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Chapter 3: Conformations of Alkanes and Cycloalkanes



Summary | Key Terms | Diagrams | Simple Alkanes | Higher Alkanes | Cycloalkanes | Substituted Cyclohexanes | Polycyclic Systems | Heterocycles | Interesting Molecules | Self Assessment | Quiz |


Substituted Cyclohexanes

Chapter 3: Conformations of Alkanes and Cycloalkanes

In order to view some of the structures for this section, you will need the web "plug-in", "CHIME". If you do not have it already installed, you should be able to download it for free from the linked Website. CHIME is a browser that allows you to visualize and manipulate molecules as 3D structures.  Check here if you don't know how to use Chime.

Substituents on cyclohexane can, in principle, occupy either axial or equatorial positions. However, in general, equatorial substituents are more preferred since they are more stable because of reduced steric interactions.

This is shown in the following example for methycyclohexane.
In the equatorial system, the methyl group is anti to the C-C bonds in the rest of the ring system.  However, in the axial conformation, a steric interaction of the methyl group with the two axial hydrogen atoms on the same face of the ring destabilizes the axial conformation. In the images below, this 1,3-diaxial interaction can be highlighted and contrasted with the equatorial conformer. The effect is most obvious when viewed in the spacefilling model.
 
EQUATORIAL
AXIAL
Click here to highlight methyl hydrogen atoms 
Click here to reset colors 
Click here to highlight methyl hydrogen atoms 
Click here to highlight 1,3-diaxial hydrogen atoms 
Click here to reset colors 

The larger the alkyl substituent is, the greater the preference for the equatorial position since the larger the group the greater the steric interaction with the axial hydrogens.

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