Carboxylic Acids and Its Derivatives PDF

Chemistry: Carboxylic Acids and its Derivatives -1
The C OH group which apparently contains a carbonyl group and hydroxyl group fails to
show the reactivity of carbonyl compound due to interference of OH group into the activity of
O
C group and acts as a separate functional group, called, carboxylic group.
O O
C + – OH 
→ C OH
Carbonyl hydroxyl Carboxyl
Nomenclature
Acid: The name are normally suffixed as “oic acid” when COOH group is the principal
functional group and its carbon is counted while numbering longest chain. The carboxyl carbon
is assigned number 1 in IUPAC nomenclature. For example.
COOH
H3C CH2 CH CH2 COOH
CH3
3-methyl pentanoic acid 1-Napthanoic acid
H3C CH2 CH CH2 CH2 COOH

hex-3-enoic acid
Dicarboxylic acid are named as alkanedioic acid.
C OOH
C OOH
ethanedioic acid
Acid derivatives
O
||
Esters: − C− OR in IUPAC nomenclature are named as alkyl alkanoate.
O O
H3C O CH2 CH3 H3C CH2 OC2H5

ethyl acetate ethyl propionate
O2N C OCH3
methyl 4-nitrobenzoate
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Carboxylic Anhydrides: Carboxylic anhydrides are named as alkanoic anhydride if it contains
only one type of alkyl group but when two different alkyl groups are present, then alkanoic
anhydride are in alphabetical order.
H3C O CH3 CH2 O CH3
C C H3C C C
O O O O
acetic anhydride acetic propanoic anhydride
Acid Amides: Acid amides are named as alkanamide

O O
H3C NH2 H3C NH2

ethanamide propionamide
Acid Chlorides: According to IUPAC nomenclature, acid chlorides are named as alkanoyl
chloride.
O O
H3C Cl H 5C 6 Cl
ethanoyl chloride Benzenoyl chloride
General Methods of Preparation

1. By oxidation of primary alcohol with acidic KMnO 4 or acidic K 2 Cr2 O 7 .
+
R — CH 2 OH + [O] 
KMnO 4 / H
K 2 Cr2 O7 / H +
→ RCHO + H 2 O
[O]
RCOOH
2. By oxidation of aldehydes: Aldehydes on oxidation with usual oxidizing agent gives

carboxylic acid with same number of carbon atoms as in the aldehyde.
+
R — CHO + [O] →
Tollen 's Re agent
R — COO − 
H
→ R − COOH
+
C6 H 5CHO + [O] →
Tollen 's Re agent
C6 H 5 COO − 
H
→ C6 H 5 COOH
3. By oxidation of alkenes
a) RCH = CHR ′ 
(i) conc. KMnO4 / OH – heat
(ii) H O+
→ RCOOH + R ′COOH
3
b) RCH = CHR ′ →RCOOH + R ′COOH

(i) O3
(ii) H 2 O, Distill
4. By carboxylation of Grignard Reagent

O O
R — Br 
Mg
Dry ether
→ RMgBr 
CO 2
→R OMgBr 
H 2O / H

→R
+
OH
– MgBr(OH)
5. By hydrolysis of acyl derivatives of carboxylic acid and cyanide hydrolysis with dilute
acids.
O
R NH2 + H 2 O →
HCl
R — COOH + NH 4
O
R Cl + H 2 O →
HCl R — COOH + HCl O
+
(R — CO) 2 O + H 2 O 
H
→ R — COOH + R OH
+
R — COOR ′ + H 2 O 
H
→ R — COOH + ROH
+
R — Br  → R — CN  → RCOOH
–
CN H3O
The mechanism of hydrolysis of R—CN is as follows.

+
R — C ≡ N 
(H )
→ R — C ≡ NH 
→ R — C = NH
OH 2 O
H H
H H
O
R NH2 ←
H 2O
R NH2 R NH2
OH OH OH
OH O
R NH3 
→ R + NH +4
OH OH
6. By oxidation of alkyl benzene

CH3 COOH

(i) KMnO4 / OH
(ii) H O+
→
3
Alkyl group having no α -H atom will not be oxidized to —COOH. Any alkyl group
containing at least one α -H atom will be oxidized to —COOH. What ever the length of
alkyl group attached to benzene ring. The product of oxidation will be benzoic acid.
H2 C CH2 CH3 COOH

(i) KMnO4 / OH
(ii) H O +
→
3
C(CH3)3

Neutral KMnO4
→ No oxidation
The order of benzoic acid formation by oxidation of alkyl benzene.

Methyl benzene > 1° alkyl benzene > 2° alkyl benzene
Physical Properties of Carboxylic Acid

1. These are polar substances and can form H-bonds with each other to form dimmer
structures.
+ -
O H O
R
R
- +
O H O
a) Boiling Point: Due to dimeric structure, the effective molecular mass of the acid
becomes double the actual mass. Hence carboxylic acids have higher boiling points
than alcohols of comparable molecular masses. Due to hydrogen bonding carboxylic
acid show appreciable solubility in water. Its solubility in water is greater than alcohol
because H-bonding strength is greater in carboxylic acid than alcohol.
b) Melting Point: Melting point of the carboxylic acid with even number of carbon
atoms is higher than acid with odd number of carbon atoms. Such effect is observed in
first ten members of the homologous series. This feature is based on the fact that in
the carboxylic acids with even number of carbon atoms, the terminal methyl group
and carboxylic group are on the opposite sides of zig-zag carbon chain. Hence they fit
better in the crystal lattice resulting in stronger inter molecular forces on the other
hands acids with odd number of carbon atom have carboxyl and terminal methyl
group on the same side of zig-zag carbon chain which result in poor fitting in the
crystal lattice. This causes a weak forces among molecules and results for the
relatively lower melting point.
The melting point and boiling points of benzene derivatives are usually higher than
those of aliphatic acid of comparable molecular masses. This is due to planar structure
of benzene ring in the acid which can pack closely in the crystal than aliphatic acids.
Chemical Properties of Carboxylic Acid

1. Acidity of carboxylic acid: Acidity is relative case with which it loses a proton
leaving behind the anion. Its acid strength depends upon the difference in the stability of
the acid and its anion.
O O O O
R ←
→ R H+ R ←
→ R
OH OH O O
non-equivalent structures of equivalent structures of
resonance hybrid resonance hybrid
both acid and its anion are stabilized by resonance, stabilization is far greater for the
anion than for acid because anion gives two identical resonating structure.
2. Effect of substituents on Acidity: Any factor that stabilizes the anion more than it
stabilizes the acid should increase the acidity and any factor that makes the anion less
stable should decrease the acidity of the carboxylic acid.
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a) An electron withdrawing substituents stabilizes the anion by dispersing the –ve charge
and therefore increases the acidity of carboxylic acid.
b) Electron releasing substituents intensify the –ve charge on the anion resulting in
decrease of stability of the carboxylate anion and therefore decreases the acidity of the
acid.
Carboxylic acids are weak acids and their carboxylate ions are strong conjugate bases.
They are slightly alkaline due to the hydrolysis of carboxylate anion compared to other
species. The order of acidity and basicity of corresponding conjugate bases are as follow.
Acidity— RCOOH > HOH > ROH > CH ≡ CH > NH 3 > RH

Basicity— RCOO – < OH – < HC ≡ C – < NH 2– < R –
O – O –
 
W  R 
O O
Acidity increase Acidity decrease
The effect of various number of the substituent and their distance from the carboxylic
group has been illustrated with the help of following examples.
i) The effect of number of the substituent is shown by the chloro substituted acetic
acids. The acid strength increases in the order given below.
ClCH 2 — COOH < Cl2 CHCOOH < Cl3COOH

The increase in the no. of chloro substituent on α -carbon atom of acetic acid make
the electron withdrawing effect more pronounced and hence make carboxylate ion
more stable.
When electron releasing substituent is attached to the carboxylic group then acid
strength decreases as the electron releasing power increases.
R R
↓ ↓
R → CH 2 → COOH > R → CH →→ –COOH > R → –C →→→ −COOH
↑
R
ii) The effect of nature of the substituent is illustrated by the various halo acetic acids.
Their acid strength follows the order
ICH 2 — COOH < BrCH 2 COOH < ClCH 2 COOH < F CH 2 COOH
CH3 − CH 2 — CH 2 — COOH < CH 2 = CH − CH 2 − COOH < N ≡ C — CH 2 — COOH
↑ ↑
2
(sp ) (sp)
iii) Effect of the position of the substituent: The effect of the substituent decreases as its
distances from —COOH group increases.
Cl Cl
CH3 — CH — COOH > CH 2 — CH 2 — COOH
α -chloro propanoic acid β -chloro propanoic acid
electron withdrawing effect more electron withdrawing effect less
Ortho Effect
The ortho substituted benzoic acid (whether the substituent is electron withdrawing or releasing
is comparatively stronger acid than the para and meta isomers. This effect is called ortho effect. It
occurs due to the joint operation of steric and intra molecular H-bonding where ever it takes
chance to stabilize the carboxylate anion due to nearness of the substituent. Groups like —OH,
—Cl, NO 2 will cause more stabilization to anion due to direct interaction through intra
molecular H-bonding.
OH O
H+ H
intra molecular
O H-bonding
OH stabilization
O O
o-hydroxy benzoic acid Carboxylate anion
(Salicylic acid)
COOH COOH COOH
OH
> >
OH
OH
Order of acidic character
Reaction due to cleavage of —O—H bond as acid

O
C O H
i) Reaction with active metals [alkali and alkaline metal]

O O
R OH + Na 
→ R ONa + H 2 (↑)
ii) Reaction with CaO

2R — COOH + CaO 
→ (RCOO) 2 Ca + H 2 O
iii) Reaction with Bicarbonates and Carbonates

Carboxylic acid reacts with carbonates and bicarbonates to liberate CO 2 gas
O
R — COOH 
NaHCO3
→R ONa + CO 2 + H 2 O
CaCO3 O
Ca + CO2 + H 2 O
R O
2
Illustration1: Compound A, C 4 H 8 O2 has the following properties.

i) it reacts with sodium bicarbonate to liberate CO2
ii) on fusion with alkali gives propane
iii) with Ca (OH ) 2 it gives product C 8 H 14 O4 Ca which on heating decomposes
to diiso propyl ketone. Identify (A)
Solution: i) C4 H 8O 2 react with NaHCO3 to liberate CO 2 and so —COOH group is

present in it i.e. A is C3 H 7 COOH
NaOH + CaO
ii) C3 H 7 COOH  → C3 H8 + Na 2 CO3
Thus (a) may be
O
H3C OH
COOH or H3C
CH3
I II
Since both give propane on decarboxylation
iii) However C8 H14 O 4 Ca i.e. Ca salt of acid on heating

