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14

Hydroxyl Compounds
Alcohols & Phenols

CONTENT
1

Introduction
1.1
Classification of alcohols
1.2
General formula
1.3
Nomenclature

Physical Properties of Alcohols and Phenols


2.1
Nature of the Hydroxyl Group
2.2
Boiling Points
2.3
Solubility in Water
2.4
Acidity of Alcohols and Phenols

Preparation of Alcohols
3.1
From Alkenes through Hydration
3.2
From Alkyl Halides through Nucleophilic Substitution
3.3
From Aldehydes and Ketones through Reduction
3.4
From Carboxylic Acids through Reduction

Chemical Reactions of Alcohols


4.1
Combustion
4.2
Halogenation
4.3
Dehydration
4.4
Reaction with Sodium Metal
4.5
Esterification
4.6
Oxidation
4.7
Tri-iodomethane (Iodoform) Formation

Chemical Reactions of Phenols


5.1
Reactions involving the breaking of O-H bond
5.2
Reactions involving the Electrophilic Substitution on the Benzene Ring
5.3
Complex Formation with neutral FeCl3 (aq)

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Independent
Learning
subtopic

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14 Hydroxyl Compounds

LEARNING OUTCOMES
Candidates should be able to:
(a)

recall the chemistry of alcohols, exemplified by ethanol:


(i)
(ii)
(iii)
(iv)
(v)

combustion
substitution to give halogenoalkanes
reaction with sodium
oxidation to carbonyl compounds and carboxylic acids
dehydration to alkenes

(b)

classify hydroxy compounds into primary, secondary and tertiary alcohols

(c)

suggest characteristic distinguishing reactions, e.g., mild oxidation

(d)

deduce the presence of a CH3CH(OH) group in an alcohol from its reaction with alkaline aqueous iodine to
form tri-iodomethane

(e)

recall the chemistry of phenol, as exemplified by the following reactions:

(f)

(i)

with bases

(ii)

with sodium

(iii)

nitration of, and bromination of, the aromatic ring

explain the relative acidities of water, phenol and ethanol

REFERENCES
1.

Peter Cann & Peter Hughes (2002). Chemistry for Advanced Level. Chapter 27.

2.

John McMurry (2004). Organic Chemistry. Brooks/Cole. Chapters 15-16.

3.

Philip S. Bailey, Jr. & Christina A. Bailey (2000). Organic Chemistry A Brief Survey of Concepts & Applications.
Prentice Hall. Chapter 6.

1
Introduction
Alcohols are compounds of the general formula ROH, where R is any alkyl or substituted alkyl group. All alcohols
contain the hydroxyl (OH) group, which, as the functional group, determines the properties characteristic of this
family of compounds.

CH3 OH

CH3
H

CH3CH2OH

HO
CH(CH3)2

Ethanol
Often
found
in
alcoholic
beverages and in modern
thermometers.

Crystal Cheong / Low YZ / Jolin Lim / Grace Chua

Menthol

Occurs naturally in peppermint


oil. It is well known for the
cooling sensation that it
provokes when inhaled, eaten
or applied to the skin.

HO
Estradiol

It is the predominant sex


hormone present in females. It
is an important hormone not
only on reproductive and sexual
functioning, but also affects
other organs including the
bones.

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14 Hydroxyl Compounds

Phenols are compounds in which the the hydroxyl (OH) group, is directly attached to an aromatic ring. Phenols differ
markedly from alcohols in both physical and chemical properties.

OH

1.1

Classification of alcohols

Alcohols can be subdivided into 3 different classes (similar to halogenoalkanes). An alcohol is classified as a primary,
secondary, or tertiary alcohol according to the kind of carbon that bears the OH group:

R = alkyl or aryl

Methanol, CH3OH, is classified as a primary alcohol.


1.2

General formula

Saturated aliphatic alcohols have the general formula CnH2n+1OH, where n is the number of carbon atoms.

