Patent GB-772731-A (GB)
Title: New pesticidal compositions containing phosphorus esters
Inventor: BOON WILLIAM ROBERT
IPC: C07F9/165
Filed: 1954-01-11
Abstract: Examples are given for the preparation of certain salts of phosphorothiolic acid esters of the general formula O = P(OR1)(OR2)-S-LX in which R1 and R2 are like or unlike alkyl radicals, L is a saturated straight or branched chain aliphatic hydrocarbon radical or such a radical in which the carbon atoms are interrupted by an oxygen or sulphur atom or by a nitrogen atom carrying an alkyl substituent and X is a secondary aliphatic or heterocyclic amine attached to L through the amino nitrogen atom, said salts being used in pesticidal compositions (see Groups I and VI).  In the examples: (1) the p-toluene sulphonate of O,O1-diethyl S-b -diethylaminoethyl phosphorothiolate is obtained by adding a mixture of the phosphorothiolate and diethyl ether to a solution of p-toluenesulphonic acid in ether, the salt being precipitated; (2) and (3) the hydrogen oxalate salt and the dihydrogen citrate salt respectively of the same phosphorothiolate are obtained by adding a mixture of the phosphorothiolate and methanol to oxalic acid dihydrate (or citric acid) in methanol and concentrating the resulting solution; (4) the hydrogen oxalate of O,O1-diethyl-S-1-diethyl-amino-prop-2-yl phosphorothiolate is obtained by treating the phosphorothiolate with a solution of oxalic acid dihydrate in acetone and allowing the salt to precipitate; (5) O,O1-diethyl-S-b -piperidinoethyl phosphorothiolate hydrogen oxalate is obtained by adding a solution of the phosphorothiolate in acetone to a solution of oxalic acid dihydrate in acetone, the salt being precipitated; (6) O,O1 - diethyl S - b  - morpholinoethyl phosphorothiolate p-toluene-sulphonate is obtained by adding a solution of the phosphorothiolate in ether to a solution of p-toluene sulphonic acid in ether; (7) O,O1-diethyl S-b -di-n-propylaminoethyl phosphorothiolate hydrogen oxalate is obtained by treating the ester with a solution of oxalic acid dihydrate in acetone; (8) O,O1-diethyl - S - b  - diethylaminoethyl phosphorothiolate hydrochloride is obtained by saturating a solution of the ester in ether with dry hydrogen chloride and removing the solvent and excess hydrogen chloride under reduced pressure.  Specification 738,839 is referred to.ALSO:A pesticidal plant nutrient composition comprises a phosphorothiolic acid ester of the general formula: O = P(OR1)(OR2)-S-LX in which R1 and R2 are like or unlike alkyl radicals, L is a saturated straight or branched chain aliphatic hydrocarbon radical or such a radical in which the carbon atoms are interrupted by an oxygen or sulphur atom or by a nitrogen atom carrying an alkyl substituent and X is a secondary aliphatic or heterocyclic amine attached to L through the amino nitrogen atom or a salt of such aliphatic or heterocyclic amine, and a plant nutrient (see also Group VI). Specified plant nutrients are urea and magnesium sulphate.  In an example a mixture of urea with a small amount of O,O1-diethyl S-b -diethylamino ethyl phosphorothiolate dihydrogen citrate (see Group IV(b), is dissolved in water to give a combined acaricidal and nutrient spray.  Alternatively the mixture can be compressed into granules, tablets or briquettes for convenience in handling, packaging, storing and measuring. Specification 738,839 [Group IV(b)] is referred to.ALSO:Pesticidal compositions comprise a phosphorothiolic acid ester of the general formula:-O=P(OR1)(OR2)-S-LX in which R1 and R2 are like or unlike alkyl radicals, L is a saturated straight or branched chain aliphatic hydrocarbon radical or such a radical in which the carbon atoms are interrupted by an oxygen or sulphur atom or by a nitrogen atom carrying an alkyl substituent and X is a secondary aliphatic or heterocyclic amine or a salt of such aliphatic or heterocyclic amine and a carrier and if desired an auxiliary agent and/or a plant nutrient.  As carriers there may be used liquids e.g. water or non-phytocidal organic solvents or solids e.g. talc, keiselguhr, bentonite and other colloidal clays and powdered chalk.  For concentrated solid preparations there may be used other solid carriers particularly water-soluble organic and inorganic compounds and the toxic ingredient may be incorporated with these to give a shaped tablet or block or a non-hygroscopic free-flowing granular preparation. Specified auxiliary agents are dustbinding agents such as spindle oil, glycerol, and wool fat.  Wetting, spreading and dispersing agents such as sodium dinaphthylmethane disulphonate and sodium lauryl sulphate and sticking agents such as glue and resin may also be used especially in liquid preparations.  Specified plant nutrients are urea and magnesium sulphate.  Examples are given of the following compositions: (1) one part of O : O1 - diethyl - S - b  - diethylamino - ethyl phosphorothiolate dissolved in 2000 parts of water also 1 part of O - ethyl O1 - methyl S - b  - diethylaminoethyl phosphorothiolate dissolved in 50,000 parts of water, (2) a 0.002 per cent aqueous solution of the p.toluene sulphonate salt of O, O1-diethyl S-b -diethylaminoethyl phosphorothiolate; (3) an aqueous solution of the hydrogen oxalate of O, O1-diethyl S-b -diethylaminoethyl phosphorothiolate (4) an aqueous solution of O, O1-diethyl S-b -diethylamino ethyl phosphorothiolate dihydrogen citrate; (5) an aqueous solution of the hydrogen oxalate of O, O1-diethyl S-1-diethylamino prop-2-yl phosphorothiolate; (6) an aqueous solution of O, O1 - diethyl - S - b  - piperidinoethyl phosphorothiolate hydrogen oxalate; (7) an aqueous solution of O : O1 - diethyl - S-b -morpholinoethyl phosphorothiolate p-toluene sulphonate; (8) an aqueous solution of O : O1-diethyl S-b -di-n-propylamino phosphorothiolate hydrogen oxalate; (9) an aqueous solution of a mixture of urea and a small amount of O : O1-diethyl S-b -diethylaminoethyl phosphorothiolate dihydrogen citrate; (10) an aqueous solution formed by dissolving O : O1-diethyl S-b -di-ethyl-amino-ethyl phosphorothiolate, citric acid and disodium phosphate in a large excess of water; (11) O : O1-diethyl-S-b -diethyl-aminoethyl phosphorothiolate dissolved in diacetone alcohol; (12) a non-dusting pulverulent composition formed by mixing O : O1-diethyl S-b -diethylaminoethyl phosphorothiolate with kieselguhr and spindle oil; (13) an aqueous solution of a mixture of sodium dinaphthylmethane disulphonate and a small amount of O : O1-diethyl S-b -piperidinoethyl phosphorothiolate or its hydrogen oxalate; (14) an aqueous solution of O : O1-diethyl S - b  - diethyl-aminoethyl phosphorothiolate hydrochloride.  The preparation of the specified salts of the phosphorothiolate esters is described (see Group IV(b)). Specification 738,839 [Group IV(b)] is referred to.