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Although alkyl trifluoroacetates are known to undergo nucleophilic acyl substitution reactions in the gas phase, that process would be endothermic with a carboxylate as the nucleophile and therefore is not competitive in this system: McDonald, R. N.; Chowdhury, A. K. J. Am. Chem. Soc. 1982, 104, 901.
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85039501907
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note
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3 bond than a C-Br bond).
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18
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4544285042
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Neutral thermochemical data
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Mallard, W. G., Linstrom, P. J., Eds.; National Institute of Standards and Technology: Gaithersburg, MD
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Afeefy, H. Y.; Liebman, J. F.; Stein, S. E. Neutral Thermochemical Data. In NIST Chemistry WebBook, NIST Standard Reference Database Number 69; Mallard, W. G., Linstrom, P. J., Eds.; National Institute of Standards and Technology: Gaithersburg, MD, 2004; http://webbook.nist.gov.
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Salvador, P.48
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Daniels, A.D.52
Strain, M.C.53
Farkas, O.54
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Ortiz, J.V.59
Cui, Q.60
Baboul, A.G.61
Clifford, S.62
Cioslowski, J.63
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Liu, G.65
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Piskorz, P.67
Komaromi, I.68
Martin, R.L.69
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Keith, T.71
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85039499785
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The low E2 rate for ethyl iodide adds some uncertainty to the ratios. It is possible that some of the observed proton-transfer products with ethyl iodide result from reaction with a small HI impurity rather than from an E2 reaction with ethyl iodide. Therefore, the true E2 rate with ethyl iodide could be smaller and thus all of the rate ratios proportionally larger.
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33
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0002513170
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85039489086
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N2 barrier is marginally smaller (1-2 kcal/mol) than the E2 barrier. See ref 35.
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36
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85039488039
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note
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We were not able to test this level thoroughly in these systems. It may be satisfactory, but it is possible that higher levels would be needed to obtain data that is consistent with all the iodide experiments.
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