Name

Structural formula

methanol

CH3OH

ethanol

CH3CH2OH

propan-1-ol

CH3CH2CH2OH

propan-2-ol

CH3CH(OH)CH3

Displayed formula

1.3
Nomenclature
Alcohols are named by replacing the terminal e of the corresponding alkane name with ol.

H
H C H
H

H
H C OH
H

Methane

Methanol

The longest carbon chain containing the hydroxyl group is considered the parent structure.

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14 Hydroxyl Compounds

Number the alkane chain beginning at the end nearer the hydroxyl group, and use the appropriate number to
indicate the position of the OH group.

OH
Heptan-3-ol

Number the substituents according to their positions on the chain, and write the name listing the substituents in
alphabetical order.

The OH functional group is named as a hydroxy substituent when it appears on a structure with a higher priority
functional group or when the structure is too difficult to name as a simple alcohol.

CH3

OH

CH

CH2 C

OH

3-hydroxybutanoic acid
Compounds that have a hydroxyl group directly attached to a benzene ring are called phenols.

Exercise 1
Name and classify the following alcohols or phenols.
CH3 OH

(i)
CH3

CH

(ii)
CH2 Br

OH

(iii)

CH2OH
Br

CH3

CH3

1-bromo-3,3-dimethylbutan-2ol
o
(2 alcohol)

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phenylmethanol
o
(1 alcohol)

5-bromo-2-methylphenol

(phenol)

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14 Hydroxyl Compounds

Physical Properties of Alcohols and Phenols

2.1

Nature of the Hydroxyl Group (*INDEPENDENT LEARNING SUBTOPIC*)

Alcohols and phenols have nearly the same geometry around the oxygen atom as water.

The oxygen atom has two lone pairs of electrons.

Oxygen is more electronegative than carbon and hydrogen

Hence, alcohols have polar CO and OH bonds.

2.2

Boiling Points (*INDEPENDENT LEARNING SUBTOPIC*)

Alcohols and phenols have significantly higher boiling points than those of the hydrocarbons with similar relative
molecular masses.
o

Compound

Mr

b.p. / C

Compound

Mr

b.p. / C

C2H6

30

-88

CH3OH

32

65

C3H8

44

-42

C2H5OH

46

78

C4H10

58

C3H7OH

60

97

C5H12

72

36

C4H9OH

74

118

C6H5CH3

92

111

C6H5OH, phenol

94

182

Comparison between alkanes and alcohols

The boiling point of an alcohol is higher than that of an alkane of similar relative molecular mass.

Reason: More energy is required to overcome the intermolecular hydrogen bonding in alcohols which is
stronger than the dispersion forces in alkanes.

Comparison within the homologous series


Boiling point of alcohols increases as the number of carbon atoms increases.
Hydrogen bonding is the main type of intermolecular forces between the OH groups. There are also
dispersion forces between the alkyl chains.
Hydrogen bonding will be similar for all the alcohols, while the strength of dispersion forces increases as the
alkyl chains get longer. These forces get stronger as longer molecules have more electrons and are more
polarisable.
Thus, more energy is required to overcome the dispersion forces, and so the boiling point increases.

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2.3

14 Hydroxyl Compounds

Solubility in Water (*INDEPENDENT LEARNING SUBTOPIC*)

Alcohols are more soluble in water compared to their corresponding alkanes due to their ability to form
hydrogen bonds with water molecules.

Solubility of alcohols in water decreases with increasing carbon number due to the increasing length of the
hydrophobic non-polar hydrocarbon chain.
CH3CH2CH2CH2CH2CH2 OH
non-polar

2.4

polar

Phenols are moderately soluble in water due to their large hydrophobic non-polar phenyl group; but dissolve
completely when warmed.

Acidity of Alcohols and Phenols


+

Alcohols and phenols dissociate to slight extent by donating a proton each to water, generating a H 3O and an

alkoxide ion, RO , or a phenoxide ion, C6H5O , respectively.


