1. The taming of halogen azides, improved syntheses, and some reaction chemistry of fluorine azide and chlorine azide.
- Author
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Wilson, William W., Vij, Ashwani, Boatz, Jerry A., and Christe, Karl O.
- Subjects
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CHEMICAL reactions , *FLUORINE , *CHLORINE , *HALOGENS , *COMPUTATIONAL chemistry , *HYDROFLUORIC acid , *FLUOROCARBONS - Abstract
• Safer methods for the syntheses of the very shock-sensitive compounds FN 3 , ClN 3 , and HN 3 were developed. • The compounds were characterized by Raman spectroscopy and computational chemistry. • The improved syntheses allowed to study some of their reaction chemistry. Scalable methods for the safe production and handling of the highly explosive FN 3 and ClN 3 were developed by direct fluorination of HN 3 or (CH 3) 3 SiN 3 in inert fluorocarbon or SO 2 solutions using elemental fluorine or ClF, respectively. As an alternate method for FN 3 , the metathetical preparation of thermally unstable NF 4 N 3 which can decompose to FN 3 and NF 3 is proposed. The use of these methods allows the safe scale up of the FN 3 production from 20 mg to a multi gram scale and to study its reaction chemistry. It was also found that HF protonates HN 3 to yield [H 2 N 3 ]+[HF 2 ]−, and that the reaction of FN 3 in CF 3 CFHCF 3 with HF/SbF 5 solutions at −64°C produces [NH 2 F 2 ]+[SbF 6 ]−. Furthermore, FN 3 can be added across the C = C double bonds of CFCl=CF 2 and CF 2 CFCF 3 , and results with trans -stilbene in the formation of a triazole. [Display omitted] [ABSTRACT FROM AUTHOR]
- Published
- 2022
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