Alkylation of 3-nitro-1,2,4-triazole with allyl bromide and cyclohexa-1,3-diene in acid medium

Grigoriev, Yuri V.; Войтехович, Сергей В.; Ивашкевич, Олег А.

doi:10.1134/s1070428012040288

Cited by 5 publications

(3 citation statements)

References 11 publications

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“…The latter did not probably participate in the primary reaction; instead, it was consumed during polymerization. As opposed to the conditions considered, unsaturated alicycles have successfully been used to alkylate azoles in acidic media [41,42].…”

Section: Resultsmentioning

confidence: 99%

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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Section: Resultsmentioning

confidence: 99%

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

et al. 2022

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“…Additionally, 1,2,4-triazole nitro derivatives (for example, 3-nitro-1,2,4-triazole) are quite valuable intermediates for organic synthesis because they can be chemically transformed into other useful compounds being employed to produce practically important, functional materials of many uses [23]. This type of building block offers the advantages of having a great number of reactive sites for the incorporation of different substituents, and these sites can be functionalized through electro-and nucleophilic substitution reactions [24][25][26][27]. For instance, the 3-nitro-1,2,4-triazole molecule has three endocyclic reactive sites-nitrogen atoms (N(1)-, N(2)-and N(4)-)-and one more, quite reactive, exocyclic NO 2 group (Figure 1).…”

Section: Introductionmentioning

confidence: 99%

“…Such a starting polyfunctional synthon is capable of diverse chemical transformations and opens up broad opportunities for the molecular design of compounds based thereon. The alkylation reaction is a common and quite well-studied method for the functionalization of 1,2,4-triazole nitro derivatives, and all the three nitrogen heteroatoms of the 1,2,4-triazole ring can be the object of an attack by the corresponding alkylating agent, depending on the reaction conditions [24][25][26][27]. The forth exocyclic reactive site on the carbon atom in the 3-nitro-1,2,4-triazole molecule is functionalized via the nucleophilic substitution of the NO2 group by various O-and N-nucleophilic agents [28,29].…”

Section: Introductionmentioning

confidence: 99%

Alkyl Substituent in Heterocyclic Substrate, Carbon Skeleton Length of O-Nucleophilic Agent and Conditions Influence the Product Composition from Competitive Reactions of SNipso Substitution by Aliphatic Oligoethers

Bosov,

Pivovarova,

Krupnova

et al. 2023

Materials

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Using 1H NMR spectroscopy, we studied the relative mobility of the NO2 group in 1-alkyl-5-nitro-1,2,4-triazoles in the reaction of nucleophilic heterocyclic substitution by aliphatic oligoethers. The main pathways of the SNipso substitution process and the composition of resultant products from competitive reactions were examined, and the key factors influencing the relative mobility of the nitro group, such as the nitrotriazole substrate constitution, the carbon skeleton length of the O-nucleophilic agent and the process conditions, were discussed. Several independent competitive reactions directed towards the substitution of the nitro group at position C(5) in the alkyltriazole substrate by different types of nucleophiles such as alkoxide-, hydroxide- and triazolonate anions were observed to take place under conditions used. The major reaction yielded oligoethers containing terminal alkyltriazole heterocycles. Secondary reactions occurred to form the corresponding triazolone and N–C triazolyl triazolone structures in the reaction system. Additionally, in excess of the alkaline agent, alkaline hydrolysis was observed to proceed at the final stages of the process involving the O-nucleophile having a longer oligoether backbone in the series studied, leading to the formation of new O-nucleophilic sites. The obtained findings can provide a foundation for devising a method for the modification of a wide range of commercially available aliphatic oligo- or polyethers to prepare functional macromolecules whose terminals carry bioactive 1,2,4-triazole heterocycles located at a desired distance from each other.

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