2

Organic
Chemistry
William H. Brown &
Christopher S. Foote

2-1

Alkanes
and
Cycloalkanes
Chapter Two
2-2

2 Structure
Hydrocarbon:

a compound composed only of

carbon and hydrogen
Saturated hydrocarbon: a hydrocarbon
containing only single bonds
Alkane: a saturated hydrocarbon whose carbons
are arranged in a open chain
Aliphatic hydrocarbon: another name for an
alkane

2-3

2 Structure
Shape

tetrahedral about carbon

all bond angles are approximately 109.5

2-4

2 Nomenclature
Alkanes

have the general formula CnH2n+2

Name

Mole cular
Formula

Conde nsed
Structural Formula

CH4
C2 H6

CH 4
CH 3 CH3

butane

C3 H8
C4 H10

CH 3 CH2 CH 3
CH 3 (CH 2 ) 2 CH 3

pen tane

C5 H12

CH 3 (CH 2 ) 3 CH 3

hexane

C6 H14

CH 3 (CH 2 ) 4 CH 3

heptane

C7 H16

CH 3 (CH 2 ) 5 CH 3

methane
ethane
propane

2-5

2 Nomenclature
Alkanes

(contd.)

octane

C 8 H18

CH3 (CH 2 ) 6 CH3

nonane

C 9 H20

CH3 (CH 2 ) 7 CH3

decane

C 10 H22
C 12 H26

CH3 (CH 2 ) 8 CH3

dodecane
hexadecane

C 14 H30
C 16 H34

octade cane
eicos ane

C 18 H38
C 20 H42

te tradecane

CH3 (CH 2 ) 10 CH3

CH3 (CH 2 ) 12 CH3
CH3 (CH 2 ) 14 CH3
CH3 (CH 2 ) 16 CH3
CH3 (CH 2 ) 18 CH3

2-6

2 Constitutional Isomerism
Constitutional

isomers: compounds with the

same molecular formula but a different
connectivity (order of attachment of their atoms)
example: C4H10

CH3
CH3 CH2 CH2 CH3
Butane

CH3 CHCH3
2-Methylpropane
2-7

2 Constitutional Isomerism
Mole cular
Formula
CH 4

Constitutional
Is ome rs

C5 H1 2

1
3

C1 0 H2 2

75

C1 5 H3 2

4,347

C2 5 H5 2

36,797,588

C3 0 H6 2

4,111,846,763

World population
is about
6,000,000,000

2-8

2 Nomenclature - IUPAC
Suffix

-ane specifies an alkane

Prefix tells the number of carbon atoms
Pre fix Carbons
meth1
eth2
prop3
but4
pent5
hex6
7
heptoct8
non9
dec10

Carbons
Pre fix
unde c11
dodec12
tride c13
te tradec14
pentadec- 15
hexadec16
heptadec- 17
octade c18
nonadec19
eicos 20
2-9

2 Nomenclature - IUPAC
Parent

name: the longest carbon chain

Substituent: a group attached to the parent chain
alkyl group: a substituent derived by removal of a
hydrogen from an alkane; given the symbol RAlk ane

Name

Alk yl group Name

CH4

Methane

CH3 -

Methyl group

CH3 CH3

Eth ane

CH3 CH2 -

Eth yl group

2-10

2 Nomenclature
1.The name of a saturated hydrocarbon with an
unbranched chain consists of a prefix and suffix
2. For branched alkanes, the parent chain is the longest
chain of carbon atoms
3. Each substituent is given a name and a number
CH 3
CH 3 CHCH 3

2
1

2-M ethylpropane

4. If there is one substituent, number the chain from the

end that gives it the lower number
CH3
CH3 CH2 CH2 CHCH3

2-Methylpentane

4 3
5

2
1

2-11

2 Nomenclature
6. If there are two or more different substituents,
list them in alphabetical order
number from the end of the chain that gives the
substituent encountered first the lower number
CH3
CH3 CH2 CHCH2 CHCH2 CH3

2
1

6
7

CH2 CH3
3-Ethyl-5-methylheptane

2-12

2 Nomenclature
7. The prefixes di-, tri-, tetra-, etc. are not
included in alphabetization
CH3 CH2 CH3
CH3 CCH2 CHCH2 CH3
CH3

2 3

4-Ethyl -2,2-dimethylhexane

8. Substituents are named by the same set of

rules.

