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ITS DERIVATIVES
1
Structure
R C OH
RCOOH or RCO2H
(R ≡ alkyl, aryl or H)
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NOMENCLATURE
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IUPAC Nomenclature &
Common Name
CH3CH2CH2COOH CH3CH2CH2CH2COOH
Butanoic acid Pentanoic acid
Butyric acid Valeric acid
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IUPAC Nomenclature
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
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• Two COOH groups, the compound will be named as
alkanedioic acid’
(Example: ethanedioic acid, propanedioic acid and etc)
O O
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O CH3 O
H CH2 COOH
C C
HOOC CH2 H
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• When R is an aryl group, the parent name is benzoic
acid
Cl COOH
4-chlorobenzoic acid
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• An aromatic dicarboxylic acid is named as
1,x-benzenedicarboxylic acid
HOOC
COOH
COOH
2-isopropyl-1,4-benzenedicarboxylic acid
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• A cyclic carboxylic acid is named as cycloalkanecarboxylic
acid
1 COOH
cyclopentanecarboxylic acid
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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
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PHYSICAL PROPERTIES OF
CARBOXYLIC ACIDS
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
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Hydrogen bond
O H O
R C C R
O H O
Hydrogen bond
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Solubility
a) Solubility in water
O H O H O
R C H C R
O H O H O
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• 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
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b. Solubility in non polar solvent
O H O
R C C R
O H O
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Acidity of Carboxylic Acid
• The acidity of carboxylic acid is influenced by:
i. Resonance effect
ii.Inductive effect
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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
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-
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
30
ii) The electronegativity of electron-
withdrawing group in the compound
• Example:
CH3CHF-COOH and CH3CHCl-COOH
• Example:
CH3C(Cl)2-COOH and CH3CHCl-COOH
32
iv) The position of electron-attracting group
• Example:
CH3CH2CH(Cl)COOH and CH2(Cl)CH2CH2COOH
• Acidity :
CH3CH2CH(Cl)COOH > CH2(Cl)CH2CH2COOH 33
(v ) The inductive effect of electron- releasing
(electron-donating) group in the compound
• Example:
CH3COOH and CH3CH2COOH
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 COOH
Δ
+ CO2 + H2O
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3. Formation and Hydrolysis of nitrile
NaCN H2O,H+
R CH2 X R CH2 CN R CH2 COOH
NaCN H2O,H+
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4. Carbonation of Grignard Reagents
CO2
+ Mg(OH)Br
H2O, H+
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CHEMICAL PROPERTIES OF
CARBOXYLIC ACIDS
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• 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
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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+
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COOH COO – Na+
+ NaOH + H2O
Sodium benzoate
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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
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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 minera
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
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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 NH2 + H2O
1o amide
O O
RNH2
R C OH R C NHR + H2O
(1o amine) 2o amide
O
R2NH
R C NR2 + H2O
(2 amine)
o
(3o amide)
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Exercise :
NH3
CH3 O
CH3 NH2
CH C Cl
CH3
CH3 NH
CH3
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c. The reaction that involves the reduction with
LiAlH4 to primary alcohol
LiAlH4
R C O R' R CH2 OH + R’OH
ether
1o alcohol
O
LiAlH4
CH3 CH C O CH2 CH3 CH3 CH CH2 OH
ether
CH3 CH3
+ HO—CH2CH3 51
Methanoic acid, HCOOH as a reducing agent
O O
and
C OH H C
carbonyl
carboxylic
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KMnO4 / H+
O CO2 + H2O + MnO2
(Brown)
H C OH
Ag(NH3)2+ Ag↓ + CO2 + H2O
53
DERIVATIVES OF
CARBOXYLIC ACIDS
O O O
R C Cl R C O C R
acid chloride
acid
anhydride
O
O
R C NH2
amide
R C O R'
ester
54
Reactions of carboxylic acid derivatives
i. Hydrolysis of acid chlorides
O O
H2O
R C Cl R C OH + HCl
acid chloride carboxylic acid
O O O
H2O
R C O C R 2 R C OH
acid carboxylic acid
anhydride
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Reactions of carboxylic acid derivatives
iii. Hydrolysis of esters
O
H2O
O R C OH + ROH
H+
carboxylic acid alcohol
R C OR
O
ester
H2O -
NaOH R C O Na+ + ROH
alcohol
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Reactions of carboxylic acid derivatives
O O
H2O
R C NH2 H+ + NH4+
R C OH
Ammonium ion
amide Carboxylic
acid
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Reactions of carboxylic acid derivatives
O O
H2O
OH- + NH3
R C NH2 R C O-
ammonia
amide Carboxylate ion
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Reactions of carboxylic acid derivatives
- if dilute acid is added to the carboxylate salt, the carboxylic acid are formed.
O O
R C O- + H+ R C OH
Carboxylate ion Carboxylic acid
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Example :
O
H2O
C Cl
benzoyl chloride
O O
H2O
CH3 C O C CH3
ethanoic anhydride
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Example :
O
H2O
CH3 C O CH3
H+
methyl ethanoate
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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
62
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 NH2
acid acid ester carboxylic amide
chloride anhydride acid
reactivity increases
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ACYL CHLORIDE
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ANHYDRIDE ACID
O O
R C O C R'
• This makes the carbonyl carbon becomes more
electropositive and can be easily attack by
nucleophile.
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ESTER
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AMIDE
R H R H
+
N N
-
O H O H
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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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