Patent GB-701225-A (GB)
Title: Improvements in and relating to phosphorus acid esters
IPC: C07F9/117
Filed: 1951-05-07
Abstract: The invention comprises a phosphoric or thiophosphoric acid ester of the general formula <FORM:0701225/IV (b)/1> wherein R represents a D -1:2-cyclohexeneone -yl radical which may be alkyl substituted, X represents oxygen or sulphur and Y and Y1 each represent the same or different alkoxy or alkylmercapto group.  Such compounds are obtained by reacting phosphorus halide derivatives of the formula <FORM:0701225/IV (b)/2> (wherein Hal represents chlorine or bromine) with alkyl-substituted or unsubstituted enolisable 1:2- or 1:3- cyclohexanediones or their metal salts.  Benzene, toluene, dioxan or ethyl acetate are suitable reaction media.  Y and Y1 may be derived from such alcohols and mercaptans as methanol, ethanol, n-propanol, isopropanol, butyl- and amyl alcohols, and methyl, ethyl-, n-propyl-, isopropyl-, butyl-, amyl- and allyl mercaptans.  The esters in which X is sulphur can also be obtained by reacting compounds of the formula Hal-P.YY1 with the cyclohexandiones specified and treating the product of formula RO.PYY1 with sulphur or compounds yielding sulphur, e.g. sodium polysulphides or phosphorus pentasulphides. Alternatively the cyclohexandione may be first reacted with phosphoric acid halides or thiophosphoric acid halides and reacting the resultant phosphoric acid monoester dichloride with the aliphatic alcohol or mercaptan.  Specified enolisable cyclohexandiones are cyclohexandione-(1:2) and -(1:3) (dihydroresorcinol), 5-methyl- and 5:5-dimethyl dihydroresorcinol, 1-methyl cyclohexanedione-(2:3, -(2:4), and -(2:6), 1-methyl-cyclohexanedione-(3:4), 1:3-dimethyl-cyclohanedione-(4:5), 1-isopropyl cyclohexanedione-(2:3), 1:1:2-trimethyl cyclohexanedione-(4:5), 1-methyl-4-isopropyl cyclohexanedione -(2:3) [p-menthadione-(2:3)], and 1-methyl - 4 - isopropyl - cyclohexanedione (2:6).  In examples (1) diethyl thiophosphoric acid chloride is reacted with the reaction product of dihydroresorcinol and potassium carbonate to give (cyclohexene-D 1:2-one(3)-yl) diethyl thiophosphate.  (2) diethylphosphoric acid chloride is reacted with the sodium derivative of 5:5-dimethyl dihydroresorcinol to give [5:5-dimethylcyclohexene-D 1:2-one(3)yl] diethyl phosphate.  Other compounds are obtained of the above general formula in which (a) R is cyclohexene-D 1:2-one(3)-yl, X = O or S, and Y and Y1 are methoxy-, n-propoxy-, isopropoxy-, methylmercapto- and ethylmercaptoradicals; (b) R is 5-methylcyclohexene-D 1:2-one(3)-yl, X = O or S, Y and Y1 are methoxy or ethoxy; (c) R is 5:5-dimethylcyclohexene-D 1:2-one(3)yl, X = O or S, Y and Y1 are methoxy or ethoxy; (d) R is 3-methyl-cyclohexene D 1:2-one(3)-yl, X is O or S, Y and Y1 are ethoxy or methoxy; (e) R is 2:4-dimethyl-cyclohexene-D 1:2-one(6)-yl X is O or S, and Y and Y1 are ethoxy or methoxy.  The products are of use as insecticides and their solutions are of use as impregnants, e.g. for textiles (see Group VI).ALSO:A composition for combating pests comprises phosphoric or thiophosphoric acid ester of the formula <FORM:0701225/VI/1> wherein R represents a A1:2-cyclohexeneoneyl radical either unsubstituted or alkyl substituted, X represents oxygen or sulphur, and Y and Y1 each represent the same or different alkoxy or alkylmercapto group and a carrier or diluent.  