a quantum chemical study of unexpected reaction of α-chloroacyl chlorides with 1,2-dichloroethylene in the presence of aluminum chloride：意想不到的反应α-氯代酰氯在氯化铝存在下1的量子化学研究.pdfVIP

Computational and Theoretical Chemistry 1073 (2015) 116–122 Contents lists available at ScienceDirect Computational and Theoretical Chemistry journal homepage: /locate/comptc A quantum chemical study of unexpected reaction of a-chloroacyl chlorides with 1,2-dichloroethylene in the presence of aluminum chloride Vladimir A. Shagun, Galina G. Levkovskaya, Alexandr V. Popov, Igor B. Rozentsveig ⇑ A. E. Favorsky Irkutsk Institute of Chemistry, Siberian Branch of the Russian Academy of Sciences, 664033 Irkutsk, Russian Federation a r t i c l e i n f o a b s t r a c t Article history: The reactions of acetyl chloride and chloroacetyl chloride with 1,2-dichloroethylene in the presence of Received 14 July 2015 aluminum chloride have been mechanistically studied at the M06/6-311+G(d,p) level of theory. The reac- Received in revised form 3 September 2015 tion with acetyl chloride proceeds via the classical channel to afford the expected 1,2-dichlorovinyl Accepted 14 September 2015 ketone. The reaction with chloroacetyl chloride occurs through the alternative channel delivering Available online 28 September 2015 dichloromethyl-2-chlorovinylketone instead of anticipated chloromethyl-1,2-dichlorovinylketone. The quantum-chemical calculations have shown that the difference between classical and alternative Keywords: channels is due to the competitive processes occurring at the first stage of