L.S.T. Leung Chik Wai Memorial School chapt. 34: p.

1
F.6 Chemistry
Chapter 34: Hydroxy-Compounds 羥基化合物

HYDROXY—COMPOUNDS (ALCOHOLS AND PHENOLS)

I. Introduction

(A) Alcohols

Alcohols are compounds containing one or more hydroxyl groups (—OH) attached to a
saturated carbon atom.
The saturated carbon may be a carbon or a simple alkyl group.

Monohydric aliphatic alcohols — alcohols containing one hydroxyl groups.

Examples:
CH3

CH3CH2 CHCH3 H3C CCH3

CH3CH2OH OH OH
ethanol ________________________ ______________________

Polyhydric aliphatic alcohols — alcohols containing two or more hydroxyl groups

Examples:

CH2 CH2 CH2 CH2 CH2 CH2 CH CH2

OH OH OH OH OH OH OH

__________________ ___________________ _____________________

Note <1> The saturated carbon atom which is attached to the hydroxyl group can be of an alkenyl
or alkynyl group.
Examples

CH2=CHCH2CH2OH OHCH2C CH ClCH2CH=CHOH

___________________ _____________________ ____________________

<2> The carbon atom may be attached to the side chain of a benzene ring.

CH3

CH2OH CH3 CH2CH2OH

OH

_____________________ ________________________ _____________________

(B)Phenols (Aromatic alcohols or alcohols)

Phenols are compounds in which the hydroxyl group is directly attached to the benzene ring.

Examples:
Br

OH OH O2N OH
 L.S.T. Leung Chik Wai Memorial School chapt. 34: p.2
F.6 Chemistry
Chapter 34: Hydroxy-Compounds 羥基化合物

II. Preparation of Alcohols

(A) Hydrolysis of halogenoalkanes through (SN) reaction

— to prepare primary and secondary alcohols from a primary and secondary halogenoalkanes.
Mechanism:

CH2 Br Slow HO CH2 Br

HO CH2
OH- +
CH2 CH3 CH2CH3
CH2CH3

Note: Tertiary alkvl halides undergo ELIMINATION too easily to be of use for synthesizing
tertiary lcohols.

(B) Reduction of aldehydes or ketones

— to prepare primary and secondary alcohols from an aldehyde and a ketone (both contain the
carbonyl group >C=O

1. Reduction by using hydrogen gas under high pressure with Pt or Ni as catalyst

R high pressure R
C O + H2 CH OH

R R

2. Reduction by using Lithium tetrahydridoaluminate (LiAlH4) which can release hydride ion (H-)

+
R H R
R
H + C O CH OH
CH O

from LiAlH4 R
R from dil. acid R

Note : <1> Since LiAlH4 reacts violently with water, it is necessary to use an inert solvent such as
ether (ethoxyethane). Hydrolysis of the intermediate b dilute acid gives the
desired alcohol.
<2> A less powerful reducing agent, sodium tetrahydridoborate (NaBH4) can also be used. It
is more convenient because it can be used in aqueous or methanolic solution.

R NaBH4 R
C O CH OH
methanol / water
R R

Example:

1
. LiAlH4 / dry ether
CH3CH2CHO
2. H3O+
 1. LiAlH4 / dry ether
O

2. H3O+

O 1. LiAlH4 / dry ether

HOOCCH2 C CH3
. H3O+
2

O O . LiAlH4 / dry ether

1

CH3O CCH2 C CH3

2
. H3O+

Note : LiAlH4 can also reduce carboxylic acid, acid chloride, acid anhydride and esters groups
to alcohols.

(C) Hydration of Alkenes

— to prepare secondary and tertiary alcohols from alkenes.

In the presence of acid catalyst, water can be added onto an alkene to form a secondary or a
tertiary alcohol (except for ethene) . The reaction reversible and the mechanism is just the
reverse of that for dehydration of an alcohol.

Mechanism:

H H OH2
+
H H H H
H +
H C C H H C C H H C C H
+
H H O H OH
H H

In practice. the alkene is bubbled into conc. sulphuric acid to form an alkyl
hydrogensulphonate. When this is diluted with water and distilled, an alcohol is formed:

CH2=CH2 + H2SO4  CH3CH2HSO4

CH3CH2HSO4 + H2O  CH3CH2OH + H2SO4

(D) Hydrolysis of Esters with alkali

— to prepare prinary, secondary and tertiary alcohols
Example:
CH3COOC2H5 + NaOH 
(E) Oxidation of alkenes by alkaline KMnO4
— to prepare a diol from alkenes.
Example :ethane-1,2-diol can be prepared by bubbling ethene into alkaline potassium
 manganate(VII) solution.

