Phosphate esters monoester

There is a similar difference in mechanism between closely related groups of compounds in hydrolysis of phosphate esters. Monoester hydrolysis proceeds by an initial dissociative step, but hydrolysis of anions of diesters takes place by bimolecular nucleophilic attack of solvent at phosphorus. Further studies of mechanisms of reaction of phosphate esters have been described. ... 

Kirby AJ, Varvoglis AG. The reactivity of phosphate esters, monoester hydrolysis. J Am Chem Soc. 1967 89 415-423. 

Phosphate Esters. The phosphorylation of sucrose using sodium metaphosphate has been reported (78). Lyoptulization of a sodium metaphosphate solution of sucrose at pH 5 for 20 hours followed by storage at 80°C for five days produced a mixture of sucrose monophosphates. These products were isolated by preparative hplc, with a calculated yield of 27% based on all organic phosphate as sucrose monoesters. Small proportions of glucose and fmctose were also formed. 

There are some means for synthesis of defined primary or secondary esters. Monoester salts of phosphoric acid, for instance, are prepared by addition of alcohol or ethoxylated alcohol, alkali fluoride, and pyrophosphoryl chloride (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 base. Thus, 32.3 g (C12P0)20 was treated at -50°C with 23.9 g lauryl alcohol in the presence of 0.7 g KF and the mixture was slowly warmed to room temperature and hydrolyzed with H20 and 40% NaOH to give 83% sodium monolauryl phosphate. The monoester salts showed comparable or better washing and foaming efficiency than a commercial product [12]. 

The preparation of phosphate esters has been reviewed and full details have appeared of the use of 2-chloromethyl-4-nitrophenyl esters (reported last year) in the synthesis of monoesters and mixed dialkyl esters of phosphoric acid. 

Many mechanistic aspects of the hydrolysis of phosphate esters in protic media remain uncertain. In spite of predictions that racemization at phosphorus should be the final outcome if indeed the (hypothetical) metaphosphate intermediate is involved in the solvolysis of monoesters, the results of several studies on the methanolysis of appropriately O-isotopically labelled compounds are consistent with reactions proceeding with inversion of configuration, as observed for all enzymic and non-enzymic systems so far examined this has resulted in the suggestion that if metaphosphate is actually formed, then it must be in a masked form. 

A structurally characterized example of a dinuclear zinc complex with a bridging phosphate monoester was provided by Kitajima and co-workers using the tris(pyrazolyl)borate ligand system. The P—O bond in a tris- or bis-phosphate ester is cleaved by a hydroxo zinc complex resulting in the monoester compound.443... 

Two dinuclear complexes, with five-coordinate zinc centers, derived from tris((2-pyridyl)-methyl) amine were synthesized and bridging phosphate or phosphate ester groups. The X-ray structure of the phosphate monoester complex shows a syn-anti bridging mode in contrast to alkaline phosphatase in which it is syn-syn 448 Fenton and co-workers have also studied other related dizinc species of compartmental ligands 449... 

The mechanism of phosphate ester hydrolysis by hydroxide is shown in Figure 1 for a phosphodiester substrate. A SN2 mechanism with a trigonal-bipyramidal transition state is generally accepted for the uncatalyzed cleavage of phosphodiesters and phosphotriesters by nucleophilic attack at phosphorus. In uncatalyzed phosphate monoester hydrolysis, a SN1 mechanism with formation of a (POj) intermediate competes with the SN2 mechanism. For alkyl phosphates, nucleophilic attack at the carbon atom is also relevant. In contrast, all enzymatic cleavage reactions of mono-, di-, and triesters seem to follow an SN2... 

The mechanisms of phosphate ester cleavage vary significantly between monoesters, diesters, and triesters (Thatcher and Kluger, 1989). Each of these is a target for antibody cleavage and progress has been reported for all three cases. 

Figure 10. Models of complexes between long-chain phosphate esters (sodium salts of the monoesters) and insulin based on Raman spectroscopy. Shorter chains (e.g. C10) have a protein environment whereas lipid regions with disordered chains are formed when chains are longer (>CJ.

Almost all the starches investigated contain some phosphorus.124-126 In addition to phospholipids, phosphorus is also commonly found in starch as monostarch phosphate esters.6,7 Inorganic phosphate is present in some starches.124-126 Monostarch phosphate esters and phospholipids have different effects on starch paste properties.133,135 Monostarch phosphate esters, found in potato, shoti and other starches,6,7,136-140 increase paste clarity and paste viscosity.79 Little phosphate monoester is found in cereal starch.121,124,141,142 Phospholipids, found in normal cereal starches (e.g. wheat, rice and maize) decrease paste clarity and viscosity.133 31P-nmr spectroscopy has... 

Introduction of a phosphate monoester and removal of its protecting groups was a serious impediment in a synthesis of the serine-threonine phosphatase inhibitor Calyculin A by Evans and co-workers [Scheme 7,22].38 The four phosphate protecting groups evaluated were 2-cyanoethyl and 2-(trimethylsi]y])ethyl (see below), benzyl and p-methoxybenzyl. Of these, the p-methoxybenzyl phosphate ester offered the best compromise between base stability (it survived a Wittig reaction in the presence of a metal amide base) and acid lability required for the final deprotection step in which three secondary terf-butyldimethylsiiyl... 

Monoalkyl phosphate and phosphate esters are special types of phosphoms-contain-ing anionic surfactants that are of great industrial importance. They are used for flameproofing, as antistatic for textiles, for foam inhibition, as an extreme pressure (EP) lubricant additive, as a surfactant component for alkaline, and as acid cleaners and for special cosmetic preparations (5). The commercially available phosphate ester products are complex mixtures of monoester and diester, free phosphoric acid, and free nonionic. 

Phosphoryl transfer reactions have essential roles throughout biochemistry. The enzymes that catalyze these reactions result in tremendous rate enhancements for their normally unreactive substrates. This fact has led to great interest in the enzymatic mechanisms, and debate as to whether the mechanisms for enzyme-catalyzed hydrolysis of phosphate esters differ from those of uncatalyzed reactions. This review summarizes the uncatalyzed reactions of monoesters, diesters and triesters. A selection of enzymatic phosphoryl transfer reactions that have been the most studied and are the best understood are discussed, with examples of phosphatases, diesterases, and triesterases. 

The kinetic stability of monoesters and diesters is due largely to their negative charge when ionized, which repels nucleophiles. Thus, it is not surprising that as neutral compounds, triesters are the most reactive of the three classes of phosphate esters. A significant portion of the mechanistic studies on triesters have been carried out using six-membered ring cyclic triesters (Fig. 12).46 Such esters react at comparable rates to their acyclic counterparts, in contrast to five-membered cyclic phosphate esters, which react at much faster rates. 

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