Organic Chemistry, 7th Edition

L. G. Wade, Jr.

Chapter 10
Structure and Synthesis
of Alcohols

Copyright 2010 Pearson Education, Inc.

Alcohols
Hydroxyl groups in natural compounds.

Structure of Water and Methanol

Oxygen is sp3 hybridized and tetrahedral.

The HOH angle in water is 104.5.
The COH angle in methyl alcohol is 108.9.
Chapter 10

Classification of Alcohols
Primary: carbon with OH is bonded to
one other carbon.
Secondary: carbon with OH is bonded
to two other carbons.
Tertiary: carbon with OH is bonded to
three other carbons.
Aromatic (phenol): OH is bonded to a
benzene ring.
Chapter 10

Examples of Classifications
OH

CH3
CH3

CH3

CH CH2OH
*

Primary alcohol

CH CH2CH3

Secondary alcohol

CH3
CH3

C* OH

Tertiary alcohol

CH3

Chapter 10

IUPAC Nomenclature
Find the longest carbon chain containing the
carbon with the OH group.
Drop the -e from the alkane name, add -ol.
Number the chain giving the OH group the
lowest number possible.
Number and name all substituents and write
them in alphabetical order.

Chapter 10

Examples of Nomenclature
OH

CH3
CH3
3

CH3

CH CH2OH
2

2-methyl-1-propanol
2-methylpropan-1-ol

2
CH3

CH3
1
C OH

CH3

CH CH2CH3
2

2-butanol
butan-2-ol

2-methyl-2-propanol
2-methylpropan-2-ol

Chapter 10

Alkenols (Enols)
Hydroxyl group takes precedence. Assign the
carbon with the OH the lowest number.
End the name in ol, but also specify that there is
a double bond by using the ending ene before -ol
OH

CH2
5

CHCH2CHCH3
4

2 1

4-penten-2-ol
pent-4-ene-2-ol

Chapter 10

Naming Priority
Highest ranking

Lowest ranking

1. Acids
2. Esters
3. Aldehydes
4. Ketones
5. Alcohols
6. Amines
7. Alkenes
8. Alkynes
9. Alkanes
10. Ethers
11. Halides
Chapter 10

Hydroxy Substituent
When OH is part of a higher priority class of
compound, it is named as hydroxy.
carboxylic acid

OH
CH2CH2CH2COOH
4

4-hydroxybutanoic acid
also known as g-hydroxybutyric acid (GHB)
Chapter 10

10

Common Names
Alcohol can be named as alkyl alcohol.
Useful only for small alkyl groups.
OH

CH3
CH3

CH CH2OH

isobutyl alcohol

CH3

CH CH2CH3

sec-butyl alcohol

Chapter 10

11

Naming Diols
Two numbers are needed to locate the two
OH groups.
Use -diol as suffix instead of -ol.
1

hexane-1,6- diol
Chapter 10

12

Glycols
1, 2-diols (vicinal diols) are called glycols.
Common names for glycols use the name of the
alkene from which they were made.

ethane-1,2- diol
ethylene glycol

propane-1,2- diol
propylene glycol
Chapter 10

13

Phenols
Naturally occurring phenols: a hydroxyl group
directly attached to an aromatic ring.

Phenol Nomenclature
OH group is assumed to be on carbon 1.
For common names of disubstituted phenols,
use ortho- for 1,2; meta- for 1,3; and para- for
1,4.
Methyl phenols are cresols.
OH

OH
H3C

Cl

3-chlorophenol
(meta-chlorophenol)

4-methylphenol
(para-cresol)
Chapter 10

15

Solved Problem 1
Give the systematic (IUPAC) name for the following alcohol.

Solution
The longest chain contains six carbon atoms, but it does not contain the carbon bonded to the hydroxyl
group. The longest chain containing the carbon bonded to the OH group is the one outlined by the
green box, containing five carbon atoms. This chain is numbered from right to left in order to give the
hydroxyl-bearing carbon atom the lowest possible number.

The correct name for this compound is 3-(iodomethyl)-2-isopropylpentan-1-ol.

Chapter 10

16

Physical Properties
Alcohols have high boiling points due to
hydrogen bonding between molecules.
Small alcohols are miscible in water, but
solubility decreases as the size of the
alkyl group increases.

Chapter 10

17

Physical Properties of Alcohols

The hydrogen- (H-) in hydroxyl groups

intermolecularly attracts water molecules

Alcohols with small carbon chains are miscible in

water (they mix in any ratio).

Alcohols with large carbon chains do not readily

mix with water.

Physical Properties of Alcohols

octanol-water partitioning

Molecules with large hydrophobic groups are generally

insoluble in water.
Alcohols with three or less carbons are generally water
miscible.
Alcohols with more than three carbons are not miscible,
and their solubility decreases as the
size of the hydrophobic group increases.

