B.Sc. - II, DSC-D4 Sem. –IV Chem-VIII Notes by Dr. M.M.

Mane

Carboxylic acids and their derivatives

Organic compound containing carboxilic group( –COOH) are called carboxilic acids. They are
classified depending on number of –COOH groups. Like monocarboxylic,
dicarboxylic,tricarboxylic,tetracarboxylic etc.
Monocarboxylic acid
They are organic compounds containing one carboxylic acid group.They are represented as,

R-COOH OR Ar-COOH

They are classified depending on nature of side chain attached to –COOH group.

e.g. i) Saturated acids

Here –COOH group is attached to alkyl moiety.

e.g. CH3-COOH, CH3-CH2-COOH

Acetic acid propanoic acid

ii) Unsaturated acid Here –COOH gr. Is attached to alkenyl moiety,

e.g. CH2=CH-COOH CH3- CH=CH-COOH

acrylic acid crotonic acid

iii) Aromatic acid Here –COOH gr. Is attached yo aromatic moiety

e.g.
O OH

CH CH COOH

Benzoic acid Cinnamic acid

Method of Preparation
1) From Alcohol:
Primary alcohols on oxidation gives aldehyde which oxidized easily to give carboxylic
acid with the same number of carbons. Where as secondary alcohol on oxidation gives
ketone which oxidized to give carboxylic acid with the less number of carbons. Tertiary
alcohol requires drastic conditions.

R.B.M. College Chandgad. Dept. of Chemistry

B.Sc. - II, DSC-D4 Sem. –IV Chem-VIII Notes by Dr. M.M.Mane

H2 H2
(O) (O) H2
C OH C H
H3C C H3C C OH
H2 H3C
O
O

OH
O (O)
C (O)
H3C OH
H3C H CH3
H3C CH3
O

Strong oxidizing agents like Potassium permagnet, potassium dichromate, nitric acid and
chromic acid can be used.

2) From Aldehydes and Ketones

Aldehyde oxidized easily to give carboxylic acid with the same number of carbons.
Where as ketones oxidized to give carboxylic acid with the less number of carbons.
H2
(O) H2
C H
H3C C OH
H3C
O
O

O (O)
H3C OH
H3C CH3
O
3) From Nitrile
Cyano group (-CN) on hydrolysis under acidic or basic medium gives carboxylic acids.
H2 +
H3O H2
C C OH
H 3C N H3C
O Propanoic acid
Propane nitrile

CN + COOH
H3O

Benzonitrile Benzoic acid

4) From Alkyl Benzene: Alkyl benzene on oxidation with KMnO4 or Potassium

dichromate forms aromatic acids.

R.B.M. College Chandgad. Dept. of Chemistry

B.Sc. - II, DSC-D4 Sem. –IV Chem-VIII Notes by Dr. M.M.Mane

CH3 COOH
(O)

Tolune Benzoic acid

CH3
C COOH
H CH3 (O)

Isopropyl benzene Benzoic acid

Alkyl benzene lacking benzylic hydrogen does not oxidize

H3C
CH3
CH3 (O)
No reaction

t-butyl benzene

Haloacid

Haloacids are substituted carboxylic acids obtained by replacing one or more H atoms in side
chain (R) by corresponding number of halogen atoms. Haloacids are subgrouped depending on
number and position of halogen atoms, like α,β,γ haloacids.

e.g. i) α haloacid ;- Here halogen atom present at α carbon

Cl
Cl
Cl CH COOH

Cl-αCH2-COOH Cl CH COOH Cl

Monochloro acetic acid dichloroacetic acid trichloro acetic acid

ii) β Haloacid Here halogen atom present at β carbon

Br-CH2-CH2-COOH β-bromo propanoic acid

iii) γ Haloacid Here halogen atom is on γ carbon

Br –CH2--CH2-CH2-COOH γ-bromo butanoic acid

R.B.M. College Chandgad. Dept. of Chemistry

B.Sc. - II, DSC-D4 Sem. –IV Chem-VIII Notes by Dr. M.M.Mane

Methods of formation
I) Monochloro acetic acid It can be prepared by following method,
i) Hell-Vohlard-Zelinsky( HVZ) method

Chlorination of acetic acid is carried out in presence of sunlight and red P.