H3C O
H3C CH3
H3C
gives di isopropyl ketone and thus chain in acid is also not straight. Thus structure
(II) is correct i.e. A is
H3C
COOH
H3C
2-methylpropanoic acid
H3 C H3C CH3
∆
2 COO Ca  → CO + 2CaCO 3
H3 C H3C CH3
2
Illustration 2: Identify X, Y and Z in the following synthetic scheme and write their structures.
The product z when treated with HBr gives compound A which on reductive
ozonolysis gives formaldehyde as one of the product deduce entire scheme.
CH 2 = CH — Br  
(i) Mg / ether
→ X 
(ii) CO 2
(iii) H + O
→ Y →
LiALH 4
3
Z  
HBr
→ A 
O3 / H 2 O / ZnS
→H CH + ?
Solution: CH 2 = CH — Br 
Mg / ether
→ CH 2 = CH— MgBr →
(ii) CO2
(X)
H 3O +
H2C CH C O MgBr 
→ H2C CH C OH
(Y)
O O
Y 
LiAlH 4 / AlCl3
→ CH 2 = CH — CH 2OH  
HBr
→ H2C CH CH2 OH
(Z)
H
CH 2 O + OCH — CH 2 Br ←  CH 2 = CH — CH 2 Br ← CH 2 = CH — CH 2

–
O3 / H 2 O / 2H Br
(A)
CH 2 — CH = CH 2
(Ally carbocation )
Reaction Involving Cleavage of —OH Group
1. Esterification: When carboxylic acid reacts with alcohol in the presence of conc.
H 2SO 4 to form ester, which is known as esterification
O O
H+
R OH + H — OR ′ R OR ′ + H 2O
O OH OH
H+ +
OH 
→ R OH  →
H
R OH R
OR′ OR'
+
O O H OH
+
R −H
OR' ←
 R ←
 R OH2
OR' OR'
The relative reactivity of alcohol to ester formation markedly dependent on their

structure. The greater the bulk of the substituents near the —OH group, the slower the
reaction would be same facts is followed by acid as well
CH3OH > CH 3CH 2 OH > (CH3 )2 CHOH > (CH3 )3 COH

H — COOH > CH 3COOH > (CH 3 ) 2 CHCOOH > (CH 3 )3 CCOOH
2. Formation of acid chloride

+ PCl5

C5 H5 N
→ R — COCl + HCl + POCl3
+ SOCl2
R — COOH —→
C5 H5 N
R — COCl + SO 2 ↑ + HCl
+ SO 2 Cl 2

C5 H 5 N
→ R — COCl + SO3 ↑ + HCl
Formation of Acid Anhydride: Carboxylic acid on treatment with any dehydrating agent
as P2O5 to form anhydride by elimination of water molecule.
O
O
R
2R OH 
P2 O5
∆
→ O + H 2O
R
O
CH2COOH CH2CO

P2 O5
→ O + H 2O
∆
CH2COOH CH2CO
succinic acid suceinic anhydride
Formation of Amides
1. O O
R OH + MeNH 2 
→ R O NH3 →
heat
R — CONH — Me
− H2O
Me
O
R NH
Me
The lone pair electron on N atom undergoes resonance and hence N atom carries partial
+ve charge on it
O O
+
R NH ←
→ R N H
Me Me
Thus extent of H-bonding increases which makes the boiling and melting points of
amides higher than other acid derivatives.
Reactions Involving —COOH Group

1. Schmidt Reaction: Carboxylic acid reacts with hydrazoic acid in the presence of
conc. H 2SO 4 at 90°C forming primary amine.
R — COOH + N3 H →
conc. H 2SO 4
90° C
R — NH 2 + N 2 + CO 2
O OH OH
– ⊕
H — N — N≡N
R OH R OH  → R C OH
+
H N N N
OH –H 2 O
R OH
Chemistry: Carboxylic Acids and its Derivatives - 10
O
+ + +
R N N N 
–H
→ R N N N 
– N2
→ R 
rearrangement
→ nitrene intermediate
O H O N
– H+ / H+
R N C O 
H2 O
→ R N C O R NH O
O OH
H H
+ –
RNH 2 ←
H
 R — N H + CO 2
For example
COOH NH2
+ N 3 H →
conc. H 2SO4
90° C
+ N 2 + CO 2
benzoic acid aniline
2. Soda lime Decarboxylation: Carboxylic acid on heating with soda lime (NaOH
and CaO) give alkane with one carbon atom less than the parent acid.
R — COOH 
soda lim e
∆
→ R — H + CO 2
The reaction proceeds as
R — COOH + NaOH 
CaO
→ RCOONa + H 2 O
R — COONa + NaOH 

CaO
→ RH + Na 2 CO3
CH OH  → CH 3CH 2 OH
Soda lim e
H3 C ∆
COOH
3. Hunsdicker Reaction
R — COOH 
Ag 2 O
→ R — COO – Ag + Br2
in CCl4
→ R — Br + AgBr + CO 2
Mechanism: Reaction proceeds through free radical mechanism in various steps.

O O
R C O Br 
→ R C O + Br
Chain propagation step

O
R C → R + CO 2
O 
O O
R C O Br + R 
→ R — Br + R C O
4. With excess of organometallic compounds
RCOOH 
CH 3MgBr
→ RCOO – Mg + Br + CH 4
CH3 Li
R — COO – Li + CH 4
CH 3Li
OH
R C (O Li)2 
2H 2 O
Hydrolysis
→ R C OH 
→R C O
CH3 CH3 CH3

acetone
2 moles of organometallic compounds are needed to form ketone
5. Decarboxylation of Carboxylic Acid

The reaction in which carboxylic acid loses CO 2 is called decarboxylation
O
R C OH 
Decarboxylation
→ R — H + CO 2
The usual stability of carbon dioxide result in exothermic decarboxylation of carboxylic

acid but reaction is not always easy to carry out because of slow rate of reaction. But
some groups present in molecule help decarboxylation to be rapid enough.
Acids having a carbonyl group on β -carbon atom, called β -keto acids, decarboxylate
readily when they are heated to 100–150°C.
O O O
R C CH2 C 100–150° C
OH  →R C CH3 + CO 2
β -keto acid
There are two facts on which ease of decarboxylation depends.
i) When the carboxylate ion decarboxylate, it forms a resonance stabilized enolate

anion.
O O O O
H+
R C CH2 C O 
— CO 2
→ R C CH2 → R C CH3
R C CH2
Resonance stabilized enolate anion
−
This anion is much more stable than the anion R C H 2 formed by decarboxylation of
an ordinary carboxylic acid anion.
ii) When the acid itself decarboxylates it can do so through a six-membered cyclic
transition state β -keto acid on warming alone or in presence of a base undergoes
rapid removal of CO 2 .
H3C C CH2 C
∆
OH  → H3C C CH3 + CO 2
O O O
CH2
CH2 Ar
Y C C O Y C C O 
→ Y C CH2 + CO 2
∆
 →
O O O OH
H H
Tautomerisation
6 membered transition state
Y C CH3
O
keto form
Here y can be substituents like
OH — diacid
R — β -keto acid
H — β aldehyde acid
X — β halo acid
Br O Br O
OH  → O  → Ph CH2 +CO2

KOH –CO2
Ph base
Ph
This decarboxylation proceeds through elimination
Illustration 3: A compound with a molecular formula C5H10 (A) is inert with Conc. H2SO4. (A)
on reaction with bromine at 1270C and followed by reaction with sodium
butynide gives (B) C9H14 which on reaction with KMnO4 in acidic medium gives
(C) and propanoic acid. (C) on reaction with soda-lime gives cyclopentane.
What is (A) to (C)?
Br C CCH 2CH 3
0
127 C NaNH2
Solution: + Br2 + CH3CH2C CH
(A) (B)
KMnO 4 +
H
COOH
NaOH/CaO
+ CH3CH2COOH
(C)
Hell-Volhard-Zelinsky Reaction
This is α -halogenation of a carboxylic acid.
Br
OH OH
R 
Re d p / Br2
→ R
O O
α-bromo acid
Possible Mechanism for the Reaction is
Br
COBr  →H3CBr
COOH  PBr3
→ H3C COBr
2
H3C or (Re d P + Br2 )
H 2O
Br
H3C COOH
The purpose of PBr3 is to convert —OH into —Br to make α -hydrogen atom more acidic to be
replaced by Br atom of Br2 . The reaction does not stop at monosubstitution but continues till the
α -hydrogen are replaced.
O
H3C COOH 
Cl 2
Red P
→ H2C 
Cl2
→ CHCl2 COOH 
Cl 2
→ CCl3COOH
Red P Red P
Cl OH
The reaction has a great synthetic importance as the halogen atom can be replaced by a number
of other groups giving useful products.
NH2
+ NH3 α -amino acid

→
– HCl
R
COOH
OH
Cl R
+ KOH(aq)
 → α -hydroxy acid
– KCl COOH
R
COOH R

KOH (alco)
– HCl
→ COOH α, β -unsaturated acid
COOH

KCN
– KCl
→ R
CN
H 2O / H +
COOH
R
COOH
Heating of Dicarboxylic Acids

CH2 CH2
O C 
– H 2O
→
C O
O O O
O
O Succinic anhydride
H H
Succinic acid
(CH2) 3 
→
O O O
HOOC COOH
Glutanic acid Glutanic anhydride
Heating of α, β and γ Hydroxy Acid
i) O
H3C CH3
∆
O
2 H3C α COOH  →
O
H H
OH O
Lactides
ii) CH2 H3C O

∆
H3C CH C O  →
OH OH OH
β -hydroxy Acid α, β -Unsaturated Carboxylic Acid
iii) β α
CH2 CH2
γ H
∆
H3C CH C O  →
O O
H3C
OH OH
5-methyldihydrofuran-2(3H)-one
Reaction of α, β and γ halo carboxylic acid with aq. NaOH.
COOH  → H3C

–
OH
H3C α COO
Br OH
H
H3C β COO
COOH 
OH–
E2
→ H3C
Br
β - haloacid
CH2 Br
H2C CH2

→
OH – CH2 
SN 2 (Br)
→
Br C O O O O
O
HO
Cyclization of γ haloacid
Illustration 4: A hydrocarbon [X] C8H8 gave the following reactions:

