ISSN:
0894-3230
Keywords:
Organic Chemistry
;
Physical Chemistry
Source:
Wiley InterScience Backfile Collection 1832-2000
Topics:
Chemistry and Pharmacology
,
Physics
Notes:
The deprotonation of nitroalkanes and ketones was studied through the intersecting state model of Formosinho. The anomalous Brønsted coefficients observed when substituted nitroalkanes react with a common base are explained in terms of variable transition-state electronic structures. These are very sensitive to substitution in the nitroalkane, owing to the high electron affinity of the nitro group. In ketones, such electronic effects are much attenuated. The transition states are characterized by the bond order, n,*, which is quantitatively correlated to the field/inductive and resonance effects of the substituents. The deprotonation of fluorence and other carbon acids was also studied. The theoretical model applied shows that all these reactions follow a mechanistic continuum, dictated by the extent into which the group directly bonded to the acidic carbon is mixed in the reaction coordinate.
Additional Material:
8 Ill.
Type of Medium:
Electronic Resource
URL:
http://dx.doi.org/10.1002/poc.610041205
