CHAPTER 1:

ALCOHOLS
By the end of this chapter, the students should be able to:
• General formulas: ROH, ArOH (IUPAC & common name)
• Classification of alcohols
• Physical properties of alcohols (bp & solubility)
• Acidity & Basicity
• Preparations of alcohols.
• Reactions of alcohols.
• Tests to distinguish classes of alcohols.
Alcohol is an organic compound in which the hydroxyl
functional group (-OH) is bound to a carbon atom.

General formula of alcohol is CnH2n+1 OH.

CLASSIFICATION OF ALCOHOLS
Alcohols are classified as primary, secondary and tertiary alcohols depend on
the number of carbon atoms bonded to the carbon with the –OH group.

Primary alcohols (1o) Secondary alcohols (2o) Tertiary alcohols (3o)

The carbon which carries the – The carbon which the -OH The carbon with the -OH group
OH group is only attached to group bonded is joined directly is bonded directly to three
one alkyl group. to two alkyl groups, which may alkyl groups, which may be any
be the same or different. combination of same or
different.
CH3
CH3
CH3 C OH
CH3 CH CH2OH
CH3

OH
OH CH3 CH CH2CH3
NOMENCLATURE
IUPAC NAME
• Alcohols are named with the suffix –ol to replace –e in
alkane.
• Longest carbon chain with –OH group is selected as
parent chain.
• Numbering starts from the end closer to –OH group. If
double bonds exist in the parent chain, the –OH group
still has higher priority.
• In cyclic alcohol, the –OH group takes number one
position.
• When an OH group is bonded to a ring, the ring is
numbered beginning with the OH group.
• Because the functional group is at C1, the 1 is usually
omitted from the name.
• The ring is then numbered in a clockwise or
counterclockwise fashion to give the next substituent
the lowest number.
08/05/2024
Unsaturated alcohols
• Hydroxyl group takes precedence. Assign that carbon
the lowest number.
• Use alkene or alkyne name.

OH 4-penten-2-ol (old)
CH2 CHCH2CHCH3 pent-4-ene-2-ol (new)
Diols
• Two numbers are needed to locate the two -OH
groups.
• Use -diol as suffix instead of -ol.

HO OH

1,6-hexanediol
Glycols
• Two hydroxyl (―OH) groups are attached to
different carbon atoms.
• Common names for glycols use the name of the alkene
from which they were made.
CH2CH2 CH2CH2CH3
OH OH OH OH
1,2-ethanediol 1,2-propanediol
ethylene glycol propylene glycol
COMMON NAME
• Alcohol can be named as alkyl alcohol.
• Useful only for small alkyl groups.
• Examples:
CH3 OH
CH3 CH CH2OH CH3 CH CH2CH3

isobutyl alcohol sec-butyl alcohol

Phenol
• OH group is assumed to be on carbon 1.
• For common names of disubstituted phenols:
OH
ortho- for 1,2
meta- for 1,3 H3C
OH
para- for 1,4 4-methylphenol
para-cresol
Cl
3-chlorophenol
meta-chlorophenol
PHYSICAL
PROPERTIES
Boiling Point
• The boiling points of alcohols are always higher than that of
hydrocarbons with the same number of carbon atoms.
• The boiling points of the alcohols increase with increasing
number of carbon atoms.
• The existence of intermolecular attractions; hydrogen
bonding, dipole-dipole attraction and van der Waals forces in
alcohols results in higher boiling points than hydrocarbons.
• The presence of oxygen atom in alcohol brings an extra 8
electrons. As a result, the strength of the van der Waals
dispersion forces increases and so the boiling point.
Solubility
• Small alcohols are completely water
soluble in all proportions.
• However, solubility declines as the
number of carbon atom increases.
• Drastic decrease in solubility is apparent
for four carbons or more, which two
layers are formed.
• Ethanol is completely soluble in water.
The main intermolecular attraction in Solubility decreases as the
size of the alkyl group
either ethanol or water is hydrogen increases.
bonds.
ACIDITY & BASICITY
• Alcohols are both weak acids and weak bases.
• pKa range: 15.5-18.0 (water: 15.7)
• Acidity decreases as alkyl group increases.
• Halogens increase the acidity.
• Phenol is 100 million times more acidic than
cyclohexanol. .
PREPARATION OF
ALCOHOLS
1) Synthesis of Grignard reagent
2) Hydrolysis of alkyl halides
3) Industrial preparations of ethyl alcohol
1. SYNTHESIS OF GRIGNARD REAGENT
• A Grignard reagent has a formula RMgX where X is a halogen,
and R is an alkyl or aryl group.
• Grignard reagents are prepared by adding the alkyl halide to
small pieces of magnesium in a flask containing ethoxyethane
(diethyl ether).
• The flask is fitted with a reflux condenser, and the mixture is
warmed over a water bath for 20 - 30 minutes.
• The reaction condition must be perfectly dry because Grignard
reagents react with water.
(CH3CH2)2O
R X + Mg R Mg X
Grignard reagents

