- STEREOSPECIFIC SYNTHESIS OF COMPONENTS OF THE NATURAL SEX PHEROMONE OF Pectinophora gossypiella
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A multistage stereospecific synthesis of components of the natural pheromone was realized.Conditions were found for stereospecific trans-reduction of the triple bonds.A procedure was developed for regiospecific dehydrohalogenation of 1,2-dibromoalkanes.Conditions giving the Z and E isomers in ratio of 96 : 4 were found for the Wittig reaction.
- Matveeva, E. D.,Kvasha, M. P.,Kurts, A.L.
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p. 1017 - 1021
(2007/10/02)
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Coupling reactions of lithium compounds, (Z)-carbonyl olefination of phosphonium ylides and 'crossed' Wittig olefination of bisylides are the key reaction steps in the synthesis principle for nonconjugated, bisolefinic Lepidoptera pheromones and structural analogs. Double unsaturated (E,Z)- and (E,E)-1-vinyl halides are converted into the corresponding (E,Z)- and (E,E)-1-vinyl lithium compounds and coupled selectively to (E,Z)- and (E,E)-alkadienols, alkadienals and alkadienyl acetates with different carbon chain length, geometry and relative positions of double bonds. 'Crossed' Wittig reactions of 1,ω-alkylidene bisylides with two different alkanals gives rise to the formation of corresponding (Z,Z)-dienic sex attractants and derivatives. A monounsaturated (E)-1-vinyl iodide is the synthon for the preparation of an (E)-alkenyl bromide which is converted to an (E)-alkenyl phosphonium salt and (Z)-selectively olefinated to (Z,E)-isomers of moth sex pheromones.
- Bestmann,Zeibig,Vostrowsky
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p. 1039 - 1047
(2007/10/02)
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- SYNTHETIC INVESTIGATIONS IN THE FIELD OF INSECT ATTRACTANTS (SEX ATTRACTANTS). X. SYNTHESIS OF THE ACETATES OF CIS-7,CIS-11- AND CIS-7,TRANS-11-HEXADECADIEN-1-OL, THE SEX PHEROMONES OF THE PINK BOLLWORM MOTH Pectinophora gossypiella S. (LEPIDOPTERA, GELECHIIDAE) AND THE GRAIN MOTH Sit...
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The synthesis of the acetates of cis-7,cis-11- and cis-7,trans-11-hexadecadien-1-ol, which are the sex pheromones of the pink bollworm moth Pectinophora gossypiella and the Angoumois grain moth Sitotroga cerealella, and their geometric isomers on the basis of the Wittig reaction and of the unsaturated functionally ω-substituted aldehydes is described.The alkylation of the dilithium derivative of 4-pentyn-1-ol by 2-(6-bromohexyloxy)tetrahydropyran in a mixture of liquid ammonia and THF gave a 40percent yield of 11-(2-tetrahydropyranyloxy)-4-undecyn-1-ol, which was hydrogenated selectively to 11-(2-tetrahydropyranyloxy)-cis-4-undecen-1-ol or was reduced to 11-(2-tetrahydropyranyloxy)-trans-4-undecen-1-ol.Both alcohols were oxidized by pyridinium chlorochromate to 11-(2-tetrahydropyranyloxy)-cis-4-undecenal and 11-(2-tetrahydropyranyloxy)-trans-4-undecenal.The reaction of both aldehydes with amyltriphenylphosphonium bromide under stereocontrolled conditions followed by acetolysis gave the acetates of cis-7,cis-11-, cis-7,trans-11-, trans-7,cis-11-, and trans-7,trans-11-hexadecadien-1-ols and a mixture of the acetates of cis-7,cis-11- and cis-7,trans-11-hexadecadien-1-ol (gossyplure).
- Kovalev, B. G.,Avdeeva, L. A.,Sorochinskaya, A. M.
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p. 641 - 646
(2007/10/02)
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