A NEW SYNTHESIS OF 6-O-ACYLSUCROSES AND OF MIXED 6,6'-DI-O-ACYLSUCROSES

Various 6-O-acylsucroses were synthesized in good yields from unprotec ted sucrose in N,N-dimethylformamide and the appropriate 3-acylthiazol idine-2-thiones 6 or 3-acyl-5-methyl-1,3,4-thiadiazole-2(3H)-thiones 7 . A selective ionization of the free sugar by sodium hydride or trieth ylamine, followed by acylation with 6, gave 2-O-acylsucroses which wer e subjected in situ to intramolecular isomerizations using 1,8-diazabi cyclo[5.4.0]undec-7-ene (DBU) or an aqueous solution of triethylamine to yield 6-O-acylsucroses. The later were otherwise obtained directly when sucrose was acylated with 6 or 7 in the presence of DBU. Moreover , mixed 6,6'-di-O-acylsucroses were readily obtained from 6'-monoacyla tes by using a Mitsunobu reaction without involving the concomitant fo rmation of the 3',4'-epoxide.