Conformations of Alkanes and Cycloalkanes

I. Conformations of Alkanes
A. Ethane: torsional strain

H
C
C
H
H
H
staggered
conformation

rotate 60

H C C H
H
H
in between:
skewed

eclipsed
conformation

Newman projections: sight along C-C bond

H
H

H
H

H
H

H
H

Chem3D

H
H

H
H

Stereoisomers:
Isomers with the
same connectivity,
but different 3-D
orientation of their
atoms in space.
2

I. Conformations of Alkanes
A. Ethane: torsional strain

H
H

H
H

H
H

H
H

H
H

H
H

lower energy

higher energy

DG ~ 3 kcal/mol
K ~ 0.01
torsional strain

Ea ~ 3 kcal/mol

= barrier to free rotation

DG

(but at room temp most

molecules have KE > Ea so
rotation is essentially free)

0
H
H

H
H

H
H

H
H

H
H

H
H
H

H
H

H
H

krot ~ 106 s-1

I. Conformations of Alkanes
B. Butane: steric repulsions

CH3
CH3
I
anti
(180)

CH3

H3C

CH3

CH3CH2CH2CH3

CH33

CH3
CH3

CH3

H3C

CH3
II

III
gauche
(60)

IV

gauche ~ 0.8 kcal higher energy than anti

- van der Waals repulsions
= steric strain
eclipsed: 3 kcal torsional strain
+ 0.3 kcal each CH3-H eclipse
+ ~ 3 kcal each CH3-CH3 eclipse

V
gauche
(60)

VI

Chem3D

I. Conformations of Alkanes
B. Butane: steric repulsions
CH3

CH3

H3C

CH3

CH33

CH3
CH3

CH3

H3C

CH3
I

CH3
II

III

IV

VI

4
DG
~6
2

3.6

0.8

0.8

3.6

0
I

II

III

IV

VI

II. Conformations of Cycloalkanes

A. Stabilities of cycloalkanes

Ring strain = bond angle strain

+ torsional strain (eclipsing)
+ steric strain (van der Waals)

II. Conformations of Cycloalkanes

A. Stabilities of cycloalkanes
DHcomb

per CH2

small

normal

medium

large > C12

Total
ring strain

166.6 kcal

31.5 kcal

162.7

26.4

157.3

7.0

156.1

157.0

6.3

157.3

9.6

156.2

1.2

angle strain and

torsional strain

minimal strain

transannular
steric strain
7

II. Conformations of Cycloalkanes

A. Stabilities of cycloalkanes

H H

poor overlap = bond angle strain

(i.e., 109.5 sp3 in 60 triangle)

H
H

H
H

plus ,

H
H

H
H

all Hs eclipsed =
torsional strain

H
Chem3D
8

II. Conformations of Cycloalkanes

A. Stabilities of cycloalkanes

H
H

Chem3D

H
H

H
H

H
H

planar, 90
but all eclipsed

H
H

puckered, 88
slightly more angle strain,
but less eclipsing strain

envelope
relieves eclipsing
planar, 108
but all eclipsed
9

II. Conformations of Cycloalkanes

B. Conformations in cyclohexane
1. chair and boat conformations

H
H

H
H
H

H
H

flagpole interaction

H
H

H
H

H
H

H
H

chair conformation
- all staggered
- no eclipsing
- no steric strain
no ring strain
(99.99% at room temp.)

DG ~ 7 kcal

Chem3D

boat conformation
- eclipsing ~ 4 kcal
- steric strain ~ 3 kcal
ring strain ~ 7 kcal
skewed boat ~ 1.5 kcal
more stable than boat
(0.01% at room temp.)

