Patent GB-785990-A (GB)
Title: Improvements in or relating to pesticidal organic phosphorus compounds
IPC: C07F9/655
Filed: 1955-06-07
Abstract: The invention comprises dithiophosphate compounds of the general formula: <FORM:0785990/IV (a)/1> wherein m = 0, 1 or 2 and n = 1 or 2, R = lower alkyl or halo lower alkyl, the lower alkyl radical containing from 1 to 4 carbon atoms, R1 = alkyl, haloalkyl, nitroalkyl, or halonitro-alkyl, or, when m = 2 and n = 2, the two R1 groups may together constitute -CH2-CH2-, with the added provisos that when m = 0 and n = 2 the points of substitution are 2, 3 or 2, 5; when m = 1, n also = 1 and the substituent groups are on adjacent carbon atoms, and when m = 2, n also = 2 and like substituents are on adjacent carbon atoms. They may be prepared by reacting a compound of the formula: <FORM:0785990/IV (a)/2> with n molecular proportions of a compound of the formula (RO)2P(S)SH or a salt thereof, the symbols m, n, R and R1 being as defined above, and X being chlorine or bromine. The products in which m is 0 and n is 1 may also be obtained by reacting p-dioxene with a compound of the formula (RO)2.P(S).SH. The first type of process is preferably carried out by heating the reactants at between 20 DEG  and 200 DEG  C., e.g. between 30 DEG and 110 DEG  C., in a non-aqueous medium such as benzene, toluene, xylene, cyclohexane, hexane, dioxane, or an anhydrous alcohol.  When the diester of dithiophosphoric acid is used in the form of the free acid, the hydrogen halide liberated is preferably sequestered by adding a suitable material, e.g. a tertiary amine such as pyridine, trimethylamine, tributyl amine, triamyl amine, and dimethyl aniline or an inorganic base such as ammonia, an alkali metal hydroxide, carbonate or bicarbonate, or an alkaline earth metal hydroxide or carbonate.  Alternatively, the organic or inorganic base may first be reacted with the diester of the dithiophosphoric acid to form a salt of the latter prior to the reaction with the halo-dioxane compound. The second type of process is preferably effected by heating the p-dioxene and the dithiophosphoric acid at between 20 DEG  and 200 DEG  C. and may be carried out in the presence of a small amount of a solvent such as benzene, toluene, xylene, cyclohexane, hexane, acetone, carbon tetrachloride, chloroform, dioxane, or an anhydrous alcohol.  No catalyst is required and the condensation is preferably carried out in the absence of water.  Examples are given for the production of: (1) to (5) 2,3-p-dioxanedithiol S,S - bis (O,O - diethyl phosphorodithioate) and the corresponding diisopropyl, di-n-propyl, di-sec.-butyl and dimethyl homologues; (6) to (10) 2,5-p-dioxanedithiol S,S-bis (O,O-diethyl phosphorodithioate) and its diisopropyl, di-n-propyl, di-sec. butyl and dimethyl homologues; (11) 2,3 - p - dioxanedithiol S,S - bis (O,O-bis (2 - chloroethyl) phosphorodithioate); (12) and (13) bis (bis (a -trichloroethyl) dithiophosphate of p-dioxane-2,3-dithiol and the corresponding bis (fluoroethyl) compound; (14) 2 - p - dioxanethiol S - (O,O - diethyl phosphorodithioate) which is obtained by reacting O,O-diethyl dithio phosphoric acid with p-dioxene in the presence of benzene and a small amount of hydroquinone; (15) to (18) the diisopropyl, di-n-propyl di-sec. butyl and dimethyl homologues of the product of (14) which are prepared by a similar procedure; (19) to (27) 2,3-diethoxy-p-dioxane-5,6-dithiol S,S-(O,O-diethyl phosphorodithioate) and the corresponding compounds of the above general formula in which R1 is ethyl and R is butyl, methyl, a -chloroethyl, or a -trichloroethyl; R1 is isopropyl and R is ethyl or butyl; and R1 is butyl and R is ethyl or butyl, all these compounds being obtained by reacting the corresponding dichloro-2,3-dialkoxy (or 2,3-dichloralkoxy) - p - dioxanes with the appropriate dialkyldithio phosphoric acid in the presence of pyridine and benzene; (28) to (32) 3-(2,2,2-trichloroethoxy) - 2 - p - dioxanethiol S - (O,O-diethyl phosphorodithioate) and the corresponding compounds of the above general formula in which R is ethyl and R1 is CH2CCl3, CH(CH2NO2)CCl3, CH2C(CH2Cl)3, CH2C(NO2) (CH3)CH3 and -CH(CH3)C(CH3)3 respec tively; (33) to (37) 1,4,5,8 - tetraoxaoctahydronaphthalene - 2,3 - dithiol S,S - bis (O,O-diethyl phosphotodithioate) and the corresponding di - n - propyl, bis (a  - chloroethyl), di - n - butyl and diisopropyl homologues, these products being obtained by reacting dichloro - 1,4,5,8 - tetraoxaoctahydronaphthalene with the appropriate O,O-dialkyl (or chloroalkyl)-dithio phosphoric acid in the presence of pyridine and benzene.  Other products of the above general formula which may be prepared are also mentioned including compounds in which R is a -bromoethyl, a -bromopropyl, a -fluoropropyl and fluorobutyl and compounds in which R1 is nitrochloropropyl, 2-trichloromethyl 2-nitroethyl, and nitroisobutyl.  