(i) On shaking with Br2 & water, a compound with M.F. C8H9OBr (Y).
(ii) The rapid oxidation of hydrocarbon with hot alkaline KMnO4 gave a mono
basic acid of M.F. C7H6O2 (Z)
(iii) The acid (Z) on distillation with sodalime gave a compound, which can be
generated by trimerisation of ethyne in red hot Fe.
Deduce the structure of X, Y and Z.
OH
Solution: HC CH2 HC CH2
Br2 Br
H2O
COOH
(X) (Y)
[O] sodalime
HOt alk. KMnO4
(Z)
3 HC CH + Red hot Fe tube
Oxidation of Carboxylic Acid at Alkyl Group: Acid on treatment with mild oxidizing
agent such as H 2 O 2 , is oxidized at the β position
β α
CH 3 C H 2 — C H 2 COOH + [O] 
H 2 O2
→ H3C
COOH
OH
3-hydroxybutanoic acid
Oxidation can also occur at α carbon atom on treatment with oxidizing agent like selenium
dioxide SeO 2
RCH 2 COOH + [O] 
SeO 2
∆
→ R COOH + Se + H 2 O
O
α Keto acid
Abnormal Behaviour of Formic Acid

The behaviour of formic acid is different from other carboxylic acid due to presence of aldehydic
group.
O
Aldehydic Group H C OH Carboxylic Group
Reaction with
1. Tollen’s reagents: formic acid behaves as a reducing agent and reduces Tollen’s reagent
or Felhing solution. But others acid fail to do so.
H – COOH + Ag 2 O  → CO 2 + H 2 O + 2Ag ↓ Silver mirror
H — COOH + 2CuO 
→ CO 2 + H 2 O + Cu 2 O ↓ Red ppt.
2. Reaction with HgCl2 : Formic acid forms white ppt of Hg 2 Cl 2 with HgCl2 which is
converted to Grey ppt of mercury.
2HCOOH + HgCl 2 
→ CO 2 + Hg 2 Cl 2 ↓ + 2HCl
white ppt.
Derivatives of Carboxylic Acid

The —OH of an acid can be replaced by –– Cl — OR, or NH 2 group to yield an acid chloride an
ester or an amide. These compounds are called functional derivatives of acid and they all contain
acyl group. The functional derivatives are all readily converted into the acid by simple
hydrolysis.
O O
R 
→ R
OH Z
O

→— OH
+X
R Acyl halide
X
O
O 
— OH
+ NH3
→ R Amide
NH2
R
O
OH
→
— OH
+ ROH
R Ester
OR

— OH
+ RCOOH
→ R O R
Anhydride
O O
Relative Reactivity of Acid Derivatives

The reactivity of the acid derivatives towards nucleophilic substitution has the following order.
RCOCl > (RCO)2 O > RCOOR > R — CONH 2
This extent of reactivity of acid derivatives towards nulceophilic substitution can be explained on
the basis of two facts.
i) basicity of leaving group and

ii) resonance effects
Acid derivatives undergo nucleophilic substitution in two steps.
a) First step involves addition of nucleophile to electron deficient carbon atom of

carbonyl group leading to formation of tetrahedral intermediate.
b) In second step: The intermediate formed from an acyl compound usually eliminates a
leaving group. Elimination leads to regeneration of carbon oxygen double bond and to
a substitution product. The overall process in case of acyl substitution are nucleophilic
addition elimination.
[
O O
−
R 
Nu
→ R
L Nu L
I Step: II Step: Elimination of
Nueleophilic leaving group L.
addition
Step (1) is same as the nueleophitic addition to aldehyde and ketone so it should be
favoured by electron withdrawal and hindered by +I effect or presence of bulky
groups.
Second step depends on the basicity of the leaving group. The weaker a base, the
better it is as leaving group.
Basicity of leaving groups: Weaker the basic character of the leaving group more will be the
ease with which the leaving group leaves the compound and hence more is the reactivity Cl – ion
being weakest base are most reactive leaving group.
The order of basicity of the leaving group and their leaving tendency follows the order.
H 2 N – > RO – > RCOO – > Cl –

Basicity ←

Re activity 
→
Resonance Effect
R R
O ←
→ O
L L
Resonanting Structure
Due to resonance, the carbon to leaving group (L) bond acquires a double bond character due to
which stabilization occurs. Now more is stabilization, lesser is the reactivity and vice-versa. As
the stabilization is the least in the case of acid chloride because of high magnitude of –I effect of
Cl atom. Therefore its reactivity is the most.
Nucleophilic acyl substitution should be catalysed by acids because the protonation of the acyl
compound would facilitate step (i) for nuceleophilic attack.
Acyl Chloride RCOCl

These are the derivatives of carboxylic acid in which hydroxyl (—OH) part of carboxyl group is
replaced by halo group. The most reactive compound of halo leaving group is chloro compounds.
Methods of Preparation
Carboxylic acid chloride can be prepared by the reaction of carboxylic acid with PCl5 or SOCl 2
or PCl3 or SO 2 Cl 2

PCl5
C5 H 5 N
→ RCOCl + HCl + POCl3

PCl3
C5 H 5 N
→ RCOCl + H 3 PO3
R — COOH

SOCl2
C5 H5 N
→ RCOCl + SO 2 + HCl

SO 2 Cl2
C5 H 5 N
→ RCOCl + SO 3 + HCl
Chemical Properties
1. Acylation reaction
O O O
R C ONa 
→R C O C R
Anhydride
O

ROH, base
→ R C OR
ester
O

NH3
→ R C NH2
amide
O O
R C Cl 
→
CH3 NH 2
R C NH CH3
N-methylacetamide
O R

→
(R )2 NH R C N
R
N,N-dimethylacetamide
O
→
H 2 O ( water )
R C OH
O
 → O + Cl
–
OH (aq.) base
R C
2. Acylation of aromatic compound [Friedel Craft’s reaction]
R O
+ RCOCl 
and AlCl3
→ + HCl
R
+ CH 3COCl 
→ Acetophenone
+ C 6 H 5COCl 
→
benzophenone
[
3. Catalytic hydrogenation (Rosenmund’s reaction)
O
H 3C C Cl + H 2 Pd
BaSO 4
→ RCHO + HCl
RCOCl + 4H 
LiAlH 4 or NaBH 4
or C2 H5 OH + Na
→ R — CH 2 OH + HCl
Mechanism
O O O OH
R C Cl → R
LiAlH 4
— H–
C Cl 
→R —Cl
C 
LiAlH 4
→R CH2
H Alchohal
H
intermediate aldehyde
4. Reaction with KCN

O O O
+
Cl + KCN 
→ R CN  →R
H3 O
R C C C COOH
α keto acid
Pyruvic acid
5. Reaction with AgNO3
O O
R C Cl + AgNO3 
→ R C OH + AgCl ↓ + HNO3
The aliphatic acid chlorides are readily decomposed by water therefore aqueous solution
of acid chloride gives white ppt. with AgNO3 .
6. Reaction of acyl chloride with diazomethane in presence of Ag 2 O and water. (Arndt –

Eistert synthesis)
This reaction convert acyl chloride to carboxylic acid with one carbon atom more.
O O
R C Cl + 2CH 2 N 2 
→ R C CH N2 + CH 3Cl + N 2
O O
Ag + 
Wolf rearrangement
→ R — CH = C = O 
H2O
→ R — CH 2 — COOH
R C CH N2 
→ – N2
R ketene
CH
Amides
O
R C NH2
1. Amides from Acyl chloride  → Primary amines, secondary amines and ammonia all
react rapidly with acid chloride to form amides. An excess of ammonia or amine is used
to neutralize the HCl that would be formed otherwise.
O
R — COCl + NH3 
→ R C NH2 + NH 4 Cl
R — COCl + RR ′NH 
→ RCON(R)R ′ + RR ′N + H 2 Cl –
N, N − disubstituted amide
2. Amides from acid anhydride

O
O +
O + 2NH 3 
→R NH2 + RCOO NH 4
–
C
R C 2
O
O
O + 2R ′ — NH 2 
→R C NHR' + R — COO – NH 3+ R ′
R C
2
O O O
C C NH2 C NH2
H + / H 2O
O + 2NH 3 
→ H 2O

→
C C ONH4 C OH
O O O
Phthalamic acid
both amide and acid
3. From Esters (Ammonolysis): Ester undergoes nucleophilic substitution at their acyl

carbon by nucleophilic ammonia or its derivative
O R' O R
R C OR + H N 
→ R C N + R ′OH
R" R"
4. By partial hydrolysis of alkyl nitriles.

+
R — C ≡ N + H 2 O 
H or
OH –
→ R — CO — NH 2
Physical Properties: All amides except formamide are crystalline solid at room
temperature. They have relatively high melting and boiling point due to association of amide
molecules by inter molecular hydrogen bonds.
O C N H O C N H
R H R H
Chemical Properties
1. Amphoteric character: Amides are very feeble bases due to involvement of pair of
electron present on N atom in resonance with carboxyl groups. As a result N atom
receives partial +ve charges showing feeble acidic character as well
O O
R C NH2 ←
→ R C NH
(I) (II)
i) Acidic character: Due to structure II amide can act as acid.

O
H3C C NH2 + CaO 

→ (CH 3CONH)2 Ca + H 2 O
As acid
1
→ CH 3CONH – Na + +
CH3CONH 2 + Na  H2
Acid 2
ii) Basic Character: Due to structure I having lone pair of electrons on N atom it acts
as base
→ CH 3CONH +2 HCl−
CH3CONH 2 + HCl 
As base Acid Salt
2. Reaction with nitrous acid

R — CONH 2 + HONO 
→ R — COOH + N 2 + H 2 O
The reaction proceeds via the attack of electrophilic species NO + generated from HNO3
3. Hoffmann’s Bromide Reaction: Amides react with bromine in the presence of alkali to
form a primary amine having one carbon atom less than the parent amides
R — CO — NH 2 + Br2 + 4KOH  → RNH 2 + K 2 CO3 + 2KBr + 2H 2 O
CONH2 NH2
+ Br2 + 4KOH 
→ + K 2 CO3 + 2KBr + 2H 2 O
Mechanism: 2NaOH + Br2 

→ NaOBr + NaBr + H 2 O
i) O O
R C NH2 + OBr 
→R C N Br + OH –
H
N-bromoacetamide
ii) O H O
R C N Br + OH – 
– H2 O
→R C N Br
Rearrangement
R — NH 2 + CO 2 ←
H2 O
 R—N=C=O
− OH
4. Reaction with PCl5 or PCl3 or SOCl 2

O
R C NH2 →
PCl5 or PCl3
or SOCl 2
RCN + H 2 O
O O
NH2  →R NH PCl4  →

PCl5 – HCl
R C HCl
C
R C N PCl3
POCl3 + R — C ≡ N ←
R C N PCl3
5. Reduction
O
R C NH2 
Na / C2 H5 OH
→ R — CH 2 NH 2 + H 2 O
O
+ −
R C NH2 
Li AlH 4
→ R — CH 2 — NH 2
Mechanism
H AlH3 H
R C NH2 
→ R C NH2 
→ R — CH = NH 2
O O AlH3 LiAlH 4
Aldehyde-ammonia state
R — CH 2 — NH 2
Ester (RCOOR)
Esters are the derivatives of the carboxylic acid in which the —OH part of the carboxylic group
has been replaced by —OR group where R may be alkyl or aryl group.
By reaction of acids with alcohol or diazomethane in presence of ether.

