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4-1 Naming Cycloalkanes

◼ Cycloalkanes (or alicyclic compounds) :

saturated cyclic hydrocarbons
◼ general formula : CnH2n

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Naming Cycloalkanes
1. Find the parent.
Count the number of carbon atoms in the ring.

If the number of carbon atoms is equal to or greater than the number

of carbon atoms in the substituent, the compound is named as an
alkyl-substituted cycloalkane.

Otherwise, the compound is named as a cycloalkyl-substituted alkane.

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Naming Cycloalkanes
2. Number the substituents, and write the name.
Choose a point of attachment as carbon 1 and number the
substutuents on the ring so that the second substituent has as low a
number as possible.

If ambiguity still exists, number so that the third or fourth substituent

has as low a number as possible, until a point of difference is found.

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(a) When two or more different alkyl groups that could potentially receive
the same number are present, number them by alphabetical priority,
ignoring numerical prefixes as di- and tri-.

(b) If halogens are present, treat them just like alkyl groups:

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Some additional examples:

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Problem 4-1 Give IUPAC names for the following
cycloalkanes:

Br
CH3

CH3

CH3 C(CH3)3

Problem 4-2 Draw structures corresponding to the following IUPAC

names:
(b) 3-Cyclobutylhexane
(d) 1,3-Dibromo-5-methylcyclohexane

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 4-2 Cis-Trans Isomerism in
Cycloalkanes
◼ Cycloalkanes are less flexible than open-chain (acyclic) alkanes
→There is much less conformational freedom in cycloalkanes
Ex) Cyclopropane

(a) Rotation occurs around the C-C bond. (b) No rotation is possible
around the C-C bonds in
cyclopropane without breaking
open the ring.

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◼ The rotational freedom of rings increases as
the ring size increases:

1) C3-C7: These ring sizes are severely restricted in

their molecular motions
2) C25 and up: They are so floppy that they are nearly
indistinguishable from open-chain alkanes

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◼ Because of their cyclic structure, cycloalkanes have 2 faces as viewed
edge-on, a “top” face and a “bottom” face
Therefore, isomerism is possible in substituted cycloalkanes

Ex) two different isomers of 1,2-dimethylcyclopropane

Two methyl groups Two methyl groups

on the same face on opposite faces
cis : “on the same side” trans : “across”
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 Stereoisomerism
◼ Compounds which have their atoms connected in the
same order but differ in 3-D orientation are called
stereochemical isomers or stereoisomers.

# cis-trans isomers:
members of a subclass of stereoisomers
 4-3 Stability of Cycloalkanes: Ring Strain
◼ Angle strain (각무리): the strain induced in a molecule when bond
angles are forced to deviate from the ideal 109o tetrahedral value.

Baeyer Strain Theory:

Although numerous compounds containing 5- and 6-membered rings
were known, smaller and larger rings had not been prepared, despite
many efforts.
Under assumption that cyclic compounds are flat, Baeyer proposed that
small and large rings might be unstable due to the angle strain (1885).

◼ Baeyer: since carbon prefers to have bond angles of approximately

109°, ring sizes other than five and six may be too strained to exist
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 What are the facts?

Heat of combustion per CH2 unit :

(CH2)n + (3n/2)O2 → nCO2 + nH2O + Heat

⇒ The more energy (strain) the compound contains, the more

energy (heat) is released on combustion.

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 Stability of Cycloalkanes:

◼ Cycloalkane strain energies can be calculated by taking the

difference between cycloalkane heat of combustion and acyclic
alkane heat of combustion.
→ Small and medium rings are strained, but cyclohexane rings are
strain-free: Baeyer’s theory is wrong, because he assumed all
cyclic compounds to be flat
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 Summary: Types of Strain

# In fact, most cycloalkanes adopt puckered 3-dimensional

conformations that allow bond angles to be nearly tetrahedral.
Angle strain occurs only in 3- and 4-membered rings that have little
flexibility.
For most ring sizes particularly medium-ring cycloalkanes (C7-C11),
torsional strain and steric strain are the most important factors.

