Synthesis of cis-9-tetradecen-1-ol acetate, the sex pheromone of the fall armyworm

Warthen, David

doi:10.1021/jm00308a045

Cited by 24 publications

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“…Treatment of 0.2 g of polymers 14 or 15 with 0.5 g of potassium tert-butoxlde in fertbutyl alcohol overnight under refiux and then following the modified Volhard analysis (16) Prepararion of Polynrer-bo~md Alkyrzes [18][19][20] To a solution of 10 rnniol of 1-lithio-1-butyne (17), a r e~a r e d in 40 ml of THF under argon at -10-C from 0 . 8 k l of 1-butyne in 8 mi THF and 4 ml of 2.5 M nbutyllithii~m in 28 ml THF, was added 2.0 g of polymer 10 containing 0.28 mmol of 131g of 10, and 30 ml HMPT.…”

Section: Preparation Of Diol Monomeg~lafes 11-13mentioning

confidence: 99%

“…similarly, hydrogenation and acetylation of 22 gave Poly~ner-bound Trityl Etlzer Alkenes 42, 43, and 45 7-dodecen-1-01 acetate (18) (28) portions of THF, one 20 ml portion of ethanol, four Sinlilarly, 23 yieldeil 9-tetradecen-1-ol acetate (19,26) 20 ml portions of water, two 20 ml portions of ethanol, (29) in high yield (Table 1). two 20 ml portions of dioxane, and three 20 ml portions ,-ompounds 28-30 were analyzed by and hplc of ether, and air dried to give polymer-bound alkene 42, to determine the amount of product in the supwhich did not exhibit a carbony1 absorption in its inposedly pure cis cornpounds and the data are recorded in frared spectrum.…”

Section: Preparation Of Diol Monomeg~lafes 11-13mentioning

confidence: 99%

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The use of polymer supports in organic synthesis. VIII. Solid phase syntheses of insect sex attractants

Leznoff¹,

Fyles²,

Weatherston³

1977

Can. J. Chem.

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Section: Preparation Of Diol Monomeg~lafes 11-13mentioning

confidence: 99%

Section: Preparation Of Diol Monomeg~lafes 11-13mentioning

confidence: 99%

The use of polymer supports in organic synthesis. VIII. Solid phase syntheses of insect sex attractants

Leznoff¹,

Fyles²,

Weatherston³

1977

Can. J. Chem.

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“…packed with 10% UC W-98 on Chromosorb W, 80/100 mesh, which was temperature programmed from 110°C to 22S°C. The column effluent was collected in 1 min fractions in glass tubes as described elsewhere (Underhill et al October 19771976). The biological activity of each fraction was assayed first by EAG (Roelofs and Comeau 1971), and later by olfactometer behavioural responses.…”

Section: Methodsmentioning

confidence: 99%

A SEX PHEROMONE MIXTURE FOR THE BERTHA ARMYWORM MOTH, MAMESTRA CONFIGURATA: (Z)-9-TETRADECEN-1-OL ACETATE AND (Z)-11-HEXADECEN-1-OL ACETATE

1977

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An abdominal tip extract of female bertha armyworm moths, Mamestra configurata (Walker), was found to contain two sex pheromone components. One corresponded to (Z)-11-hexadecen-1-ol acetate, previously identified from this source, and the other to a tetradecen-1-ol acetate, identified by gas chromatography – mass spectrometry. Data obtained from the EAG profile of isomeric tetradecen-1-ol acetates indicated the active component to be (Z)-9-tetradecen-1-ol acetate. Neither of these two acetates was by itself attractive to males in field tests; however, mixtures were attractive, with the best attraction occurring with a C16:C14 acetate ratio of about 19:1.

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“…A complete solid phase synthesis of cis insect sex attractants would require that the stereoselective cis reduction of an internal alkyne be accomplished directly on the polymer support. In this report we describe the synthesis of insect sex attractants on solid phases by a two-step alkyne coupling route using only acetylene and alkyl halides (9,10). In addition, the stereoselective reduction of a polyn~er-bound alkyne to a polymer-bound cis-alkene by an examination of a variety of soluble reducing agents is described.…”

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confidence: 99%

The use of polymer supports in organic synthesis. XII. The total stereoselective synthesis of cis insect sex attractants on solid phases

Fyles¹,

Leznoff²,

Weatherston³

1977

Can. J. Chem.

