Documenti di Didattica
Documenti di Professioni
Documenti di Cultura
The most common cyclic compounds well see are derivatives of cyclohexane,
because six-membered rings are the most stable. Although cyclohexane is often shown in
a top-down view, thats not how it exists in space its puckered into a chair-like shape,
which is called chair cyclohexane.
This shows how to draw both forms, but it doesnt tell us anything about which form is
most favored. It turns out that almost every group prefers being equatorial to being axial.
If a group is axial, it experiences 1,3-diaxial strain from bumping against the two other
groups that are axial and pointing in the same direction.
H CH3
OCH3 H H
H
H3CO * = 1,3 diaxial strain interaction
CH3 H
Cl* H Cl
Each group has a set cost for being axial, but generally if youre comparing the two forms
of a molecule, you can just count how many groups are where. For the left form in the
above picture, theres only one group axial. For the right form, there are two groups axial.
So the left form would be the most stable.
Why does this preference exist? You can explain it using Newman projections
from before. Again, we choose a bond to sight along, but the ring is made up of parallel
lines. So were actually sighting along two bonds simultaneously. We can do this along
either of the two bonds attached to the carbon that has the group of interest on it. When
we do, it becomes apparent that the biggest difference between being axial or equatorial
is gauche interactions. Being axial means that a group has two more gauche interactions
than it otherwise would, with part of the ring itself. Which part of the ring appears gauche
depends on which two bonds you sight along, but in reality both parts are gauche all the
time that the group is axial.
gauche
OCH3 H
OCH3 H CH3
H
H
H H
H CH3 H H
Cl H Cl H
H H
gauche
OCH3 H OCH3 H
H CH3
H
H H
H CH3
Cl H Cl
H H
H H
Loudon Chapter 7 Review: Cyclic Compounds
CHEM 3311, Jacquie Richardson, Spring 2010 - Page 4
Br Br
Br2
Anti addition
Br Br
H H
Br2, ROOR
Br Br
Random addition
H H
Br Br
One last thing to point out: anti addition is not the same thing as anti-Markovnikov!
Hydroboration is an anti-Markovnikov-style addition, but its not an anti addition.