A New and Convenient Synthesis of 1,2-Diamino-3-hetarylpyrrole Derivatives

Volovenko, Yulian M.; Tverdokhlebov, Anton V.; Gorulya, Alexandr P.; Шишкина, Светлана В.; Zubatyuk, Roman I.; Шишкин, Олег В.

doi:10.1002/1099-0690(200202)2002:4<663::aid-ejoc663>3.0.co;2-a

Cited by 11 publications

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References 22 publications

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“…In the IR spectra of the derivatives 1a-h there is strong absorption above 3000 cm -1 , due to the stretching vibrations of the N-H bonds, and there is also a strong broad band in the region of 1560-1600 cm -1 , which is not present in the spectra of the initial nitriles 2a-h. It is probably due to the deformation vibrations of the primary amino group, although it is quite likely that it may also include the stretching vibrations of the strongly polarized [17,46] C=C bond of the pyrrolone ring. In some cases this band has a clearly defined shoulder at 1640-1645 cm -1 , which can be assigned to the stretching vibrations of the carbonyl group contained in the β-enamino ketone fragment.…”

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Synthesis of 5-amino-4-hetaryl-2,3-dihydro-1h-3-pyrrolones

Tverdokhlebov

Lyashenko

Volovenko

et al. 2004

Chem Heterocycl Compd

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The interest in derivatives of 2-aminopyrrole has arisen in connection with their prospective use as medicines [1][2][3][4][5][6][7][8] and as components of dyes in photography [9][10][11]. The principal methods for the synthesis of these compounds are the condensation of methylene-active nitriles with derivatives of α-aminocarbonyl compounds [12][13][14][15][16][17] or amination of substituted 4-halobutyronitriles [18][19][20][21][22][23][24] or their synthetic equivalents [25][26][27]. Both approaches have been successfully applied to the synthesis of 1-R 1 -2,2-R 2 ,R 3 -5-amino-4-hetaryl-2,3-dihydro-3-pyrrolones [28][29][30][31][32][33][34][35][36][37]. However, they cannot be used for the production of similar derivatives unsubstituted at position 1 since, on the one hand, the N-unsubstituted α-aminocarbonyl compounds quickly dimerize to pyrazine derivatives and, on the other, the use of ammonia in the reaction together with the need for heat and a nonaqueous medium give rise to certain technical difficulties. For this reason we developed a different method for the synthesis of N-unsubstituted 2,3-dihydro-1H-3-pyrrolones 1a-h, and this method is described here.The key compounds in the synthesis of the dihydropyrrolones 1 are 2-hetaryl-3-oxo-4-phthalimidobutyronitriles 2a-e and the corresponding pentanonitriles 2f-h, obtained by acylation of the hetarylacetonitriles 3a-e with the chlorides of N-phthaloylglycine 4a and alanine 4b (see the scheme). It should be noted that acylation of the sodium salts of simple methylene-active compounds with the chlorides [38-41] and esters [17,42,43] of protected α-amino acids was used earlier for construction of the pyrrole ring. However, the acid chlorides often gave the products from bis-C,C-and bis-C,O-acylation [38,40] of complex mixtures [39], while the esters gave the enolates of the corresponding acyl derivatives. During transformation of the latter into the conjugate acids it was not always possible to avoid side processes associated with hydrolysis of the protecting groups [42,43]. We obtained the monoacyl derivatives 2a-h with yields of more than 90% as the only products (Scheme 1).The composition and structure of the nitriles 2a-h were confirmed by the results of elemental analysis (Table 1) and also by data from the IR and 1 H NMR spectra (Table 2). According to the spectral data, compounds 2a-h exist exclusively in the form of NH tautomers with an intramolecular hydrogen bond, as known for the acyl derivatives of hetarylacetonitriles [44]. Thus, the 1 H NMR spectra of the butyronitriles 2a-e

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Synthesis of 5-amino-4-hetaryl-2,3-dihydro-1h-3-pyrrolones

Tverdokhlebov

Lyashenko

Volovenko

et al. 2004

Chem Heterocycl Compd

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“…The Hantzsch reaction remains one of the most reliable routes to thiazoles and it involves the reaction of a αbromomethylketone with a thioamide in refluxing ethanol or THF and treatment of the resulting thiazolyl hydrobromide with aqueous ammonia [29]. The reaction mechanism is well-known and described in the literature [30].…”

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An environmentally Benign Synthesis of 2-Cyanomethyl-4-Phenylthiazoles under FocusedMicrowave Irradiation

Deligeorgiev¹,

Kaloyanova²,

Lesev³

et al. 2011

GSC

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“…It should be noted that the synthesis of pyrrole derivatives with a thiazole substituent in position 3(4) is considerably less documented [11,14,15] than that of their 2(5)-substituted analogs. We recently developed a preparation procedure for 4-(2-thiazolyl)-3-pyrrolones I based on the use of 2-thiazolylacetonitriles [6,7,18,19]. In extension of research in this field we attempted a synthesis of isomeric pyrrolones aiming at further comparative study of the chemistry of compounds I and II.…”

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“…Hence we developed a convenient method for preparation of 5-amino-4-(4-aryl-2-thiazolyl)-2,3-dihydro-2-pyrrolones VI and VII, isomers of formerly obtained compounds I [6,7,18,19]. The method is based on application of accessible initial compounds and simple experimental procedures and thus it is more attractive compared to more complex and labor-consuming ways of building up the pyrrole ring used in the syntheses of thiazolylpyrroles [5,6,16,17].…”

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“…The method is based on application of accessible initial compounds and simple experimental procedures and thus it is more attractive compared to more complex and labor-consuming ways of building up the pyrrole ring used in the syntheses of thiazolylpyrroles [5,6,16,17]. The comparative study of the chemistry of compounds I and VI, VII is now in progress, and its results will be published elsewhere.…”

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