Esters of pyrophosphoric acid

These esters have been prepared by a number of reactions of which the following may be mentioned  

is classed as a systemic insecticide, unstable to water, and is referred to in Chapter ix. 

Dibenzyl hydrogen phosphate and thionyl chloride give a small yield of the pyrophosphate. 

The reaction, which is instantaneous, takes place at room temperature in an inert solvent and excellent yields are obtained. 

Recently Sir A. R. Todd and his co-workers have shown that pyrophosphates are obtained by the action of an imidoyl phosphate on a hydrogen phosphate 

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Although this monograph is concerned primarily with compounds containing one phosphorus atom, some account has already been given of esters of pyrophosphoric acid (p. 103) attention must also be drawn to some recent important contributions to the organic chemistry of polyphosphorus compounds made by M. Tolkmith. He has prepared decamethyltriphosphor-amide1 (XX) by the action ... 

Adducts (6) and (7) from amides and chlorophosphoric acid aiyl esters or dichlorophosphoric acid aryl esters respectively are well known. - The adducts are formed in a 1 1 ratio. They have been applied to the synthesis of mixed anhydrides from diarylphosphoric acids and carboxylic acids, as well as mixed substituted esters of pyrophosphoric acid. The adduct formation between primary or secondary carboxamides and dichlorophosphates has been used to prepare nitriles and isonitriles respectively. The adduct from DMF and phenyldichlorophosphate is a useful reagent for the preparation of carboxylic acid esters from the corresponding acids and alcohols, 3-lactams from imines and carboxylic acids," carboxylic acid anhydrides, carboxylic acid esters and thiol esters. Adducts of amides with ester amides or diamides of chlorophosphoric acid have been studied. ... 

DCC reacts rapidly and nearly quantitatively at 25° in ether solution with mono and di esters of phosphoric acid to yield the corresponding di or tetra esters of pyrophosphoric acid, with immediate precipitation of dicyclohexylurea. It appears... 

Arhuzov, A.E., and Ahmov, P.L, Products of condensation of esters of pyrophosphorous acid with aldehydes, Izv. Akad. Nauk SSSR, Otdel. Khim. Nauk, 530, 1951 Chem. Abstr.. 47, 696, 1953. 

Esters of orthophosphoric acid have been used extensively as plasticizers and lubricant additives. Others have been used as flame retardants. Many sulfur analogues find use as insecticides, while the introduction of P—C bonds give phosphonic and phosphinic acids. Esters of pyrophosphoric acid (H4P2O7) are also of interest as are amide derivatives. 

Esters of pyrophosphoric acid (Table 5.27) are also efficient complexing agents as well as dial-kylamino derivatives such as HMPA and OMPA (Chapter 7) and diphosphonates (Chapter 6.18). Typical complexes formed by tributyl phosphate (TBP) are... 

Of the organotin compounds with inorganic acids, salts of tributyl-tin and diphenyltin with the dioctyl ester of orthophosphoric acid or the dihexyl ester of pyrophosphoric acid [230] ... 

This part of history is well-known (Koelle, 1963,1981 Bajgar, 2006 Tuorinsky 2008 Klement et al., 2013). First synthesis of OP was described in the second half of the eighteenth century. For a long time the first OP (its toxicity was described later) was considered to be TEPP, which was synthesized by Clermont (1854-1855). Philippe de Clermont was a well-known chemist in Sorbonna. Charles Adolph Wurtz dedicated his work to the synthesis of esters of pyrophosphoric acid. These data were specified by Petroianu (2008), and thus he contributed to the discovery that the first synthesis of this OP—TEPP— was performed by Vladimir Moshnin of... 

Blackburn, G.M., England, D.A., and Kolkinann, F., Monofluoro- and difluoro-methylenebisphospho-nic acids, Isopolar analogues of pyrophosphoric acid, J. Chem. Soc., Chem. Commun., 930, 1981. McKenna, C.E., and Shen, P.-D., Fluorination of methanediphosphonate esters by perchloryl fluoride. Synthesis of fluoromethanediphosphonic acid and difluoromethanediphosphonic acid, J. Org. Chem., 46, 4573, 1981. 

Esters of pyrophosphorous add can be prepared by using sodium dialkyl phosphite and a dialkyl phosphorochloridite (5.321). If a phosphorochloridate ester is used, an ester of hypophosphoric acid is obtained (5.322). 

The main purpose of this section is to introduce derivatives of phosphoric acid. The acid chloride derivative is C1P0(0H)2, chlorophosphoric acid, and the amide derivative is phosphoramic acid, HgN-POCOHlg. These acid derivatives will not be discussed because they will not be used in this book. There are three ester derivatives of phosphoric acid a monoester 203, a diester 204, and a triester 205. There are also derivatives of pyrophosphoric acid (diphosphoric acid, 206), which include various esters. 

Esters of phosphoric acid, pyrophosphoric acid, and triphosphoric acid are important biological molecules. Each OH group of the acid can be esterified monoesters and diesters are the most common biological molecules. ATP is a monoester of triphosphoric acid. We have seen that the components of cell membranes are monoesters or diesters of phosphoric acid (Section 16.13), and that many of the coenzymes are monoesters or diesters of either phosphoric acid or pyrophosphoric acid (Chapter 24). In Section 26.1, we will see that DNA and RNA are diesters of phosphoric acid. 

Corby, N S, Kenner, G W, and Todd, A R (1952) The preparation of tetra-esters and pyrophosphoric acid from diesters of phosphoric acid by means of exchange reactions. J. Chem. Soc. (Lond.) 1234-1243... 

Most of the chemistry of PA is determined by its acidic nature. It is a strong acid whose ionization constant of 1.6 x 10"1 (Ref 31) makes it comparable in acid strength to pyrophosphoric acid and trichloroacetic acid. PA readily forms salts with bases and esters with alcohols. The salts are known as Picrates. Many of them are expl and will be described in a separate article in this Vol. The esters are phenol ethers, eg, Trinitro-anisolc (see Vol t, A450-L)... 

Several of these steroid derivatives underwent elimination of phosphorodichloridate anion, giving hydrocarbon products, rather than ester formation when treated with methanolic pyridine. Pyrophosphoric acid itself has been used to phosphorylate (2-hydroxymethyl)pyridine. ... 

Most of the coenzymes are esters of phosphoric or pyrophosphoric acid. The main reservoirs of biochemical energy, adenosine triphosphate (ATP), creatine phosphate, and phosphoenolpyruvate are phosphates. Many intermediary metabolites are phosphate esters, and phosphates or pyrophosphates are essential intermediates in biochemical syntheses and degradations. The genetic materials DNA and RNA are phosphodiesters. 

Derivatives of phosphoric acid, pyrophosphoric acid, and related compounds are very important in biological systems. Pyrophosphoric acid is an anhydride of phosphoric acid. Adenosine triphosphate, an energy carrier that is universally found in living organisms, has a phosphorus dianhydride connected to an adenosine group by a phosphate ester linkage. Phosphorus ester bonds are used to form the polymeric backbone of DNA (see Chapter 27). 

A nucleoside pyrophosphoric ester of this uronic acid, UDP-d-galacturonic acid, was shown to be present in mung beans. " In this plant were also found enzymes that led to the formation of this uronic acid derivative of a nucleoside pyrophosphate by the following pathway ... 

In the case of pyrophosphoric (diphosphoric) acid, four esters are possible and one of these has two possible isomeric forms. 

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