Patent GB-663270-A (GB)
Title: Improvements relating to the preparation of phosphate esters
IPC: C07F9/09
Filed: 1949-01-27
Abstract: A phosphate ester of the general formula <FORM:0663270/IV (b)/1> in which R1 and R2 are alkyl, (including unsaturated or cycloaliphatic), or aralkyl or aryl radicals which may be nitro- or halogen-substituted, R3 and R4 are hydrogen or alkyl, hydroxyalkyl, aryl or nitroaryl radicals, X1, X2, and X3 are sulphur or oxygen and m is 1 to 4 inclusive, is prepared when X3 is oxygen by reacting a halogen substituted amide <FORM:0663270/IV (b)/2> where Z is chlorine or bromine with a phosphate of the general formula <FORM:0663270/IV (b)/3> in which Y is an equivalent of an alkali-forming metal (or ammonia); or alternatively by employing the corresponding acid phosphate (Y=H) in the presence of sufficient basic alkali-forming metal or ammonium compound to neutralize the acid phosphate. Compounds of the above general formula in which X3 represents sulphur are prepared by reacting a compound R3R4.S with a cyanoalkyl phosphate <FORM:0663270/IV (b)/4> Examples of R1 and R2 are methyl, ethyl, n-propyl, isopropyl, isobutyl, sec.-amyl, n-hexyl, 2-ethylhexyl, n-octyl, n-decyl, n-dodecyl, oleyl, cetyl, ceryl, allyl, bromomethyl, 2-chloroethyl, cyclohexyl, benzyl, phenyl, p-chlorphenyl and o-, m-, and p-nitrophenyl.  The products are used as pesticides, corrosion inhibitors, plasticizers, flotation agents and petroleum additives.  Suitable basic alkaliforming metal compounds are sodium, potassium, barium, magnesium or lithium carbonates, sodium, potassium, calcium, strontium or magnesium hydroxides, sodium hydrosulphide, sodium borate, tripotassium arsenate or arsenite, sodium, magnesium or potassium pyrophosphate, barium phosphate and trisodium phosphate.ALSO:As petroleum additives there are specified compounds of the general formula <FORM:0663270/III/1> in which R1 and R2 are alkyl, aralkyl or aryl radicals, which may carry nitro or halogen substituents, R3 and R4 are hydrogen or alkyl, hydroxyalkyl, aryl, or nitroaryl radicals, X1, X2, and X3 are sulphur or oxygen and m is 1 to 4 inclusive.  R1 and R2 may be methyl, ethyl, n-propyl, isopropyl, isobutyl, sec amyl, n-hexyl, 2-ethylhexyl, n-octyl, n-decyl, n-dodecyl, oleyl, cetyl, ceryl, allyl, bromomethyl, 2-chloroethyl, cyclohexyl, benzyl, phenyl, p-chlorophenyl or o-, m- or p-nitrophenyl.  The preparation of the above compounds is described (see Group IV(b)).  Products obtained include (1) S-carbamylmethyl O, O-diethyl dithiophosphate, (2) and (5) O, O-diethyl S-(N-phenylcarbamyl) methyl or ethyl dithiophosphate, (3) O, O-diethyl S-(N-p-nitrophenyl carbamyl) methyl dithiophosphate, (4) S-2-carbamylethyl O, O-diethyl dithiophosphate, (6) O, O-diethyl S-(N-hydroxymethyl) carbamylmethyl dithiophosphate, (7), (8) S-carbamylmethyl O, O-dimethyl or diethyl dithiophosphate, (9) and (10) O, O-di-n-butyl or diphenyl S-carbamylmethyl dithiophosphate, (11) S-(N-butylcarbamyl) methyl O, O-diethyl dithiophosphate, (12) carbamylmethyl diethyl phosphate, (13) S-carbamylmethyl O, O-diethylthiophosphate, (14) O, O-diethyl S-thiocarbamylmethyl dithiophosphate.ALSO:As flotation agents are specified compounds of the general formula <FORM:0663270/II/1> in which R1 and R2 are alkyl, aralkyl or aryl radicals, which may carry nitro or halogen substituents, R3 and R4 are hydrogen or alkyl, hydroxyalkyl, aryl or nitroaryl radicals, X1, X2 and X3 are sulphur or oxygen and m is 1 to 4 inclusive.  R1 and R2 may be methyl, ethyl, n-propyl, isopropyl, isobutyl, sec amyl, n-hexyl, 2-ethylhexyl, n-octyl, n-decyl, n-doderyl, oleyl, cetyl, ceryl, allyl, bromomethyl, 2-chloroethyl, cyclohexyl, benzyl, phenyl, p-chlorophenyl, or o-, m-, or p-nitrophenyl.  The preparation of such compounds is described (see Groub IVb).  Products obtained include (1) S-carbamyl-methyl O, O-diethyl dithiophosphate, (2) and (5), O, O-diethyl S-(N-phenylcarbamyl) methyl or ethyl dithiophosphate, (3) O, O-diethyl S- (N-p-nitrophenylcarbamyl) methyl dithiophosphate, (4) S-2-carbamylethyl O, O-diethyl dithiophosphate, (6) O, O-diethyl S-(N-hydroxymethyl) carbamylmethyl dithiophosphate, (7), (8), S-carbamethyl O, O-dimethyl or diethyl dithiophosphate, (9) and (10), O, O-di-n-butyl or diphenyl S-carbamylmethyl dithiophosphate, (11) S-(N-butylcarbamyl) methyl, O, O-diethyl dithiophosphate, (12) carbamylmethyl diethyl phosphate, (13) S-carbamylmethyl O, O-diethylthiophosphate, (14) O, O-diethyl S-thiocarbamylmethyl dithiophosphate.