42308-28-1

Upstream product

• 2101-86-2 p-methylazidobenzene 
• 71-43-2 benzene 
• 623-10-9 N-(4-methylphenyl)hydroxylamine 
• 583-68-6 2-bromo-p-toluidine 
• 3900-89-8 2-Chlorobenzeneboronic acid 
• 4870-23-9 2-p-toluidino-isoindoline-1,3-dione 
• 539-44-6 N-4-methylphenylhydrazine 

Downstream Products

• 54682-59-6 3-methyl-9-(phenylsulfonyl)-9H-carbazole 
• 1283746-93-9 N-(5-methyl-[1,1'-biphenyl]-2-yl)benzenesulfonamide 
• 1330574-17-8 ethyl 2-(5,6-dihydro-2-methyl-5-tosylphenanthridin-6-yl)acetate 
• 1312447-90-7 N-Ts-4-methyl-2-phenylaniline 
• 95702-97-9 3-methyl-9-phenylphenanthrene 
• 1809289-04-0 N¹,N²-bis(5-methyl-[1,1'-biphenyl]-2-yl)oxalamide 
• 1909333-82-9 N¹-benzyl-N²-(5-methyl-[1,1'-biphenyl]-2-yl)oxalamide 

Relevant academic research and scientific papers

"transition-metal-free" synthesis of carbazoles by photostimulated reactions of 2′-halo[1,1′-biphenyl]-2-amines

An efficient and simple protocol for the preparation of a series of 9H-carbazoles by photostimulated SRN1 substitution reactions is presented. Substituted 9H-carbazoles were synthesized in low to excellent yields (up to 96%) through an intramolecular C-N bond formation of 2′-halo[1,1′-biphenyl]-2-amines by the photoinitiated SRN1 mechanism under mild and "transition-metal-free" conditions. The biphenylamines used as substrates were obtained with isolated yields ranging from 21% to 84% by two approaches: (A) the cross-coupling Suzuki-Miyaura reaction and (B) the radical arylation of anilines. Some key aspects of the proposed mechanism were evaluated at the B3LYP/6-311+G? level.

Selective Aromatic N-Substitution with N-(4-Tolyl)hydroxylamine by Addition of Polar Aprotic or Diethereal Solvent

Amination of anisole and toluene with N-(4-tolyl)hydroxylamine in trifluoroacetic acid was tuned to regioselectively provide the corresponding diarylamine by partial replacement of trifluoroacetic acid with a polar aprotic or a diethereal solvent. Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003.

Reaction of n-aminophthalimide derivatives with aluminum chloride in benzene

The reaction of N-aminophthalimide derivatives with AlCl3 in benzene has been investigated. From N-amino- and N-benzamidophthalimide (1a and 1b), N-amino- and N-benzamido3,3-diaryl-2,3-dihydroisoindol-1-ones (2) are obtained in high yield by initial attack of benzene on the imide carbonyl, assisted by the neighboring nitrogen atom. From N-arylaminophthalimide derivatives (4), the N-N bond is cleaved heterolytically to give an arylnitrenium ion and canonical forms involving the arene which are trapped by benzene to give aminobiaryls and N-arylanilines.

INTER- AND INTRA-MOLECULAR AROMATIC N-SUBSTITUTION BY ARYLNITRENIUM-ALUMINIUM CHLORIDE COMPLEXES GENERATED FROM ARYL AZIDES IN THE PRESENCE OF ALUMINIUM CHLORIDE

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.

N- and C-Attacks of Phenylnitrenium Ions Generated from Phenyl Azides in the Presence of Trifluoroacetic Acid and/or Trifluoromethanesulphonic Acid

Phenylnitrenium ions were generated from phenyl azides in the presence of trifluoroacetic acid (TFA) and/or trifluoromethanesulphonic acid (TFSA).Unsubstituted phenylnitrenium ions and those with an electron-withdrawing group such as NO2 or CN undergo aromatic N-substitution, whereas those with an electron-donating group such as Me, OMe, CH2Ph, or Ph undergo C-substitution, hydrogen abstraction, and tar formation.The special character of TFA and TFSA as compared with other acids is discussed.

A TRIFLUOROMETHANESULFONIC ACID-CATALYZED REACTION OF ARYLHYDRAZINES WITH BENZENE

Arylhydrazines reacted with benzene in the presence of trifluoromethanesulfonic acid (TFSA) to give aminobiphenyls.This is a general method for the synthesis of aminobiphenyls.

Acid-Catalyzed Reactions of N-Arylhydroxylamines and Related Compounds with Benzene. Iminium-Benzenium Ions

N-Arylhydroxylamines react with benzene in the presence of trifluoroacetic acid (TFA) at room temperature to give diphenylamines.When TFA was replaced by a strong acid, trifluoromethanesulfonic acid (TFSA), the major products were aminobiphenyls.The nature of the reaction was explored by reactions of 4-substituted phenylhydroxylamines and dialkylaniline N-oxides with benzene.Thus, it was demonstrated that the reactive intermediates are onium-benzenium dications which are trapped by benzene to give aminobiphenyls by a mechanism similar to the Friedel-Krafts alkylation.Further evidence for the proposed reaction mechanism was the observation that nitrosobenzene and azoxybenzene reacted with benzene to give analogous products in the presence of the stronger acid.