KMnO4 / OH-
H2C CH2 H2C CH2
OH OH
III. Preparation of phenol
(A) By fusion of sodium hydroxide with the sodium salt of benzenesulphonic acid :
SO2ONa +
O Na
+
NaOH + Na2SO3

Phenol is then released from sodium phenoxide with dilute acid:

+
O Na OH
+
+ H

(B) By warming of an aqueous solution of benzene-diazonium chloride

(a common laboratory method)
+
N N Cl OH

+ H2O + N2 + HCl

(C) By the hydrolysis of chlorobenzene with sodium. hydroxide, under he drastic conditions of 150
atm. and at 400 0C
(an industrial method)

+
Cl O Na + OH
2 NaOH
H

IV. Reactions of Alcohols and Phenols : Basic consideration

Both alcohols and phenols contain the hydroxyl group (—OH) However, as this group is
attached to the benzene ring for phenols and to the saturated Carbon for alcohols. the reactions
of such compounds are quite different.
(A) Reactions of Alcohols

There are two main types of reactions for alcohols:

1. Reactions involving fission of R—OH bond (or just C—O bond)

C O H alkyl hydroxy fission

2. Reactions involving fission of RO—H bond (or just O—H bond)

alkoxy hydrogen fission

C O H

(B) Reactions of phenols

There are two main types of reactions for phenols:
1. Reactions involving the —OH group.

2. Reactions involving the benzene ring.

Note : For phenols. the direct attachment of a hydroxyl group to the benzene ring has mutual
effects on the reactivity of both the —OH group and the benzene ring.
The electron—rich benzene ring in phenol can make it undergo electrophilic aromatic
substitution.
The reactivity of the —OH group can also be modified by the benzene ring through
delocalization effects.

V. Reactions of Alcohols

(A) Reaction involving fission of R—OH bond (cleavage of C—0 bond)

1. Dehydration
(a) intramolecular dehydration (forming alkene)

The conditions for dehydrating alcohols depend closely on the structure of individual alcohols.
<i> For primary alcohols, the conditions required are conc. sulphuric acid a temperature of
1700C
CONC. H2SO4
CH3CH2OH CH2=CH2 + H2O

1700C

<ii> Secondary alcohols dehydrate under milder conditions than primary alcohols.

OH
85 % H3PO4
+ H2O

165 – 1700C

<iii>Tertiary alcohols dehydrate under even milder conditions.

 CH3
20 % H2SO4
H3C C OH H3C C CH2

CH3 CH3

Mechanism:
For secondary and tertiary alcohols, the following mechanism is generally accepted.

+
C C + H
H OH

Note : <1> The main function of the acid is to transform the poor leaving group —OH into the very
good leaving group. —OH2

<2> The ease of dehydration of alcohols is

tertiary > secondary > primary

Reason : Tertiary carbocation is the most stable one.

i.e. The order of stability of the carbocations follows the number of electron
releasing groups

CH3 H H H
+ + + +
H3C C H3C C H C H C
CH3 CH3 CH3 H

most stable least stable

 <3> Dehydration of secondary and tertiary alcohols containing more than three carbon atoms
will give a mixture of alkenes whose amounts will be determined by the following rule
Alcohol dehydrations generally produce the more highly substituted alkenes.
i.e. the major product is that contains the higher number of alkyl groups attached to the
C=C bond.
e.g.
+
CH3 CH CH2CH3 H -H2O
CH3 CH CH2CH3 +
+ CH3 C CH2CH3
OH O H
H H

(a) Intermolecular dehydration (forming ether)

When the dehydration is carried out at a temperature of 1400C with an excess of alcohol. ether will
be formed.
CONC. H2SO4
2 CH3CH2OH CH3CH2OCH2CH3 + H2O

2. Halogenation
Alcohols react with hydrogen halide and phosphorus halides give halogenoalkanes.

(a) Reaction with hydrogen halides

Mechanism:

Step1: Protonation of the alcohols (same process for 1°, 2° and 3° alcohols)
The alcohol acts as a weak base and accept the proton donated by the hydrogen halide.
The equilibrium lies well
+
ROH + H R O
+
H
H
Step 2 : Displacement the halide on for a water molecule.

