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Structure
R C OH
RCOOH or RCO2H
(R ≡ alkyl, aryl or H)
2
3
IUPAC Nomenclature &
Common Name
CH3CH2CH2COOH CH3CH2CH2CH2COOH
Butanoic acid Pentanoic acid
Butyric acid Valeric acid
4
IUPAC Nomenclature
•The longest chain must contain the carboxyl group.
5
Br CH3 O
CH3 CH CH CH2 C OH
4-bromo-3-methylpentanoic acid
CH3 O
O CH3
HO C CH2 CH CH CH CH3
5-methyl-3-hexenoic acid
6
• Two COOH groups, the compound will be
named as alkanedioic acid’
(Example: ethanedioic acid, propanedioic acid
and etc)
O O
pentanedioic acid
7
O CH3 O
H CH2 COOH
C C
HOOC CH2 H
8
• When R is an aryl group, the parent name is
benzoic acid
Cl COOH
4-chlorobenzoic acid
9
• An aromatic dicarboxylic acid is named as
1,x-benzenedicarboxylic acid
HOOC
COOH
COOH
2-isopropyl-1,4-benzenedicarboxylic acid
10
• A cyclic carboxylic acid is named as cycloalkanecarboxylic
acid
1 COOH
cyclopentanecarboxylic acid
11
1 COOH
cyclohexanecarboxylic acid
CH3
Br 1 COOH
4-bromo-2-methylcyclohexanecarboxylic acid
12
A cyclic dicarboxylic acid is named as
1,x-cycloalkanedicarboxylic acid
COOH
COOH
1,2-cyclohexanedicarboxylic acid
COOH
Cl COOH
4-chloro-1,2-cyclohexanedicarboxylic acid
13
• When a compound contains a carboxyl group and other
functional group(s), the priority is given to the carboxylic
acid as the parent name.
COOH
CH3
3-methyl-2-cyclohexenecarboxylic acid
14
15
Boiling Point
The boiling point of carboxylic acid is higher than
an alcohol, a ketone or an aldehyde (with Mr that
almost the same) because:
i. it exists as stable dimers that form
hydrogen bond.
ii. molecules in dimers are arranged closely
packed, therefore the hydrogen bonds are
relatively strong.
iii. high energy is needed to overcome the
intermolecular forces ,
boiling point 16
Hydrogen bond
O H O
R C C R
O H O
Hydrogen bond
17
Solubility
a) Solubility in water
Hydrogen Bonds H
O H O H O
R C H C R
O H O H O
18
• The solubility of carboxylic acid in water is almost
the same as alcohol.
O
hydrophilic
hydrophobic R C OH
19
• Aromatic carboxylic acids are slightly soluble in
water due to the huge aromatic ring.
20
Example : Descending order of solubility
COOH COOH
>
CH3 CH2 CH2 CH2
21
b. Solubility in non polar solvent
O H O
R C C R
O H O
22
Acidity of Carboxylic Acid
23
Resonance Effect
O
Carboxylate ion : R C O-
O-
Phenoxide ion :
24
• Carboxylic acids are more acidic due to the resonance
stabilisation of the carboxylate ion.
OH
> H2O
R C OH > > R OH
26
-
O O O
R C + H2O ⇌ R C
-
R C + H3O+
OH O O
carboxylic acid carboxylate ion
(resonance structure)
-
OH + H2O ⇌ O +
H3O+
phenol phenoxide ion
(resonance structure)
• Acidity :
– CH3CHCl-COOH > CH3CH2COOH
31
ii) Number of electron-attracting group in
the compound.
• Example:
CH3C(Cl)2-COOH and CH3CHCl-COOH
32
iii) The position of electron-attracting group
• Example:
CH3CH2CH(Cl)COOH and CH2(Cl)CH2CH2COOH
• Acidity :
CH3CH2CH(Cl)COOH > CH2(Cl)CH2CH2COOH
33
B.2 The inductive effect
Electron-Donating Group (EDG) in the
compound
• Example:
CH3COOH and CH3CH2COOH
• -R is an electron–releasing group.
