ALCOHOLS, ETHERS AND THIOLS

Bettelheim, Brown, Campbell and Farrell Chapter 14

Review of Carbon Classification

Type of C

Attached to

1o (primary) C

one other carbon

2o (secondary) C

two other carbons

3o (tertiary) C

three other carbons

4o (quaternary) C

four other carbons

2

ALCOHOLS
Alcohol: Has an -OH (hydroxyl) group
bonded to a tetrahedral carbon
methanol, CH3OH, is the simplest alcohol

CLASSIFICATION OF ALCOHOLS
Aliphatic general formula CnH2n+1OH - provided there are no rings
the OH replaces an H in a basic hydrocarbon skeleton

Aromatic

in aromatic alcohols (or phenols)

the OH is attached directly to the ring
an OH on a side chain of a ring behaves
as a typical aliphatic alcohol

The first two compounds are

classified as aromatic alcohols
(phenols) because the OH group
is attached directly to the ring.

Structural differences
alcohols are classified according to the environment of the OH group
chemical behaviour, eg oxidation, often depends on the structural type

CLASSIFICATION OF ALCOHOLS
Depends on the C which has the OH
group attached
CH 3 CH 2 OH

OH

OH

ethanol

CH 3 CH CH 3

CH3 C CH3

2-propanol

CH3
2-methyl-2-propanol

1o Alcohol
attached to
one C

2o Alcohol
attached to
two Cs

3o Alcohol-attached to
three Cs
5

ALCOHOL NOMENCLATURE
1. Find longest carbon chain that contains the OH group (parent chain)
2. Number chain from end that gives the -OH
the lower number
3. Change the ending -e to -ol
4. Use a number to show the location of the -OH
group
5. For cyclic alcohols, the carbon with the -OH
group is C-1
6. Name and number substituents and list them
in alphabetical order
6

NOMENCLATURE
OH
OH
Ethan ol
(Ethyl alcohol)

OH
1-Propan ol
(Prop yl alcohol)

2-Prop anol
(Is op ropyl alcohol)

OH
OH
1-Butan ol
(Bu tyl alcohol)

OH
2-Bu tanol
(sec-Bu tyl alcohol)
OH

2-Methyl-2-p ropan ol
(t ert -Butyl alcoh ol)

2-Meth yl-1-propanol
(Is ob utyl alcoh ol)
OH

Cycloh exanol
(Cycloh exyl alcoh ol)

NOMENCLATURE
Write the IUPAC name for each alcohol
OH

(a)

OH
(b)

OH
(c)

(d)

OH

NOMENCLATURE

(a)
5

OH

OH

(b )

4-Methyl-2-pentan ol

t rans-2-Meth ylcycloh exanol

OH
(c)
2

2-Heptanol

(d)

OH

2,2-D imeth yl-1-p ropanol

NOMENCLATURE
Alcohols containing more than one hydroxyl
groups are named as a diol, a triol, and so on

IUPAC names for diols, triols, and so on retain

the final "-e" in the name of the parent alkane
Compounds containing two hydroxyl groups
on adjacent carbons are commonly called
glycols
CH2 CH2
OH OH

CH3 CHCH2
HO OH

1,2-Eth anediol
(Eth ylen e glycol)

1,2-Propan ediol
(Propylene glycol)

CH2 CHCH2
OH OHOH
1,2,3-Propan etriol
(Glycerol, Glycerin)

10

NAME THE FOLLOWING

OH
CH2CH 2CH2
OH

OH

HO

11

NAME THESE:
CH3
CH3

CH CH2OH

2-methyl-1-propanol

OH
CH3

CH CH2CH3
2-butanol

CH3
CH3

OH

C OH
CH3

2-methyl-2-propanol

Br

CH3

3-bromo-3-methylcyclohexanol
=>
12

PHYSICAL PROPERTIES
Alcohols are polar molecules
the C - O and O - bonds are both polar
covalent

13

PHYSICAL PROPERTIES
Alcohol molecules

can form hydrogen

bonds with each other

14

 Alcohols can also form

hydrogen bonds with water

15

PHYSICAL PROPERTIES OF ALCOHOLS

Boiling point increases as MW increases
Solubility in water decreases as MW increases
Molecular
Weigh t

bp
(C)

