Aldononitriles acetates

B. A. Dmitriev, L. V. Backinowsky, O. S. Chizhov, B. M. Zolotarev, and N. K. Kochetkov, Gas-liquid chromatography and mass spectrometry of aldononitrile acetates and partially methylated aldononitrile acetates, Carbohydr. Res., 19 (1971) 432 135. 

Poly-O-acetyl-benzothiazol-2-yl acyclo C-nucleosides 184 were prepared in good yields from the aldononitrile acetates (183) [69ACH(62)179 82ACH(109)229] or aldonoyl chloride acetates 38 [69ACH(62)179] by reaction with 2-aminothiophenols (Scheme 54). 

Aldononitrile acetates are suitable for analysis of sugars by g-l.c., and give characteristic mass spectra that are easy to interpret. The molecular ion is not seen, but ions are found at (M — 73) and (M — 98) , corresponding to loss of CH2OAC and CH(OAc)CN moieties, respectively. Primary fragments are formed by a-cleavage of the alditol chain, as depicted in 40. The ions m/e 98 and 170, expected from fission... 

Secondary fragments were formed by single or consecutive eliminations of acetic acid or ketene, as already described (see Section IV,1 p. 53). Partially methylated aldononitrile acetates have been investigated by Kochetkov and coworkers. They found that this class of compounds is fragmented in a manner analogous to that described for partially methylated alditol acetates (see Section IV,5 p. 58). 

Investigations that have involved separations of trimethylsilyl ethers of alditols are listed in Table XXV (see p. 88) Tables XXVI (see p. 89), XXVII (see p. 99), and XXVIII (see p. 100) record separations based on alditol acetates, trifluoroacetates, and aldononitrile acetates, respectively. The retention times of alditol acetates have been tabulated. ... 

The compositions of the different forms of PS-60 are shown in Figure 3. Approximately 50% of native PS-60 is a car-bohydrate fraction comprised of neutral sugars and a uronic acid. The neutral sugars were identified by paper chromatography and quantitated as the aldononitrile acetate derivatives after acid hydrolysis - rhamnose and glucose were shown to be present in a molar ratio of... 

Sugar alcohols and reducing sugars, added to agar culture media for the purpose of identifying specific Gram-negative bacteria, have been determined by g.l.c. as their alditol acetates and aldononitrile acetates, respectively. ... 

Per-O-acetyl aldononitriles and methylated aldononitrile acetates have been separated by g.I.c. on a mixed liquid phase. Chemical ionization m.s. showed the presence of peaks at M + 1 in each instance. The retention times of a number of partially methylated alditol acetates have been recorded on a variety of stationary phases. Using a combination of silica gel chromatography and g.I.c., fifteen methyl ethers of methyl a-D-galactopyranoside have been isolated from the partial methylation products of D-galactose. ... 

The turnover rate for glucose in humans has been evaluated by infusion of [6,6- HJglucose and analysis as its aldononitrile acetate derivative by g.c.-m.s. with selected ion monitoring. The products of partial acetylation of 1,2-0-isopropylidene-a-D-glucofuranose were identified by g.c.-m.s. ... 

The 3 to 6-fold increase in free D-galactose, but not other sugars or myo-inositol, in ripening tomato fruit has been-confirmed capillary g.l.c. of the aldononitrile acetate derivatives. 

---