HYDROXY COMPOUNDS

(ALCOHOLS)
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INTRODUCTION
Alkane

with hydroxyl group (OH)

General formula for aliphatic
alcohol, CnH2n+1OH
Aromatic

alcohol phenol (-OH

attached to the benzene rings)

INTRODUCTION
OH

CH2-OH

CH3CH2-OH

ALIPHATIC ALCOHOL (OH group attached

directly to the alkyl group)
3

INTRODUCTION
OH

OH

OH

CH3

Br

AROMATIC ALCOHOL (OH group attached

directly to the aryl group)
4

CLASSIFICATION
Methyl

10

alcohol

Alcohols

20

Alcohols

30

Alcohols

CH3-OH

R-CH2-OH

R
R-CH-OH
R
R-C-OH
R
5

NOMENCLATURE
Structure

General name

IUPAC name

CH3-OH

methyl alcohol

methanol

CH3CH2-OH

ethyl alcohol

ethanol

CH3CH(OH)CH3

isopropyl alcohol

2-propanol

OH

cyclohexyl
alcohol

cyclohexanol

Naming the alcohol

1.The suffix e in the alkane parent name
is replaced by ol
2.The location of the OH on the longest
chain is given by the smallest possible
number

IUPAC rules for naming

alcohols
1.Determine parent name
2.Give the lowest number to the carbon
bearing the OH group
3.Identify substituent groups and their
position
4.Name the alcohol
8

Naming Alcohols, R-O-H:

CH3
CH3CHCH2CHCH3
OH
4-methyl-2-pentanol

CH3
CH3CCH2CH2CH3
OH
2-methyl-2-pentanol

2o

3o

CH3
HO-CHCH2CH3

CH3CH2CH2-OH

sec-butyl alcohol
2-butanol

n-propyl alcohol
1-propanol

2o

1o

Naming Alcohols

10

For phenol, C attach to the OH group is C 1

OH

OH

CH2CH3

3-ethylphenol

OH

CH3

Br

3-bromophenol

2-methylphenol

11

Alcohol with 2 hydroxy groups

Structure
CH2(OH)CH2-OH
CH3CH(OH)CH2-OH
HO-CH2CH2CH2-OH
OH-CH2CHCH2-OH
OH

General name

IUPAC name

ethylene glycol

1,2-ethanediol

propylene glycol

1,2-propanediol

trimethylene
glycol
glycerol

1,3-propanediol
1,2,3-propanetriol

12

Benzene derivatives with 2 OH groups are

name as benzenediol

OH

OH
1,4-benzenediol
(hydroquinone)

OH

OH

OH

OH
1,3-benzenediol
(resorcinol)

1,2-benzenediol
(catechol)

13

EXCERCISE
1. Name the following compounds using IUPAC nomenclature
(a)

(b)

-CH2CH(CH3)CH2-OH

-OH
NO2

(b)

-OH
Br
14

PHYSICAL PROPERTIES
Most

simple alcohols are liquids

MeOH & EtOH are volatile liquids, b.p.
65oC & 78oC respectively
Mr , b.p.
ROH

with C > 12 are solids

15

PHYSICAL PROPERTIES
No.

of OH , b.p.
b.p. ROH > alkane & RX because
of H-bonding
b.p. ROH straight chain > ROH
branch
b.p. 1o ROH > 2o ROH > 3o ROH
16

PHYSICAL PROPERTIES
(ii)
Boiling point
As molecular weight increase, van der Waals
forces increase, boiling point will increase too.

For isomeric alcohol (same molecular

formula)
increase in boiling point with increasing carbon
number.
decrease in boiling point with branching.
boiling point in descending order:1 alcohol 2 alcohol 3 alcohol
17

PHYSICAL PROPERTIES
(Solubility)
Alcohols and water have the ability to form
inter-molecular H-bonding
Methanol, ethanol & propanol are completely
soluble in water
Solubility decreases with relative Mr because of
the bigger hydrophobic area
Solubility increases with the no. of -OH groups
18

PHYSICAL PROPERTIES
(Solubility)
+

R
H
R

O
-

Hydrophilic area

OH

H
H

Hydrogen
bonding

Hydrophobic area

19

PHYSICAL PROPERTIES
(Solubility)
Phenol is not completely soluble in water below
66oC, but completely soluble above this temp.
Phenol is a colourless crystalline solid which is
hygroscopic
4-nitrophenol is more soluble in water than 2nitrophenol because can form H-bonding with
water molecules

