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The two have equal free energy; neither is more stable, so neither predominates compared to the other. A negative difference in free energy means that a conformer interconverts to a thermodynamically more stable conformation, thus the equilibrium constant will always be greater than 1.
One category of reactions under Curtin–Hammett control includes transformations in which the more stable conformer reacts more quickly. This occurs when the transition state from the major intermediate to its respective product is lower in energy than the transition state from the minor intermediate to the other possible product.
The gauche effect is very sensitive to solvent effects, due to the large difference in polarity between the two conformers.For example, 2,3-dinitro-2,3-dimethylbutane, which in the solid state exists only in the gauche conformation, prefers the gauche conformer in benzene solution by a ratio of 79:21, but in carbon tetrachloride, it prefers the anti conformer by a ratio of 58:42. [9]
Cyclohexane is the most stable of the cycloalkanes, due to the stability of adapting to its chair conformer. [4] This conformer stability allows cyclohexane to be used as a standard in lab analyses. More specifically, cyclohexane is used as a standard for pharmaceutical reference in solvent analysis of pharmaceutical compounds and raw materials.
Another implication of TST is the Curtin–Hammett principle: the product ratio of a kinetically-controlled reaction from R to two products A and B will reflect the difference in the energies of the respective transition states leading to product, assuming there is a single transition state to each one:
The conformer of methylcyclohexane with equatorial methyl is favored by 1.74 kcal/mol (7.3 kJ/mol) relative to the conformer where methyl is axial. In organic chemistry, a ring flip (also known as a ring inversion or ring reversal) is the interconversion of cyclic conformers that have equivalent ring shapes (e.g., from a chair conformer to ...
More complex molecules, such as butane, have more than one possible staggered conformation. The anti conformation of butane is approximately 0.9 kcal mol −1 (3.8 kJ mol −1) more stable than the gauche conformation. [1] Both of these staggered conformations are much more stable than the eclipsed conformations.
At higher temperatures when microscopic reversal is easier, the more stable thermodynamic product is favored because these intermediates have time to rearrange. Whether run at high or low temperatures, the mixture of the kinetic and thermodynamic products eventually reach the same ratio, one in favor of the more stable thermodynamic product ...