Chemically activated CH3CHFCH2Cl was prepared in the gas phase with approximately 90 kcal/mol of internal energy by the combination of CH3CHF and CH2Cl radicals. Results for the CH3CHFCH2Cl systems will be compared to the CH2FCH2Cl and CF3CHFCH2Cl systems as part of a continuing effort to document the F-Cl interchange reaction and to determine the effect of electron-donating and electron-withdrawing substituents on the threshold energy for F-Cl interchange.  The dominant unimolecular pathway for energized CH3CHFCH2Cl is 2,3-HF elimination.  The 1,2-HF elimination rate is slower by 0.75 and produces a cis-/trans-CH3CH=CHCl ratio of 1.7.  The relative rate ratios for 3,2-HF : 1,2-HF : FCl-interchange : 1,2-HCl = 2.8 : 2.2 : 2 : 1.  The F-Cl interchange reaction converts CH3CHFCH2Cl into CH3CHClCH2F that rapidly reacts by HCl and HF elimination to form CH2=CHCH2F, cis- and trans-CH3CH=CHF and CH3CCl=CH2.  For CH3CHClCH2F the 3,2-HCl elimination (forming CH2=CHCH2F) was the dominant pathway, which was twice as fast as 1,2-HCl elimination.  The cis/trans ratio for the 1,2-HCl elimination reaction giving CHF=CHCH3 was 1.2.  The 2,1-HF elimination reaction was the slowest unimolecular pathway for CH3CHClCH2F.   DFT calculations were done to determine the transition state structures and to predict the threshold energies for the elimination reactions both CH3CHClCH2F and CH3CHFCH2Cl.

Experimental and computational investigation of CH<sub>3</sub>CHFCH<sub>2</sub>Cl: An examination of the effect of an electron-donating group on the F-Cl interchange unimolecular reaction

246th National Meeting (2013)

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Experimental and computational investigation of CH3CHFCH2Cl: An examination of the effect of an electron-donating group on the F-Cl interchange unimolecular reaction

Experimental and computational investigation of CH₃CHFCH₂Cl: An examination of the effect of an electron-donating group on the F-Cl interchange unimolecular reaction