(CH3CH2)2O
H3C Br + Mg H3C Mg Br
Methylmagnesium
bromide
Preparation of Primary Alcohols

O OH
[1] R Mg-X
H C H H C H
[2] H2O R
Methanal / 1O R-OH
formaldehyde
CH3 H H CH3 H
H3C C CH2 C MgBr C O CH3 CH CH2 CH2 C O MgBr
H
H H H

CH3 H
HOH
CH3 CH CH2 CH2 C O H
H
Preparation of Secondary Alcohols

O OH
[1] R Mg-X
R C H R C H
[2] H2O
R
Aldehyde 2O R-OH
CH3 H H3C CH3 CH3
H3C C CH2 C MgBr C O CH3 CH CH2 CH2 C O MgBr
H
H H H

CH3 CH3
HOH
CH3 CH CH2 CH2 C O H
H
Preparation of Tertiary Alcohols

O OH
[1] R Mg-X
R C R R C R
[2] H2O
R
Ketone 3O R-OH
CH3 H H3C CH3 CH3
H3C C CH2 C MgBr C O CH3 CH CH2 CH2 C O MgBr
H3C
H H CH3

CH3 CH3
HOH
CH3 CH CH2 CH2 C O H
CH3
2. HYDROLYSIS OF ALKYL HALIDE
• Alkyl halides, RX can be converted to alcohols using water
or hydroxide as the nucleophile.
• In this nucleophilic substitution reaction, the halogen atom
is replaced by an OH group to yield an alcohol.
• Primary, secondary and tertiary alkyl halides react with OH-
to form 1o, 2o and 3o ROH, respectively.
• The reaction follows either SN1 or SN2 mechanism, which 1o
RX usually through SN2.
SN2
CH3CH2 Br + -OH CH3CH2 OH

1o RX
nucleophile product
3. INDUSTRIAL PREPARATIONS OF ETHYL ALCOHOL
• Industrially, ethanol is prepared by reacting ethene with steam
in the presence of a catalyst, solid silicon dioxide coated with
phosphoric (V) acid. This hydration reaches equilibrium.
H3PO4
CH2=CH2 + H2O(g) CH3CH2OH(g)

• Since only 5% of the ethene is converted into ethanol at each

pass through the reactor, ethanol formed is removed from the
equilibrium.
REACTION OF
ALCOHOLS
1) Formation of alkoxide
2) Esterification
3) Dehydration (mechanisms)
4) Halogenation
5) Oxidation
1. FORMATION OF ALKOXIDE
• Alcohols react with sodium metal at room temperature
to form salts of alcohols (sodium alkoxides).

CH3CH2 OH + Na room temp.

ethanol sodium

CH3CH 2 O- Na+ + 1/2 H2

sodium ethoxide
(salt)
2. ESTERIFICATION
• Esterification is the reaction between the carboxylic acid
and the alcohol under reflux to produce ester.
• The reaction needs the presence of a strong acid like
concentrated sulfuric acid.
O
R' OH + R C conc. H2SO4
OH
alcohol carboxylic acid

O
R C O R' + H2 O
ester
• Another common esterification method is through the
reaction between acyl and alcohol in the presence of a
base such as pyridine, C5H5N.
3. DEHYDRATION
• It is an elimination reaction to form an alkene where the
organic molecule loses an -OH atom from one carbon (α-
carbon) and a H atom from an adjacent carbon (β- carbon)
to form a molecule of water.
• Dehydration of an alcohol requires an acid catalyst and
heat.
• Sulfuric acid (H2SO4) or phosphoric acid (H3PO4) are the
most used acid catalyst.
a. Dehydration of alcohols using aluminium oxide

When ethanol vapor is passed over heated aluminum

oxide powder, Al2O3 the ethanol is converted to ethene
and water vapor.
b. Dehydration of alcohols using an acid catalyst.
• Upon heating with strong acid, alcohols undergo
dehydration to form alkenes.
• The type of reaction is 1,2 or b-elimination.
conc. H2SO4
CH2CH2 (excess) CH2 CH2 + H2O
180oC ethene
H OH
ethanol
Primary alcohols are the most
(primary)
difficult to dehydrate because it
needs high temperature.
Dehydration of 1° alcohols – E2 Mechanism

H H
proton transfer
H3C C H H3C C H + HSO4-
OH H2O

H OSO3H

• The oxygen atom is protonated and converts the poor

leaving group (OH-) into a good leaving group (H2O).
H H HSO4- H
H C C H H C C H
H H
H2O
+ H2O + H2SO4

Relative reactivity order

dehydration of alcohols:
3o > 2o > 1o
• The dehydration of secondary or tertiary alcohols
which has two or three different β-carbons, follows
the Zaitsev’s rule.

