Patent GB-1497570-A (GB)
Title: Compounds containing an unsaturated aliphatic chain having an insecticidal action and having an inhibiting effect on the development and metamorphosis of insects
IPC: C07C69/65
Filed: 1975-01-13
Abstract: 1497570 Chlorovinylated compounds and their preparation MONTEDISON SpA 13 Jan 1975 [11 Jan 1974 18 Oct 1974] 1366/75 Heading C2C Compounds having the general formula in which: X represents a hydrogen or chlorine atom, n and t are each 1 or 2, m, p, q, r and s are each 0, 1 or 2, each R represents a hydrogen atom or a C 1-3  alkyl group which may be branched and/or substituted with the proviso that in the group -(CR = CR) n - at least one of the groups R represents -CH 3  or -C 2 H 5 , A and B each represents a hydrogen atom, or A and B together represents and extra bond so forming a double bond between the two carbon atoms to which they are attached, Z represents OR<SP>1</SP>, or -SR<SP>1</SP>, -SCSOR<SP>1</SP>, -CN, -NR<SP>11</SP>R<SP>111</SP> or -COY R<SP>1</SP> represents a C 1-3  alkyl group a C 2-4  alkenyl group, an oxalkyl group, or C 6 H (5-Á) W Á , Á is 0, 1, 2 or 3, W represents a hydrogen or halogen atom, a C 1-5  alkyl group a C 2-4  alkenyl group, an alkoxy group, an alkylthio group, an alkoxy carboxyl group, a keto group, an alkyl carboxyl, -NO 2 , -CN, a phenyl group, a methylanedioxy group linked for example at the 3, 4 positions to the C 6 H (5-Á)  nucleus, or an amino group optionally substituted with one or more monovalent substituents or with a substitutuent which together with the nitrogen atom completes a heterocyclic ring, R<SP>11</SP> and R<SP>111</SP>, which may be the same as or different from one another, each represents a hydrogen atom or an alkyl group containing 1 to 4 carbon atoms or an alkenyl group containing 2 to 4 carbon atoms or the group; or R<SP>11</SP> and R<SP>111</SP>, together with the nitrogen atom form a 5, 6 or 7-membered heterocyclic ring, Y represents a hydrogen atom, or an alkyl group containing 1 to 5 carbon atoms, an alkoxy group containing 1 to 5 carbon atoms, -OH, -O-metal, a cycloalkyl group or an aryl group, and M represents -CH 2 - or -CO-. The compound may be prepared in a series of reactions in which (a) carbon tetrachloride is reacted with a diene of formula to give a chloro-derivative of the formula CCl 3 -CH 2 -CR=CH-CH 3 Cl, (b) the latter is reacted with a keto-acid of the formula in which R<SP>1</SP> has the same meanings as R, to obtain a compound of the formula (c) the product of step (b) is decarboxylated to give the compound  (d) HCl is removed from the product of step (c) to give the ketone of formula or the compound obtained in step (c) is hydrogenated to give the saturated compound which is subsequently converted, by removal of HCl, to an unsaturated ketone of the formula (e) the unsaturated ketone obtained in step (d), generically denoted A-COR wherein A is the radical CCl 2  = CH-CR = CH-CH 2 -CHR<SP>1</SP>- or the radical CCl 2  = CH-CHR-(CH 2 ) 2 -CHR<SP>1</SP>-, is reacted either with a vinyl magnesium bromide of formula R-CH=CR-Mg-Br, or with a vinyllithium salt of formula in order to give the unsaturated alcohol of the general formula (f) the alcohol from step (e) is dehydrated and halogenated to give the compound  in which X<SP>1</SP> represents a halogen atom, and (g) the product from step (f) is reacted with a compound of formula ZH. The carbon chain of the product thus obtained may be lengthened further by reacting the halogen derivative obtained in step (f) with a keto-acid of the formula R-CO-CHR<SP>1</SP>-COOC 2 H 5  in a manner similar to that employed in step (b), to give a keto-ester of the formula which may then be reacted further as in steps (c), (d), (e) and (f) above. Products in which Z  represents -COY may be obtained by reacting the ketone of the formula A-COR according to a Wittig reaction with a phosphine of the general formula or with a phosphonate of the formula or according to another Wittig synthesis. The products possess insecticidal properties.