Patent GB-470328-A (GB)
Title: Manufacture of esters of ortho-phosphoric acid
IPC: C07F9/08
Filed: 1935-11-08
Abstract: Neutral mixed esters or mixtures of neutral esters of orthophosphoric acid are made by reacting a phosphorus pentahalide or oxyhalide or phosphorus pentoxide with at least two primary monohydric straight-chain alcohols or alcoholates, or with at least one such alcohol or alcoholate and with a phenol, the alcohol or alcoholate (when only one is taken), or at least one of the alcohols or alcoholates (when more than one is taken), containing at least eight carbon atoms, and the proportions of the reagents being such that neutral orthophosphoric esters are obtained.  A suitable alcohol mixture is that obtained by reducing a fatty oil such as coconut oil. The process may be effected in a single operation, or the phosphoric acid derivative taken as starting material may be esterified in stages.  When phosphorus oxychloride is taken, the reaction may be effected by adding the liquid or vaporized oxychloride to a solution of the alcohols in benzene, toluene, chloroform or like solvent at 0--100 DEG  C., preferably at 0--30 DEG  C., the mixture being then kept under reduced pressure, to eliminate hydrogen chloride; powdered copper or a metal chloride may be present, as a catalyst.  When phosphorus pentoxide is taken, the reaction may be effected in ether or in pyridine or other tertiary base.  In an example, lauryl alcohol is treated with dicresyl phosphoryl chloride to yield dicresyl-lauryl phosphate.  Other mixed esters specified as obtainable are hexyl-laurylstearyl phosphate, dilauryl-ethyl phosphate, myristy-octyl-cresyl phosphate, butyl-nonyloleyl phosphate, di-eleostearyl-decyl phosphate and diricinoleyl-decyl phosphate. An alternative process for producing products of the same kind comprises the treatment of silver orthophosphate with a mixture of straight-chain alkyl halides, one at least of which contains at least eight carbon atoms, in a proportion sufficient to yield neutral orthophosphoric esters.  The products are useful as plasticizers for cellulose ester and ether compositions, particularly for coating compositions for use on wood, metal, cloth or paper.  The Specification as open to inspection under Sect. 91 refers generally to the manufacture of mixed neutral or acid esters of the acids of phosphorus, the esters containing at least one alkyl group of at least eight carbon atoms and at least one other alkyl group or a phenol residue.  The manufacture of esters of metaphosphoric, pyrophosphoric, phosphorous and hypophosphorous acids and of mixtures of phosphorus acids is referred to.  The esters may be prepared by reacting appropriate alcohols, with or without a phenol, with the chloride or anhydride of the acid, the reaction being effected in one operation or in stages.  The alcohols may be replaced by the corresponding alcoholates.  Mixed esters of pyroor meta-phosphoric acid may also be obtained by treating silver pyro- or meta-phosphate with mixed alkyl halides, one at least of which contains at least eight carbon atoms. Neutral esters obtained as described above may be converted into acid esters by heating them with acids, or into salts of acid esters by heating them with aqueous caustic soda.  The following examples are given: (1) a mixture of lauryl and myristyl alcohols is treated with phosphorus oxychloride to yield a mixture of dialkyl orthophosphates; (2) a mixture of lauryl alcohol, myristyl alcohol, and alcohols obtained by hydrogenating sperm oil is treated with phosphorus oxychloride to yield a mixture of mixed esters; (3) a mixture of octyl, decyl and lauryl alcohols, obtained by fractionating the alcohol mixture resulting from the hydrogenation of coconut oil or its acids, is treated with phosphorus oxychloride to yield a mixture of dialkyl orthophosphates; (4) a water-washed alcohol mixture, obtained by hydrogenating coconut oil, is treated with phosphorus oxychloride.  Other products stated to be obtainable are sodium ethyl-lauryl phosphate, oleyl - lauryl phosphate, octyl - lauryl - stearyl phosphite, lauryl-myristyl hypophosphite, undecyl-myristyl-heptadecyl acid pyrophosphate, and the esters of metaphosphoric acid with the alcohols from coconut oil.  The acid esters obtainable as described above, and their alkali, ammonia and amine salts, triethanolamine and methylglucamine salts being specified, are useful as wetting agents, detergents, and textile lubricants.  The acid phosphates are useful also as additions to lubricating oils, and their cobalt and manganese salts are useful as catalysts for the oxidation of drying oils.  