Synthesis of 6,1',6'-tri-O-(mesitylenesulfonyl)sucrose, further examination of "tri-O-tosylsucrose", and the chemistry of 3,6:1',4':3',6'-trianhydrosucrose.
Selective trimolar mesitylenesulfonylation of sucrose resulted in the formation of a highly crystalline trimesitylenesulfonate (1), which was isolated in greater than 50% yield without recourse to chromatography. As anticipated, the sulfonyl groups in 1 were located at the primary positions, as treatment with alkali afforded 3.6:1',4':3',6'-trianhydrosucrose (4) in high yield. Fractionation of "tri-O-tosyl-sucrose" by high-pressure liquid chromatography effected separation of the minor isomer from the known, preponderant 6,1',6'-isomer 3. 13C-N.m.r. spectroscopy indicated that the minor isomer was 2,6,6'-tri-O-p-tolylsulfonylsucrose (2). The trianhydride 4 was found to be dimorphous and was further characterized as the diacetate (5), the dibenzoate (6), the di-p-toluenesulfonate (7), and the dimethyl ether (8). Considerable differences in the reactivities toward acylation and etherification of the two axial hydroxyl groups in 4 permitted the preparation, in good yields, of the 4-acetate (9) and of the 4-methyl ether (12). Several derivatives of methyl 3,6-anhydro-alpha-D-glucopyranoside (13) were prepared for comparison with corresponding derivatives of 4, and the hydroxyl groups in 13 also showed differences in reactivities analogous with those of 4.
D055598:Chemical Phenomena; D002621:Chemistry; D009682:Magnetic Resonance Spectroscopy; D008968:Molecular Conformation; D013395:Sucrose / Q000031:analogs & derivatives* / Q000138:chemical synthesis; D013451:Sulfonic Acids; D014105:Tosyl Compounds
D013451:Sulfonic Acids; D014105:Tosyl Compounds; D013395:Sucrose