JEEMAIN.

GURU

CARBOXYLIC ACID AND THEIR DERIVATIVES

Organic compounds having –COOH group called Carboxylic group.This functional group is composed of
O
Carbonyl ( C ) and hydroxyl (—OH) group.

O O

C + —OH  C OH
Carbonyl group Hydroxyl group Carboxylic group
The properties of the carboxylic group are not simply the combined properties of these two groups, but it has
its own distinctive properties.The acidic nature of carboxylic acids is due to the presence of replaceable H-atom
in the Carboxylic group.The general formula is CnH 2nO2 .
 Classification :
Monocarboxylic acid (RCOOH) :
Having one carboxylic group, also called monobasic acid. General formula - CnH2nO2 ( n = 1, 2, 3, ........).Higher
mono carboxylic acids are called fatty acids.
Example : CH 3COOH acetic acid
Dicarboxylic acid : Having two carboxylic groups, also called dibasic acid.

COOH
Example : Oxalic acid
COOH
Tricarboxylic acid : Having three carboxylic groups also called tribasic acid.

CH2COOH
Example : HO C COOH Citric acid

CH2COOH

N O M E N C L AT U R E
Acid Common name IUPAC name
HCO OH Formic acid (formica-red ants) Methanoic acid
CH 3 COOH Acetic acid (acetum-vinegar) Ethanoic acid
CH 3 CH 2 COOH Propionic acid (Propan-first pion-fat) Propanoic acid
CH 3 CH 2 CH 2 COOH Butyric acid (Butter-butyrums) Butanoic acid
CH 3 CH 2 CH 2 CH 2 COOH Valeric acid (valerian-plant root) Pentanoic acid
C 5 H 11 COOH Caproic acid Hexanoic acid
C 7 H 15 COOH Caprylic acid Octanoic acid
C 9 H 19 COOH Capric acid Decanoic acid

Last three acids are found in goat fat word - (Caper-Goat).

 General Met ho d of Preparat ion
1. By oxidation of primary alcohol with acidic KMnO 4 or acidic K 2 Cr 2 O 7 :

KMnO / H 
4
R–CH2OH + [O] 
K Cr O / H 
RCHO + H2O 
[O ]
 RCOOH
2 2 7
JEEMAIN.GURU
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.

H 
–
R–CHO + [O]   R–COO 
Tollen 's Re agent  R–COOH

C6H 5CHO + [O]   H 

Tollen ' s Re agent
 C 6H 5COO   C 6H 5COOH
3. By oxidation of alkenes :

( i ) conc. KMnO 4 / OH heat
(a) RCH = CHR'  ( ii ) H O 
 RCOOH + R'COOH
3

(i ) O 3
(b) RCH = CHR'   RCOOH + R'COOH
( ii ) H 2 O, Distill

4. By Carboxylat ion of Grignard Reagent :

O O
Mg CO 2   H2 O / H 
R–Br 
Dry ether
RMgBr  R––C––OMgBr  
 R—C—OH
 MgBr ( OH )

5. By hydrolysis of ac yl derivat ive s of carboxylic acid :

O
H
R––C––Cl + H2O   R–COOH + HCl

O

(R – CO)2O + H2O H
 R–COOH + R––C––OH

R – COOR' + H2O H
  R–COOH + ROH

O

H
R––C––NH2 + H2O  R–COOH + NH4

6 Cya nide hydrolysis w it h di lute acids :

3H O
R – CN  RCOOH
The mechanism of hydrolysis of R–CN is as follows.

H 
R––CN R––C NH R––C=NH
:

OH2 
O
H H
H H
O
H2O  
R NH2 R NH2 R NH2
OH OH OH

OH O

R NH3 R + NH
4

OH OH
JEEMAIN.GURU
6. By oxidation of alkyl benzene :

CH3 COOH

(i) KMnO4/OH
(ii) H3O

Alkyl group having no -H atom will not be oxidized to –COOH. Any alkyl group containing at least one -H
atom will be oxidized to –COOH. The product of oxidation will be benzoic acid.

H2C––CH2CH3 COOH


(i) KMnO4/OH
(ii) H3O

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 Proper t ie s of Carboxylic Acid :
These are polar substances and can form H-bonds with each other to form dimmer structures.

O -----H ––O
R R
O––H -----O

 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.
 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 result for the relatively lower
melting point.
The melting point and boiling points 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.
JEEMAIN.GURU
 Chemical Proper t ie s 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  R R
H
••
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 subst ituent s on Acidit y :
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.
(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 > NH3 > RH
Basicity ––RCOO– < OH– < HC  C– < NH2– < R–

 
O O
R 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 < Cl 2 CHCOOH < Cl 3 CCOOH
The increase in the no. of chloro substituent on -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
JEEMAIN.GURU
(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
CH 3 –CH 2 –CH 2 –COOH < CH 2 = CH–CH 2 –COOH < NC–CH 2 –COOH
 
(sp2) (sp)
(iii) Effect of the position of the substituent : The effect of the substituent decreases as its distance from
—COOH group increases.

