Patent GB-788690-A (GB)
Title: Improvements in or relating to thiophosphoric acid esters having pesticidal properties
IPC: A01N57/10
Filed: 1956-01-20
Abstract: The invention comprises compounds having the general formula: <FORM:0788690/IV (b)/1> wherein R1 and R2 are aliphatic hydrocarbon radicals containing at most 6 carbon atoms, R3 is an alkyl or aralkyl radical which may be substituted, R4 is the group -COOR5, <FORM:0788690/IV (b)/2> or -C­N, R5, R6 and R7 are aliphatic hydrocarbon radicals containing at most 6 carbon atoms with the proviso that R1, R2, R3, R5 R6 and R7 may be similar or dissimilar radicals, and Y is an oxygen or sulphur atom.  The compounds may be prepared by reacting a compound of the formula X-CH(R4)-S-R3 with a compound of the formula <FORM:0788690/IV (b)/3> wherein R1, R2, R3, R4 and Y are as defined above, X is a halogen atom and Y is a salt-forming cation, e.g. ammonium or an alkali metal.  The process is preferably carried out at between 40 DEG  and 150 DEG  C. and in the presence of a solvent, e.g. acetone, benzene, toluene, xylene, chlorobenzene, water, or a mixture of such solvents.  Examples are given for the production of compounds in which (1) to (4) R3 is C2H5, R4 is COOC2H5, R1 and R2 are both CH3 or are both C2H5 respectively, and Y is O or S, (5) to (7) R1 and R2 are CH3, Y is S, R3 is CH3 and R4 is COOCH3, COOCH(CH3)2, and COOCH2CH2CH2CH3 respectively; (8) to (11) R1 and R2 are CH3, R3 is C2H5, Y is S and R4 is COOCH3, COOCH2CH2CH3, C­N and CON(C2H5)2 respectively; (12) and (13) R1 and R2 are CH3, R3 is CH2,CH2,CH3, Y is S and R4 is COOC2H5 and COOCH(CH3)2 respectively; (14) to (19) R1 and R2 are C2H5, R3 is C2H5, Y is S and R4 is C­N, COOCH3, COOCH(CH3)2, COOCH2,CH2,CH3, COO,iso-C5H11, and COOCH2,CH2,CH2,CH3 respectively; (20) to (23) R2 and R3 are C2H5, Y is O or S, R3 is CH2,CH3,CH3 and R4 is COOC2H5\t and COOCH (CH3)2 respectively; (24) and (25) R1 and R2 are CH3, Y is S, R3 is CH(CH3)2 and R4 is COOCH3 and COOCH(CH3)2 respectively; (26) and (27) R1 and R2 are CH3, Y is O, R3 is C2H5 and R4 is COOCH3 and COOCH(CH3)2 respectively; (28) and (29) R1 and R2 are C2H5, Y is S, R3 is CH3 and R4 is COOCH3 and COOCH(CH3)2 respectively; (30) and (31) R1 and R2 are C2H5, Y is S, R4 is COOCH3\t and R3 is n-C4H9 and CH(CH3)2 respectively; (32) to (34) R1 and R2 are C2H5, Y is O, R3 is C2H5 and R4 is COOCH3, CON(C2H5)2, and C­N respectively; and (35) R1 and R2 are C2H5, Y is O, R3 is CH2,C6H5 and R5 is CON(C2H4)2.  The compounds are stated to be valuable as pesticides (see Group VI). The alkyl esters of alkylmercapto- or aralkylmercapto-chloracetic acid which may be used as starting materials may be obtained by reacting the corresponding alkyl ester of chloracetic acid with an alkali metal salt of the corresponding alkyl or aralkyl mercaptan and chlorinating the alkyl or aralkyl mercaptoacetic acid ester thus obtained.  Alternatively, they may be obtained by reacting an alkali metal salt of a thioglycollic acid ester with an alkylating or aralkylating agent and then chlorinating the resulting alkyl (or aralkyl) mercaptoacetic acid ester.  