Synthesis, structure, and properties of tert-butyl perfluorobiphenyl nitroxide

Synthesis, structure, and properties of tert-butyl perfluorobiphenyl nitroxide Full article

Journal

Russian Chemical Bulletin
ISSN: 1573-9171 , E-ISSN: 1066-5285

Output data

Year: 2022, Volume: 71, Number: 7, Pages: 1474-1482 Pages count : 9 DOI: 10.1007/s11172-022-3553-8

Authors

Fedyushin P.A. ¹ , Akyeva A.Ya. ¹ , Syroeshkin M.A. ¹ , Rybalova T.V. ² , Stass D.V. ³ , Korolev V.A. ¹ , Tretyakov E.V. ¹ , Egorov M.P. ¹

Affiliations

1	N. D. Zelinsky Institute of Organic Chemistry, Russian Academy of Sciences, 47 Leninsky prosp., 119991 Moscow, Russian Federation
2	N. N. Vorozhtsov Novosibirsk Institute of Organic Chemistry, Siberian Branch of the Russian Academy of Sciences, 9 prosp. Akad. Lavrentieva, 630090 Novosibirsk, Russian Federation
3	V. V. Voevodsky Institute of Chemical Kinetics and Combustion, Siberian Branch of the Russian Academy of Sciences, 3 ul. Institutskaya, 630090 Novosibirsk, Russian Federation

The reaction of perfluorobiphenyl with tert-butylamine in an autoclave affords the aminodefluorination product, N-tert-butyl-2,2′,3,3′,4′,5,5′,6,6′-nonafluorobiphenyl-4-amine, and the oxidation of the latter with meta-chloroperbenzoic acid gives the new stable nitroxide radical, N-tert-butyl-N-(2,2′,3,3′,4′,5,5′,6,6′-nonafluorobiphenyl)amine N-oxide, in quantitative yield. According to the X-ray diffraction analysis, the crystallization from heptane results in the spontaneous precipitation of the solid paramagnet as one of the two polymorphs, either triclinic or monoclinic (P21/n). The electrochemical oxidation and reduction of nitroxide occur irreversibly. The heating of a toluene solution of the paramagnet leads to the oxidation of the solvent and the generation of the corresponding hydroxylamine and the benzyl radical, which enters into the recombination reaction with the initial radical to form alkoxyamine.

Fedyushin P.A. , Akyeva A.Y. , Syroeshkin M.A. , Rybalova T.V. , Stass D.V. , Korolev V.A. , Tretyakov E.V. , Egorov M.P.
Synthesis, structure, and properties of tert-butyl perfluorobiphenyl nitroxide
Russian Chemical Bulletin. 2022. V.71. N7. P.1474-1482. DOI: 10.1007/s11172-022-3553-8 WOS Scopus OpenAlex

Web of science:	WOS:000838081600015
Scopus:	2-s2.0-85135690038
OpenAlex:	W4300517165

DB	Citing
OpenAlex	6
Scopus	6
Web of science	4