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Oxidation of allenes bearing 1,8‐diphenoxy or diaryloxyacridene moieties
Author(s) -
Fukuen Shinichi,
Yamamoto Junki,
Furukawa Ko,
Hashizume Daisuke,
Kawata Naomi,
Yamamoto Yohsuke
Publication year - 2017
Publication title -
journal of physical organic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.325
H-Index - 66
eISSN - 1099-1395
pISSN - 0894-3230
DOI - 10.1002/poc.3665
Subject(s) - allene , chemistry , singlet state , photochemistry , resonance (particle physics) , electron paramagnetic resonance , singlet oxygen , diradical , nuclear magnetic resonance , organic chemistry , catalysis , excited state , atomic physics , oxygen , physics
New allene compounds bearing 1,8‐diphenoxy or bis(3,5‐di‐ tert ‐butylphenyl) oxyacridene (diaryloxyacridene) moieties were synthesized. These compounds were more easily oxidized than Cl‐substituted compounds. The allene compounds were oxidized to generate thermally stable triplet carbenes. Electron spin resonance and electron spin transient nutation spectra of the oxidation reaction products suggested the generation of triplet species; however, the main isolated product from the 1,8‐diphenoxy allene was a cyclized compound that was characterized by X‐ray analysis. The product derived from diaryloxy allene was also characterized by X‐ray analysis as a singlet species, which included a vinyl cation stabilized by a neighboring O(3,5‐di‐ tert ‐butylphenyl) group. This singlet species was stable even at room temperature and did not show any electron spin resonance signals in solution, indicating that the triplet species was not in equilibrium with the singlet. Copyright © 2016 John Wiley & Sons, Ltd.