2-13

2 Nomenclature
Alkyl

groups

Name

Conde nsed
Structural Formula

Name

butyl

- CH 2 CH2 CH2 CH 3

methyl

Conde nsed
Structural Formula
- CH 3

2-methylpropyl
(isobutyl)

- CH 2 CHCH3

ethyl

- CH 2 CH3

propyl

- CH 2 CH2 CH3

1-methylpropyl
(sec- butyl)

- CH CH 2 CH3

CH3
CH3

1-methylethyl - CH CH 3
(isopropyl)
CH3

CH3
1,1-dimethylethyl - CCH3
(tert- butyl)
CH3

2-14

2 Classification of C & H
Primary

(1) C: a carbon bonded to one other

carbon
1 H: a hydrogen bonded to a 1 carbon
Secondary

(2) C: a carbon bonded to two other

carbons
2 H: a hydrogen bonded to a 2 carbon
Tertiary

(3) C: a carbon bonded to three other

carbons
3 H: a hydrogen bonded to a 3 carbon
Quaternary

(4) C: a carbon bonded to four other

carbons
2-15

2 Cycloalkanes
General

formula CnH2n

five- and six-membered rings are the most common

Structure

and nomenclature

to name, prefix the name of the corresponding openchain alkane with cyclo-, and name each substituent
on the ring
if only one substituent, no need to give it a number
if two substituents, number from the substituent of
lower alphabetical order
if three or more substituents, number to give them the
lowest set of numbers and then list substituents in
alphabetical order
2-16

2 Cycloalkanes
Line-angle

drawings

each line represents a C-C bond

each angle represents a C
C C
C C

C
C C
C

H2 C
H2 C

CH2

CH3

CH CH
CH2

CH3

C8 H1 6

2-17

2 Cycloalkanes
Example: name these cycloalkanes
(a)

(b)

(c)

(d)

2-18

2 Bicycloalkanes
Bicycloalkane:

an alkane that contains two rings

that share two carbons

Bicyclo[4.4.0]decane
(De calin)

Bicyclo[4.3.0]nonane
(Hydrindane)

Bicyclo[2.2.1]heptane
(Norbornane)

2-19

2 Bicycloalkanes
Nomenclature

parent is the alkane of the same number of carbons as

are in the rings
number from a bridgehead, along longest bridge back
to the bridgehead, then along the next longest bridge,
etc.
show the lengths of bridges in brackets, from longest
to shortest

bicyclo[2.2.1]heptane

2-20

2 IUPAC - General
prefix-infix-suffix

prefix tells the number of carbon atoms in the parent

infix tells the nature of the carbon-carbon bonds
suffix tells the class of compound
Infix

Nature of Carbon-Carbon
Bonds in the Pare nt Chain

Suffix

Class

-e

hydrocarbon

-an-e n-

all single bonds

-ol

alcohol

one or more dou ble bon ds

-al

aldehyde

-yn-

one or more triple bonds

-amine
-one

amine

-oic acid

k etone
carboxylic acid

2-21

2 IUPAC - General
CH3 CH=CH 2
prop-en-e = propene
OH
eth-an-ol = ethanol
HC CH
but-an-one = butanone
but-an-al = butanal
pent-an-oic acid = pentanoic acid CH3 CH2 NH 2
cyclohex-an-ol = cyclohexanol
O
eth-yn-e = ethyne
CH3 CH2 CH2 CH
eth-an-amine = ethanamine

O
O
CH3 CCH2 CH 3

CH3 CH2 OH

CH 3 CH 2 CH 2 CH 2 COH

2-22

2 Conformations
Conformation:

any three-dimensional
arrangement of atoms in a molecule that results
from rotation about a single bond
Newman projection: a way to view a molecule by
looking along a carbon-carbon bond

2-23

2 Conformations
Staggered

conformation: a conformation about a

carbon-carbon single bond in which the atoms
on one carbon are as far apart as possible from
the atoms on an adjacent carbon
H
H

H
H

2-24

2 Conformations
Eclipsed

conformation: a conformation about a

carbon-carbon single bond in which the atoms
on one carbon are as close as possible to the
atoms on an adjacent carbon
H

H
H

HH

2-25

2 Conformations
Torsional

strain: the force that opposes the

rotation of one part of a molecule about a bond
while the other part of the molecule is held fixed
the torsional strain between eclipsed and staggered
ethane is approximately 12.6 kJ (3.0 kcal)/mol

+12.6 kJ/mol

2-26

2 Conformations

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2-27

2 Conformations
anti

conformation

a conformation about a single bond in which the

groups lie at a dihedral angle of 180
CH3
H

H
CH3

2-28

2 Conformations
Nonbonded

interaction strain:

the strain that arises when atoms not bonded to each

other are forced abnormally close to one another
butane - gauche conformation; nonbonded interaction
strain is approx. 3.8 kJ (0.9 kcal)/mol
CH3
H

CH3

H
H

2-29

2 Conformations

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2-30

2 Cyclopropane
angle strain: the C-C-C bond angles are
compressed from 109.5 to 60
torsional strain: there are 6 sets of eclipsed
hydrogen interactions
strain energy is about 116 kJ (27.7 kcal)/mol
H