In such esters R-O- may be the residue from dihydroresorcinol, cyclohexanedione-(1:2), 5-methyl- or 5:5-dimethyl-dihydroresorcinol, 1-methyl cyclohexanedione - (2:3), -(2:4),-(3:4) or -(2:6), 1:3-dimethyl cyclohexanedione - (4:5), 1-isopropyl cyclohexanedione (3:5), 1:1:2-trimethyl cyclohexanedione-(4:5), 1-methyl 4-isopropyl cyclohexanedione - (2:3) (p-menthadione-(2:3)) and 1-methyl-4-isopropyl cyclohexanedione -(2:6); Y and Y1 may be alkoxy and alkylmercapto groups derived from e.g. methanol, ethanol, n-propanol, isopropanol, butyl and amyl alcohols, methyl-, ethyl-, n-propyl-, isopropyl-, butyl-, and amyl mercaptans.  The preparation of the esters is described (see Group IV(b)).  As pesticides the esters may be used in combination with solid carriers, e.g. calcium carbonate, kaolin, bole, bentonite, talcum, powdered magnesia, kieselguhr, boric acid, tricalcium phosphate, powdered wood, cork or other vegetable material.  For preparing other compositions there may be added also wetting and emulsifying agents, e.g. cation active compounds, such as quaternary ammonium compounds, anion active agents such as soap, aliphatic monoesters of sulphuric acid and aliphatic aromatic sulphonic acids, non-ionogenic emusifiers e.g. condensation products of ethylene oxide; protective colloids and adhesives, e.g. fatty acids, resins, glue casein and alginates; solvents, e.g. kerosene and other mineral oils, methylnaphthalenes, xylenes, trichlorethylene, tetrachlorethane, ethylene chloride, benzene, xylene, chlorobenzene, the solutions being suitable for impregnating wood, packing materials and textiles; ointment bases, e.g. petroleum jelly; propellant agents for aerosols, e.g. fluoro-trichloromethane and difluorochloromethane; lures, e.g. sugar for use in sprays and fly-catchers.  To form emulsion concentrates may be added acetone, alcohols, cyclohexanone, benzene, toluene, xylene, tetrahydronaphthalene, alkylated naphthalenes, phthalic acid esters, mineral and vegetable oils and water.  There may also be added bactericides, e.g. chlorinated phenols and quaternary compounds; fungicides, e.g. sulphur in all its forms such as lime sulphur, copper compounds such as copper oxychloride or Bordeaux liquid, and fluorides; insecticides, e.g. synthetic products such as 1:1-bis-(p-chlorophenyl)-2 : 2 : 2-trichlorethane-g -hexachlorocyclohexane, hexaethyl tetraphosphate, tetraethyl pyrophosphate, chlorinated camphene, 1:2:4:5:6:7:8:8 - octochloro- 4:7 -methano 3a -:4:7:7a tetrahydroindane and 5.5-dimethyldihydroresorcinol dimethyl carbamate, and vegetable products, e.g. pyrethrin and rotenone. Examples describe (3) a composition of an ester of the above formula, e.g. dihydroresorcyl diethyl thiophosphate, and talcum to which an adhesive may added; (4) a spraying agent comprising the ester, a wetting agent, e.g. the sodium salt of dibutyl naphthalene, a dispersing agent, e.g. casein, blood albumen or sulphite waste liquor, and a carrier, e.g. chalk, kaolin or bentonite; (5) an emulsion comprising the ester in a solvent with, as emulsifying agent, sulphonates of fatty acid esters or of ricinoleic acid butyl ester, quaternary compounds, or condensation products of ethylene oxide with alkyl phenols or fatty alcohols; (6) a spraying solution of the ester in xylene and kerosene.  The products of (5) and (6) are suitable for impregnating textiles.