R-O-H + H2O R-O + H3O

Compound

CH3CH2OH

H2O

C6H5OH

pKa

16

15.7

10

As can be seen from the pKa values, CH3CH2OH is a weaker acid as compared to water, while phenol is a stronger acid
as compared to water.
2.4.1 Alcohols

CH3CH2

In alcohols, the OH bond can break to give H and RO (alkoxide ion). The extent of dissociation is lower
than that of water. Therefore alcohols do not turn litmus red.
H O
+ H+
hydroxide ion

CH3CH2 O
ethoxide ion

pKa = 15.7

H+

pKa = 16

Why do alcohols have lower acidity than water?

Alkyl groups are electron-donating and will intensify the negative charge on the alkoxide ion.

Thus the alkoxide ion is destabilized. Deprotonation does not take place as easily.
electron donating effect

H
CH3

C
H

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inductive effect of ethyl


of ethyl
group increases
group
increases
the
electron
density
on theon
the electron
density
oxygen
anion,
the
oxygen
anion,
destabilizing the anion

destabilizing the anion.

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14 Hydroxyl Compounds

2.4.2 Effect of Substituents on Acidity of Alcohols


The presence of electron-withdrawing groups (e.g., NO2, F, Cl, Br, I, COCH3, CO2H, CN, CO2R, NH2, OH,
OCH3) help to stabilize the alkoxide ion formed by dispersing the negative charge on the alkoxide ion, thus promoting
the ionisation process.
However, the presence of electron-releasing groups (e.g., CH3) decreases the acidic strength of alcohols by
intensifying the negative charge on the alkoxide ion, thus destabilising it.
CF3
CF3 C OH
CF3
nonafluoro-tert-butyl
nonafluoro-tert-butylalcohol
pK
pKaa==5.4
5.4

H
H C OH
H
methanol
pKa = 15.5

CH3
CH3 C OH
CH3
2-methyl-propan-2-ol
pKa = 18

Exercise 2
Arrange the alcohols in order of acid strength, giving your reasoning.
CH3CH2OH
In order of increasing acid strength:
(CH3)3COH <

CH2ClCH2OH

(CH3)3COH

(CH3)2CHOH

(CH3)2CHOH < CH3CH2OH < CH2ClCH2OH

Reasons:

The more stable the alkoxide formed, the stronger is the alcohol as an acid.

Alkyl groups are electron-donating, intensifying the negative charge on the alkoxide ion and thus
destabilizing it.

(CH3)3COH with three methyl groups, followed by (CH 3)2CHOH which has two methyl groups and CH3CH2OH
which has one methyl group.

Electron-donating effect on the alkoxide is most in (CH3)3COH followed by (CH3)2CHOH and then
CH3CH2OH.

CH2ClCH2OH has an electron-withdrawing group (chloro group) thus it disperses the negative charge on
alkoxide ion and stabilizes it.

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14 Hydroxyl Compounds

2.4.3 Phenol
3

Phenols are more acidic than alcohols. The pH of a 0.1 mol dm phenol solution in water is 5.4 so it will turn universal
indicator solution yellow.
CH3CH2

CH3CH2 O

O H

Ka = 1.0 x 10-16 mol dm-3

H+

Ka = 1.3 x 10-10 mol dm-3

H+

The negative charge on the phenoxide ion can be delocalised over the benzene ring as shown in the diagrams below.
This stabilises the phenoxide ion.

electron delocalization in phenoxide is represented by resonance among the structures

In the phenoxide ion, a p-orbital of the oxygen is able to overlap with the -orbital of the carbon atom in the ring. The
negative charge is able to spread around the benzene ring to some extent, thus the phenoxide anion is stabilised by
resonance. The phenoxide anion is less likely to accept a proton to form phenol. This makes phenols slightly stronger
acids than aliphatic alcohols.
2.4.4 Effect of Ring Substituents on Acidity of Phenols
Similar to alcohols, the presence of electron-withdrawing groups (e.g., NO2, F, Cl, Br, I, COCH3, CO2H, CN,
CO2R), in the ring enables the ring in turn to withdraw more electron density from the oxygen, thus stabilising the
phenoxide ion further and promoting the ionisation process.
OH
Cl

