Patent GB-903795-A (GB)
Title: Thiophosphonic acid esters
IPC: C07F9/40
Filed: 1960-02-16
Abstract: The invention comprises compounds of the general formula:-(R)(R1O)P(X)SCH2SR2 in which R is an alkyl, cycloalkyl, alkenyl (but excluding vinyl), or unsubstituted or substituted phenyl radical, R1 is an alkyl radical, R2 is a nitrile group or a -C(:X)R3 group in which R3 is an alkyl, phenyl, alkoxy, or dialkylamino group, or R2 is a P(X)(R4)(R5) group in which R4 and R5 are selected from alkyl, cycloalkyl, alkenyl, alkoxy, phenyl, chlorophenyl or dialkylamino groups, or R2 is an unsaturated nitrogen containing heterocyclic ring, including the <FORM:0903795/IV (b)/1> group in which A is a fused benzenic ring system, and X is an oxygen or sulphur atom.  They may be obtained by reacting a compound (R)(R1O)P(X)Hal in which Hal is a halogen atom with an appropriately substituted mercaptan HS.CH2.SR2 in the presence of an acidbinding agent or by reacting a thio- or dithiophosphonic acid (R)(R1O)P(X)SH (or salt thereof) with a compound HalCH2SR2, the reaction being carried out in the presence of an acid binding agent when the free acid is used.  A preferred method for preparing the products in which X is sulphur and R is alkyl or aryl comprises reacting alkyl or aryl thiono O-alkyl ester thiolphosphonic acid alkali metal salts with chlorobromomethane to form compounds of the formula (R)(R1O) P(S)SCH2Cl which are then reacted with compounds of the formula R2SH, the latter being generally used in the form of their alkali metal salts.  Examples of the R2SH compounds are thiocarboxylic acids, dithiocarbamic acids, thiocyanic acid, xanthates, unsaturated heterocyclic mercaptans and appropriate thiol acids of the phosphoric diester, phosphonic ester and phosphinic series or derivatives thereof, e.g. amides.  When R2 is a heterocyclic group it is preferably of the thiazole, thiadiazole, imidazole, pyrazole, or triazole series, or is one of their benzeneannealed derivatives. Several examples are given, the specified products including the compounds:-  <FORM:0903795/IV (b)/2> <FORM:0903795/IV (b)/3> <FORM:0903795/IV (b)/4> <FORM:0903795/IV (b)/5> The products have insecticidal properties (se Group VI).  The compound (C2H5)(C2H5O)P(S)SCH2Cl used as a starting material is obtained by reacting (C2H5)(C2H5O)P(S)SK with BrCH2Cl at 30-40 DEG C. in acetonitrile.ALSO:An insecticidal composition comprises as active ingredient in conjunction with a solid or liquid inert diluent or carrier a thiophosphonic ester of the formula (R)(R1O)P(X)SCH2SR2 in which R is an alkyl, cycloalkyl, alkenyl (but excluding vinyl) or unsubstituted or substituted phenyl radical, R1 is an alkyl radical, R2 is a nitrile group or a -C( : X)R3 group in which R3 is an alkyl, phenyl, alkoxy or dialkylamino group, or R2 is a -P(X)(R4)(R5) group in which R4 and R5 are selected from alkyl, cycloalkyl, alkenyl, alkoxy, phenyl, chlorophenyl, or dialkylamino groups or R2 is an unsaturated nitrogen-containing heterocyclic ring, including the <FORM:0903795/VI/1> group in which A is a fused benzenic ring system, and X is an oxygen or sulphur atom (see Group IV (b)).  In an example, the compound (C2H5)(C2H5O)P(S).S.CH2.S.C(S)OC 2H5 or the compound (CH3)(C2H5O)P(S)SCH2SP(S)(OC 2H5) (CH3) is mixed with the same amount of acetone, an emulsifier consisting of benzyl hydroxydiphenylpolyglycol ether is added and the mixture is diluted with water.