Synthesis and study of the azide-tetrazole tautomerism in 2-azido-4-(trifluoromethyl)-6-R-pyrimidines (R = H, 4-ClC6H4)
- 作者: Nikolaenkova Е.1, Aleksandrova N.1, Mamatyuk V.1,2, Krivopalov V.1
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隶属关系:
- N. N. Vorozhtsov Institute of Organic Chemistry, Siberian Branch of the Russian Academy of Sciences
- Novosibirsk State University
- 期: 卷 67, 编号 5 (2018)
- 页面: 893-901
- 栏目: Full Articles
- URL: https://journals.rcsi.science/1066-5285/article/view/242543
- DOI: https://doi.org/10.1007/s11172-018-2154-z
- ID: 242543
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详细
Azide-tetrazole equilibrium in azidopyrimidines bearing trifluoromethyl group on the example of 2-azidopyrimidines has been studied. The latter were synthesized via nitrosation of 2-hydrazino-4-trifluoromethylpyrimidine and reaction of NaN3 with 4-trifluoromethyl-2- chloro-6-(4-chlorophenyl)pyrimidine. The tautomeric equilibrium 5-trifluoro methyl tetrazolo[1,5-a]pyrimidine ⇆ 2-azido-4-trifluoromethylpyrimidine was observed in the absence of solvent and in DMSO-d6 solution, whereas in CDCl3 only an azide form exists. For 2-azido- 4-trifluoromethyl-6-(4-chlorophenyl)pyrimidine, only an azide isomer was detected in CDCl3 solution, and in DMSO-d6 solution it is in equilibrium with 5-(trifluoromethyl)-7-(4-chlorophenyl) tetrazolo[1,5-a]pyrimidine (the tautomer ratio is 99 : 1). Thermodynamic and kinetic parameters of 5-trifluoromethyltetrazolo[1,5-a]pyrimidine ⇆ 2-azido-4-trifluoromethylpyri midine tautomeric rearrangement in DMSO-d6 for 5-trifluoromethyltetrazolo[1,5-a]pyrimidine were determined using the exchange spectroscopy (EXSY) technique.
作者简介
Е. Nikolaenkova
N. N. Vorozhtsov Institute of Organic Chemistry, Siberian Branch of the Russian Academy of Sciences
Email: krivic@nioch.nsc.ru
俄罗斯联邦, 9 prosp. Akad. Lavrentieva, Novosibirsk, 630090
N. Aleksandrova
N. N. Vorozhtsov Institute of Organic Chemistry, Siberian Branch of the Russian Academy of Sciences
Email: krivic@nioch.nsc.ru
俄罗斯联邦, 9 prosp. Akad. Lavrentieva, Novosibirsk, 630090
V. Mamatyuk
N. N. Vorozhtsov Institute of Organic Chemistry, Siberian Branch of the Russian Academy of Sciences; Novosibirsk State University
Email: krivic@nioch.nsc.ru
俄罗斯联邦, 9 prosp. Akad. Lavrentieva, Novosibirsk, 630090; 2 ul. Pirogova, Novosibirsk, 630090
V. Krivopalov
N. N. Vorozhtsov Institute of Organic Chemistry, Siberian Branch of the Russian Academy of Sciences
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Email: krivic@nioch.nsc.ru
俄罗斯联邦, 9 prosp. Akad. Lavrentieva, Novosibirsk, 630090