Module D

Cycloalkanes
Cycloalkanes  Cycloalkanes (CnH2n) are alkanes (CnH2n+2) whose ends are joined
Based on Bruice’s Organic Chemistry: Chapter 3 to make a ring
 They are named according to the alkane for the number of
carbon atoms, then add cyclo- as a prefix
Learning Outcomes: By the end of this module, you will learn:  Due to the ring structure, cycloalkanes do not have as many
1. How do cycloalkanes differ from alkanes? degrees of freedom to rotate as alkanes
2. What kinds of strain are found in cycloalkanes?
3. What are the most stable conformational isomers of various cycloalkanes?
4. How to visualize and draw the chair conformers of cyclohexane?
5. How to analyze the relative stabilities of interconverting cyclohexane
conformers?

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Complex Cycloalkanes Properties of Cycloalkanes

 Numerous naturally occurring materials contain cycloalkane
structures
 Boiling points increase
uniformly with molecular
(cyclopropane) weight and vdw forces

 Melting points are affected by

the shapes and the way that
(cyclopentane) crystals pack, so they do not
increase uniformly with
molecular weight
(cyclohexanes and cyclopentane)

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 Stereoisomers of Cycloalkanes
 Rotation about C-C bonds in cycloalkanes is restricted
by the ring structure
 Thus, ring compounds have two distinct “faces”
Less stable Eclipsed
Stereoisomers of Cycloalkanes
 Additional examples:
Stereoisomers of Cycloalkanes
 There are two distinct 1,2-dimethylcyclopropane stereoisomers—
same connectivity but different arrangements in space
 They cannot be interconverted by a C-C bond rotation
 A cis stereoisomer has same substituents on same face
 A trans stereoisomer has same substituents on opposite faces
Eclipsed
cis-1,2-dimethylcyclopropane trans-1,2-dimethylcyclopropane
Module D
Cycloalkanes
Based on Bruice’s Organic Chemistry: Chapter 3
Learning Outcomes: By the end of this module, you will learn:
1. How do cycloalkanes differ from alkanes?
7 2. What kinds of strain are found in cycloalkanes?
3. What are the most stable conformational isomers of various cycloalkanes?
4. How to visualize and draw the chair conformers of cyclohexane?
5. How to analyze the relative stabilities of interconverting cyclohexane
conformers?
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 Strain in Cycloalkanes
 Cycloalkanes have a range of stabilities and energies
 Each cycloalkane is found (and spends most time) in
There is a stable conformation of
cyclohexane that is STRAIN free!
9 10
Angle Strain
 Since sp3-hybridized carbon prefers to have bond angles
of approximately 109°, rings that cannot adopt this angle
experience angle strain
 So why is cyclohexane strain-free?
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Strain in Cycloalkanes
the most stable conformation that minimizes the total
overall strain, contributed from:
 Torsional strain - eclipsing of bonds on adjacent atoms
 Steric strain - repulsive interactions between groups of atoms
in close proximity
 One example already introduced was gauche interactions
 but in addition:
 Angle strain - expansion or compression of bond angles away
from angle of sp3-hybridization (109°)
The 3-D Conformations of Rings
 Cyclohexane is not flat!.
 In fact, all cycloalkanes larger than 3 atoms are not planar, in
order to minimize angle strain and torsional strain.
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 Module D The 3-D Conformations of Rings
Cycloalkanes
Based on Bruice’s Organic Chemistry: Chapter 3

Learning Outcomes: By the end of this module, you will learn:

1. How do cycloalkanes differ from alkanes?
2. What kinds of strain are found in cycloalkanes?
3. What are the most stable conformational isomers of various cycloalkanes?
4. How to visualize and draw the chair conformers of cyclohexane?
5. How to analyze the relative stabilities of interconverting cyclohexane chair
conformers?  Larger rings have many more possible conformations than smaller
rings and are more difficult to analyze (cycloalkanes ≥7C will not be
discussed in this course)
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Cyclopropane Bent Bonds of Cyclopropane

 Electron density of the C-C bond is found to be displaced
 A 3-membered ring must have a planar structure outside of the internuclear axis
 So all C-H bonds are eclipsed!
 Symmetrical conformation, with C–C–C bond angles of 60°
 Requires that sp3 based bonds are bent (and weakened)

60°

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 Cyclobutane Cyclopentane
 “Planar” cyclopentane would have no angle strain
 Perfectly planar cyclobutane has less angle strain than but very high torsional strain
cyclopropane, but more torsional strain because of a greater  The most stable conformation of cyclopentane is
number of eclipsing C-H bonds the envelope conformation which is non-planar to
 So for overall stability, the most favorable conformation of reduce torsional strain
cyclobutane is slightly bent out of plane  Four carbon atoms are in a plane
 Although this bending increases angle strain, it decreases torsional strain, resulting  The fifth carbon atom is above or below the plane
in overall more stability than remaining planar

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17

Conformations of Cyclohexane Conformations of Cyclohexane

 The chair conformation is free of angle strain
 The cyclohexane ring is free of angle strain and torsional strain
and torsional strain
 The most stable conformation is called a chair conformation

All bonds are staggered!

