The water‐promoted Diels–Alder reaction in quaternary ammonium salts |
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Authors: | Amit S Nagare Arpan Manna Pramod D Sonawane Anil Kumar |
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Affiliation: | 1. Physical and Materials Chemistry Division, CSIR‐National Chemical Laboratory, Pune, India;2. Department of Chemistry, MES Abasaheb Garware College, Pune, India |
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Abstract: | Prevailing classification of salts based on their effect in solubility and stability of proteins in aqueous solution predicts that tetraalkylammonium salts, guanidinium chloride (GnCl), LiClO4 act as salting‐in (S/I) and LiCl, NaCl act as salting‐out (S/O) in aqueous conditions. In the same context the behaviour of GnCl, LiClO4 and LiCl are contradictory in polar solvents like ethylene glycol and formamide. In these solvents, expected salt effect shows just opposite nature from their usual expectation. However, in the aqueous solution salts like tetraalkylammonium halide (R4NX, R = alkyl group, X = Br group) behave like salting‐in salts. The physicochemical origin of the salting in effect of R4NX type of salts has been discussed elaborately in the present work. The role of cations in terms of substitution of various alkyl groups on R4NX has been systematically presented here on the basis of experimental kinetic and thermodynamic studies. The abnormal behaviour of R4NX salts in aqueous solution has also been explained by the Setschenov equation (ks) and Δμsolvation values, which highlights their individual nature out of common properties of R4NX. Copyright © 2015 John Wiley & Sons, Ltd. |
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Keywords: | Diels– Alder reaction kinetic study ks solubility tetraalkylammonium salts viscosity Δ Gsolvation |
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