• According to Zaitsev’s Rule, the major product is

obtained when a proton is removed from the carbon
that is bonded to the least hydrogen.
HH
H2SO4
CH 2CCHCH3
H OH
2-butanol (secondary) CH2 CHCH2CH3 + H2O
1-butene (minor)

CH3CH CHCH3 + H2O

2-butene (major)
Dehydration of 2° & 3o alcohols – E1 Mechanism

CH3 CH3

H3C C CH3 H3C C CH3

OH OH2
H OSO3H
+ HSO4-

• Oxygen atom is protonated, converts a poor leaving group

(OH-) into a good leaving group (H2O).
CH3 CH3
slow
H3C C CH3 H3C C CH3
OH2
+ H2O

• The C-O bond is broken and forms a carbocation.

CH3 CH3
+
H3C C CH2 H3C C CH2 + H3O
H
H2O

• A base removes a proton from a carbon adjacent to the

carbocation and the pi bond is formed.
4. HALOGENATION – nucleophilic substitution (SN1)

• The reaction of alcohols with HX (X = Cl, Br, I) is a

general method to prepare 1°, 2°, and 3° alkyl halides.
• This reaction involves the breaking (cleavage) of the C-O
bond in an alcohol to replace with X.
ZnCl2
CH3CH2OH + HCl
heat
ethanol (primary)
CH3CH2Cl + H2O
chloroethane
Reaction of alcohol with HCl
• 3o alcohols react reasonably rapidly with concentrated
HCl acid, but for 1o or 2o alcohols the reaction rates are
too slow.
• A 3o alcohol such as tert-butanol reacts if it is shaken
with concentrated HCl acid at room temperature. A
tertiary haloalkane or alkyl halide is formed.
3O ROH
Reaction of alcohol with HBr

• Instead of using HBr acid, alcohol is treated with a

mixture of NaBr or KBr and concentrated H2SO4 acid.
• This produces HBr which reacts with the alcohol.
• The mixture is warmed to distill off the bromoalkane
(alkyl bromide).
Reaction of alcohol with HI
When alcohol is treated with NaI or KI and concentrated
phosphoric(V) acid, H3PO4, and the iodoalkane (alkyl
iodide) is formed.
Reaction of alcohol with PX3 and SOCl2
5. OXIDATION

Only 1o and 2o ROH

can oxidize using
inorganic oxidizing
agents, such as
KMnO4, CrO3, and
Na2Cr2O7 or by
more selective,
expensive reagents.
Partial oxidation to aldehyde
• Oxidation of 1o alcohols with a mild oxidizing agent such
as pyridinium chlorochromate (PCC), C5H5NH+CrO3Cl- in
dichloromethane, CH2Cl2 as solvent yield aldehydes
(RCHO).

1o ROH Aldehyde
Complete oxidation to carboxylic acid
• 2o alcohols are oxidized to ketones. When alcohol is
treated with chromic acid, H2CrO4 (in acetone) or
potassium dichromate(VI), K2Cr2O7 solution acidified
with dilute H2SO4, and heated, a ketone is formed.

2o ROH Ketone
TESTS OF
ALCOHOLS
1. OXIDATION
• Potassium dichromate is an
oxidizing agent.

• The bright orange dichromate ion is reduced to the green

Cr3+ ion.

• If the orange color changes to green an oxidation reaction has

occurred.

• If the color remains orange, no reaction has occurred (3°

alcohols).
2. SHIFT TEST
• A quite reliable test to distinguish between 1o and 2o
alcohols is Schiff's test.
• Schiff's reagent is decolorized by passing sulfur dioxide
through it.
• In the presence of even small amounts of an aldehyde
(from primary alcohol), it turns bright magenta.
• If the color does not change, or only a trace of pink
color formed within a minute or so, aldehyde does not
form and the compound is not a primary alcohol.
• Since the color change when treated with acidified
potassium dichromate (VI) solution, then the
compound is a secondary alcohol.
3. LUCAS TEST
Lucas test is used to differentiate between primary,
secondary and tertiary alcohols.
Type of Alcohols Observation with
Lucas Reagent
primary No cloudiness
secondary The solution turns cloudy within
five minutes
tertiary The solution turns cloudy
immediately