H
H

2-31

2 Cyclobutane
puckering from planar cyclobutane reduces torsional
strain but increases angle strain
the conformation of minimum energy is a puckered
butterfly conformation
strain energy is about 110 kJ (26.3 kcal)/mol

2-32

2 Cyclopentane
puckering from planar cyclopentane reduces torsional
strain, but increases angle stain
the conformation of minimum energy is a puckered
envelope conformation
strain energy is about 42 kJ (6.5 kcal)/mol

2-33

2 Cyclohexane
Chair

conformation: the most stable puckered

conformation of a cyclohexane ring
all bond angles are approx. 109.5
all bonds on adjacent carbons are staggered

2-34

2 Cyclohexane
In

a chair conformation, six H are equatorial and

six are axial

2-35

2 Cyclohexane
For

cyclohexane, there are two equivalent chair

conformations
all C-H bonds equatorial in one chair are axial in the
alternative chair, and vice versa

2-36

2 Cyclohexane
Boat

conformation: a puckered conformation of a

cyclohexane ring in which carbons 1 and 4 are
bent toward each other
less stable than a chair conformation by 27 kJ (6.5
kcal)/mol

2-37

2 Cyclohexane
Twist-boat

conformation

approx. 41.8 kJ (5.5 kcal)/mol less stable than a chair

conformation
approx. 6.3 kJ (1.5 kcal)/mol more stable than a boat
conformation

2-38

2 Cyclohexane

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2-39

2 Methylcyclohexane
Equatorial

and axial methyl conformations

CH3
+7.28 k J/mol
CH3

2-40

2 G axial ---> equatorial

axial --> equatorial
Group

G
(k J/mol)

Group

C N
F

0.8
1.0

C CH
I

1.7
1.9

Cl

2.2

CH2 CH3

Br

2.4
3.9

CH( CH 3 ) 2 9.0
C( CH3 ) 3
21.0

OH

N H2
COOH
CH= CH2

G
(k J/mol)
5.9
5.9
7.1
7.28

CH3

7.3

2-41

2 Cis,trans Isomerism
Cis,trans

isomers have:

the same molecular formula

the same connectivity
a different arrangement of their atoms in space due to
the presence of either a ring or a carbon-carbon
double bond (see Chapter 5)

2-42

2 Cis,trans Isomerism
1,2-dimethylcyclopentane

H
H H

H
H H

H
CH3

CH3

cis-1,2-Dimethylcyclopentane

CH3

H
CH3

trans- 1,2-Dimethylcyclopentane
2-43

2 Cis,trans Isomerism
1,4-dimethylcyclohexane

planar hexagon representations

H
H3 C

CH3
H

t rans-1,4-D i meth yl cy clo hexane

H
H3 C

H
CH3

ci s-1,4-D i meth yl cy cl oh exane

2-44

2 Cis,trans Isomerism
trans-1,4-dimethylcyclohexane

the diequatorial-methyl chair conformation is more

stable by approximately 2 x (7.28) = 14.56 kJ/mol
CH3
H

H
H3 C

CH3
CH3
(less s table)

H
(more s table)

2-45

2 Cis,trans Isomerism
cis-1,4-dimethylcyclohexane
H

H
CH3

H3 C

H
CH3

conformations are of equal stability

CH3

2-46

2 Cis,trans Isomerism
H

H
H
t rans-decalin

cis-decalin

2-47

2 Physical Properties
Intermolecular

forces of attraction

ion-ion (Na+ and Cl- in NaCl)

ion-dipole (Na+ and Cl- solvated in aqueous solution)
dipole-dipole and hydrogen bonding
dispersion forces (very weak electrostatic attraction
between temporary dipoles)

2-48

2 Physical Properties
Low-molecular-weight

alkanes
(methane....butane) are gases at room
temperature
Higher molecular-weight alkanes (pentane,
decane, gasoline, kerosene) are liquids at room
temperature
High-molecular-weight alkanes (paraffin wax) are
semisolids or solids at room temperature

2-49

2 Physical Properties
Constitutional

isomers have different physical

properties
Name

mp
( C)

bp
( C)

Density
(g/mL)

hexane
2-methylpentane
3-methylpentane
2,3-dimethylbutane
2,2-dimethylbutane

-95
-154
-118
-129
-98

68.7
60.3
63.3
58.0
49.7

0.659
0.653
0.664
0.661
0.649

2-50

2 Oxidation of Alkanes
Oxidation

is the basis for their use as energy

sources for heat and power
heat of combustion: heat released when one mole of a
substance in its standard state is oxidized to carbon
dioxide and water
H
k J (k cal)/mol
CH4 + 2 O 2

CO 2 + 2 H2 O

-890 (-212)

