Phosphoric acid phosphorylation

The arsenate considerably accelerates the fermentation of hexose diphosphate,10 and inhibits the combination of sucrose with phosphoric acid (phosphorylation).11... 

Phosphorylation O-Benzyl phosphorus 0,0-diphenylphosphoric anhydride. 2-Cyanomethyl phosphate. Dibromomalonamide. Di-p-nilrobenzylphosphoryl chloridate. Dioxane diphosphate. Diphenylphosphorochloridate. Ethoxyacetylene. Metaphosphoric acid. o-Phenyl-ene phosphorochloridate. Phosphoric acid, anhydrous. Phosphorodimorpholidic chloride. Phosphorus pentoxide-Phosphoric acid. Phosphoryl chloride. Polyphosphoric acid. Pyro-phosphoryl tetrachloride. Silver dibenzyl phosphate. Silver diphenyl phosphate. Tetra-p-nitrophenyl pyrophosphate. 

Plimmer RH (1941) Esters of phosphoric acid phosphoryl hydroxyamino-acids. Biochem J 35 461-469... 

Phosphoric Acid-Based Systems for Cellulosics. Semidurable flame-retardant treatments for cotton (qv) or wood (qv) can be attained by phosphorylation of cellulose, preferably in the presence of a nitrogenous compound. Commercial leach-resistant flame-retardant treatments for wood have been developed based on a reaction product of phosphoric acid with urea—formaldehyde and dicyandiamide resins (59,60). 

Phosphorus. Eighty-five percent of the phosphoms, the second most abundant element in the human body, is located in bones and teeth (24,35). Whereas there is constant exchange of calcium and phosphoms between bones and blood, there is very Httle turnover in teeth (25). The Ca P ratio in bones is constant at about 2 1. Every tissue and cell contains phosphoms, generally as a salt or ester of mono-, di-, or tribasic phosphoric acid, as phosphoHpids, or as phosphorylated sugars (24). Phosphoms is involved in a large number and wide variety of metaboHc functions. Examples are carbohydrate metaboHsm (36,37), adenosine triphosphate (ATP) from fatty acid metaboHsm (38), and oxidative phosphorylation (36,39). Common food sources rich in phosphoms are Hsted in Table 5 (see also Phosphorus compounds). 

The cyclization of 5-(2-carboxyanilino)pyrimidine (170) with sulfuric acid/phosphoric acid leads to the 7-chloropyrimido[5,4-A]quinolinetriones (171) (57JCS4997, 74KGS131), the 2,4,10-trichloro compounds being obtained with phosphoryl chloride (72JHC91), whilst a formally similar cyclization of 4(6)-arylamino-5-ethoxycarbonylpyrimidines gives... 

The corresponding phosphoryl and thiophos-phoryl pseudohalides are also known, i.e. P0(NC0)3, PS(NC0)3, etc. Preparations are by standard procedures such as those on the diagram for PCI3 (p. 497). As indicated there, P(CN)3 has also been made it is a highly reactive white crystalline solid mp 203° which reacts violently with water to give mainly phosphorous acid and HCN. 

Proceeding from 5 -0-acetylazauridine (80), a mixture of 2 - and 3 -monophosphates (81, 82) was prepared by phosphorylation with polyphosphoric acid, and these were converted into the 2, 3 -cyclic phosphate (83). From the 2, 3 -0-isopropylidene derivative of 3-methyl-6-azauridine the 5 -phosphate was prepared by treatment with cyanoethylphosphate and the corresponding diphosphate from its morpholidate through the action of phosphoric acid. ° Furthermore, a diribonucleoside phosphate (85) with a natural 3 -5 internucleotide linkage was prepared from 6-azauridine, The starting material for the preparation of such derivatives was 5 -0-acetyl-2 -0 -tetrahydro-pyranyluridine-3 -phosphate (84) which was condensed with di-G-acetylazauridine (86) or with 2b3 -0-isopropylidene-6-azauridine (76) with the aid of dicyclohexylcarbodiimide. ... 

Preparation of 6-azacytidine-5 -phosphate by direct phosphorylation with cyanoethylphosphate was not successful. The substance could be prepared, however, on ammonia treatment of 4-thio-6-azauridine-5 -phosphate which was obtained by phosphorylation of 2, 3 -isopropyl-iden-4 thio-6-azauridine with pyrophosphoryl chloride. From mor-pholidate of 6-azacytidine-5 -phosphate, 6-azacytidine-5 -diphosphate was prepared by the action of phosphoric acid. ... 

CF = cardanol-formaldehyde resin (cured) MCPAF = monocar-danyl phosphoric acid-formaldehyde resin (cured) BrCF = bromo derivative of CF BrMCPAF = bromoderivative of MCPAF PF = phenol-formaldehyde (cured) MPPAF = monophenyl phosphoric acid-formaldehyde (cured), BrPF = bromo derivative of PF BrMPPAF = bromoderivative of MPPAF PPF = phenol-formaldehyde resin phosphorylated (cured). 

Phosphoric acid, 100 Phosphorus oxychloride (Phosphoryl chloride], 4... 

The phosphorylation of OH-containing nonionic surfactants with P4O,0 gave a mixture of mono- and diesters of phosphoric acid with the surfactants. The optimum surfactant/P4O10 ratio was 2.5-3 1. The yield of mono- and diesters did not depend on the reaction temperature but was significantly influenced by the water content of the starting materials [7]. 

