88893-52-1

Upstream product

• 88-73-3 2-Chloronitrobenzene 
• 100-51-6 benzyl alcohol 
• 1020-39-9 N-(2-chlorophenyI)benzamide 
• 95-51-2 o-chloroaniline 
• 100-39-0 benzyl bromide 
• 109808-29-9 N-benzyl-N-(2-chlorophenyl)benzamide 
• 88284-48-4 2-(trimethylsilyl)phenyl trifluoromethanesulfonate 
• 103-49-1 dibenzylamine 

Downstream Products

• 1380395-20-9 methyl 1-benzyl-2-phenyl-1H-indole-3-carboxylate 

Relevant academic research and scientific papers

1,2-Aminohalogenation of arynes with amines and organohalides

An unprecedented use of inexpensive organohalides as halogen electrophiles to trap the zwitterion intermediates generated from amines and arynes has been developed to access structurally diverse tertiary 2-haloanilines. Effective organohalides include carbon tetrachloride, hexachloroethane, N-chlorosuccinimide, carbon tetrabromide, fluorotribromomethane, N-bromosuccinimide, carbon tetraiodide, and N-iodosuccinimide.

N-Alkylation of Aniline and Its Derivatives by Alcohols in the Presence of Copper Compounds

N-Alkyl- and N,N-dialkyl-substituted anilines were obtained in the reaction of aniline and its derivatives with primary and secondary alcohols in the presence of catalysts CuCl2·2H2O, CuBr2 and halomethanes as promoters.

Unexpected Rearrangement of 2-Bromoaniline under Biphasic Alkylation Conditions

Alkylation of 2-bromoaniline with benzyl bromide under ostensibly basic N-alkylation conditions resulted in migration of bromine from the 2- to the 4-aryl position. Herein we report our studies to elucidate the mechanism of this rearrangement with the objective of suppressing this unexpected outcome. We find that careful choice of reagents is critical, and that this behavior may be extrapolated to alkylation reactions of electron-rich bromo- and iodoanilines in general.

Selective catalytic Hofmann: N -alkylation of poor nucleophilic amines and amides with catalytic amounts of alkyl halides

Using only catalytic amounts of alkyl halides in the reactions of poor nucleophilic amines/amides and alcohols led to a selective Hofmann N-alkylation reaction catalytic in alkyl halides, providing a practical and efficient method for the practical synthesis of mono- or di-alkylated amines/amides in high selectivities. This new method avoids the use of large amounts of bases, alkyl halides, and solvents, and generates water as the only byproduct. Preliminary mechanistic studies showed that alkyl halides are key intermediates/catalysts regeneratable in the reaction cycle.

N-alkylation of amines by homogeneous ruthenium complexes in the presence of free diphosphines

Chemoselective N-alkylation of amines by ruthenium complexes in the presence of free diphosphine ligands under mild conditions is described. Octyl amine and aniline were chosen as aliphatic and aromatic amines to investigate the effect of different phosphines, reaction times, and temperature on conversion, as well as selectivity towards related secondary and tertiary amines. After optimization of the reaction conditions, this catalytic system was used for N-alkylation of other amines and has shown moderate to very good yields. The reaction products were monitored by GC-MS. The crystal structure of [Ru(NO3)2CO(PPh3)2] with a monodentate and a bidentate nitrate was determined by X-ray crystallographic analysis.

Ruthenium-catalyzed tertiary amine formation from nitroarenes and alcohols

A highly selective ruthenium-catalyzed C-N bond formation was developed by using the hydrogen-borrowing strategy. Various tertiary amines were obtained efficiently from nitroarenes and primary alcohols. The reaction tolerates a wide range of functionalities. A tentative mechanism was proposed for this direct amination reaction of alcohols with nitroarenes.