Patent GB-1399315-A (GB)
Title: Polyene compounds and a process for the manufacture thereof
IPC: C07C239/00
Filed: 1973-06-15
Abstract: 1399315 Polyene compounds F HOFFMANN-LA ROCHE & CO AG 15 June 1973 [16 June 1972 29 June 1972] 28572/73 Heading C2C Polyene compounds of general formula wherein R 1  represents an alkyl group (1-6 C), R 2 , R 3 , R 4  and R 5  represent a hydrogen atom or alkyl group (1-6 C), A represents a hydrogen atom or a hydroxy, alkoxy (1-6 C), or alkyl group (1-6 C) and B represents a hydrogen atom or A and B represent an additional bond or an oxygen bridge, X represents a grouping -COOR 6 , -CH 2 OR 6 , -CH 2 O-CONH-R 7 , -COSR 6 , - -COR 10  or -CN in which R 6  represents an alkyl, alkenyl, or alkynyl (1-6 C), R 7  represents a hydrogen or an alkyl (1-6 C), R 8  and R 9  each represent a hydrogen atom or an alkyl (1-6 C) and R 10  represents a hydrogen or an alkyl, alkenyl, or alkynyl (1-6 C) and n stands for 0 or 1, are prepared by reacting a carbonyl compound with (a) a phosphine oxide wherein X<SP>1</SP> represents -COOR 6 , -CN or in which R 11  and R 12  may be alkyl (1-6 C) or aryl, substituted or unsubstituted, and (b) a phosphorone  wherein R 13 , R 14  and R 15  represent aryl or dialkylamino; a carbonyl compound with (a) a phosphine oxide and (b) a phosphorane a compound with a compound J-R 6  in which one of K and J represent chlorine, bromine or iodine or tosyloxy group, and the other represents -OM where M is an alkali metal or alkaline earth metal; by epoxidizing a polyene I where A and B represent an additional bond to an oxygen bridge; by reacting a carbonyl with or a carbonyl with and dehydrating the products; reacting an alcohol with a compound R 7 -N = C = O or by oxidizing to the aldehyde; forming esters or amides of an acid or reacting the acid with an organo-lithium compound. The products can be used in pesticides. Examples describe the preparation of 7,11- dimethyl-2,4-dodecadienoic acid, 7,11-dimethyl- 2,4,10 - dodecatrienoic acid, 7,10,11 - trimethyl - 2,4 - dodecadienoic acid and 7,11 - dimethyl - 11 - methoxy - 2,4 - dodecadienoic acid methyl esters from the corresponding aldehydes and 1-carbomethoxy-1-propenyl-diethylphosphonate ; 10,11 - epoxy - 7,11 - dimethyl- 2,4-dodecadienoic acid methyl ester from the 7,11 - dimethyl - 2,4 - 10 - dodecatrienoic acid methyl ester; the propargyl esters of 7,11-dimethyl - 2,4 - dodecadienoic and 7,11 - dimethyl - 11 - methoxy - 2,4 - dodecadienoic acids and the isopropylester of 7,11-dimethyl-11- methoxy - 2,4 - dodecadienoic acid; the methyl esters of 11-methoxy-2,7,11-trimethyl-2 4-dodecadienoic and 2,7,11-trimethyl-2,4,10- dodecatrienoic acids from the aldehydes and diethylphosphono-α-methyl-crotonic acid methyl ester; the ethyl ester of 2,7,11-trimethyl-2,4, 10-dodecatrienoic acid, the isopropyl and propargyl esters of 11-methoxy-2,7,11-trimethyl- 2,4-dodecadienoic acid by reaction with the bromides; the thioethyl and thioisopropyl esters of 7,11 - dimethyl - 2,4 - dodecadienoic acid and the thioethyl esters of 7,11-dimethyl-11- methoxy-2,4-dodecadienoic acid and the thiobutyl ester of 2,7,11-trimethyl-2,4-dodecadienoic acid. The preparation of 3,6,7-trimethyloctan - 1 - al, 7,11 - dimethyl - 2,4 - dodecadienoic, 2,7,11 - trimethyl - 2,4,10 - dodecatrienoic, 7,11 - dimethyl - 2,4,10 - dodecatrienoic, 7,10,11 - trimethyl - 2,4 - dodecadienoic and 11 - methoxy - 2,7,11 - trimethyl - 2,4- dodecadienoic acids which are starting materials are described.