OH

OH

Cl

Cl

Cl

2,4,6-trichlorophenol
pKa = 7.6

4-chlorophenol
pKa = 9.4

phenol
pKa = 10

The presence of electron-releasing groups (e.g., CH3, NH2, OH, OCH3) decreases the acidic strength of phenols by
reducing the delocalisation of negative charge on oxygen into ring, and destabilising the conjugate base.
OH

OH

OH

CH3

benzene-1,4-diol
pKa = 10.35
Crystal Cheong / Low YZ / Jolin Lim / Grace Chua

4-methylphenol
pKa = 10.3

OH

phenol
pKa = 10
8

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14 Hydroxyl Compounds

Conclusions

Phenols are more acidic than water as the phenoxide ion can be stabilized by the delocalization of the negative
charge over the benzene ring.

Alcohols are weaker acids than water as alcohols have electron donating alkyl groups which intensify the negative
charge on the alkoxide ion, thus destabilizing it.

Electron-withdrawing groups stabilize the conjugate bases (i.e., alkoxide or phenoxide anions) formed by
dispersing the negative charge on the alkoxide or phenoxide ion, resulting in increased acidity.

Electron-donating groups destabilise the conjugate bases (i.e., alkoxide or phenoxide anions) formed by
intensifying the negative charge on the alkoxide or phenoxide ion, resulting in decreased acidity.

Exercise 3
Arrange the following phenols in order of acidity (1 for the most acidic, 5 for the least acidic).

Preparation of Alcohols

Alcohols occupy a central position in organic chemistry. They can be prepared from many other organic compounds
(alkenes, alkyl halides, aldehydes, etc.) and they can be transformed into an equally wide assortment of organic
compounds.

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3.1

14 Hydroxyl Compounds

From Alkenes through Hydration

There are two methods commonly used for the hydration of alkenes to form alcohols.
Industrial method

Laboratory method
1. Conc. H2SO4
2. H2O, warm

3.2

From Alkyl Halides through Nucleophilic Substitution (or Alkaline Hydrolysis)

Nucleophilic substitution of alkyl halides produces the corresponding alcohols in high yield.
RCH2 X

3.3

+ OH
heat under reflux

RCH2 OH + X

From Aldehydes and Ketones through Reduction

LiAlH4
in dry ether

LiAlH4
in dry ether

Reduction of aldehydes yield primary alcohols.

Reduction of ketones yield secondary alcohols.

Tertiary alcohols cannot be formed with this method.

For the reduction of aldehydes and ketones, the reducing agents used may be:
o Lithium aluminium hydride in dry ether
o hydrogen with nickel catalyst, high T & high P
o sodium borohydride (NaBH4) in methanol

3.4

From Carboxylic Acids through Reduction


LiAlH4
in dry ether

Reduction of carboxylic acids yield primary alcohols.

For the reduction of carboxylic acids, the only reducing agent used is:
o Lithium aluminium hydride in dry ether

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+ H2O

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14 Hydroxyl Compounds

Chemical Reactions of Alcohols

Alcohols are versatile starting materials for the preparation of a variety of organic compounds. Alcohols undergo
reactions involving various combinations of the cleavage of the CO and OH bonds of the hydroxyl group.

This bond is able to break


releasing H+ ions and the alcohols
are converted to alkoxides.
This bond is broken when alcohols
are subjected to acid-catalysed
dehydration or converted to alkyl
halides.
4.1

Combustion

Ethanol can be used as a fuel. It burns in air to form carbon dioxide and water.
CH3CH2OH(l) + 3O2(g) 2CO2(g) + 3H2O(l)
4.2

Hc = 1367 kJ mol

Halogenation

Alcohols can be converted to alkyl halides using many different methods. However, all these methods involve the
substitution of the OH group with the halogen atom via the breaking of the CO bond.