The dialkyl amides of alkyl (or aralkyl) mercaptochloracetic acids which may be used as starting materials may be obtained by reacting a chloracetic acid dialkyl amide with an alkali metal salt of the corresponding alkyl (or aralkyl) mercaptan and chlorinating the resulting alkyl (or aralkyl) mercapto acetic acid dialkylamide.  The alkyl (or aralkyl) mercapto acetonitriles which may also be used as starting materials may be obtained by reacting chloracetonitrile with an alkali metal salt of an alkyl or aralkyl mercaptan and then chlorinating the product.ALSO:A pesticidal composition comprises as the active ingredient a thiophosphoric acid ester of the formula <FORM:0788690/VI/1> wherein R1 and R2 are aliphatic hydrocarbon radicals containing at most 6 carbon atoms, R3 is an alkyl or aralkyl radical which may be substituted, R4 represents the group -COOR5, <FORM:0788690/VI/2> or -C­N, R5, R6 and R7 represent aliphatic hydrocarbon radicals containing at most 6 carbon atoms with the proviso that R1, R2, R3, R5, R6 and R7 may be similar or dissimilar radicals, and Y is an oxygen or sulphur atom (see Group IV(b)).  The pesticidal composition may comprise the thiophosphoric acid ester dispersed in water in the presence of an emulsifier, e.g. a polyglycol ether formed from a high molecular weight alcohol, mercaptan, or alkyl phenol, by addition of ethylene oxide, and an organic solvent, e.g. a mono- or polyhydric alcohol, aromatic hydrocarbon, or mineral oil may be incorporated into the mixture as solubilizer.  The thiophosphate ester may also be used in conjunction with a solid carrier, e.g. talc, kaolin, kieselguhr, bentonite, or a mixture thereof, and an adhesive may also be added.  Several examples of suitable compositions are given and these include: (1) an aqueous emulsion containing an ester of the above formula in which R1 and R2 are C2H5, Y is S, R4 is COOC2H5 and R3 is C2H5, and iso-octylphenylheptaglycol ether; (2) an aqueous solution containing lauryl hexaglycol ether, xylene, and an ester in which R1 and R2 are CH3, Y is S, R3 is C2H5 and R4 is COOC2H5; (3) an aqueous emulsion containing tert.-dodecylmercaptoundecaglycol ether, a mineral oil, and an ester in which R1 and R2 are CH3, Y is S, R3 is CH3, and R4 is COOCH3; (4) an aqueous emulsion containing laurylhexaglycol ether, xylene and an ester in which R1 and R2 are C2H5, Y is O, R3 is CH2CH2CH3 and R4 is COOC2H5; (5) an aqueous emulsion containing diisohexyl/heptyl-phenyl-hexaglycol ether, propylene glycol, butoxy-ethoxy-ethanol and an ester in which R1 and R2 are CH3, Y is O, R3 is C2H5 and R4 is COOCH3; (6) a powder containing tert.-dodecyl mercapto undecaglycol ether, powdered silica gel, kaolin, and an ester in which R1 and R2 are CH3, Y is O, R3 is C2H5 and R4 is COOC2H5; (7) a dust made by grinding a mixture of talc and an ester in which R1 and R2 are CH3, Y is S, R3 is C2H5 and R4 is CON(C2H5)2; (8) an aqueous emulsion containing laurylhexaglycol ether, xylene and an ester in which R1 and R2 are CH3, Y is S, R3 is C2H5 and R4 is COOCH2CH2CH3; and (9) an aqueous emulsion containing laurylhexaglycol ether, butoxy-ethoxy ethanol, a mineral oil, a technical alcohol mixture consisting mainly of n-octanol and an ester in which R1 and R4 are C2H5, Y is S, R3 is C2H5 and R4 is COOCH (CH3)2.  Several other esters of the above formula which may be used as the active ingredients are also specified.