Premium
Stereoselectivities and reaction rates in Diels‐Alder reactions promoted by non‐aqueous solvents and their aqueous mixtures: Correlations with non‐adjustable parameters
Author(s) -
Kumar Anil
Publication year - 1996
Publication title -
journal of physical organic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.325
H-Index - 66
eISSN - 1099-1395
pISSN - 0894-3230
DOI - 10.1002/(sici)1099-1395(199605)9:5<287::aid-poc808>3.0.co;2-e
Subject(s) - chemistry , diels–alder reaction , solvent , aqueous solution , reaction rate , polarity (international relations) , solvent polarity , solvent effects , computational chemistry , kinetic energy , scale (ratio) , organic chemistry , catalysis , biochemistry , physics , quantum mechanics , cell
Stereoselectivities and rates of Diels‐Alder reactions in different solvents were correlated with a parameter, Q , defined based on internal pressure, which is normalized with respect to a polarity scale. The polarity scale or index, although purely empirical in nature, can be calculated from the refractive index of the solvent. These correlations were linear for both stereoselectivities and reaction rates. Using expressions derived in this study, it is possible to represent the kinetic profiles of several Diels‐Alder reactions in about 75 pure and mixed solvent media. The activation volume of a reaction can be directly estimated from the regression of data on rates and Q in various solvents using the proposed correlations.