20

PHYSICAL PROPERTIES
(Solubility)
4-nitrophenol

2-nitrophenol
+

H
- O

O + O
N

Intramolecular H-bonding

O +
- H

Intermolecular H-bonding
21

Acidity of phenol & alcohol

phenol > water > alcohol
Ethanol, very weak acid & only can react
with strong base such as Na or K to
produce a conjugate base (ethoxide ion)
CH3CH2-OH
CH3CH2-O- + H+

22

Acidity of phenol & alcohol

CH3CH2O-

is e- richer than OH-, thus H2O

> acidic than CH3CH2OH

Phenol

> acidic than H2O & CH3CH2OH

because phenoxide ion formed is more
stable
The phenoxide ion formed is stabilised
by resonance effect
23

Acidity of phenol & alcohol

O -

H
release proton

+ H+
Phenoxide ion

24

Phenoxide ion stability

O -

O-

25

Example:
OH

CH2CH2-OH

CH2-OH

OH

acidity increase

26

Example:
COOH

OH

>
Na2CO3
NaHCO3
Weak bases

> CH CH -OH
3

KOH
NaOH
Strong bases

ACIDITY
DECREASE

K, Na
NaH
Very strong bases
27

EXCERCISE
1. Arrange the following compounds in the order of increasing
boiling point. Explain your answer.
1,2-ethanediol , n-butane , 1-propanol , 1,3-propanediol
2. Predict which of the compound is more soluble in water.
Briefly explain your answer.
(a) propane & 1-propanol
(b) 1-propanol & 1,2-propanediol
(c) 2-propanol & 2-pentanol
28

PREPARATION OF
ALCOHOLS
1. Fermentation of carbohydrate

-fermentation of sugars by yeast to

form ethanol
C6H12O6

2CH3CH2OH + 2CO2

29

PREPARATION OF
ALCOHOLS
2. Hydration of Alkenes
follows Markovnikovs rule
Example:CH3CH=CH2

H2O / H2SO4

CH3CH-CH3
OH

30

PREPARATION OF
ALCOHOLS
Mechanism
CH3CH=CH2 + H+

CH3CH-CH3 2o carbonium
+

OH

CH3CH-CH3
OH

31

PREPARATION OF
ALCOHOLS
3. Hydrolysis of Haloalkanes
RX + OH- (aq)

CH2Cl

ROH + X -

CH2OH

+ NaOH(aq)

32

PREPARATION OF
ALCOHOLS
4. Addition of Grignard reagent to

carbonyl compounds

10, 20 & 30 alcohols can be prepared by

addition of Grignard reagent with carbonyl
compounds followed by hydrolysis

33

PREPARATION OF
ALCOHOLS
(a) Formation of 1o alcohols (Grignard reagent + methanal)

CH3CH2-MgCl + H2C=O
OMgCl
methana

CH3CH2CH2-

H3O+
1o
Alcohol

CH3CH2CH2-OH
+ Mg(OH)Cl
34

PREPARATION OF
ALCOHOLS
(b) Formation of 2o alcohols (Grignard reagent + aldehyde)
CH3
CH3CH2-MgCl + HC=O
ethan
OMgCl
al

CH3
CH3CH2CHH3O+
CH3
2o Alcohol CH3CH2CH-OH

+ Mg(OH)Cl
35

PREPARATION OF
ALCOHOLS
(c) Formation of 3o alcohol (Grignard reagent + ketone)
O-MgCl

O
CH3-MgCl + CH3-C-CH3
propanon
e

CH3-C-CH3
CH3
H3O+
O-H

3o
Alcohol

CH3-C-CH3 +
Mg(OH)Cl
CH
3

36

EXCERCISE
1. Write the chemical equation for the following reaction:
i. tert-butyl alcohol from an alkene
ii. isopropyl alcohol from an alkyl halide
2. Draw the structure of A, B and C:
i.
CH3
O
CH3-C-MgCl +
ii.