+
RCOOH + C 2 H 5 OH 
H / H 2O
→ R — COOC 2 H 5 + H 2 O
R — COOH + CH 2 N 2 
ether
→ RCOOCH3 +N 2
Ester
O O
R C Cl + C 2 H 5 OH 
C5 H 5 N
→R C O C 2 H 5 + HCl
[
O O
R C O + R ′OH 
C5 H 5 N
→ R C O R ′ + R — COOH
2
Chemical Properties
1. Conversion to other esters: Transesterifications

O O
H+
R C OR' + R ′′ — OH R C OR" + R ′ — OH
2. Conversion to amides
O O
R" R"
R C OR' + HN 
→ R C N + R ′ — OH
R" R"
3. Reaction with Grignard Reagent
O OMgX
OR + 2R ′′MgX → R
diethylether
R C C R"
H+
OH R"
R C R" + R ′OMgX
R"
3° alcohol
4. Reduction of ester
MeCOCH 2COOC 2 H 5 
Na / Hg
→ MeCH(OH) CH 2 CO 2 C 2 H 5
LiAlH 4
MeCH(OH)CH 2 — CH 2 OH + C 2 H 5OH
O OH
C CH2
O 
LiAlH 4
→
C CH2 OH
O
Phthalic anhydride
5. Reaction of NH 3 with keto ester

R — CO — CH 2 CO 2 C 2 H 5 + NH 3 
→ R — C = CHCO 2 C 2 H5 + H 2 O
NH 2
Mechanism:
O
R C CH2 COOC2H5
NH 3
OH O
+
R C CH CO2C2H5 ←
 R C CH2 COOC2H5←
H
R C CH2 COOC2H5
NH2 NH2 NH2
Attack will occur at carbonyl group first because of high degree of +ve charge on
carbonyl carbon atom.
6. Acyloin condensation
O
2R C 
Na / Xylene
→R C O
OR
R CH OH
α-hydroxyl ketone
Mechanism: It is the intermolecular, sodium promoted condensation of two moles of

ester or the intra molecular condensation of a ester to α -hydrox ketone (acyloin)
2R C OR 
Na

Electron donation
→ 2R C OR →
dim erisation
O ONa
OR OR
R  → R  →
–2OR 2 Na
2R C C R C C
O O O O
+
R 
→R R  →R
tautomerisation
7. R C C C C 2H
C C R R C CHR
O O O O OH OH O OH
Na + Na +
acyloin
Hydrolysis of Acyl Derivatives
Ester hydrolysis can be carried out in mechanistic pathways A AC1 , A AC2 , A AL1 , BAC2 .
Here A or B stand for acid or base catalysed and Ac or Al stand for acyl–oxygen or alkyl–oxygen
cleavage and 1 or 2 stands for unimolecular or bimolecular.
A AC1 :
CH3 CH3
O O CH3
Fast +
H3C H3C O
H+
H
OCH3
CH3 CH3
slow
CH3 CH3
O + CH 3OH
+
H3C C O ←
→ H3C C
CH3 CH3
CH3 CH3
OH
H3C C O H 2O H3C C O +H
CH3 CH3
A AC2
O OH
+
Fast H
H3C C OC2H5 H3C C OC2H5
O H OH OH
Slow H 2 O
H3C C OC2H5 H3C C OC2H5 H3C C OC2H5
O H H OH
+ C2 H 5OH + H +
H3C OH
A AL1
O CH3 OH CH3
+
H 3C C O C CH3 
Fast H
→ H3C C O CH3
CH3 CH3
OH CH3 CH3 CH3

H 2 O(– H + )
H3C C O CH3 H 3C C → H3C C OH
CH3 CH3 CH3
H 3C C OH
BAC2
O O
O
Fast
:OH –
H3C C OH H3C
H3C
OH
OC2H5 OC2H5
+ OC 2 H 5
proton exchange
-
O O
H3C ←
→ H3C + C 2 H 5OH
-
O O
Acid Anhydrides
O O
R C O C R
Acid anhydrides are considered to be derived from carboxylic acids by the removal of a molecule
of water from the two molecules of the acid.
O
O
R C
2R C OH O + H 2O
carboxylic acid R C
O
acetic anhydride
Method of Preparation
1. Acylation: Carboxylic acid reacts with acyl chloride in the presence of pyridine to give
carboxylic acid anhydride.
O O O O
R C OH + R' C Cl + 
→R C O C R + Cl –
N N
2. Sodium salt of carboxylic acids also react with acyl chlorides to give
O O O O
R C ONa + R C Cl 
→ R C O C R + NaCl –
In this reaction a carboxylate ion acts as a nucleophile and brings about a nueleophilic
substitution reaction at the acyl carbon of acyl chloride.
3. Cyclic anhydrides: By simple heating the appropriate dicarboxylic acid. This

method leads to a five or six membered ring.
West Delhi Centre: 15, Central Market, West P unjabi Bagh, New D elhi - 110 026. Ph.: 32001147/48/49
O O
CH2 OH CH2
300° C
 → O + H 2O
CH2 OH CH2
O O
succinic acid
O
O
C OH
230° C
 → O + H2O
C OH
O
O
phthalic acid
phthalic anhydride
Chemical Properties: Acid anhydride are good acylating agents. Their reactions are less
vigorous than the corresponding acyl halides.
O O

ROH
→ R C OR + R' C OR
O O
O O 
NH3
→ R C NH2 + R' C NH2
O O
R C O C R

H2O
hydrolysis
→ R C OH + R' C OH
O O
 → + R'
–
OH / H 2 O
R C O C O
Illustration 5: An organic compound (A) on treatment with ethyl alcohol gives a carboxylic
acid (B) and a compound (C). Hydrolysis of (C) under acidic condition gives (B)
and (D). Oxidation of (D) with KMnO4 also give (B). The compound (B) on
heating with Ca (OH ) 2 gives (E), C 3 H 6 O . (E) does not give Tollen’s reagent
test and does not reduce fehling’s solution but forms 2, 4 dinitrophenyl
hydrazone.
Solution: The compound E must be a ketonic compound as it does not give Tollen’s test and
does not reduce Fehling’s solution but forms a 2, 4 dinitrophenyl hydrazone.
Therefore, its structure would be
O
i) (E) = E = H3C C CH3
West Delhi Centre: 15, Central Market, West P unjabi Bagh, New D elhi - 110 026. Ph.: 32001147/48/49
ii) Since E is obtained by heating (B) with Ca(OH) 2 the compound (B) must be
CH 3COOH . So the given compound (A) must be CH 3COOCOCH 3 . So the
given reactions are.
O O
H3C C O C CH3 

C2 H5 OH
→ CH 3COOH + CH 3COOC2 H 5
(A) (B) (C)
+
H
CH 3COCH 3 ←
Ca (OH) 2
 CH 3COOH + C 2 H 5OH
∆
(B) (D)
KMnO 4
[
Solved Problems
OBJECTIVE
Problem 1: Which of the following compound would be expected to decarboxylates when

heated
O O O O
(a) (b)
H3C OH H3C CH3
O O O O
CH3 OH
(c) H3C (d) H3C
O CH2
O O O
Solution: ∆
 → HC CH3
H3C OH 3
In case of β -keto acid, the ready decarboxylation occurs due to 6-membered low energy
transition state formation.
∴ (a)
O
Problem 2:
CH3OH
 →A A is :-
O
(a) CH2—CH2 (b) CH2—CH2
OH COOCH3 COOH OCH3

(c) both are correct (d) None is correct
O O
Solution: ⊕
This bond breaks hence intermediate is
O O–
+
CH3OH
O
OCH3
OH
∴(a)
Problem 3: End product of the following sequence of reaction is

O
1. I2 + NaOH,∆
 →
C—CH3 2. H+ ,∆
O
(a) O (b) O
Yellow ppt. of CHI3, Yellow ppt. of CHI3,
COOH CHO
(c) O (d)
Yellow ppt. of CHI3, COOH
Yellow ppt. of CHI3, COOH
Solution: O
Intermediate is
COOH
Which loses CO2 on heating (β-keto acid)
∴(c)
O
||
1.NaBH4
Problem 4: End product of this conversion CH 3 − C− CH 2 − CH 2 − CH 2 − CO 2 H → +
2.H2O,H
is
H3C
O
(a) O (b) O
H3C O
OH O
(c) O (d)
O
H3C H
Solution: NaBH4 reduces reactant to

CH3—CH—CH2—CH2—CH2—CO2H which forms ester
OH
∴ (a)
Problem 5: When acetic acid reacts with ketene, product formed

(a) ethyl acetate (b) aceto - acetic ester
(c) acetic anhydride (d) no reaction
Solution: CH3COOH + CH 2 = C = O → acetc anhydride

(Ketene)
∴(c)
Problem 6: R—CH2—CH2OH can be converted in R—CH2CH2COOH. The correct

sequence of reagents is
(a) PBr3, KCN, H+ (b) PBr3, KCN, H2
(c) KCN, H+ (d) HCN, PBr3, H+
PBr3 KCN
Solution: RCH2CH2OH  → RCH2CH2Br  → RCH2CH2CN
H 2O/H +
→ RCH2CH2COOH
∴ (a)
Problem 7: The pKa of acetylsalicylic acid (aspirin) is 3.5 . The pH of gastric juice in
human stomach is about 2-3 and pH in the small intestine is about 8. Aspirin
will be.
(a) Unionized in the small intestine and in the stomach
(b) Completely ionized in the stomach and almost unionized in the small
intestine.
(c) Ionized in the stomach and almost unionized in the small intestine
(d) Ionised in the small intestine and almost unionised in the stomach
Solution: More ionized in basic medium and less ionized in acidic medium, common ion
effect
∴ (d)
Problem 8: On subjecting mesityl oxide to the iodoform reaction, one of the products is the
sodium salt of an organic acid. Which acid is obtained?
(a) (CH3)2C=CH—CH2COOH (b) (CH3)2CH—COOH
(c) (CH3)2C=CH—COOH (d) (CH3)2C=CH—CO—COOH
Solution: O O
CH3 NaOH / I2
CH3
C=CH—C—CH3   → C=CH—C—OH + CHI3
CH3 mesityl oxide CH3
∴ (c)
Problem 9: The ease of alkaline hydrolysis is more for

COOCH3 COOCH3
(a) (b)
NO2 Cl
COOCH3 COOCH3
(d)
(c)
OCH3
Solution: COOCH3
Then is more electron deficiency on

carbonyl carbon.
NO2
∴ (a)
Problem 10: Which of the following does not undergo Hell - Volhard Zelinsky reaction?
(a) HCOOH (b) CCl3COOH
(c) C6H5COOH (d) All
Solution: None of these contain alpha H atom

∴ (d)
Problem 11: How many number of optically active isomers are possible for 2, 3-dibromo
butane 1, 4-dioic acid
(a) 2 (b) 3
(c) 4 (d) 1
Solution: (a)
Problem 12: Meso-tatric acid and dextro- tartaric acid are

(a) position isomers (b) racemic mixture
(c) enantiomers (d) diastereomers
Solution: (d)
Problem 13: Number of stereo isomers existing for

HOOC COOH
(a) 1 (b) 2
(c) 3 (d) 4
Solution: HOOC COOH H COOH HOOC H
H H HOOC H H COOH
Problem14:
O
CO2H
The above conversion can be done by which of the following process?