4.2.1 Using hydrogen halides


Tertiary alcohols are readily converted into alkyl chlorides by treatment of HCl.
Primary and secondary alcohols are much more resistant to the acid thus require a different treatment.
For tertiary alcohols only,

conc HCl

For primary and secondary alcohols,


For chlorination, anhydrous ZnCl2 is added as a catalyst and heating is required.
conc HCl / ZnCl2
heat

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14 Hydroxyl Compounds

For bromination, HBr is produced by heating solid NaBr in the presence of concentrated H2SO4. The acid serves as
both a catalyst and as a dehydrating agent, removing water as it is formed.
NaBr / conc H2SO4
heat

4.2.2 Using phosphorus halides


Phosphorus pentahalide:
Phosphorus pentachloride, PCl5, is a good chlorinating agent that reacts with alcohols to produce the respective
chloro-containing compound.

Reagents & Conditions: PCl5(s), room temperature


Observations:
Dense white fumes of HCl
(*good distinguishing test for the presence of the OH group*)
Phosphorus trihalides:

Reagents & Conditions:

Comments:

PCl3 (phosphorus trichloride), room temperature or


PBr3 (phosphorus tribromide), room temperature or
P, I2, heat
Phosphorus triiodide, PI3, is prepared in situ by heating red phosphorus
with iodine. Phosphorus tribromide can also be prepared in this manner.
2P + 3X2 2PX3

X = Br, I

4.2.3 Using Sulfur Oxide Dichloride, SOCl2 (Thionyl Chloride)


Another good chlorinating agent is thionyl chloride, SOCl2. When the alcohol is reacted with thionyl chloride the
corresponding chloro-compound is formed together with SO2 and HCl gases.

Reagents & Conditions: SOCl2(l), warm


Observation: SO2(g) and white fumes of HCl(g)
Comments:
both gaseous by-products are easy to separate from the
halogenoalkanes formed.

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4.3

14 Hydroxyl Compounds

Dehydration

+ H2O
Reagents & Conditions:

excess concentrated H2SO4, 170 C

Dehydrating agents and conditions:


o
o excess concentrated H2SO4, heated to 170 C
o Aluminium oxide, Al2O3, heat
Dehydration is only possible on molecules containing at least 1 hydrogen atom on the carbon atom adjacent to the
carbon atom with the hydroxyl group.

Dehydration cannot take place when there is no hydrogen atoms bonded to the carbon atom adjacent to the carbon
atom with the hydroxyl group.
Examples:
H
R H

C H

R C C H
R OH

OH

or

Sometimes a mixture of alkenes is formed, depending on the position of the hydroxyl group.
H H H
H H H
H H H
CH3

OH H

- H2O

CH3 CH
C3CH
C2CH=CH
C H2

Hbut-1-ene
but-1-ene

+ 3 C CCHC3CH=CHCH
CH
H
3
cis-but-2-ene
&
H
trans-but-2-ene
but-2-ene

Exercise 4
Give structures of all products formed when 1-methylcyclohexanol reacts with each of the following reagents.
(a) phosphorus pentachloride
(b) NaBr, conc H2SO4, heat
(c) hot concentrated sulfuric acid (excess)

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CH3

OH
1-methylcyclohexanol

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4.4

14 Hydroxyl Compounds

Reaction with Sodium Metal

Alcohols react with reactive metals such as sodium and potassium to form alkoxides together with hydrogen gas. This
reaction involves the breaking of the OH bond.

