Pyrazoles in the Intersection of Mesomeric Betaines and N-Heterocyclic Carbenes: Formation of NHC Selenium Adducts of Pyrazolium-4-aminides

Abstract

Starting from 4-nitropyrazole, eight mesoionic pyrazolium-4-aminides were prepared by a six-step reaction sequence. The deprotonation of 1,2-disubstituted 4-amido-1H-pyrazolium salts by an anion exchange resin in its hydroxide form is the final step of the synthesis. A tautomeric equilibrium between the mesoionic compounds (pyrazolium-4-aminides) and N-heterocyclic carbenes (pyrazol-3-ylidenes) can be formulated; however, the NHC tautomers were not detected by means of NMR spectroscopy in polar aprotic solvents such as DMSO-d ₆ or MeCN-d ₃. Apart from tautomerism, anionic N-heterocyclic carbenes can be formulated as a result of a deprotonation of the mesoionic compounds­. Trapping reactions were performed with selenium, which resulted in the formation of pyrazole-3-selenones. Methylation at the selenium atom gave the corresponding 3-(methylselanyl)-4-amido-1H-pyrazolium salts, which were deprotonated to give new mesomeric betaines, 3-(methylselanyl)-1H-pyrazolium-4-aminides as unique compounds­. DFT-calculations as well as ⁷⁷Se NMR spectroscopic measurements were carried out.

Key words

pyrazol-3-ylidenes - mesoionic compound - pyrazol-3-selenone - selenium ether - ⁷⁷Se NMR - selone - mesoionic imine

Publication History

Received: 04 February 2022

Accepted after revision: 17 February 2022

Article published online:
20 April 2022

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