Aldonic acids trimethylsilyl derivatives

In model experiments,205 it was found that concentration of an aqueous solution of the aldonic acids in the presence of hydrochloric acid gives exclusively the 1,4-lactones, which, on subsequent trimethyl-silylation, give only one peak on the chromatogram. This method was successfully employed for the separation of D-galacturonic, D-glucuronic, and D-mannuronic acids. Of the 1,4-lactones examined, only the trimethylsilyl ether of D-mannono-1,4-lactone was obtained in crystalline form. However, all of the derivatives showed characteristic differences in their infrared spectra in the range of 1500 to 600 cm"1. When this method was applied to the determination of uronic acids in a variety of polysaccharides,205 it was impossible to find any hydrolytic conditions under which the uronic acids were quantitatively released and then reduced, a problem experienced by other workers.20 The method was, however, successful in affording a qualitative, microscale procedure for the identification of hexuronic acids (which otherwise are difficult to detect). 

Samuelson and coworkers499 have also reported the separation of aldonic acids as their O-trimethylsilyl derivatives the results confirmed Perry s observation that concentration in the presence of... 

The relationship between structure and paper-chromatographic mobility of aldono-1,4-lactones has been discussed.65 Butanone, saturated with water, is suitable for the preparative separation of lactones on cellulose columns free acids and reducing sugars move very slowly in this system. Separation of aldono-1,4-lactones and of aldonic acids as their O-(trimethylsilyl) derivatives has been accomplished.66 The mass spectra of such derivatives are characteristic, so that it is possible to identify aldonic acids67 and lactones68 by means of combined gas chromatography-mass spectrometry. 

G. Peterson, Mass spectrometry of aldonic and deoxyaldonic acids as trimethylsilyl derivatives, Tetrahedron, 26 (1970) 3413-3428. 

Acyclic, trimethylsilyl derivatives of aldonic, deoxyaldonic, aldaric, deoxyaldaric, and hexulosonic acids have been investigated by m.s. " A series of fragments is obtained by C-C a-cleavages, as for the per( tri-... 

The trimethylsilyl derivatives of 4- and 5-hexulosonic acids also give the rearrangement ion at m/e 292. In addition, the 5-hexulosonic acid derivative is degraded by a similar rearrangement-process, to form the ion m/e 306 (see Scheme 34). Aldonic acids can also be characterized by g.l.c. -m.s. of the corresponding per (trimethylsilyl) ated aldonolac-... 

Trioses and tetroses have been separated as their trimethylsilylated oximes by g.l.c. mass-spectral data for these derivatives were also recorded. Mixtures of xylitol, arabinitol, mannitol, glucitol, and maltitol have been separated efficiently by h.p.l.c. of the corresponding 4-nitrobenzoates. Alditols have been determined in the presence of neutral sugars by oxidation with acidified sodium periodate and colorimetric measurement of the formaldehyde released. G.l.c. retention data have been reported for the TMS derivatives of a large number of aldonic acids and their lactones and aldaric acids. ... 

Petersson, G., Riedl, H. and Samuelson, O. (1967), Gas chromatographic separation of aldonic acids as trimethylsilyl derivatives. Sv. Papperstidn., 70,371. 

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