IMIDAZOLE RING FORMATION AND TERTIARY AMINE CLEAVAGE UPON BASE-MEDIATED NUCLEOPHILIC SUBSTITUTION IN 1,1,3-TRICHLORO-1<i>H</i>-ISOINDOLE WITH α-(<i>N</i>-ALKYLAMINO) KETONES

Authors

  • Olga V. Hordiyenko Faculty of Chemistry, Taras Shevchenko National University of Kyiv, 64/13 Volodymyrska St., Kyiv 01601
  • Yuri V. Balitskyy Faculty of Chemistry, Taras Shevchenko National University of Kyiv, 64/13 Volodymyrska St., Kyiv 01601
  • Aleksandr Yu. Usenko Faculty of Chemistry, Taras Shevchenko National University of Kyiv, 64/13 Volodymyrska St., Kyiv 01601
  • Irina S. Konovalova State Scientific Institution ''Institute for Single Crystals'' of National Academy of Sciences of Ukraine, 60 Nauky Ave., Kharkiv 61072
  • Svitlana V. Shishkina State Scientific Institution ''Institute for Single Crystals'' of National Academy of Sciences of Ukraine, 60 Nauky Ave., Kharkiv 61072

DOI:

https://doi.org/10.1007/6531

Keywords:

α-(N-alkylamino) ketone, enols, imidazole, oxazole, 1, 3-trichloro-1H-isoindole, nucleophilic substitution, radicals, tertiary amine cleavage

Abstract

Interaction between α-(N-alkylamino) ketones and 1,1,3-trichloro-1H-isoindole in the presence of tertiary amine leads to nucleophilic substitution of three chlorine atoms and formation of 3-amino-1H-isoindol-1-ylidene-1-aminium quaternary salts possessing two amino ketone residues. Both substituents at nitrogen in aminium salts can adopt either (Z)- or (E)-configuration. Their treatment with bases in air leads via blue enolates (λmax 595.5 nm, CHCl3) to a relatively stable free radical, probably of a bisspiro structure. Reaction can also proceed further with isoindole ring opening and formation of (1H-imidazol-2-yl)phenyl-1,3-oxazol-3-ium derivative. Oxazolium moiety undergoes easy hydrolytic ring cleavage leading to 2-(1H-imidazol-3-ium)benzamide derivative. When N,N-dimethylbenzylamine is used as a base, the reaction proceeds via its cleavage and formation of unsymmetrical aminium salt containing both dimethylamino group along with α-(N-alkylamino) ketone residue.

Author Biography

Olga V. Hordiyenko, Faculty of Chemistry, Taras Shevchenko National University of Kyiv, 64/13 Volodymyrska St., Kyiv 01601

Associate Professor, Faculty of Chemistry

Published

2022-11-17

Issue

Section

Original Papers