Solubility
in Water

Structu ral Formula

N ame

CH3 OH
CH3 CH3

methanol
ethan e

32
30

65
-89

infinite
ins olub le

CH3 CH2 OH

ethan ol
propane

78
-42

infinite

CH3 CH2 CH 3

46
44

CH3 CH2 CH 2 OH
CH3 CH2 CH 2 CH3

1-propanol
bu tane

60
58

97
0

CH3 CH2 CH 2 CH2 OH

1-bu tanol

74

117

CH3 CH2 CH 2 CH2 CH3

pen tane

72

36

ins olub le
infinite
ins olub le
8 g/100 g
ins olub16
le

CHEMICAL PROPERTIES OF ALCOHOLS

Acid-Base Chemistry
Dehydration
Oxidation

Combustion Reactions (they burn in O2)

17

ACIDITY OF ALCOHOLS
Alcohols have about the same pKa values
as water
Aqueous solutions of alcohols have the same
pH as that of pure water
Phenols have lower pKa values than normal
alcohols do (are more acidic)

18

ACIDITY OF ALCOHOLS
Alcohols and phenols both contain an OH group
Phenols are weak acids and react with strong bases
such as NaOH to form water-soluble salts
pKa = 9.89 for phenol 15 for alcohol
OH + NaOH
Phenol

H2 O

O Na

+ H2 O

S od ium phenoxide
(a w ater-soluble salt)

Alcohols are much weaker acids and do not react in

this manner
19

TABLE OF Ka VALUES

CH3

OH

20

WHY ARE PHENOLS MORE ACIDIC THAN ALCOHOLS?

Aromatic ring and O have delocalization of
electrons Less pull on H, so it is more acidic.

21

DEHYDRATION
Dehydration : Removal of water from
adjacent carbons to form an alkene
CH3 CH2 OH
Ethan ol

H2 SO4
180C

CH2 =CH2 + H2 O
Ethylen e

most often occurs by heating an alcohol with

either 85% H3PO4 or concentrated H2SO4

22

Dehydration essentially the reverse of

hydration (addition of water to double
bond)
Conditions required depend on kind of
alcohol

23

ELIMINATION OF WATER (DEHYDRATION)

Reagent/catalyst
Conditions

conc. sulphuric acid (H2SO4) or conc. phosphoric acid (H3PO4)

reflux at 180C

Product

alkene

Equation

e.g.

C2H5OH(l) > CH2 = CH2(g) + H2O(l)

Mechanism

Step 1
Step 2
Step 3

Alternative
Method

protonation of the alcohol using a lone pair on oxygen

loss of a water molecule to generate a carbocation
loss of a proton (H+) to give the alkene

Pass vapour over a heated alumina (aluminium oxide) catalyst

ACID-CATALYZED DEHYDRATION
1o ca 180oC needed
Hard

CH3 CH2 OH
Ethan ol

OH

2o lower
temperatures

Moderate
3o

slightly
above room
temperature
Easy

Cyclohexanol

H2 SO4
180C

H2 SO4
140C

CH2 =CH2 + H2 O
Ethylen e

+ H2 O
Cyclohexene

CH3
CH3
H2 SO4
CH3 CCH3
CH3 C=CH2 + H2 O
50C
OH
2-Meth yl-2-p ropanol
2-Methylpropene
(Isobutylene)
(t ert -Butyl alcoh ol)
25

DEHYDRATION
Zaitsevs Rule: When two alkene products are
possible, the alkene having the greater number
of alkyl groups (i.e., C atoms) on the double
bond generally predominates (forms major
product)
Major product favored.
OH
CH3 CH2 CHCH3
2-Butanol

H3 PO4
-H2 O

CH3
H2 SO4
CH3 CHCHCH3
-H2 O
OH
3-Meth yl-2-b utanol

CH3 CH=CHCH3 + CH3 CH2 CH=CH2

2-Bu tene
(80%)
CH3
CH3 C=CHCH3

1-Butene
(20%)
+

2-Methyl-2-b utene
(major prod uct)

CH3
CH3 CHCH=CH2
3-Methyl-1-bu tene
26
(minor product)

OH
CH3 CH2 CHCH3
2-Butanol

H3 PO4
-H2 O

CH3
H2 SO4
CH3 CHCHCH3
-H2 O
OH
3-Meth yl-2-b utanol

CH3 CH=CHCH3 + CH3 CH2 CH=CH2

2-Bu tene
(80%)

