Patent GB-712795-A (GB)
Title: Mixed phosphoric and thiophosphoric acid anhydrides and their preparation
IPC: C10L1/26
Filed: 1952-06-17
Abstract: The invention comprises mixed acid anhydrides of formula <FORM:0712795/IV (b)/1> where <FORM:0712795/IV (b)/2> is the acyl residue of an aromatic monocarboxylic acid, -O-R11 is the residue of an aliphatic monohydric alcohol R11OH, m is 1, 2 or 3 and n is 3 - m, and of formula <FORM:0712795/IV (b)/3> where <FORM:0712795/IV (b)/4> is the residue of an organic amine <FORM:0712795/IV (b)/5> -O-R1 is the residue of an alcohol or phenol R1OH, X is O or S, m is 1, 2 or 3 and n is 3 - m.  They may be made, with other mixed anhydrides, by heating a neutral ester of phosphoric or thiophosphoric acid with an acid halide of a dissimilar acid to form one or more mixed acid anhydrides containing an acyl group of each reactant.  Thus triethyl phosphate with dimethylcarbamyl chloride yields the mixed anhydride of dimethylcarbamic acid and diethyl phosphoric acid.  Up to three of the valencies of the phosphoryl or thiophosphoryl radicle may be satisfied by the acyl group of the dissimilar acid.  The acid halides used are those of oxy-acids of polyvalent oxide-forming non-metallic elements other than phosphorus and analogues of such oxy-acids wherein the oxygen is replaced by sulphur.  Catalysts and solvents or diluents may be present.  Advantageously the organic halide is separated from the reaction mixture during the course of the reaction.  The product may be recovered by distillation, selective solvents or adsorption but when used in pesticides, c.f. Group VI, isolation may not be necessary.  Preferred temperatures of reaction are about 75-250 DEG  C., especially about 100-175 DEG  C.  When the desired anhydride contains one anhydro-grouping and two acyl groups (one from each acid) the amount of acid halide is desirably about 0.1-about 1.5 mols., preferably about 0.2-1 mol., per mol. of ester. When the anhydride contains two or three acyl groups of the dissimilar acid proportionately larger amounts of acid halide are used, e.g. 5, 10, 15 or more mols. of halide per mol. of ester. Reaction may be effected under substantially anhydrous conditions under pressure especially when the reaction temperature is above the atmospheric boiling-point of a reactant.  Catalysts mentioned are mineral and organic acids, representative of those specified being sulphuric, hydrobromic, arsenic, salicylic, p-toluenesulphonic, and formic acids, strong acids being preferred, and bases, other than those which combine with acid halides to form salts or amides, representative of those specified being triethylamine, N,N - dimethylaniline, pyridine and benzyltrimethylammonium salts. Catalyst concentrations of about 0.001-about 5 per cent are mentioned.  In examples: triethyl phosphate is reacted with (1), (2), (3) and (4) benzoyl chloride to yield the corresponding mixed anhydrides; (3) showing the use of triethylamine and p-toluenesulphonic acid as catalysts; and in (5) with phenylacetyl chloride to yield the mixed anhydride of phenylacetic acid and diethyl phosphoric acid and lesser amounts of the mixed anhydride of phenylacetic acid, ethyl phosphoric acid and phosphoric acid; in (6) trimethyl and (7) tributyl phosphate are reacted with benzoyl chloride to yield the corresponding mixed anhydrides; in (8) acetyl chloride, (9) propionyl chloride, (10) furoyl chloride, (11) dimethylcarbamyl chloride, (12) diethylthiocarbamyl chloride, (13) methanesulphonyl chloride and (14) chloroacetyl chloride are reacted with triethyl phosphate to yield the corresponding mixed anhydrides.  Representative of many other mixed anhydrides specified are those obtained from p-toluic acid and dibutylphosphoric acid, p-nitrobenzoic acid and monoisopropyl phosphoric acid, p-chloro-m-methyl benzoic acid and di-2-cyanoethyl phosphoric acid, o-carbethoxybenzoic acid and di-2-isothiocyanoethyl phosphoric acid, p - tert. - butylbenzoic acid and diallyl phosphoric acid, p-allylbenzoic acid and diethyl phosphoric acid, pyridine N-carboxylic acid and butyl phosphoric acid, bis (p-chlorophenyl) carbamic acid and dimethyl phosphoric acid, 4-chlorobutyl N - (3 - chloroallyl) - isopropyl - carbamic acid and diethyl phosphoric acid, ditetrahydrofurfurylcarbamic acid and dipropyl phosphoric acid, dicyclohexylcarbamic acid and dimethyl phosphoric acid and diethylthiocarbamic acid and p-nitrophenyl phosphoric acid.  