Patent GB-825107-A (GB)
Title: Halogenated adipates and method of preparation thereof
IPC: C07C69/44
Filed: 1957-06-21
Abstract: The invention comprises compounds of the general formula <FORM:0825107/IV (b)/1> where X is chlorine or bromine and R is an alkyl, alkoxyalkyl, aralkyl, cycloalkyl or alkyl-cycloalkyl group containing up to 14 carbon atoms, the R groups being the same or different.  The compounds may be prepared by treating a diester of a -methylene-a 1-methyl adipic acid with chlorine or bromine in the temperature range -70 DEG  to 100 DEG  C.  The preferred range is -20 DEG  to 50 DEG  C. and the reaction may be carried out in the absence of a solvent or in the presence of an inert volatile halogenated hydrocarbon such as chloroform, carbon tetrachloride or methylene chloride, disubstituted amides such as dimethylformamide or N-substituted lactams such as N-methyl pyrrolidone may also be present as catalysts.  Reactants which may be used are the dimethyl, diethyl, methyl octyl, ethyl decyl, dimethoxyethyl, methyl hexoxyethyl, methyl benzyl, dibenzyl, ethyl cyclopentyl, dicyclobutyl, methyl octylcyclohexyl and ethyl naphthylethyl esters of a -methylenea 1-methyl adipic acid.  Derivatives may be formed by starting with the dimethyl or diethyl ester and transesterifying the halogenated product with the appropriate alcohol in the presence of a strongly acidic esterifying catalyst. This transesterification process may be carried out at 100-275 DEG  C. and small amounts of organic solvents such as toluene or xylene may be added.  The methanol or ethanol is distilled off until the theoretical amount has been collected.  In this way one or both ester groups may be transesterified.  In examples: (1) chlorine is bubbled through a mixture of dimethyl a -methylene-a 1-methyl adipate, chloroform and dimethyl formamide, the product is dimethyl a  - chloro - a  - chloromethyl - a 1 - methyl adipate; the dimethoxyethyl, methyl benzyl, dicyclobutyl and ethyl naphthylethyl esters may be similarly prepared; (2) bromine is added to diethyl a -methylene-a 1-methyl-adipate to give the a -bromo-a -bromomethyl-a 1-methyl adipate, the ethyl decyl, methyl hexoxyethyl, dibenzyl and methyl octylcyclohexyl esters may be similarly prepared; (3) diethyl a chloro - a  - chloromethyl - a 1 - methyl adipate is transesterified with octanol in the presence of sulphuric acid to give the mono- and di-octyl ester; (4) chlorine is added to a cooled solution of dibenzyl a -methylene-a 1-methyladipate to give dibenzyl a  - chloromethyl - a  - chloro - a 1 - methyl adipate; (5) chlorine is added to a solution of dimethoxyethyl a  - methylene - a 1 - methyl adipate to give dimethoxyethyl a -chloromethyl - a  - chloro - a 1 - methyladipate; the dioctyl and dibenzyl esters are similarly prepared.  The compounds may be used as insecticides or as plasticizers.ALSO:Compounds of the formula <FORM:0825107/IV (a)/1> in which X is chlorine or bromine, and R is an alkyl, alkoxyalkyl, aralkyl, cycloalkyl or alkylcycloalkyl group containing up to fourteen carbon atoms, the R groups being the same or different, are used as plasticizers, particularly for polyvinyl chloride.  A composition comprising 52 parts of polyvinyl chloride, 35 parts of a plasticizer of the stated formula, 0.88 part of tribasic lead sulphate, and 0.48 part of stearic acid may be formed into a tough, flexible film.  The chlorinated dimethyl ester compounds are specially mentioned.  Other specified compounds include the dioctyl, dibenzyl and dimethoxyethyl a -chloromethyl-a -chloro-a 1-methyladipates, and diethyl a  - bromoethyl - a -bromo-a 1-methyladipate.ALSO:Compounds of the formula <FORM:0825107/VI/1> in which X is chlorine or bromine, and R is an alkyl, alkoxyalkyl, aralkyl, cycloalkyl, or alkylcycloalkyl group of up to 14 carbon atoms, the R groups being the same or different, are used as fungicides and insecticides.  For the latter purpose they may be employed in the form of dusts in amounts of about 10% by weight in an inert carrier.  For use as fungicides they may be applied in concentrations of 0.01 to 1% by weight in an inert medium. Specified compounds of the stated formula include the dimethyl, dioctyl, dibenzyl, and dimethoxyethyl a  - chloromethyl - a  - chloro - a 1 - methyladipates, and diethyl a -bromomethyl-a -bromo-a -methyl adipate.