CH3
|
(a) HBr peroxide; CH3 − C − O − at high temperature, O3 – H2O
|
CH3
(b) HBr; CH3CH2O– at high temperature; O3 – H2O
(c) HI, CH3O– at high temperature, O3 – H2O in presence of Zn
(d) HCl peroxide
Solution: Br
O O

→
HBr

CH3CH 2 O
→
−

O3
→
∆ H 2O H3C OH
Problem 15: Which of the following compound is formed as major product when ethyl
propanoate and ethyl methanoate are reacted in the presence of sodium
ethoxide in ethyl alcohol followed by acidification?
O O
O
H5C 2O C CH C OC2H5 OC2H5
(a) (b) H
CH3
O
O O
O O
C C
(c) H OC 2H5 (d)
H3C CH 2 C C OC 2H5
CH3
Solution: (c)
Problem 16: CH3
H2C CH C COOH 

NaOH
CaO / ∆
→X
CH3
X will be
CH3
CH3
(a) (b) H2C CH C CH3
H3C CH C CH3
H
CH3
CH3
(c) (d) H2C CH C COONa
H3C CH C CH 2OH
CH3
Solution : (a)
Problem 17: CH3

O
H2O / H+
H3C O CH3 A (an acid) + B
18
CH3
Where A and B are, respectively,
O O
18
(a) H3C and Me3C OH (b) H3C and Me3C OH
OH OH
18
O O
18
(c) H3C and Me3C OH (d) H3C and Me3C OH
18 18
OH OH
Solution:
OH
O
H+
CMe3 slow
CMe3 H3C O
H3C O 18
18
OH
+ Me3C 
H 2O
→ Me3C − OH + H +
H3C O
18
The above mechanism of ester hydrolysis is known as alkyl-oxygen cleavage
unimolecular.
Problem 18: The iso-electric point of the α-amino acid (acidic) whose conjugate acid is as
shown below:
HOOC (CH2)3CH COOH
NH3
will lie in between the pH

(a) 2 and 4 (b) 5 and 7
(c) 9 and 11 (d) 12 and 14
Solution: pka 2 pka1

HOOC (CH2)3 CH COOH
NH3pKa3
pk a1 ≈ 2, pk a 2 ≈ 4 and pk a3 ≈ 9 (These data you need to know)
pka1 + pka 2
PI =
2
CH3
+
Problem19: H3C CH3 H ,
A + B
CH3
A → . A carboxylic acid (C)
Hot KMnO4
+
C + B →
H
A sweat smelling compound (D).
Compound (D) is
O O
(a) CH3C O (b) C O CH3
O CH3 O
(c) C O C CH3 (d) H3C CH C O

CH3 CH3
Solution: A= CH3 B = CH3 C CH2
CH3
Problem 20: Silver benzoate will react with bromine in acetone to give
Br
(a) (b)
COOAg O
(c) C OBr
(d)
Br
Solution: (b) Borodine Hunsdicker reaction.
Problem 21: The product formed in the reaction is
CH3 C CH2 C OC2H5 D+

Product
O O
(a) CH3 C CD2 C OC2H5 (b) CH3 C CH C OC2H5
O O OH O
(c) CD3 C CH C OC2H5
O OH (d) none
Solution: (a) Tautomerism in acidic medium.
Problem 22: An organic compound A (mol wt = 180) is acylated with CH3COCl to get
acylated compound of mol wt. 390. The no. of amino groups present per
molecule of the compound A is
(a) 2 (b) 5
(c) 4 (d) 6
Solution: (b)
Problem 23: The organic compound formed in the reaction

(i) Li.AlH4
C6H5COOCH3 +
(ii) H3O
(a) C6H5CH2OH & CH3OH (b) C6H5CH3 & CH3OH
(c) C6H5COOH & CH4 (d) C6H5CH3 & CH4
Solution : (a)
Problem 24: In the following reaction C is
CH2OH
CH2OH
CH3CH2COOH  → A 
SOCl 2
 → B
H2 ,Pd / BaSO 4
C
(a) CH3CH2CH2 CH CH2
O (b) CH3CH2CHO
O
(c) CH3CH2 CH
O (d) none of these
Solution: (c)
SoCl2
Solution : CH3CH2COOH CH3CH2CoCl H 2 ,Pd/BaSO4
CH3CH2CHO
CH 2 OH
CH 2 OH
O CH2
CH3 CH2 CH
O CH2
Problem 25: Identify the compound X in the following reaction

COOH
OH
Br2
CH 3 COOH
X
OH
COOH COBr
OH OH
(a) (b)
OH OH
COOH COOH
Br OH
(c) (d)
Br OH
OH OH
Solution: (d)
Problem 26: Acetoacetic ester behaves as

(a) an unsaturated hydroxy compound
(b) a keto compound
(c) Both of these ways
(d) None of these
[CET 2000]
Solution: (c)
Problem 27: Number of oxygen atoms in a acetamide molecule is
(a) 1 (b) 2
(c) 3 (d) 4
[BIT 1984]
Solution: (a)
Problem 28: Laboratory method for the preparation of acetyl chloride is

(a) CH3COOH + SOCl2 → CH3COCl
(b) CH3COOH + PCl3 → CH3COCl
(c) CH3COONa + PCl3 → CH3COCl
(d) all of these
[CET 2003]
Solution: (a)
Problem 29: C2H2 

HgOH 1%
H 2 SO4
→( A) 
[O ]
→ B , B is
(a) An acid (b) An aldehyde
(c) A ketone (d) Ethanol
[BIT 1991]
Solution: (a)
Problem 30: Rearrangement of an oxime to an amide in the presence of strong acid is called
(a) Curtius rearrangement (b) Fries rearrangement
(c) Backman rearrangement (d) Sandmeyer reaction
[Kerala CET 2000]
Solution: (c)
Problem 31: What is obtained, when propene is treated with N-bromo succinimide
(a) CH3 − C = CH 2 (b) BrCH2 – CH = CH2
|
Br
(c) BrCH2 – CH = CHBr (d) BrCH 2 − CH = CH 2 Br
|
Br
[MP PMT 2003]
Solution: (b)
Problem 32: The vapour of a carboxylic acid HA when passed over MnO2 at 573 K yields
propanone. The acid HA is
(a) Methanoic acid (b) Ethanoic acid
(c) Propanoic acid (d) Butanoic acid
Solution: (c)
Problem 33: What will happen if LiAlH4 is added to an ester

(a) Two units of alcohol are obtained
(b) One unit of alcohol and one unit of acid is obtained
(c) Two units of acids are obtained
(d) none of these
[CET 2000]
Solution: (d)
Problem 34: 2CH3COOH  MnO

3000 C
→ A, product ‘A’ in the reaction is
(a) CH3CH2CHO (b) CH3 – CH2 – OH
(c) CH3COCH3 (d) CH3 − C− O − C− CH3
|| ||
O O
[BIT 2003]
Solution: (d)
Problem 35: In the following sequence of reactions, what is D

CH3
[O] SOCl2 NaN3 Heat
A B C D
(a) Primary amine (b) An amide

(c) Phenyl isocyanate (d) A chain lengthened hydrocarbon
[UPSEAT 2002]
Solution: (b)
Problem 36: Which of the following reactions are not possible?

O
(a) H2C CH 2COOH 

Mg / Ether
→ H2C CH 2 C OH
Br MgBr
Br MgBr
H2 C H2C
(b)
+ Mg 
Ether
→
MgBr
O O O O
(c) C C
ONa  → CH MgBr
H3C 3 H3C ONa
Ether
CH3
MgBr
O O O O
(d) C
H H
CH3 
CH3 MgBr
→ CH3
CH3
Solution : (a, b)
Problem 37: Which of the following molecule shows the optical isomerism
NO2 COOH COOH
(a) (b)
COOH NO NO2
2
Cl CH3 Cl CH3
(c) C (d) C
H3C H3C CH3
Cl
Solution : (a, c)
Problem 38: Which of the following does/do not give positive Fehling solution test :
CHO
(a)
CHO (b) HCOOH
CHO
(c) HCHO (d)
Solution : (a, d)
Problem 39: Which of the following will liberate CO2 on reaction with NaHCO3:
(b) O 2N OH
(a) OH
NO2
(c) COOH (d) SO 3H
Solution: (b, c, d)
O 18
OH
Problem 40: C CH2 CH2 CH2 Br Products
OH
18
O18 O O
C (CH2)2 CH2 OH (b) C CH2
(a)
OH CH2 CH2
18
O O
(c) C
(d) None of the above
Solution: (b, c)
Problem 41: Match the List – I to List - II
List – I List – II (pKa)

O O
(a) C C CH3 (p) 3
H3 C O
O O
(b) C C (q) 5
H 3C OH
O O
(c) C C (r) 9
H3C CH3
O O
(d) C C (s) 11
H H
Solution : (a) → (s), (b) → (p), (c) → (r), (d) → (q)
Write-up I
An organic compound (A) having M.F. C9H9OCl (having no geometrical isomer) on oxidation with
KMnO4/H+ give 4 chloro, 2 hydroxy benzoic acid, give the answer of following questions based on
compound (A).
1. Compound A on reaction with Br2 /excess OH– gives

OH
CH2
CH3
(a) (b)
Cl O Br Br
Cl OH
CH2 CH2 CH 2
Br
(c) (d)
Br O
Cl OH Cl OH
2. Which of the following test is given by compound (A)?

