Synthesis of hydrofluorocycloolefins through dehydrofluorination of hydrofluorocycloalkanes in amide solvents

Zhang, Wenni; Zhang, Chengping; Guo, Qin; Lu, Fengniu; Quan, Hengdao

doi:10.1016/j.jfluchem.2019.06.008

Cited by 2 publications

(7 citation statements)

References 31 publications

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“…In contrast with F6A, fluorination of both F7A and F8A induced the more positive ESP on hydrogens and allowed the easier dehydrofluorination to F6E and F7E, consistent with the experiment phenomenon. 24 Both chlorination and C�C bonds contributed to present more but positive ESP minima. This is more conveniently observed from the average local ionization energy (ALIE) analysis.…”

Section: Molecular Electrostatic Potential Analysismentioning

confidence: 99%

“…With similar fate, F8E underwent an hydrodefluorination to produce cis-F8A. 24 For F6-12, in DMF with AlCl 3 , it could be obtained from F8E and F7-1 through Cl–F exchange reaction, the yields of which reached 86.8 and 87.5%, respectively. 27 …”

Section: Introductionmentioning

confidence: 99%

“…With similar fate, F8E underwent an hydrodefluorination to produce cis-F8A. 24 For F6-12, in DMF with AlCl 3 , it could be obtained from F8E and F7-1 through Cl−F exchange reaction, the yields of which reached 86.8 and 87.5%, respectively. 27 Nevertheless, before an industrial-scale application, the attractive properties of c-C 5 Fs give us desire of worthily persistent exploration of their environmental performances including the 100-year global warming potential (GWP 100 ).…”

Section: Introductionmentioning

confidence: 99%

“…However, no elimination occurred in F6A possibly due to its extremely weak acidity as fluorine was introduced. 24 F7-1 and F8E were reported to be obtained from the selective fluorination of F6-12 and 1,4-dichlorohexafluorocyclopentene (F6-14), the yield of which reached up to 78.8 and 32.5%, respectively. 25 On the other hand, as a facile raw material, F6-12 could produce F6-1 with zinc in DMF (yield = 76.4%) or DMAC (yield = 84.3%), while, in contrast, F7-1 was able to selectively generate F7E (yield up to 5.8%) and F6-1 by hydrodehalogenation.…”

Section: Introductionmentioning

confidence: 99%

“…To produce F7A, F7-1 was reacted with hydrogen in the presence of a Pd-based catalyst (yield >90%), where byproducts including F7E and F6A were found. , Subsequently, F6E was effectively prepared by F7A in solvents of DMF or DMAC, and F7E could be obtained from F8A by similar dehydrofluorination as well. However, no elimination occurred in F6A possibly due to its extremely weak acidity as fluorine was introduced . F7-1 and F8E were reported to be obtained from the selective fluorination of F6-12 and 1,4-dichlorohexafluorocyclopentene (F6-14), the yield of which reached up to 78.8 and 32.5%, respectively .…”

Section: Introductionmentioning

confidence: 99%

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Substitution Effects on the Reactivity and Thermostability of Five-Membered Ring Fluorides

Zhang

et al. 2022

ACS Omega

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Recently, five-membered ring fluorides (c-C 5 Fs) have been significantly desirable in green chlorofluorocarbon substitutes due to their practically flexible application in various fields and environmental friendliness. Detailed knowledge regarding different substitution effects on their environmental properties and thermal stability is very limited due to their high-cost experiments. Here, comprehensive density functional theory and ab initio molecular dynamics calculations were performed to explore the relative electrophilic and nucleophilic reactivity and thermostability of c-C 5 F chemicals. The electronic properties induced by substitution effects of c-C 5 Fs were first explored. The environmental friendliness of c-C 5 Fs including 1,1,2,2,3,3-hexafluorocyclopentane (F6A), 1,1,2,2,3,3,4-heptafluorocyclopentane (F7A), cis-1,1,2,2,3,3,4,5-octafluorocyclopentane (F8A), 3,3,4,4,5,5-hexafluorocyclopentene (F6E), 1,3,3,4,4,5,5-heptafluorocyclopentene (F7E), octafluorocyclopentene (F8E), 1-chloro-3,3,4,4,5,5-hexafluorocyclopent-1-ene (F6-1), and 1-chloro-2,3,3,4,4,5,5-heptafluorocyclopent-1-ene (F7-1) was validly confirmed. Besides, their thermal stabilities at 600 K temperature were concluded due to their flexible carbon skeletons, where both in-plane stability and slight aromaticity of F6E were in peculiar found to contribute substantially. We also would like to stress the future application of F6-1 due to its significant out-plane stability. This study may pave the way for the development of chlorofluorocarbon substitutes.

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Section: Molecular Electrostatic Potential Analysismentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%