Patent GB-705646-A (GB)
Title: O,o-di(polyhalophenyl) n-substituted amidothiophosphates
Inventor: MOYLE CLARENCE LLEWELLYN
IPC: C08K5/5399
Filed: 1952-06-26
Abstract: The invention comprises as new compounds amidothiophosphates having the formula <FORM:0705646/IV (b)/1> wherein X is bromine or chlorine, n is 3, 4, or 5, R1 is hydrogen or an alkyl or cycloalkyl radical and R11 is a cycloalkyl or alkyl radical.  The compounds may be prepared by reacting an alkali metal polyhalophenolate with an N-substituted dichlorothiophosphoramide having the formula <FORM:0705646/IV (b)/2> wherein R1 and R11 are as defined above.  The reaction may be carried out in an inert organic solvent, e.g. a lower alkanol such as methanol, ethanol, propanol or butanol, thus a sodium polyhalophenolate may be prepared by reacting one molecular proportion of sodium with one molecular proportion of a polyhalophenol in methyl alcohol and the resulting phenolate solution then added portionwise to one-half molecular proportion of the N-substituted dichlorothiophosphoramide at 30 to 110 DEG C. The solvent is then removed by evaporation and the residue dispersed in an inert solvent such as benzene, carbon tetrachloride or methylene dichloride and the solvent mixture may then be washed with dilute aqueous sodium or ammonium hydroxide and water, and then dried with anhydrous sodium sulphate. Alternatively the process may be carried out by adding the N-substituted dichlorothiophosphoramide portionwise to the solvent solution of the alkali metal phenolate.  The N-substituted dichlorothiophosphoramides may be prepared by reacting a monoalkyl, monocycloalkyl, dicycloalkyl, dialkyl or N-alkyl cycloalkylamine with an excess of thiophosphoryl chloride at 10 DEG to 80 DEG C.  Examples describe the production by the above methods of 0, 0-di (2, 4, 5-trichlorophenyl) N, N-di-methylamidothiophosphate; 0, 0-di (4-bromo-2, 6- dichlorophenyl) N-isopropylamidothiophosphate; 0, 0-di (2, 3, 4, 6-tetrachlorophenyl)-N-ethylamidothiophosphate; 0, 0-di (pentachlorophenyl) N-ethylamidothiophosphate; 0, 0-di (2, 4, 6-trichlorophenyl) N-normal-amylamidothiophosphate; and 0, 0-di (2, 4, 5-trichlorophenyl) N-cyclohexylamidothiophosphate.  It is stated that the following compounds may also be prepared in a similar manner: 0, 0-di (pentachlorophenyl) N-normal octylamidothiophosphate; 0, 0- di (2, 4, 6-tribromophenyl) N- (4-phenylcyclohexyl)- amidothiophosphate; 0, 0-di (2, 3, 4, 6- tetrachlorophenyl) N, N- -disecondary butyl amidothiophosphate; 0, 0-di (2, 4, 6-trichlorophenyl) N, N-dicyclohexylamidothiophosphate; 0, 0-di (pentachlorophenyl) N-(2, 4-dimethylcyclohexyl)- amidothiophosphate; 0, 0-di (2, 4, 6-trichlorophenyl) N-normal dodecylamidothiophosphate; 0, 0-di (2, 3, 4, 6-tetrachlorophenyl)-N-(4-methyl cyclohexyl) amidothiophosphate, and 0, 0-di (2, 4, 5-tribromophenyl) N-methyl N-cyclohexyl-amidothiophosphate.  It is stated that the products may be employed as modifying agents in plastic compositions, as constituents of extreme pressure lubricants, and as constituents of insecticide and fungicide compositions (see Group VI).ALSO:Amidothiophosphates having the formula: <FORM:0705646/VI/1> wherein X is bromine or chlorine, n is 3, 4, or 5 R1 is hydrogen or an alkyl or cycloalkyl radical, and R11 is a cycloalkyl or alkyl radical (see Group IV(b)) may be employed as constituents of insecticide and fungicide compositions.  The products may be employed in aqueous spray compositions at concentrations within the range of 0.5 to 3 pounds per 100 U.S. gallons of spray mixture which may also contain wetting and emulsifying agents.  They are also stated to be effective for the control of certain insects by allowing the latter to feed on white flour containing 1 per cent by weight of the toxicant.