35
1. Oxidation of primary alcohol and aldehyde
H R R
oxidizing oxidizing
R C OH agent C O agent C O
H H HO
1o alcohol aldehyde carboxylic acid
oxidizing
R agent COOH
Cl Cl
CH3
KMnO4 , H+
CH CH3 Δ
COOH
+ CO2 + H2O
37
3. Formation and Hydrolysis of nitrile
NaCN H2O,H+
R CH2 X R CH2 CN R CH2 COOH
NaCN H2O,H+
38
4. Carbonation of Grignard Reagents
CO2
H2O, H+ + Mg(OH)Br
39
CHEMICAL PROPERTIES OF
CARBOXYLIC ACIDS
40
• Main reactions of carboxylic acid,
a. The reaction that involves the donation of
H+ from –OH group.
b. The reaction that involves the substitution
of OH group
c. The reaction that involves the reduction
with LiAlH4 to primary alcohol
41
a. The reaction that involves the donation of
H+ from –OH group
1. Neutralisation
• Carboxylic acids are acidic, it can react with base such as
NaOH (aq) to give metal carboxylate salts,
O O
R C + NaOH R C + H2O
-
OH O Na+
42
COOH COO – Na+
+ NaOH + H2O
Sodium benzoate
43
2. Reaction with electropositive metals such as Na,
K, Ca, Mg and Fe.
O O
R C OH + M R C O M + H2
Exercise:
Cl O
C
OH
+ K
44
b. The reaction that involves the substitution
of –OH group (to form its derivatives)
1. Acid chloride formation
Acid chloride can be prepared from the reaction of
carboxylic acids with thionyl chloride, SOCl2 ; phosphorous
pentachloride, PCl5 ; phosphorous trichloride, PCl3
O
SOCl2
R C Cl + SO2 + HCl
O O
PCl5
R C OH R C Cl + POCl3 + HCl
O
PCl3
R C Cl + H3PO3 45
Exercise :
SOCl2
O
PCl5
CH3 CH C OH
CH3
PCl3
46
2. Esterification
Carboxylic acids react with alcohols in the presence of
mineral acid catalyst to produce esters.
O O
H+
R C OH + H—OR’ ⇌ R C O R' + H2O
carboxylic acid alcohol ester
O O
+ H2O
47
3. Acid anhydride formation
Acid anhydrides can be prepared from carboxylic acids by
the loss of water through heating.
O O O O
R C OH + HO C R heat R C O C R + H2O
acid anhydride
O O O O
+ H2O
48
4. Amides formation
Reaction of carboxylic acids with an
ammonia or amine give amide.
O
NH3
R C NH 2 + H2O
1o amide
O O
RNH2
R C OH R C NHR + H2O
(1o amine) 2o amide
O
R2NH
R C NR 2 + H2O
(2o amine)
(3o amide)
49
Exercise :
NH3
CH3 O
CH3 NH2
CH C OH
CH3
CH3 NH
CH3
50
c. The reaction that involves the reduction with
LiAlH4 to primary alcohol
CH3 CH3
51
Methanoic acid, HCOOH as a reducing agent
O O
and
C OH H C
carbonyl
carboxylic
52
KMnO4 / H+
O CO2 + H2O + MnO2
(Brown)
H C OH
Ag(NH3)2+ Ag + CO2 + H2O
(Silver)
53
DERIVATIVES OF
CARBOXYLIC ACIDS
54
Reactions of carboxylic acid derivatives
O O O
H2O
R C O C R 2 R C OH
acid carboxylic acid
anhydride
55
Reactions of carboxylic acid derivatives
O
H2O
O H+ R C OH + ROH
carboxylic acid alcohol
R C OR
O
ester
H2O -
NaOH R C O Na
+ + ROH
alcohol
56
Example :
O
H2O
C Cl
benzoyl chloride
O O
H2O
CH3 C O C CH3
ethanoic anhydride
57
Example :
O
H2O
CH3 C O CH3
H+
methyl ethanoate
58
Relative Reactivity Of
Carboxylic Acid Derivatives
• The reactivity of a carboxylic acid derivative
depends on the basicity of the substituent
(leaving group) that attached to the acyl group
59
Relative basicities of the leaving group (substituent)
O O O O O O
R C Cl , R C O C R , R C OR , R C OH , R C NH 2
acid acid ester carboxylic amide
chloride anhydride acid
reactivity increases
60
ACYL CHLORIDE
61
ANHYDRIDE ACID
62
ESTER
• Ester is less reactive towards nucleophile because the
delocalization of electron makes the positive charge of
carbon can be shifted to oxygen.
63
AMIDE
• Amide is the least reactive because, NH2 group is an
electron-donating group that makes the carbonyl less
electropositive.
R H R H
+
N N
-
O H O H
64
The Uses of Carboxylic Acid
Carboxylic acid / derivatives Uses
Polyamide (Nylon) carpet, apparel
Ester Artificial flavors
Acetic acid Vinegar
Ethanoic anhydride Drug aspirin
Salicylic acid analgesic
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