Phosphoric acid esters phosphate

Fig. 9 Preparation of dextran phosphoric acid esters (phosphates) with polyphosphoric acid...

A. Classification and Prototypes The indirect-acting cholinomimetic drugs fall into two major chemical classes carbamic acid esters (carbamates neostigmine is a prototype) and phosphoric acid esters (phosphates, organophosphates echothiophate is a prototype). A third class has only one member edrophonium is an alcohol (not an ester) with a very short duration of action. 

Esters of saccharides are natural components of virtually all foods. The most common sugar esters are phosphoric acid esters (phosphates), which serve as key intermediates in metabolism by animals, plants and microorganisms. Examples are phosphates of D-glucose (D-glucose 1-phosphate and D-glucose 6-phosphate, 4-89), but many other sugar phosphates also take part in the metabolic... 

Hydrogen Chloride as By-Product from Chemical Processes. Over 90% of the hydrogen chloride produced in the United States is a by-product from various chemical processes. The cmde HCl generated in these processes is generally contaminated with impurities such as unreacted chlorine, organics, chlorinated organics, and entrained catalyst particles. A wide variety of techniques are employed to treat these HCl streams to obtain either anhydrous HCl or hydrochloric acid. Some of the processes in which HCl is produced as a by-product are the manufacture of chlorofluorohydrocarbons, manufacture of aUphatic and aromatic hydrocarbons, production of high surface area siUca (qv), and the manufacture of phosphoric acid [7664-38-2] and esters of phosphoric acid (see Phosphoric acid and phosphates). 

The largest-volume phosphoms compounds are the phosphoric acids and phosphates (qv), ie, the oxide derivatives of phosphoms ia the + 5 oxidation state. With the exception of the phosphoric acid anhydride, P O q, and the phosphate esters, these materials are discussed elsewhere (see Phosphoric acids and phosphates). An overview of phosphoms compounds other than the phosphoric acids and phosphates is given herein. These compounds constitute a large variety of phosphoms compounds that are either nonoxide derivatives or derivatives of phosphoms ia oxidation states lower than + 5. These phosphoms compounds are manufactured only from elemental phosphoms (qv) obtained by reduction of naturally occurring phosphate rock (calcium phosphate). 

For extraction of uranium from sulfate leach Hquors, alkyl phosphoric acids, alkyl phosphates, and secondary and tertiary alkyl amines are used in an inert diluent such as kerosene. The formation of a third phase is suppressed by addition of modifiers such as long-chain alcohols or neutral phosphate esters. Such compounds also increase the solubihty of the amine salt in the diluent and improve phase separation. 

Phosphoric acid esters having a low content of arsenic can be obtained by treating with 0.1-10% adsorbents such as activated clay, active carbon, alumina, and silica gel to decrease the arsenic content. Thus, 100 parts lauryl phosphate containing 10.3 ppm As and 2 parts activated clay were mixed at 60-70°C for 2 h and filtered to give lauryl phosphate only containing 0.6 ppm As [28]. 

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). 

Acid ester phosphates with an alkyl chain up to C6 have little solubility whereas neutralized esters are soluble in water. In ethanol and isopropanol most of phosphoric acid esters and their salts are soluble. If the products are based on ethoxylated alcohols their solubility in water will increase as the degree of ethoxylation increases. The solubility in organic solvents like gasoline, benzene, perchlorethylene, and other apolar liquids recedes with an increase in the degree of ethoxylation but are increased by a higher alkyl chain. 

Foamability of phosphoric acid esters in aqueous solutions is in general only moderate, with the acid phosphates showing a better stability against water hardness than the alkali or amine salts. 

Phosphates and phosphonates are valuable contents of cleaners used for technical purposes especially when anticorrosive behavior is also required. Phosphoric acid esters are a component of aqueous cleaning compositions for printed circuit boards [212]. 

Emulsions containing a water-solubile herbicide salt and a herbicide soluble in an organic solvent are prepared by a mixture of water, dioctyl phthalate, and isophorone. In this case ethoxylated poly ary lphenol phosphate neutralized with triethanolamine and ethoxylated acid phosphoric acid esters is used as emulsifier [231],... 

