Patent GB-969029-A (GB)
Title: Thiophosphoric acid esters
IPC: C07F9/165
Filed: 1961-05-02
Abstract: The invention comprises compounds of the general formula: <FORM:0969029/C1/1> in which X and Y stand for oxygen or sulphur, R and R1 stand for alkyl radicals containing 1-4 carbon atoms, R2 stands for a cycloalkyl or alkyl group containing 6-12 carbon atoms, an alkyl group substituted by one or more chlorine atoms, a nitrochlorophenyl, an alkyl-substituted alkylmercaptophenyl or a cyano-substituted phenyl group and when Y is oxygen R2 can also be an alkylmercaptoalkyl group, when X and Y are not both oxygen R2 can also be a nitrophenyl group, and when X and Y are not at the same time sulphur and oxygen, respectively, R2 can also be a phenyl, chlorophenyl or alkylmercaptoalkyl group, the alkyl groups, unless otherwise defined, being hydrocarbon radicals containing 1-4 carbon atoms, the compounds O, S-diethyl-thionophosphoric acid -O- (4-nitrophenyl) ester and O, S-diethyl-thionophosphoric acid -O- (3-methyl -4- methylmercaptophenyl) ester being disclaimed. The compounds are prepared by (a) reacting an O, S-dialkylphosphorous acid chloride with an alcohol, phenol or mercaptan and then with the approximately equivalent quantity of sulphur, (b) reacting an O, S-dialkylphosphorous acid monochloride with an alcohol, phenol or mercaptan and then with about the calculated quantity of hydrogen peroxide, or (c) reacting an O, S-dialkylphosphorous acid chloride with an alkylene oxide, the O, S-dialkyl -O- chloroalkylphosphorous acid ester thus formed being reacted with about the equivalent amount of sulphur or hydrogen peroxide. The starting materials of the formula: <FORM:0969029/C1/2> in which R and R1 are as defined above, are stated to be novel and are prepared by reacting together in the presence of a tertiary base equivalent amounts of a mercaptan and an O-alkyl-phosphorous acid dichloride or of an alcohol and an S-alkyl-phosphorous acid dichloride. Examples are given. The compounds are used as insecticides (see Division A5). Specifications 898,418, 916,704 and 924,034 are referred to.ALSO:Pesticidal compositions comprise a liquid or solid dilient or carrier and a compound of the general formula <FORM:0969029/A5-A6/1> in which X and Y stand for oxygen or sulphur, R and R1 stand for alkyl radicals containing 1-4 carbon atoms, R2 stands for a cycloalkyl or alkyl group containing 6-12 carbon atoms, an alkyl group substituted by one or more chlorine atoms, a nitrochlorophenyl, an alkylsubstituted alkylmercaptophenyl or a cyanosubstituted phenyl group and when Y is oxygen R2 can also be an alkylmercaptoalkyl group, when X and Y are not both oxygen R2 can also be a nitrophenyl group, and when X and Y are not at the same time sulphur and oxygen, respectively, R2 can also be a phenyl, chlorophenyl or alkylmercaptoalkyl group, the alkyl groups, unless otherwise defined, being hydrocarbon radicals containing 1-4 carbon atoms, compositions containing the compounds o,s-diethyl-thionophosphoric acid -o-(3-methyl-4-methylmercaptophenyl)ester and o,s-diethyl-thionophosphoric acid -o-(4-nitrophenyl)ester being disclaimed.  Specified as solid carriers are talc, chalk, bentonite and clay, and as liquid carriers are water (an emulsifier being added if necessary), alcohols such as methanol and ethanol, ketones such as acetone and methyl ethyl ketone, and liquid hydrocarbons.  The compounds may be used in conjunction with each other or with known insecticides and/or fertilizers.  An example describes a composition comprising o,s-diethyl-thionophosphoric acid -o-(2-ethylmercaptoethyl) ester, water, dimethyl formamide, and a benzyl hydroxy polyglycol ether containing about 10-15 glycol residues.  Specifications 898,418, 916,704 and 924,034 are referred to.