Photochemistry of Benzanilide I Photocyclization of Benzanilides

벤즈아닐리드류의 광화학 (제1보). 벤즈아닐리드류의 광고리화 반응

  • Yong-Tae Park (Department of Chemistry, Kyungpook National University) ;
  • Sang-Rok Do (Department of Chemistry, Kyungpook National University) ;
  • Kap-Duk Lee (Department of Food Technology, Kyung-pook Junior College)
  • 박용태 (경북대학교 자연과학대학 화학과) ;
  • 도상록 (경북대학교 자연과학대학 화학과) ;
  • 이갑득 (경북전문대학 식품학과)
  • Published : 1985.08.20


Preparative and kinetic photochemical reactions of several benzanilides were studied. Several substituted benzanilides were synthesized by acylation of substituted anilines with substituted benzoyl chlorides. While benzanilide gave a photo-Fries type reaction product, 2-chlorobenzaniline, 2-bromobenzanilide, and 2-methoxybenzanilide gave a photocyclization reaction product, phenanthridone. Since 8-chlorophenanthridone was obtained from 2,2'-dichlorobenzanilide, the carbonyl phenyl is the excited site. Quantum yield of photocyclization of 2-chlorobenzanilide, 2'-chlorobenzanilide, and 2-methoxybenzanilide were obtained. 2-Chlorobenzanilide was photocyclized effectively and 2'-chlorobenzanilide ineffectively. Since the oxygen present in the reaction medium retarded the photocyclization reaction of 2-chlorobenzanilide, the triplet state of 2-chlorobenzanilide is involved. The mechanism of the photocyclization of 2-chlorobenzanilide is suggested: $\pi-complex$ between carbonyl phenyl and N-phenyl was formed from the triplet state of 2-chlorobenzanilide; neighbour phenyl (N-phenyl) assists for leaving of chlorine from carbonyl phenyl to make an intermediate, cyclized conjugated radical, because electron donating group on the N-phenyl ring accelerated the reaction; hydrogen detachment from the intermediate is obviously not a rate determined step because there was no isotope effect on the rate of photocyclization. The photocyclization reaction rate of 2-methoxybenzanilide was faster in the presence of oxygen than in the absence of oxygen. Thus, the singlet excited state of 2-methoxybenzanilide is involved in the reaction. Probably, the intermediate, methoxyhydro-phenanthridone is oxidized by oxygen in the medium to give phenanthridone.



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