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From Simple Diols to Carbohydrate Derivatives of Phenylarsonic Acid

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journal contribution
posted on 02.02.2009, 00:00 by Richard Betz, Peter Klüfers
A series of spiro-arsoranes bearing a phenyl moiety as the fifth substituent were synthesized applying open-chain, as well as cyclic vicinal diols, as chelating molecules by condensation reactions in aprotic solvents. The products synthesized are the spiro compounds of the general formula PhAs(DiolH−2)2 derived from the vicinal diols meso-2,3-butanediol, PhAs(meso-2,3-ButdH−2)2 (1), exo-cis-2,3-norbornanediol, PhAs{exo-cis-NobdH−2}2 (2), cis-1,2-cyclopentanediol, PhAs(cis-1,2-CptdH−2)2 (3), anhydroerythritol, PhAs(AnErytH−2)2 (4), cis-1,2-cyclohexanediol, PhAs(cis-1,2-ChxdH−2)2 (5), and rac-trans-1,2-cyclohexanediol, rac-{PhAs(trans-1,2-ChxdH−2)2} (6) which were identified as mononuclear compounds. A novel dimeric double-spiro environment for oxyarsoranes was found in the reaction products derived from the sterically demanding diols 1,1′-bicyclohexyl-1,1′-diol {PhAs(BhxdH−2)O}2 (7) and perfluorpinacol, {PhAs(FpinH−2)O}2 (8). The stability of the compounds in acidic and neutral aqueous media in the presence of organic co-solvents was investigated. A convenient synthetic procedure for spiro-oxyarsoranes, applying water as the solvent, was developed and proven to be advantageous. All of the compounds synthesized in this study were characterized by means of melting-point measurement, single-crystal X-ray analysis, NMR, IR, Raman, UV/vis, and mass spectrometry. The principles found for these reactions were valid for the methyl glycosides of β-d-ribofuranose and α-d-mannopyranose. The spiro-arsorane derived from methyl α-d-mannopyranoside, PhAs(Me-α-d-Manp2,3H−2)2 (9), is the first example of a structurally characterized carbohydrate-arsenic(V) compound.