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Updated: Aug 13, 2025

Microwave-assisted Intramolecular Dehydrogenative Diels-Alder Reactions for the Synthesis of Functionalized Naphthalenes/Solvatochromic Dyes
Published on: April 1, 2013
N-Fluorobenzamide-Directed Formal [4+2] Cycloaddition Reaction with Maleic Anhydride: Access to Fluorescent
Tianyu Lu1, Boyi Wang1, Weixing Chang1
1State Key Laboratory and Institute of Elemento-Organic Chemistry, College of Chemistry, Nankai University, Tianjin 300071, P. R. China.
Abstract:
We have developed a formal [4+2] cycloaddition reaction of N-fluorobenzamides and maleic anhydride in the presence of CuI and LiOH, and a series of fluorescent 1-amino-2,3-naphthalic anhydrides were produced in good yields. This reaction proceeded via a multistep process involving nitrogen-centered radical generation, 1,5-hydrogen atom transfer, and benzylic radical addition to the amide carbonyl oxygen to generate an N-(tert-butyl) isobenzofuran-1(3H)-imine intermediate, which isomerized to an N-(tert-butyl) isobenzofuran-1-amine via deprotonation and protonation with the aid of LiOH; finally, the amine underwent a [4+2] cycloaddition reaction with maleic anhydride to give the 1-amino-2,3-naphthalic anhydride product upon dehydrating aromatization. Notably, the corresponding naphthalic anhydride products could be transformed into a diverse array of naphthalimides. Both the naphthalic anhydrides and the naphthalimides exhibited similar fluorescent features.
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