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CARBOXYLIC ACID AND

ITS DERIVATIVES

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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

HCOOH CH3COOH CH3CH2COOH


Methanoic acid Ethanoic acid Propanoic acid
Formic acid Acetic acid Propionic acid

CH3CH2CH2COOH CH3CH2CH2CH2COOH
Butanoic acid Pentanoic acid
Butyric acid Valeric acid

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IUPAC Nomenclature

• The longest chain must contain the carboxyl group.

• The carboxyl group is at the terminal, therefore the carbon


of the carboxyl group is not numbered.
One COOH – carboxyl group is at one end
Two COOH – carboxyl groups are at both ends

• Name the compound as alkane, drop ‘e’ in alkane and


add ‘oic acid’ (eg: methanoic acid)

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Br CH3 O

CH3 CH CH CH2 C OH
4-bromo-3-methylpentanoic acid

CH3 O

HO CH CH2 CH2 CH2 C OH


5-hydroxyhexanoic acid

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

HO C CH2 CH2 CH2 C OH


pentanedioic acid

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O CH3 O

HO C CH2 CH CH2 CH2 C OH


3-methylhexanedioic acid

H CH2 COOH

C C

HOOC CH2 H

trans 3-hexenedioic acid

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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

1,3-benzenedicarboxylic acid HOOC


CH3
CH CH3

COOH
2-isopropyl-1,4-benzenedicarboxylic acid
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• A cyclic carboxylic acid is named as cycloalkanecarboxylic
acid

• The C atom which is attached to —COOH is numbered as


C1

1 COOH

cyclopentanecarboxylic acid

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1 COOH

cyclohexanecarboxylic acid

CH3

Br 1 COOH

4-bromo-2-methylcyclohexanecarboxylic acid

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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
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• 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

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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

• Carboxylic acids are soluble in water due to the


formation of hydrogen bond between the water
molecules and carboxylic acid molecules.
Hydrogen Bonds H

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.

• Aliphatic carboxylic acids with C > 5 are insoluble in water. Size of R ↑,


hydrophobic area ↑.

O
hydrophilic
hydrophobic R C OH

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• Aromatic carboxylic acids are slightly soluble in
water due to the huge aromatic ring.

• Dicarboxylic acids are relatively more soluble since


more hydrogen bonds are formed.

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Example : Descending order of solubility

COOH COOH COOH


> >
CH3 CH CH2 CH2 CH3 CH2 CH2

COOH COOH
>
CH3 CH2 CH2 CH2

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b. Solubility in non polar solvent

• Carboxylic acids are soluble in non polar solvent such as


benzene due to the Van der Waals forces between the
benzene and alkyl group of carboxylic acids .

O H O

R C C R

O H O

Van der Waals forces Van der Waals forces


Hydrogen bonds

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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 :

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• Carboxylic acids are more acidic due to the resonance
stabilisation of the carboxylate ion.

• The electrons in carboxylate ion are delocalised


between two oxygen atoms, whereas in phenoxide
ion, the electrons are delocalized in the benzene ring.

• The C=O group in carboxylic acid is a electron-


withdrawing group which reduce the electron density
of –OH, therefore the –OH bond becomes weaker.

• Thus H+ is easily donated and carboxylic acid is more


acidic than phenol.
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• Carboxylic acid is relatively a weak acid, however it is
stronger than phenol & alcohol

OH

R C OH > > H2O


> R 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)

R—O—H + H2O ⇌ R—O– + H3O+


alcohol alkoxide ion
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Inductive Effect
O O
EWG C EDG C
- -
O O
An electron withdrawing An electron donating
group (deactivating group) group, (activating group)
that attached to a will destabilise the
carboxylate ion will carboxylate ion and
delocalise the negative decreases acidity.
charge, thereby stabilises
the carboxylate ion and
increases acidity. 28
i. The inductive effect
electron-withdrawing group in the
compound
• electron-withdrawing groups
(e.g –NO2 ,-F,-Cl,-Br, -I ) reduce the electron
density of
–O H.

• Thus the O-H bond becomes weaker and H+ can


be easily released.

• The compound is said to be more acidic


∴ Electron- withdrawing group increases the
acidity.
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• Example:
CH3CHCl-COOH and CH3CH2COOH

• Cl is an electron-withdrawing groups, therefore reduce the


electron density of –OH.

• Thus the O-H bond becomes weaker and H+ can be easily


released.

• Acidity :
– CH3CHCl-COOH > CH3CH2COOH

• Electron-withdrawing groups increase the acidity.

