John E.

McMurry

www.cengage.com/chemistry/mcmurry

Chapter 3
Organic Compounds:
Alkanes and Their Stereochemistry

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Learning Objectives
(3.1)
Functional groups
(3.2)
Alkanes and alkane isomers
(3.3)
 Alkyl groups
(3.4)
Naming alkanes
(3.5)
 Properties of alkanes
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Learning Objectives
(3.6)
Conformations of ethane
(3.7)
 Conformations of other alkanes

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Functional Groups
 Collection of atoms at a site that have a
characteristic behavior in all molecules where
they occur
 Group reacts in a typical way, generally
independent of the rest of the molecule
 Example
 Double bonds in simple and complex alkenes
react with bromine in the same way

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Figure 3.1 - The Reactions of Ethylene
and Menthene With Bromine

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Functional Groups with Multiple Carbon–
Carbon Bonds
 Alkenes have a double bond
 Alkynes have a triple bond
 Arenes have alternating double and single C–C
bonds in a six-membered ring

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Table 3.1 - Structures of some
Common Functional Groups

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Table 3.1 - Structures of some
Common Functional Groups

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Table 3.1 - Structures of some
Common Functional Groups

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Table 3.1 - Structures of some
Common Functional Groups

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Functional Groups with Carbon Singly
Bonded to an Electronegative Atom
 Alkyl halides (haloalkanes), alcohols, ethers,
alkyl phosphates, amines, thiols, sulfides, and
disulfides have a carbon singly bonded to a
electronegative atom
 The bonds are polar

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Functional Groups with Carbon Singly
Bonded to an Electronegative Atom

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Functional Groups with a Carbon– Oxygen
Double Bond (Carbonyl Groups)
 Carbonyl groups are present in a large majority
of organic compounds and biological molecules
 Behave similarly in many aspects
 Differ depending on the identity of the atoms
bonded to the carbonyl-group carbon

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Functional Groups with a Carbon-Oxygen
Double Bond (Carbonyl Groups)

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Worked Example
 Identify the functional groups the molecules of
methionine

 Solution:

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Alkanes and Alkane Isomers
 Alkanes: Compounds with C–C single bonds
and C–H bonds
 Connecting carbons can lead to large or small
molecules
 Described as saturated hydrocarbons
 At times called aliphatic compounds

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Alkanes and Alkane Isomers
 Formula for an alkane with no rings in it must be
CnH2n+2
 Where the number of C’s is n
 Alkanes are saturated with hydrogen

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Alkane Isomers
 CH4 = methane, C2H6 = ethane, C3H8 = propane
 Molecular formula of an alkane with more than
three carbons can give more than one structure
 C4 (butane) = butane and isobutane
 C5 (pentane) = pentane, 2-methylbutane, and
2,2-dimethylpropane

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Alkane Isomers
 Straight-chain alkanes: Alkanes with C’s
connected to no more than 2 other C’s
 Also called normal alkanes
 Branched-chain alkanes: Alkanes with one or
more carbon atoms connected to 3 or 4 carbon
atoms
 Isomers: Compounds that have the same
number and kind of atoms but differ in the way
the atoms are arranged

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Constitutional Isomers
 Isomers that differ in how their atoms are
arranged in chains
 Compounds other than alkanes can be
constitutional isomers of one another

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Condensed Structure of
Alkanes
 Represent an alkane in a brief form or in many
types of extended forms
 Condensed structure does not show bonds but
lists atoms, such as:
 CH3CH2CH2CH3 (butane)
 CH3(CH2)2CH3 (butane)

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Table 3.3 - Names of Straight Chain
Alkanes

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Worked Example
 Draw structures of the five isomers of C6H14
 Solution:
 Drawing all possible six-carbon skeletons and
adding hydrogens to ensure that all carbons
have four bonds
 The six-carbon straight-chain skeleton is drawn
 Drawing a five-carbon chain, identifying different
types of carbon atoms on the chain, and adding a
–CH3 group to each of the different types of carbons,
generating two skeletons

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Worked Example
 Repeating the process with the four-carbon chain to
gives rise to the last two skeletons

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Alkyl Groups
 Partial structure that remains after the removal of one H
from an alkane
 Not stable compounds, parts of larger compounds
 Named by replacing –ane ending of alkane with –yl
ending
 –CH is methyl from methane (CH4)
 –CH2CH3 is ethyl from ethane (CH3CH3)

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Table 3.4 - Some Straight-
Chain Alkyl Groups

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Alkyl Groups
 Prefixes are used to represent the number of
other carbon atoms attached to the branching
carbon atom

 Symbol R is used in organic chemistry to

represent a generalized organic group

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Alkyl Groups

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Worked Example
 Draw structures of alkanes that meet the
following descriptions:
 An alkane with two tertiary carbons
 An alkane that contains an isopropyl group
 An alkane that has one quaternary and one
secondary carbon
 Solution:
 An alkane with two tertiary carbons

