Patent GB-804538-A (GB)
Title: Thiophosphoric acid esters
IPC: C07F9/165
Filed: 1957-05-15
Abstract: The invention comprises thiophosphoric esters of the general formula <FORM:0804538/IV (b)/1> wherein R represents an alkyl or aromatic radical, R1 and R2 represent C1-4 alkyl radicals or form together with N a cyclic amine which may contain further hetero-atoms, R3 and R4 represent C1-4 alkyl radicals and X represents oxygen or sulphur. The esters may be obtained by reacting salts of O,O-dialkylthiolphosphoric or thionothiolphosphoric acids with 1-(substituted amino) - 3 - (substituted mercapto) - 2-halopropanes. Suitable salts include the ammonium, potassium and sodium salts; suitable substituted amino groups include di-methyl-, diethyl-, diisopropyl- and dibutyl-amino radicals and piperidino, pyrrolidino, pyrimidino, piperazino, morpholino, thiomorpholine and like radicals; suitable substituted mercapto groups include methyl-, ethyl-, phenyl-, p-chlorophenyl- and p-nitro-phenyl-mercapto groups.  The reaction is generally carried out in an inert solvent such as water, methanol, ethanol, acetone, methyl-ethyl ketone, benzene, toluene or xylene.  Usually the reaction temperature will be between about 0 DEG C. and 100 DEG  C., generally between about 20-80 DEG  C.  The esters are generally valuable insecticides and plant-protecting agents (see Group VI). Examples describe the preparation of S-[2-phenylmercapto-1-dimethylamino-methyl] - ethyl - O,O - diethyl phosphorothiolate and phosphorothiolothionate; S-[2-phenyl-mercapto - 1 - morpholinomethyl] - ethyl - O,O-diethyl phosphorothiolothionate; S - [2-phenylmercapto - 1 - piperidinomethyl] - ethyl-O,O - diethyl phosphorothiolate and phosphorothiolothionate; S-[2-ethylmercapto-1-dimethylaminomethyl] - ethyl - O,O - diethyl phosphorothiolate and phosphorothiolothionate.  1 - dimethylamino - 3 - thiophenyl - 2 - chloro-propane, 1 - morpholino - 3 - thiophenyl - 2-chloropropane, 1 - piperidino - 3 - thiophenyl - 2-chloropropane and 1 - dimethylamino - 3 - thioethyl-2-chloropropane used as starting materials in the examples are prepared by the action of thionyl chloride on the corresponding hydroxy compounds in methylene dichloride solution.ALSO:Insecticidal compositions comprise thiophosphoric esters of the general formula <FORM:0804538/VI/1> where R represents an alkyl or aromatic radical, R1 and R are C1-4 alkyl radicals or form together with N a cyclic amine which may contain further hetero atoms, R3 and R4 are C1-4 alkyl radicals and X is oxygen or sulphur. Substituted amino groups mentioned are dimethyl-, diethyl-, diisopropyl- and dibutyl-amino radicals and pyrrolidino, pyrimidino, piperazino, morpholino, thiomorpholino and piperidino radicals.  Substituted mercapto groups mentioned are methyl-, ethyl-, phenyl-, p-chlorophenyl- and p-nitromercapto.  The compounds may be applied in dilution or solution with solid or liquid carriers such as chalk, talc, bentonite, water, alcohols or liquid hydrocarbons.  Other active agents may be present. Concentrations of 0.0001 to 1.0 per cent may be used.  They may be applied by spraying, dusting or as aerosols.  A composition is prepared by dissolving S-(2-phenylmercapto - 1 - dimethylaminomethyl) - ethyl - O,O - diethyl phosphorothiolate in acetone and adding benzene hydroxy diphenyl polyglycol ether and water.  A number of other esters are prepared (see Group IV (b)).