CH3
CH3 C=CHCH3

1-Butene
(20%)

2-Methyl-2-b utene
(major prod uct)

CH3
CH3 CHCH=CH2
3-Methyl-1-bu tene
27

DEHYDRATION-HYDRATION RELATED
Acid-catalyzed hydration of alkenes and
acid-catalyzed dehydration of alcohols are
competing reactions
Equilibrium between alkene and alcohol
exists
dehydration
C C

+ H2 O

h yd ration
An alk ene

C C
H OH
An alcoh ol

Large amounts of water favor alcohol

formation, while removal of water from the
equilibrium mixture favors alkene formation
Chatelier's principle)

(Le
28

DEHYDRATION VS OXIDATION
Dehydration: Remove OH and H
OH from one C : H from adjacent C

Oxidation : Remove two H atoms

One H from OH group :
Other H from C that has the OH attached

29

OXIDATION OF ALCOHOLS
Oxidation of a 1 alcohol gives an aldehyde
or a carboxylic acid, depending on the
experimental conditions
Oxidation of a 1 alcohol to a carboxylic acid
is carried out using an oxidizing agent such as
potassium dichromate, K2Cr2O7, in aqueous
sulfuric acid

CH3 ( CH2 ) 6 CH2 OH

1-Octanol

K2 Cr2 O7
H2 SO4

O
O K Cr O
2 2 7
CH3 ( CH2 ) 6 CH
CH3 (CH2 ) 6 COH
H2 SO4
30
Octanoic acid
Octanal

OXIDATION OF ALCOHOLS
Can sometimes stop the oxidation at the
aldehyde stage by distilling the mixture
(Aldehydes usually have lower boiling
points than either the 1 alcohol or the
carboxylic acid)
CH3 ( CH2 ) 6 CH2 OH
1-Octanol
Alcohol

K2 Cr2 O7
H2 SO4

O
O K Cr O
2 2 7
CH3 ( CH2 ) 6 CH
CH3 (CH2 ) 6 COH
H2 SO4
Octanoic acid
Octanal
Aldehyde

Carboxylic acid
31

OXIDATION OF ALCOHOL
Oxidation of a 2 alcohol gives a ketone
K2 Cr2 O7
OH

H2 SO4

2-Is opro py l-5-methy lcy clo hexano l

(Mentho l)

2-Iso pro py l-5-methy lcyclo hexan on e

(Menth on e)

Tertiary alcohols are resistant to oxidation

CH3
OH
1-Meth ylcyclopen tanol

K2 Cr2 O7
H2 SO4

(no oxidation )
32

OTHER REACTIONS OF ALCOHOLS

OXYGEN

Alcohols make useful fuels

C2H5OH(l)

3O2(g) >

2CO2(g) + 3H2O(l)

Advantages have high enthalpies of combustion

do not contain sulphur so there is less pollution
can be obtained from renewable resources

OTHER REACTIONS OF ALCOHOLS

OXYGEN

Alcohols make useful fuels

C2H5OH(l)

3O2(g) >

2CO2(g) + 3H2O(l)

Advantages have high enthalpies of combustion

do not contain sulphur so there is less pollution
can be obtained from renewable resources

SODIUM
Conditions

room temperature

Product

sodium alkoxide and hydrogen

Equation

2CH3CH2OH(l) + 2Na(s)

Notes

alcohols are organic chemistrys equivalent of water

water reacts with sodium to produce hydrogen and so do alcohols
the reaction is slower with alcohols than with water.

> 2CH3CH2O Na +
sodium ethoxide

Alkoxides are white, ionic crystalline solids

+ H2(g)

e.g. CH3CH2O Na+

BROMINATION OF ALCOHOLS
Reagent(s)

conc. hydrobromic acid HBr(aq) or

sodium (or potassium) bromide and concentrated sulphuric acid

Conditions

reflux

Product

haloalkane

Equation

C2H5OH(l) + conc. HBr(aq)

Mechanism

The mechanism starts off similar to that involving dehydration

(protonation of the alcohol and loss of water) but the carbocation
(carbonium ion) is attacked by a nucleophilic bromide ion in step 3

Step 1
Step 2
Step 3

>

C2H5Br(l) + H2O(l)

protonation of the alcohol using a lone pair on oxygen

loss of a water molecule to generate a carbocation (carbonium ion)
a bromide ion behaves as a nucleophile and attacks the carbocation

