2H-Hexafluoropropyl Azide

[2991-70-0]  · C3HF6N3  · 2H-Hexafluoropropyl Azide  · (MW 193.07)

(mild fluorinating reagent for oxidative fluorination of PIII compounds1-3)

Alternate Name: hexafluoroazidopropane.

Physical Data: bp 51-53 °C.

Solubility: insol water; sol most organic solvents.

Preparative Methods: readily prepared from hexafluoropropene (CF2=CFCF3) and Sodium Azide in alcohols.1,4 Synthesis of up to 134 g has been described.1

Handling, Storage, and Precautions: easily handled and stored (several months in dark glass vessel at rt), provided due care is taken: avoid sharp strikes and heating. Explosions have not been reported, but a protective shield should always be used. Use in a fume hood.

Fluorination.

The reaction of CF3CHFCF2N3 with various PIII-containing substrates results in oxidative fluorination (eq 1).1-3 Usually the reactions are performed without solvent, the highly volatile CF3CHFCN byproduct (bp 39-41 °C) being easily removed. The reaction has been applied to fluorophosphites, trialkyl phosphites, halophosphines, amidophosphites, and hydrophosphoryl compounds.

An unusual Arbuzov rearrangement was observed in the case of alkyl difluorophosphites, ROPF2. If R = isobutyl or neopentyl, rearrangment to a corresponding tertiary group is observed (eq 2).1

Other Properties.

The azide decomposes slowly under heat or UV irradiation to give 3H-hexafluoro-2-aza-1-butene (eq 3).5


1. Lermontov, S. A.; Sukhojenko, I. I.; Popov, A. V.; Pushin, A. N.; Martynov, I. V.; Zefirov, N. S.; Stang, P. J. HC 1994, in press.
2. Lermontov, S. A.; Popov, A. V.; Sukhojenko, I. I.; Martynov, I. V. IZV 1989, 215 (CA 1989, 111, 115 353v).
3. Lermontov, S. A.; Popov, A. V.; Sukhojenko, I. I.; Pushin, A. N.; Martynov, I. V. IZV 1990, 933 (CA 1990, 113, 59 342t).
4. Knunyants, I. L.; Bykhovskaya, E. G. DOK 1960, 131, 1338 (CA 1960, 54, 20 840d).
5. Banks, R. E.; Berry, D.; McGlinchey, M. J.; Moore, G. J. JCS(C) 1970, 1017.

Nikolai S. Zefirov & Sergei A. Lermontov

Moscow State University, Russia



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