Bulletin of the Chemical Society of Japan p. 2140 - 2147 (1991)
Update date:2022-08-05
Topics:
Sakurai, Tadamitsu
Mizuno, Hisashi
Kubota, Tsuneari
Inoue, Hiroyasu
Title hydroxylamines (1) undergo benzophenone-sensitized photolysis to give N-benzylidenebenzylamine (2), p-substituted benzoic acids (3), and monosubstituted benzenes (4) derived from decarboxylation of p-substituted benzoyloxyl radicals.Analysis of the linear Stern-Volmer plots, both for the sensitized photolysis of 1 and for the phosphorescence quenching of benzophenone by 1, demonstrates the participation of triplet 1 in this photolysis.The logarithm of the ratio (kr/kd), where kr is the rate constant for homolytic cleavage of the N-O bond in triplet 1 and kd is that for its deactivation, used as a measure of the triplet-state reactivities of 1, exhibited a good Hammett-type relationship against the substituent constant (?) with a slope (ρ) of -0.75.This indicates the exclusive occurence of homolysis of the N-O bond in the first excited triplet state of 1.Thus the decomposition of 1 activated by triplet benzophenone is classified as an imine-forming radical elimination.The results of deuterium isotope and micellar effects on the sensitized photolysis suggest that the "out-of-cage" products 4 are obtained by decarboxylation and subsequent hydrogen abstraction of p-substituted benzoyloxyl radicals which escaped from the triplet cage in competition with spin inversion to the singlet cage.In this singlet cage, hydrogen abstraction giving 2 and 3 and recombination affording the starting 1 were found to take place exclusively.
View MoreBeijing Harmony Chemical Co., Ltd.
Contact:86-010-84956928
Address:Room 207, Jin feng he B building, No 8 Xin Jie Kou Wai Street, Xi Cheng District, Beijing,PRC. 10008
Longhui qunfeng Chemical Co., Ltd
Contact:86-731-82173407
Address:South-east Industrial Park, Longhui County, Hunan Province, China
Contact:86-574-83851061 86-574-87083208
Address:Room 905, No.3 Building,East Business Center, 456 Xingning Road, Ningbo City,China
Zibo Fuxi'er Chemical Co.,Ltd (Shanxian Fuxi'er Chemical Co.,Ltd)
Contact:+86-533-2091422
Address:Eastern 4 on the 3th Road ,Liangxiang Industrial Park, Zibo city ,Shandong,China
Yicheng Goto Pharmaceuticals Co.,Ltd.
Contact:+86 710 3423122
Address:5th Floor,East Gate of Building #2,Servo-Industrial Park,1st Qilin Road,Xiangyang,Hubei,China
Doi:10.3998/ark.5550190.0013.318
(2012)Doi:10.1039/c2ob06991a
(2012)Doi:10.1246/cl.1991.1591
(1991)Doi:10.1021/jm300042x
(2012)Doi:10.1002/asia.201100781
(2012)Doi:10.1002/ejic.201101385
(2012)