(a) Gives white ppt with AgNO3 (b) Gives red ppt with Fehling solution
(c) Decolourised cold KMnO4 (d) Gives effervescence with NaHCO3
3. Oxidation of (A) followed by decarboxylation a compound is formed which reacts with Zn dust to
give another compound (B). The compound (B) is
Cl
Cl
(a) (b)
OH
Cl
Cl
(c) (d)
OH
Cl
Solution: 1. (d) 2. (c) 3. (a)
Write-up II
An organic compound A (C4H9ON) yields B (C3H9N) with Br2 and NaOH; Compound B on reaction with
NaNO2 + HCl gives a compound C, compound C on reaction with Cu at 300°C gives a compound
identical to that obtained by distillation of dry calcium salt of acetic acid.
1. Compound A will be
CH3
O
(a) CH NH2 (b)
H3C C
H3C NH2
O
CH3 NH
(c) (d) H3C CH3
N
H3C OH O
2. O
+ compound (B) 
∆
→D
Structure of D will be,

N CH3 OH
NH
(a) (b) CH3
CH3
CH3
N CH3
(c) (d) N
CH2
3. Compound (C) + I2 + OH– → E & F, E & F are

(a) CH3COONa + CHI3 (b) HCOONa + CHI3
OH
|
(c) CH3CHO + CHI3 (d) CH3 − CH − CH 3 + CHI3
Solution: 1. (a) 2. (a) 3. (a)
Subjective
Problem 1: Give structure of A, B, C and D

(a) A (C4H8) which add on Baeyer’s reagent gave optically active compound
(B) C4H10O2.
(b) A (C4H8) which add on per acid followed by hydrolysis in acidic medium
gave optically inactive compound (C) C4H10O2 [ an isomer of B].
(c) Isomer of [A], [D] gave two mono-bromo derivative on addition of HBr in
presence of peroxide and without peroxide and gave acetone on ozonolysis.
CH3 H CH3
Solution: dil. KMnO4 HO H
C C Baeyer's
reagent H OH
H CH3
(A) CH3
trans - 2- butene (Optically acitve)
Problem 2: Convert
COOH
NaOH Cl2 hν Na
Solution: COOH Cl
CaO ether
Problem 3: (i) An unknown compound (A) C7H12 discharge colour of Br2 and is oxidised
by KMnO4 / H + / ∆ to optically active carboxylic acid C4H9COOH. What will
be (A)?
(ii) A hydrocarbon (A) C7H10 on reduction with H2 /Pt gives compound (B) .
(A) does not react with H2, Ni / B (A) on oxidation with KMnO4 / H + / ∆ gives
3-oxohexanoic acid as the only organic product. What will be (A)?
Solution: (i) CH3 – CH2 – CH – CH = CH2

|
CH3
(ii)
CH2
or
Problem 4: Write the products:
KMnO4, ∆
A
KMnO4, cold
B
OH
Solution:
OH
O O
(A) (B) OH
Oxidative cleavage product syn hydroxylation product
NaOH / CaO Cl / uv Mg / ether D O

Problem 5: CH3COONa    → 2→   → 2→ X : X is
Solution: CH3D
Problem 6: A hydrocarbon A (m.f. C9H10) upon complete hydrogenation requires 4 moles

of H2 per mole of it. It gives a white precipitate with Tollen's reagent. Treatment
with NBS followed by alc.KOH gives hydrocarbon B (m.f. C9H8) which upon
drastic oxidation and subsequent decarboxylation yields benzene. The
compound A upon ozonolysis gives dioxal, formic acid and OHC—CH2—
CH(CHO)—CH2COOH. Identify A and B and give the reactions involved in
their identification. What will be final product when B is successively treated
with NaNH2, CH3I and Li - liq. NH3
Solution:
CH2—C≡CH CH2—C≡CH
and
(A) (B)
Reactions involved:
Br
CH2—C≡CH
CH2—C≡CH
NBS
 
→
(bro min ation at
allylic position)
(A) EtO-
-HBr
COOH CH2—C≡CH
← 
Na −Salt
[O]
heated with
sodalime
(B)
CH2—C≡CH CH2—COOH
Ozonolysis OHC + HCOOH
   →
+ CHO
CHO
CHO
H
C6H5CH2
NaNH2 CH3I Li−liq.NH C=C
C6H5CH2C≡CH   →  →    
3
→ CH3
H
Trans-1-phenyl,2-butyne
Problem 7: Treatment of 2, 4-pentanedione with KCN and CH3COOH, followed by

hydrolysis yields two products, (A) and (B). Both (A) and (B) are dicarboxylic
acids of formula C7H12O6. (A) melts at 98°C. When heated,(B) gives first a
lactonic acid (C7H10O5) and finally a dilactone (C7H8O4).
a) What structure must (B) have that permits ready formation of both a
monolactone and a dilactone ?
b) What is the structure of (A) ?
Solution: CH3 CH3 CH3 CH3
C O HO C COOH HO C COOH HOOC C OH
CH2 →
(i) KCN / CH 3COOH
(ii) H3O +
CH2 CH2 CH2
C O HO C COOH HOOC C OH HO C COOH
CH3 CH3 CH3 CH3
14444
4244444
3
(A) Meso Racemic
(B)
Compound (B) is a recemic modification. It gives monolactone (II), but the

remaining —OH and —COOH are cis; (II) can react further to form the dilactone.
O
OH COOH OH COOH O C
CH2 CH2
H3C C CH2 C CH3 
→ C C ∆
– H2O
→ C C
C O C O
COOH OH H3C CH3 H3C CH3
O O
(B) (II) Monolactone Dilactone
Problem 8: An organic compound (A) of formula C6H10O decolourises Br2/CCl4 colour but
has no reaction with ammonical cuprous chloride solution. (A) reacts with
Schiff’s reagent and also reduces Fehling’s solution. (A) on treatment with
silver oxide suspended in aqueous base gives compound (B). C6H10O2, which
evolves CO2 from aqueous NaHCO3. (B) on ozonolysis yields one mole each of
propanal and pyruvic acid. What are (A) and (B)?
Solution: Compound (A) contains olefinic double bond as it discharges the red colour of
Br2/CCl4. It also contains —CHO group as it gives positive tests for this group.
Since compound (B) liberates CO2 from NaHCO3 hence it contains —COOH
group. The structure of (B) is determined from its products of ozonolysis as
follows :
H COOH H COOH
C O + O C 
→
–2[O]
C C
C2 H5 CH3 C2 H 5 CH3
(A)
Propanal Pyruvic acid
Since (B) is obtained by the oxidation of (A) hence (A) is :

H CHO
C C
C2 H 5 CH3
Problem 9: A salt (A) of the formula C4H5O2Ag on refluxing with bromine gives (B),
C3H5Br. Compound (B) on heating with alcoholic KOH yields (C), C3H4, which
decolourises Br2/CCl4 and cold dilute KMnO4 solution, but does not react with
ammonical AgNO3 or Cu2Cl2. (C) on ozonolysis gives (D), C3H4O4, which on
heating eliminates CO2 to give acetic acid. What are (A) to (D ?
Solution: H2 C H2 C
CH Br  →
KOH
CH COOAg 
Br2
Re flux
→ C2 H 5 OH
H2 C H2 C
(A) (B)
H2 C COOH
∆
CH → H2C
(i) O3

– CO 2
→ CH 3COOH
(ii) H 2 O
Acetic acid
COOH
HC
(C) (D)
Problem 10: A neutral liquid of formula C7H14O2 is hydrolysed to an acid (A), and an
alcohol (B). Acid (A) has a neutralization equivalent of 74. Alcohol (B) is not
oxidized with an acid solution of Na2Cr2O7. What is the formula and name of
the original compound?
Solution: O
C CH3 CH3
H3 C O CH3 
HOH
→ H3C CH2 COOH + H3C C OH
CH3
CH3 (A)
CH3 (B)
H3 C C OH 
Na 2 Cr2 O7
+ Dil. H 2SO 4
→ No oxidation
CH3
Problem 11: An ester of molecular formula C8H16O2 on hydrolysis affords an acid (A) and
an alcohol (B). Oxidation of alcohol (B) with Na2Cr2O7 gives rise to an acid (C).
Sodium salts of acids (A) and (C) on fusion with solid NaOH yield propane in
each case. What is the structural formula of the original ester ?
Solution: O
CH 3CH 2 CH 2 — C — OCH 2 CH 2 CH 2 CH 3 
HOH
H+
→ CH 3CH 2 CH 2 COOH
(A )
+ CH 3CH 2 CH 2 CH 2 OH
(B)
Problem 12: Compound (A), C3H7Cl, reacts with alcoholic KOH to form (B), C3H6.
Compound (B) discharges Br2/CCl4 solution. Reaction of (A) with Mg in ether
and subsequent treatment with CO2 and dilute acid gives (C), whose molecular
formula is C4H8O2. When we add compound (C) to aqueous NaHCO3 solution,
bubbles are evolved. What are (A) to (C)?
Solution: Cl COOH
(A) = H C CH (B) = H3C CH (C) = H3C CH
3
CH3 CH2 CH3
Problem 13: Compound (A) has a neutralization equivalent of 116. It forms a semicarbazone
or phenyl hydrazone, and gives positive iodoform test. Compound (A) reacts
with SOCl2 to give (B) which on Rosenmund’s reduction gives (C). Clemmenson
reduction of (C) gives n-pentane. What are (A), (B) and (C)?
Solution: i) Since (A) forms semicarbazone and phenyl hydrazone, hence it has a >C=O
group.
O
As it also gives iodoform test hence it contains H3C C group in its

molecule.
ii) The neutralization equivalent of (A) is 116, hence it also contains a —COOH
group. Its formula can be deduced as follows :
O
116 – H3C C — + —COOH) = 116 – (43 + 45) = 28
The value 28 corresponds to two methyl groups.
Hence, (A) is
O
β α
H3C C — CH 2 CH 2 — COOH
( − keto valeric acid)
O O O
H3C 
→ H3C
SOCl2

→ H3C H2

8[H]
–2H 2 O
→ HC CH3
Pd / BaSO 4 3
n-pentane
COOH COCl CHO

(A) (B) (C)
Problem 14: An organic acid A, C3H4O3 is catalytically reduced in presence of ammonia to

give B, C3H7NO2. B reacts with acetyl chloride, hydrochloric acid and alcohols.
It can also react with nitrous acid to give another compound C, C3H6O3, along
with the evolution of nitrogen. What are A, B and C. Give reasons?
Solution: Compound A is acid having one –COOH group only, the remaining part C2H3O
can be
O
||
CH3 – C – only. Hence, structural formula of A is
O
||
CH3 – C – COOH
on catalytic reduction keto group is converted into secondary alcohol which with
ammonia will give amino acid, i.e.,
O OH
NH2
|| |
|
CH3 – C – COOH  → CH3 – CH – COOH 
–H2