Red P
H3C COOH + Cl 2 Cl CH2 COOH + HCl

Monochloro acetic acid

ii) Industrially it is prepared by oxidation of ethylene chlorohydrin
(O)
Cl CH 2 CH 2 OH Cl CH 2 COOH
HNIO3

II) Dichloro acetic acid

It is prepared by following methods,
1) HVZ method
red P
H3 C COOH + 2 Cl2 Cl CH COOH + 2 HCl
373 K
Cl
dichloro acetic acid
2) Trichloro acetic acid It is prepared by,
i) HVZ-method
Cl
red P
H3C COOH + 3 Cl2 Cl C COOH + 3 HCl
373 K
Cl

ii) It is also prepared by oxidation of chloral with HNO3

Cl
HNO3
Cl
CCl 3 CHO + (O) C COOH

Cl
Chloral trichloro acetic acid

Substitution reaction of Monochloro acetic acid

Compared with alkyl halides, the α-halogen of halo acid is more reactive due to presence of
electron withdrawing –COOH gr.Hence monochloroacetic acid undergoes nucleophilic
substitution at alkyl carbon more easily.

R.B.M. College Chandgad. Dept. of Chemistry

B.Sc. - II, DSC-D4 Sem. –IV Chem-VIII Notes by Dr. M.M.Mane

i) Action of potassium Cyanide:

Chloroacetic acid reacts with aqueous KCN to form Cyano acetic acid.

Cl CH2 COOH + KCN NC CH2 COOH + KCl

Aq. Cyano acetic acid

ii) Action of alkali:
With strong alkali like NaOH/KOH, monochloro acetic acid forms glycolic
Acid,

Cl CH2 COOH + NaOH HO CH2 COOH + NaCl

glycolic acid
iii) Action of potassium iodide( KI )
Monochloro acetic acid reacts with aq. KI to form iodo acetic acid,

Cl CH2 COOH + KI I CH2 COOH + KCl

iodo acetic acid

iv) Action of ammonia ( NH3)
With conc. Solution of ammonia chloro acetic acid forms glycine,

Cl CH2 COOH + 2 NH3 H2N CH2 COONH4

Ammonium amino acetate

acidification
H2 N CH2 COONH4 + HCl H2 N CH2 COOH + NH4Cl

glycine

Strength of chloro acetic acid

Due to electron withdrawing inductive effect of Cl atoms, the positive charge on H of –COOH
gr. Increases, further it also helps to stabilise carboxylate ion after loss of H + from –COOH gr.,
hence chloro acetic acids are more stronger than acetic acid.More the number of such Cl atoms
more will be the acidic strength. Hence trichloroacetic acid is stronger than dichloro and which is
more stronge than monochloro.

Thus acidic strength of chloro acids varies,

Cl3C-COOH > Cl2CH-COOH > ClCH2-COOH > CH3-COOH

R.B.M. College Chandgad. Dept. of Chemistry

B.Sc. - II, DSC-D4 Sem. –IV Chem-VIII Notes by Dr. M.M.Mane

Hydroxy acids Acid containing –OH group in the side chain is called hydroxy acid.

HO HO CH COOH

H3C CH COOH H2C COOH

e.g. HO-CH2-COOH

glycolic acid lactic acid Malic acid

Malic acid It is found in unripe apples, grapes etc.

HO CH COOH

H2C COOH

Preparation
It is prepared by following methods’

1) From Maleic acid: Maleic acid on heating with dil.H2SO4 under pressure, undergo
hydration to form malic acid.

HC COOH dil.H2SO4 HO HC COOH

+ H2O

HC COOH CH 2 COOH
Maleic acid Malic acid
2) From α – bromo succinic acid
α–bromo succinic acid on treatment with moist silver oxide( Ag 2O ) forms malic acid,

Br CH COOH hydrolysis HO HC COOH

+ AgOH + AgBr
H2C COOH CH 2 COOH

α–bromo succinic

Reactions of Malic acid:

Malic acid gives reactions of both –OH and dibasic acids.
1) Action of heat: Malic acid on heating at 423-453 K underge dehydration to form
mixture of Maleic unhydride and fumaric acid,

R.B.M. College Chandgad. Dept. of Chemistry

B.Sc. - II, DSC-D4 Sem. –IV Chem-VIII Notes by Dr. M.M.Mane

CO COOH
HC
HO CH COOH 
HC
O +
H2 C CO
COOH HOOC
Malic acid Maleic anhydride Fumaric acid

2) Reaction with HI ( reduction)

Malic acid on reduction with hydroiodic acid gives succinic acid.

