Patent GB-792608-A (GB)
Title: New organic thiophosphoric acid derivatives, process for their preparation and compositions containing same
IPC: A01N57/14
Filed: 1956-02-29
Abstract: The invention comprises a phosphorus derivative of the general formula: <FORM:0792608/IV (b)/1> in which Ar is a phenylene group which may be substituted by one or more halogen atoms or lower alkyl, lower alkoxy or nitro groups, R1 and R2 are the same or are different and each represents a lower alkyl group, and R3 is a saturated or unsaturated aliphatic group containing 1 to 4 carbon atoms (e.g. a hydrocarbon group substituted by one or more hydroxy groups or halogen atoms) or a phenyl group which may be substituted by one or more halogen atoms or lower alkyl, lower alkoxy, or nitro groups, the terms "lower alkyl" and "lower alkoxy" being defined as alkyl and alkoxy groups containing not more than 4 carbon atoms.  The group -SO2R3 may be in the ortho, meta or para position.  The compounds which are stated to be useful as insecticides (see Group VI) may be obtained by reacting a phosphorochloridothionate of the general formula (R1O)(R2O)P(S)Cl with a phenol of the formula HO-Ar-SO2R3 wherein Ar, R, R2 and R3 are as defined above.  The reaction is preferably effected in an organic solvent medium at a temperature below 150 DEG  C. in the presence of an alkali metal or an alkaline condensing agent, e.g. an hydroxide, hydride, amide, carbonate, alcoholate, or organo-metallic derivative of an alkali metal. Preferred solvents are aliphatic alcohols, e.g. methyl or ethyl alcohol, aliphatic ketones, e.g. acetone or methyl ethyl ketone, and chlorinated hydrocarbons.  Examples are given for the production of compounds in which Ar-SO2R3 is p-methylsulphonylphenyl and R1 and R2 are both methyl, ethyl and isopropyl respectively; ArSO2R3 is p-chloromethylsulphonylphenyl and both R1 and R2 are methyl, ethyl and isopropyl respectively; ArSO2R3 is m-chloro-p-methylsulphonylphenyl, and R1 and R2 are both methyl and both ethyl respectively; R1 and R2 are both ethyl and ArSO2R3 is o-chloro-p-methylsulphonyl phenyl, p-phenylsulphonylphenyl, and o - methyl - p - methylsulphonylphenyl respectively.  m - Chloro - p - methylsulphonylphenol used to prepare the compounds in which ArSO2R3 is m-chloro-p-methylsulphonylphenyl is obtained by the action of hydrobromic acid on m-chloro-p-methyl sulphonylanisole which is itself obtained by methylation of o-chloro-p-methoxythiophenol to form p-methylmercapto-m-chloroanisole followed by oxidation of the latter.  o-Chloro-p-methoxythiophenol is prepared from o-chloro-p-methoxyaniline by diazotization and coupling of the resulting diazo compound with potassium ethylxanthate. o-Chloro-p-methylsulphonylphenol used to prepare the compound in which ArSO2R3 is o-chloro-p-methylsulphonylphenyl is obtained by the action of hydrobromic acid on o-chloro-p-methylsulphonylanisole which is itself prepared by methylation with methyl sulphate of m-chloro-p-methoxybenzenesulphinic acid, the latter being obtained by the reduction with sodium sulphite of m-chloro-p-methoxybenzenesulphonyl chloride. o-Methyl-p-methylsulphonylphenol used to prepare the corresponding phosphones derivative is obtained by demethylation of o-methyl-p - methylsulphonylamide with hydrobromic acid, the o-methyl-p-methylsulphonylanisole being itself obtained by methylation of m-methyl-p-methoxybenzenesulphinic acid using methyl sulphate.ALSO:An insecticidal composition comprises an inert diluent and a phosphorus derivative having the general formula (R1O)(R2O)P(S)OArSO2R3 (see Group IV (b)) in which Ar is a phenylene group or a phenylene group substituted by one or more halogen atoms or lower alkyl, lower alkoxy or nitro groups, R1 and R2 are the same or are different and each represents a lower alkyl group, and R3 is a saturated or unsaturated aliphatic group containing 1 to 4 carbon atoms or a phenyl group which may be substituted by one or more halogen atoms or lower alkyl, lower alkoxy or nitro groups, the terms "lower alkyl" and "lower alkoxy" being defined as alkyl and alkoxy groups containing not more than 4 carbon atoms.  The group-SO2R3 may be in the ortho, meta, or para position.  The diluent may be a powdered solid such as talc, a clay, e.g. kaolin or bentonite, limestone, calcined magnesia, kieselguhr, tricalcium phosphate or cork powder, or it may be a liquid in which the phosphorus derivative is dissolved or dispersed.  The composition may be in the form of an aerosol or as a suspension, emulsion or solution in an organic or aqueous organic medium, e.g. an aromatic hydrocarbon such as toluene or xylene; or a mineral, animal, or vegetable oil, or a mixture of such media.  Wetting, dispersing or emulsifying agents of the ionic or non-ionic type may be present, e.g. sulphoricinoleates, quaterternary ammonium derivatives, or ethylene oxide condensates, e.g. condensates with octyl phenol, or fatty acid esters of anhydrosorbitols which have been solubilized by etherifying the free hydroxyl groups with ethylene oxide.  Other insecticides including substances having a synergistic effect may be present.  Specified phosphorus derivatives are O,O-dimethyl (diethyl- and diisopropyl-) O-p-methylsulphonyl phenylphosphorothionates; O,O-dimethyl (diethyl- and diisopropyl-) O-p-chloromethyl-sulphonyl phenyl phosphorothionates; O,O-diethyl O - o - methyl - p - methylsulphonyl-phenylphosphorothionate; O,O-dimethyl (and diethyl-) O-m-chloro-p-methylsulphonylphenyl-phosphorothionates; O,O-diethyl O-o-chloro-p-methylsulphonyl phenylphosphorothionate, and O,O-diethyl O-p-phenylsulphonyl phenylphosphorothionate. Examples of various insecticidal compositions containing some of these derivatives are given.