105184-46-1Relevant articles and documents
Photoinduced ullmann C-N coupling: Demonstrating the viability of a radical pathway
Creutz, Sidney E.,Lotito, Kenneth J.,Fu, Gregory C.,Peters, Jonas C.
, p. 647 - 651 (2012)
Carbon - nitrogen (C-N) bond-forming reactions of amines with aryl halides to generate arylamines (anilines), mediated by a stoichiometric copper reagent at elevated temperature (>180°C), were first described by Ullmann in 1903. In the intervening century, this and related C-N bond-forming processes have emerged as powerful tools for organic synthesis. Here, we report that Ullmann C-N coupling can be photoinduced by using a stoichiometric or a catalytic amount of copper, which enables the reaction to proceed under unusually mild conditions (room temperature or even -40°C). An array of data are consistent with a single-electron transfer mechanism, representing the most substantial experimental support to date for the viability of this pathway for Ullmann C-N couplings.
Synthesis of carbazoles from o-cyclohex-2-enylanilines
Majumdar,Das,Kundu
, p. 1593 - 1600 (1998)
Several carbazoles (4a-f) have been synthesised from o-cyclohex-2- enylanilines by treatment with pyridine hydrotribromide in methylene chloride at 05 °C for 2 h followed by refluxing with Pd-C in diphenyl ether for 1 h.
Acid-Catalyzed Intermolecular Rearrangement of N-Chlorocarbazole
Rosa, Michael De,Quesada, Andres P.,Dodsworth, David J.
, p. 173 - 175 (1987)
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.
Energetics of photocyclization of polyphenylamines and assignment of the intermediate: A time-resolved photoacoustic calorimetric study
Chattopadhyay,Serpa,Arnaut,Formosinho
, p. 3690 - 3695 (2001)
The photocyclization reactions of diphenylamine (DPA), N-methyldiphenylamine (MDPA) and triphenylamine (TPA) have been studied in methanol solvent through nanosecond/microsecond flash photolysis and time-resolved photoacoustic calorimetry (TRPAC). It is confirmed for all the amines that the long-lived dihydrocarbazole intermediate (1XDHC0) is formed through a cascade of processes. However, DPA behaves differently from the other two members of the series so far as the rates of the individual processes are concerned. The quantum yield of triplet formation and the quantum yield of the photocyclization of the amine triplet have been estimated for the DPA system. In conjugation with the experiments, theoretical calculations, employing AM1-SCI method, have been performed to propose a structure for the intermediate. For all the amines, the intermediate has been proposed to be of zwitterionic nature in the ground state. The enthalpies of formation of the intermediate (1XDHC0) from MDPA and TPA have been determined experimentally to be around 51 kcal mol-1 and the values agree well with the calculated ones.
Dearomatization-Rearomatization Strategy for Synthesizing Carbazoles with 2,2′-Biphenols and Ammonia by Dual C(Ar)-OH Bond Cleavages
Cao, Dawei,Yu, Jing,Zeng, Huiying,Li, Chao-Jun
, p. 13200 - 13205 (2020)
Carbazole is an essential building block in various pharmaceuticals, agrochemicals, natural products, and materials. For future sustainability, it is highly desirable to synthesize carbazole derivatives directly from renewable resources or cheap raw materials. Phenolic compounds are a class of degradation products of lignin. On the other hand, ammonia is a very cheap industrial inorganic chemical. Herein, an efficient dearomatization-rearomatization strategy has been developed to directly cross-couple 2,2′-biphenols with ammonia by dual C(Ar)-OH bond cleavages. This strategy provides a greener pathway to synthesize valuable carbazole derivatives from phenols.
Diels-Alder reactions of N-tosyl-3-nitroindole and dienamides: Synthesis of intermediates of Aspidospermine alkaloids
Biolatto, Betina,Kneeteman, Maria,Mancini, Pedro
, p. 3343 - 3346 (1999)
N-tosyl-3-nitroindole undergoes high yielding Diels-Alder reactions with 1-(N-acyl-N-alkylamino)-1,3-butadienes in a regioselective manner, to afford advanced intermediates for the synthesis of Aspidospermine alkaloids.
Dehydrogenation of 1,2,3,4-tetrahydroquinoline and its related compounds: Comparison of Pd/C-ethylene system and activated carbon-O2 system
Tanaka, Takanori,Okunaga, Ken-Ichi,Hayashi, Masahiko
, p. 4633 - 4635 (2010)
Dehydrogenation of substituted 1,2,3,4-tetrahydroquinoline, 1,2,3,4-tetrahydroisoquinoline, and 1,2,3,4-tetrahydrocarbazole proceeded using Pd/C-ethylene system (method A) or activated carbon-O2 system (method B) to give the corresponding heteroaromatic compounds.
Thermal decomposition reactions of N-alkylated 2-aminobiphenyls to carbazole and phenanthridine
Creencia, Evelyn Cuevas,Horaguchi, Takaaki
, p. 1441 - 1446 (2006)
Thermal cyclization reactions were examined by passing vapors of N-alkylated 2-aminobiphenyls 1a-c and 2 over calcium oxide at 450-600°C under nitrogen carrier gas. The reactions yielded 9-methylcarbazole 3, carbazole 4, phenanthridine 5 and phenanthrene 6. The major product for the reactions of 1a, 1b and 2 was phenanthridine 5 while that of 1c was carbazole 4.
INTER- AND INTRA-MOLECULAR AROMATIC N-SUBSTITUTION BY ARYLNITRENIUM-ALUMINIUM CHLORIDE COMPLEXES GENERATED FROM ARYL AZIDES IN THE PRESENCE OF ALUMINIUM CHLORIDE
Takeuchi, Hiroshi,Maeda,Munenori,Mitani, Michiharu,Koyama, Kikuhiko
, p. 57 - 60 (1987)
Reactions of phenyl azide with aromatic compounds ( i. e. benzene, toluene, ethylbenzene, cumene, anisole, and bromobenzene ) in the presence of AlCl3 gave diarylamines, whwreas those of phenyl azides with an electron-donating group such as Me and OMe yield little of the corresponding diarylamines ( tarformation takes place ).The reaction of 4-nitrophenyl azide with benzene in the presence of AlCl3 gave 4-nitrophenyl(phenyl)amine and a C-substitution product, 2-amino-5-nitrobiphenyl.Decomposition of 2-azidophenyl(phenyl)methane and 2-azidobiphenyls in CH2Cl2 in the presence of AlCl3 underwent an N-cyclization to afford 9,10-dihydroacridine and carbazoles, respectively, in good yields.The kinetic data on the decomposition of aryl azides and a Hammet plot ( with p= -6.0 ) for the formation of diarylamines suggest that the products are formed by an aromatic N-substitution of arylnitrenium-AlCl3 complexes via azide-AlCl3 complexes.We further argue the character of arylnitrenium-AlCl3 complexes.
Synthesis of Terminal Vinylindoles via RhIII-Catalyzed Direct C?H Alkenylation with Potassium Vinyltrifluoroborate
Zhou, Chun-Ni,Xie, Hao-Hao,Zheng, Zi-Ang,Xiao, Yuan-Chao,Li, Gen,Shen, Yang-Huan,Peng, Wang-Ming,Wang, Liang
, p. 5469 - 5473 (2018)
An efficient RhIII-catalyzed direct C2-alkenylation of indoles using readily available potassium vinyltrifluoroborate under mild conditions has been developed. This protocol features wide substrate scope and excellent functional group compatibi