Thus three kinds of strain contribute to the overall energy of

a cycloalkane:

1) Angle strain (각무리) - expansion or compression of bond angles

(from 109o)
2) Torsional strain (비틀림무리) - eclipsing of bonds on neighboring
atoms
3) Steric strain (입체무리) - repulsive interactions between nonbonded
atoms in close proximity
Problem 4-8 Each H-H eclipsing interaction in ethane costs about 4.0 kJ/mol.
How many such interactions are present in cyclopropane? What fraction of the
overall 115 kJ/mol strain energy of cyclopropane is due to torsional strain?

H
eclipsed
H
H H

H
H H C

H H
H H H
eclipsed

Cyclopropane has 6 pairs of H-H eclipsed interactions. Therefore,

6 x 4.0 kJ/mol = 24 kJ/mol
(24/115)100 = 21%
4-4 Conformations of Cycloalkanes
Cyclopropane
◼ 3-membered ring must have planar structure
◼ Symmetrical with C–C–C bond angles of 60°
◼ Requires that sp3 based bonds are bent (and weakened)
◼ All three pairs of C-H bonds are eclipsed

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 Bent Bonds of Cyclopropane
# In an unstrained alkane, maximum bonding is achieved when two
atoms have their overlapping orbitals pointing directly toward each
other.
In cyclopropane, however, the orbitals can’t point directly toward each
other: they overlap at an angle. Thus, cyclopropane bonds are weaker
and more reactive than typical alkane bonds.

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 Cyclobutane
◼ Cyclobutane has less angle strain than cyclopropane but more
torsional strain because of its larger number of ring hydrogens

◼ Cyclobutane is slightly bent out of plane : one carbon atom is about

25° above

◼ This slight bend increases angle strain but decreases

torsional strain

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 Cyclopentane
◼ Planar cyclopentane would have no angle strain but very high torsional
strain
◼ Actual conformations of cyclopentane are nonplanar, reducing torsional
strain
◼ Four carbon atoms are in a plane: the fifth carbon atom is above or
below the plane – looks like an envelope

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4-5 Conformations of Cyclohexane
◼ Substituted cyclohexanes occur widely in nature
◼ Cyclohexane adopts a strain free, a chair conformation (의자 형태).
◼ Chair cyclohexane has neither angle strain nor torsional strain
because all C-C-C bond angles are near the tetrahedral value and
all neighboring C-H bonds are staggered.

Figure 4.7 The strain-free chair conformation of cyclohexane.

All C-C-C bond angles are 111.5o, close to the ideal 109.5o tetrahedral angle,
and all neighboring C-H bonds are staggered.
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How to Draw Cyclohexane

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# When viewing cyclohexane, it’s helpful to remember that
the lower bond is in front and the upper bond is in back:

# The twist-boat conformation is also nearly free of angle strain.

However, it has both steric and torsional strain and is about 23 kJ/mol
higher than the chair conformation.

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 4-6 Axial and Equatorial Bonds in
Cyclohexane
◼ The chair conformation has two kinds of positions for substituents on
the ring: axial (수직의) positions and equatorial (수평의) positions

◼ Chair cyclohexane has six axial hydrogens perpendicular to the ring

(parallel to the ring axis) and six equatorial hydrogens near the plane
of the ring

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 Axial and Equatorial Positions
◼ Each carbon atom in cyclohexane has one axial and one
equatorial hydrogen
◼ Each face of the ring has three axial and three equatorial
hydrogens in an alternating arrangement

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Drawing the Axial and Equatorial
Hydrogens

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Conformational Mobility of Cyclohexane
◼ Chair conformations readily interconvert, resulting in the
exchange of axial and equatorial positions by a ring-flip
(고리뒤집기)

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Ex: axial bomocyclohexaxne becomes equatroial
bromocyclohexane after ring-flip:

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4-7 Conformations of
Monosubstituted Cyclohexanes
Even though cyclohexane rings rapidly flip between chair
conformations at room temperature, two conformations of a
monosubstituted cyclohexane aren’t equally stable.

# We can calculate the percentage of two isomers at equilibrium

using the following equation:

ΔE = -RT lnK

where ΔE is the energy difference between two isomers, R is the

gas constant, T is the Kelvin temperature, and K is the equilibrium
constant between two isomers.

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 Figure 4-12 A plot of the percentage of two isomers at
equilibrium versus the energy difference between them.

