Synthesis of S-linked glucosaminyl-4-thiohex-2-enopyranosides via allylic SN2' substitution of a tosylhexenose.

Treatment of 2-acetamido-3,4,6-tri-O-acetyl-2-deoxy-1-thio-beta-D-glucopyranose with 1,6-anhydro-3,4-dideoxy-2-O-p-toluenesulfonyl-beta-D-erythro-hex-3-enopyranose gave 2-acetamido-3,4,6-tri-O-acetyl-2-deoxy-beta-D-glucopyranosyl-(1-->4)-1,6-anhydro-2,3-dideoxy-4-thio-beta-D-erythro-hex-2-enopyranose in 86% yield. Its 1,6-anhydride bond was cleaved with methanol to give a mixture of methyl glycosides (alpha/beta approximately 5:1), from which the alpha anomer was separated by crystallization and converted into its 6-acetate, 6-methanesulfonate, or deacetylated to obtain the corresponding free methyl thiodisaccharide. The structure of the new compounds was confirmed by 1H and 13C NMR spectra.

Selective N-debenzylation of benzylamino derivatives of 1, 6-anhydro-beta-D-hexopyranoses

When the series of 2-, 3-, and 4-(benzylamino)-2-, 3-, and 4-deoxy derivatives of 1,6-anhydro-beta-D-hexopyranoses in the D-gluco, D-lyxo, and D-arabino configurations were reacted with diisopropyl azodicarboxylate, N-benzyl groups were selectively cleaved in the presence of O-benzyl groups. The yields ranged from 51 to 97%. The debenzylation of some aliphatic benzylamines is also discussed.

[The stratified tuberculoma caused by Mycobacterium kansasii with cavitation (author's transl)]. / Das durch Mycobacterium kansasii hervorgerufene, geschichtete Tuberkulom mit Zerfallshöhle.

Report on a 39 years old female textile worker with an acute cavity. M. kansasii was repeatedly isolated by cultivation from the sputum. The patient became negative by treatment with INH, SM, PAS, Ethionamide, but the cavity persisted. Therefore seven months after the onset of the disease the left upper lobe was resected. A colliquative Stratified tuberculoma and some lesions of caseated bronchitis and peribronchitis were found in the neigh bourhood. Clusters and microcolonies of M. kansasii could be observed as well in the wall of the cavity as in the centre of caseated bronchial lesions. The mycobacteria had a characteristic shabe of long segmentated rods. All about the microcolonies situated in the lumina of small bronchi and bronchioli caseated lesions were present, surrounded by specific granular tissue consisting of epithelial cells, some Langhans giant cells, lymphocytes and fibrocytes. The alterations caused by M. kansasii did not differ from those lesions caused by M. tuberculosis (human.) formerly described as stratified tuberculoma and caseated bronchial lesions with mycobacteria centrally located.