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Imidazole ring formation and tertiary amine cleavage upon base-mediated nucleophilic substitution in 1,1,3-trichloro-1H-isoindole with α-(N-alkylamino) ketones

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Chemistry of Heterocyclic Compounds Aims and scope

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.

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Authors and Affiliations

  1. Faculty of Chemistry, Taras Shevchenko National University of Kyiv, 64/13 Volodymyrska St, Kyiv, 01601, Ukraine

    Olga V. Hordiyenko, Yuri V. Balitskyy & Aleksandr Yu. Usenko

  2. State Scientific Institution “Institute for Single Crystals” of National Academy of Sciences of Ukraine, 60 Nauky Ave, Kharkiv, 61072, Ukraine

    Irina S. Konovalova & Svitlana V. Shishkina

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  1. Olga V. Hordiyenko
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  2. Yuri V. Balitskyy
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  3. Aleksandr Yu. Usenko
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Correspondence to Olga V. Hordiyenko.

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Published in Khimiya Geterotsiklicheskikh Soedinenii, 2022, 58(11), 628–633

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Hordiyenko, O.V., Balitskyy, Y.V., Usenko, A.Y. et al. Imidazole ring formation and tertiary amine cleavage upon base-mediated nucleophilic substitution in 1,1,3-trichloro-1H-isoindole with α-(N-alkylamino) ketones. Chem Heterocycl Comp 58, 628–633 (2022). https://doi.org/10.1007/s10593-022-03136-0

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