<i> For primary and secondary alcohols, it is a SN2 reaction.

+ R-CH2-X
X RCH2 O H
H
<ii> For tertiary alcohols, it is a SN1 reaction.
R
+
+
R3C O H C
R R
H
R
R
+
X C C
R
R R X R
 Note <1> Secondary alcohols also proceed through a mechanism involving the formation
of carbocation.
<2> Reactions of primary and secondary alcohols with hydrogen halide are catalysed
by zinc chloride in the Lucas reagent. (a solution of ZnCl2 in conc. HCI).

+ HCl Reflux +
C2H5OH C2H5Cl H2O
ZnCl2 Catalyst
Example Chlorination of 2-methylpropan-2-ol in a solution of ZnCl2 and conc. HCl

(i) Mechanism for this reaction : ( a ____ reaction )

(ii) Energy profile for this reaction:

(iii) Rate of the reaction for 10 , 20 and 30 alcohols:

The order of rates of reaction:

30 alcohol > 20 alcohol > 10 alcohol

The rate can be shown by the turbidity in the aqueous layer since the
chloroalkane formed is immiscible with water.

(iv) Dependence of the chloride anion concentration.

For tertiary alcohols, the rate is independent of the concentration of chloride
ion because it is a SN1 reaction.

Example: Bromination of ethanol in a mixture of conc. H2SO4 and solid NaBr

conc. H2SO4 / NaBr

C2H5OH C2H5Br + H2O
heating
 (b) Reaction with phosphorus halides

Alcohols react with phosphorus tribromide and phosphorus tri iodide to form bromo— and
iodoalkanes respectively.

+
3 R-OH PBr3 3 R-Br + H3PO3

3 R-OH + PI3 + H3PO3

3 R-I

Note :<1>The phosphorus trihalides are prepared by the reaction of red phosphorus and the halogen.

<2> Phosphorus pentahalide or thionlychloride are used to prepare chloroalkanes at room

temperature
R-OH + PCl5 R-Cl + HCl + POCl3

R-OH + SOCl2 R-Cl + SO2 + HCl

Exercise : -
The following apparatus is used to prepare bromoethane (b.p. 38”C) from ethanol; using red
phosphorus and bromine.

(a) What advantage is there in using red phosphorus instead of white phosphorus?
(b) What is the purpose of the soda lime tube?
(c) Why is a water condenser included in the set-up.
(d) Explain why a cold water bath is used while bromine is added?
(e) The mixture has to be refluxed for 30 minutes after addition of bromine. Why?

After the heating process the apparatus is converted for distillation and he product is collected in
a receiver immersed in cold water. The distillate is then washed with water before drying.

(f) How can you tell when the distillation is complete?

(g) Suggest one impurity that can be removed by washing with water.
(h) Give the name of a drying agent for bromoethane.
(I) What further treatment is required in order to obtain pure bromoethane?
(j) What would you do when setting up the apparatus and reagents, bromine liquid is
accidentally split on our hand?
(B) Reaction involving fission of RO—H bond (cleavage of O—H bond)

1. Reaction with active metals (e.g. sodium)

Alcohols are very acids because the alkyl group pushes electrons towards the —OH group, so
that the oxygen does not strongly attract the electrons in the —OH bond.

Furthermore. once a RO- ion is formed. it cannot be stabilized by the delocalization of the
charge. Thus. alcohols react only to a very slight extent with alkalis, but will react wtth very
electropositive metals under anhydrous conditions to give alkoxide.

Example: reaction of ethanol with sodium

2CH3CH2OH + 2Na  2CH3CH2O- Na+ + H2

Addition of water will regenerate the alcohol readily.

CH3CH2O-Na+ + H2O  CH3CH2OH + NaOH

Note <1> The reaction is much slower then the reaction of water with sodium.

<2> The reaction of alcohol with sodium can be used to depose the excess sodium in
the laboratory.

