Patent GB-1209190-A (GB)
Title: Tridecatrienoic acid derivatives, a process for the manufacture thereof and pest-control compositions containing same
Inventor: ATHERTON FRANK RATCLIFFE
IPC: C07C45/68
Filed: 1967-12-18
Abstract: 1,209,190. Derivatives of tridecatrienoic acid. ROCHE PRODUCTS Ltd. 14 Aug., 1968 [18 Dec., 1967], No. 57283/67. Heading C2C. [Also in Division A5] Novel tridecatrienoic acid derivatives of the Formula I in which X and the C 4-13  moiety at carbons 2 and 3 have a cis/trans or cis configuration, the C 1-5  and C 8-13  moieties at carbons 6 and 7 have a trans configuration and the C 1-9  and ethyl moieties at carbons 10 and 11 have a cis/trans or a cis or a trans configuration and X is a cyano, carboxy, alkoxy-carbonyl, aminocarbonyl or alkylaminocarbonyl group, are prepared either by reacting a ketone of the Formula II in which the C 1-4  and C 7-12  moieties at carbons 5 and 6 have a trans configuration and the C 1-8  and ethyl moieties at carbons 9 and 10 have a cis/trans or a cis or trans configuration, with a phosphorane of the formula in which X<SP>1</SP> is a cyano, alkoxycarbonyl, aminocarbonyl or alkylaminocarbonyl group and R<SP>1</SP>, R<SP>2</SP> and R<SP>3</SP> are aryl or dialkylamino groups, or with a phosphine oxide or phosphonate of the formula in which R<SP>4</SP> and R<SP>5</SP> are aryl, alkoxy or aryloxy groups, in the presence of an alkali metal alcoholate or hydride at a temperature between 0 C. and the b.pt. of the reaction mixture, to obtain a compound of the Formula V in which X<SP>1</SP> and the C 4-13  moiety at carbons 2 and 3 have a cis/trans or cis configuration, the configuration at the other bonds being as above, and, if desired, after isolating the 2-cis-isomer, epoxidizing this compound with an organic peracid or by treatment with aqueous N-bromosuccinimide to form the bromohydrin followed by dehydrobromination with a base, or by epoxidizing by the same methods, the ketone of the Formula II above to obtain an epoxide of the formula having the same configuration as ketone II, and reacting this compound with a phosphine oxide or phosphonate of the Formula IV above under the same reaction conditions as above, and, if desired, isolating the 2-cis-isomer, and, if required, saponifying an ester obtained by either method. The 2-cis/trans isomer mixtures can be separated, e.g. by chromatographic or fractional distillation methods, either at the final product stage or at an intermediate stage by separation of isomers of the Formula V above, or the bromohydrins thereof. Phosphonates of the Formula IV above in which R<SP>4</SP> and R<SP>5</SP> are aryloxy groups yield a high proportion of the 2-cis-isomer. Examples describe the preparation of various isomers of the free acid, the methyl and ethyl esters and the N,N-diethyl amide thereof. The tridecatrienoic acid derivatives are used as pest control agents (see Division A5). The starting ketone II, 6-ethyl-10-methyldodecadien - 5,9 - one - 2, is prepared from 3- methylpenten-1-ol-3 by bromination with allylic rearrangement to give cis/trans - 1 - bromo - 3 - methylpentene-2, followed by condensation with propionylacetic acid ethyl ester to cis/trans-7- methyl - nonen - 6 - one - 3 which is converted to the ketal cis/trans-3,3-ethylenedioxy-7-methylnonene-6 by reaction with ethylene glycol/BF 3  etherate; the ketal is separated into the cis and trans isomers and each hydrolysed to the ketone which is reacted with acetylene to obtain 3- ethyl - 7 - methylnonen - 6 - yn - 1 - ol - 3 which is partially hydrogenated to cis or trans 3-ethyl-7- methylnonadien-1,6-ol-3 which is either reacted with isopropenyl ether and rearranged, or brominated with allylic rearrangement to 1 - bromo - 3 - ethyl - 7 - methylnonadiene - 2,6 which is condensed with an acetoacetic acid ester to obtain the 5-cis/trans; 9-cis or 9-trans isomers of the required ketone which can be separated to the four isomeric forms.