Int. J. Mol. Sci. 2011, 12(2), 1161-1174; doi:10.3390/ijms12021161
Article

Correlation of the Rates of Solvolysis of Neopentyl Chloroformate—A Recommended Protecting Agent

1 Department of Chemistry, Wesley College, 120 N. State Street, Dover, DE 19901, USA 2 Department of Chemistry and Biochemistry, Northern Illinois University, DeKalb, IL 60115, USA
* Authors to whom correspondence should be addressed.
Received: 6 January 2011; in revised form: 30 January 2011 / Accepted: 9 February 2011 / Published: 15 February 2011
(This article belongs to the Special Issue Correlation Analysis Applied to Solvolysis Reactions)
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Abstract: The specific rates of solvolysis of neopentyl chloroformate (1) have been determined in 21 pure and binary solvents at 45.0 °C. In most solvents the values are essentially identical to those for ethyl and n-propyl chloroformates. However, in aqueous-1,1,1,3,3,3-hexafluoro-2-propanol mixtures (HFIP) rich in fluoroalcohol, 1 solvolyses appreciably faster than the other two substrates. Linear free energy relationship (LFER) comparison of the specific rates of solvolysis of 1 with those for phenyl chloroformate and those for n-propyl chloroformate are helpful in the mechanistic considerations, as is also the treatment in terms of the Extended Grunwald-Winstein equation. It is proposed that the faster reaction for 1 in HFIP rich solvents is due to the influence of a 1,2-methyl shift, leading to a tertiary alkyl cation, outweighing the only weak nucleophilic solvation of the cation possible in these low nucleophilicity solvents.
Keywords: solvolysis; 1,2-methyl shift; LFER; addition-elimination; Grunwald-Winstein equations; ionization; neopentyl chloroformate

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MDPI and ACS Style

D’Souza, M.J.; Carter, S.E.; Kevill, D.N. Correlation of the Rates of Solvolysis of Neopentyl Chloroformate—A Recommended Protecting Agent. Int. J. Mol. Sci. 2011, 12, 1161-1174.

AMA Style

D’Souza MJ, Carter SE, Kevill DN. Correlation of the Rates of Solvolysis of Neopentyl Chloroformate—A Recommended Protecting Agent. International Journal of Molecular Sciences. 2011; 12(2):1161-1174.

Chicago/Turabian Style

D’Souza, Malcolm J.; Carter, Shannon E.; Kevill, Dennis N. 2011. "Correlation of the Rates of Solvolysis of Neopentyl Chloroformate—A Recommended Protecting Agent." Int. J. Mol. Sci. 12, no. 2: 1161-1174.

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