ChemInform Abstract: Gem‐Dinitro Compounds in Organic Synthesis. Part 3. Syntheses of 4‐ Nitro‐1,2,3‐triazoles from gem‐Dinitro Compounds.

Baryshnikov, A. T.; Erashko, V. I.; Zubanova, N. I.; Уграк, Б. И.; Шевелев, С. А.; Fainzil'berg, A. A.; Laikhter, A. L.; Mel'nikova, L. G.; Семенов, В. В.

doi:10.1002/chin.199412193

Cited by 3 publications

(8 citation statements)

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“…In this case heterocyclization is accompanied by the elimination of one of the nitro groups [11,31,32]. In the opinion of the authors the reaction of dinitroalkenes with sodium azide takes place as a two-stage intramolecular cyclization.…”

Section: Ch Chmentioning

confidence: 99%

“…In these papers several approaches to the key dinitroethenes 29 were proposed during searches for a preparative method for the synthesis of N-unsubstituted nitrotriazoles [33]. The esters of dinitroacetic acid 30 and various derivatives of 1,1-dinitro-and 1,1,1-trinitroalkanes 31 were used as initial gem-dinitroethenes [11]. A similar approach was used in the synthesis of bis(4-nitro-1,2,3-triazol-5-yl) (32) by the reaction of the diacetate of 1,1,4,4-tetranitrobutane-2,3-diol (33) In the opinion of the authors the reaction takes place through the formation of the intermediate tetranitrobutadiene [31].…”

Section: Ch Chmentioning

confidence: 99%

“…Apart from the nitro group, chemical modifications of other substituents in nitrotriazole molecules have been described in the literature. Thus, a whole series of derivatives of N-unsubstituted 4-nitro-1,2,3-triazoles, including the difficultly obtainable 4,5-dinitro-1,2,3-triazole, were synthesized by successive transformation of the functional groups [11]. The starting compound for these transformations was 5-methyl-4-nitro-1,2,3-triazole (71).…”

Section: Alk Alkmentioning

confidence: 99%

“…At the same time in [11] it was shown that the nitration of 4-hydroxy-2-phenyl-1,2,3-triazole 10 and also of the corresponding triazole 1-oxide with a nitrating mixture even with cooling is accompanied by decomposition of the molecule. Nevertheless, the hydroxyl group in the triazole 10, as in phenol, creates such favorable conditions that nitration of the heterocycle occurs under the influence of milder nitrating agents such as dilute nitric acid or a mixture of nitric and acetic acids.…”

mentioning

confidence: 97%

“…Thus, for example, an aminopicryl substituent at one of the carbons in the triazole 20 directs attack by the nitronium cation at the C-2 atom of the heterocycle [16]. The presence of a nitro group at position 4 of the triazole ring prevents the nitration of 4-nitro-1,2,3-triazole and its 5-alkyl-substituted derivatives with fuming nitric acid or a nitrating mixture on account of destruction of the substrate molecules [11]. At the same time if such nitrating agents as nitronium borofluoride (in acetonitrile at 0°C, in methylene chloride at 20°C) and acetyl nitrate are used nitration takes place at the nitrogen atoms of the ring with the formation of the 1,4-dinitro-(21) and 2,4-dinitro-1,2,3-triazoles and (22) (AcONO 2 ) + 2,4-Dinitrophenyltriazole 22 is thermally unstable and decomposes during isolation.…”

mentioning

confidence: 99%

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Synthesis and properties of nitro-1,2,3-triazoles (Review)

