CHAPTER 3

Hydroxyl Compounds: Alcohol & Phenol

OUTLINE
 Alcohol
 Structure
 Classification
 Physical properties (solubility, boiling point,acidity and basicity)
 Nomenclature
 Preparation
 Reactions
 Chemical tests to identify 1, 2 and 3 alcohols
 Sources and uses of alcohols

 Phenol
 Structure and physical properties
 Reactions
 Identification test with FeCl3(aq)
 Uses and importance of phenol
 Introduction (Structure)
 Alcohol (R-OH)
 a hydroxy group bound to an alkyl chain
general formula = CnH2n+1OH

 Phenol (Ar-OH)
 a hydroxy group bound to an aryl group
Classification of alcohols
H H H

H C OH H C C OH

H
H H
Methanol
1° alcohol
(methyl alcohol)
CH2CH3
CH3
H3C C OH

C OH

2° alcohol
3° alcohol
Physical properties of alcohols
a) Solubility
Alcohols of shorter number of carbon atoms are soluble in water (polar

solvent) and insoluble in non-polar solvent

Alcohols can form hydrogen-bond with water due to polar –OH group and

being a polar molecule it is soluble in H2O

However, as number of carbon increases, solubility of alcohols in water

decreases. (eg: decanol is not soluble in water)

b) Boiling point
 Alcohols have higher boiling points than alkanes or haloalkanes of

similar molecular mass

Ethanol, Mr = 46 Propane, Mr = 44
Boiling point = 78°C Boiling point = -42°C

 This is because alcohols form stronger hydrogen bond between

molecules.
 Polyhydric alcohols have higher boiling point and more soluble than
normal alcohols. This is due to extra-OH group which makes them
form stronger (more) hydrogen bond with molecules and with water

 Branching decreases boiling points of alcohols and boiling point:

3° alcohol < 2° alcohol < 1° alcohol.

Properties of Phenols
 Phenol is a crystalline solid and has a melting point of 43°C

 It has a strong characteristic smell and high boiling point (due to

strong hydrogen bond between molecules)

 It only sparingly soluble in water

 The –OH group in phenol forms hydrogen bonds to water, whilst the

benzene ring reduces the solubility because it forms only weak van der
Waals forces with another molecules

 When solid or liquid phenol comes into contact with the skin, causes

burns
Naming Alcohols and Phenols
 Alcohols are named by identifying the longest carbon to which the –

OH group is directly attached

 The suffix –ol is labelled at lower carbon

 The substituent are also placed at lower carbon and follow

alphabetical order.
a) Monohydric alcohols (contain only ONE-
OH group)
b) Unsaturated alcohol
c) Polyhydric alcohols- contain more than
one hydroxyl group
d) Phenol Compounds
 For phenol with at least 2 substituent, the rules followed are similar to

benzene/ arene compounds

Question Part 1
1. Arrange the following compounds according to decreasing boiling point:
OH
a) Br

b) Propane-1,2,3-triol, ethane-1,2-diol, ethanol

c) Butane, 2-methylpropane, 2-chlorobutane, butane-2-ol

2. Arrange the compounds below according to increasing solubility in water:

1-pentanol, butanoic acid, pentane

Preparation of alcohol
1. Industrial preparation of methanol

2. Fermentation of carbohydrates

3. Hydration of alkenes

4. Hydrolysis of haloalkanes

5. Addition of Grignard reagents to carbonyl compounds

1. Industrial preparation of methanol
 Methanol is an industrial chemical

 End uses: solvent, antifreeze, fuel

 Principal use: preparation of formaldehyde

 Prepared by hydrogenation of carbon monoxide

CO + 2H2 → CH3OH
2. Fermentation of carbohydrates
 Ethanol, CH3CH2OH can be made by fermentation of sugar in the

presence of enzymes (zymase) in yeast to form carbon dioxide as the

side product

z ym a se
C6H12O6 2CH3CH2OH + CO2
3. Hydration of alkenes
+
H2C CH2 + H2O/H CH 3CH 2OH


H3C +
CH2 + H2O/H ?

4. Hydrolysis of haloalkanes
Reagent: NaOH (or KOH) Conditions: Reflux
Reactivity: Iodoalkane > Bromoalkane > Chloroalkane

 Haloalkanes is more reactive (a stronger nucleophile) with aqueous

NaOH or KOH (under reflux) to form alcohol. The nucleophile is

hydroxide ion, OH-.
Nucleophilic substitution reaction
a) Bimolecular Nucleophilic Substitution (SN2)

 SN2 is a second order reaction whereby it is first order with respect to

each haloalkane and nucleophile.

The rate equation: Rate = k[RX][Nu‾]

 Nucleophilic attack occurs at the same time the leaving group

(halogen) leaves the molecule. Bond breaking of C-X (halogen) bonds
occurs simultaneously as the bond formation C-OH.