An electric conductive rubber base containing carbon black is laminated with an electric conductive cover layer of phosphoric acid ester plasticizer and other ionic surfactants to prepare antistatic mats, where the covers have colors other than black. It is also reported that alkyl acid phosphates act as color stabilizer for rubber. Small amounts of phosphate esters are helpful in restoring reclaimed rubber to a workable viscosity [284,290]. Esters of phosphoric acid are used in the production of UV-stable and flame-retarded alkylbenzenesulfonate copolymer compositions containing aliphatic resins and showing a high-impact strength... 

A mixture of monolauryl phosphate sodium salt and triethylamine in H20 was treated with glycidol at 80°C for 8 h to give 98% lauryl 2,3-dihydro-xypropyl phosphate sodium salt [304]. Dyeing aids for polyester fibers exist of triethanolamine salts of ethoxylated phenol-styrene adduct phosphate esters [294], Fatty ethanolamide phosphate surfactant are obtained from the reaction of fatty alcohols and fatty ethanolamides with phosphorus pentoxide and neutralization of the product [295]. A double bond in the alkyl group of phosphoric acid esters alter the properties of the molecule. Diethylethanolamine salt of oleyl phosphate is effectively used as a dispersant for antimony oxide in a mixture of xylene-type solvent and water. The composition is useful as an additive for preventing functional deterioration of fluid catalytic cracking catalysts for heavy petroleum fractions. When it was allowed to stand at room temperature for 1 month it shows almost no precipitation [241]. 

The above enzymes are not the only ones able to cleave phosphoric acid esters. Indeed, the cleavage of some organophosphates can be catalyzed by monooxygenases, as illustrated below. Furthermore, glutathione S-transfe-rases can also act on some methyl and ethyl phosphates [73], but these reactions will not be covered here. 

Fig. 9.7. a) Mechanism of activation of (phenytoin-3-yl)methyl phosphate (9.25) to release phenytoin. Phosphoric acid ester hydrolysis is mediated by alkaline phosphatase, b) (Phospho-ryloxy)methyl prodrugs of tertiary amines, whose activation occurs by the same two-step mechanism shown in a [79]. 

In whole blood, phosphatase activity is associated primarily with red blood cells, but it is recognized that blood has a low phosphatase activity compared to other tissues such as the kidney, brain, liver, lung, and heart ([87] [88] and refs. cit. therein). Thus, studies with blood preparations should underestimate the in vivo rate of hydrolysis of phosphoric acid esters, a point of significance in the development of phosphate prodrugs. 

Esterification. The hydroxyl groups of monosaccharides can form esters with acids. In metabolism, phosphoric acid esters such as glucose 6-phosphate and glucose 1-phosphate (6) are particularly important. 

Phosphoric acid esters of the ketopentose D-ribulose (2) are intermediates in the pentose phosphate pathway (see p.l52) and in photosynthesis (see p.l28). The most widely distributed of the ketohexoses is D-fructose. In free form, it is present in fruit juices and in honey. Bound fructose is found in sucrose (B) and plant polysaccharides (e.g., inulin). 

Monosaccharides also form phosphate esters with phosphoric acid. Monosaccharide phosphate esters are important molecules in biological system. For example, in the DNA and RNA nucleotides, phosphate esters of 2-deoxyribose and ribose are present, respectively. Adenosine triphosphate (ATP), the triphosphate ester at C-5 of ribose in adenosine, is found extensively in living systems. 

The lubrication system is extremely complex. The mechanism of lubrication is partly dictated by the nature of interactions between the lubricant and the solid surface. Additives blended into lubricating oil formulations either adsorb onto the sliding surfaces, eg., fatty alcohols, fatty amines, amides, phosphoric acid esters (friction modifiers), or react with the surface, eg., ZDDP, MoDTC, MoDDP organic phosphates (extreme pressure). Some interactions affecting the surfaces of metals include adsorption, chemisorption, and tribochemical reactions-these form new compounds on the surface and lubrication by reaction products (Bhushan and Gupta, 1991 Briscoe et al., 1973 Briscoe and Evens, 1982 Heinicke, 1984 Hsu and Klaus, 1978 and 1979 Klaus and Tewksbury, 1987 Lansdown, 1990 Liston, 1993 McFadden et al., 1998 Studt, 1989). 

Figure 11.28 Structure of terminal phosphate groups of polyester-polyurethane by degradation with phosphoric acid esters...

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