Patent GB-819850-A (GB)
Title: New phosphoric esters, process for their preparation and compositions containing same
IPC: C07F9/6541
Filed: 1957-11-26
Abstract: The invention comprises thiophosphoric esters of general formula <FORM:0819850/IV (b)/1> wherein Y, X and X2 are each oxygen or sulphur, at least one of X1 and X2 being sulphur, and R is C1-4 alkyl.  The fused benzene nucleus may be substituted, e.g. by halogen, C1-4 alkyl, C1-4 alkoxy or nitro groups. They are prepared by condensation of a benzoxazole or benzthiazole of formula <FORM:0819850/IV (b)/2> with a phosphorus derivative of formula <FORM:0819850/IV (b)/3> one of Q and Z representing the group -X1D, where D is H or alkali metal, and the other a reactive ester residue such as a halogen atom or a sulphuric or sulphonic acid residue, especially the p-toluenesulphonic residue.  The reaction may be effected by heating the reactants in an inert solvent such as ethanol, an aromatic hydrocarbon, e.g. benzene or toluene, a halogenated aliphatic or aromatic hydrocarbon, e.g. chlorobenzene, an ether, e.g. anisole, or a ketone, e.g. acetone or methyl ethyl ketone.  A basic condensation agent may be used, preferably an alkali metal or one of its derivatives such as a hydroxide, hydride, amide, carbonate, alcoholate or alkali metal organometallic compound, or a tertiary amine such as pyridine, dimethylaniline or triethylamine. The products are pesticides (see Group VI).  In examples: (1) 2 - (o,o - dimethyldithiophosphorylmethyl)-benzthiazole is prepared by reacting sodium o,o-dimethyldithiophosphate with 2-hydroxymethylbenzthiazole p - toluenesulphonate in acetone; (2) 2 - (o,o - diethyldithiophosphorylmethyl)- benzoxazole is prepared similarly from potassium o,o-diethyldithiophosphate and 2-hydroxymethylbenzoxazol p - toluenesulphonare; (3) a mixture of the diethylthiolo- and diethylthionophosphates of 2-hydroxymethylbenzthiazole is obtained from 2-hydroxymethylbenzthiazole and diethylchlorothiophosphate in anhydrous pyridine; (4) 2-(o,o-diethyldithiophosphorylmethyl) - benzthiazole is prepared as in (1) from 2-hydroxymethylbenzthiazole p - toluenesulphonate and potassium diethyldithiophosphate; and (5) 2-(o,o - dimethylthiolophosphorylmethyl) - benzthiazole is prepared similarly from 2-hydroxymethylbenzthiazole p-toluenesulphonate and sodium dimethylthionophosphate.  2 - Hydroxymethylbenzthiazole p - toluenesulphonate and 2 - hydroxymethylbenzoxazole p-toluenesulphonate are prepared by the action of p-toluenesulphonyl chloride on the hydroxy compounds.ALSO:Pesticidal (insecticidal and acaricidal) compositions comprise thiophosphoric esters of formula <FORM:0819850/VI/1> wherein Y, X1 and X2 are each oxygen or sulphur, at least one of X1 and X2 being sulphur, and R is C1-4 alkyl.  The fused benzene nucleus may be substituted, e.g. by halogen, C1-4 alkyl, C1-4 alkoxy or nitro groups.  Solid or liquid diluents may be used such as talc, a clay, limestone, magnesia, kieselguhr, tricalcium phosphate, cork powder, an aromatic hydrocarbon, or a mineral, animal or vegetable oil.  Wetting, dispersing and emulsifying agents may be present, such as sulphoricenoleates, quaternary ammonium derivatives or ethylene oxide condensates.  The active ingredient preferably comprises 0.005 to 5 per cent for solid and 0.005 to 0.1 per cent by weight for liquid compositions.  Other pesticides may be present.  Example (6) describes the preparation of a composition comprising 2-(o,o-dimethylthiolo-phosphorylmethyl) - benzthiazole, acetone, toluene and non-ionic emulsifying agent which forms an emulsion with water, and Example (7) describes a composition formed by crushing together 2 - (o,o -dimethyl - dithiophosphoryl-methyl) - benzthiazole, emulsifying agent and talc which may be used as such or in aqueous suspension.