O → CH3 – C – COOH
reduction HNH 2
|
H
with nitrous acid, B, react to give
NH2 OH
| |
CH3 – CH – COOH + HNO2 →CH3 – CH – COOH + N2↑ + H2O
(B) (C)
Problem 15: Compound A, C5H8O3, when heated with soda lime gives B which reacts with
HCN to give C, C reacts with PCl5 to give D which reacts with KCN to form E.
E, on alkaline hydrolysis gives a salt which is isolated and heated with soda lime
to produce n-butane. A, on careful oxidation with K2Cr2O7 gives acetic acid and
malonic acid. Give structural formulae of A to E.
Soda −lim e
Solution: (C5H8O3)   → Compound B → Compound (C)
HCN
PCl5
Careful oxidation with Compound E ← Compound D,

KCN
K2Cr2O7
COOH Alk. hydrolysis
CH3COOH + CH2 soda −lim e
Salt    → n-butane
COOH ∆
On Oxidation only two –COOH groups can be introduced, i.e., one to each carbon
undergoing C–C fission, but in the resulting products we have three –COOH
groups. Hence, one –COOH group is already there in compound A, the remaining
portion C4H7O–, resembles with Keto substituted alkyl group
C3H7 – C –
||
O
This indicates that the given organic compound A is Keto substituted acid. To
assign position to Keto group in carbon chain, we know that keto acids on careful
O
||
oxidation undergo C–C bond fission at a place where - C - is situated, further Keto
group is also converted into –COOH and remains with acid having small number
of carbon atoms. From the above discussion it is clear that acetic acid is formed
from.
O O
|| ||
CH3 − C − Arrangement C3H7CO – has CH3 − C− CH 2 − CH 2 − structure and
O
||
compound A is CH3 − C − CH2 − CH2 − COOH
A, with soda-lime undergoes decarboxylation to give
CH3 – CO – CH2– CH3 (B)
B, being Ketone will give addition product with HCN to form

OH
|
CH3 – C – CH2 – CH3 (C)
|
CN PCl5
Cl
|
CH3 – C – CH2 – CH3 (D)
|
CN KCN
CN
|
CH3 – C – CH2 – CH3
|
Alkaline hydrolysis
CN
COONa
|
Soda −lim e
CH3 – C – CH2 – CH3   → CH3 – CH2 – CH2 – CH3
| ∆ (n-butane)
COONa
Problem 16: a) Can the aromatic ring in benzoic acid stabilize the benzoate anion by π-
electron delocalization? Illustrate
b) Discuss the electronic effect of the p–NO2 group in p–NO2C6H4COO–
Solution: a) The only contributing structure I that delocalizes electron density from
PhCOO– has a positive charge on an O atom with only six electrons.
•• +
O
••
•
•
C
•• –
•–
O
••
•
I
The contribution from this extremely high energy resonance structure
is nil.
b) There is no direct resonance interaction between –COO– and –NO2. The
resonance interaction of the NO2 with the ring induces some positive charge
on the ring C bearing the COO– II, from which a strong electron with drawing
inductive effect is generated. This effect is base stabilizing and thus acid
strengthening.
O– O
+
N + C
O– O
II
[
KVPY
1. The compound that will give lactide on heating is – (2007)
(A) CH3 CH2 CH ( OH) COOH (B) CH3CH2CH(NH2)COOH
(C) CH3CH(OH)CH2COOH (D) CH3CH(NH2)CH2COOH
2. A compound that shows a distinct colour change on treatment with alcoholic ferric chloride is (2007)
(A) Anisole (B) Aspirin (C) Salicylic acid (D) Methyl benzoate
3. Which of the following is an anhydride? (2013)
(B)
(A)
(D)
(C)
Answer Key
1:A 2:C 3:B
Assignments (New Pattern)

SECTION – I Single Choice Questions
Level - I
1. Which of the following carboxylic acids is not reduced to the corresponding 1° alcohol by
LiAlH4?
(a) CH3CH(CH3)COOH (b) (Z)-CH3CH=CHCH2COOH
(c) p-O2NC6H4COOH (d) Cyclohexanecarboxylic acid
2. Which of the following dicarboxylic acids gives a cyclic anhydride on heating?

H2C COOH
(a) CH2(COOH)2 (b)
H2C COOH
(c) HOOC(CH2)4COOH (d) HOOC(CH2)5COOH
3. Which of the following dicarboxylic acids gives a linear polymeric anhydride?

(a) HOOC(CH2)3COOH (b) HOOC(CH2)4COOH
(c) HOOC(CH2)5COOH (d) HOOC(CH2)6COOH
4. Which of the following orders of reactivity of acid derivatives towards a nucleophile is

correct?
(a) acid chloride > anhydride > ester (b) acid chloride < anhydride < ester
(c) acid chloride > ester > anhydride (d) anhydride > acid chloride > ester
5. Which of the following orders regarding the base strength of a leaving group in a reaction
of an acid derivative with a nucleophile is correct?
(a) Cl– > RCOO– > RO– (b) Cl– > RO– > RCOO–
(c) RO > RCOO > Cl
– – –
(d) RO– > Cl– > RCOO–
6. Which of the following amides does not react with HNO2?
(a) CH3CONH2 (b) CH3CONHCH3
(c) CH3 CON — CH3 (d) HCONH2
|
C H5
2
7. The correct sequence of decreasing order of reactivity of hydrolysis of acid chlorides is
(a) PhCOCl > p-O2NC6H4COCl > p-CH3OC6H4COCl
(b) PhCOCl > p-CH3OC6H4COCl > p-O2NC6H4CoCl
(c) p-O2NC6H4COCl > PhCOCl > p-CH3OC6H4COCl
(d) p-O2NC6H4COCl > p-CH3OC6H4Cl > PhCOCl
8. Acetic acid in the vapour state has a molecular weight of 120 because :
(a) its molecule gets solidified
(b) its molecule gets stabilized by resonance
[
(c) it undergoes intermolecular H-bonding and exists as the dimer
(d) it forms anhydride in this condition.
9. Carbonation of alkyl magnesium halide followed by acidification gives :

(a) a carboxylic acid (b) an alcohol
(c) an anhydride (d) an aldehyde.
10. Reaction between solid ice and methyl magnesium bromide gives an addition compound
which on acidification yields :
(a) ethanoic acid (b) propanoic acid
(c) ethanal (d) ethanol.
11. Which reducing agents of the following can be used for the following transformation ?
CH3—CH=CH.COOH  → CH3CH=CH.CH2OH.
(a) LiAlH4 (b) BH3, THF
(c) H2/Ni (d) Na + C2H5OH.
12. Which of the following reactions is used to bring about the following conversion?
O
NH2
OH   → H3C
(i) N 3 H
H3C (ii) Conc. H 2SO4
(a) Hofmann reaction (b) Curtius reaction

(c) Ritter reaction (d) Schmidt reaction.
13. Which of the following compound would be expected to decarboxylates when heated
O O O O
(a) (b)
H3C OH H3C CH3
O O O O
CH3 OH
(c) H3C (d) H3C
O CH2
14. O
CH3OH
 →A A is
O
(a) CH2—CH2 (b) CH2—CH2
OH COOCH3 COOH OCH3

(c) both are correct (d) None is correct
15. The relative order of esterification of alcohols is

(a) 1° < 2° < 3° (b) 1° > 2° > 3°
(c) 1° > 3° > 2° (d) 1° < 3° < 2°
16. The treatment of an ester with LiAlH4 followed by acid hydrolysis produces
(a) two alcohols
(b) two acids
(c) two aldehydes
(d) one molecule of alcohol and another of carboxylic acid
17. Which of the following reagent/solution can be used to distinguish between methanoic
acid and ethanoic acid?
(a) Tollens reagent (b) FeCl3 solution
(c) NaOH solution (d) Na2CO3 solution
18. The Hell-Volhard-Zelinsky reaction is used in the synthesis of

(a) aldehydes (b) α-haloacids
(c) acid halides (d) ketones
19. Which of the following reducing agents can be used to reduce RCOOH to RCH2OH?
(a) NaBH4 (b) Na/EtOH
(c) LiAlH4 (d) H2/Catalyst
20. The acid in which —COOH is not present is :

(a) ethenoic acid (b) picric acid
(c) lactic acid (d) palmitic acid.
LEVEL - II
1. Which of the following reactants produces benzophenone on heating?

(a) Calcium formate + Calcium benzoate (b) Calcium acetate + Calcium benzoate
(c) Calcium benzoate (d) Calcium acetate + Calcium formate
2. Which of the following reactants would produce acetophenone on heating?

(a) Calcium acetate + Calcium formate (b) Calcium formate + Calcium benzoate
(c) Calcium acetate + Calcium benzoate (d) Calcium acetate
3. Which of the following sequences of rate of alkaline hydrolysis of esters is correct?

(a) CH3CH2COOCH3 < (CH3)2 CHCOOCH3 < (CH3)3CCOOCH3
(b) CH3CH2COOCH3 > (CH3)2 CHCOOCH3 > (CH3)3CCOOCH3
(c) CH3CH2COOCH3 > (CH3)2 CHCOOCH3 < (CH3)3CCOOCH3
(d) CH3CH2COOCH3 < (CH3)2 CHCOOCH3 > (CH3)3CCOOCH3
4. When propionic acid is treated with aqueous sodium bicarbonate, CO2 is liberated. The C
from CO2 comes from
(a) methyl group (b) carboxylic acid group
(c) methylene group (d) Bicarbonate
5. Which of the following carboxylic acids is not reduced to the corresponding 1° alcohol by
BH3/THF?
(a) CH3CH(CH3)CH2COOH (b) p-CH3COC6H4COOH
(c) m-O2NC6H4COOH (d) (Z)-CH3CH=CHCH2COOH
6. Which does not react with Fehling’s solution ?

(a) CH3CHO (b) C6H5CHO
[
(c) C6H12O6 (d) HCOOH.

7. Which does not form a phenyl hydrazone?
O O
(a) H3C C.COOH (b) H3C C CH2 CH3
O O
(c) H3C C OH (d) H3C C H
.
8. Which does not have a carbonyl group ?

(a) benzoic acid (b) ethanoic acid
(c) picric acid (d) aspirin.
9. Which of the following does not give iodoform?

(a) pyruvic acid (b) lactic acid
(c) actophenone (d) propionic acid.
10. The sodium salt of the acid which does not form an alkane when subjected to electrolysis
(a) sodium formate (b) sodium acetate
(c) sodium propionate (d) sodium butanoate
SECTION – II More than one Choice Questions
1. Which of the following is used to perform following transformation ?

