ABSTRACT
The mechanistic insight of the thermal 1,3-chlorine migration reactions of N-chloroacetanilides under neutral conditions has been investigated. The results indicate that the 1,3-chorine migration reaction is initiated by the radical reaction of the homocleavage of the Cl-N bond and subsequent radical combination of the Cl-C bond on the aromatic rings. The radical mechanism was verified by the thermal rearrangement of N-chloro-N-(4-methylphenyl)acetamide in cumene. After generation of hydrochloric acid in the radical mechanism, the migrations occurred through the acid-catalyzed rearrangement as well as the acid-catalyzed Orton reaction. The current results provide a comprehensive understanding on the mechanistic insights in the Orton reaction under different conditions.
Funding
This work was supported in part by the National Basic Research Program of China (No. 2013CB328905), the National Natural Science Foundation of China (Nos. 21372025 and 21572017).