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Chlorodifluoroacetyl azide, ClF2CC(O)N3: preparation, properties, and decomposition
Luis A Ramos1, Xiaoqing Zeng, Sonia E Ulic
1CEQUINOR (UNLP-CONICET), Departamento de Química, Facultad de Ciencias Exactas, Universidad Nacional de La Plata, 47 esq. 115, 1900 La Plata, Argentina.
Researchers synthesized and studied chlorodifluoroacetyl azide. Its decomposition, via photolysis or heat, yielded a novel chlorodifluoroacetyl isocyanate, suggesting a concerted reaction pathway.
Area of Science:
- Organic Chemistry
- Spectroscopy
- Chemical Kinetics
Background:
- Organofluorine compounds are crucial in various industries.
- Azides and isocyanates are reactive intermediates with diverse applications.
- Understanding decomposition pathways is key to controlling chemical reactions.
Purpose of the Study:
- To synthesize and characterize chlorodifluoroacetyl azide.
- To investigate the photo and thermal decomposition pathways of this azide.
- To explore the conformational properties and rearrangement mechanisms of the resulting isocyanate.
Main Methods:
- Infrared (IR) and Raman spectroscopy for vibrational analysis.
- Nuclear Magnetic Resonance ((19)F, (13)C NMR) for structural elucidation.
- UV-vis spectroscopy for electronic properties.
- Matrix isolation techniques for studying reactive intermediates.
- Theoretical calculations for conformational analysis and reaction pathways.
Main Results:
- Chlorodifluoroacetyl azide was successfully prepared and characterized, existing as a single gauche-syn conformer.
- Both photolytic and thermal decomposition yielded a new isocyanate species, chlorodifluoroacetyl isocyanate.
- Theoretical studies indicated a preference for a concerted decomposition mechanism for the predominant conformer.
Conclusions:
- The study provides a comprehensive characterization of chlorodifluoroacetyl azide and its decomposition products.
- The findings shed light on the reaction mechanisms of fluorinated carbonyl azides.
- The research contributes to the understanding of Curtius rearrangement in organofluorine chemistry.
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