The products of the above general formula in which m = 2 and n = 2 may be prepared by reacting a 2,3-dialkoxy - 5,6 - dichloro (or dibromo) - p - dioxane with the desired ester of dithiophosphoric acid and the products in which m = 1 and n = 1 may be obtained by reacting 2,3-dichloro (or dibromo) - p - dioxane with an alcohol R1OH, which may be used in the form of its sodium or potassium salt, to produce the corresponding 2-halodioxane substituted in the 3-position with an R1O group and then reacting this intermediate with the desired diester of dithiophosphoric acid. The dithiophosphate products are stated to be valuable pesticides (see Group VI).  The dithiophosphoric acid esters used as starting materials may be obtained by reacting the appropriate aliphatic alcohol with P2S5 preferably in an inert solvent such as benzene, toluene, xylene, hexane or cyclohexane and at a temperature between 50 DEG  and 120 DEG  C. and if desired a mixture of such alcohols may be used.  Specified alcohols which may be reacted in this manner include methyl, ethyl, isopropyl, n-propyl, n-butyl, sec.-butyl, isobutyl, a -chloroethyl- and a -trichloroethyl alcohols.  The 2,3-dialkoxy-p-dioxanes used to produce starting materials from which the products in which m = 2 and n = 2 are formed may be obtained by reacting 2,3-dichlorodioxane with an alcohol R1OH or the corresponding alkali or alkaline earth metal alkoxide and are converted to the 2,3 - dialkoxy - 5,6 - dichloro - p - dioxane by chlorination with chlorine gas, if desired in the presence of a solvent such as chloroform, carbon tetrachloride, nitrobenzene or pentachlorethane.  The 2,3-diethoxy-p-dioxane used to prepare the starting material in Example (19) is obtained by refluxing a solution of 2,3-dichloro-p-dioxane in toluene and anhydrous ethanol at 80 DEG C. and is then treated with chlorine gas in the presence of ultraviolet light and of carbon tetrachloride as solvent to form 2, 3-diethoxydichloro-p-dioxane. 2-Chloro-2-(2,2,2-trichloroethyoxy)-p-dioxane used in Example (28) is obtained by refluxing a solution of 2,3-dichloro-p-dioxane and 2,2,2-trichlorethanol in toluene at about 110 DEG  C. for about 30 hours. Dichloro-1,4,5,8-tetraoxaoctahydronaphthalene used in Example (33) is obtained by passing chlorine gas into a solution of 1,4,5,8-tetraoxaoctahydronaphthalene in carbon tetrachloride in the presence of ultraviolet light.ALSO:A pesticidal composition comprises an insecticidal adjuvant and a compound of the general formula <FORM:0785990/VI/1> wherein m=0, 1, or 2 and n=1 or 2, R=lower alkyl or halo lower alkyl, the lower alkyl radical containing 1 to 4 carbon atoms, R1= alkyl, haloalkyl, nitroalkyl, or halonitroalkyl, or when m=2 and n=2, the two R1 groups may together constitute -CH2-CH2-, with the added provisos that when m=0 and n=2 the points of substitution are 2, 3 or 2, 5; when m=1, n also =1 and the substituent groups are on adjacent carbon atoms and when m=2, n also = 2 and like substituents are on adjacent carbon atoms (see Group IV (b)).  Other pesticidal agents may be present, e.g. toxaphene, D.D.T., thanite, chlordane, rotenone or pyrethrin.  The compositions may comprise the dithiophosphate compound diluted with a solid carrier or dispersed in water or an organic solvent, e.g. an alcohol, pine oil or a hydrocarbon e.g. kerosene or a mineral oil and a surface-active dispersing agent may be present.  They may also be formulated as aerosols, in which difluorodichloromethane may form the propellant vehicle. Suitable surface active dispersing agents for use in the compositions include neutral soaps of resin, alginic and fatty acids with alkali metals, alkyl amines, or ammonia; saponins, gelatins, milk, soluble casein, flour and soluble proteins thereof, sulphite lye, lignin pitch, sulphite liquor, long-chain fatty alcohols having 12-18 carbon atoms and alkali metal salts of the sulphates thereof, salts of sulphated fatty acids, salts of sulphonic acids, esters of long-chain fatty acids and polyhydric alcohols containing free alcohol groups, clays, omega-substituted long-chain polyethylene glycols, especially those in which the omega substituent is aryl, alkyl, or acyl.  Synergists and/or adhesive or sticking agents may also be present.  Examples are given to show the pesticidal effects of compositions comprising the following compounds mixed with benzene and a sorbitan monolaurate polyoxyalkylene derivative and then diluted with water; (1) to (5) 2,3-p-di-oxanedithiol S,S - bis(O,O - diethylphosphorodithioate) and its diisopropyl, di-n-propyl, di-sec.-butyl and dimethyl homologues; (6) to (10) 2,5 - p - dioxanedithiol S,S - bis(O,O - diethyl phosphorodithioate) and its diisopropyl, di-n-propyl di-sec.-butyl and dimethyl homologues; (11) 2,3-p-dioxane dithiol S,S-bis(O,O-bis(2-chloroethyl) phosphorodithioate); (12) and (13) bis(bis(b  - trichloroethyl) dithiophosphate) of p-dioxane-2,3-dithiol and the corresponding bis-(fluoroethyl) compound; (14) to (18) 2-p-dioxanethiol S-(O,O-diethyl phosphoro dithioate), and its diisopropyl, di-n-propyl, di-sec.-butyl and dimethyl homologues; (19) to (27) 2,3 - diethoxy -