Publisher Summary This chapter discusses the analysis of hexosamines in bacterial polysaccharides by chromatographic procedures. Amino sugars found to date in bacteria, with the single exception of sialic acid, include only hexose derivatives. The naturally occurring amino sugars retain aldose and amino group functions, they vary widely in properties and no single specific assay is available for the combined estimation of amino sugars. However, by use of colorimetry, ionophoresis, cation exchange chromatography, and paper or thin layer chromatography, combined with staining and comparison of ninhydrin degradation products, reasonable identifications can be made for most of the naturally occurring representatives. Cell wall mucopeptide and associated polysaccharides are prepared from both gram positive and gram negative bacterial cells. Amino sugars are detected on paper or thin layer cellulose chromatograms with (1) alkaline silver nitrate, (2) ninhydrin, (3) Elson–Morgan reagent, (4) with Morgan–Elson reagents after N -acetylation, (5) indole after deamination with nitrous acid, (6) p-anisidine HCl, (7) aniline hydrogen phthalate, and (8) silver nitrate after ninhydrin degradation. The separation of 6-deoxy-allosamine from 6-deoxy-galactosamine and 6-deoxy-gulosamine has been achieved by gas liquid chromatography of their trimethylsilyl derivatives.

[4] Analysis of hexosamines in bacterial polysaccharides by chromatographic procedures

Publisher Summary This chapter discusses a substantial proportion of the antibiotics that contain carbohydrate moieties, which covers a wide range of structures. Many of the syntheses involve changes as the conversion of a trans-1,2-glycol into a cis-1 ,2-glycol, a trans-1-2-amino alcohol into a cis-1, 2-amino alcohol, or replacement of a hydroxyl group by some other functional group; in classical aliphatic or alicyclic chemistry, these changes are accomplished by conventional, nucleophilic-displacement reactions of the S N 2 type2 on a sulfonic ester of a hydroxyl group. The secondary sulfonates on sugar rings are, however, very unreactive toward S N 2 displacements; when most of this synthetic work on rare sugars is initiated, the only useful reaction of this type that had been reported of 1, 2: 5, 6-di-O-isopropylidene-3-O-p-tolylsulfonyl-α-D-glucofuranose. This chapter considers all of the intramolecular displacements in sugars, except for the three general classes of reaction.

Neighboring-Group Participation in Sugars

Publisher Summary This chapter discusses the deamination of carbohydrates amine and related compounds. An attempt is made to rationalize the different kinds of behavior of carbohydrate amines—including the cyclitol amines, upon deamination. In addition, the potential use and limitations of these reactions in synthesis and in elucidation of structure are discussed in the chapter. A characteristic feature of deamination reactions is that rearrangement occurs to a greater extent, and more products are often formed, than in related solvolyses. This behavior has been related to the low activation-energies involved in the conversion of the diazonium ion into products, there being smaller differences in the activation energies for the competing pathways than for solvolysis. The activation energy for heterolysis of the alkanediazonium ion is presumed to be very low and according to the Hammond postulate, there should be relatively little bond-formation in the transition state. The relative unimportance of the “migratory aptitude” of a neighboring group in deamination is consistent with a nonconcerted mechanism.

Deamination of Carbohydrate Amines and Related Compounds

Branched-chain sugars have recently been isolated in larger numbers from microorganisms and higher plants as glycoside components of antibiotics or phenolic compounds They also occur in plants in cell wall polysaccharides Sugars with methyl, hydroxymethyl,formyl, hydroxyethyl, and glycoloyl branches have so far been found in nature Many new methods have been developed for the synthesis of these sugars With one exception, the branched sugars known at present can be divided biogenetically into three groups Sugars with methyl branches are formed by C1 transfer, sugars with hydroxyethyl branches by C2 transfer to a hexose chain, and sugars with hydroxymethyl or formyl branches by rearrangement of a hexose or pentose chain

Chemistry and biochemistry of branched-chain sugars.

The oxidation of some carbohydrate derivatives, using acid anhydride-methyl sulphoxide mixtures and the pfitzner-moffatt reagent. Facile synthesis of 3-acetamido-3-deoxy-D-glucose and 3-amino-3-deoxy-D-xylose

The antibiotic kanamycin was degraded with methanolic hydrogen chloride and was determined to be composed of three compounds: deoxystreptamine, 6-amino-6-deoxy-D-glucopyranose and 3-amino-3-deoxy-D-glucopyranose. From the chemical and physical data on the antibiotic and its fragments, kanamycin was shown to be O-α-6-amino-6-deoxy-D-glucopyranosyl-(1→4 or 6)-O-[α-3-amino-3-deoxy-D-glucopyranosyl-(1→6 or 4)]-1, 3-diamino-1, 2, 3-trideoxy-myo-inositol.

The Structure of an Antibiotic Kanamycin

Chemistry of Kanamycin. VI. Deamination Reaction of Methyl 3-Glucosaminide with Nitrous Acid

On the Spectrophotometric Determination of Tetracycline

Molecular Complexes of Tetracycline Acid Salts:Part III. Molecular Complexes of 5-Hydroxytetracycline Acid Salts and the Separtation of Tetracycline, 5-Hydroxytetracycline and 7-Chlorotetracycline by Complex Formation

Shigeharu Inoue

Papers

The Structure of an Antibiotic Kanamycin

Chemistry of Kanamycin. VI. Deamination Reaction of Methyl 3-Glucosaminide with Nitrous Acid

On the Spectrophotometric Determination of Tetracycline

Molecular Complexes of Tetracycline Acid Salts:Part III. Molecular Complexes of 5-Hydroxytetracycline Acid Salts and the Separtation of Tetracycline, 5-Hydroxytetracycline and 7-Chlorotetracycline by Complex Formation

Verfahren zur Herstellung von reinen Tetracyclinsalzen bzw. reinem Tetracyclin