A large number of acid halides are specified for reaction with the triesters, representative being acetyl, pelargonyl, stearyl, methacrylyl, tetrolyl, oleyl, naphthoyl, cinnamyl, methylcarbamyl, diallylcarbamyl, N-piperidinecarbonyl, dimethylcyclopentanecarbonyl, adipyl, phthallyl, thioacetyl, 2,3 - dichlorothiobutyryl, p - nitrophenylthioacetyl, benzene sulphonyl and benzene sulphinyl chlorides and the seleno, telluro, borono, silico and arseno analogues of the sulphonic and sulphinic halides, p-chloroformylbenzoic acid, phosgene and propyl and phenyl chloroformate.  Preferred acid halides are those derived from carboxylic acids.  The halides may contain inert substituents such as cyano, nitro, mercapto, halogen, e.g. Cl, Br or F, ether, ester, thioether or ketonic groups.  Chlorides and bromides are preferred halides although iodide and fluorides may be used.  A large number of triesters are specified, representative being tris(2-chloroethyl), tris (2-ethoxyethyl), tris (3,5,5-trimethylhexyl), diethyl cyanoethyl, tricresyl, diethyl phenyl, dinaphthyl butyl, tris (p-nitrophenyl) and bis (p-carbethoxyphenyl) ethyl phosphates, tripropyl and triphenyl thiophosphate, lower trialkyl esters being preferred.  The triesters may contain inert substituents such as cyano, halogen, alkoxy, carboalkoxy, isocyano or mercapto radicles, but are preferably of unsubstituted lower aliphatic alcohols.ALSO:Mixed anhydrides of formula <FORM:0712795/III/1> where <FORM:0712795/III/2> is the acyl residue of an aromatic monocarboxylic acid, -O-R11 is the residue of an aliphatic alcohol R11OH, m is 1, 2 or 3 and n is 3-m and of formula <FORM:0712795/III/3> where <FORM:0712795/III/4> is the residue of an organic amine <FORM:0712795/III/5> , -O-R1 is the residue of an alcohol or phenol R1OH, X is O or S, m is 1, 2 or 3 and n is 3-m, together with other mixed anhydrides obtained by heating a neutral ester of phosphoric or thio-phosphoric acid with an acid halide of a dissimilar acid and conforming to the formula <FORM:0712795/III/6> where R is the acyl group of the dissimilar acid.  R1 is the ester residue of the phosphoric or thiophosphoric acid ester, X is O or S, x is 1, 2 or 3 and x+y=3 are additives for gasolines and other fuels. Representative of many anhydrides mentioned are those obtained from triethyl phosphate and benzoic, acetic, furoic, dimethylcarbamic, methane sulphonic and chloroacetic acids, phenylacetic and diethyl phosphoric acids, p-nitrobenzoic and monoisopropyl phosphoric acids, p-chloro-m-methyl-benzoic and di-2-cyanoethyl phosphoric acids, #s-carbethoxybenzoic and di-2-isothiocyanoethyl phosphoric acids, p-tert-butylbenzoic and diallyl phosphoric acids, pyridine N-carboxylic and butyl phosphoric acids, ditetrahydrofurfurylcarbamic and dipropyl phosphoric acids and dicyclohexylcarbamic and dimethyl phosphoric acids.ALSO:Mixed anhydrieds of formula <FORM:0712795/VI/1> where R1-C- is the aryl residue of an aromatic monocarboxylic aid, -O-R11 is the residue of an aliphatic alcohol R11OH, m is 1, 2 or 3 and n is 3-m and of formula <FORM:0712795/VI/2> where <FORM:0712795/VI/3> is the residue of an organic amine <FORM:0712795/VI/4> , -O-R1 is the residue of an alcohol or phenol R1OH, X is O or S, m is 1, 2 or 3 and n is 3-m, are used in pesticidal compositions.  They may be applied with liquid or finely divided solid diluents and in conjunction with known pesticides. Representative of many anhydrides mentioned are those obtained from triethyl phosphate and benzoic, acetic, furoic, dimethyl-carbamic, methane sulphonic and chloroacetic acids, phenylacetic and diethyl phosphoric acids, p-nitrobenzoic and monoisopropyl phosphoric acids, p-chloro-m-methyl-benzoic and di-2-cyanoethyl phosphoric acids, p-tert-butyl-benzoic and diallyl phosphoric acids, d -carbethoxybenzoic and di-2-isothiocyanoethyl phosphoric acids, pyridine-N-carboxylic and butyl phosphoric aids, ditetrahydrofurfurylcarbamic and dipropyl phosphoric acids, diethylthiocarbmic acid and diethyl phosphoric and ethyl phosphoric acids and dicyclohexylcarbamic and dimethyl phosphoric acids.  The compounds are used in diluent oils in amounts of 0.1 to 1 weight per cent and illustrations are provided showing the use of such sprays containing mixed anhydrides of acetic and diethyl phosphoric aids, acetic and dibutyl phosphoric acids and dimethylcarbamine and diethylphosphoric acids upon plants with pea aphid and milkweed bug.