Boiling Points of alcohols

Alcohols have higher boiling points than ethers and

alkanes because alcohols can form hydrogen bonds.
The stronger interaction between alcohol molecules
will require more energy to break them resulting in a
higher boiling point.
Chapter 10

20

Solubility in Water

Small alcohols are miscible in

water, but solubility decreases as
the size of the alkyl group
increases.
Chapter 10

21

Methanol

Wood alcohol
Industrial production from synthesis gas
Common industrial solvent
Toxic Dose: 100 mL methanol
Used as fuel at Indianapolis 500

Fire can be extinguished with water

High octane rating
Low emissions
Lower energy content
Invisible flame
Chapter 10

22

Ethanol
Fermentation of sugar and starches in
grains
1215% alcohol, then yeast cells die
Distillation produces hard liquors
Azeotrope: 95% ethanol, constant boiling
Denatured alcohol used as solvent
Gasahol: 10% ethanol in gasoline
Toxic dose: 200 mL
Chapter 10

23

Nomenclature of Alcohols
IUPAC name - The OH group is a site of
reactivity (a functional group)
Functional group is denoted by the suffix, ol

CH3OH

CH3CH2OH

methanol

ethanol

Prentice Hall 2001

Chapter 2

24

Nomenclature of Alcohols
IUPAC name - The OH group is a site of
reactivity (a functional group)
Functional group is denoted by the suffix, ol

CH3OH

CH3CH2OH

methanol

ethanol

Prentice Hall 2001

Chapter 2

25

IUPAC Nomenclature of
Alcohols
1. Parent Hydrocarbon is the longest
continuous chain that contains the OH
2. Number the chain in direction that gives
functional group the lowest number
3. If both a substituent and a functional
group are present, the functional group
gets the lower number
Prentice Hall 2001

Chapter 2

26

IUPAC Nomenclature of
Alcohols
4. If the functional group gets the same
number when counted from both
directions, use direction which gives the
substituent the lower number
5. If there is more than one substituent, cite
substituents in alphabetical order

Prentice Hall 2001

Chapter 2

27

IUPAC Nomenclature of
Alcohols
System is summarized as [Substituent]
[Parent Hydrocarbon] [Functional Group]

Prentice Hall 2001

Chapter 2

28

Classification and Nomenclature of Some Alcohols

Condensed Structural
Formula

Class of Alcohol

Common Name

IUPAC Name

CH3OH

methyl alcohol

methanol

CH3CH2OH

primary

ethyl alcohol

ethanol

CH3CH2CH2OH

primary

propyl alcohol

1-propanol

(CH3)2CHOH

secondary

isopropyl alcohol

2-propanol

CH3CH2CH2CH2OH

primary

butyl alcohol

1-butanol

CH3CH2CHOHCH3

secondary

sec-butyl alcohol

2-butanol

(CH3)2(CH3)2CHCH2OH

primary

isobutyl alcohol

2-methyl-1-propanol

(CH3)3COH

tertiary

tert-butyl alcohol

2-methyl-2-propanol

secondary

cyclohexyl alcohol

cyclohexanol

Chapter 10

29

This table shows that alcohols (in red) have higher boiling points and greater solubility in H 2O than haloalkanes and alkanes with the same number of carbons. It also
shows that the boiling point of alcohols increase with the number of carbon atoms.

Physical Properties of Alchols and Selected Analogous Haloalkanes and Alkanes

o

Melting Poing ( C)

Compound

IUPAC Name

Common Name

CH3OH

Methanol

Methyl alcohol

-97.8

65.0

Infinite

CH3Cl

Chloromethane

Methyl chloride

-97.7

-24.2

0.74 g/100 mL

CH4

Methane

-182.5

-161.7

3.5 mL (gas)/ 100

mL

CH3CH2OH

Ethanol

Ethyl alcohol

-114.7

78.5

Infinite

CH3CH2Cl

Chloroethane

Ethyl chloride

-136.4

12.3

0.447 g/100 mL

CH3CH3

Ethane

-183.3

-88.6

4.7 mL (gas)/ 100

mL

CH3CH2CH2OH

1-Propanol

-126.5

97.4

Infinite

CH3CH2CH3

Propane

-187.7

-42.1

6.5 mL (gas)/ 100

mL

Propyl alcohol

Boiling Point ( C)

Solubility in H2O at
o
23 C

CH3CH2CH2CH2OH 1-Butanol

Butyl alcohol

-89.5

117.3

8.0 g/100 mL

CH3(CH2)4OH

Pentyl alcohol

-79

138

2.2 g/100 mL

1-Pentanol

Chapter 10

30