H2 C COOH
HO CH COOH
+ H2O + I2
+ 2 HI
H2 C COOH
H2 C COOH
Succinic acid
3) Oxidation Malic acid on oxidation with KMnO4 gives oxalo acetic acid,

COOH HOHC- COOH

O=C
HO CH COOH (O)
H2 C COOH HC COOH
H2 C COOH KMnO4
Keto form enol form

Uses: Malic acid is used as,

i) Substituent for citric acid in beverage
ii) For preparing medicines
iii) For preparation of useful esters and salts
iv) As food acidulant.

Citric Acid
H2C COOH
OH
C
COOH
H2C COOH It occurs naturally in unripe citrus fruits.

Preparation

R.B.M. College Chandgad. Dept. of Chemistry

B.Sc. - II, DSC-D4 Sem. –IV Chem-VIII Notes by Dr. M.M.Mane

1) From Glycerol
Glycerol gives citric acid by following reactions,
H2 C H2C Cl H2 C Cl
H2 C OH Cl
HCl (O) HCN OH
C=O C
CH OH CH OH CN
HNO3
H2 C Cl H2 C Cl H2C Cl
H2 C OH

Glycerol 1,3-dichloro acetone

H2C CN H2C COOH
KCN H+
OH OH
C C
CN Hydrolysis COOH
-2 KCl
H2C CN H2C COOH
1,2,3-tri cyano 2- hydroxyl Citric acid
Propane

Chemical Properties
1) Acetylation Citric acid on treatment with acetic anhydride or Acetyl chloride undergo
acetylation to give mono acetyl derivative.
H2 C COOH
-
H2 C COOH O COCH 3
C
OH COOH
C
COOH
+ ( CH 3COO )2 O
-CH3COOH CH 2 COOH
CH 2 COOH
Mono acetyl derivative

2) Reduction ( HI ) Citric acid on reduction with HI gives tricarballylic acid

H2C COOH H2C COOH

OH H
C
COOH
+ 2 HI C
COOH
+ H2O + I2

CH 2 COOH CH 2 COOH
Tri carballylic acid

3) Action of heat Citric acid on heating at 423 K loses water to form aconitic acid

H2C COOH HC COOH

OH 
C C COOH
COOH -H2O
CH2 COOH CH2 COOH

Aconitic acid

R.B.M. College Chandgad. Dept. of Chemistry

B.Sc. - II, DSC-D4 Sem. –IV Chem-VIII Notes by Dr. M.M.Mane

Uses It is used as,

i) In confectionary and synthetic fruit drinks,

ii) For cleansing metals
iii) In dye industry
iv) Magnessium citrate is used as laxative and as antioxidant.
v) As solvent in plastic industry

Unsaturated acid
Organic acids containing unsaturation in the side chain is called unsaturated acid,

Structure Common name IUPAC name

CH2=CH-COOH Acrylic acid Prop-2-enoic acid

CH3-CH=CH-COOH Crotonic acid But-2-enoic acid

COOH Cinnamic acid 3-Phenyl-2-propenoic acid
CH CH

Acrylic acid ( CH2=CH-COOH )

Preparation

1) From Acrolein Acrolein on oxidation with tollens reagent( Ammonical Silver

nitrate ) gives Acrylic Acid

NH4OH
COOH
H2C CH CHO + (O)
AgNO3
H2C CH

Acrolein acrylic acid

2) From β-Hydroxy propionic acid β-Hydroxy propionic acid on heating with

ZnCl2undergo dehydration to give acrylic acid.


H2C CH2 COOH + (O)
aq.NaOH
H2C CH COOH + H2O
OH

β -hydroxy propionic acid

R.B.M. College Chandgad. Dept. of Chemistry

B.Sc. - II, DSC-D4 Sem. –IV Chem-VIII Notes by Dr. M.M.Mane

3) From acetylene
Acetylene on treatment with HCN followed by hydrolysis, gives acrylic acid,

HCN H3O+
H2C CH CN H2C CH COOH
HC CH
addition hydrolysis
Acetylene

Physical properties

It is stronger acid than acetic acid, misicible with water , B.P.=-415 K , colourless liquid

Chemical properties
It gives reaction s of –COOH and C=C groups.

1) Addition of Water In presence of HgSO4 OR H2SO4 , Acrylic acid undergo hydration

to give
H+
H2C CH COOH + H2O
Addition
H2C CH 2 COOH

, OH

β-hydroxy propionic acid

2) Reduction On reduction with Na- in Ethanol acrylic acid gives Propanoic acid

Na/ C2H5OH
H2C CH COOH + 2 [H]
Reduction
H3C CH 2 COOH

Propanoic acid

Uses It is used as,

i) Modifying agent for thermosetting resin

ii) Acrylonitrile is used for synthesis of Synthetic fibers and rubbers ( Polymers)

iii) For preparing esters

R.B.M. College Chandgad. Dept. of Chemistry

B.Sc. - II, DSC-D4 Sem. –IV Chem-VIII Notes by Dr. M.M.Mane

Cinnamic Acid
COOH
CH CH

It exists in cis and trans isomers. The cis isomer is called cinnamic acid and trans is called
allocinnamic acid. It is found in oil of cinnamon.

