Patent GB-713757-A (GB)
Title: Production of new esters of phosphoric acid
Inventor: ZENFTMAN HENRYK
IPC: C07F9/12
Filed: 1951-06-18
Abstract: The invention comprises p-tertiary-octyl-aryl esters of phosphoric acid of the general formula <FORM:0713757/IV (b)/1> wherein X is an optional alkyl substituent and R1 and R2 are primary alkyl radicals of which one contains from 4 to 12 carbon atoms and the other contains from 1 to 12 carbon atoms.  Such esters are produced by treating at a reaction temperature a p-tertiary-octyl-aryloxy phosphoryl dihalide containing only carbon and hydrogen in its aryl group with sufficient of a primary monohydric aliphatic alcohol containing from 4 to 12 carbon atoms in its molecule to replace one of the halogen atoms with the corresponding primary alkoxyl radical and treating the resulting organic phosphoryl monohalide formed as an intermediate product with sufficient of a primary monohydric alcohol having from 1 to 12 carbon atoms in its molecule to replace the remaining halogen atom present in said intermediate product with the respective corresponding primary alkoxyl radical and removing the hydrogen halide formed in the successive stages of the reaction.  The reaction with the first alcohol may be effected at above 40 DEG  C., and the intermediate product treated at p  below 10 DEG  C. with an excess of a primary monohydric alcohol having 1 to 3 carbon atoms in the molecule, hydrogen halide being removed at each stage.  To produce products having two identical primary alkoxyl radicals the p-tertiary-octyl-aryloxy-phosphoryl dihalide is reacted in a single stage with at least sufficient of the monohydric alcohol to react with both halogen atoms of the phosphoryl halide.  Any hydrogen halide left in the final product may be removed by washing with water.  Specified as alcohols containing 4 to 12 carbon atoms are butyl, isobutyl, amyl, hexyl, octyl, nonyl, decyl and lauryl alcohols.  The reaction may be carried out in the presence of a hydrogen halide acceptor, e.g. a tertiary amine such as pyridine or dimethylaniline. #c-Tertiary-octylphenoxy-phosphosphoryl dichloride and p-tertiary - octyl - cresoxy - phosphoryl dichloride are the preferred dihalides.  Impurity in the product may be the corresponding secondary esters, containing one alkoxy group and one hydroxy group in place of halogen.  Such compounds may be removed by conversion to salts and washing out with water.  In examples (1) butyl alcohol and p-tertiary-octylphenoxy-phosphoryl dichloride are reacted to give dibutyl p-tertiary-octyl-phenyl phosphate; (2) p-tertiary octyl-phenoxy-phosphoryl chloride is reacted with butyl alcohol at 90-95 DEG  C. and the product is reacted at 5 DEG  C. with ethanol to give ethyl butyl p-tertiary-octyl-phenyl phosphate; (3) p-tertiary-octyl-phenoxy-phosphoryl dichloride is reacted at 4 DEG to 6 DEG  C. with isobutyl alcohol; hydrogen chloride is removed by heating the di-isobutyl p-tertiary octylphenyl phosphate produced; di-n-octyl-p-tertiary-octyl-phenyl phosphate is produced by reacting n-octyl alcohol and p-tertiary-octylphenoxy-phosphoryl dichloride. The products are of use as additives for lubricating oils and also in such compositions as those described in Specification 713,758, [Group XXI].ALSO:p-Tertiory-octyl-aryl esters of the general formula <FORM:0713757/III/1> wherein X is an optional alkyl substituent and R1 and R2 are primary alkyl radicals of which one contains from 4 to 12 carbon atoms and the other contains from 1 to 12 carbon atoms are useful in improving the lubricating properties of oils under extreme pressure or high temperaconditions and also reduce corrosion of the metals at the working surfaces.  Liquid paraffin containing about 3 per cent. of such esters may be used to lubricate mild steel plates. The preparation of such compounds is described (see Group IV (b). Examples of products with butylisobutyl and n-octyl radicals at R1 and/or R2 are given.