Synthesis of 3,3,3-trifluoropropyne from chlorotrifluoropropene isomers in liquid phase

Chlorotrifluoropropene isomers including 1‑chloro-3,3,3-trifluoroproene (HCFO-1233zd(Z/E)) and 2‑chloro-3,3,3-trifluoropropene (HCFO-1233xf) were adopted as the dehydrochlorination materials to produce 3,3,3-trifluoropropyne (TFPY) by one-pot method were reported. The experimental data indicated that HCFO-1233zd(Z) was the most favorable synthetic raw material in this process, followed by HCFO-1233xf, and HCFO-1233zd(E) then. However, DFT calculations demonstrated the superiority of HCFO-1233zd(E) to HCFO-1233xf according to the reaction energy barrier. By further referring to the thermodynamic calculations and the computed water solubility, the reaction priority herein was identified as HCFO-1233zd(Z) > HCFO-1233xf > HCFO-1233zd(E). Therefore, compared to kinetic effects, the reactivity of HCFO-1233zd(Z/E) and HCFO-1233xf was evidently determined by their thermodynamic properties and solubility. This work thus provides guidance for similar hydrogen halide removal in liquid phase.