2. Esterification

Alcohols and carboxylic acids react to give esters.The functional groups of acids and esters are
(where R is an alkyl group)

O O
C C
OH O-R

Carboxylic acid Carboxylic ester

Esterification takes place much faster in the presence of a catalyst such as conc. H2SO4.
Example :

conc. H2SO4 O
O
CH3CH2 C + CH3CH2OH CH3CH2 C + H2O
OH OCH2CH3
Reflux

Alcohols can also react with acid chlorides and acid anhydrides to form esters.

Example:
O O
CH3CH2 C + CH3CH2OH CH3CH2 C + HCl
Cl OCH2CH3
propanoyl chloride
O O
CH3CH2 C + CH3CH2OH CH3CH2 C + CH3CH2COOH
O OCH2CH3
CH3CH2 C
O
propanoic anhydride
3. Oxidation
Alcohols can he oxidized by various oxidizing agents to aldehyde, ketones or carboxylic acids.
depending on the nature of the alcohol and the strength of the oxidizing agents being used.

Oxidizing agents used:

Acidic or alkaline potassium permanganate, acidified potassium dichromate,
chromic acid or dilute nitric acid.

(a) Primary alcohols are readily oxidized through aldehydes to carboxylic acids.

O O
R-CH2OH C C
R H R OH
Primary alcohol Aldehyde Carboxylic acid

Note: The alcohol , aldehyde and acid preserve the same number of carbon atoms.

(b) Secondary alcohols are oxidized to ketones under normal conditions

Secondary alcohol Ketone

Note The ketone formed has to be undergo prolonged drastic treatment before it can be
broken down into acids with smaller number of carbon atoms.

OH O O O O
+
CH3 C CH3 CH3 C OH CO2
CH3 CH CH3

(c) Tertiary alcohols are normally resistant to oxidation in the neutral or alkaline medium.
because it would involve the breakage of the high energy C—C bonds in the alcohol
molecule.
CH3
H3C CH3 NO reaction
OH
In acidic solutions, tertiary alcohols can he oxidized to give a mixture of ketone and acid,
both with fewer carbon atoms
than the alcohol.
CH3
H3C + CH3COOH
H3C CH2CH3 O

OH H3C

Note: Characterization of the oxidation products of alcohols is a means of distinguishing

between primary , secondary and tertiary alcohols.
<1> The aldehyde may be detected by its reaction with 2,4-dinitrophenylhydrazine. Tollen’s reagent
or Schiff’s reagent.
<2> Ketones may be detected by its reaction with 2,4-dinitrophenylhydrazine but not with Tollen’s
reagent or Schiff’s reagent.
<3> Carboxylic acids can be detected by reaction with sodium hydrogencarbonate solutions or ester
formation.

Reactions of Ethanol, a Typical Aliphatic Alcohol

Ethoxyethane CH3CH2OCH2CH3 Ethene CH2=CH2

CH3CH2Cl

PCl5 / SOCl2 Sodium ethoxide CH3CH2ONa

conc. H2SO4

KBr / conc. H2SO4 Na

CH3CH2Br C2H5OH
+
Ethanal CH3CHO
K2Cr2O7 / H
CH3COCl
I2 + red P OR KMnO4
+
CH3COOH H
Ethanoic acid CH3COOH
CH3CH2I Ethyl ethanoate CH3COOCH2CH3
Iodo ethane

Methods of distinguishing between 10 , 20 and 30 alcohol

Reagents Primary alcohol Secondary alcohol Tertiary alcohol

Acidified Aldehyde, Ketone, No observable change
K2Cr2O7 RCHO formed R2CO formed
Solution change from Solution change from
orange to green orange to green

Conc. H2SO4 Alkene formed slowly Intermediate in speed Alkene formed fast

Conc. HCl Cloudiness due to Cloudiness appear in Cloudiness appears in

+ formation of RCl is slow 5 minutes 1 minute owing to
ZnCl2 to appear. the formation of RCl,
Add to alcohol and place which is insoluble in
in boiling water bath water
Exercise
1. Predict the main product in the following reactions.
(a) Primary alcohol added dropwise to acidified potassium permanganate.
(b) Acidified potassium permanganate added dropwise to the primary alcohol
ANSWER

2. (a) Write all possible structural isomers corresponding to the molecular formula C4H10O