3 CO 2 + 4 H2 O

-2220 (-530)

Methane
CH3 CH2 CH3 + 5 O 2
Propane

2-51

2 Heat of Combustion
Heat

of combustion for constitutional isomers

Hydrocarbon

Structural formula

H 0
[k J (k cal)/mol]

Octane

-5470.6 (-1307.5)

2-Methylheptane

-5465.6 (-1306.3)

2,2-Dime thylhexane

-5458.4 (1304.6)

2,2,3,3-Tetramethylbutane

-5451.8 (1303.0)

2-52

2 Heats of Combustion
For

constitutional isomers [kJ (kcal)/mol]

-5470.6 (-1307.5)

-5465.6 (-1306.3)

-5458.4 (1304.6) -5451.8 (1303.0)

8 CO 2 + 9 H2 O

2-53

2 Heat of Combustion
ring strain as determined by heats of combustion

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2-54

2 Sources of Alkanes
Natural

gas

90-95% methane
Petroleum

gases (bp below 20C)

naphthas, including gasoline (bp 20 - 200C)
kerosene (bp 175 - 275C)
fuel oil (bp 250 - 400C)
lubricating oils (bp above 350C)
asphalt (residue after distillation)

Coal

2-55

2 Gasoline
Octane

rating: the percent 2,2,4-trimethylpentane

(isooctane) in a mixture of isooctane and heptane that

has equivalent antiknock properties
CH3 CH 3
CH3 ( CH 2 ) 5 CH 3

CH 3 CCH2 CH CH3
CH3

Heptane
(octane rating 0)

2,2,4-Trimethylpen tane
(octane rating 100)

2-56

2 Synthesis Gas
A

mixture of carbon monoxide and hydrogen in

varying proportions which depend on the means
by which it is produced
C +
Coal
CH4 +
Methane

H2 O

1
O2
2

heat

catalyst

CO + H2

CO + 2 H2

2-57

2 Synthesis Gas
Synthesis

gas is a feedstock for the industrial

production of methanol and acetic acid
CO + 2 H2

catalyst

CH 3 OH
Methanol

CH 3 OH +
Methanol

CO

catalyst

O
CH 3 COH
Acetic acid

it is likely that industrial routes to other organic

chemicals from coal via methanol will also be
developed
2-58

2 Prob 2.19
Which sets represent pairs of constitutional isomers?
(a) CH3 CH2 OH and CH3 OCH3

O
O
(b) CH3 CCH3 and CH3 CH2 CH

O
O
(c) CH3 COCH 3 and CH3 CH2 COH

OH
O
(d) CH3 CHCH2 CH3 and CH3 CCH2 CH 3

(e )

(f)

and CH3 CH2 CH2 CH2 CH3

and CH2 = CHCH2 CH2 CH3

2-59

2 Prob 2.22
Write the IUPAC name of each compound.
(a)

(d)

(b)

(c)

(e )

2-60

2 Prob 2.24
Explain why each is an incorrect IUPAC name, and write
the correct IUPAC name.
(a) 1,3-dimethylbutane
(b) 4-methylpentane
(c) 2,2-dimethylbutane
(d) 2-ethyl-3-methylpentane
(e) 2-propylpentane
(f) 2,2-diethylheptane
(g) 2,2-dimethylcyclopropane
(h) 1-ethyl-5-methylcyclohexane

2-61

2 Prob 2.26
Write the IUPAC name of each compound.
O
(a) CH3 CH2 CCH 3

O
(b) CH 3 CH2 CH

O
(c) CH3 CH2 CH2 CH2 CH 2 COH

OH
(d) CH3 CHCH 3

(e )

(f)

(g) CH3 CH= CH 2

OH

(h )

2-62

2 Prob 2.40
Complete the table for cis,trans and equatorial,axial
substituted cyclohexanes.
Pos ition of
Subs titution
1,41,3-

cis
a,e or e,a
____ or ____

trans
e,e or a,a
____ or ____

1,2-

____ or ____

____ or ____

2-63

2 Prob 2.43
Draw alternative chair conformations for each.
HO

OH

(a )
H

OH
(b)

OH

H
CH2 OH

OH
H
(c )
HO

CH3
H

H
OH

(d)
H

HO

OH
H

2-64

2 Prob 2.44
Draw the more stable chair conformation of glucose.
OH
HO

HO

OH
OH

2-65

2 Prob 2.51
Given these heats of combustion, which constitutional
isomer is the more stable?
O

O
CH3 -CH

H2 C CH2

Acetaldehyde
-1164 kJ (-278.8 kcal)/mol

Ethylene oxide
-1264 kJ (-302.1 kcal)/mol

2-66

Alkanes
and
Cycloalkanes
End Chapter 2
2-67