 SN2 favours methyl haloalkane 1°>2°>3° due to increasing steric factor.

Reaction mechanism
CH3-Cl + Na+OH- CH3-OH + Na+Cl-
b) Unimolecular Nucleophilic Substitution (SN1)

 SN1 ia a first order reaction whereby rate reaction only depends on the

concentration of haloalkane.

The rate equation; rate = k[RX]

 SN1 favours 3°>2°>1°>methyl haloalkane. Tertiary halolalkane (tertiary

carbocation) in which there are 3 electron donating groups which

make the carbocation stable.

 Consider the following reaction:

 Differences between SN1 and SN2
reactions
SN1 SN2
a) Carbocation is involved No carbocation is involved

b) Rearrangement is possible Rearrangement is not possible

c) First order reaction Second order reaction
d) 2 steps reaction 1 step reaction
e) Favours 3°>2°>1°> methyl Favours methyl > 1°>2°>3° haloalkane
haloalkane

f) Stearic factor is less important Steric factor is important

g) Weak nucleophile Strong nucleophile

5. Addition of Grignard reagents to
carbonyl compounds
Reactions of alcohols and phenols
1. Reaction with Na
2. Reaction with NaOH
3. Esterification
 with Carboxylic Acid
 with Acyl Chloride
4. Dehydration to form Alkene
5. Dehydration to form Ether
6. Oxidation
7. Halogenation
 Triiodomethane / Iodoform reaction
 Reaction with ZnCl2 and concentrated HCl
 Reaction with Phosphorus halide (PCl3, PCl5, PBr3, PI3) and SOCl2
 Reaction with hydrogen halide (HCl, HBr, HI)
8. Electrophilic Sustitution Reactions
9. Hydrogenation with Ni or Pt/H2 180°C
1. Reaction with Na
 Both alcohol and phenol react with Na to form sodium alkoxide and

hydrogen gas which will give ‘pop’ sound with glowing splinter

( A chemical test for alcohol)

Na + CH3OH NaOCH3 + 1
2
H2
sodium methoxide
 The reaction involves breaking of RO—H bond and they act as

Bronsted Lowry acid acid (proton donor). It involves heterolytic

cleavage.

 The reaction can be used as a chemical test for hydroxyl,-OH group

2. Reaction with NaOH
 Only phenol can react with NaOH to form sodium phenoxide and

water, involves breaking of RO-H bond. This involves heterolytic

cleavage

 This is because phenol is more acidic than aliphatic alcohols

3. Esterification : with carboxylic acid
 Alcohols react with carboxyllic acid in the presence of catalyst,

concentrated sulphuric acid under reflux to form ester and water. The
reaction involves breaking of bond

 Phenol DOES NOT react with carboxyllic acid to form ester.

Pharmaceutical Application
 The reaction can be applied in the preparation of methyl salycylate ( a

counter-irritant) which is an ESTER

 Methyl salicyclate is also present in ointment such as “minyak cap

kapak”
3. Esterification: with Acyl Chloride
 Both alcohols and phenols react with acyl chloride to form ester and

hydrochloric acid. The reaction is not reversible unlike esterification

with carboxyllic acid. Involves breaking of RO-H bond

 The advantages of this reaction is the yield of ester is higher and

reactions conditions are milder

Question Part 2
 Draw the structures of the esters produced in the following reactions:
a) Benzoic acid with cyclohexanol
b) 1,4-butanedioic acid (HOOCCH2CH2COOH) with methanol
c) Oxalic acid (HOOC-COOH) with phenylmethanol
d) Ethanoyl chloride with phenol in sodium hydroxide
e) Benzoic acid with 2-propanol

 Name the carboxyllic acids and alcohols from which each of the
following ester is derived:
a) HCOOCH3
b) CH3OOCCH2CH2COOCH3
c) COOCH3 d)
COOCH2CH=CH2
4. Dehydration: to form alkene
 Alcohols is dehydrated using conc. H2SO4 or conc. H3PO4 at 170°C to

form alkene and the water. The major product is predicted using
Saytzeff’s Rule
 Phenols DO NOT undergo this reaction

According to Saytzeff’s Rule; in elimination reactions, the

major reaction product is the alkene with the more highly
substituted (more stable) double bond.
Question Part 3
 Draw the structures of all possible alkenes formed (if any) when the

following alcohols are subjected to dehydration with excess

concentrated sulphuric acid. Where isomeric alkenes are possible,
predict which alkene is the major product:

a) CH3OH e) 1-phenylethanol

b) 2-propanol f) 4-methylphenol

c) 2-methyl-2-propanol g) 2-methylcyclohexanol

d) phenylmethanol h) 1,4-butanediol
5. Dehydration: to form ether (Williamson
synthesis)
 Involves the reaction of an alkoxide ion with a

primary alkyl halide via an SN2 reaction

R-OH + NaH R O-NA+ + H2

R O-NA+ + R-X R-O-R + NaX

Example :

