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Updated: Aug 7, 2026

Protocol for the Synthesis of Ortho-trifluoromethoxylated Aniline Derivatives
Published on: January 19, 2016
New method for the synthesis of N-tert-alkoxyarylaminyl radicals
Yozo Miura1, Yoshikazu Muranaka, Yoshio Teki
1Department of Applied Chemistry, Graduate School of Engineering, Osaka City University, Sumiyoshi-ku, Osaka 558-8585, Japan. miura@a-chem.eng.osaka-cu.ac.jp
Abstract:
The reactions of 2,4-diaryl-6-tert-butylnitrosobenzenes with 2,2'-azobis[2-(methoxycarbonyl)propane] (5a), 2,2'-azobis(2-cyano-4-methylpentane) (5b), and 2,2'-azobis(2-cyano-4-methyl-4-methoxypentane) (5c) in refluxing benzene gave stable N-tert-alkoxy-2,4-diaryl-6-tert-butylphenylaminyls, which were successfully isolated as radical crystals in 13-52% yields after column chromatography. The radical yields depended on the reaction time and the molar ratio of azo compounds to nitroso compounds. In the same manner, acetyl- and cyano-group-carrying N-tert-alkoxyarylaminyls were generated by the reaction of 2-phenyl-4-(4-acetylphenyl)-6-tert-butylnitrosobenzene and 2-phenyl-4-(4-cyanophenyl)-6-tert-butylnitrosobenzene with 5a and 5b, and they were isolated as radical crystals. X-ray crystallographic analyses were performed for two radicals, and their molecular structures were discussed in detail. The magnetic properties were measured for the two isolated radicals with SQUID in the temperature range 1.8-300 K. One radical showed a weak ferromagnetic interaction (theta = 0.2 K) between the radicals, and the other showed a weak antiferromagnetic interaction (theta = -3.8 K). The ferromagnetic interaction was analyzed based on the X-ray crystallographic structure.
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