10

II. Conformations of Cycloalkanes

B. Conformations in cyclohexane
2. equatorial and axial positions

H
H

H
H

H
H

H
H

H
H

H
H

H
H

axial positions

equatorial positions

3. chair-chair interconversion

H
H
H
H

H
H

H
H

H
H

H
H

Ea ~ 10 kcal

H
H

H
H

H
H

11

II. Conformations of Cycloalkanes

B. Conformations in cyclohexane
4. drawing cyclohexane chairs

12

II. Conformations of Cycloalkanes

Ray

C. Substituted cyclohexanes

CH3

1,3-diaxial
repulsions

CH3
H
H

CH3
H
equatorial
(95%)
no steric strain
(anti)

Chem3D

DG ~ 1.8 kcal
(or 0.9 kcal
per CH3-H
repulsion)

axial
(5%)
steric repulsions
(gauche)
13

II. Conformations of Cycloalkanes

C. Substituted cyclohexanes

More pronounced effect with larger groups:

(99.99%)

DG ~ 5.5 kcal

(0.01%)

locked in equatorial conformation

14

II. Conformations of Cycloalkanes

D. Disubstituted cyclohexanes
CH3

CH3

CH3

CH3

trans-

cis-1,4-dimethylcyclohexane
stereoisomers

*configurational
conformational
(cannot convert from
(can be converted from
one to another without
to another by rotation
breaking bonds)
about a bond)
*geometric isomers
15

II. Conformations of Cycloalkanes

D. Disubstituted cyclohexanes
CH3

CH3
CH3
CH3

CH3
H

CH3

DG ~ 3.6 kcal

CH3

H
CH3

diequatorial
no repulsions

diaxial
4 1,3-diaxial repulsions
= 4 x 0.9 = 3.6 kcal
16

II. Conformations of Cycloalkanes

D. Disubstituted cyclohexanes
CH3

CH3

H3C

CH3

CH3

H
CH3

equatorial-axial
2 x 0.9 = 1.8 kcal

CH3

CH3

DG = 0 kcal

axial-equatorial
2 x 0.9 = 1.8 kcal
17

II. Conformations of Cycloalkanes

D. Disubstituted cyclohexanes
CH3
CH3

CH3
H

CH3

CH3
H

1 gauche interaction
= 0.9 kcal

DG ~ 2.7 kcal

H
CH3

4 1,3-diaxial repulsions
= 4 x 0.9 = 3.6 kcal

18

II. Conformations of Cycloalkanes

D. Disubstituted cyclohexanes
CH3

CH3

CH3
CH3

H3C

no repulsions

DG ~ 5.4 kcal

CH3

2 1,3-diaxial CH3-H = 1.8 kcal

1 1,3-diaxial CH3-CH3 = 3.6 kcal

19

II. Conformations of Cycloalkanes

D. Disubstituted cyclohexanes
Larger groups predominate in determining conformation:
CH3

tBu

CH3

DG ~ 3.7 kcal
CH3

1.8 kcal

5.5 kcal
20

II. Conformations of Cycloalkanes

D. Disubstituted cyclohexanes
Question 3-1. Draw the most stable chair form of the following compounds.
Explain. Click on the arrow to check your answers.
CH(CH3)2

CH3

CH3

CH3

CH3

Check Answer

21

II. Conformations of Cycloalkanes

D. Disubstituted cyclohexanes
Answer 3-1. Draw the most stable chair form of the following compounds.
Explain. Click on the arrow to check your answers.
CH(CH3)2

CH3

CH3

CH3

CH3
CH3

CH3
CH3

CH3

All groups can be equatorial. This

chair form is more stable than the
other, where all are axial.

CH(CH3)2

Isopropyl is bigger than a methyl

group, so more stable chair is where
22
larger group is equatorial.

III. Polycyclic Rings

borneol OH

decalin
bicyclic
Bicycloalkanes:

Cy
C
Cx

Cz

adamantane

prismane

tricyclic

tetracyclic

bicyclo[x.y.z]alkane (x y z)
numbering starts at a bridgehead,
proceeds around the largest bridge first,
then around successively smaller
bridges
23

III. Polycyclic Rings

bicyclo[4.0]decane

bicyclo[2.2.1.]heptane

bicyclo[4.1.0]heptane

bicyclo[3.2.1]octane
24

IV. Heterocyclic Compounds

O
O

ethylene oxide
oxirane
oxacyclopropane

H
N
pyrrolidine
azacyclopentane

oxetane
oxacyclobutane

O
tetrahydrofuran
oxacyclopentane

N
piperidine
azacyclohexane

O
tetrahydropyran
oxacyclohexane

furan

pyran
25