ESTERIFICATION OF ALCOHOLS
Reagent(s)

carboxylic acid + strong acid catalyst (e.g conc. H2SO4 )

Conditions

reflux

Product

ester

Equation

Notes

e.g. CH3CH2OH(l) + CH3COOH(l)

ethanol
ethanoic acid

CH3COOC2H5(l) + H2O(l)
ethyl ethanoate

Concentrated H2SO4 is a dehydrating agent - it removes water

causing the equilibrium to move to the right and increases the yield

ESTERIFICATION OF ALCOHOLS
Reagent(s)

carboxylic acid + strong acid catalyst (e.g conc. H2SO4 )

Conditions

reflux

Product

ester

Equation

e.g. CH3CH2OH(l) + CH3COOH(l)

ethanol
ethanoic acid

CH3COOC2H5(l) + H2O(l)
ethyl ethanoate

Notes

Concentrated H2SO4 is a dehydrating agent - it removes water

causing the equilibrium to move to the right and increases the yield

Uses of esters

Esters are fairly unreactive but that doesnt make them useless
Used as flavourings

Naming esters

Named from the alcohol and carboxylic acid which made them...
CH3OH + CH3COOH
from ethanoic acid

CH3COOCH3

CH3COOCH3 + H2O
from methanol

METHYL ETHANOATE

38

COMMON ALCOHOLS
Ethanol
Ethyl alcohol, grain alcohol
Produced by fermentation
Natural fermentation of sugars and
starches in grains, corn, molasses, fruits,
vegetables
Found in beer, wine, and other spirits
C6H12O6 2 CH3CH2OH + 2 CO2
glucose

ethanol

carbon dioxide
39

COMMON ALCOHOLS
Methanol
Methyl alcohol or wood alcohol
Distilled from wood pulp originally
Very toxic, even in small amounts
Reacts to make formaldehyde (a fixative)
CH3OH
methanol

CH2=O
formaldehyde
40

COMMON ALCOHOLS
Isopropyl alcohol
2-propanol rubbing alcohol
Evaporates quicklyused to reduce fever
Solvent in many cosmetics, perfumes, etc.

OH
CH 3 CH CH3
2-propanol
41

COMMON ALCOHOLS
1,2-ethanediol
Ethylene glycol
Very soluble in water
Used as antifreeze

Glycerol
1,2,3-propanetriol
Very soluble in water
Sweet taste
Part of fats and oils

42

PREPARATION OF IMPORTANT ALCOHOLS

Many alcohols (or their derivatives) can
be formed by reacting smaller molecules.

Coal
or
methane

2H2

CO
Carbon
monoxide

CO
catalyst
CH3 OH
Methanol

CH3 COOH
Acetic acid

O2
CH2 O
oxidation Formaldehyde
43

PREPARATION OF IMPORTANT ALCOHOLS

H2 O, H2 SO4
CH2 =CH2
Ethylen e

O2
catalyst

CH3 CH2 OH
Ethanol

180C

O
H2 O, H2 SO4
H2 C CH2
Ethylene
oxide

H2 O, H2 SO4
CH3 CH=CH2
Propene

H2 SO4

several s teps

CH3 CH2 OCH2 CH3

Dieth yl eth er

HOCH2 CH2 OH
Ethylene glycol

OH
CH3 CHCH3
2-Propan ol
OH
HOCH2 CHCH2 OH
Glycerin, glycerol

44

ETHERS
The functional group of an ether is an
oxygen atom bonded to two carbon
atoms
Simplest ether is dimethyl ether
Most common ether is diethyl ether
Often called just ether

CH3 -O-CH3

CH3 CH2 -O-CH2 CH3

D imethyl ether

Dieth yl eth er

45

ETHER NOMENCLATURE
Generally use common names for small
(low-molecular-weight) ethers
common names are derived by listing the alkyl
groups bonded to oxygen in alphabetical
order and adding the word "ether
alternatively, name one of the groups on
oxygen as an alkoxy group
CH3 CH2 OCH2 CH3
D iethyl eth er

OCH3
Cyclohexyl meth yl eth er
(Methoxycycloh exane) 46

ETHER NOMENCLATURE
Cyclic ether: an ether in which one of the
atoms in a ring is oxygen
Cyclic ethers also known by their common
names
ethylene oxide is an important building block
for the organic chemical industry; it is also used
as a fumigant in foodstuffs and textiles, and in
hospitals to sterilize surgical instruments
tetrahydrofuran is a useful laboratory and
industrial solvent
O
Eth ylene oxide

