Patent GB-978866-A (GB)
Title: Pesticidal compositions
IPC: C07F9/02
Filed: 1962-08-20
Abstract: Organo-phosphorus compounds having the general formula: <FORM:0978866/C1/1> are prepared by halogenating the corresponding vinyl esters having the general formula <FORM:0978866/C1/2> wherein, in the above formulae, n is 1 or 2, and m+n=2; each of the groups R individually represents a substituted or an unsubstituted hydrocarbon group; each of the groups R1 individually represents a hydrogen or halogen atom or a substituted or unsubstituted hydrocarbon group; R11 represents a halogen atom, a substituted or unsubstituted hydrocarbon group, or a functional organic group as specified below; and hal represents a halogen atom; with the proviso that the two groups R or the two groups R1 may be linked to form a divalent alkylene group. When R1 and R11 are halogen atoms, they and, also, hal are preferably bromine or chlorine. The hydrocarbon groups represented by R, R1 and R11 may be alkyl, cycloalkyl, aryl, aralkyl and alkaryl, and when substituted may contain, for example, one or more chlorine or bromine atoms, nitro groups, amino groups represented by the formula <FORM:0978866/C1/3> or ether groups R2-O-, wherein m and n have the meanings given above and R2 represents a hydrocarbon group.  The functional organic group represented by R11 is a carboalkoxy or alkoxyalkyleneoxy carbonyl group; a carboalkoxy alkyloxy group; an aralkyloxy-carbonyl or phenyloxy carbonyl group which may be substituted with one or more halogen atoms, or nitro, methyl or methoxy groups; a phenoxyethoxy carbonyl group; an ether group R-O-, wherein R has the meaning given above; an acyl group or an acyloxy alkoxy carbonyl group wherein acyl means a group <FORM:0978866/C1/4> , R having the meaning given above; or an amido group <FORM:0978866/C1/5> wherein R2, m and n have the meanings given above.  The halogenation is generally carried out by contacting the vinyl ester with free halogen in the presence of a solvent, if necessary, e.g. methylene dichloride.  The halogen is preferably added at a low temperature, generally below 40 DEG C., e.g. between -5 DEG C. and 30 DEG C., after which the reaction mixture may be warmed, e.g. up to 60 DEG C., to complete the reaction.  The reaction may be promoted by actinic radiation, e.g. ultraviolet light. The phosphorus compounds are used in pesticidal compositions (see Division A5).  Specifications 775,085 and 783,697 are referred to.ALSO:Stabilized pesticidal compositions, suitable for use as insecticides and fungicides, comprise a pesticidal phosphorus compound having the general formula <FORM:0978866/A5-A6/1> wherein n is 1 or 2, and m + n = 2; each of the groups R individually represents a substituted of an unsubstituted hydrocarbon group; and M represents the group <FORM:0978866/A5-A6/2> or <FORM:0978866/A5-A6/3> wherein each of the groups R1 individually represents a hydrogen or halogen atom or a substituted or unsubstituted hydrocarbon group, R11 represents a halogen atom, a substituted or unsubstituted hydrocarbon group, or a functional organic group as specified below, and hal represents a halogen atom; with the proviso that the two groups R or the two groups R1 may be linked to form a divalent alkylene group, and that when M represents the group <FORM:0978866/A5-A6/4> at least one of the groups R1 or R11 represents a halogen atom; in admixture with an inert liquid carrier, a surface-active agent, and an epoxyhaloalkane having the general formula <FORM:0978866/A5-A6/5> wherein hal represents a halogen atom, and each group Ra represents a hydrogen atom or an alkyl group of from one to six carbon atoms.  In the above formul , when R1 and R11 are halogen atoms, they and, also, hal are preferably bromine or chlorine.  The hydrocarbon groups represented by R, R1 and R11 may be alkyl, cycloalkyl, aryl, aralkyl and alkaryl, and when substituted may contain, for example, one or more chlorine or bromine atoms, nitro groups, amino groups represented by the formula <FORM:0978866/A5-A6/6> or ether groups R2-O-, wherein m and n have the meanings given above and R2 represents a hydrocarbon group.  The functional organic group represented by R11 is a carboalkoxy or alkoxyalkyleneoxy carbonyl group; a carboalkoxyalkyloxy group; an aralkyloxycarbonyl or phenyloxycarbonyl group which may be substituted with one or more halogen atoms, or nitro, methyl or methoxy groups; a phenoxyethoxycarbonyl group; an ether group R-O-, wherein R has the meaning given above; an acyl group or an acyloxyalkoxycarbonyl group wherein acyl means a group <FORM:0978866/A5-A6/7> R having the meaning given above; or an amido group <FORM:0978866/A5-A6/8> wherein R2, m and n have the meanings given above.  Many specific examples of the organophosphorus compounds are listed. The surface-active agent used in the pesticidal compositions is preferably non-ionic, e.g. a saponin; a condensation product of ethylene and/or propylene oxide with a fatty acid, alcohol, ester or alkylphenol; an ester of a fatty acid and a glycol or polyalkylene glycol; an ester of a fatty acid and a polyhydroxy compound; an amide or amine having polyoxyethylene substituents on the nitrogen atom; a condensation product of an alkylene oxide and a thiol; an ester reaction product of a higher alkyl dihydrogen phosphate with ethylene oxide or a polyglycol; fatty acid monoesters of polyhydroxy compounds; and phosphatides. Epoxy-haloalkane ingredients specified are epichlorohydrin, epibromohydrin, 1 - chloro - 2,3 - epoxybutane, 1 - chloro - 2,3 - epoxyhexane, 1 - chloro - 2,3 - epoxy - 4 - methylpentane, 3 - chloro - 4,5 - epoxyoctane and 1-bromo-2,3-epoxyhexane.  The inert liquid carrier can be any conventional liquid carrier suitable for horticultural application.  Optional ingredients include stickers, extenders, hormones, soil conditioners, nematocides, soil amenders, fertilizers, e.g. ammonium sulphate, urea, ammonium phosphate, and potassium nitrate, fungicides, e.g. copper salts, and insecticides, e.g. pyrethrum, rotenone, sabadilla, D.D.T., benzene hexachloride, thiodiphenylamine, cyanides, tetraethyl pyrophosphate, dimethyl p-nitrophenyl thiophosphate, lindane, azobenzene, and arsenic, lead and/or fluorine compounds.  Specifications 775,085 and 783,697 are referred to.