1-Vinylphosphonic acid

Several appHcations have been found for bis(2-chloroethyl) vinylphosphonate as a comonomer imparting flame retardancy for textiles and specialty wood and paper appHcations. Its copolymerization characteristics have been reviewed (76,109). This monomer can be hydrolyzed by concentrated hydrochloric acid to vinylphosphonic acid, polymers of which have photoHthographic plate coating utiHty (see Lithography). It is also an intermediate for the preparation of an oligomeric vinylphosphonate textile finish, Akzo s Fyrol 76 [41222-33-7] (110). 

Fluoroalkanephosphonic acid can be obtained by addition of iodine perfluoroalkane to vinylphosphonic acid dichloride followed by saponification and deiodination by sodium amalgam [141]. Fluoroalkanephosphonic acids can be transformed to fluoroalkanephosphonic acid glycil esters by 2 mol of epi-chlorhydrin in a water-free solution followed by reaction with alkalines or amines [142]. Compounds of this kind with an alkyl chain of 8-20 carbon at-... 

Diazoalkanes add readily to the double bond of esters of vinylphosphonic acid, giving the pyrazoline derivatives (100), which can lose nitrogen to give esters of cyclopropylphosphonic acids. In a similar reaction, acyl-phosphonic acid esters (101) were converted to epoxy-derivatives (102). A -Phenylsydnone adds to diethyl prop-l-ynephosphonate, giving the pyra-zole (103). The addition of cyclopentadiene to dimethyl vinyl phosphate leads to an exojendo quotient of 1.2, but with hexachlorocyclopentadiene only e/ii/o-isomer is formed. ... 

Detailed interpretations of the n.m.r. spectra of vinylphosphonic acid," phosphoenolpyruvate, and some TV -phosphorylaziridines have been carried out. The vibrational spectra of ethyl phosphorodichloridate and its 1,1-dideuterio- and 2,2,2-trideuterio-derivatives have been examined. 

Wilson, A. D. Ellis, J. (1989). Poly-vinylphosphonic acid and metal oxide or cermet or glass-ionomer cements. British Patent Application 2, 219, 289A. 

Ellis and Wilson studied cements formed from concentrated solutions of poly(vinylphosphonic acid) (PVPA) and oxides and silicate glasses, which they termed metal oxide and glass polyphosphonate cements (Wilson ... 

Ellis, J., Anstice, M. Wilson, A. D. (1991). The glass polyphosphonate cement a novel glass-ionomer cement based on poly(vinylphosphonic acid). Clinical Materials, 7, 341-6. 

In contrast with the behaviour of typical vinylphosphonic acid derivatives, the carbon-carbon double bond in the 1,2-oxa-phospholene (167) is remarkably unreactive towards a broad spectrum of reagents including electrophiles, most epoxidizing and organometallic reagents, as well as to dipolar addition reactants. Exceptional reagents are, however, N-bromoacetamide (NBA), ozone, dimethyllithiumcuprate, and sodium-naphthalene. 

An interesting reaction was studied by A. Schwartz (1997) UV irradiation of phosphate solutions containing acetylene gave vinylphosphonic acid. 

Fig. 4.11 The assumed mechanism of the synthesis of vinylphosphonic acid via addition of the phosphite radical to acetylene (de Graaf et al., 1997)...

What importance could vinylphosphonic acid have for the synthesis of important biomolecules Its photolysis gives many oxidized products, including phosphoac-etaldehyde. This analogue of glycol aldehyde phosphate seems to be of interest its formation involves the recombination of hydroxyl radicals with vinylphosphonic acid radicals. 

Andreae, S. and Seeboth, H., Synthesis of 2-furyl- and 5-nitro-2-furyl-sub-stitued vinylphosphonic acids, Collect. Led. Int. Symp. Furan Chem., 3rd Slovak Tech. Univ., Fac. Chem. Technol., Bratislava, Czechoslovakia, 1979, p. 117. 

ENANTIOSELECTIVE RUTHENIUM-CATALYZED HYDROGENATION OF VINYLPHOSPHONIC ACIDS... 

ASYMMETRIC HYDROGENATION OF VINYLPHOSPHONIC ACIDS CARRYING A PHENYL SUBSTITUENT AT C2... 

Nagarajan R, Tripathy S, Kumar J et al (2000) An enzymatically synthesized conducting molecular complex of polyaniline and poly(vinylphosphonic acid). Macromolecules 33 9542-9547... 

The IL polymers were prepared from polymerizable anions and free imidazolium cations. To investigate the effect of the anion structure on the properties, four kinds of IL monomers were synthesized by neutralizing A-ethylimidazole with acryhc acid, -styrenesulfonic acid, vinylsulfonic acid, and vinylphosphonic acid, respectively, as shown in Figure 29.6 [32]. Table 29.1 summarizes the properties of IL monomers composed of the polymerizable anion and an ethylimidazolium cation. They are liquid at room temperature and show quite low Tg s in the range of —100 to —60°C. EImVS showed the lowest Tg of 95°C among these four IL monomers. In addition it showed the highest ionic conductivity of about 10 S cm at 30°C, which is comparable to that of the best ILs such as the l-ethyl-3-methylimidazolium salts. 

Proton conducting copolymers of vinylphosphonic acid and 4-vinylimidazole have been reported recently by Bozkurt et al. [7]. Since the imidazole ring can act as a proton hopping site in the polymer matrix [8-10], these copolymers had ionic conductivity of about 10 S cm at 60°C without solvent or salt. To realize fast proton transport in copolymer systems, it is essential to design an ion conductive paths that uses the IL domain. 

Most importantly for a successful imprinting by an ion template is the formation of a well-defined polymerisable metal complex in solution prior to polymerisation. Hence metal specific ligands are of particular interest and attempts to improve selectivity have been focused on them. Vinylimidazoles [127], diesters of vinylphosphonic acid [128,129], 4-vinyl-2,2 -bipyridines [130, 131] and methacrylic acid with vinylpyridine [132] are the most intensely studied ligands [133]. 

Trammell, B.C. Hilhnyer, M.A. Carr, P.W. A study of the Lewis acid-base interactions of vinylphosphonic acid-modified polybutadiene-coated zirconia. Anal. Chem. 2001, 73, 3323-3331. 

Asymmetric hydrogem esters in chiral form are cn esters, respectively, on h>d The hydrogenation of < vinylphosphonic acids. ha Allylic alcohols from a obtained in high ee. 

The hydrogenation of other prochiral alkenes, such as substituted acrylic acids and vinylphosphonic acids, has also been scrutinized. 

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