Reagents & Conditions:


Observation:

Na(s), room temperature


Slow effervescence of hydrogen gas

In this reaction, the alcohols act as acids. The reaction is similar to that of sodium with water except that it is much
+
slower (ethanol is a much weaker acid than water). This reaction shows that alcohols have replaceable H . However,
they are not acidic enough to either react with alkalis (e.g., NaOH) or liberate CO2 from carbonates.
4.5

Esterification

Alcohols react with carboxylic acids and acyl chlorides to form esters in a condensation process.
4.5.1 With carboxylic acids

heat under reflux

Reagents & Conditions: Carboxylic acid and alcohol with few drops of conc. H2SO4,
heat under reflux
Observation:
Sweet smelling liquid formed

This reaction is slow and reversible. Concentrated sulfuric acid acts as both a catalyst as well as a dehydrating agent.
4.5.2 With acyl chlorides

Reagents & Conditions: Acyl chloride and alcohol, room temperature


Observations:
Sweet smelling liquid formed, white fumes of HCl observed

This reaction is very rapid due to the high reactivity of the acyl chloride and does not require heating.

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4.6

14 Hydroxyl Compounds

Oxidation

For the oxidation of alcohols, the alcohols must have at least one hydrogen atom bonded to the carbon atom to
which the hydroxyl group is attached.

Two common reagents and conditions used for the oxidation of alcohols:
o

K2Cr2O7 / dilute H2SO4, heat

KMnO4 / dilute H2SO4, heat

The product of oxidation is governed largely by the type of the alcohol.

4.6.1 Oxidation of Primary Alcohols


Primary alcohols are readily oxidised to aldehydes on heating. With excess oxidising agent, the reaction proceeds
further, yielding the carboxylic acid.

Oxidation to aldehydes

Controlled oxidation of primary alcohols yields aldehydes.

Once the aldehyde is formed in the reaction vessel, it will come into contact with more oxidant and this will
lead to further oxidation to form carboxylic acid. This can be avoided by distilling the aldehyde away from
the reaction mixture as soon as it forms. This is possible as the aldehyde lacks intermolecular hydrogen
bonding and thus has a lower boiling point than the corresponding alcohol.

Figure 1. Experimental setup for


the distillation of aldehydes by
oxidising
primary
alcohols.
(Diagram taken from Chemistry for
Advanced Level by P. Cann and P.
Hughes; Hodder Murray)

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14 Hydroxyl Compounds

K2Cr2O7 / dilute H2SO4


heat with immediate distillation

Reagents & Conditions:


Observations:
Comment:

K2Cr2O7, dilute H2SO4, heat with immediate distillation


2
3+
Orange solution (Cr2O7 ) turns green (Cr )
Only K2Cr2O7 is selective enough to oxidise primary
alcohols to the aldehydes, whereas KMnO4 will simply
oxidise them to the carboxylic acids.

Oxidation to carboxylic acids


To obtain carboxylic acids from primary alcohols, the reacting solution needs to be heated under reflux. This allows
the alcohol to be converted to carboxylic acid.

K2Cr2O7 / dilute H2SO4


heat under reflux

Reagents & Conditions:


Observations:

Crystal Cheong / Low YZ / Jolin Lim / Grace Chua

K2Cr2O7/dil H2SO4 or KMnO4/dil H2SO4, heat under reflux


2
3+
Orange solution (Cr2O7 ) turns green (Cr ) or

2+
Purple solution (MnO4 ) turns colourless (Mn )

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14 Hydroxyl Compounds

4.6.2 Oxidation of Secondary Alcohols


Secondary alcohols are oxidised to ketones which are resistant to oxidation.

K2Cr2O7 / dilute H2SO4


heat under reflux

Reagents & Conditions:


Observations:

K2Cr2O7/dil H2SO4 or KMnO4/dil H2SO4, heat under reflux


2
3+
Orange solution (Cr2O7 ) turns green (Cr ) or

2+
Purple solution (MnO4 ) turns colourless (Mn )

4.6.3 Oxidation of Tertiary Alcohols

Tertiary alcohols have no hydrogen on their hydroxyl-bearing carbon and thus are not oxidized.

However, in the presence of strong oxidising agents at elevated temperatures, the oxidation of tertiary
alcohols leads to the cleavage of various carbon-carbon bonds at hydroxyl-bearing carbon atom, resulting in a
complex mixture of products.