CH3-CH2OH + NaH CH3CH2O-Na+ + H2

CH3CH2O-Na+ + CH3CH2Cl CH3CH2-O-CH2CH3 + NaCl

Question Part 4
Write chemical equations for all steps for the formation of following
ethers using any suitable reagents and condition by Williamson
synthesis:

a) Methyl propyl ether

b) CH2OCH(CH3)2
6. Oxidation
[O]
1° alcohol Carboxyllic acid

1° alcohol [O] Aldehyde

PCC

2° alcohol [O] Ketone

Phenol & 3° alcohol [O] Cannot be oxidized

Oxidising agents : Acidified warm potassium manganate (VII),

Acidified warm sodium dichromate (VI) or
PCC (pyridinium chlorochromate)

HOWEVER, PCC can oxidized 1° alcohol ONLY until aldehyde

 Final
product

This reaction can be used as a chemical test for alcohols

Question Part 5
1. Draw the structures of the products formed (if any) when the following
compounds are heated with acidified potassium permanganate (VII).
2. Show how you would differentiate between the following pairs of
compounds:
7. Halogenation: Triiodomethane / Iodoform
reaction
 This reaction can be used as a chemical test for some alcohols

R C CH3
 Alcohols with general structure, show positive result (yellow
OH

precipitate of CHI3, triiodomethane) when reacted with iodine, I2 in

alkaline solution, NaOH

( R=H/ phenyl/any carbon chain)

Only B and C give yellow precipitate with iodine in alkaline solution.
Phenol DOES NOT give positive result with triiodo methane test.
Question Part 6
 State whether the following Alcohols will give a positive or negative iodoform test:
 Methanol
 Ethanol
 1-Propanol
 2-Propanol
 2-Methyl-2-propanol
 Phenylethanol
 4-Methylphenol
 Cyclohexanol
 2-Phenylethanol
7. Halogenation: Reaction with ZnCl3 and
concentrated HCl
 Lucas reagent consists of concentrated HCl and ZnCl2 as catalyst. It can

be used to differentiate 1°, 2° and 3° alcohols and suitable for alcohols

(less than 6 carbon atoms).

1° does not turns cloudy (two layer formed)

even after a long time.
Phenol DOES NOT react with Lucas reagent
7. Halogenation: Reaction with Phosphorus
Halide (PCl3, PCl5, PBr3, PI3) and SOCl2
 Used to convert alcohols to haloalkane. Phenol DO NOT undergo this reaction.

 Reactions i) and iii) Can be used as a chemical test for –OH group since a white

acidic fume, HCl is formed. Involves breaking of R-OH bond.

 Reaction with SOCl2 is a better way to convert alcohols to alkylhalides because

all the by-products are gases which are easily separated from the
chloroalkanes.
7. Halogenation: Reaction with Hydrogen
Halide (HCl, HBr, HI)
8. Electrophilic Substitution Reactions
 These reactions involve benzene rings and only phenols undergo this

reaction

 This –OH group phenol is an activating group and ortho-para directing.

The reactions are faster and easier than that of benzene; conditions
required are milder
Identification test of phenol
HO HO
FeCl 3

+ FeCl 3 (aq)

Purple complex(solution)

The reaction above is chemical test for phenol

Acidity of alcohols and phenols
 Generally acidity of

 This can be proved from the values of Ka (acid ionization constant.

 Phenol is the most acidic because the phenoxide ion or conjugate base

is stable. This is because the negative charge on oxygen can be

delocalised onto the benzene ring.
 Reactions Alcohols Phenol Notes

Form H2 and sodium

Reaction with Na
alkoxide

Esterification with carboxylic Acid Form ester and water

Esterification with Acyl Chloride Form ester and HCl

Dehydration Form alkene and

water

Oxidation 1°and 2° alcohol [O]. 3° and phenol not [O]

Can differentiate
Reaction with Lucas Reagent 1°,2°,3° alcohols
Chemical test for
Triiodomethane / Iodoform rxn some alcohol only.

Reaction with Phosphorus halide Form haloalkane

Form haloalkane and

Reaction with hydrogen halide water

Reaction with NaOH Phenol is more acidic

-OH group phenol is

Electrophilic Sustitution Reactions activating group

Hydrogenation with Ni or Pt/H2 Form cyclohexanol

 Application of alcohols and phenols

HO
HO OH HO

HO
N O
H
HO OH
OH
glucose
Salbutamol
(Drug for asthma)
HO

NH

HO

OH
Adrenaline