Patent GB-955754-A (GB)
Title: New unsaturated organophosphorus esters
IPC: C07F9/6578
Filed: 1962-02-12
Abstract: The invention comprises a phosphorus compound having the general formula: <FORM:0955754/C2/1> wherein R, R1 and R2 each represent a substituted or unsubstituted hydrocarbon group, R3 is hydrogen or a group represented by R, m, n, p and q each is 0 or 1, and X and Y each represent an oxygen or sulphur atom or the group NH or NR0 wherein R0 is a group represented by R, with the proviso that when m and n are each 1 and X and Y each represent an oxygen or sulphur atom, R and R1 may be linked together to form a divalent group, and that when either or both of X and Y represent the group NR0 the groups R and R0, or R1 and R0, may be linked together to form a divalent group. The groups R, R1, R2, R3 and R0 may be aliphatic, cycloaliphatic, aromatic or aliphatic-aromatic hydrocarbon groups, e.g. alkyl, cycloalkyl, phenyl, naphthyl, aralkyl or alkaryl groups. When the hydrocarbon groups are substituted the preferred substituents are halogen, preferably bromine or chlorine, the nitro group, cyano group or a group of the formula: -N(R)w-(H)v wherein R is as defined above, v is 0, 1 or 2 and v+w=2, an aliphatic oxycarbonyl group, e.g. a carboalkoxy or carboalkoxy-alkylene group of up to 8 carbon atoms, an RO-group, or an amido group including the grouping NHC(O)R, wherein R is as defined above. When R and R1 form a divalent group the latter is preferably an alkylene group of up to 10 carbon atoms having a chain of 1 to 5, preferably 2 to 3, carbon atoms linked to X and Y and when R and R0 or R1 and R0 form a divalent group the latter is preferably an alkylene group of up to 10 carbon atoms with 4 or 5 carbon atoms in the chain thereof which is bonded with its ends to the nitrogen atom, thus the divalent chain may form with the nitrogen atom a piperidino group. Preferred compounds are those in which m and n in the general formula are each 1, X and Y represent oxygen, both R and R1 are C1-C4 alkyl groups, and R3 is hydrogen. Examples of suitable substituted hydrocarbon groups are haloalkyl groups, nitroalkyl groups, haloaryl groups, and amino-substituted groups, e.g. 2-aminoethyl, 2-diethylaminoethyl, the aniline group, p-dimethylaminophenyl and p-ethylaminobenzyl. The thiovinyl compounds, i.e. those in which p and q are zero, may be obtained by reacting a compound of the formula: <FORM:0955754/C2/2> wherein alkyl is an alkyl group preferably an unbranched C1-C4 alkyl group, with an ester of an alpha-halothioacetic acid of the formula hal.CH(R3). CO.SR2 wherein hal is halogen, e.g. Br or Cl. The sulphinylvinyl and the sulphonylvinyl compounds, i.e. those in which either or both of p and q are 1 may be obtained by oxidising the thiovinyl compounds (in which p and q are zero). The reaction to form the thiovinyl compounds is preferably effected at from 40 DEG C. to 150 DEG C. and it is preferred to use an excess of the phosphorus compound. The oxidation of the thiovinyl compounds to form the sulphinylvinyl and the sulphonylvinyl compounds is preferably effected in a controlled manner by means of a per acid, e.g. peracetic or monoperphthalic acid, and a polthaloalkane, e.g. chloroform, may be present as solvent. Suitable temperatures are from 10 DEG  to 40 DEG C. The products have pesticidal properties (see Division A5).  The alpha-halothiolacetic acids of the formula hal. CH(R3).CO.SR2 may be obtained by reacting a haloacetyl halide with an aqueous solution of an alkali metal salt of the appropriate mercaptan and an example is given for the production of S-phenyl chlorothiolacetate by reacting chloroacetyl chloride with thiophenol in the presence of sodium hydroxide and water.ALSO:A pesticidal composition contains as active ingredient a phosphorus compound of the general formula:  <FORM:0955754/A5-A6/1> wherein R, R1 and R2 each represent a substituted or unsubstituted hydrocarbon group, R3 is hydrogen or a group represented by R, m, n, p and q each is 0 or 1, and X and Y each represent an oxygen or sulphur atom or the group NH or NR DEG  wherein R DEG  is a group represented by R, with the proviso that when m and n are each 1 and X and Y each represent an oxygen or sulphur atom, R and R1 may be linked together to form a divalent group, and that when either or both of X and Y represent the group NR DEG  the groups R and R DEG , or R1 and R DEG , may be linked together to form a divalent group.  The groups R, R1, R2, R3 and R DEG  may be aliphatic, cycloaliphatic, aromatic or aliphatic-aromatic hydrocarbon groups, e.g. alkyl, cycloalkyl, phenyl, naphthyl, aralkyl or alkaryl groups.  When the hydrocarbon groups are substituted the preferred substituents are halogen, preferably bromine or chlorine, the nitro group, cyano group or a group of the formula -N(R)w-(H)v wherein R is as defined above, v is 0, 1 or 2, and v + w = 2, an aliphatic oxycarbonyl group, e.g. a carboalkoxy or carboalkoxy-alkylene group of up to 8 carbon atoms, an RO-group, or an amido group including the grouping NHC(O)R, wherein R is as defined above.  When R and R1 form a divalent group the latter is preferably an alkylene group of up to 10 carbon atoms having a chain of 1 to 5, preferably 2 to 3, carbon atoms linked to X and Y and when R and R DEG  or R1 and R DEG  form a divalent group the latter is preferably an alkylene group of up to 10 carbon atoms with 4 or 5 carbon atoms in the chain thereof which is bonded with its ends to the nitrogen atom, thus the divalent chain may form with the nitrogen atom a piperidino group.  Preferred compounds are those in which m and n in the general formula are each 1, X and Y represent oxygen, both R and R1 are C1-C4 alkyl groups, and R3 is hydrogen. The composition may be in the form of a solution or dispersion and a carrier and/or surface active or spreading agent may be present.  The carrier may be a finely divided solid or may be water, acetone, or a light mineral oil, e.g. kerosene.  The composition may also be in a form suitable for use as an aerosol. Other insecticides may be present, e.g. pyrethrum, rotenone, sabadilla, DDT, benzene hexachloride, thiodiphenylamine, cyanides, tetraethyl pyrophosphate, diethyl p-nitrophenyl thiophosphate, dimethyl 2,2-dichlorovinyl phosphate, 1, 2-dibromo - 2,2 - dichloroethyl dimethyl phosphate, azobenzene and compounds of lead, arsenic and/or fluorine.  Hormones and fertilizers may also be present.  The active ingredient may also be used for the destruction of nematodes and fungi in soil by intimately disseminating it in the soil.