5599-71-3Relevant articles and documents
N,N-di(4-halophenyl)nitrenium ions: Nucleophilic trapping, aromatic substitution, and hydrogen atom transfer
Thomas, Selina I.,Falvey, Daniel E.
, p. 4626 - 4634 (2008/02/07)
(Figure Presented) The reactive intermediates N,N-di(4-chlorophenyl) nitrenium ion and N,N-di(4-bromophenyl)nitrenium ion were generated through photolysis of the corresponding N-amino(2,4,6,-collidinium) ions. The behavior of these diarylnitrenium ions was characterized by laser flash photolysis, analysis of the stable photoproducts, and ab initio calculations with density functional theory. The latter predict these species to have singlet ground states. The halogenated diarylnitrenium ions are significantly longer lived than the unsubstituted diphenylnitrenium ion. Specifically, cyclization to form carbazole derivatives occurs negligibly, if at all, with the halogenated derivatives. They do, however, carry out most of the characteristic reactions of singlet arylnitrenium ions, including combining with nucleophiles on the aryl rings, adding to arenes, and accepting electrons from readily oxidized traps. Interestingly these species also abstract H atoms from 1,4-cyclohexadiene and various phenol derivatives. The implication of the latter process in relation to the computed singlet-triplet energy gaps of ca. -12.5 kcal/mol is discussed.
Acid-Catalyzed Intermolecular Rearrangement of N-Chlorocarbazole
Rosa, Michael De,Quesada, Andres P.,Dodsworth, David J.
, p. 173 - 175 (2007/10/02)
The chlorination of carbazole with sodium hypochlorite in CH2Cl2, CHCl3, or CCl4 gave N-chlorocarbazole in 63-95percent yield.It rearranged in refluxing methanol to give carbazole, 3-chlorocarbazole, 1-chlorocarbazole, 3,6-dichlorocarbazole, and 1,6-dichlorocarbazole.These chlorocarbazoles were formed in an acid-catalyzed intermolecular reaction.In the presence of potassium carbonate dechlorination of N-chlorocarbazole was observed.No evidence for an intramolecular rearrangement was found.