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Module D How to Draw the Chair Conformation
Cycloalkanes
Based on Bruice’s Organic Chemistry: Chapter 3

Learning Outcomes: By the end of this module, you will learn:

1. How do cycloalkanes differ from alkanes?
Envelope
2. What kinds of strain are found in cycloalkanes? Conformation
3. What are the most stable conformational isomers of various cycloalkanes? Of cyclopentane
4. How to visualize and draw the chair conformers of cyclohexane?
5. How to analyze the relative stabilities of interconverting cyclohexane
conformers?

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Chair Conformations Chair Conformation

 Next, consider the bonds at each carbon atom of
the cyclohexane ring in the chair conformation:
 Moodle has a worksheet for you to
practice drawing these

This is understood without the

need to show bolder bonds

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 Axial and Equatorial Positions Axial and Equatorial Positions
 The chair conformation has two kinds of positions for the  Cyclohexane in the chair conformation:
rest of the bonds on the ring  Has six equatorial protons on the equator of the ring
 Axial positions and equatorial positions  Has six axial protons: 3 up on the top face, 3 down on the bottom face
Axial C-H bonds are
perpendicular, pointing above
or below equatorial plane

Equatorial C-H bonds are

parallel to the equatorial plane
Animated model of chair cyclohexane and “radiate” from the ring
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Axial and Equatorial Axial and Equatorial Positions

Positions  Each carbon atom in the chair has one axial and one
equatorial hydrogen atom
 Another view:

*
*
Equatorial C-H bonds are parallel to the *
equatorial plane and “radiate” from the ring

Axial C-H bonds are perpendicular,

pointing above or below equatorial plane

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 Axial and Equatorial Positions
 Each face of the ring has 3 axial and 3 equatorial hydrogen
atoms in an alternating arrangement
Top face
Axial and Equatorial Positions
 The terms axial and equatorial can also be used
to refer to substituents other than hydrogen on a
chair conformer

*
*

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Drawing Axial and Equatorial Bonds Drawing Axial and Equatorial Bonds

equatorial
bonds

Completed chair
conformer:

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 Drawing Axial and Equatorial Bonds Hints on drawing the chair conformation

Axial bonds

Equatorial bonds

 Make sure you can find the parallel bonds in your finished
Completed chair
drawing
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Common Errors Exercise D1

How NOT to draw chair conformers… Draw the following molecule in a chair conformation.
Draw all the hydrogens on the ring.

OH

The chair has been drawn The axial hydrogens The red hydrogens
with the middle bonds have been drawn have been drawn at
HORIZONTAL, so the alternating up and down the wrong ANGLES.
upper points of the chair on the WRONG carbons. They are not parallel to
are not level. The axial This structure is any ring bonds
hydrogens are not impossible because Advice: check for the
Check: can you find the W and the M in your drawing of the chair conformer?
perpendicular to the face NONE of the carbons parallel lines and “W”
of the cyclohexane are tetrahedral and “M”  Moodle has a worksheet for you to practice drawing
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 Module D Two Limiting Chair Conformations
Cycloalkanes  Cyclohexane has two chair conformations, characterized
by the same numbers of axial/equatorial bonds
Based on Bruice’s Organic Chemistry: Chapter 3

Learning Outcomes: By the end of this module, you will learn:

1. How do cycloalkanes differ from alkanes?
2. What kinds of strain are found in cycloalkanes?
3. What are the most stable conformational isomers of various cycloalkanes?
4. How to visualize and draw the chair conformers of cyclohexane?
5. How to analyze the relative stabilities of interconverting cyclohexane
conformers?
 You should be able to draw both chair conformers

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Dynamic Conformational Conversions Dynamic Conformational Conversions

 The two chair conformations readily interconvert by a  The ring-flip results in the interchange of axial and
ring-flip process through C-C bond rotations equatorial positions

pull this
carbon
down

Move this
39 carbon up 40
 Dynamic Conformational Conversions Dynamic Conformational Conversions
 When bromocyclohexane ring-flips, we can see clearly that the
position of Br changes between equatorial and axial  IMPORTANT! Ring flip is NOT the same conformer doing a
somersault!
 At room temperature the ring-flip is very fast and the structure is
seen as the weighted average

Still an axial Br
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Exercise D2 Dynamic Conformational Conversions

 The two chair conformers are the end results, but the
Draw the ring flipped chair conformation. actual ring flip process is more complicated:

pull this
carbon
down

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 Boat Conformation of Cyclohexane Conformations of Substituted Cyclohexanes
 Boat conformation: less stable  The two chair conformations of bromocyclohexane are
than chair cyclohexane by ~29 NOT equal in energy: the chair conformer with equatorial
kJ/mol due to steric and Br is more stable
torsional strain
“flagpole interaction”

