METODĂ DE SINTEZĂ A RACEMATULUI DE 8-METILDECAN-2-IL PROPANOAT, COMPONENTA DE BAZĂ A FEROMONULUI SEXUAL AL VIERMELUI VESTIC AL RĂDĂCINILOR DE PORUMB, DIABROTICA VIRGIFERA VIRGIFERA LE CONTE

Andrei NEGUȚA, Elena NEGUȚA

Abstract


În lucrare este relatată o metodă de sinteză a racematului de 8-metildecan-2-il propanoat din materii prime disponibile comercial. Aceasta implică cuplarea încrucișată a 2-brombutanului cu reactivul Grignard, format din hexametilenclorhidrină și magneziu, pentru a obține 7-metilnonan-1-olul care este oxidat cu până la aldehidă cu clorcromat de piridiniu. Ulterior, aldehida este cuplată cu reactivul Grignard, format din iodură de metil și magneziu, iar alcoolatul obținut este esterificat cu anhidridă propanoică. Racematul de 8-metildecan-2-il propanoat este utilizat în calitate de feromon sexual al viermelui vestic al rădăcinilor de porumb.

 

METHOD OF SYNTHESIS OF RACEMIC 8-METHYLDECAN-2-YL PROPANOATE, THE BASIC COMPONENT OF THE SEX PHEROMONE OF THE WESTERN CORN ROOTWORM, DIABROTICA VIRGIFERA VIRGIFERA LE CONTE

This paper relates a synthesis method of 8-methyldecan-2-yl propanoate racemate from commercially available chemicals. It implies cross-coupling of 2-bromobutane with Grignard reagent formed of hexamethylene chlorohydrin and magnesium. The obtained 7-methylnonan-1-ol is oxidized to aldehyde with pyridinium chlorochromate and coupled with the Grignard reagent obtained from methyl iodide and magnesium. The resulted alcohol was esterified with propanoic anhydride. The racemate of 8-methyldecan-2-yl propanoate is applied as a sex pheromone of the western corn root­worm.


Keywords


8-methyldecan-2-yl propanoate, 8-methyldecan-2-ol, 7-metthylnonan-1-ol, 7-methylnonanal, Diabrotica virgifera virgifera Le Conte, synthesis, pheromones, western corn rootworm.

Full Text:

PDF

References


GUSS, P.L., TUMLINSON, J.H., SONNET, P.E. and PROVEAUX, A.T. Identification Of A Female-Produced Sex Pheromone Of The Western Corn Rootworm. In: Journal of Chemical Ecology, 1982, vol.8, no.2, p.545, https://doi.org/10.1007/BF00987802

MORI, K., WATANABE, H. Synthesis of the propionates of (2R, 8R)- and (2S, 8R)-8-methyl-2-decanol, the pheromone of the western corn rootworm, employing chiral compounds of microbial origin as starting materials. In: Tetrahedron, 1984, vol.40, no.2, p.299-303, https://doi.org/10.1016/S0040-4020(01)91175-5

SONNET, P.E., CARNEY, R.L., HENRICK, C. Synthesis of stereoisomers of 8-methyl-2-decanol and esters attractive to several Diabrotica Sp. In: Journal of Chemical Ecology, 1985, vol.11, no.10, p.1371-1387. https://doi.org/10.1007/BF01012138

ABRAMS, S.R., SHAW, A.C. Preparation of 8-methyl-2-decanol: General synthesis of diastereomeric mixtures of alkyl branched insect pheromones. In: Journal of Chemical Ecology, 1987, vol.13, no.8, p.1927-1933. https://doi.org/10.1007/BF01013241

GUSS, P.L., TUMLINSON, J.H., SONNET, P.E. and PROVEAUX, A.T. Synthetic Pheromone 8-Methyl-2-Decanol Propanoate, Patent US 4,734,524, Mar. 29, 1988

FERREIRA, B., SIMONELLI, F. Synthesis of two stereoisomers of the propanoate ester of 8-methyl-2-decanol using remote asymmetric induction. In: Tetrahedron, 1990, vol.46, no.18, p.6311-6318. https://doi.org/10.1016/S0040-4020(01)96003-X

NAOSHIMA, Y., MUNAKATA, Y., YOSHIDA, S., FUNAI, A. Synthesis of chiral alcohol and ester pheromones through enzyme-catalysed hydrolysis using Pseudomonas fluorescens lipase: preparation of (2R,6S,10S)-6,10–14-Trimethylpentadecan-2-ol and the propionate of (2R,8R)-8-methyldecan-2-ol. In: Journal of the Chemical Society, Perkin Transactions 1, 1991, p.549-553. https://doi.org/10.1039/P19910000549

MORI, K. New Syntheses of 1,7-Dimethylnonyl Propanoate, the Western Corn Rootworm Pheromone, in Four Different Ways via Cross Metathesis, Alkylation and Coupling Reactions. In: Biosci. Biotechnol. Biochem., 2010, vol.74, no.3, p.595–600. https://doi.org/10.1271/bbb.90805

ZHI-FENG SUN, TAO ZHANG, JINYANG LIU, ZHEN-TING DU, HUAIJI ZHENG Asymmetric Total Synthesis of Four Stereoisomers of the Sex Pheromone of the Western Corn Rootworm. In: Molecules, 2018, vol.23, p.667 https://doi.org/10.3390/molecules23030667

GUSS, P.L., SONNET, P.E., CARNEY, R.L., BRANSON, T.F., TUMLINSON, J.H. Response of Diabrotica virgifera virgifera, D.v. zeae and D.porracea to stereoisomers of 8-methyl-2-decyl propanoate, In: Journal of Chemical Ecology, 1984, vol.10, no.7, p.1123, https://doi.org/10.1007/BF00987518

CAHIEZ, G., ALEXAKIS, A., NORMANT, J.F Derives organomagnesiens ω-alcoolates: Preparation et proprieties. In: Tetrahedron Letters, 1978, no.33, p.3013-3014.

CAHIEZ, G., GUERRET, O., MOYEUX, A., DUFOUR, S. and LEFEVRE, N. Eco-Friendly and Industrially Scalable Synthesis of the Sex Pheromone of Lobesia botrana. Important Progress for the Eco-Protection of Vineyard, In: Organic Process Research & Development, 2017, no.21, p.1542-1546, https://doi.org/10.1021/acs.oprd.7b00206


Refbacks

  • There are currently no refbacks.