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The features of nucleophilic substitution of the nitro group in 4-alkyl-6-nitro-1,2,4-triazolo[5,1-c][1,2,4]triazines

E. N. Ulomsky, D. N. Lyapustin, V. V. Fedotov, O. S. El'tsov, I. M. Sapozhnikova, D. N. Kozhevnikov, E. M. Mukhin

Abstract


The nucleophilic substitution of the nitro group of 4-alkyl-6-nitro-4,7-dihydro-1,2,4-triazolo[5,1-c][1,2,4]triazine-7-ones on the example of interactionwith morpholine was studied. It is established that under the action of excess cycloalkylimine at room temperature the unusual easy disclosure of triazine cycle with the formation of sterically hindered hydrazones occurs which are the key intermediates for further transformations. The carrying of reaction at elevated temperatures leads to the formation of products of substitution of the nitro group with the amine and also with morpholyl hydrazones which are the products of hydrolysis of amides of hydrazones and subsequent decarboxylation. Thus, the nucleophilic substitution of the nitro group in the described triazolotriazines flows through the ANRORC mechanism.

Keywords


nucleophilic substitution; ANRORC; the transformation of 4-alkyl-6-nitro-1,2,4- triazolo[5,1-c][1,2,4]triazine-7-ones; morpholine

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References


Reddy PL, Khan SI, Ponnan P, Tripathi M, Rawat DS. Design, synthesis and evaluation of 4-aminoquinoline-purine hybrids as potential antiplasmodial agents. Eur J Med Chem. 2017;126:675–86. doi:10.1016/j.ejmech.2016.11.057

Charushin VN, Chupakhin ON, editors. Metal Free C-H Functionalisation of Aromatics. Nucleophilic Displacement of Hydrogen. Cham (Switzerland): Springer International Publishing; c2014. 283 p. doi:10.1007/978-3-319-07019-3

Ding H, Chen Zh, Zhang C, Xin T, Wang Y, Song H, Jiang Y, Chen Yu, Xu Yo, Tan Ch. Synthesis and Cytotoxic Activity of Some Novel N-Pyridinyl-2-(6-phenylimidazo[2,1-b]thiazol-3-yl)acetamide Derivatives. Molecules. 2012;17(4):4703–16. doi:10.3390/molecules17044703

Tewari S, Chauhan B, Fatima NCh. Syntheses and antifi larial profi le of 7-chloro-4-(substituted amino) quinolines: a new class of antifilarial agents. Bioorg Med Chem Lett. 2000;10(13):1409–12. PMID: 10888320

Van der Plas HC. Advances in Heterocyclic Chemistry. Amsterdam (Netherlands): Elsevier Academic Press; 1999. Chapter III, SN(ANRORC) Reactions in Azaheterocycles Containing an “Inside” Leaving Group; p. 87-151. doi:10.1016/S0065-2725(08)60810-7

Uliankina IV, Zavodskaya AV, Parfenov VE, Gidaspov AA, Shiryaev AK, Selezneva EV, Bakharev VV. Alkylation of [1,2,4]triazolo[1,5-a][1,3,5]triazine-7(3H)-ones. Chem Heterocycl Compd. 2016;52(12):1054–60. doi:10.1007/s10593-017-2006-z

Parfenov VE, Bakharev VV, Gidaspov AA, Shiryaev AK, Slepukhin PA. Alkylation reactions of 5-amino-substituted tetrazolo[1,5-a][1,3,5]triazin-7(3H)-ones with alkyl halides. Chem Heterocycl Compd. 2016;52(12):1061–9. doi:10.1007/s10593-017-2007-y

Danagulyan GG, Panosyan GA, Sahakyan LG. Recyclization of pyrimidinium salts into 1,2,4-triazole derivatives. Chem Heterocycl Compd. 2007;43(8):1175–9. doi:10.1007/s10593-007-0155-1

Rusinov VL, Chupakhin ON, Ulomsky EN, Petrov AY, Sharonov EA. Nitroazines. 9. Characteristic features of nucleophilic substitution of the nitro group in dihydroazolo[5,1-c][1,2,4]triazines. Chem Heterocycl Compd. 1989;25(2):209-13. doi:10.1007/BF00479921

Rusinov VL, Chupakhin ON, Ulomski EN, Rusinov GL, Chernyshev AI, Aleksandrov GG. Nitroazines. 7. Alkylation of 6-nitro-7-oxo-4,7-dihydroazolo[5,1-c][1,2,4]-triazines and identification of the products. Chem Heterocycl Compd. 1987:23(11):1543–50. doi:10.1007/BF00479378




DOI: http://dx.doi.org/10.15826/chimtech.2017.4.1.020

Copyright (c) 2017 E. N. Ulomsky, D. N. Lyapustin, V. V. Fedotov, O. S. Eltsov, I. M. Sapozhnikova, D. N. Kozhevnikov, E. M. Mukhin

© Chimica Techno Acta, 2014-2018
ISSN 2411-1414 (Online), ISSN 2409-5613 (Print)

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