-C-H

CH3
-CH=CH-CH3

H2O / H+

B + C
37

REACTIONS OF ALCOHOL
(a) As an acid
In an aqueous solution alcohol reacts as a very weak acid
ROH + H2O

RO - + H3O+

Reacts with Na or NaH & form a very strong base

alkoxide ion

CH3CH2OH + Na

CH3CH2O-Na+ + 1/2H2

38

REACTIONS OF ALCOHOL
(a) As a base
With the presence of lone pair of e- at the O atom,
alcohol can accept proton from an acid

CH3CH2-O-H + HA

CH3CH2O+-H + AH

39

REACTIONS OF ALCOHOL
(1) Esterification
Alcohol reacts with carboxylic acid under reflux &
is catalysed by mineral acids (H2SO4 or HCl) to
form ester.
General
reaction:O
R-C-OH + R-OH
acid

alcohol

H ,
+

R-C-OR + H-O-H
ester

water
40

REACTIONS OF ALCOHOL
(1) Esterification
Example:O

CH3C-OH + CH3-OH
ethanoic acid methanol

H+,

CH3C-OCH3 + H-O-H
methyl ethanoate

41

REACTIONS OF ALCOHOL
(1) Esterification
Alcohol reacts with acyl chloride to form ester
O

CH3C-Cl +

CH3-OH

base

ethanoil chloride methanol

CH3C-OCH3 + HCl
methyl ethanoate

42

REACTIONS OF ALCOHOL
(2) Dehydration of alcohol
Involve formation of carbocation
Possible of rearrangement
CH3CH2CH2OH
propanol

H2SO4(con.)
180
C

CH3CH=CH2
propene

43

REACTIONS OF ALCOHOL
(3) Formation of haloalkane
ROH reacts with HX to form RX
The reaction rates are in the order
HI > HBr > HCl (HF non-reactive)
Reactivity of alcohols
3o ROH > 2o ROH > 1o ROH > phenol
44

REACTIONS OF ALCOHOL
General Reaction
ROH + HX

RX + H2O

Example:CH3CH2CH2OH + HBr

CH3CH2CH2Br + H2O
45

REACTIONS OF ALCOHOL
(3) Formation of haloalkane
ROH reacts with PX3, PX5 , SOCl2
General reaction:
(i)3ROH + PX3

3RX + H3PO3

(ii)ROH + PCl5

RCl + POCl3 + HCl

(iii)ROH + SOCl2

RCl + SO2 + HCl

46

REACTIONS OF ALCOHOL
(4) Oxidation of alcohols
Common oxidising agents are potassium
permanganate (VII), (KMnO4/H+) and
potassium dichromate (K2Cr2O7/H+)
Oxidation product depends on the class of
alcohol used
47

REACTIONS OF ALCOHOL
(4) Oxidation of 1o alcohol
1o R-OH can be oxidised to give an aldehyde.
Further oxidation would give a carboxylic acid
O
[O]
RCH2OH
RC-H
1o alcohol

aldehyde

[O]

O
RC-OH
carboxylic acid

48

REACTIONS OF ALCOHOL
(4) Oxidation of 1o alcohol
Example:CH3CH2OH

K2Cr2O7/H

O
CH3C-H

K2Cr2O7/H

O
CH3C-OH + Cr 3+
green

orange

49

REACTIONS OF ALCOHOL
(4) Oxidation of 1o alcohol
Sarett-Collins reagent is a special oxidation
agent to change a 1o alcohol to an aldehyde
CrO3 is added to excess pyridine to form
pyridinium chlorochromate (PCC)
CH3CH2CH2OH + PCC
propanol

O
CH3CH2C-H
propanal
50

REACTIONS OF ALCOHOL
(4) Oxidation of 2o alcohol
form ketone which cannot be oxidised
further under normal conditions
R
R
RCH-OH
2o alcohol

CH3
CH3CH-OH
2-propanol

[O]

RC=O + H2O
ketone

CH3
KMnO4/H
CH3C=O + H2O
+

propanone
51

REACTIONS OF ALCOHOL
(4) Oxidation of 3o alcohol
Does not undergo oxidation under normal
condition

R
R-C-OH
R

[O]

no reaction

3o alcohol
52

Chemical test for R-OH

Lucas

test

Lucas reagent : HCl + ZnCl

3 R-OH + Lucas reagent reacts
(con.)

immediately to form cloudy haloalkane

2o R-OH + Lucas reagent takes about 5-10
minutes to form cloudy
1o R-OH + Lucas reagent no visible
changes unless heated
53

Example:
1

OBSERVATIONS :

