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Richard F. Daley and Sally J. Daley



Organic

Chemistry

Chapter 3

Molecular Conformations

3.1 Representing Three-Dimensional Molecules in Two

Dimensions 125

3.2 Dihedral Angles

127

3.3 The Conformations of Ethane

129

3.4 Conformational Analysis of Butane 131

3.5 Angle Strain in Cycloalkanes

134

3.6 Conformations of Cyclohexane

136

3.7 Conformational Inversion of Cyclohexane 142

3.8 Conformational Analysis of Monosubstituted

Cyclohexanes

143

3.9 Naming Stereoisomers

147

3.10 Conformational Analysis of Disubstituted

Cyclohexanes 149

Special Topic ? Computer Modeling

155

3.11 Conformations of Other Cycloalkanes 157

3.12 Naming Polycyclic Ring Systems 159

3.13 Polycyclic Ring Systems

164

Sidebar - Higher Polycyclic Structures

166

Key Ideas from Chapter 3 168

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Copyright 1996-2005 by Richard F. Daley & Sally J. Daley All Rights Reserved.

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Chapter 3

Molecular Conformations

Chapter Outline

3.1

3.2 3.3 3.4 3.5 3.6 3.7

3.8

3.9 3.10

3.11 3.12 3.13

Representing Three-Dimensional Molecules in Two Dimensions

Different methods for drawing a molecule in three dimensions

Dihedral Angles

Examination of the angles between atoms on adjacent atoms

The Conformations of Ethane

Rotation about the C--C bond in ethane

Conformational Analysis of Butane

Rotation about the C2--C3 bond in butane

Angle Strain in Cycloalkanes

The effect of bond angle strain on the stability of cycloalkanes

Conformations of Cyclohexane

The effect of bond angles on the shape of cyclohexane

Conformational Inversion of Cyclohexane

An examination of the various changes in the conformation of cyclohexane

Conformational Analysis of Monosubstituted Cyclohexanes

How a substituent affects the conformation of cyclohexane with a single substituent

Naming Stereoisomers

Naming cis and trans cycloalkanes

Conformational Analysis of Disubstituted Cyclohexanes

The effect of adding a second substituent to cyclohexanes

Conformations of Other Cycloalkanes

The shapes of cyclopropane, cyclobutane, and cyclopentane

Naming Polycyclic Ring Systems

Naming spiro and bicyclic ring systems

Stereochemistry of Polycyclic Ring Systems

Spiro, fused, and bridged bicyclic systems



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Objectives

Learn how to draw three-dimensional molecules in two dimensions and how to visualize three-dimensional molecules from twodimensional representations

Understand the conformational preferences in the structure of acyclic compounds

Be able to name cycloalkanes, substituted cycloalkanes, and bicyclic compounds

Know how ring size affects the stability of cycloalkanes Visualize the different conformations of cyclohexane Recognize how one or two substituents affect the conformation of

cyclohexane Know the shapes of cyclopropane, cyclobutane, and cyclopentane Understand the various types of bicyclic compounds

Full of nimble fiery and delectable shapes. --Shakespeare

Conformations are the shapes a molecule assumes by rotating about its bonds.

Conformational analysis is the study of the effect of rotation on the properties of a molecule.

T

he rotational symmetry of a bond (a carbon--carbon single bond) allows the atoms or groups of atoms connected

by that bond to rotate about it. As a result of this kind of rotation,

many molecules assume several different three-dimensional shapes.

Chemists call these different shapes conformations. Some

conformations of a particular molecule are more stable than others

are. Knowing this will help you understand how many chemical

reactions proceed.

Conformational analysis is the examination of the positions

a molecule takes and the energy changes it undergoes as it converts

among its different conformations. This chapter covers in detail the

conformational analysis of ethane, butane, and cyclohexane. It also

gives an overview of other cyclic and polycyclic hydrocarbons.

Because each of the various conformations of a molecule has

different properties, the conformation the molecule normally adopts

has a profound influence on its physical and chemical properties.

Organic chemists use conformational analysis to understand the



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behavior of molecules in chemical reactions. Biochemists and molecular biologists also use conformational analysis to study the ways molecules interact with each other in living systems.

3.1 Representing Three-Dimensional Molecules

in Two Dimensions

For a reaction to proceed the conformation of the individual molecules must allow them to collide at points where they will react. Conformational analysis visualizes the three-dimensional structures of various conformations. Because two-dimensional illustrations are limiting, invest in a set of molecular models and learn how to use them. Make a model of any molecule you are studying and twist the model back and forth into the molecule's various possible conformations. Continue manipulating the model until you have a thorough understanding of all the possible conformations. Working with a three-dimensional model set will help you learn to visualize molecular structures from a two-dimensional drawing.

Molecular models are an invaluable aid for visualizing the interactions between atoms in a molecule and in seeing how a chemical reaction proceeds. Even the most experienced chemist makes frequent reference to models in order to clarify questions of molecular structure. As you work your way through this text, using a molecular model set will make learning the material much easier.

A molecular model of ethane (CH3CH3) is shown in Figure 3.1. The white spheres represent the hydrogen atoms, and the black spheres represent the sp3 hybridized carbon atoms. The lines connecting the spheres represent the bonds between the atoms. Make a model of ethane to help you visualize this structure in three dimensions.

Figure 3.1. A ball-and-stick model of ethane.



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