(b) One of these isomers. X. has the following reactions. Deduce the molecular formula of
X from the following reactions. showing what structural information each
reaction conveys.
<1> X reacts slowly with sodium metal.
<2> Vigorous oxidation of X yields a product Y, without loss of carbon atoms.
<3> Y reacts with 2,4—dinitrophenylhydrazine to give a yellow crystal but not with sodium
metal.
<4> Dehydration of X gives a mixture of hydrocarbon A and B. each containing 85.7% of
carbon.
ANSWER
4. Haloform reaction
CH3
C OH
Alcohols which contain the group H can be oxidized under suitable conditions into the

C O
H3C
group . This group will readily undergo the haloform reaction:

CH3
NaOH / X2
RCOONa + CH3X
R C OH
H

Mechanism : The reaction takes place in following three steps.

1. Oxtdation of alcohol. to an aldehyde or ketone.

2. Substitution of halogen atoms in the methyl group.

3. Hydrolysis under alkaline conditions to form. the haloform

Note <1> The reaction is usually carried out with warm alkaline solution of halogen (NaOH/X2) or
a solution of potassium halide and sodium halate(I) (KX/NaOX).

In the Iodoforrrt reactton, the triiodomethane precipitates as yellow crystals. The

reaction mechanism can be described as follow:

CH3 H3C
+
R C OH + I2 + NaOH C O + NaI H2O
H
R
I2 + NaOH

RCOONa + CH3X

<3> Ethanol and 2 alcohols can be distinguished from the other alcohols by using iodoform test
because the triiodomethane formed is a yellow crystal.
Exercise
When an alcohol A is refluxed with conc. H2SO4, at 170°C. compound B is formed as the major
product. If B is treated with ozone and then hydrolysed by water. 2 organic products are formed. one is
ethanal and the other is propanal. A gives a positive iodoform test. Deduce the structures and give the
names of A and B.
ANSWER
VI. Reactions of Phenols

1 Reactions of phenols can he classified into:

(A) those involving the -OH group
(B) those involving the benzene ring attached to it

(A) Reactions of the —OH group

1. Dissociation (Acidic properties — salt formation)

Phenol can dissociate in water

OH
O

+ H2O + H3O+

It behaves as a weak acid because its dissociation occurs to only a light extent
(pKa = 10.0)

Thus, phenol can react with sodium metal

+
OH O Na

2
+ Na
2 + H2

Unlike alcohol, it can react with NaOH and is a stronger acid than alcohol.

Note : <1> Explanation of the higher acidity of phenol than aliphatic alcohol.

In phenol. the O—H bond breaks more readily and the resultant phenoxide anion is
stabilized by resonance.

In the phenoxide ion, a p orbital of the oxygen atom overlaps with the  orbital of the ring
carbon atoms.

Therefore. the equilibrium favours dissociation of phenol into H3O+ and the phenoxide ion.
Thus it can be seen that owing to the direct attachment to the benzene ring. the acidity of phenol
is greatly enhanced by resonance. and is very different from aliphatic alcohol.
<2> The phenoxide ion formed from the reaction of phenol with alkalis can act as a powerful
nucleophile and can be used in the synthesis of certain organic compounds.

OH ONa
+ NaOH + H2O

<3> When comparing the acidity with carbonic acid and carboxylic acid, phenol is the weakest.

Methods to distinguish between alcohols, phenols, and carboxylic acid:

(a) Carboxylic acid can liberate CO 2 when treated with sodium hydrogen carbonate solution
whereas alcohols and phenols cannot.

(b) Phenols can react with NaOH to give a salt whereas alcohols cannot.

Example: A scheme outlining the chemical reactions of the following compounds A, B and C is
listed as below:
OH

CH3CH2OH CH3COOH

A B C

Mixture of A, B and C in ethoxyethane is shaken with NaHCO3 solution.

separate

Ethereal layer Aqueous layer

Shaken with aq.

NaOH, then acidify with dil.HCl,
separate extract with ether
again,
evaporate ether

A
Aqueous layer Ethereal layer

Add H+aq, then Evapourate ether

filter
C B
2. Other reactions of the –OH group
As stated before, the –OH group of phenol behave differently from those of aliphatic alcohols,
as a result of the delocalization of electrons with the benzene ring directly attached to it.

OH

The resonance effect strengthens the C-O bond, the partial double bond character between the
carbon atom and the oxygen is confirmed by its bond length being shorter than that of normal C
—O bond.

