The influence of hydrogen bonding on the solvolytic reactivity of nicotinates in fluorinated alcohols

✍ Scribed by Branko Juršić; Dionis E. Sunko; Mladen Ladika

• Book ID: 104205248
• Publisher: Elsevier Science
• Year: 1987
• Tongue: French
• Weight: 574 KB
• Volume: 43
• Category: Article
• ISSN: 0040-4020
• DOI: 10.1016/s0040-4020(01)90312-6

✦ Synopsis

A systematic investigation of solvolytic reactivities of allylic and benzylic nicotinates and their N-•ethylated derivatives in 80% EtOH, 97% TFE and 97% HFIP was undertaken. The nicotinates in 97% HFIP are slightly more reactive than the corresponding p-nitrobenzoates, whereas the ratio of these reactivities is inverse in 80% EtOH and 97% TFE. This observation was explained by the stronger hydrogen bonding of HFIP with nicotinate leaving group than with the p-nitrobenzoate group, which is in keeping with the larger basicity of the former comparing with the latter group. N-Methylnicotinyl esters under the same conditions show approximately 50 times greater solvolytic reactivities than the corresponding p-nitrobenzoates. These relative re-