Scholar
  20. Vig, O.P., Sharma, M.L., Verma, N.K., andMalik, M. 1980. A new synthesis of (Z)-heneicos-6-en-11-one, sex pheromone of Douglas fir LepidopteraOrgyia pseudotsugata.Ind. J. Chem. 19B:950–951.Google Scholar
  21. Vig, O.P., Sharma, M.L., Taneja, K.C., andMalik, N. 1981. Synthesis of (Z)-7-nonadecen-11-one and (Z)-7-eicosen-11-one, sex pheromone components of peach fruit moth,Carposina niponensis Walsingham.Ind. J. Chem. 208:863–865.Google Scholar
  22. Wang, S.S., Gisin, B.F., Winter, D.B., Mafofske, R., Kulesha, I.D., Tzougraki, C., andMeinhofer, J.J. 1977. Facile synthesis of amino acid and peptide esters under mild conditions via cesium salts.J. Org. Chem. 42:1286–1290.PubMedGoogle Scholar

Copyright information

© Plenum Publishing Corporation 1983

Authors and Affiliations

  • Philip E. Sonnet
    • 1
  1. 1.Insect Attractants, Behavior, and Basic Biology Research LaboratoryAgricultural Research Service, USDAGainesville

Personalised recommendations