Patent GB-806280-A (GB)
Title: O-aryl o-loweralkyl n-alkenyl phosphoroamidothioates
IPC: C07F9/24
Filed: 1957-07-10
Abstract: The invention comprises O-aryl O-lower alkyl N-alkenyl phosphoroamidothioates having the formula <FORM:0806280/IV (b)/1> in which R is an haloaryl radical, X is a lower alkyl radical containing 1 to 4 carbon atoms and Y is allyl or methallyl.  They may be obtained by reacting an O-haloaryl O-lower alkyl phosphorochloridothioate of the formula <FORM:0806280/IV (b)/2> with allylamine or methallylamine in the presence of an inert organic solvent, e.g. acetone or methylene chloride.  The reaction takes place smoothly at temperatures of from - 10 DEG  to 30 DEG  C. and it is preferred to employ at least two molecular proportions of the amine for each molecular proportion of the phosphorochloridothioate. The reaction mixture which comprises the desired product and amine hydrochloride is treated to recover the product by washing with water or diluting with a waterimmiscible solvent which is then removed by evaporation or distillation under reduced pressure.  Examples are given for the production of (1) O-(3,4-dichlorophenyl) O-methyl N-allyl phosphoroamidothioate; (2) and (3) O-(2,4,5 - trichlorophenyl) - and O - (2 - bromo - 4 - tertiarybutylphenyl) - O - methyl N - allyl phosphoroamidothioates; (4) O - (4 - chlorophenyl) O-ethyl N-allyl phosphoroamidothioate, and (5) O-(2,4,5-trichlorophenyl) O-methyl N-methallyl phosphoroamidothioate. Other products which are stated to be obtainable by the above defined procedure are O-(2,4-dichlorophenyl) O-ethyl N-allyl-, O-(2,4-dibromophenyl) O-n-butyl N-allyl-, O-(2-methyl-4-chlorophenyl) O-methyl N-methallyl-, O-(4-bromophenyl) O-isopropyl N-methallyl-, and O-(2,4,5-trichlorophenyl) O-ethyl N-allyl-phosphoroamidothioates. The products are stated to be effective as pesticides (see Group VI). O-Haloaryl O-lower alkyl phosphorochloridothioates in which the lower alkyl group contains 1 to 4 carbon atoms may be obtained by reacting substantially equimolecular proportions of an alkali metal (preferably sodium) alcoholate and an O-haloaryl phosphorodichloridothioate at 20 DEG  to 90 DEG  C.  In carrying out the reaction the alcoholate in the corresponding alcohol is added portionwise to the phosphorodichloridothioate dispersed in the same alcohol.ALSO:O-Haloaryl O-lower alkyl N-alkenyl phosphoroamido thioates having the formula <FORM:0806280/VI/1> in which R is a haloaryl radical, X is a lower alkyl radical containing from 1 to 4 carbon atoms and Y is allyl or methallyl (see Group IV (b)) are stated to be effective as pesticides and may be dispersed on a finely divided carrier and employed as dusts or they may be employed in oils, as constituents in water emulsions or in water dispersions.  A suitable composition comprises an aqueous composition containing 100 parts by weight of O-(2,4,5-trichlorophenyl) O-methyl N-allyl phosphoroamidothioate per million parts of the mixture.  Other products specified are O-(3,4-dichlorophenyl)- and O-(2-bromo - 4 - tertiarybutylphenyl) O - methyl N - allyl phosphoroamidothioates, O - (4 - chlorophenyl) O-ethyl N-allyl phosphoroamidothioate, and O - (2,4,5 - trichlorophenyl) O - methyl N-methallyl-, O - (2,4 - dichlorophenyl) O - ethyl N - allyl -, O - (2,4 - dibromophenyl) O - n - butyl N-allyl-, O-(2-methyl-4-chlorophenyl) O-methyl N-methallyl-, O-(4-bromophenyl) O-isopropyl N-methallyl-, and O-(2,4,5-trichlorophenyl) O-ethyl N-allyl-phosphoroamidothioates.