CH2OH
HCl / ZnCl2

Does not turn

cloudy

HCl / ZnCl2

Turn cloudy
within 5 minute

OH

54

3o

CH3
OH
HCl / ZnCl2

OBSERVATIONS :
Turn cloudy
immediately

55

Haloform Reaction

Methyl carbinol cleavage to give Carboxylic

acids and Haloform
H

CH 3 C H
OH
H
CH 3 C R
OH

X2 , H+
OH-

X2 , H+
OH-

HCX 3 + H C OH
O

HCX 3 + R

C OH
O
56

IODOFORM TEST
OH

base (OH-)

CH3CH2CCH3 + 3I2
2-butanol
CH3CH2COO- + CHI3
yellow precipitate
(iodoform)

57

PHENOL
Manufacture of phenol by Cumene process
(a) Friedel-Crafts reaction
CH3-CH-CH3
+ CH3CH=CH2

AlCl3
Isopropylbenzene
Isopropylbenzene
(cumene)
(cumene)
58

PHENOL
(b) Oxidation of Cumene
CH3-CH-CH3

O -OH
CH3-C-CH3

+ O2

1200C

Cumene
hydroperoxide

(c) Decomposition & rearrangement

CH3
-C-O-OH

H2SO4

O
-OH + CH3CCH3

CH3
59

Reactions of Phenol
1. Reaction at functional group -OH
(a) Reaction with Na
O-Na+

OH

+ Na

+ H2

60

Reactions of Phenol
1. Reaction at functional group -OH
(b) Reaction with NaOH
OH

O-Na+
+ NaOH

CH3CH2OH + NaOH

+ H2 O
no reaction

61

Reactions of Phenol
2. Electrophilic substitution reactions
(a) Halogenation (Bromination)
-OH is ortho-para director
in Br2, aqueous solution, white precipitate 2,4,6tribromophenol will form
OH
OH
Br

Br

+ 3Br2 / H2O

+ 3HBr
Br

62

Reactions of Phenol
2. Electrophilic substitution reactions
(a) Bromination to get monobromination (catalyst:
FeBr3 or CS2)
OH

OH
+ Br2

OH
Br

CS2
50C

+ HBr

Br
63

Reactions of Phenol
2. Electrophilic substitution reactions
OH

OH

(b) Nitration
OH

NO2

Dilute HNO3
Room temp.

+
NO2
OH
O2N

NO2

Concentrated HNO3

Yellow
precipitate

NO2

64

Reactions of Phenol
3. Esterification

phenol is a weaker nucleophile than alcohol

since the lone pair e- of O atom are delocalised
to the benzene ring
reacts with an acid derivative such as acid
chloride to form an ester
CH3
OH

O-C=O
Cl
+ CH3-C=O

+ Cl65

Reactions of Phenol
4. Identification test for phenols
phenol reacts with aqueous solution of iron (III)
chloride giving a light purple complex
OH

OH
+ FeCl3 (aq)
Purple
complex
66

FeCl3

EXERCISE 1
Suggest a chemical test to differentiate the following pairs of
compounds. State the reagents, observations and write
chemical equations involved.
(a) methanol from ethanol
(b) 2-methyl-1-propanol from 2-methyl-2-propanol
(c) cyclohexanol from cyclohexane
(d) phenol from benzyl alcohol
(e) o-methylphenol from 2-methylcyclohexanol

67

EXERCISE 2
Compound A (C4H10O) undergoes oxidation to form compound
B (C4H8O). Oxidation of B gives compound C (C4H8O2).
Reaction of A with hot concentrated sulphuric acid yields
compound D (C4H8). Hydration of D gives compound E
(C4H10O) which cannot be oxidised. A and E are isomeric.
Suggest the structure of A, B, C, D and E. Rasionalise your
answer.

68

Common Used Of Alcohol

And Phenol
Ethyl

alcohol is a poison. LD50 =

~10g/Kg orally in mice.- Nausea,
vomiting, flushing, mental excitement or
depression, drowsiness, impaired
perception, loss of coordination, stupor,
coma, death may occur. (intoxication)
Phenol is an important industrial
chemical. Major use is in phenolic resins
for adhesives and plastics.
69

Phenols in Medicine
Many phenols are used as antiseptics and
disinfectants.
OH
OH
OH

OH

OH
CH2CH2CH2CH2CH2CH3

Phenol

Resorcinol
(antiseptic)

4-Hexylresorcinal
(antiseptic)
70

Derivatives of Phenol

Compounds of phenol are the active ingredients in the

essential oils of cloves, vanilla, nutmeg, and mint.

71