REACTIONS OF QUINOLINECARBALDEHYDES WITH ARENES UNDER SUPERELECTROPHILIC ACTIVATION. NMR AND DFT STUDIES OF DICATIONIC ELECTROPHILIC SPECIES

Authors

  • Marina А. Borisova Saint Petersburg State Forest Technical University, 5 Institutskiy Pereulok, Saint Petersburg 194021, Russia
  • Dmitry S. Ryabukhin Saint Petersburg State Forest Technical University, 5 Institutskiy Pereulok, Saint Petersburg 194021, Russia All-Russia Research Institute for Food Additives, Branch of V. M. Gorbatov Federal Research Center for Food Systems of Russian Academy of Sciences, 55 Liteyny Ave., Saint Petersburg 191014, Russia
  • Alexander Yu. Ivanov Center for Magnetic Resonance, Research Park, Saint Petersburg State University, 26 Universitetskiy Ave., Saint Petersburg 198504, Russia
  • Irina A. Boyarskaya Institute of Chemistry, Saint Petersburg State University, 7/9 University Embankment, Saint Petersburg 199034, Russia
  • Dar’ya V. Spiridonova Research center for X-Ray Diffraction Studies, Research Park, Saint Petersburg State University, 26 Universitetskiy Ave., Saint Petersburg 198504, Russia
  • Mikhail O. Kompanets L. M. Litvinenko Institute of Physical-Organic Chemistry and Coal Chemistry, 50 Kharkivske Shose, Kyiv 02160, Ukraine
  • Aleksander V. Vasilyev Saint Petersburg State Forest Technical University, 5 Institutskiy Pereulok, Saint Petersburg 194021, Russia Institute of Chemistry, Saint Petersburg State University, 7/9 University Embankment, Saint Petersburg 199034, Russia

DOI:

https://doi.org/10.1007/6311

Keywords:

quinolines, carbocations, DFT calculations, Friedel–Crafts reaction, superelectrophilic activation.

Abstract

N,O-Diprotonated forms (dications) of various quinolinecarbaldehydes were theoretically studied by DFT calculations. It was found that the most reactive electrophilic dications are expected to be generated from 2- and 4-quinolinecarbaldehydes compared to the other quinolinecarbaldehydes. Experimental studies of protonation of quinoline-2(6,8)-carbaldehydes in Brønsted acids (CF3SO3H, H2SO4) by means of 1H, 13C, and 15N NMR revealed the formation of the corresponding N-protonated O-protosolvated species. Reactions of quinoline-2(6,8)-carbaldehydes with arenes in the presence of Brønsted (TfOH) and Lewis acids (AlX3, X = Cl, Br) or acidic zeolites led to the formation of the corresponding 2(6,8)-(diarylmethyl)quinolines. However, 6- and 8-quinolinecarbaldehydes gave additionally unusual products – 6(8)-(arylmethyl)quinolines.

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Published

2021-10-21

Issue

Vol. 57 No. 10 (2021)

Section

Original Papers