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Chapter 6: Reactions of Alkenes Solutions 123

Problem 6.23 Draw a structural formula for the alkene of molecular formula C5H10 that reacts with Br2 to give each
product.

(a) *
. *
(c) B r
.
Br (b) B r * .

Br Br Br

.
. .

A chiral center is created in each case, so the products of these bromine addition reactions are actually racemic
mixtures.
Problem 6.24 Draw the alternative chair conformations for the product formed by the addition of bromine to 4-tert-
butylcyclohexene. The Gibbs free energy differences between equatorial and axial substituents on a cyclohexane ring are 21
kJ (4.9 kcal)/mol for tert-butyl and 2.0 – 2.6 kJ (0.48 - 0.62 kcal)/mol for bromine. Estimate the relative percentages of the
alternative chair conformations you drew in the first part of this problem.

00
Br
00
(CH3 ) 3 C H
(CH3 ) 3C H
000
+ Br2 Br 000
+
(CH3 ) 3C H

Br
Br
000
00
H 000
00
Note that the bromine atoms are trans with respect to each other in the product due to anti addition geometry of
the bromination reaction. Recall that large substituents are sterically disfavored in axial positions. The upper
product has the large tert-butyl group in the strongly favored equatorial position along with both bromine
atoms in the somewhat disfavored axial positions. The lower product has the large tert-butyl in the strongly
disfavored axial position along with both bromine atoms in the somewhat more favored equatorial positions.
The conformational energy difference based on the axial vs. equatorial tert-butyl group is 21 kJ/mol, and we will
use an intermediate value of 2.3 kJ/mol for the conformational energy difference for the axial vs. equatorial
bromine atoms. Thus, the relative conformation energy can be estimated as being favorable for the upper
structure by an amount equal to the value that is favorable for the tert-butyl group (21 kJ/mol) minus the
disfavorable contributions of the two bromine atoms (2 x +2.3 kJ/mol) for a total of 16.4 kJ/mol.
At equilibrium the relative amounts of each form are given by the equation:
ΔG° = -RTlnKeq
Here Keq refers to the ratio of the alternative chair conformations. Rearranging gives
- ΔG°
lnKeq =
RT

Solving gives:
- Δ G°
RT
Keq = e
Plugging in the values for Δ G°, R, and 298 K gives the final answer:

- − (− 16 .4 kJ/mol)
HC
(8.314 x 10 -3 kJ/mol K)(298 K) 6.62
Keq = e =e = 7.50 x 102

Thus, the structure with the tert-butyl group equatorial will be favored by about 750 to 1 at equilibrium at room
temperature.