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INTRODUCTION
Alkane
INTRODUCTION
OH
CH2-OH
CH3CH2-OH
INTRODUCTION
OH
OH
OH
CH3
Br
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
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
OH
CH2CH3
3-ethylphenol
OH
CH3
Br
3-bromophenol
2-methylphenol
11
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
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
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.
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
22
Phenol
O -
H
release proton
+ H+
Phenoxide ion
24
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
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
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+
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
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
(iii)ROH + SOCl2
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
test
Example:
1
OBSERVATIONS :
CH2OH
HCl / ZnCl2
HCl / ZnCl2
Turn cloudy
within 5 minute
OH
54
3o
CH3
OH
HCl / ZnCl2
OBSERVATIONS :
Turn cloudy
immediately
55
Haloform Reaction
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
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
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
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
71