Phosphates metaphosphates

Table 4. Calculated free energies of addition and elimination of water and ethanol in the phosphate/metaphosphate system 981...

TrialkylPhosphates. Triethyl phosphate [78-40-0] C H O P, is a colorless Hquid boiling at 209—218°C containing 17 wt % phosphoms. It may be manufactured from diethyl ether and phosphoms pentoxide via a metaphosphate intermediate (63,64). Triethyl phosphate has been used commercially as an additive for polyester laminates and in ceHulosics. In polyester resins, it functions as a viscosity depressant as weH as a flame retardant. The viscosity depressant effect of triethyl phosphate in polyester resins permits high loadings of alumina trihydrate, a fire-retardant smoke-suppressant filler (65,66). 

Several crystalline condensed phosphates may also be formed by the dehydration of monosodium phosphate (MSP). Maddrell s salt exists as Form 11 (high temperature MaddreU, NaPO -ll, insoluble metaphosphate-11) and Form 111 (low temperature MaddreU, NaPO -lll, insoluble metaphosphate-111). Both forms are highly polymerized and difficult (slow) to dissolve in water. Mixtures of the two forms are marketed as a dental abrasive for toothpaste formulations containing soluble fluoride. Maddrell s salt is also used with disodium phosphate as a cheese emulsifying aid. 

The only tme metaphosphate (ring stmcture) of significant commercial interest is sodium trimetaphosphate (STMP), Na P O. Because of the strain inherent in the small ring stmcture, STMP is more reactive toward nucleophiles than chain phosphates. In the presence of NaOH, for example, STMP forms sodium tripolyphosphate. 

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. 

Sohd uranium—phosphate complexes have been reported for the IV and VI oxidation states, as well as for compounds containing mixed oxidation states of U(IV) and U(VI). Only a few sohd state stmctures of U(IV) phosphates have been reported, including the metaphosphate U(P03)4, the pyrophosphate U(P202), and the orthophosphate, CaU(PO4)2. The crystal stmcture of orthorhombic CaU(POis similar to anhydrite (194). Compounds of the general formula MU2(PO4)3 have been reported for M = Li, Na, and K, but could not be obtained with the larger Rb and Cs ions (195). In the sohd state, uranium(IV) forms the triclinic metaphosphate, U(P03)4. Each uranium atom is eight-coordinate with square antiprismatic UOg units bridged by... 

Uranium(VI) phosphates have been widely investigated and can be divided in several stmcture types orthophosphates M(U02) (PO4) XH2O, hydrogenphosphates M(U02) (H P04) XH2O, pyrophosphates U 0 P202, metaphosphates (U02) (P03) XH2O, and polyphosphates (U04,(PP,).- Hp (188). 

Calcium metaphosphate [13477-39-9] is made by reaction of P2O3 in HPO3 with rock phosphate. The insoluble, polymeric product must be hydrolyzed before it can act as a fertilizer (13) ... 

An abrasive is usually chemically inert, neither interacting with other dentifrice ingredients nor dissolving in the paste or the mouth. Substances used as dentifrice abrasives include amorphous hydrated silica, dicalcium phosphate dihydrate [7789-77-7] anhydrous dicalcium phosphate [7757-93-9] insoluble sodium metaphosphate [10361-03-2], calcium pyrophosphate [35405-51-7], a-alumina trihydrate, and calcium carbonate [471-34-1]. These materials are usually synthesized to specifications for purity, particle size, and other characteristics naturally occurring minerals are used infrequently. Sodium bicarbonate [144-55-8] and sodium chloride [7647-14-5] have also been employed as dentifrice abrasives. 

Chemical Designations - Synonyms Sodium phosphate is generic term and includes the following (1) monosodium phosphate (MSP sodium phospWe, monobasic), (2) disodium phosphate (DSP sodium phosphate dibasic), (3) trisodium phosphate (TSP sodium phosphate, tribasic), (4) sodium acid pyrophosphate (ASPP SAPP disodium pyrophosphate (TSPP), (6) sodium metaphosphate (insoluble sodium metaphosphate), (7) sodium trimetaphosphate, and (9) sodium tripolyphosphate (STPP TPP) Chemical Formula (1) NaHjPO (2) Na HPO (3) NajPO (4) Na H P O, (5) Na P O, (6) (NaPOj) (7) (NaP03)3 (8) (NaP03) NaO (9) Na,P30,o. 

Sodium fluoride also attacks silica, as do sodium metaphosphate and sodium polyphosphate, and to a lesser extent sodium carbonate and sodium cyanide. Attack is particularly vigorous for fused alkalis, alkali halides and phosphates. 

Also introduced was sodium metaphosphate [Hagan phosphate or Calgon , represented at the time by the formula (NaP03)6, although it tends to have a different formula today]. 

Phosphate esters have a variety of mechanistic paths for hydrolysis. Both C-O and P-0 cleavage are possible depending on the situation. A phosphate monoanion is a reasonable leaving group for nucleophilic substitution at carbon and so 8 2 or SnI reactions of neutral phosphate esters are well known. PO cleavage can occur by associative (by way of a pentacoordinate intermediate), dissociative (by way of a metaphosphate species), or concerted (avoiding both of these intermediates) mechanisms. 

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. 

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. 

In the quest for free metaphosphate, racemization has been observed for phosphoryl transfer from phenyl dihydrogen (R)-[ 0, " 0, 0]-phosphate to tert-butyl alcohol in MeCN. ... 

The involvement of monomeric metaphosphate in the phosphoryl transfer from phosphate monoesters, and of pentaco-ordinate intermediates from phosphotriesters represent two extremes in the mechanistics of the phosphoryl transfer process. Between the extremes are the (S 2)p processes involving transition states having various bond orders, but no true... 

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