Exercise 5
Draw the structures of the organic compounds formed by oxidation of each of the following compounds.
K2Cr2O7 / dilute H2SO4

(a)
heat under reflux

KMnO4 / dilute H2SO4


heat under reflux

O
O
HO

O
OH

CH3

(b)

K2Cr2O7 / dilute H2SO4

heat with distill

KMnO4 / dilute H2SO4

CO2H
CO2H

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4.7

14 Hydroxyl Compounds

Tri-iodomethane (Iodoform) Formation

Reagents & Conditions:


Observation:

I2 (aq), NaOH(aq), warm


Yellow ppt (CHI3) formed

This reaction can only take place for an alcohol containing a methyl group and a hydrogen atom attached to
the carbon with the hydroxyl group.

R group can be a hydrogen atom or a hydrocarbon group (alkyl or aryl).

Ethanol (R = H) is the only primary alcohol that gives positive tri-iodomethane test.
The tri-iodomethane reaction is also a method of breaking a CC bond and removing a methyl, CH3 group. It is
therefore a useful method of shortening a carbon chain by a single carbon atom (step-down reaction).
Examples:
H

I2 (aq)
/ NaOH
(aq)
aq
alkaline
iodine
CH3

H
CHI3

warm

+
O

OH

CH2CH3
CH3

I2 (aq)
/ NaOH
(aq)
aq
alkaline
iodine

CH3CH2
CHI3

warm

OH

Exercise 6
Which of the following alcohols give positive tri-iodomethane reaction?

OH

OH

OH
OH

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Answer: A & D

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14 Hydroxyl Compounds

Exercise 7
The video clip, (http://www.youtube.com/watch?v=W4gmxGHIwIs), shows the reactions of four organic
compounds, labelled as A, B, C and D.
The compounds are ethanol, propan-1-ol, 2-methylpropan-2-ol and cyclohexene but not necessarily in that order.
Watch the video and identify the compounds from your knowledge of the reactions of organic compounds that you
have learnt.

Reaction with Na
Reaction with hot
acidified K2Cr2O7
Tri-iodomethane
test

A
Effervescence
Solution remains orange
2-methylpropan-2-ol
x

B
No effervescence
cyclohexene
x
x

C
Effervescence

D
Effervescence

Orange solution
turns green
Yellow ppt
ethanol

Orange solution turns


green
No ppt
propan-1-ol

Chemical Reactions of Phenols

Phenols are compounds containing a hydroxyl group attached to an aromatic ring.


o

Most phenols are colourless solids. The melting point of phenol is 42 C. The presence of hydrogen bonds makes the
melting point of phenols higher than those of hydrocarbons of comparable relative molecular mass.
There are two sites for reaction to take place in phenol:

O
H
A comparison with alcohols
Phenols
Breaking of C-O bond

More difficult than alcohols

Breaking of O-H bond

More readily than alcohols

Why is the breaking of C-O bond for phenol more difficult than alcohols?
The C-O bond in phenol is very strong, due to the delocalisation of the lone pair of electrons on the oxygen over the
benzene ring.
This gives rise to the partial double bond character and thus strengthens the C-O bond.
Hence, for phenols, there are no reactions in which the C-O bond breaks, unlike the case of alcohols.
Thus, phenols do not react with PCl5 or SOCl2 or HCl or HBr.
The absence of fumes of HCl on adding PCl5 to phenols clearly distinguishes a phenol from an alcohol.

Why does the breaking of O-H bond for phenol occur more readily than alcohols?
See Section 2.4.3.

Crystal Cheong / Low YZ / Jolin Lim / Grace Chua

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Hwa Chong Institution 2013

5.1

14 Hydroxyl Compounds

Reactions involving the breaking of O-H bond

5.1.1 Reaction with Sodium Metal and Sodium Hydroxide


Phenols reacts with reactive metals to yield the phenoxide ion and hydrogen gas. Phenols are also acidic enough to
react with bases like NaOH to give salt and water. This is seen as a cloudy solution in water dissolving in aqueous
NaOH to form a homogeneous colorless solution.