The iron, nickel, cobalt and manganese salts of the acid esters retard the absorption of ultra-violet light by nitrocellulose films, and their lead salts are of pharmaceutical value.  The sodium salts of the esters are useful for emulsifying oils or higher alcohols in water.  This subject-matter does not appear in the Specification as accepted.ALSO:Neutral mixed esters or mixtures of neutral esters of orthophosphoric acid are made by reacting a phosphorus pentahalide or oxyhalide or phosphorus pentoxide with at least two primary monohydric straight-chain alcohols or alcoholates, or with at least one such alcohol or alcoholate and with a phenol, the alcohol or alcoholate (when only one is taken), or at least one of the alcohols or alcoholates (when more than one is taken), containing at least eight carbon atoms, and the proportions of the reagents being such that neutral orthophosphoric esters are obtained.  A suitable alcohol mixture is that obtained by reducing a fatty oil such as coconut oil. The process may be effected in a single operation, or the phosphoric acid derivative taken as starting material may be esterified in stages.  In an example, lauryl alcohol is treated with dicresyl phosphoryl chloride to yield dicresyl-lauryl phosphate.  Other mixed esters specified as obtainable are hexyl-lauryl-stearyl phosphate, dilauryl-ethyl phosphate, myristyl-octyl-cresyl phosphate, butyl-nonyl-oleyl phosphate, dieleostearyl-decyl phosphate, and diricinoleyldecyl phosphate.  An alternative process for producing products of the same kind comprises the treatment of silver orthophosphate with a mixture of straight-chain alkyl halides, one at least of which contains at least eight carbon atoms, in a proportion sufficient to yield neutral orthophosphoric esters.  The products are useful as plasticizers for cellulose ester and ether compositions, particularly for coating compositions for use on wood, metal, cloth or paper.  The Specification as open to inspection under Sect. 91 refers generally to the manufacture of mixed neutral or acid esters of the acids of phosphorus, the esters containing at least one alkyl group of at least eight carbon atoms and at least one other alkyl group or a phenol residue.  The manufacture of esters of metaphosphoric, pyrophosphoric, phosphorous and hypophosphorous acids and of mixtures of phosphorus acids is referred to.  The esters may be prepared by reacting appropriate alcohols, with or without a phenol, with the chloride or anhydride of the acid, the reaction being effected in one operation or in stages.  The alcohols may be replaced by the corresponding alcoholates.  Mixed esters of pyro- or metaphosphoric acid may also be obtained by treating silver pyro- or metaphosphate with mixed alkyl halides, one at least of which contains at least eight carbon atoms. Neutral esters obtained as described above may be converted into acid esters by heating them with acids, or into salts of acid esters by heating them with aqueous caustic soda.  The following examples are given: (1) a mixture of lauryl and myristyl alcohols is treated with phosphorus oxychloride to yield a mixture of dialkyl orthophosphates; (2) a mixture of lauryl alcohol, myristyl alcohol, and alcohols obtained by hydrogenating sperm oil is treated with phosphorus oxychloride to yield a mixture of mixed esters; (3) a mixture of octyl, decyl and lauryl alcohols is treated with phosphorus oxychloride to yield a mixture of dialkyl orthophosphates; (4) an alcohol mixture, obtained by hydrogenating coconut oil, is treated with phosphorus oxychloride. Other products stated to be obtainable are sodium ethyl-lauryl phosphate, oleyl-lauryl phosphate, octyl-lauryl-stearyl phosphite, lauryl-myristyl hypophosphite, undecyl-myristyl-heptadecyl acid pyrophosphate, and the esters of metaphosphoric acid with the alcohols from coconut oil.  The acid esters obtainable as described above, and their alkali, ammonia and amine salts, triethanolamine and methylglucamine salts being specified, are useful as detergents and textile lubricants.  The acid phosphates are useful also as additions to lubricating oils, and their cobalt and manganese salts are useful as catalysts for the oxidation of drying oils.  Their iron, nickel, cobalt and manganese salts retard the absorption of ultra-violet light by nitrocellulose films, and their sodium salts are useful for emulsifying oils or higher alcohols in water.  This subject-matter does not appear in the Specification as accepted.