Of phosphoric acid derivatives

Esters of phosphorous acid derived from aUphatic alcohols and unhindered phenols, eg, tris(nonylphenyl)phosphate (24), hydrolyze readily and special care must be taken to minimize decomposition by exposure to water or high humidity. The phosphorous acid formed by hydrolysis is corrosive to processing equipment, particularly at high temperatures. 

Monoester salts of phosphoric acid derived from fatty alcohol ethylene oxide adduct or alkylphenol ethylene oxide adduct useful as surfactants are prepared by addition of R(OCH2CH2) OH, alkali fluoride and (C12P0)20 in a molar ratio of 0.9-1.5 0.05-1 1.0 at -50 to + 10°C and hydrolysis of the Cl-containing intermediates with a base. The monoester phosphates showed comparable or better washing and foaming efficiency than commercial products [12]. 

B. Solvolysis of Phosphoric Acid Derivatives.—Interest continues in neighbouring-group participation in the solvolysis of phosphate esters. As a potential model compound for investigating the mechanism of ribo-nuclease action, the phenyl hydrogen phosphate ester of c/j-3,4-tetrahydro-furandiol (24) has been the subject of a detailed study. Above (and probably also below) pH 4 hydrolysis gives solely the cyclic phosphate (25)... 

J. P. Guthrie, Hydration and Dehydration of Phosphoric Acid Derivatives Free Energies of Formation of the Pentacoordinate Intermediates for Phosphate Ester Hydrolysis and of Monomeric Metaphosphate, J. Am. Chem. Soc. 1977, 99, 3391. 

Phosphorus containing additives include esters of phosphoric acids, derivatives of thiophosphoric acids, phosphites (Davey, 1950 Sakuri and Sato, 1970), and the metal salts of dithiophosphoric acid diesters, the best known of these compounds being the ZDDPs. The structure of ZDDP films, the composition of the film formed, and the mechanism of action on the molecular level are summarized in Chapter 4. 

Uses of Phosphoric Acid Derivatives.- The resolution of the cyclic phosphoric acid (78 X = OH), prepared from... 

Solvolyses of Phosphoric Acid Derivatives.— There has been relatively little work reported on the solvolysis of simple phosphate esters. Instead, attention has been given to situations where intramolecular participation or other special features are likely to be important. 

Reactions of Phosphoric Acid Derivatives.— Interest in HMPT both as a solvent and as a reactant continues. In this solvent / -unsaturated carboxylic acids are reduced by lithium to mixtures of the saturated analogues and synunetrically substituted adipic acids addition of lithium acetate gives reasonable yields of substituted glutaric acids, probably by initial metallation by lithium diethylamide (Scheme 2). Butyl-lithium, however, cleaves... 

The use of phosphorous acid derivatives in synthesis has been reviewed. ... 

Solvolyses of Phosphoric Acid Derivatives.—The solvolysis of organic phosphates has been reviewed. A significant 0 isotope effect was observed in the solvolysis of the dianion of 2,4-dinitrophenyl phosphate, and since no such isotope effect is observed in the alkaline solvolysis of the dibenzyl ester this has been adduced as evidence for a monomeric metaphosphate elimination in the former case. The nucleophilic attack of hydroxide ion on bis-(2,4-dinitrophenyl) phosphate is inhibited by micelles of non-anionic detergents and this is attributed to binding of the substrate. Hydrolysis of 3,4-dimethoxyphenyl phosphate proceeds by way of the monoanion, the neutral molecule, and the conjugate acid, and is thus in accord with earlier results on other methoxyphenyl phosphates. ... 

The published experimental data until quite recently supported the belief that for reaction to occur, R could not be tertiary. Thus, Arbuzov and Azanovskaya (21) found that esters of phosphorous acid derived from tetramethylethylene glycol and a primary alcohol interact with an alkyl halide only at the less substituted carbon atom. 

Reactions of Phosphoric Acid Derivatives.- Polar substituent effects in... 

REACTION OF PHOSPHORIC ACID DERIVATIVES WITH ELECTROPHILES... 

A = Ba, Ca, Ce, K, Na, Pb, Sr, Y, X = As, P, Si, V and Z = F, Cl, O, OH, H2O. Solid-solution between end-members is extensive, but complete only in certain cases. Carbonate ion may partially replace the XO4 group, with appropriate charge compensation [2,3]. Fluorapatite (Ca5(P04)3F) is the most common member of the group and the major constituent of phosphorites, which are the main raw materials for the manufacture of phosphoric acid derivatives including fertilizers, foods, pharmaceuticals and other chemicals. Fluorapatite in phosphorites is usually partially carbonated and hydroxylated. Hydroxyapatite (Ca5(P04)30H) is the primary mineral constituent of bones and teeth and hosts a variety of chemical substituents in its structure. These materials are stable for billions of years, even during tectonic events, and over a wide range of solution pH and geological conditions, as can be inferred from the existence of ancient sedimentary phosphorites [4]. 

In the past year, the development of chemistry of phosphoric acid derivatives has been connected mainly with the topic of synthesis for biological applications. In this section, there will be discussed syntheses of various biological molecules in the form of free phosphoric acids and their salts as well as amide, diester or dithioster derivatives. 

Tetramethylammonium salts of phosphoric acid derivatives convert... 

In this chapter, mainly the ROP of cyclic P-containing monomers is discussed. The synthesis of P-containing polymers by the polyaddition is discussed only for the reaction of phosphoric acid derivatives with diepoxides. 

Nonspecific Phosphoesteroses. These enzymes cleave a variety of phosphoric acid derivatives, even synthetic substrates and lecithins (diesters of phosphoric acid with glycerol and choline). Such enzymes occur among other places in snake venom, and in the intestinal mucosa. Snake venom phosphatases specifically split 3 -phos-phate bonds, giving rise to 5 -monophosphates, whereas chemical hydrolysis yields a mixture of the 2 - and 3 -monophosphates. Free 3 -phosphate groups (the monoesters) are inhibitory in the enzymic reaction. 

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