SN1 reactions in supercritical carbon dioxide in the presence of alcohols: the role of preferential solvation?
Organic & Biomolecular Chemistry Pub Date: 2016-06-07 DOI: 10.1039/C6OB01097K
Abstract
Ethanol (3b) inhibits SN1 reactions of alkyl halides 1 in supercritical carbon dioxide (scCO2) and gives no ethers as products. The unexpected behaviour of alcohols 3 in the reaction of alkyl halides 1 with 1,3-dimethoxybenzene (2) in scCO2 under different conditions is rationalised in terms of Br?nsted and Lewis acid–base equilibria of reagents, intermediates, additives and products in a singular solvent characterised by: (i) the strong quadrupole and Lewis acid character of carbon dioxide, which hinders SN2 paths by strongly solvating basic solutes; (ii) the weak Lewis base character of carbon dioxide, which prevents it from behaving as a proton sink; (iii) the compressible nature of scCO2, which enhances the impact of preferential solvation on carbon dioxide availability for the solvent-demanding rate determining step.
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Journal Name：Organic & Biomolecular Chemistry
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CAS no.: 89640-58-4
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