Thus, Reactions of the —OH group of phenol are quite different from that of alcohol:

(a) Displacement of the —OH group by halogen, pcurs only at more extreme conditions.
(b) Phenol is not oxidized to some breakdown products but form complex polymers.
(c) Phenols does not undergo elimination as primary and secondary alcohol do.

In alkaline medium, phenol generate the phenoxide ion C6H5O-. Such anion is a more powerful
nucleophile than /the neutral phenol molecule, and can take place in some nucleophilic reactions.

+
OH O Na
NaOH

room temp.

O
H3C
O
CH3CH2Br CH3COCl
H3C
O
OCH2CH3 OOCCH3 OOCCH3

Note : The reaction between sodium phenoxide and bromoethane is a typical SN2 reaction in
which the rate depends on the availability of electron pairs at oxygen.

O
CH3CH2Br

If there is an electron withdrawing group (e.g. —NO group) attached to the benzene
ring, the rate will be reduced.

O
N O
O
(B) Reactions of the benzene ring — Substitution

Phenol is more reactive than benzene towards electrophilic reagents because there is an
interaction between the lone pairs on the oxygen atom in —OH or —O and the ring; which
increase the availability of electrons in the aromatic ring.

Note : The greater activity of the ring in phenol than in the simple benzene molecule is
reflected in the milder

1. Nitration

Monosubstituted compound is obtained with dilute nitric acid at room temperature.

OH
dil. HNO3 OH OH
NO2
+

NO2
If conc. nitric acid is used. trisubstituted product is obtained readily.

OH
OH
dil. HNO3 O2N NO2

NO2
2. Halogenation (Bromination)
(a) Chlorine, in the absence of solvent, gives 2— and 4—chlorophenol.

(b) Bromine, in a non—polar solvent (e.g. CS2 or CCl4) gives 2— ,4—bromophenol.

OH
OH OH
CS2 Br
+ Br2 +

Br
(c) Bromine water gives a precipitate of 2,4,6—tribromophenol.

The faster reaction in water is due to the presence of phenoxide ions.

OH
OH
Br Br

+ Br2

Br
 3. Sulphonation

When phenol is treated with concentrated sulphuric acid. different substituted products will
result, depending on the reaction temperature.
OH
OH SO3H

OH

SO3H
Exercise
Arrange the following compound in order of increasing rate of reaction with concentrated
sulphuric acid. Give reasons for your order.
OH OH

CH3
VII. Alkanediols

Alkanediols are examples of polyhydric alcohols which contain more than one —OH group in
their structures.

Example 1 : Ethane-1,2-diol (ethylene glycol)

(A) Preparation

Ethene is bubbled into alkaline solution of potassium manganate(VII), the purple fades out
as ethene ids oxidized to ethane—1 . 2—diol.
+
MnO4- H
CH2=CH2 CH2 CH2
OH OH

A brown suspension of manganese (IV) oxide also appears.

(B) Properties

The properties are similar to those of monohydric alcohols.

(C) Uses 1
It as used antifreeze in car radiators and as a radiators and as a de-icing fluid on aeroplane
wings.

Note : Alkanetriols Propane—1.2,3— triol (glycerol)

It is the by—product in the manufacture of soap. Glycerol is used for the manufacture
of ester which it forms from nitric acid, propane—1,2.3—triyl trinitrate.

CH2 OH CH2 O-NO2

CH OH + 3 HNO3 CH O-NO2 + 3 H2O

CH2 OH CH2 O-NO2

glycerol 甘油 propane-1,2,3-triyl trinitrate 硝化甘油

This ester is also called nitroglycerine. It is used as both explosivee and a drug in
medicine to treat heart diseases.
 O
Br Br
OCH2CH3 OCOCH3

Br

Br2
CH3CH2Br +
O Na (CH3CO)2O
Cl
SO3Na
NaOH NaOH

+
OH- H
Conc. HNO3
OH N2Cl
OH
O2N NO2 OH
NO2 HNO3 H2O
Diazonium salt

NO2
Conc. H2SO4

OH

Cl2 In FeCl3
FeCl3
SO3H

OH
Soluble in NaOH, but
it does not react with NaHCO3 to give CO2

Violet colour (Test for a phenol)

Cl
Reaction of Phenol