Patent GB-866562-A (GB)
Title: Novel organic phosphorothiolate compounds and their preparation
Inventor: VEGTER GEERT CASPER
IPC: C07F9/20
Filed: 1959-02-03
Abstract: The invention comprises compounds having the general formula: <FORM:0866562/IV (b)/1> wherein R is a substituted or unsubstituted aliphatic, alicyclic, araliphatic, or aromatic group and X and X1 are fluorine, chlorine, or bromine atoms.  R is preferably an aliphatic group, e.g. methyl, ethyl or propyl, and X and X1 are preferably atoms of the same halogen, preferably chlorine.  The compounds may be obtained by treating a compound of the formula: <FORM:0866562/IV (b)/2> wherein X is as defined above and R and R1 have the meaning assigned to R above and may either be the same or different groups with a halogenating agent which is preferably a sulphuryl halide or the halogen itself and is more preferably sulphuryl chloride or chlorine.  The treatment is suitably effected at from 30 DEG C. to 0 DEG C. and an example is given for the production of ethyl phosphorochloridotholic chloride by adding sulphuryl chloride to diethyl phosphorothionochloridate cooled to -20 DEG C., the reaction being completed at -10 DEG C.  The products are useful as intermediates for the production of other phosphorus compounds suitable for use as insecticides or as lubricating oil additives or detergents.  Thus the products may be reacted with: (1) olefinically unsaturated compounds, e.g. cyclohexene, ethylene, propylene, butylene, methyl vinyl sulphone, vinyl acetate, itaconic esters, fumaric esters, maleic esters, conjugated dienes or allyl chloride; (2) with primary or secondary amines, alcohols or mercaptans, when a primary amine (R1NH2 wherein R1 is as defined above) is used the product may be an intermediate product of the type RO.P(O)(C1)S.NHR1 or may be of the type ROP(O)(NHR1)S.NHR1 or two mols of the intermediate product may react with one mol of the amine to give a sulphenimide; the reaction with alcohols and mercaptans yields esters and thioesters respectively; (3) with compounds containing an activated aromatic nucleus e.g. dimethylaniline, naphthylamine or 1 : 3-dimethyoxy benzene, the reaction involving nucleur substitution in the para-position to the activiting group, e.g. with dimethylaniline the products are of the type: - p.dimethylaminophenyl-S-P(O)(Cl)OR; (4) with compounds containing an active methylene group, e.g. ketones, or dicarboxylic acids such as malonic acid or its esters, the product obtained by reaction with acetyl acetone being of the type: ROP(O)(C1)S.CH(COCH3)2.  The further reaction products when they still contain a p-halogen group may be reacted with amines, alcohols or mercaptans e.g. to yield compounds of the type (RO)(R1Y)P(O)S.Z where Y is O, S, NH or NR2, Z is an organic radical and R, R1 and R2 are hydrocarbyl or substituted hydrocarbyl radicals and particularly compounds in which R and R1 are different radicals. In further examples: ethyl phosphorochloridothiolic chloride obtained as described above is reacted with cyclohexene to form O-ethyl S-2-chlorocyclohexyl phosphorochloridothiolate and the latter is further reacted with (1) aniline to yield an anilide, and with isobutyl, methyl, and isopropyl-, alcohols respectively to yield the corresponding O-ethyl O-alkyl S-2-chlorocyclohexyl phosphorothiolate compound.  Also, ethyl phosphorochloridothiolic chloride is reacted with dimethylaniline and the product is reacted with isopropyl alcohol to form O-ethyl O-isopropyl S-4-dimethylaminophenylphosphorothiolate.