57103-00-1Relevant articles and documents
One-electron photooxidation of N-ethylcarbazole in the presence of carbon tetrachloride. Products and mechanism of the photochemical reaction
Zelent, Bogumil,Durocher, Gilles
, p. 1654 - 1665 (2007/10/02)
The mechanism of the photodecomposition of N-ethylcarbazole (NEC) in the presence of carbon tetrachloride has been discussed on the basis of the photoproducts identified.The photodissociation of the N-ethyl bond and the electron transfer in the transiently formed ex-CT complex, 1(NEC?+...CCl4?-)*, have been proposed as the primary photochemical processes involved in the singlet excited NEC molecule.The latter, treated as the main process, leads to the radical cation of NEC, chloride ion, and trichloromethyl radical in the solvent cage, +.Cl-.CCl3>.The other reactions in the system studied are analysed following the decomposition of NEC+. in the presence of Cl- and .CCl3, which can occur by the N-ethyl group and (or) by the aromatic ring.The formation of intermediate products such as αr, αk, and γ'i(i=1,2,3, or 4) in the solvent cage gives rise to secondary photochemical reactions in the system studied.The polarity and chemical activity of the reaction media used strongly influence the nature of the secondary photochemical transformations both in and outside the solvent cage.The formation mechanism of the photochemical reaction products in CCl4 when ammonia was used, after and during irradiation, has been explained mainly by the transformations of the radical αr and cation αk as well as by the carbazyl radical β, which is also formed in the reaction medium.On the other hand, reaction of the cation γ'i explains the formation of the photoproducts in the irradiated solution of NEC with CCl4 in ethanol.These photochemical results have been compared to the photochemical reactions involved in the carbazole-CCl4 system.
