A novel catalytic pathway for perfluoroacyl peroxide synthesis

Area of Science:

• Organic Chemistry
• Catalysis
• Fluorine Chemistry

Background:

• Bis(perfluoroacyl) peroxides (BPFAP) are important compounds with various applications.
• Existing synthesis methods for BPFAP may have limitations in efficiency or scope.
• Perfluoroacyl anhydrides and hydrogen peroxide are readily available starting materials.

Purpose of the Study:

• To develop a new, efficient catalytic method for the synthesis of bis(perfluoroacyl) peroxides (BPFAP).
• To investigate the reaction mechanism and confirm the irreversibility of the synthesis.
• To explore the synthesis of novel acetyltrifluoroacetyl peroxides.

Main Methods:

• Catalytic reaction using hydrogen peroxide and perfluoroacyl anhydrides.
• Employing a carboxylate salt (R(f)COO-M+) as a catalyst.
• Utilizing Density Functional Theory (DFT) calculations to support experimental findings.

Main Results:

• Bis(perfluoroacyl) peroxides (BPFAP) were synthesized quantitatively in situ.
• The reaction proceeds efficiently with a peroxide to anhydride ratio greater than or equal to 2:1.
• Experimental data and DFT calculations confirmed the essentially irreversible nature of the reaction.
• New acetyltrifluoroacetyl peroxides were successfully synthesized.

Conclusions:

• A novel and efficient catalytic method for BPFAP synthesis has been established.
• The reaction is highly effective, yielding products quantitatively.
• The developed method provides a reliable route for accessing novel perfluorinated peroxide compounds.