Preparation

1) From perkin reaction Benzaldehyde when refluxed with acetic amhydride in presence
of sodium acetate, formscinnamicm acid.

COOH
CHO H3C CO CH3COONa CH CH
+ O
H3C CO -CH3COOH

Acetic anhydride Cinnamic acid

2) From Knoevengel condensation In presence of base benzaldehyde reacts with

diethyl malonate to form unsaturated ester, which on further hydrolysis and
decarboxylation gives cinnamic acid.

COOEt

CHO COOEt pyridine CH C

COOEt
+ H2C
COOEt -H2O
Benzaldehyde diethyl malonate

COOH COOH

i) KOH CH C  CH CH
COOH
ii) HCl -CO2

Cinnamic acid

Chemical Properties
1) Action of Bromine Cinnamic acid undergo addion reaction with bromine to form
dibromo cinnamic acid

R.B.M. College Chandgad. Dept. of Chemistry

B.Sc. - II, DSC-D4 Sem. –IV Chem-VIII Notes by Dr. M.M.Mane

COOH
CH CH CH(Br) CH(Br) COOH
addition
+ Br2

2) Oxidation Cinnamic acid on oxidation with chromic acid gives mixture of

benzaldehyde and benzoic acid.
CH CH COOH CHO
(O) (O) COOH

Benzaldehyde Benzoic acid

Uses It is used as,
i) In synthesis of pharmaceuticals
ii) In perfume industry
iii) As preservative for fruits and vegetables.

Dicarboxylic acid Carboxylic acid containing two –COOH grs. is called dicarboxylic acid.
In IUPAC they are named by placing suffiw ‘dioic acid’ to the name of parent alkane.
Structure Common naqme IUPAC name

COOH Oxalic acid Ethane dioic acid

COOH

COOH Malonic acid Propane-1,3-dioic acid

H2C
COOH

H2 C COOH Succinic acid Butane-1,4,-dioic acid

H2 C COOH

COOH Phalic acid Benzene-1,2-dicarboxylic acid

COOH

Succinic acid
H2 C COOH

H2 C COOH

R.B.M. College Chandgad. Dept. of Chemistry

B.Sc. - II, DSC-D4 Sem. –IV Chem-VIII Notes by Dr. M.M.Mane

Preparation
1) From ethylene dibromide Ethylene dibromide on treatment with KCN followed by
hydrolysis gives succinic acid.
H2C Br 2 KCN H2C CN H O /H+ H2C COOH
2

H2C Br -2 KBr H2C CN Hydrolysis H2C COOH

2) From Maleic acid Maleic acid on reduction with H2 in presence of Ni gives, succinic
acid.
HC COOH H2/Ni H2 C COOH

HC COOH H2 C COOH
Maleic acid
Chemical properties
1) Action of heat Succinic acid on heating above its melting point undergo dehydration
to give corresponding anhydride.
H 2C COOH  H2C CO
O
H 2C COOH -H2O H2C CO
Succinic anhydride
2) Action of NaHCO3 Succinic acid on treatment with sodium bicarbonate forms its
sodium salt.

H2C COOH aHC H2C COONa H2C COONa

aHC
H2C COOH H2C COOH H2C COONa
Monosodium salt disodium salt
3) Action of Ethanol In presence of acid succinic acid acid reacts with ethanol to give
mono as well as diester
H2C COOH C H OH / H SO H2C COOC2H5 H2C COOC2H5
2 5 2 4 C2H5OH / H2SO4
H2C COOH H2C COOH H2C COOC2H5

Mono ester Diester

Uses It is used as,
i) In manufacture of dyes and perfumes
ii) In medicine

R.B.M. College Chandgad. Dept. of Chemistry

B.Sc. - II, DSC-D4 Sem. –IV Chem-VIII Notes by Dr. M.M.Mane

iii) As laboratory reagent in volumetric analysis

Phthalic Acid
Preparation
i)From o-Xylene
o-Xylene on oxidation with KmnO4 gives Phthalic acid.
CH3 COOH
(O)