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ii) The electronegativity of electron-
withdrawing group in the compound
• Example:
CH3CHF-COOH and CH3CHCl-COOH

• Both F and Cl are electron-attracting group.

• The electronegativity of F > Cl

• The electron density of –OH in CH3CHF-COOH is less,


thus the –OH bond is weaker than in
CH3CHCl-COOH. Therefore, H+ is easily donated.

• Acidity : CH3CHF-COOH > CH3CHCl-COOH


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iii) Number of electron-attracting group in
the compound.

• Example:
CH3C(Cl)2-COOH and CH3CHCl-COOH

• CH3C(Cl)2-COOH contains 2 Cl atoms that make the


bond of –OH weaker than CH3CHCl-COOH (with only
one Cl atom). Thus, H+ is easily donated.

• Acidity : CH3C(Cl)2-COOH > CH3CHCl-COOH

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iv) The position of electron-attracting group
• Example:
CH3CH2CH(Cl)COOH and CH2(Cl)CH2CH2COOH

• The distance between Cl atom and carboxyl group in


CH3CH2CHCl-COOH is nearer compare to in
CH2ClCH2CH2-COOH.

• The –OH bond in CH3CH2CH(Cl)COOH is weaker than


in CH2ClCH2CH2-COOH, so H+ is easily donated.

• 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

• -R is an electron –releasing group.

• The size of –R group in CH3CH2COOH is larger than in


CH3COOH, so CH3CH2- is a stronger releasing group
than CH3-.

• The electron density of –OH in CH3CH2COOH


increases and H+ is difficult to be donated.

∀ ∴ Electron-releasing groups reduce the acidity of a34


carboxylic acid.
SYNTHESIS OF
CARBOXYLIC ACIDS

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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

Common oxidizing agents are :


•KMnO4 / H2SO4
potassium permanganate

•K2Cr2O7 @ Na2Cr2O7 /H2SO4


potassium /sodium dichromat (VI)
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2. Oxidation of Alkyl Benzene

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

CH2 Br CH2 CN CH2 COOH

NaCN H2O,H+

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4. Carbonation of Grignard Reagents

R—MgX O C O R—COOH + Mg(OH)X


H2O, H+

CH2 MgBr CH2 COOH

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

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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

CH3 CH2 C OH + HOCH2CH3 H CH3 CH2 C OCH2 CH3


+

propanoic acid ethanol ethyl propanoate

+ 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

CH3 C OH + CH3 C OH heat CH3 C O C CH3


ethanoic anhydride

+ H2O

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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

Carboxylic acid are reduced to primary alcohols by


reaction with lithium aluminium hydride, LiAlH4 .
O

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

• Methanoic acid molecule, H C OH has both

O O
and
C OH H C
carbonyl
carboxylic

• It shows the properties of both carboxylic acid and aldehyde.

• It also shows reducing properties in reactions with acidified


KMnO4 or K2Cr2O7 and Tollens’ reagent.

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KMnO4 / H+
O CO2 + H2O + MnO2
(Brown)
H C OH
Ag(NH3)2+ Ag↓ + CO2 + H2O

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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

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Reactions of carboxylic acid derivatives
i. Hydrolysis of acid chlorides

O O
H2O
R C Cl R C OH + HCl
acid chloride carboxylic acid

ii. Hydrolysis of acid anhydrides

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

iii. Hydrolysis of amide (acidic hydrolysis)

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

iii. Hydrolysis of amide (alkaline hydrolysis)

O O
H2O
OH- + NH3
R C NH2 R C O-
ammonia
amide Carboxylate ion

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Reactions of carboxylic acid derivatives

iii. Hydrolysis of amide (alkaline hydrolysis)

- 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

• The less basic the substituent, the more reactive the


carboxylic acid derivative.

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Relative basicities of the leaving group (substituent)

Cl– < RCOO– < RO– < HO– < NH2–

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

• Acyl chloride is the most reactive because of its


electropositive carbonyl group is attach to the
electronegative Cl atom (which is a releasing group).

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ANHYDRIDE ACID

• Anhydride acid is more reactive than ester and


amide because the carboxyl group of anhydride is
attached to the carbonyl carbon.

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

• Ester is less reactive towards nucleophile because the


delocalization of electron makes the positive charge of
carbon can be shifted to oxygen.

• That makes the carbonyl carbon less electropositive.

H3C H3C H3C


+ - -
C O C O C O
+
R O R O R O

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AMIDE

• Amide is the least reactive because, NH2 group is an


electron-donating group that makes the carbonyl less
electropositive.

• The resonance structure of amide shows that the


carbonyl carbon is not electropositive.

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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