Patent GB-767950-A (GB)
Title: Manufacture of organic compounds containing phosphorus
Filed: 1953-08-20
Abstract: The invention comprises phosphorus compounds of the formula <FORM:0767950/IV(b)/1> in which R, R1, R9 and R10 each represent an alkyl, alkenyl, cycloalkyl, aralkyl, aryl or heterocyclic residue which may contain substituents, and R and R1 on the one hand (when X and Y each represent -O-), and R9 and R10 on the other may form part of a ring system, R2 to R8 each represent hydrogen or an alkyl residue, X and Y each represent -O-, -S-, -NH-, or -NR1-; Z, Z1, Z2 and Z3 each represent oxygen or sulphur, at least one of the Z's being sulphur, and the indices n, n1 and n2, each represent zero or a small whole number from 1 to 4, provided that when n is zero at least n1 or n2 is other than zero.  Such compounds are obtained by reacting a compound of the formula <FORM:0767950/IV(b)/2> with a compound of the formula <FORM:0767950/IV(b)/3> where Hal represents a halogen atom, advantageously chlorine, and Me represents a metal, advantageously an alkali metal.  Aliphatic residues which R to R10 may represent include methyl, ethyl, propyl, isopropyl, butyl, hexyl, 2-ethylbutyl, octyl, 2-butyl-octyl, dodecyl, octadecyl, allyl and 2-chlorethyl groups, and also radicals containing thiocyano, cyano or ester groups.  R, R1, R9 and R10 may also represent mono- or polynuclear aromatic radicals such as phenyl, 2- or 4-chlorophenyl, 2 : 4 - dichlorophenyl, 4 - methoxyphenyl, 4-nitrophenyl, naphthyl and 4-diphenylyl radicals, araliphatic radicals such as benzyl, cycloaliphatic radicals such as cyclohexyl and heterocyclic radicals such as tetrahydrofurfuryl. As starting materials of the third formula above may be used b -mercapto-acetaldehydediethyl acetate, 2 - hydroxypropane - dithiol-(1 : 3)-dimethyl ether-(1 : 3), propane-trithiol - (1 : 2 : 3) - dimethyl ether - (1 : 3), (g -mercapto - propylene) - isopropylidene dioxide and di-thia-cyclohexanol.  The products may be used in pesticides (see Group VI).  In Example (1) (g -mercaptopropylene)-isopropylidene dioxide and diethyl chloro-thiophosphate are reacted in the presence of sodium to give a product of the formula <FORM:0767950/IV(b)/4> Similarly reacted are (2) (g -mercaptopropylene) - isopropylene dioxide and diethyl chlorophosphate, (3) and (6) b -mercapto-acetaldehyde diethyl acetal and diethyl chlorophosphate; (4) and (5) propane-tri-thiol-(1 : 2 : 3)-dimethyl ether-(1 : 3) and (4) diethyl chlorophosphate; and (5) diethyl chloro-thiophosphate; (7) 2-hydroxy - propane - diethol - (1 : 3) - dimethyl ether-(1 : 3) and diethyl-chloro-thiophosphate; (9) diphenyl chlorophosphate and 2-hydroxypropane dithiol-(1 : 3)-dimethyl ether-(1 : 3); (10) propane - tri - thiol - (1 : 2 : 3) - dimethyl ether - (1 : 3) and tetramethyl - diaminochlorophosphate, the product having the formula <FORM:0767950/IV(b)/5> (11) ethylene chlorothiophosphate (prepared by reacting sulphur with ethylene-chlorophosphite) and (g  - mercapto propylene) - isopropylidene dioxide; and (12) 2-hydroxypropane - dithiol - (1 : 3) - dimethyl ether-(1 : 3) and 1 : 2 - propylenechlorothiophosphate, the product being of the formula <FORM:0767950/IV(b)/6>ALSO:A pesticidal composition comprises a compound of the formula <FORM:0767950/VI/1> in which R, R1, R9 and R10 each represent an alkyl, alkenyl, cycloalkyl, aralkyl, aryl or heterocyclic residue which may contain substituents and R and R1 on the one hand (when X and Y each represent -O-), and R9 and R10 on the other may form part of a ring system; R2 to R8 each represent hydrogen or an alkyl residue; X and Y each represent -O-, -S-, -NH- or -NR1-; Z, Z1, Z2 and Z3 each represent oxygen or sulphur, at least one of the Z's being sulphur; and n, n1 and n2 each represent zero or a small whole number from 1 to 4, provided that when n is zero at least n1 or n2 is other than zero, together with a liquid or solid diluent.  Aliphatic radicals which R to R10 may represent include methyl, ethyl, propyl, isopropyl, butyl, hexyl, 2 - ethylbutyl, octyl, 2 - butyloctyl, dodecyl, octodecyl, allyl and 2 - chlorethyl groups and also radicals containing thiocyano, cyano or ester groups R, R1, R9, and R10 may also represent aromatic radicals such as phenyl, 2 - or 4 - chlorophenyl, 2:4 - dichlorophenyl, 4 - methoxyphenyl, 4 - nitrophenyl, naphthyl and 4 - diphenylyl radicals, araliphatic radicals such as benzyl, cycloaliphatic radicals such as cyclohexyl, and heterocyclic radicals such as tetrahydrofurfuryl. The compounds can be prepared as emulsions or solutions in water, alcohol, petroleum or a tar distillate. Other diluents mentioned are kaolin, gypsum, bentonite, sulphite cellulose waste liquor, cellulose derivatives and other insecticides and fungicides may be added.  In example (8) a compound of the formula <FORM:0767950/VI/2> is dissolved in diethylene diglycol and emulsified in water.