Ex: The equatorial conformer of methyl cyclohexane (~95%) is more stable

than the axial conformer by 7.6 kJ/mol (~5%). 31
 1,3-Diaxial Interactions
◼ The energy difference between axial and equatorial conformations is
due to steric strain caused by 1,3-diaxial interactions
(1,3-이축방향 상호작용)
◼ Hydrogen atoms of the axial methyl group on C1 are too close to the
axial hydrogens (three carbons away) on C3 and C5, resulting in 7.6
kJ/mol of steric strain

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 Relationship to Gauche Butane
Interactions
◼ Gauche butane is less stable than anti butane by 3.8
kJ/mol because of steric interference between hydrogen
atoms on the two methyl groups
◼ The four-carbon fragment of axial methylcyclohexane
and gauche butane have the same steric interaction
→ In general, equatorial positions give more stable
isomer

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Problem 4-15 What is the energy difference between the axial
and equatorial conformations of cyclohexanol?
(diaxial H-OH interaction: 2.1 kJ/mol in Table 4.1)

H OH
H

OH

Problem 4-16 Why do you suppose an axial cyano (-CN) substituent

causes pratically no 1,3-diaxial steric strain (0.4 kJ/mol)?
Use molecular models to help your answer.

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Problem 4-17 Look at Figure 4.12 (a plot of the percentages of two
isomers at equilibrium versus ∆E), and estimate the percentage of
axial and equatorial conformation at equilibrium in
bromocyclohexane.

→ About 70% of bromocyclohexane molecules have the Br atom

equatorial at any given instant and about 30% have the Br atom axial
 4-8 Conformations of Disubstituted
Cyclohexanes
◼ In disubstituted cyclohexanes the steric effects of both substituents
must be taken into account in both conformations

◼ There are two isomers of 1,2-dimethylcyclohexane: cis and trans

1) cis isomer
Both methyl groups are on the same face of the ring, and the
compound can exist in two chair conformations.
Both conformations are equal in energy
H CH3
H
ring-flip CH3
CH3
H
H CH3
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H CH3
H
ring-flip CH3
CH3
H
H CH3

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 2) Trans-1,2-Dimethylcyclohexane

→ The trans isomer exists almost exclusively (>99%) in the

diequatorial conformation (ΔE = 11.4 KJ/mol). (See Figure 4-12.)
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# The situation becomes more complex as the number of
substituents increases. For example, which do you think is
more strained, glucose or mannose?

⇒ In glucose, all substituents on the six-membered ring are equatorial,

while in mannose, one of the –OH groups is axial, making
mannose more strained.

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Problem 4-18 Draw the most stable chair conformation of the
following molecules, and estimate the amount of strain in each:

(a) trans-1-Chloro-3-methylcycloheaxne
(d) cis-1-tert-Butyl-4-ethylcyclohexane
(a) Cl H Cl
H ring-flip
CH3 H
H
H CH3
2 x 1.0 kJ/mol = 2.0 kJ/mol 2 x 3.8 kJ/mol = 7.6 kJ/mol

(d) H Et
t-Bu H
H
ring-flip H
t-Bu
Et
H
H
2 x 4.0 kJ/mol = 8.0 kJ/mol 2 x 11.4 kJ/mol = 22.8 kJ/mol
4-9 Conformations of Polycyclic Molecules

1. Decalin
- consists of two cyclohexane rings joined to share two carbon atoms
(the bridgehead carbons, C1 and C6) and a common bond
Two isomeric forms:
cis-decalin - hydrogen atoms at the bridgehead carbons are on
the same face of the rings
trans-decalin - the bridgehead hydrogens are on opposite faces

◼ Both compounds can be represented using chair cyclohexane

conformations
◼ Flips and rotations do not interconvert the cis and trans isomers

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 Polycyclic compounds are common in nature, and many
valuable substances have fused-ring (접합고리) structures.
Ex: steroids

Although steroids look complicated, the same principles that apply to

the conformational analysis of simple cyclohexane rings apply equally
well to steroids.

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2. Norbornane
- ‘bicycloalkane’ because two rings would have to be broken
open to generate an acyclic structure.
- Systematic name: bicyclo[2,2,1]heptane ; has three bridges of 2,
2, and 1 carbon atoms connecting the two bridgehead carbons

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 Homework

28, 29, 30, 37, 38, 40-b,c

42, 47, 48

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