Ring Strain Angle & Torsional Strain

Cyclopropane is 44 kJ/mol less stable than cyclohexane per CH2 group. It is highly strained and very reactive due to:
1.

Cyclohexane Chair Conformation

ZERO ring strain in optimal CHAIR conformation

2.

Angle strain: Bond angles of 60 cause electron pair repulsion in adjacent bonds Inefficient sigma bond overlap Torsional strain: Eclipsing CH bonds all the way around the ring
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1.

No angle strainangles must be_______ No torsional strainall adjacent CH bonds must be __________ WHY is this called the CHAIR?

2.

Cyclohexane Boat Conformation

Other conformations of hexane exist but are a bit less stable. Consider THE BOAT.

Conformational Changes During Inversion (Ring Flipping) of Cyclohexane

Why is the halfchair so unstable?

1. 2. 3.

No angle strainangles are 109.5. Considerable torsional strain

Many of the Hs are eclipsed

The twist boat alleviates some of the torsional strain in the boat.

Steric strainflagpole interactions. WHERE?

WHY is this called the BOAT?

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Drawing Chairs
It is critical to draw a CHAIR properly
Follow Guidelines in Skill Builder 4.9 Notice three sets of parallel lines in chair structure

Drawing Chairs
The other SIX atoms attached to a chair are in equatorial positions.
Equatorial substituents are positioned at angles parallel to the sets of parallel lines making up the chair itself.

SIX of the atoms attached to the chair are axial.

Axial groups point straight up and down alternating around the ring. 1) Identify each of the substituents as either axial or equatorial 2) Indicate whether they are pointing up or down

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Monosubstituted Cyclohexane Ring Flipping

When energy (45 kJ/mol) is available, can flip from one chair form to another

NOTE: we are NOT breaking any bonds, just changing the conformation
Flipping a chair is NOT like flipping a pancake! Flipping a chair is the result of C-C single bonds rotating only.

Bonds remain up (above ring) & down (below ring)

During a ring flip: all axial substituents become equatorial and all equatorial substituents become axial
The location (above or below) of each substituent with respect to the plane of the ring remains the same
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Monosubstituted Cyclohexane
If both versions of the CHAIR were equally stable, you would have a 50/50 mixture of axial/equatorial. Consider methylcyclohexane:

Monosubstituted Cyclohexane
The axial substituent causes additional steric strain.

Why does the equatorial chair dominate the equilibrium? Does the axial substituent cause additional angle or steric strain?
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Such steric crowding is called 1,3-diaxial strain.WHY?

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Monosubstituted Cyclohexane
1,3-diaxial interactions are equivalent to gauche interactions.

1,3-Diaxial Interactions
Table 4.8

When the substituent is in the equatorial position, it is equivalent to an anti interaction. What conclusion can be drawn from this table?

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Disubstituted Cyclohexane
When multiple substituents are present, the positioning of the groups on the chair must be shown by using solid or dashed wedges or by showing the groups in either axial or equatorial positions.

Disubstituted Cyclohexane - Cis-trans Isomerism

Are these two structures constitutional isomers? Why?

What chair conformation is more stable? Why?

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Disubstituted Cyclohexane - Stability

Consider both chair conformations for the following molecule:

Concept Check Substituted Cyclohexanes

Draw the two chair conformations for the following molecule and indicate which one is more stable (NOTE: Ph = a phenyl ring)

Ph O

Cl

Which is more stable? WHY?

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Section 4 - Key Points Homework: 1) Define each term below 2) Review section 4 learning objectives

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