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46

Conformations of Substituted Cyclohexanes Stability and Equilibrium

 The two chair conformers of a methylcyclohexane are
not equal in energy  The relative amounts of the
 Equatorial methyl conformation is more stable by 7.6 kJ/mol two conformers depend on
the difference in their
energies E = RT ln K

Percent
 R is the gas constant
 T is the temperature in K
 K is the equilibrium constant
between isomers

7.6 kJ/mol
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Conformations of Substituted Cyclohexanes 1,3-Diaxial Interactions
 The difference in energy between axial methyl conformer and equatorial
 The two chair conformers of a methylcyclohexane are methyl conformer is due to a kind of steric strain caused by 1,3-diaxial
not equal in energy interactions
 Equatorial methyl conformation is more stable by 7.6 kJ/mol More stable chair

5% 95%

49 50

1,3-Diaxial Interactions 1,3-Diaxial Interactions

 In general, the chair conformation with the substituent
at the equatorial position is more stable because there
are no 1,3-diaxial interactions

 The actual amount

CH3 of steric strain
depends on the size
of the substituents
at the 1,3-positions

Equatorial
methylcyclohexane

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 Conformational Analysis of
Demonstration Problem
cis-1,2-dimethylcyclohexane (A)
 Is there one dominant (more stable) chair conformation of
cis-1,2-dimethylcyclohexane (A) ?
trans-1,2-dimethylcyclohexane (B) ?

A B
cis trans

 This is a conformational analysis problem

 Solution: You must analyze, evaluate and compare the energies of
both chair conformers of A, and then B
 You must be able to draw all the chair conformations
 Then consider the sum of all interactions for each chair
 Each chair has one equatorial and one axial methyl group
 Conclusion: both conformers are equal in energy, A is 50/50 mix
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Conformational Analysis of Conformational Analysis of

trans-1,2-dimethylcyclohexane (B) trans-1,2-dimethylcyclohexane (B)

Conclusion: B exist almost

exclusively (>99%) in this
conformation

 The first chair conformation of B has both methyl groups equatorial and  The second chair conformation of B has total steric strain of 4  3.8
there is a gauche butane interaction between them (3.8 kJ/mol) and no kJ/mol = 15.2 kJ/mol, thus it is 11.4 kJ/mol less stable than the first 56
1,3-diaxial interactions 55
conformer
 Conformational Analysis of Conformations of Other Six-membered
Polysubstituted Cyclohexanes Ring Compounds
 Similar analyses can be done for other disubstituted cyclohexanes  Glucose, also adopt chair conformations
and polysubstituted cyclohexanes
 Note that all the substituents adopt equatorial positions
 But to be able to do this, you need to first know how to draw both
chair conformations accurately
Cl

Cl

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Conformations of Polycyclic Molecules Conformations of Polycyclic Molecules

 Two isomeric forms of decalin:
 Decalin consists of two cyclohexane rings joined (or
 cis-Decalin has bridgehead protons on the same face of the rings
fused) by sharing two carbon atoms (the bridgehead
 trans-Decalin has bridgehead protons on opposite faces
carbons, C1 and C6) and a common bond
 Is one stereoisomer more stable?

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 Conformations of Polycyclic Molecules Conformations of Polycyclic Molecules
 The cis-isomer has 1,3-diaxial interactions  The structures of even more complex polycyclic molecules can be
understood and analyzed in a similar way
 Example: Testosterone
 The two central cyclohexanes are in chair conformations, ie. found in their most
stable conformations
 There are 1,3-diaxial interactions
 The cyclopentane is in an envelope conformation

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Module D
Major Topics of Bruice Chapter 3
Cycloalkanes (Modules B, C, D)
Based on Bruice’s Organic Chemistry: Chapter 3  Compound Nomenclature
Check that you have achieved these learning outcomes, and can  How to draw compounds: skeletal structures, Newman
give examples to explain and answer each of these questions: Projection
1. How do cycloalkanes differ from alkanes?
 Conformations of acyclic molecules
2. What kinds of strain are found in cycloalkanes?
3. What are the most stable conformational isomers of various cycloalkanes?  Chair conformation of cyclohexane
4. How to visualize and draw the chair conformers of cyclohexane?  Axial/equatorial positions
5. How to analyze the relative stabilities of interconverting cyclohexane  Ring flip process
conformers?
 Relative stabilities of substituted cyclohexanes

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After completing Modules B-D, you should be able to:
 Derive correct IUPAC names for organic molecules having
common functional groups
 Draw Newman projections of any conformer of any bond of any
acyclic molecule
 Recognize and classify strain: torsional, angular, steric (in
eclipsed, gauche, staggered conformers, cycloalkane conformers)
 Draw chair conformations of any substituted cyclohexane, identify
and draw the axial and equatorial bonds, convert chairs by the
ring-flip process, and analyze the relative stabilities of the two
chair conformations

Towards Course Learning Outcome 1

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