CD3CD2CHF2 was prepared with approximately 90 kcal mol-1 of internal energy by the combination of CD3CD2 and CHF2 radicals.  The 1,2-DF elimination forms cis- and trans-CD3CD=CHF in a 1.2 ratio favoring the cis-isomer.  The 1,1-HF elimination reaction forms the CD3CD2CF: carbene that subsequently transfers a D giving a cis-/trans-CD3CD=CDF ratio that is near 4 at the highest pressures and declines to 2.5 at the lowest pressures.  This pressure effect suggests that the 1,1-HF elimination process preferentially forms the cis-isomer that isomerizes to the trans-geometry as the pressure is lowered.  The ratio of CD3CD=CHF/CD3CD=CDF is the relative rates for the 1,2-DF/1,1-HF pathways and it is constant at 3.0 for the trans-isomer.  The ratio of cis- CD3CD=CHF/CD3CD=CDF declines from about 8 at the highest pressures to a low pressure limit approaching 6.  The competition between the 1,2- and 1,1-HF/DF elimination and the results from DFT calculations for the various reaction channels will be discussed.

Experimental measurement of the branching ratio for the competitive 1,2-DF/1,1-HF and the cis-/trans-CD3CD=CHF and CD3CD=CDF for the unimolecular elimination of HF/DF from CD3CD2CHF2

247th National Meeting (2014)

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