Solvolysis–decomposition of N-1-adamantyl-N-p-tolylcarbamoyl chloride in hydroxylic solvents

✍ Scribed by Dennis N. Kevill; Veena Upadhyay

• Publisher: John Wiley and Sons
• Year: 1997
• Tongue: English
• Weight: 77 KB
• Volume: 10
• Category: Article
• ISSN: 0894-3230
• DOI: 10.1002/(sici)1099-1395(199708)10:8<600::aid-poc928>3.0.co;2-q

✦ Synopsis

In hydroxylic solvents, N-1-adamantyl-N-p-tolylcarbamoyl chloride undergoes a facile rate-determing ionization with very little assistance from nucleophilic solvation (very low sensitivity to changes in solvent nucleophilicity). In the relatively nucleophilic aqueous ethanol or aqueous acetone, the cation formed reacts directly with the solvent. In fluoroalcohols, the low nucleophilicity of the solvent allows an effective competition from a pathway involving disproportionation to the 1-adamantyl cation and p-tolyl isocyanate, followed by reaction of the new cation either with solvent or with the chloride ion formed in the initial ionization. Grunwald-Winstein plots against Y C1 values show for different binary solvent systems a marked dispersion, which can be considerably reduced by incorporation into the analyses of a term governed by the aromatic ring parameter. (I).