O
Tetrahydrofu ran
47
(THF)

48

PHYSICAL PROPERTIES OF ETHERS

Ethers are polar compounds
O has a partial negative charge
Each C bonded to it has a partial positive
charge
Only weak forces of attraction exist between ether
molecules in the pure liquid
Boiling points of ethers are close to those of
hydrocarbons of similar molecular weight
Have lower boiling points than alcohols of the
same molecular formula
CH3 CH2 OH
Ethanol

CH3 OCH3
Dimethyl ether

bp 78C

b p -24C

49

REACTIONS OF ETHERS
Ethers not very reactive (like hydrocarbons)
Do not react with oxidizing agents such as
potassium dichromate
Do not react with reducing agents such as H2
in the presence of a transition metal catalyst
Not affected by most acids or bases at
moderate temperatures

Good solvents for carrying out organic

reactions, because of their general inertness
and good solvent properties
Diethyl ether and THF (tetrahydrofuran)

50

THIOLS
Thiol: a compound containing an -SH
(sulfhydryl) group
Also called mercaptans
Low-molecular-weight thiols STINK
Responsible for smells such as those from
rotten eggs and sewage
the scent of skunks is due primarily to these
two thiols
CH3
CH3 CH=CHCH2 SH
CH3 CHCH2 CH2 SH
2-Bu ten e-1-thiol
3-Methyl-1-bu tanethiol 51

THIOLS - NOMENCLATURE
IUPAC names are derived in the same
manner as are the names of alcohols
Retain the final -e of the parent alkane and
add the suffix -thiol
Common names for simple thiols are derived
by naming the alkyl group bonded to -SH and
adding the word "mercaptan"
CH3
CH3 CH2 SH
Ethaneth iol
(Ethyl mercap tan)

CH3 CHCH2 SH
2-Methyl-1-propan ethiol
(Isobu tyl mercaptan)

52

53

THIOL PHYSICAL PROPERTIES

S-H bonds are nonpolar covalent
Small difference in electronegativity between
sulfur and hydrogen (2.5 - 2.1 = 0.4)
No hydrogen bonding
Lower boiling points than comparable alcohols
Less soluble in water and other polar solvents
than comparable alcohols
Thiol
methanethiol
ethan ethiol
1-bu tanethiol

bp (C)
6
35
98

Alcoh ol
methanol
ethan ol
1-bu tanol

bp (C)
65
78
117

54

REACTIONS OF THIOLS
Thiols are weak acids (pKa~10), and are
comparable in strength to phenols
thiols react with strong bases such as NaOH
to form water-soluble thiolate salts

CH3 CH2 SH + NaOH

Ethanethiol
(pKa 10)

H2 O

CH3 CH2 S Na + H2 O
Sodium
ethanethiolate
55

REACTIONS OF THIOLS
The most important thiol reaction in
biological systems is their oxidation to
disulfides
Functional group is a disulfide (-S-S-) bond
Disulfide bonds important in protein structure

Thiols are readily oxidized to disulfides by O2

-SH group very susceptible to oxidation and
must be protected from contact with air
during storage
disulfides, in turn, are easily reduced to thiols
by several reducing agents.
56

REACTIONS OF THIOLS
Oxidation of SH groups to form S-S bonds
Reduction of S-S bonds to form SH groups

2HOCH2 CH2 SH
A thiol

oxidation
reduction

HOCH2 CH2 S-SCH2 CH2 OH

A disulfide

57

REACTIONS OF THIOLS
Oxidation of SH groups to form S-S bonds
Reduction of S-S bonds to form SH groups

58

UNSATURATED ALCOHOLS
Hydroxyl group takes precedence. Assign
that carbon the lowest number.
Use alkene or alkyne name.
OH
CH2

CHCH2CHCH3

4-penten-2-ol (old)

pent-4-ene-2-ol
(1997 revision of IUPAC rules)
=>
59

NAMING PRIORITY
1.
2.
3.
4.
5.
6.

Acids
Esters
Aldehydes
Ketones
Alcohols
Amines

7. Alkenes
8. Alkynes
9. Alkanes
10. Ethers
11. Halides

60