Phosphoric acids and derivatives

Ethylamines. Mono-, di-, and triethylamines, produced by catalytic reaction of ethanol with ammonia (330), are a significant outlet for ethanol. The vapor-phase continuous process takes place at 1.38 MPa (13.6 atm) and 150—220°C over a nickel catalyst supported on alumina, siUca, or sihca—alumina. In this reductive amination under a hydrogen atmosphere, the ratio of the mono-, di-, and triethylamine product can be controlled by recycling the unwanted products. Other catalysts used include phosphoric acid and derivatives, copper and iron chlorides, sulfates, and oxides in the presence of acids or alkaline salts (331). Piperidine can be ethylated with ethanol in the presence of Raney nickel catalyst at 200°C and 10.3 MPa (102 atm), to give W-ethylpiperidine [766-09-6] (332). 

Notes A strong mineral acid of unspecified structure. It contains a mixture of phosphoric acids and derivatives, with a high content of P2O5. Does chemistry similar to that found with Eaton s reagent. 

Organophosphorus compounds (OPs) are utilized on a large scale as flame retarding agents and plasticizers in a variety of products, such as plastic materials, rubbers, varnishes, lubricants, hydraulic fluids, and other industrial applications. This family of chemicals consists of alkylated and arylated phosphate or phosphonate esters and related compounds such as phosphites, phosphines, and related dimeric forms as well as ionic forms (Figure 31.2). " The low volatility of phosphoric acid and derivatives makes it the preferred choice of the phosphorus based FRs. These FRs are most effective in polymers that char readily. Also halogenated phosphate esters, such as tris(l-chloroisopropyl) phosphate (TCPP), and tris(2-chloroethyl) phosphate (TCEP), are widely used. These combine the properties of both the halogen and the phosphorus compounds. 

The detergent range alcohols and their derivatives have a wide variety of uses ia consumer and iadustrial products either because of surface-active properties, or as a means of iatroduciag a long chain moiety iato a chemical compound. The major use is as surfactants (qv) ia detergents and cleaning products. Only a small amount of the alcohol is used as-is rather most is used as derivatives such as the poly(oxyethylene) ethers and the sulfated ethers, the alkyl sulfates, and the esters of other acids, eg, phosphoric acid and monocarboxyhc and dicarboxyhc acids. Major use areas are given ia Table 11. 

Phospholipids. Phospholipids, components of every cell membrane, are active determinants of membrane permeabiUty. They are sources of energy, components of certain enzyme systems, and involved in Hpid transport in plasma. Because of their polar nature, phosphoUpids can act as emulsifying agents (42). The stmcture of most phosphoUpids resembles that of triglycerides except that one fatty acid radical has been replaced by a radical derived from phosphoric acid and a nitrogen base, eg, choline or serine. 

Phosphoric acids and the phosphates maybe defined as derivatives of phosphoms oxides where the phosphoms atom is in the +5 oxidation state. These are compounds formed in the M2O—P20 system, where M represents one cation equivalent, eg, H", Na", 0.5 Ca ", etc. The molecular formula of the phosphoms(V) oxide [1314-56-3] is actually P O q, but this oxide is commonly referred to in terms of its empirical formula, P2O5. StmcturaHy, four phosphoms—oxygen (P—O) linkages are arranged in an approximate tetrahedral configuration about the phosphoms atom in the phosphate anion. Compounds containing discrete, monomeric PO ions are known as orthophosphates or simply as 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). 

As is well-known, nucleic acids consist of a polymeric chain of monotonously reiterating molecules of phosphoric acid and a sugar. In ribonucleic acid, the sugar component is represented by n-ribose, in deoxyribonucleic acid by D-2-deoxyribose. To this chain pyrimidine and purine derivatives are bound at the sugar moieties, these derivatives being conventionally, even if inaccurately, termed as pyrimidine and purine bases. The bases in question are uracil (in ribonucleic acids) or thymine (in deoxyribonucleic acids), cytosine, adenine, guanine, in some cases 5-methylcytosine and 5-hydroxymethylcyto-sine. In addition to these, a number of the so-called odd bases occurring in small amounts in some ribonucleic acid fractions have been isolated. 

There also exists interference from diphosphoric acid, other more highly condensed phosphoric acids, and their organic derivatives. The free phosphoric acid can be determined as a heteropolyacid complex of phosphoric acid and ammonium molybdate. Afterward the complex is reduced by stannum II chloride to molybdenum blue. The amount of this dye can be measured photometricly at 625 nm. Organic derivatives of phosphoric acid and condensed phosphoric acids do not interfere with this method. 

An alternative sequence utilized 2-oxazolidone, which was readily synthesized from urea and ethanolamine, as the glycine equivalent. Subsequent treatment with phosphorous acid and formaldehyde produced iV-phosphonomethyl-2-oxazolidone 12 (16). Upon hydrolysis, and loss of CO2,12 provided the related derivative, iV-phosphonomethylethanolamine 13, which was oxidized at high temperature with a variety of metal catalysts including cadmium oxide (16) or Raney copper (17) to give GLYH3, after acidification. A similar oxidation route has also been reported starting from iV-phosphonomethy 1-morpholine (18). 

Nucleophilic attack of amines on fully esterified derivatives of phosphoric acid and its thio-analogues may in general occur at phosphorus or carbon. In an attempt to correlate the rates with structural factors, a study has been reported on a series of compounds of the type (49), ... 

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)... 

NMR spectroscopy of various nuclei has been used in the study of AB cements derived from various acids, including phosphoric acid and poly(acrylic acid). For example, NMR has been used in studies of dental silicate cement, i.e. the AB cement made from aqueous phosphoric add and powdered aluminosilicate glass (Wilson, 1978). In this cement, the... 

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