William H.

Brown

Thomas Poon

www.wiley.com/go/global/brown

Chapter Three
Alkanes and Cycloalkanes
Isomers

3-2
Conformation
• Eclipsed conformation: A conformation about a carbon-carbon
single bond in which the atoms on one carbon are as close as
possible to the atoms on an adjacent carbon.
H
H

H
H HH

• The lowest energy conformation of an alkane is a fully

staggered conformation.

3-3
 有機立體化學分子擴增實境

Android

iOS 多人有機

3-4
Conformations
• Torsional strain: Strain that arises when atoms separated by
three bonds are forced from a staggered conformation to an
eclipsed conformation.
• Also called eclipsed interaction strain.
strain
• The torsional strain between staggered and eclipsed ethane is
approximately 12.6 kJ/ mol(3.0 kcal/mol).

+3.0 kcal/mol

3-5
Conformational Energy of Ethane

3 kcal/mol
Energy

0° 120° 240° 360°

Torsional Angle
HH H HH H HH H HH
H H H H H H
H H H H
H HH H
H
H H HH H
H
H H HH H
H
H 3-6
H HH
Butane ( 丁烷 )

CH3 CH3
CH3

CH3

staggered gauche

H3C CH3

0.85 kcal/mol

eclipsed

3-7
Conformations
• THE ENERGY OF BUTANE AS A FUNCTION OF THE
DIHEDRAL ANGLE ABOUT THE BOND BETWEEN
CARBONS 2 AND 3.

3-8
3-9
Cycloalkanes
• Cyclopentane
• In planar cyclopentane, all C-C-C bond angles are 108°, which
differ only slightly from the tetrahedral angle of 109.5°.
• Consequently there is little angle strain.
• Angle strain: Strain that arises when a bond angle is either
compressed or expanded compared with its optimal value.

3-10
Cycloalkanes
• Cyclopentane (cont’d)
• In planar cyclopentane, there are 10 fully eclipsed C-H bonds,
which create torsional strain of approximately 42 kJ/mol (10
kcal/mol).
• Puckering to an “envelope” conformation relieves part of this
strain
• In an envelope conformation, eclipsed interactions are reduced
but angle strain is increased slightly (105°).

3-11
Cycloalkanes
• Cyclohexane
• The most stable conformation is a puckered chair conformation.
conformation
• In a chair conformation, all bond angles are approx. 109.5°, and
all bonds on adjacent carbons are staggered.

3-12
3-13
Cycloalkanes
• Chair cyclohexane
• Six H are equatorial and six H are axial.

• An axial bond extends from the ring parallel to the imaginary

axis of the ring.
• Equatorial bonds are roughly perpendicular to the imaginary
axis of the ring. 3-14
Cyclohexane
• chair cyclohexane (cont’d)
• There are two equivalent chair conformations.
• All C-H bonds equatorial in one chair are axial in the
alternative chair, and vice versa.

3-15
Cyclohexane
• Boat conformation: A puckered conformation in which carbons 1 & 4 are
bent toward each other.
• A boat conformation is less stable than a chair conformation by 27 kJ)/mol
(6.5 kcal/mol).
• Torsional strain is created by four sets of eclipsed hydrogen interactions.
• Steric strain (nonbonded interaction strain) is created by one set of flagpole
interactions.

3-16
3-17
Cyclohexane
• ENERGY DIAGRAM FOR INTERCONVESION OF CHAIR,
TWIST-BOAT AND BOAT CONFORMATIONS OF
CYCLOHEXANE.

3-18
Cyclohexane
• The alternative chair conformations interconvert via a boat
conformation.

3-19
Cyclohexane
• A group equatorial in one chair is axial in the alternative chair.
• The two chairs are no longer of equal stability.

CH3
+1.74 kcal/mol
CH3

3-20
3-21
Cis-trans Isomerism
• Cis-trans isomers have
• The same molecular formula.
• The same connectivity of their atoms.
• An arrangement of atoms in space that cannot be interconverted
by rotation about sigma bonds.

3-22
Cis-trans isomerism
• The ring is commonly viewed through an edge or from above.
H H
H H H H
H H H H H H3 C
H H H H
CH3 CH3 CH3 H

H3 C CH3
H3 C CH3
cis-1,2-Dimethyl- trans-1,2-Dimethyl-
cyclopentane cyclopentane

3-23
Cis-trans isomerism
• Cyclohexanes may be viewed as planar hexagons.

H CH3 CH3

H3 C H H3 C
trans-1,4-Dimethylcyclohexane

H H CH3

H3 C CH3 H3 C
cis-1,4-Dimethylcyclohexane
3-24
3-25
3-26
Cis-trans isomerism
• Or we can represent them as chair conformations.
• In viewing chair conformations, remember that groups
equatorial in one chair are axial in the alternative chair.
• For trans-1,4-dimethylcyclohexane, the diequatorial chair is
more stable than the diaxial chair.
CH3 equatorial
H equatorial
axial
H CH3

H CH3
axial
CH3 H
(less stable) (more stable)
trans-1,4-Dimethylcyclohexane
3-27
Cis-trans isomerism
• For cis-1,4-dimethylcyclohexane, the alternative chairs are of
equal stability.

equatorial
H H

CH3 CH3
H H
axial axial
CH3 CH3
cis-1,4-Dimethylcyclohexane
(these conformations are of equal stability)

3-28
Cis-trans isomerism
• Problem: Draw the alternative chair conformations of this
trisubstituted cyclohexane and state which is the more stable.

H3 C CH3
CH3

H H

3-29
Alkanes and
Cycloalkanes

End Chapter 3
3-30