Patent GB-942943-A (GB)
Title: Improvements in or relating to the production of pyrophosphoric acid esters
IPC: C07H19/16
Filed: 1960-04-19
Abstract: Esters of pyrophosphoric acid are obtained by reacting an acid ester of phosphoric acid having the formula: HO-P(O)(OR1)OR2 wherein R1 is an ester-forming organic group and R2 is an ester-forming organic group or a hydrogen atom with a carbamyl phosphate having the formula: R3O.P.(O)(OR5).O.C(O)NHR4 wherein R3 is a hydrogen atom, a positive ion derived from a base or an ester-forming organic group, R4 is an organic group attached to the nitrogen atom through a carbon atom of said group and R5 is a hydrogen atom or a positive ion derived from a base. The ester-forming organic groups may be alkyl, aryl, aralkyl or alkaryl groups, e.g. butyl, phenyl or benzyl. The process is preferably carried out with the exclusion of moisture and at a temperature below 50 DEG C. The reaction may advantageously be carried out in a medium containing pyridine. The process is suitable for the production of symmetrical or asymmetric pyrophosphoric acid esters and the products may suitably be isolated by precipitating them in the form of their salts, preferably lithium salts, and the lithium salts may be converted into other salts, e.g. the cyclohexyl-ammonium or barium salts. Examples are given for the production of (1) the dilithium salt of symmetrical diphenylpyrophosphoric acid and its conversion to the dicyclohexylammonium and barium salt; (2) the dilithium salt of symmetrical di-p-chlorophenylpyrophosphoric acid; (3) the dilithium salt of P1-phenyl-P2-p-chlorophenylpyrophosphoric acid; (4) the dilithium salt of P1phenyl-P2-mono-methyl glycolpyrophosphoric acid of the formula CH3OCH2CH2 O. P. (O) O Li). O. P O (O Li). O C6H5; (5) P1-b , d- 1, 2, 3, 4 - tetraacetylglucosyl - P2 - phenylpyrophosphate; (6) the trilithium salt of P1-phenylpyrophosphoric acid; (7) P1-adenosine-51-pyrophosphate, (8) the lithium salt of diphenyl pyrophosphate; and (9) the monolithium salt of symmetrical diphenylpyrophosphoric acid.  The products have pesticidal properties (see Division A5) and are useful as additives for gasoline, oils and lubricating greases. Specification 910,893 is referred to.ALSO:An insecticidal bactericidal or fungicidal composition comprises as active ingredient a partly esterified pyrophosphoric acid of the formula: R3O.P(O)(OR5).O.P(O)(OR1)OR2, wherein R1 is an ester-forming organic group, R2 is an ester-forming organic group or hydrogen, R3 is a hydrogen atom, a positive ion derived from a base or an ester-forming organic group, and R5 is a hydrogen atom or a positive ion derived from a base (see Division C2).  Suitable ester-forming organic groups include alkyl, aryl, aralkyl, and alkaryl groups, e.g. butyl, phenyl and benzyl.  The composition may be in the form of a solution, emulsion or suspension in a liquid diluent or may be in powder form on a solid, finely divided carrier and known insecticides, germicides or fungicides may be present.  Specified pyrophosphoric acid esters are the monolithium, dilithium, dicyclohexylammonium and barium salt of symmetrical diphenyl pyrophosphoric acid; the dilithium salts of symmetrical di-p-chlorophenylpyrophosphoric acid, P1-phenyl-P2-p-chlorophenylpyrophosphoric acid, and P1-phenyl-P2-monomethyl glycolpyrophosphoric acid of the formula: CH3OCH2CH2O.P(O)(OLi).O.P(O)(OLi)OC6 H5; the trilithium salt of P1-phenyl pyrophosphoric acid; P1-b ,d-1,2,3,4-tetracetylglycosyl-P2-phenyl pyrophosphate; and P1-adenosine-51-pyrophosphate. Specification 910,893 is referred to.