Catalytic Aminohalogenation Reaction of β-Nitrostyrenes with N,N-Dichloro-p-toluenesulfonamide Resulting in Dichlorinated Haloamides with Opposite Regiochemistry to Previous Systems

Sanjun Zhi; Jianlin Han; Chen Lin; Guanghui An; Yi Pan; Guigen Li

doi:10.1055/s-2008-1072567

PAPER

Catalytic Aminohalogenation Reaction of β-Nitrostyrenes with N,N-Dichloro-p-toluenesulfonamide Resulting in Dichlorinated Haloamides with Opposite Regiochemistry to Previous Systems

Sanjun Zhi^a, Jianlin Han^a, Chen Lin^a, Guanghui An^a, Yi Pan*^a,b, Guigen Li*^c
^a School of Chemistry and Chemical Engineering, Nanjing University, Nanjing 210093, P. R. of China
^b State Key Lab of Coordination Chemistry, Nanjing University, Nanjing 210093, P. R. of China
e-Mail: yipan@nju.edu.cn;
^c Department of Chemistry and Biochemistry, Texas Tech University, Lubbock, TX 79409-1061, USA
e-Mail: guigen.li@ttu.edu;

Abstract

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Abstract

Reaction of β-nitrostyrenes with N,N-dichloro-p-toluenesulfonamide (TsNCl₂) has been successfully conducted by using either copper(I) chloride or 4-dimethylaminopyridine (DMAP) as the catalyst. The reaction resulted in dichlorohaloamine products with the opposite regiochemistry to that previously observed. In the presence of DMAP, the reaction proceeded smoothly to completion within 24 hours at room temperature and gave good chemical yields (65-88%). The structure of one of the products was confirmed by X-ray crystal structure analysis. This reaction is proposed to occur through a new mechanism involving a chloronium intermediate.

Key words

aminohalogenation - β-nitrostyrenes - N,N-dichloro-p-toluenesulfonamide - 4-dimethylaminopyridine

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Referenzen

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