HA

ring-flip

HA

HB
HB

Chair conformation
flagpole hydrogens
0

1.8 A

Sum of the van der

Waals radii = 2.4 A0

Boat conformation

HH

H
H

H
H

Newman projection of the

boat conformation

The easiest way to draw a twist-boat conformation

The energy difference between the chair, boat, and twist conformation of cyclohexane are low enough

to make their separation impossible at r.t. At room temperature approx. 1 million introversions occur
each other second.
More than 99% of the molecules are estimated to be in chair conformation at any given time

Monosubstituted cyclohexane
X

X
This conformation is lower in energy

Why?

For methylcyclohexane (X=CH3), the conformer with

the methyl group axial is 7.3 kJ/mol higher in energy
than the conformer with the methyl group equatorial.
Result: 20:1 ratio of equatorial:axial conformer at 200 C

1,3-diaxial interaction
H

H
X

H
H
H

H
H

H
H
H

The black bonds are antiperiplanar

(only one pair shown)

The black bonds are synclinal

(gauche)
(only one pair shown)

Conc. of equatorial conformer

K= Conc. of axial conformer

H
Me
Et
i-Pr
t-Bu
OMe
Ph

Equilibrium Energy diff. between % with

axial and equatorial substitutent
constant
conformers
equatorial
kJ/mol

1
19
20
42
>3000
2.7
110

0
7.3
7.5
9.3
>20
2.5
11.7

50
95
95
98
>99.3
73
99

OH
OH

Preferred
conformation
t-butyl group
- a locking
group
OH

Preferred
conformation

OH

disfavoured

twist-boat conformation with both

t-Bu groups pseudoequatorial

Q. Write the prefered conformation for

Me

OH

i-Pr

Me
OH
favoured

Me
OH

CH3

CH3
CH3
CH3

CH3

CH3

1 gauche-butane interaction
0.9 kcal/mol

Difference in stability between

the conformational isomers

It should form a ()pair

CH3

CH3

4 gauche-butane interaction
4 x 0.9 kcal/mol = 3.6 kcal/mol

3.6 - 0.9 = 2.7 kcal/mol

CH3

CH3

CH3

CH3
CH3

H 3C

This has 3 gauche-butane

interactions
The two conformational isomers are mirror images

It exists as a dl-pair, but since barrier to rotation is low to allow separation.

Therefore the ()- pair is inseparable and hence the compound is optically inactive.

CH3
CH3
CH3

H3C

CH3

CH3

Very bad steric

situation ~ 5.5 kcal/mol (4 x 0.9 = 3.6 kcal/mol
+ Methyl-Methyl interaction)
CH3

CH3
CH3

H3C
CH3
CH3

It is a resolavable molecule
2-gauche-butane interaction = 1.8 kcal/mol

CH3
CH3

H3C
CH3

CH3
CH3

2-gauche-butane interaction, 2 x 0.9 = 1.8 kcal/mol

plane of symmetry : not resolavable

CH3

CH3
H3C
CH3

CH3

plane of symmetry

CH3

Why is the eclipsed conformation higher in energy than the staggered conformation?
As two nonpolar groups approach each other,
the van der Waals attractive force increases to
a maximum,then decreases and becomes
repulsive
The van der Waals radius one-half the
distance between two equivalent atoms at
the point of the energy minimum

van der Waals radii, A0

H

1.2

1.5

1.4

1.35

CH2
2.0
CH3
2.0

P
1.9

S
1.85

Cl
1.8
Br
1.95
I
2.15

The H-atoms are too small to

get in each others way-steric
factors make up < 10% of the
rotational barrier in ethane