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. Can. J. Chem. 55,4135 (1977).A 2% crosslinked divinylbenzene-styrene copolymer, incorporating trityl chloride groups (2) was used in the synthesis of insect sex attractants of Lepidoptera by a two-step alkyne coupling route. Polymer 2 reacted with the symmetrical diols, 1,s-octanediol and 1, lO-decanediol, to give the monoblocked polymer-bound diols 5 and 6 respectively. Mesylation of 5 and 6 gave the polymer-bound monomesylates 7 and 8 which on coupling with lithioacetylide gave the polymer-bound terminal alkynes 9 and 10 respectively. Acid cleavage of 9 and 10 provide 9-decyn-1-01 and 11-dodecyn-1-01 respectively. A second coupling step was performed by lithiation of 9 and 10 with n-butyllithium or tert-butyllithium followed by treatment with n-butyl bromide or ethyl bromide to give polymer-bound internal alkynes, which on acid hydrolysis gave 9-tetradecyn-1-01 (22), 11-hexadecyn-1-01 (23), and 11-tetradecyn-1-ol(24). If 10 had been lithiated with n-butyllithium and coupled with ethyl bromide, some translithiation occurred to liberate n-butyl bromide which entered into the coupling reaction eventually giving a mixture of 23 and 24. This problem was resolved by the use of tert-butyllithium in the lithiation step. Attempts were made to reduce polymer-bound internal alkynes stereoselectively to cis-alkenes with 9-borabicyclononane, diisobutylaluminum hydride, and catechol borane but all these reagents proved inadequate due to incomplete reduction, overreduction, hydrogenolysis of the alkyne from the polymer, and non-selectivity. Polymer-bound internal alkynes were quantitatively reduced exclusively to cis insect sex attractants using disiamylborane without concurrent overreduction or hydrogenolysis. THOMAS M. FYLES, CLIFFORD C. LEZNOFF et JOHN WEATHERSTON. Can. J. Chem. 55,4135 (1977).On a utilist un copolymere divinylbenzkne-styrkne rCticul.4 a 2% et incorporant des groupes chlorure de trityle (2) pour rCaliser la synthtse de l'attirant sexuel du Lepidoptera en faisant appel a un schtma de couplage d'alcynes impliquant deux Ctapes. I,e polymtre 2 rCagit avec les diols symCtriques octanediol-1,s et dtcanediol-l,l0 pour conduire suivant le cas aux diols monobloquCs 5 et 6 liCs au polymtre. La mksylation de 5 et 6 fournit les monomCsylates 7 et 8 lies au polymere qui, par couplage avec I'acCtylure de lithium, conduisent respectivement aux alcynes terminales 9 et 10 liCs au polymtre. Une scission acide de 9 et 10 conduit respectivement aux dCcyn-9 01-1 et dodCcyn-11 01-1. Une nouvelle Ctape de couplage, effectute par la lithiation I de 9 et 10 avec le n-butyllithium ou le tert-butyllithium, suivie par un traitement avec le bromure de n-butyle ou le bromure d'Cthyle conduit aux alcynes internes liCs au polymtre qui par hydrolyse acide fournissent le tCtradCcyn-9 01-1 (22), I'hexadCcyn-11 01-1 (23) et le tCtradCcyn-11 01-1 (24). Si l'on avait effectuk la lithiation de 10 avec du n-butyllithium et si on I'avait couplC avec du bromure d7Cthyle, il se serait produit un peu de translithiation pour IibCrer du bromur...

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Synthesis of cis-9-tetradecen-1-ol acetate, the sex pheromone of the fall armyworm

Cited by 24 publications

References 1 publication

The use of polymer supports in organic synthesis. VIII. Solid phase syntheses of insect sex attractants

The use of polymer supports in organic synthesis. VIII. Solid phase syntheses of insect sex attractants

A SEX PHEROMONE MIXTURE FOR THE BERTHA ARMYWORM MOTH, MAMESTRA CONFIGURATA: (Z)-9-TETRADECEN-1-OL ACETATE AND (Z)-11-HEXADECEN-1-OL ACETATE

The use of polymer supports in organic synthesis. XII. The total stereoselective synthesis of cis insect sex attractants on solid phases

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