Benzylphosphonic acid

Benzyl chloride readily forms a Grignard compound by reaction with magnesium in ether with the concomitant formation of substantial coupling product, 1,2-diphenylethane [103-29-7]. Benzyl chloride is oxidized first to benzaldehyde [100-52-7] and then to benzoic acid. Nitric acid oxidizes directly to benzoic acid [65-85-0]. Reaction with ethylene oxide produces the benzyl chlorohydrin ether, CgH CH20CH2CH2Cl (18). Benzylphosphonic acid [10542-07-1] is formed from the reaction of benzyl chloride and triethyl phosphite followed by hydrolysis (19). 

Preparation of benzylphosphonic acid — Preparation of a phosphonic acid from red phosphorus in aqueous acid23... 

Orthophosphoric and benzylphosphonic acids have been selectively alkylated with triethyl phosphite in a new synthesis of mono-, di-, and triethyl phosphates and of mono- and di-methyl phosphonates.62 A-Methylol carboxamides and sulphonamides react with trialkyl phosphites to give the phosphonate derivatives (78) and (80), respectively.63 However, the mechanism appears to be quite different in each case while the carboamides react by a transesterification-rearrange-ment pathway, the sulphonamides undergo elimination-addition via the imine (79). 

General.—Triethyl phosphite has been used to achieve stepwise O-ethylation of phosphoric and benzylphosphonic acids.5 The disulphide linkage in bis(phosphinyl) disulphides is cleaved by ammonia in a suitable solvent to yield the phosphinyl-sulphenamides (l).6... 

Methyl sulfonic acid reacts with antimony(V) chloride and water to yield Cl3Sb0(0H)(02S(0)CH3)SbCl3, a binuclear complex with bridging sulfonato groups. Binuclear Sb(V) complexes are also formed from SbCls and diphenylphospho-ric acid or benzylphosphonic acid alkyl ester in water. ... 

Krentzkamp, N., and Cordes, G., Carbonyl- and cyanophosphonic acid esters. Part 6. a-Substimted benzylphosphonic acid and its derivatives. Arch. Pharm. Ber. Dtsch Pharm. Ges., 295, 276, 1962. Schulze, W., WiUitzer, H., and Fritzsche, H., Nitrogen mustard derivatives by the reaction of N,N-iiw(P-chloroethyl)-p-(tricyanovinyl)aniline with the sodium salts of OH, NH, PH, and SH acidic compounds, Chem. Ber., 100, 2640, 1967,... 

Kreutzkamp, N., and Cordes, G., Carbonyl- and cyanophosphonic acid esters. Part 6. a-Substituted benzylphosphonic acid and its derivatives. Arch. Pharm. Ber. Dtsch. Pharm. Ges., 295, 276, 1962. 

Nitration of benzyl- and 2-phenylethyl-phosphonic acids under the usual conditions gives, as expected, the o- and p-nitro-derivatives. ° Diesters of benzylphosphonic acid may be alkylated at the benzylic position by treatment with strong base and alkyl halide mercuric acetate, however, cleaves the C—P bond, giving (98) and benzyl acetate. The related phosphinate (99) is... 

In the case of aromatic spacers, the synthesis was carried out in five steps with an overall yield of 56%. 4-(Bromomethyl)benzonitrile was first reduced using diisobutylaluminium hydride and followed by hydrolysis, to obtain the corresponding aldehyde. The latter was then reacted with triethyl phosphite. Subsequent reaction with methylamine and reduction with sodium borohydride of the resulting phosphonate allowed synthesis of the phosphonated secondary amine. Finally, the 4-(iV-methylaciylamido-methyl)benzylphosphonic acid monomer was obtained by an aciyloylation reaction, and hydrolysis of the phosphonated ester group with bromo-trimethylsilane and methanol finally led to the desired phosphonic acid moiety. 

Benzylphosphonic acid esters. A soln. of benzyl diethyl phosphite (0.1-0.2 M) in deoxygenated benzene irradiated in a quartz tube with a 450 W medium-pressure Hg-lamp - diethyl benzylphosphonate. Y 85-95%. With chiral O-benzyl groups, reaction proceeds with complete retention of configuration at the chiral carbon, F.e.s. W.G. Bentrude et al., J. Am. Chem. Soc. 110, 6908-9 (1988) stereochemistry s.a. Tetrahedron Letters 30, 1025-8 (1989). 

Sn02 or Ti02 4-(2-Pyridin-4-yl-vinyl)-benzylphosphonic acid 299... 

Stilbazole derivatives and r-conjugated compounds with a pyridine unit have been extensively studied for a wide range of applications. The grafting of phosphonic acid-derived stilbazole (4-(2-pyridin-4-yl-vinylj-benzylphosphonic acid) on Sn02 or... 

With aminobenzoic, -benzenesulfonic, and -benzylphosphonic acids in water in the presence of NaNOj, without isolation... 

Hotchkiss PJ, Li H, Paramonov PB, Paniagua SA, Jones SC, Armstrong NR, Bredas JL, Marder SR (2009) Modification of the surface properties of indium tin oxide with benzylphosphonic acids a joint experimental and theoretical study. Adv Mater 21 4496. Li H, Duan YQ, Paramonov P, Coropceanu V, Bredas JL (2009) Electronic structure of self-assembled (fluoro)methylthiol monolayers on the Au( 111) surface impact of fluorination and coverage density. J Electron Spectrosc 174 70... 

A plausible mechanism for this catalytic carbonylation was described in Scheme 4.30. The KIE kf /kg = 3.76) indicate that the C-H cleavage at the ortho position of benzylphosphonic acids is most likely involved with the rate-limiting step. The proposed catalytic cycle started by coordination of the OH group in the... 

I-) Dibromide, in E-00034 l,2-Ethenediylbis[bis(4-methylphenyl) phosphineoxide], E-00043 a-(Ethylamino)-/ -(dimethylamino) benzylphosphonic acid Et ester, in E-00064... 

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