Chair vs.

Boat Conformation of Cyclohexane

H
H CH3
gauche conformation
of butane
.
.

H CH3 .
.

Chair conformation
H

.
.
.
.

.
.
.
.

HH
Ring flip
eclipsed conformation
of butane .

HH CH
CH33 .

. .

.
Boat conformation .
Chair vs. Boat Conformation of Cyclohexane
Chair conformation

.
.

.
.

Ring flip .

.
.
.

.
.

. .
.

. .

Boat conformation
.

. .

. . .

Twisted boat conformation

.

. .

.
.
.

.
Cyclohexane: Axial vs. Equatorial
H
.

.
Axial Hydrogens
H CH3
gauche conformation
of butane
H CH3 .

H .

. .

H . .

H H
H H
H
H
H H
.

H H .
.

.
H .

. . .

. .
.

Equatorial Hydrogens
Substituted Cyclohexane: Axial vs. Equatorial
.

H
CH3
H2C H
gauche conformation
of butane . .

H H
. .

H .

H H
H CH3 H H
H H
H CH3
3.8 kj/mol H H
. .
H H
. .
H H H H
H H H H
H H . H
.

H CH3
anti conformation
H of butane
C H
H2 H

.
 Substituted Cyclohexane: Axial vs. Equatorial
.

. . .

. .

ΔG° = −RT ln Keq ΔG° = −2.303RT (log

Keq)
-7.6 kj/mol
.

logKeq = = 1.33
.

2.303(8.314x10-3 kj/mol°K)(273+25)°K

Keq = 101.33 = 21

Equatorial-Me conformer 21
Keq = = 21 =
Axial-Me conformer 1

21 1
Equatorial-Me conformer: x 100 = 95% Axial-Me conformer: x 100 = 5%
22 .

.
22 .
Substituted Cyclohexane: Axial vs. Equatorial
.

ΔG° = -21 kj/mol

. .

. .

.
Substituted Cyclohexane: Axial vs. Equatorial
.

ΔG° = -21 kj/mol

. .

. .

ΔG° = 2.303RT (−log Keq)

.

.
 Conformational Analysis of Butane
Each conformation is characterized by the associated energy.

Torsional barrier =
Steric hindrance + Orbital interactions
Disubstituted Cycloalkanes: Cis–Trans Isomers
.

. .

. .

.
Disubstituted Cyclohexanes: Cis–Trans Isomers
.

. . lower bond
. .

.
Disubstituted Cyclohexanes: Cis–Trans Isomers
.

. .

. .

trans-1,3-Dimethylcyclohexane
.
.

CH3

H3C CH3
.
ΔG° = 13.4 kj/mol
.

H H

CH3

trans-1,2-Dichlorocyclohexane
.

cis-1,2-Dichlorocyclohexane cis-1,3-Dichlorocyclohexane .
 Bicyclic and Polycyclic Alkanes
.