In order to obtain anionic polyoxyethylene phosphate surfactants, either the terminal hydroxy group of a polyoxyethylated hydrophobic substance is reacted with a phosphorylating agent or a phosphate ester is oxalkylated. Most often aliphatic and aliphatic-aromatic alcohols are first treated with an alkylene oxide and afterward with one of the phosphorylating agents, such as P4OI0, POCl3, phosphoric acid, or polyphosphoric acid [39-48]. 

If primary alcohols with a straight chain of 10-20 carbon atoms are initially alkoxylated by a mixture of ethylene and propylene oxides followed by phosphorylation, a pour point depression to 8°C will occur, whereas phosphate esters derived from nonylphenol are liquid at temperatures as low as 2°C. Phosphoric acid esters on the base of linear primary alcohols (Cn-Cl5) generally solidify below 24°C [50] (Table 2). 

The development of monoalkyl phosphate as a low skin irritating anionic surfactant is accented in a review with 30 references on monoalkyl phosphate salts, including surface-active properties, cutaneous effects, and applications to paste and liquid-type skin cleansers, and also phosphorylation reactions from the viewpoint of industrial production [26]. Amine salts of acrylate ester polymers, which are physiologically acceptable and useful as surfactants, are prepared by transesterification of alkyl acrylate polymers with 4-morpholinethanol or the alkanolamines and fatty alcohols or alkoxylated alkylphenols, and neutralizing with carboxylic or phosphoric acid. The polymer salt was used as an emulsifying agent for oils and waxes [70]. Preparation of pharmaceutical liposomes with surfactants derived from phosphoric acid is described in [279]. Lipid bilayer vesicles comprise an anionic or zwitterionic surfactant which when dispersed in H20 at a temperature above the phase transition temperature is in a micellar phase and a second lipid which is a single-chain fatty acid, fatty acid ester, or fatty alcohol which is in an emulsion phase, and cholesterol or a derivative. 

Next, an ammonia moiecuie reacts with the phosphorylated form of glutamic acid, producing phosphoric acid and giutamine ... 

A. Synthetic Methods.—There have been no strikingly new approaches to the general problem of phosphorylation, but several ingenious methods of preparing suitable active esters under mild conditions have been reported. Typical of these is the reactive intermediate (1) formed from reaction of a mono- or di-ester of phosphoric acid with (2), itself produced by reaction of triphenylphosphine with bis(2-pyridyl) disulphide (preferably in the presence of mercuric ion as scavenger for the 2-mercaptopyridine liberated). 

Solvent effects on the magnitude of spin-spin coupling constants in phosphoryl compounds have been reported, as have the solvent effects on the relative strengths of phosphoric acid and some of its partially esterified derivatives.The variation of i.r. frequencies of (122) and (123)... 

When AMP is heated under reflux in DMF, the 2, 3 -cyclic phosphate is formed, and cyclic phosphates can also be obtained from nucleosides and ortho-, pyro-, or poly-phosphoric acids under the same conditions. Promotion of phosphorylation by DMF is well known and the reaction with AMP is probably intermolecular as no 3, 5 -cyclic AMP can be detected. Minor products in the latter reaction are the 2, 3 -cyclic 5 -diphosphate and the 2 (30,5 -diphosphate. The synthesis of adenosine 2 (3 )-phosphate 5 -pyrophosphate has been achieved by the phosphoromorpholidate method used in a synthesis of Co A. ... 

Carboxylic acids can also be activated by the formation of mixed anhydrides with various phosphoric acid derivatives. Diphenyl phosphoryl azide, for example, is an effective reagent for conversion of amines to amides.140 The proposed mechanism involves formation of the acyl azide as a reactive intermediate. 

As will be shown below in subsequent chapters, CDI reacts in a corresponding way with sulfonic acids, which lead via the corresponding imidazolides to sulfonamides or sulfonic esters, and with phosphoric acid, which reacts with CDI to give the corresponding imidazolides of phosphoric acids that can in turn be used for phosphorylations. 

Analogously, the corresponding tristriazolide of phosphoric acid was prepared from POCI3 and IV-trimethylsilyl-1,2,4-triazole in 60% yield.1261 Both trisazolides are used for the phosphorylation of nucleosides. 

The condensation reactions are preferentially carried out in pyridine. As reactive species for phosphorylation of the nucleoside R OH (synthesis of a phosphortriester), the phosphoric acid azolide has been assumed. The mixed phosphoric sulfonic anhydride and a pyrophosphate tetraester have been suggested as intermediates leading to the phosphoric acid azolide. 

A labeled phosphoric acid triester is formed by phosphorylation of an alcohol with a labeled phosphoric diester imidazolide [187],[188]... 

The monomeric metaphosphate ion itself commands a fair amount of attention in discussions of metaphosphates. It is postulated as an intermediate of numerous hydrolysis reactions of phosphoric esters 52 S4,S5) and also of phosphorylation reactions S6> kinetic and mechanistic studies demonstrate the plausibility of such an assumption. In addition, the transient formation of ester derivatives of meta-phosphoric acid — in which the double-bonded oxygen can also be replaced by thio and imino — has also been observed they were detected mainly on the basis of the electrophilic nature of the phosphorus. 

A further important group of derivatives is that of amino acids activated by phosphoric acid or its esters. In nature, phosphorylation processes play an important activating role in peptide and protein synthesis. 

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