Nucleophilic substitution of the nitro group in 1-substituted 3-nitro-1H-1,2,4-triazoles in ethanolic potassium hydroxide

Hasratyan, Ani H.; Sukoyan, Astkhik А.; Shakhatuni, A. G.; Danagulyan, G. G.; Attaryan, H. S.

doi:10.1007/s10593-020-02780-8

Cited by 2 publications

(1 citation statement)

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“…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 NO 2 group by various Oand N-nucleophilic agents [28,29]. However, the S N ipso substitution reaction of the nitro group and the key reaction pathways and the parameters governing the nitro group activity in this type of reaction remain underexplored among N-alkyl-substituted nitro derivatives of 1,2,4-triazole.…”

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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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