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Worked Example
 An alkane that contains an isopropyl group

 An alkane that has one quaternary and one

secondary carbon

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Naming Alkanes
 International Union of Pure and Applied
Chemistry (IUPAC) system of nomenclature

 Steps in naming in complex branched-chain

alkanes
 Find parent hydrocarbon chain
 Identify the longest continuous chain of carbon
atoms, use the name of that chain as the parent
name
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Naming Alkanes

 If two different chains of equal length are present,

choose the one with the larger number of branch
points as the parent

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Naming Alkanes
 Number the atoms in the longest chain
 Beginning at the end nearer the first branch point,
number each carbon atom in the parent chain

 If there is branching at an equal distance away from

both ends of the parent chain, begin numbering at the
end nearer to the second branch point

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Naming Alkanes
 Identify and number substituents
 Assign a number, or locant, to each substituent to
locate its point of attachment to the parent chain

 If there are two substituents on the same carbon,

give both the same number

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Naming Alkanes
 Write the name as a single word

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Naming Alkanes
 Name a branched substituent as though it were
itself a compound

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Worked Example
 Give IUPAC names for the following
compounds:
 a)

 b)

 Solution:
 a) 2,4-Dimethylpentane
 b) 2,2,5-Trimethylhexane
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Worked Example
 Give the IUPAC name for the following
hydrocarbon and convert the drawing into a
skeletal structure

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Worked Example
 Solution:

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Properties of Alkanes
 Called paraffins because they do not react as
most chemicals
 Low affinity compounds
 Burn in a flame, producing carbon dioxide, water,
and heat
 Methane reacts with Cl2 in the presence of light
to produce:

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Physical Properties of Alkanes
 Boiling points and melting points increase as
size of alkane increases
 Dispersion forces increase as molecule size
increases, resulting in higher melting and boiling
points

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Figure 3.4 - A Plot of Melting and Boiling Points
Versus Number of Carbon Atoms for the C1–C14

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Conformations
 Stereochemistry: Branch of chemistry
concerned with the 3 dimensional aspects of
molecules
  bonds are cylindrically symmetrical
 Rotation is possible around C–C bonds in open-
chain molecules

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Conformations
 Different arrangement of atoms resulting from
bond rotation
 Conformers: Molecules that have different
arrangements
 Called conformational isomers
 Can be represented in 2 ways

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Torsional Strain
 Strain in a molecule caused by electron
repulsion between eclipsed bonds
 Perfectly free rotation is not observed
 There is a barrier to rotation, and some
conformers are more stable than others
 Staggered conformation: Most stable
 All 6 C–H bonds are as far away as possible
 Eclipsed conformation: Least stable
 All 6 C–H bonds are as close as possible to each
other

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Figure 3.7 - A Graph of Potential Energy
Versus Bond Rotation in Ethane

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Conformations of Other
Alkanes
 Eclipsed conformer of propane has 3
interactions - Two ethane-type H–H interactions,
and one H–CH3 interaction

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Conformations of Other
Alkanes
 Conformational situation is more complex for
larger alkanes
 Not all staggered conformations have same
energy
 Not all eclipsed conformations have same energy
 Anti conformation: Geometric arrangement
around a C–C single bond in which the two
largest substituents are 180˚apart
 As viewed in a Newman projection

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Conformations of Butane

 Gauche conformation: Conformation of butane

in which the two methyl groups lie 60˚apart

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Steric Strain
 Repulsive interaction that occurs when atoms
are forced closer together than their atomic radii
allow

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Figure 3.9 - A Plot of Potential Energy
Versus Rotation for the C2–C3 Bond in
Butane

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Table 3.5 - Energy Costs for
Interactions in Alkane Conformers

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Worked Example
 Sight along the C2–C3 bond of
2,3-dimethylbutane
 Draw a Newman projection of the most stable
conformation
 Solution:

 This conformation of 2,3-dimethylbutane is the

most stable because it is staggered
 Has the fewest CH3↔CH3 gauche interactions
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Summary
 Group of atoms within a larger molecule that has
a characteristic chemical reactivity is called a
functional group
 Chemical reactions of an organic molecule are
determined by its functional groups
 Alkanes are a class of saturated hydrocarbons
 Alkanes don’t contain functional groups, are
relatively inert, and can be either straight-chain
or branched

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Summary
 Constitutional isomers are compounds that have
the same chemical formula but different
structures which differ in their connections
between atoms
 Rotation is possible around σ bonds because of
their cylindrical symmetry
 Alkanes exist in a large number of rapidly
interconverting conformations
 Newman projections make it possible to
visualize the spatial consequences of bond
rotation
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Summary
 Staggered conformation of ethane is 12 kJ/mol
(2.9 kcal/mol) and more stable than the eclipsed
conformation because of torsional strain
 Generally all alkanes are most stable when all of
its bonds are staggered

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