Data from the last six years on the heterocyclization of thioamides containing an active methylene group are analyzed and classified.At the present time there has been a considerable increase in the number of publications on the chemistry of thioamides, and this is explained by the value of the compounds as initial reagents for further transformations and particularly for the synthesis of various sulfur-and nitrogen-containing heterocycles [1][2][3][4][5][6][7][8]. The enormous practical significant of the latter is common knowledge -they have found application as drugs, pesticides, dyes, and preservatives.Thioamides with an active methylene group are attractive synthesis units for the production of heterocycles. These polyfunctional compounds can be represented by the formula R 3 -CH 2 CS-NR 1 R 2 (where R 1 , R 2 = H, Alk, Ar; R 3 is an electron-withdrawing group such as CN, AlkCO, ArCO, (AlkO) 2 PO, AlkSO 2 , ArSO 2 , NO 2 ). The presence of another reaction center (the methylene group) makes it possible to use them as N-С-С and S-C-C components for various condensations [1][2][3][4][5][6][7][8]. A special feature of such substrates is the ability to react both with dinucleophilic and with dielectrophilic and dipolar reagents. As a rule the products of these heterocyclizations contain functional groups, which makes it possible to achieve their modification or annelation. Such characteristics of thioamides with an active methylene group substantially increase their synthetic potential and extend the range of accessible heterosystems, while the use of modern physical methods of investigation (X-ray crystallographic analysis and 1D and 2D NMR spectroscopy) makes it possible to establish the structure of the obtained compounds unambiguously. The presence of biological activity in the products of these transformations also attracts investigators to this subject [5][6][7][8].The reason for the appearance of this review was the increasing need for generalization and classification of new information on the heterocyclization of such thioamides that had not been included in previous reviews [2][3][4][5] and also to define the trends in the study of these processes. Since one of the most important reports in this field is the review [1] we undertook an analysis of the literature that has appeared in the last six years.
The direction of the reaction is governed by the basicity of the medium as well as by the structure of the initial thiourea. Acylation of thioureas (I) and (VI) in acetone occurs selectively yielding heterocycles (III) and (X), respectively. On the other hand, acylation of (I) and (VI) in the presence of potassium carbonate proceeds nonselectively furnishing compounds of cyclic, (IV), and acyclic, (V) and (VII), structure, and phenyl isothiocyanate (VIII). Thiazinones (X) do not react with hydrogen peroxide in acetic acid at room temperature, but melting them with phenacyl bromides (XI) results in dehydrogenation and formation of compounds (XII). -(BRITSUN, V. N.; ESIPENKO, A. N.; LOZINSKII, M. O.; Russ.
Derivatives of 3-aroyl-2-(methylthio)pyridine are valuable starting materials for obtaining condensed nitrogen-containing heterosystems. In spite of the significant number of studies devoted to the synthesis of these compounds [1-7] their further conversions have not been studied. This is probably explained both by the nonselectivity of the reactions obtaining them [1-3] and the difficulty of availability of the initial reactants [4][5][6][7].
scite is a Brooklyn-based organization that helps researchers better discover and understand research articles through Smart Citations–citations that display the context of the citation and describe whether the article provides supporting or contrasting evidence. scite is used by students and researchers from around the world and is funded in part by the National Science Foundation and the National Institute on Drug Abuse of the National Institutes of Health.
hi@scite.ai
10624 S. Eastern Ave., Ste. A-614
Henderson, NV 89052, USA
Copyright © 2024 scite LLC. All rights reserved.
Made with 💙 for researchers
Part of the Research Solutions Family.