OH Cl
H3C HC
→ 3
O O
(a) SOCl2 (b) PCl5
(c) PCl3 (d) SO2Cl2.
2. One can distinguish between HCOOH and CH3COOH with :

(a) NaHCO3 (b) H2SO4
(c) Tollens reagent (d) Fehling’s solution.
3. Which of the following decarboxylates readily in the temperature range 100–150°C ?

(a) CH2=CH.CH2COOH (b) O2NCH2COOH
(c) NC—CH2COOH (d) CH3COCH2COOH.
4. Formic acid and formaldehyde can not be distinguished by treating with

(a) Benedict’s solution (b) Tollen’s reagent
(c) Fehling’s solution (d) NaHCO3
+
5. CH2(COOEt)2 + BrCH2CH2CH2Br 
NaOEt
excess
→ ‘A” 
H / H 2O
∆
→B
COOEt COOH
(a) A = COOEt (b) B =
COOEt CH = CHCOOH
(c) A = (d) B =
O
||
6. (A) 
→ CH3 − C− CH3 + Aldehyde 
Ozonolysis [O ]
→ (B) 
P / Br2
→ (C) 
Hydrolysis
→ (D)
(i) HCN/CN-
Hydroxy acid
(ii) Hydrolysis
which of the following compounds can be identified as from A to D.
CH3 CH3 (b) CH3 CH COOH
(a) C CH CH
CH3 CH3 CH3
Br OH
(c) CH3 C COOH (d) CH3 C COOH
CH3 CH3
7. Which of the following statements are correct ?

(a) Formic acid is stronger acid than acetic acid
(b) o-bromobenzoic acid is weaker than o-chlorobenzoic acid
(c) lactic acid does not respond to silver mirror test
(d) benzaldehyde does not reduce fehling’s solution
8. CH3COOH and C6H5COOH can be distinguished by

(a) Flame test (b) Solubility in water
(c) physical state (d) none of these
9. Of the following orders regarding basicity which are incorrent

(a) CH3CH2NH2 > PhCONH2 > CH3CONH2 (b) CH3CH2NH2 < PhCONH2 >
CH3CONH2
(c) CH3CH2NH2 > PhCONH2 < CH3CONH2 (d) CH3CH2NH2 < PhCONH2 >
CH3CONH2
CONH2 NH2
10. + Br2 + 4KOH + K2CO3 + 2KBr + 2H2O
In above reaction, following intermediates are formed

O
(a) R C N Br
H (b) R – N = C = O
(c) R – NH2 (d) none of these
[
SECTION – III Comprehension Type Questions
Write-up I
Menthanoic acid, the first member of carboxylic acid series, when warmed with
concentrated sulphuric acid decompose in the following way and evolve carbon
monoxide.
O O +
O O
+
H C OH 
H
→ H C − H2O
OH2  → −H+
H C ←
→ H C  → C ≡ O + H+
The driving force for this reaction lies in the fact that the HC≡O+ ion is very unstable acid
and thus easily loses H+.
1. Formic acid on heating with conc. H2SO4 gives

(a) CO2 + H2 (b) CO + H2O
(c) CO (d) H2O
2. What happens when acetic acid is treated with conc. H2SO4?

(a) CO + H2O (b) CH4 + CO2
(c) CO + CH4 (d) No reaction
3. If acetic acid is replaced by triphenylacetic acid, the products formed will be

(a) (C6H5)3CH + CO (b) (C6H5)3CH + CO2
(c) (C6H5)3COH + CO (d) No reaction
4. If formic acid is replaced by benzoylformic acid, C6H5COCOOH the product formed will
be
(a) C6H5COOH + CO + CO2 (b) C6H5COOH + CO2
(c) C6H5COOH + CO (d) C6H5CHO + CO2
Write-up II
Amides undergo hydrolysis to yield carboxylic acid plus amine on heating in either
aqueous acid or aqueous base. The conditions required for amide hydrolysis are more
severe than those required for the hydrolysis of esters, anhydrides or acid chlorides, but
the mechanism is similar (nucleophilic acyl substitution). Nucleophilic acyl substitutions
involve a tetrahedral intermediate, hence these are quite different from alkyl substitution
(RCH 2 Br NaCN
→ RCH 2CN) which involves a pentavalent intermediate or transition
state.
One of the important reactions of esters is their reaction with two equivalent of Grignard
reagent to give tertiary alcohols.
5. The mechanism involved during the hydrolysis of acid derivatives is:

(a) elimination-addition (b) addition-elimination
(c) nucleophilic addition elimination (d) electrophilic addition elimination
6. Which of the following constitutes the best substrate during the acidic hydrolysis of
amides?
O O
(a) (b)
R C NH2 R C NH3
OH OH
(c) (d)
R C NH2 R C NH3
7. For which functional derivative of carboxylic acids, acidic hydrolysis is the fastest ?
(a) Acid chlorides (b) Acid amides
(c) Acid anhydrides (d) Esters
O
8. When O is treated with two equivalent of methyl magnesium iodide and the
product acidified the final product will be

OH
(a) OH (b)
OH OH
HO OH
(c) OH (d) OH
Write-up III
An aromatic hydrocarbon (A) (mol. wt. = 92) containing C = 91.3% and H = 8.7% gave on
treatment with chlorine three isomeric compounds (B), (C) and (D) each containing 28%
chlorine. On oxidation, each of three gave monobasic acids (X), (Y) and (Z) respectively.
The acid (X) can also be obtained by the oxidation of (A) while acids (Y) and (Z) contained
chlorine also. The acid (X) on distillation with sodalime gave benzene while acids Y and
Z on similar treatment gave chlorobenzne.
9. Compound ‘A’ may be

CH3
CH3 (b)
(a)
CH3
(c) Both (a) and (b) (d) None of these
10. Compound ‘B’ may be

Cl
CH2Cl CH3
(a) (b)
CH3
(c)
(d) None of these
Cl
11. Compound ‘X’ may be

COOH
COOH
(a)
(b)
Cl
Cl
HOOC
(c)
(d) None of these
12. Compound ‘Y’ may be

Cl Cl
HOOC HOOC
(a) (b)
Cl
(c) Both (a) and (b) (d) None of these
Answers to Assignments
SECTION - I
LEVEL - I
1. (c) 5. (c) 9. (a) 13. (a) 17. (a)

2. (b) 6. (c) 10. (a) 14. (a 18. (b)
3. (d) 7. (c) 11. (a) 15. (b) 19. (c)
4. (a) 8. (c) 12. (d) 16. (a) 20. (b)
LEVEL - II
1. (c) 4. (d) 7. (c) 10. (a)

2. (c) 5. (d) 8. (c)
3. (b) 6. (b) 9. (d)
SECTION - II
1. (a, b, c) 3. (a, d) 5. (a, b) 7. (a, b, d)

2. (c, d) 4. (a, b, c) 6. (a, b, c, d) 8. (a, b, c)
[Type text]
9. (b, c, d) 10. (a, b)
SECTION - III
1. (b) 2. (d) 3. (c) 4. (c) 5. (c)
6. (c) 7. (a) 8. (b) 9. (a) 10. (a)
11. (b) 12. (a)
[Type text]

Carboxylic Acids and Its Derivatives PDF

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Chemistry: Carboxylic Acids and its Derivatives -1

C group and acts as a separate functional group, called, carboxylic group.

H3C CH2 CH CH2 CH2 COOH

Dicarboxylic acid are named as alkanedioic acid.

H3C O CH2 CH3 H3C CH2 OC2H5

Acid Amides: Acid amides are named as alkanamide

H3C NH2 H3C NH2

General Methods of Preparation

2. By oxidation of aldehydes: Aldehydes on oxidation with usual oxidizing agent gives

b) RCH = CHR ′ →RCOOH + R ′COOH

4. By carboxylation of Grignard Reagent

The mechanism of hydrolysis of R—CN is as follows.

6. By oxidation of alkyl benzene

The order of benzoic acid formation by oxidation of alkyl benzene.

Physical Properties of Carboxylic Acid

Chemical Properties of Carboxylic Acid

Acidity— RCOOH > HOH > ROH > CH ≡ CH > NH 3 > RH

ClCH 2 — COOH < Cl2 CHCOOH < Cl3COOH

Reaction due to cleavage of —O—H bond as acid

i) Reaction with active metals [alkali and alkaline metal]

ii) Reaction with CaO

iii) Reaction with Bicarbonates and Carbonates

Illustration1: Compound A, C 4 H 8 O2 has the following properties.

Solution: i) C4 H 8O 2 react with NaHCO3 to liberate CO 2 and so —COOH group is

Since both give propane on decarboxylation

iii) However C8 H14 O 4 Ca i.e. Ca salt of acid on heating

CH 2 O + OCH — CH 2 Br ←  CH 2 = CH — CH 2 Br ← CH 2 = CH — CH 2

Reaction Involving Cleavage of —OH Group

The relative reactivity of alcohol to ester formation markedly dependent on their

CH3OH > CH 3CH 2 OH > (CH3 )2 CHOH > (CH3 )3 COH

2. Formation of acid chloride

Reactions Involving —COOH Group

R — COONa + NaOH 

Mechanism: Reaction proceeds through free radical mechanism in various steps.

Chain propagation step

CH3 CH3 CH3

5. Decarboxylation of Carboxylic Acid

The usual stability of carbon dioxide result in exothermic decarboxylation of carboxylic

There are two facts on which ease of decarboxylation depends.

i) When the carboxylate ion decarboxylate, it forms a resonance stabilized enolate

OH  → O  → Ph CH2 +CO2

Heating of Dicarboxylic Acids

Heating of α, β and γ Hydroxy Acid

ii) CH2 H3C O

Reaction of α, β and γ halo carboxylic acid with aq. NaOH.

COOH  → H3C

Illustration 4: A hydrocarbon [X] C8H8 gave the following reactions:

Solution: HC CH2 HC CH2

3 HC CH + Red hot Fe tube

Abnormal Behaviour of Formic Acid

Derivatives of Carboxylic Acid

Relative Reactivity of Acid Derivatives

RCOCl > (RCO)2 O > RCOOR > R — CONH 2

i) basicity of leaving group and

Acid derivatives undergo nucleophilic substitution in two steps.

a) First step involves addition of nucleophile to electron deficient carbon atom of

H 2 N – > RO – > RCOO – > Cl –

Acyl Chloride RCOCl

2. Acylation of aromatic compound [Friedel Craft’s reaction]

4. Reaction with KCN

6. Reaction of acyl chloride with diazomethane in presence of Ag 2 O and water. (Arndt –

2. Amides from acid anhydride

3. From Esters (Ammonolysis): Ester undergoes nucleophilic substitution at their acyl