CH3 KMnO4 COOH

0-Xylene Phthalic acid

ii)From Naphthalene
Naphthalene on oxidation with vanedium pentaoxide gives Phthalic anhydride, which on
hydrolysis with alkali followed by acidification gives Phthalic acid.
CO
(O) 2 H2O
O + 2 CO2 +
V2O5 CO

Naphthalene Phthalic anhydride

CO COONa COOH
2 NaOH HCl
O
- H2O COONa -2 NaCl
CO COOH

Phthalic acid
Chemical Properties
1) Action of heat
Phthalic acid on heating to its melting point undergo dehydration to form corresponding
anhydride.
COOH CO

O
COOH CO

Phthalic anhydride

R.B.M. College Chandgad. Dept. of Chemistry

B.Sc. - II, DSC-D4 Sem. –IV Chem-VIII Notes by Dr. M.M.Mane

2) Action of Sodalime
On heating with Sodalime ( NaOH + CaO ) Phthalic acid undergo decarboxyaltion to
form first Benzoic acid , which on further decarboxylation gives Benzene.
COOH
aCaO COOH aCaO

COOH -CO2 -CO2

Benzoic acid Benzene

3) Reaction with Ammonia
On heating with ammonia at 473 K phthalic acid gives phthalimide
COOH CO
NH3
NH + 2 H2O
COOH  CO

Phthlimide
Uses It is used for,
i) Formation of benzoic acid, phthalic anhydride etc.
ii) For formation of dyes.

Carboxylic acid derivaties The compounds which are formed from reactions on acid are
called carboxylic acid derivatives.
e.g.
O

H3C COOEt H3C C

i) ii) Cl

Esters Acid cloride

iii)Anhydride iv) Amide

O
H3C C
O O
H3C C
O H3C C NH2

R.B.M. College Chandgad. Dept. of Chemistry

B.Sc. - II, DSC-D4 Sem. –IV Chem-VIII Notes by Dr. M.M.Mane

Acid Halide ( Acetyl Choride)

It is obtained by replacing –OH by Halogen CH3-COCl
Preparation of( Acetyl Choride)
1) Glacial acetic acid on treatment with PCl3 gives acetyl choride.
O
O
 H3C C + H3PO3
3 H3C C + PCl 3 3 Cl
OH

Acetic acid acetyl chloride

2) It can also be prepared by reaction of acetic acid with thionyl chloride.
O
O
 + SO2
H3C C + SOCl2 H3C C
Cl
+ HCl
OH

Chemical Properties
1) Action of Water Acetyl Choride on hydrolysis gives acetic acid.
O
O
 H3C C + HCl
H3C C + H2 O
OH
Cl

Acetic acid
2) Action of alcohol: Acetyl choride on treament with alcohol gives ester.
O
O
 H3C C + HCl
H3C C + C2H5OH
OC2H5
Cl

Ethyl acetate
3) Action of ammonia : Aceyl choride on heating with ammonia forms acetamide.
O
O
 H3C C + HCl
H3C C + NH3 NH2
Cl ammonolysis

Acetamide
Uses : It is used as,
i)acetylating agent,
ii)for detection of –OH, -NH2 groups.

R.B.M. College Chandgad. Dept. of Chemistry

B.Sc. - II, DSC-D4 Sem. –IV Chem-VIII Notes by Dr. M.M.Mane

iii)For synthesis of verity of other organic compounds.

Acetic Anhydride
Preparation
1) Dehydration of acetic acid Vapours of acetic acid on passing over phosporous
pentaoxide or Thionyl Chloride (SOCl2) undergo dehydration to form acetic anhydride.

P2O5 H3C CO
2 H3C COOH O
-H2O
H3C CO

Acetic anhydride
Chemical Properties
1) Reaction with Water Acetic anhydride on hydrolysis gives acetic acid.
H3C CO H2O
O 2 H3C COOH

CO
hydrolysis
H3C

2) Reaction with alcohol: On reaction with alcohol acetic anhydride undergo

esterificatiion to give mixture of ethyl acetate and acetic acid.
H3C CO C2H5OH
O H3C COOC2H5 + H3C COOH

CO
esterification
H3C

Ethyl acetate
3) Reaction with ammonia : On reaction with ammonia acetic anhydride gives acetamide
and acetic acid.
H3C CO NH3
O
H3C CO NH + H3C COOH
ammonolysis 2
H3C CO

Acetamide
Uses It is used as,
i) As acylating agent,
ii) For detaction of –OH, -NH2 groups.
iii) For manufacture of polyners and dyes.
iv) For manufacture of pharmaceuticals like, aspirin.

R.B.M. College Chandgad. Dept. of Chemistry