Patent GB-906019-A (GB)
Title: Process for preparing novel compounds of the lactone type
IPC: C07D311/76
Filed: 1959-10-27
Abstract: Bicyclic lactones of formula <FORM:0906019/IV (b)/1> wherein R and R1 each represent hydrogen or alkyl and Z represents a hydrocarbon group or a substituted hydrocarbon group completing with the two carbon atoms to which it is linked a saturated, unsubstituted or substituted carbocyclic ring, are prepared by subjecting an unsaturated carbocyclic aldehyde or ketone of formula <FORM:0906019/IV (b)/2> where Z completes a carbocyclic ring which does not contain any further unsaturation, to a Michael addition reaction with a compound of formula <FORM:0906019/IV (b)/3> where X and Y are negative groups which can be readily hydrolysed to a carboxyl group (e.g. ester or nitrile groups), hydrogenating the resultant Michael adduct to convert the aldehyde or ketone group therein into a hydroxyl group, hydrolysing the negative groups in the hydrogenated product to give the corresponding hydroxydicarboxylic acid and simultaneously or subsequently decarboxylating said dicarboxylic acid to the corresponding hydroxy monocarboxylic acid and simultaneously or subsequently effecting ring closure between the hydroxyl and carboxyl groups to give the lactone.  The Michael reaction is preferably effected at below room temperature in an alcoholic medium to which some sodium has been added.  The hydrogenation may be effected using Raney nickel.  The hydrolysis, decarboxylation and lactonisation may be effected by heating for 1 to 4 hours at 100-150 DEG C. in an acid medium, or in an alkaline medium which is subsequently acidified. Examples describe the preparation of the lactones of: a -(2-hydroxymethylcyclopentyl) propionic acid; a mixture of a -(2-hydroxymethyl-3- and 4-monomethylcyclopentyl)propionic acids; and a -(2-hydroxymethylcyclohexyl)propionic acid.  Intermediate compounds prepared are: (1) as Michael adducts; 2-(11,11-dicarbethoxyethyl) cyclopentane carboxaldehyde, a mixture of 2-(11,11-dicarbethoxyethyl)-4- and 5-monomethylcyclopentane carboxaldehydes, and 2-(11,11-dicarbethoxyethyl)cyclohexane carboxaldehyde; (2) the corresponding hydroxymethyl compounds by the hydrogenation of the aldehyde groups; a  - (2 - hydroxymethylcyclopentyl)propionic acid; a mixture of a -(2-hydroxymethyl-3-and 4 - monomethylcyclopentyl)propionic acids; and a -(2-hydroxymethylcyclohexyl)propionic acid by alkaline hydrolysis of the compounds (2) followed by acidification.  A mixture of 4- and 5-methylcyclopentene-1-carboxaldehydes is prepared by the action of sodium iodate in nitric acid on 1-methyl-cyclohexane-3,4-diol.ALSO:Insecticidal compositions comprise bicyclic lactones of formula <FORM:0906019/VI/1> wherein R and R1 each represent hydrogen or alkyl and Z represents a hydrocarbon group or a substituted hydrocarbon group completing with the two carbon atoms to which it is attached a saturated, unsubstituted or substituted carbocyclic ring.  (For preparation see Group IV (b)). The compositions may contain an adjuvant and/or another pesticidal substance.  Specific substances tested which are not tested in the parent Specification are the lactone of a -(2-hydroxymethylcyclopentyl) propionic acid and a mixture of the lactones of a  - (2 - hydroxymethyl - 3 - and 4 - monomethylcyclopentyl) propionic acids.