Advanced

Stereochemistry and
Conformation
Lecture 7 - Cyclohexane

A. P. Davis

1
The Cyclohexane Chair Conformation

2
 a a
All carbons identical H H
a
but two types of hydrogen
H He
eH e
H
a = axial e
H He
e = equatorial He H
a
H H
a a

Axial C-H parallel to each other and to

3-fold axis of symmetry. Directions
alternate as proceed around ring. Equatorial hydrogens angled slightly up or down.
Directions alternate as proceed around ring.
a a
H H
a He
H
eH He
e
H He

He
H
a
H H
a a trans
to each other
3
The Cyclohexane Chair Conformation

4
Because the cyclohexane chair is so stable, any other conformation is much higher in energy.
The structure is therefore quite rigid. However, conformational change is possible:

H H

chair boat chair

Note that a particular H moves from equatorial to axial during this process
(though chair forms are indistinguishable, as all H are identical).

Boat is much less stable, due to eclipsing interactions along sides

H H H
H

H H
H H

H
H
H H view along C-C

5
In fact, boat is not an energy minimum.
Twist the sides relative to each other, and eclipsing interactions are relieved.
Get “twist-boat”.

H H
H H
H H † H H
* H H * H H †
H H
†
H * * † H
H H H H
H H H H

twist-boat boat twist-boat

conformer conformation conformer

6
7
The full picture…
H

boat

Energy
(KJ mol-1)

43

23

H H
H
chair

Chair to twist-boat, 23 kJ mol-1 chair

~10,000 chairs for each twist-boat H

Barrier 43 kJ mol-1
twist-boats
Happens ~100,000 times per second.

8
How do we know?
1.4 p.p.m.

D D
D D
D D
NMR of cyclohexane-d11 D H
D D
D D

At high temperature (above -50 oC) just one signal,

but splits into two on cooling

Half the molecules have Hax, half have Heq

Interconversion slow (on NMR timescale) at low temp

but fast at high temp.

Rate may be obtained from temp at which

signals coalesce.