Patent GB-1001065-A (GB)
Title: New thiophosphoric, thiophosphonic and thiophosphinic acid ester derivatives
IPC: C07F9/44
Filed: 1961-10-16
Abstract: The invention comprises phosphorus compounds of the general formula:- <FORM:1001065/C2/1> wherein R1 and R2 which may be the same or different are alkoxy, alkylmercapto, aryloxy, arylmercapto, aralkoxy, cycloalkoxy, alkyl, chloroalkyl, alkenyl, aralkyl, cycloalkyl, aryl or chloroaryl radicals, X1 is an oxygen or sulphur atom, X2 is a sulphur atom, X3 is a hydrogen atom or an alkyl or aryl radical and A is atom or an alkyl or aryl radical and A is the atomic grouping or groupings necessary to complete the residue of a malonic amide ester or thioester, a malonic acid diamide or a barbituric or thiobarbituric acid type compound. They may be obtained by reacting a halogeno-malonic acid amide ester (or thioester), ester), halogeno-malonic acid diamide, or halogeno-barbituric (or-thiobarbituric) acid type compound with a phosphorus compound of the formula: <FORM:1001065/C2/2> wherein R1, R2, X1 and X2 are as defined above, B is a hydrogen atom, alkali metal or ammonium and Hal is halogen, e.g. Cl or Br, the reaction being carried out in acid-binding agent when B is a hydrogen atom.  The reaction is preferably effected at between room temperature and 80 DEG  C. and may be carried out in the presence of water, an inert organic solvent or an aqueous organic solvent or in a two-phase sytem, e.g. water/ethylene chloride.  The products may be of the type:- <FORM:1001065/C2/3> wherein R3 and R4 are hydrogen atoms, or alkyl, aralkyl, cycloalkyl or aryl radicals which may be substituted or are radicals which may be joined with the N-atom to form a heterocyclic ring, R5 is an alkoxy, alkylmercapto, aryloxy or arylmercapto radical or another NR3R4 group as defined above (including a heterocyclic ring, e.g. morpholine, piperidine, piperazine or pyrrolidine), and R1, R2, X1, X2 and X3 are as defined above.  The barbituric acid type compounds may have the formula:- <FORM:1001065/C2/4> wherein the R1 and R2 attached to N are hydrogen atoms or alkyl radicals and Y is an oxygen or sulphur atom or an imino group and the other symbols are as defined above.  Several examples are given and the products have pesticidal properties (see Division A5).ALSO:A pesticidal composition comprises a solid or liquid diluent or carrier and a phosphorus compound of the formula:-  <FORM:1001065/A5-A6/1> wherein R1 and R2 which may be the same or different are alkoxy, alkylmercapto, aryloxy, arylmercapto, aralkoxy, cycloalkoxy, alkyl, alkenyl chloroalkyl, alkenyl, aralkyl, cycloalkyl, aryl or chloroaryl radicals, X1 is an O or S atom, X2 is a sulphur atom, X3 is a hydrogen atom or an alkyl or aryl radical and A is the atomic grouping or groupings necessary to complete the residue of a malonic amide ester (or thioester), a malonic acid diamide or a barbituric or thiobarbituric acid type compound (see Division C2).  The malonicamide type products may have the formula:- <FORM:1001065/A5-A6/2> wherein R3 and R4 are hydrogen atoms, or alkyl, aralkyl, cycloalkyl or aryl radicals which may be substituted or are radicals which may be joined with the N atom to form a heterocyclic ring, R5 is an alkoxy, alkylmercapto, aryloxy or arylmercapto radical or another NR3R4 group as defined above (including a heterocyclic ring, e.g. morpholine, piperdine, piperazine or pyrrolidine) and R1, R2,X1,X2 and X3 are as defined above.  The barbituric acid type compounds may have the formula:- <FORM:1001065/A5-A6/3> wherein R1 and R2 attached to N are hydrogen atoms or alkyl radicals and Y is O, S, or are imino group and the other symbols are as defined above.  Conventional solid and liquid diluants are specified and a suitable composition is obtained by dissolving the active ingredient in acetone, adding a commercial emulsifier and then diluting with water.  Known insecticides and/or fertilisers may also be present.