Vereschagin

Pokatilov

Kizhnyaev

2008

Chem Heterocycl Comp

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Published data on methods for the synthesis of substituted 4(5)-nitro-1,2,3-triazoles and their properties are reviewed.Against the background of the extremely large amount of published information about methods for the production of vicinal triazoles and their properties the chemistry of nitro-substituted triazoles of this series is in an embryonic state. At the same time, according to existing data, vicinal nitrotriazoles may find use in the synthesis of medicines, dyes, agents for the struggle against agricultural pests, energy-rich components of propellants, special-purpose powders, and in other regions of technology. However, the practical application of these compounds has been restrained by the lack of technologically convenient methods for their production. Until now sufficiently effective preparative methods have not been developed for their synthesis. With respect to their properties it is known only that the nitro group of the triazoles is capable of being reduced catalytically to an amino group and substituted by various nucleophilic fragments, while the triazole ring is alkylated by alkyl halides and adds to an activated multiple bond. The limited information is probably explained by the poor availability of vicinal nitrotriazoles, which is most likely due to the passivity of the 1,2,3-triazole in electrophilic substitution reactions at carbon atoms and particularly in nitration processes. In this connection it seems expedient to examine methods for the synthesis of nitro-substituted 1,2,3-triazoles by direct nitration with due regard to the conditions determining the entry of the nitro group into the azole ring and also methods for the construction of nitrotriazoles by the cyclization of open-chain nitro compounds and to assess their properties. SYNTHESIS OF NITRO-1,2,3-TRIAZOLES Nitration of 1,2,3-TriazolesThe inertness of the carbon atoms of the triazole ring toward electrophilic reagents is due to distribution of the electron density of the ring in such a way that the carbon atoms carry a partial positive charge, preventing the addition of a nitronium cation. Therefore, the path to direct nitration of the ring of unsubstituted vicinal triazole has not so far been realized. Attempts to introduce a nitro group into the ring of the heterocycle of 1-phenyl-and 4-phenyl-1,2,3-triazoles were unsuccessful. 1-Phenyl-1,2,3-triazole (1) does not form 4(5)-nitrosubstituted triazole during nitration even under rigid conditions. Here, only the phenyl ring is nitrated-initially at the para position and then at the ortho position [1-3].

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Section: Ch Chmentioning

confidence: 99%

Section: Ch Chmentioning

confidence: 99%

Section: Alk Alkmentioning

confidence: 99%

mentioning

confidence: 97%

mentioning

confidence: 99%

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Synthesis and properties of nitro-1,2,3-triazoles (Review)

Vereschagin

Pokatilov

Kizhnyaev

2008

Chem Heterocycl Comp

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N1-, N2-, and N3-Methyl-4-nitro-1,2,3-triazoles and Metal Complexes Based on Them

Filippova,

Krupnova,

Bosov

et al. 2023

Russ J Appl Chem

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Energetic Materials Based on N-substituted 4(5)-nitro-1,2,3-triazoles

et al. 2022

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The regularities and synthetic potentialities of the alkylation of 4(5)-nitro-1,2,3-triazole in basic media were explored, and new energetic ionic and nitrotriazole-based coordination compounds were synthesized in this study. The reaction had a general nature and ended with the formation of N1-, N2-, and N3-alkylation products, regardless of the conditions and reagent nature (alkyl- or aryl halides, alkyl nitrates, dialkyl sulfates). This reaction offers broad opportunities for expanding the variability of substituents on the nitrotriazole ring in the series of primary and secondary aliphatic, alicyclic, and aromatic substituents, which is undoubtedly crucial for solving the problems related to both high-energy materials development and medicinal chemistry when searching for new efficient bioactive compounds. An efficient methodology for the separation of regioisomeric N-alkyl(aryl)nitrotriazoles has been devised and relies on the difference in their basicity and reactivity during quaternization and complexation reactions. Based on the inaccessible N3-substitution products that exhibit a combination of properties of practical importance, a series of energy-rich ionic systems and coordination compounds were synthesized that are gaining ever-increasing interest for the chemistry of energy-efficient materials, coordination chemistry, and chemistry of ionic liquids.

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ChemInform Abstract: Gem‐Dinitro Compounds in Organic Synthesis. Part 3. Syntheses of 4‐ Nitro‐1,2,3‐triazoles from gem‐Dinitro Compounds.

Cited by 3 publications

References 0 publications

Synthesis and properties of nitro-1,2,3-triazoles (Review)

Synthesis and properties of nitro-1,2,3-triazoles (Review)

N1-, N2-, and N3-Methyl-4-nitro-1,2,3-triazoles and Metal Complexes Based on Them

Energetic Materials Based on N-substituted 4(5)-nitro-1,2,3-triazoles

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