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Rate and Product Studies with 1-Adamantyl Chlorothioformate under Solvolytic Conditionsopen access

Authors
Park, Kyoung HoSeong, Mi HyeKyong, Jin BurmKevill, Dennis N.
Issue Date
Jul-2021
Publisher
Multidisciplinary Digital Publishing Institute (MDPI)
Keywords
1-adamantyl chlorothioformate; Grunwald-Winstein equation; solvolysis; solvolysis-decomposition; ionization pathway; carboxylium ion
Citation
International Journal of Molecular Sciences, v.22, no.14, pp 1 - 13
Pages
13
Indexed
SCIE
SCOPUS
Journal Title
International Journal of Molecular Sciences
Volume
22
Number
14
Start Page
1
End Page
13
URI
https://scholarworks.bwise.kr/erica/handle/2021.sw.erica/116261
DOI
10.3390/ijms22147394
ISSN
1661-6596
1422-0067
Abstract
A study was carried out on the solvolysis of 1-adamantyl chlorothioformate (1-AdSCOCl, 1) in hydroxylic solvents. The rate constants of the solvolysis of 1 were well correlated using the Grunwald-Winstein equation in all of the 20 solvents (R = 0.985). The solvolyses of 1 were analyzed as the following two competing reactions: the solvolysis ionization pathway through the intermediate (1-AdSCO)(+) (carboxylium ion) stabilized by the loss of chloride ions due to nucleophilic solvation and the solvolysis-decomposition pathway through the intermediate 1-Ad(+)Cl(-) ion pairs (carbocation) with the loss of carbonyl sulfide. In addition, the rate constants (k(exp)) for the solvolysis of 1 were separated into k through a product study and applied to the Grunwald-Winstein equation to obtain the sensitivity (m-value) to change in solvent ionizing power. For binary hydroxylic solvents, the selectivities (S) for the formation of solvolysis products were very similar to those of the 1-adamantyl derivatives discussed previously. The kinetic solvent isotope effects (KSIEs), salt effects and activation parameters for the solvolyses of 1 were also determined. These observations are compared with those previously reported for the solvolyses of 1-adamantyl chloroformate (1-AdOCOCl, 2). The reasons for change in reaction channels are discussed in terms of the gas-phase stabilities of acylium ions calculated using Gaussian 03.
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