TY - JOUR
T1 - Synthesis of 3,3,3-trifluoropropyne from chlorotrifluoropropene isomers in liquid phase
AU - Zhang, Tongyun
AU - Zhang, Chengping
AU - Ma, Xiaoxun
AU - Quan, Hengdao
N1 - Publisher Copyright:
© 2022 Elsevier B.V.
PY - 2022/3
Y1 - 2022/3
N2 - 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.
AB - 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.
KW - 1‑chloro‑3,3,3-trifluoroproene
KW - 2‑chloro‑3,3,3-trifluoropropene
KW - 3,3,3-trifluoropropyne
KW - DFT
KW - Dehydrochlorination
UR - http://www.scopus.com/inward/record.url?scp=85124277608&partnerID=8YFLogxK
U2 - 10.1016/j.jfluchem.2022.109950
DO - 10.1016/j.jfluchem.2022.109950
M3 - Article
AN - SCOPUS:85124277608
SN - 0022-1139
VL - 255-256
JO - Journal of Fluorine Chemistry
JF - Journal of Fluorine Chemistry
M1 - 109950
ER -