Investigation on Cl-F exchange mechanism occurring at C(sp2) and C(sp3) orbitals of halogenated cyclopentene

Chengping Zhang; Feiyao Qing; Hengdao Quan; Akira Sekiya

doi:10.1016/j.jfluchem.2016.09.011

Investigation on Cl-F exchange mechanism occurring at C(sp²) and C(sp³) orbitals of halogenated cyclopentene

Chengping Zhang, Feiyao Qing, Hengdao Quan^*, Akira Sekiya

^*Corresponding author for this work

Research output: Contribution to journal › Article › peer-review

6 Citations (Scopus)

Abstract

The mechanism of Cl-F exchange of halogenated cyclopentene with AlCl₃in dimethylformamide (DMF) or with AlCl₄⁻in 1,1,1,3,3-pentachloropropane (HCC-240fa) was investigated. It was found that in DMF, AlCl₃preferred to attack the position with larger electron cloud density relatively like C(sp²) position, which was attributed to that AlCl₃was a strong Lewis acid, and in HCC-240fa, AlCl₄⁻preferred to attack the position with smaller electron cloud density relatively like C(sp³) position, which was attributed to that AlCl₄⁻was a Lewis base. Our experimental results showed that Cl-F exchange with AlCl₃occurred mainly on C(sp²) atom, and Cl-F exchange with AlCl₄⁻occurred mainly on C(sp³) atom.

Original language	English
Pages (from-to)	84-89
Number of pages	6
Journal	Journal of Fluorine Chemistry
Volume	191
DOIs	https://doi.org/10.1016/j.jfluchem.2016.09.011
Publication status	Published - 2016
Externally published	Yes

Keywords

AlCl
AlCl
Cl-F exchange
Halogenated cyclopentene
Lewis acid

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10.1016/j.jfluchem.2016.09.011

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@article{8d56ca51045f4ba1918ffed9cd34e5f3,

title = "Investigation on Cl-F exchange mechanism occurring at C(sp2) and C(sp3) orbitals of halogenated cyclopentene",

abstract = "The mechanism of Cl-F exchange of halogenated cyclopentene with AlCl3in dimethylformamide (DMF) or with AlCl4−in 1,1,1,3,3-pentachloropropane (HCC-240fa) was investigated. It was found that in DMF, AlCl3preferred to attack the position with larger electron cloud density relatively like C(sp2) position, which was attributed to that AlCl3was a strong Lewis acid, and in HCC-240fa, AlCl4−preferred to attack the position with smaller electron cloud density relatively like C(sp3) position, which was attributed to that AlCl4−was a Lewis base. Our experimental results showed that Cl-F exchange with AlCl3occurred mainly on C(sp2) atom, and Cl-F exchange with AlCl4−occurred mainly on C(sp3) atom.",

keywords = "AlCl, AlCl, Cl-F exchange, Halogenated cyclopentene, Lewis acid",

author = "Chengping Zhang and Feiyao Qing and Hengdao Quan and Akira Sekiya",

note = "Publisher Copyright: {\textcopyright} 2016",

year = "2016",

doi = "10.1016/j.jfluchem.2016.09.011",

language = "English",

volume = "191",

pages = "84--89",

journal = "Journal of Fluorine Chemistry",

issn = "0022-1139",

publisher = "Elsevier B.V.",

}

TY - JOUR

T1 - Investigation on Cl-F exchange mechanism occurring at C(sp2) and C(sp3) orbitals of halogenated cyclopentene

AU - Zhang, Chengping

AU - Qing, Feiyao

AU - Quan, Hengdao

AU - Sekiya, Akira

PY - 2016

Y1 - 2016

N2 - The mechanism of Cl-F exchange of halogenated cyclopentene with AlCl3in dimethylformamide (DMF) or with AlCl4−in 1,1,1,3,3-pentachloropropane (HCC-240fa) was investigated. It was found that in DMF, AlCl3preferred to attack the position with larger electron cloud density relatively like C(sp2) position, which was attributed to that AlCl3was a strong Lewis acid, and in HCC-240fa, AlCl4−preferred to attack the position with smaller electron cloud density relatively like C(sp3) position, which was attributed to that AlCl4−was a Lewis base. Our experimental results showed that Cl-F exchange with AlCl3occurred mainly on C(sp2) atom, and Cl-F exchange with AlCl4−occurred mainly on C(sp3) atom.

AB - The mechanism of Cl-F exchange of halogenated cyclopentene with AlCl3in dimethylformamide (DMF) or with AlCl4−in 1,1,1,3,3-pentachloropropane (HCC-240fa) was investigated. It was found that in DMF, AlCl3preferred to attack the position with larger electron cloud density relatively like C(sp2) position, which was attributed to that AlCl3was a strong Lewis acid, and in HCC-240fa, AlCl4−preferred to attack the position with smaller electron cloud density relatively like C(sp3) position, which was attributed to that AlCl4−was a Lewis base. Our experimental results showed that Cl-F exchange with AlCl3occurred mainly on C(sp2) atom, and Cl-F exchange with AlCl4−occurred mainly on C(sp3) atom.

KW - AlCl

KW - Cl-F exchange

KW - Halogenated cyclopentene

KW - Lewis acid

UR - http://www.scopus.com/inward/record.url?scp=84989847646&partnerID=8YFLogxK

U2 - 10.1016/j.jfluchem.2016.09.011

DO - 10.1016/j.jfluchem.2016.09.011

M3 - Article

AN - SCOPUS:84989847646

SN - 0022-1139

VL - 191

SP - 84

EP - 89

JO - Journal of Fluorine Chemistry

JF - Journal of Fluorine Chemistry

ER -

Investigation on Cl-F exchange mechanism occurring at C(sp²) and C(sp³) orbitals of halogenated cyclopentene

Abstract

Keywords

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