Covalent addition of N-chlorosaccharin to cyclohexene

✍ Scribed by Han-Son Dawn; Ian H. Pitman; Takeru Higuchi

• Publisher: John Wiley and Sons
• Year: 1970
• Tongue: English
• Weight: 217 KB
• Volume: 59
• Category: Article
• ISSN: 0022-3549
• DOI: 10.1002/jps.2600590340

✦ Synopsis

succinate also shows a negative Cotton effect. Esterification of the secondary hydroxyl group is associated with a change in optical rotation resulting in a negative ORD curve for the 0'-ester compound whose ORD curve prior to esterification was positive. Also characteristic of esterification of the 0'-hydroxyl group is a paramagnetic shift of the C( I)-H. Both of these phenomena were observed in the rearrangement of chloramphenicol-3-monosuccinate.

Complete migration of the succinyl function was ruled out on the basis of NMR and chemical data. Complete migration would have given a terminal hydroxyl. No peak corresponding to that for the C(3)-0H proton of chloramphenicol was observed. Chemical evidence indicated that the 0 + 0 migration product was incapable of existence in equilibrium with chloramphenicol-3-monosuccinate under experimental conditions.

Attempts to acetylate or methylate the isomeric compound resulted in complex reaction mixtures, presumably due to the breakdown of the cyclic structure by the reacting anion. All spectral and chemical evidence support the proposed structure.