Section 2.

11

MOLECULAR ORBITALS AND

BONDING IN METHANE

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 Canonical MOs of CH4
Thus far we have imagined bonds as arising from localized
overlap of orbitals
In general, orbitals on multiple atoms can overlap to form
delocalized molecular orbitals
Such canonical MOs describe electrons in molecules well,
but can be difficult to interpret
The canonical MOs of
methane include one low-
energy orbital derived from
overlap of s orbitals and three
degenerate, higher-energy
orbitals derived from overlap of
s and p orbitals.

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 Section 2.12

ISOMERIC ALKANES:
THE BUTANES

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 Isomeric Alkanes
Methane, ethane and propane have no constitutional isomers
Butane (C4H10) has two constitutional isomers
• Linear n-butane, CH3CH2CH2CH3

• Branched isobutane or 2-methylpropane, (CH3)2CHCH3

In both isomers, all carbons are sp3

hybridized and tetrahedral.

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 Section 2.13

HIGHER N-ALKANES

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 Higher n-Alkanes
n-Pentane (C5H12) and n-hexane (C6H14) are linear
alkanes containing five and six carbons respectively

Their structural formulas may also be written in

condensed form as CH3(CH2)nCH3

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 Section 2.14

THE C5H12 ISOMERS

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 Isomers of C5H12
The compound C5H12 may include zero, one, or two branched
methyl groups. n-Pentane contains zero methyl branches

Isopentane contains one methyl branch on an n-butane

chain

Neopentane contains two methyl branches from the central

carbon in n-propane

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 Counting and Naming Alkane
Isomers
There is not a general way
to calculate the number of Table 2.1 The Number of Constitutionally Isomeric
isomers associated with a Alkanes of Particular Molecular Formulas
molecular formula Molecular formula Number of constitutional Isomers
CH4 1
In simple cases, we can C2 H6 1
enumerate possible C3 H8 1
isomers by systematically C4H10 2
moving branches around C5H12 3
and changing their C6H14 5
composition C7H16 9
C8H18 18
The IUPAC nomenclature C9H20 35
system is a rigorous and C10H22 75
and systematic method for C15H32 4,347
naming alkanes C20H42 366,319
C40H82 62,491,178,805,831
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 Section 2.15

IUPAC NOMENCLATURE OF
UNBRANCHED ALKANES

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 Naming Linear Alkanes
The IUPAC rules are used to name all organic compounds
Alkanes are the foundation; we can think of organic compounds as
derivatives of alkanes
Linear alkane chains are named using a prefix for the number of
carbons and the suffix –ane
TABLE 2.2 IUPAC Names of Unbranched Alkanes
Number of Number of Number of
carbon atoms Name carbon atoms Name carbon atoms Name
The first ten
1 Methane 11 Undecane 21 Henicosane prefixes are
2 Ethane 12 Dodecane 22 Docosane worth
3 Propane 13 Tridecane 23 Tricosane memorizing.
4 Butane 14 Tetradecane 24 Tetracosane
5 Pentane 15 Pentadecane 30 Triacontane
6 Hexane 16 Hexadecane 31 Hentriacontane
7 Heptane 17 Heptadecane 32 Dotriacontane
8 Octane 18 Octadecane 40 Tetracontane
9 Nonane 19 Nonadecane 50 Pentacontane
10 Decane 20 Icosane 100 Hectane
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 Section 2.16

APPLYING THE IUPAC RULES:

THE NAMES OF THE C6H14
ISOMERS
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 Structural Isomers of C6H14
There are five structural or constitutional isomers with
the molecular formula C6H14
The linear isomer, CH3(CH2)4CH3, is simply called
hexane

The other isomers contain branches—short chains of

carbons attached to a longer base or parent chain
How do we name a compound with branches
systematically?
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 Naming Branched Alkanes
Consider the structure at right.

1. Identify the longest continuous carbon

chain

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 Naming Branched Alkanes-1
Consider the structure at right.

1. Identify the longest continuous carbon

chain

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 Naming Branched Alkanes-2
Consider the structure at right.

1. Identify the longest continuous carbon

chain
2. Identify the substituents, branches
attached to the parent chain

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 Naming Branched Alkanes-3
Consider the structure at right.

1. Identify the longest continuous carbon chain

2. Identify the substituents, branches attached
to the parent chain
3. Number the carbons of the longest chain such
that the substituent at the first branching point
gets the smallest number possible

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 Naming Branched Alkanes-4
Consider the structure at right.

1. Identify the longest continuous carbon chain

2. Identify the substituents, branches attached to the
parent chain
3. Number the carbons of the longest chain such that
the substituent at the first branching point gets the
smallest number possible
4. Write the name of the compound
1. List substituents in alphabetical order, preceded by their
number location
2. Write the parent chain as an alkane at the end of the name
2-methylpentane
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 Section 2.17

ALKYL GROUPS

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 Beyond the Methyl Group
What do we call substituents other than CH3?
Other alkane substituents are known collectively as
alkyl groups
The names of alkyl groups follow the IUPAC rules for
alkanes, but end in the suffix –yl

Alkyl groups are classified by their substitution pattern at

the point of attachment

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 Naming Alkyl Groups
Importantly, the parent chain of an alkyl substituent
must include the point of attachment

NOT 2-propyl!

Alkyl groups are often known by common names

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 Common Alkyl Groups

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 Section 2.18

IUPAC NAMES OF HIGHLY

BRANCHED ALKANES

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 Highly Branched Alkanes
The IUPAC rules are flexible enough to apply to
any alkane. Consider 4-ethyloctane below

When we add a methyl substituent to carbon 3…

The name becomes 4-ethyl-3-methyloctane

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 Highly Branched Alkanes-1
Multiple copies of a substituent are denoted using the
replicating prefixes di–, tri–, tetra–, etc.

4-ethyl-3,5-dimethyloctane
These prefixes as well as italicized prefixes like sec- and
tert- are ignored when alphabetizing
Complications may arise when numbering…

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 The “First Point of Difference” Rule
The two numbering schemes below both ensure that the
substituent(s) at the first branching point have the number “2”

The first scheme includes a second methyl group with the

number “2”; the next substitutent in the second scheme is a
3-methyl.
At the first point of difference, the first scheme has the
smaller number (2-methyl versus 3-methyl).
2,2,6,6,7-pentamethyloctane 2,3,3,7,7-pentamethyloctane
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