With metals

+ Na

With bases

+ NaOH

+ H2

+ H2O

However, phenol is not acidic enough to liberate CO2 from carbonates.


Comparison of reactions of Alcohols and Phenols with Na, NaOH and Na 2CO3
Reaction with

Alcohols

Phenols

Sodium metal

Alkali (e.g. NaOH)

Carbonates (e.g. Na2CO3(aq))

5.1.2 Esterification
With carboxylic acids
Phenols do not react with carboxylic acids to form esters as they are weaker nucleophiles than alcohols. This is due to
the delocalization of the lone pair of electrons on the oxygen atom into the benzene ring. Hence, phenol is not
nucleophilic enough to undergo esterification in the usual way (that is, by heating with a carboxylic acid in the
presence of a few drops of concentrated H2SO4)
With acyl chlorides
Phenoxides can react with acyl chlorides to form esters.
O

Cl
+

O
O

O
propanoyl chloride

Reagents & Conditions:

Crystal Cheong / Low YZ / Jolin Lim / Grace Chua

+ Cl-

phenoxide
phenoxide
(form from
Formed
fromphenol
phenolwith
withNaOH)
NaOH

phenyl propanoate

Acyl chloride and phenoxide, room temperature

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Hwa Chong Institution 2013

14 Hydroxyl Compounds

Phenol is first converted to the phenoxide salt by reacting with Na(s) or NaOH(aq) to form phenoxide ion, a stronger
nucleophile, before reacting with the acyl chloride to form the ester. This will give a high yield.

OH

OH -

H2O

Cl -

Cl

Reaction may also occur between phenol and acyl chlorides directly. However, this will give a lower yield.

5.1.3 Oxidation
Phenols are not oxidized because they do not have a hydrogen atom on the hydroxyl-bearing carbon.
5.2

Reactions involving the Electrophilic Substitution on the Benzene Ring

Due to the delocalisation of the lone pair of electrons of oxygen into the benzene ring, the electron density in the ring
is greatly increased, making phenol much more susceptible to electrophilic attack than benzene. Hence, the presence
of the OH group highly activates the benzene ring towards electrophilic substitution and no catalyst is required.
The hydroxyl group on phenol is 2, 4 directing.
5.2.1 Bromination
With aqueous bromine (bromine water)
Phenol reacts with aqueous bromine at room temperature without the need of a Lewis acid catalyst (e.g., FeBr 3) to
produce a white precipitate of 2,4,6-tribromophenol.

Reagents & Conditions: Aqueous bromine (bromine water), room temperature


Observation:
Yellow-orange solution decolourised and white ppt formed.

Crystal Cheong / Low YZ / Jolin Lim / Grace Chua

21

Hwa Chong Institution 2013

14 Hydroxyl Compounds

With liquid bromine in organic solvent


Monobromination of phenol can be achieved by carrying out the reaction in a non-polar organic solvent (such as CCl4)
at low temperature, conditions that reduce the electrophilic reactivity of bromine.

Reagents & Conditions:


Observation:

Liquid bromine in inert organic solvent, room temperature


Reddish-brown solution decolourised

5.2.2 Nitration
With dilute HNO3
Phenols react with dilute HNO3 at room temperature to yield mono-substituted nitro compounds.
With concentrated HNO3
Phenols react with concentrated HNO3 (without concentrated H2SO4) at room temperature to yield a tri-substituted
product.

Reagents & Conditions:


Comment:

5.3

conc. HNO3 / dilute HNO3, room temperature


To achieve di-substitution, moderately concentrated HNO3 may
be used.

Complex Formation with neutral FeCl3 (aq)

Phenol reacts with neutral aqueous iron(III) chloride to form a violet complex.

Reagents & Conditions: neutral FeCl3(aq), room temperature


Observation:
Violet complex formed

This reaction is used as a characteristic test for the presence of phenolic group. The colour of the complexes may
vary slightly if other substituents are attached to the ring.
Crystal Cheong / Low YZ / Jolin Lim / Grace Chua

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