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Paper | Special issue | Vol 79, No. 1, 2009, pp.599-608
Published online, 23rd October, 2008
DOI: 10.3987/COM-08-S(D)23
Reaction of β-Trifluoroacetylketene Acetals and β-Trifluoroacetylvinyl Ethers with 1,2-Phenylenediamines Accessing Fluorine-Containing Benzo[b][1,4]diazepine Derivatives: A Molecular Orbital Calculation Study

Norio Ota, Yasuhiro Kamitori,* Naoya Terai, Tsuneaki Sakata, and Etsuji Okada*

*Department of Chemical Science and Engineering, Graduate School of Engineering, Kobe University, 1-1 Rokkodai-cho, Nada-ku, Kobe 657-8501, Japan


β-Trifluoroacetylketene acetals (1) were found to react easily with 1,2-phenylenediamines to give dihydrobenzodiazepinols (5a) together with benzodiazepines (6a) under very mild conditions. In contrast, β-trifluoroacetyl-α-phenylvinyl ethers (2) and β-trifluoroacetylvinyl ethers (3) exclusively yielded O-N exchanged products (9) when they were reacted with 1,2-phenylenediamines. The factors determining product formation by the reaction of each of three similar substrates (1-3) with 1,2-phenylenediamine were elucidated on the basis of molecular orbital calculations. The dehydration processes converting dihydrobenzodiazepinols (5 and 7) to the corresponding benzodiazepines (6 and 8) are also discussed.