Cl Cl
CH3––CH––COOH > CH2––CH2––COOH
 -chloro propanoic acid  -chloro propanoic acid
electron withdrawing electron withdrawing
effect more effect less
 Or t ho 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, –NO2 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 + H2 ( )

(ii) Reaction with CaO :

2R –COOH + CaO  (RCOO)2Ca + H2O
JEEMAIN.GURU
(iii) Reaction with Bicarbonates and Carbonates :
Carboxylic acid reacts with carbonates and bicarbonates to liberate CO2 gas

O
NaHCO3
R–––COOH R—C—ONa + CO2 + H2O
CaC
O3
O
R––C––O Ca + CO2 + H2O
2

 React ion Involv i ng Cleavage of –OH Group :

1. Esterification :
When carboxylic acid reacts with alcohol in the presence of conc. H2SO4 to form ester, it is known as esterification
conc. H 2 SO 4
R C OH + R OH  R C OR + H2O
O O

Mechanism :
H2SO4    H+ + HSO 4–
::

+
R—C—O—H + H R—C—O—H
O OH



OH OH OH OH
+
 –H
R—C
: :

R—C—O—H + ROH R—C—OH R—C—OH2 R—C R—C—OR'


OH O OR' OR' OR' O
 H R'
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
CH 3 OH > CH 3CH 2OH > (CH 3 ) 2 CHOH > (CH 3) 3 COH
H––COOH > CH 3 COOH > (CH 3 ) 2 CHCOOH > (CH 3 ) 3 CCOOH
2. Format ion of acid chloride :

+ PCl5
R––COCl + HCl + POCl3
C6H5N

+ SOCl2
R—COOH R––COCl + SO2+ HCl
C5H5N

+ SO2Cl2
R––COCl + SO3+ HCl
C5H5N

3. Format ion of Acid Anhydride :

Carboxylic acid on treatment with any dehydrating agent as P2O 5 to form anhydride by elimination of water
molecule.
O
O
P2O5
R
2R—C—OH  O + H2O
R
O
JEEMAIN.GURU

CH2COOH P2O5
CH2CO

O + H2O
CH2COOH CH2CO
succinic acid succinic anhydride

4. Format ion of Amide s :

O O O
–  heat
..
R—C—OH + MeNH2 R—C—O NH3Me R—C—NH
–H2O

Me

The lone pair electron on N atom undergoes resonance and hence N atom carries partial +ve charge on it.

O O
.. 
R—C—NH R––C N––H
Me Me
Thus extent of H-bonding increases which makes the boiling and melting points of amides higher than other
acid derivatives.
 React ions Involv i ng –COOH Group :
1. Schmidt Reaction :
Carboxylic acid reacts with hydrazoic acid in the presence of conc. H2SO4 at 90°C forming primary amine.

2
Conc. H SO
4
R—COOH + N3H   R—NH2 + N2 + CO2
Mechanism :

O OH OH
HN3
R—C + H R—C R—C —OH

OH OH H—N —N N
–H2O
O
–H
R—C—O—H
–N2
R—N=C=O R—C 
isocyanate N—N N

–H2O N—N N

R—NH2 + CO2

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.

sada lime
R–––COOH    R––H + CO2

3. Hunsdicker Reaction :

Br2
R––COOH 
Ag 2 O –
 R––COO Ag
+   R––Br + AgBr + CO
in CCl 4 2
JEEMAIN.GURU
Mechanism : Reaction proceeds through free radical mechanism in various steps.
(i) Chain initiation :

O O
• •
R––C––O––Br R––C––O + Br

(ii) Chain propagation step :

O
R––C––O• R•+ CO2

O O
R––C––O––Br + R• R––Br + R––C––O•

(iii) Chain termination :

• •
R+ R R—R

O O
• •
R—C—O+R R—C—O—R
• •
Br+ Br Br2

4. Wit h exce ss of orga nometal lic compounds :

CH3MgBr  
RCOOH RCOO MgBr + CH4
CH3Li
 
R––COO Li + CH4
CH3Li OH
  2H2O
R––C––(O Li)2 Hydrolysis
R––C––OH R––C O

CH3 CH3 CH3

acetone
2 moles of organometallic compounds are needed to form ketone.
5. Hel l-Volhard-Zeli nsky React ion :
This is -halogenation of a carboxylic acid.
Br
OH OH
Red P/Br2
R R
O O
-bromo acid
Possible Mechanism for the reaction is :

Br Br

–Br2 H2O
H3C COOH H3C COBr H3C COBr H3C COOH

The purpose of PBr3 is to convert –OH into –Br to make -hydrogen atom more acidic to be replaced by Br
atom of Br2. The reaction does not stop at monosubstitution but continues till the -hydrogen are replaced.
JEEMAIN.GURU

Cl O
Cl2 Cl 2 Cl 2
H3C––COOH 
 H2C
Re d P
C OH 
Re d P
 CHCl COOH 
2 Re d P
 CCl COOH
3

The reaction has a great synthetic importance as the halogen atom can be replaced by a number of other
groups giving useful products.

NH2
amino acid
R
+NH3 COOH
OH
Cl +KOH(aq.) R
–KCl COOH hydroxy acid
R
COOH KOH(alco)
R
–HCl COOH unsaturated acid

COOH H2O/H
COOH
KCN R R
–KCl
CN COOH

6. Heating of  -keto acid :

O O O
100–150°C
R––C––CHC––OH
2 R––C––CH3 + CO2
 -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
–CO2 – H
R––C––CH2C––O R––C––CH2 R––C––CH3


O
R––C CH2
Resonance stabilized enolate anion

This anion is much more stable than the anion RCH 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 -keto
acid on warming alone or in presence of a base undergoes rapid removal of CO2.


H3C––C––CH2C––OH H3C––C––CH3 + CO2
O O O
Mechanism :

CH2 CH2
 Y––C C=O –CO2 Tautomerisation
Y––C C=O Y––C=CH2 Y––C––CH3
O O O O OH O
H H keto form
6 membered transition state
JEEMAIN.GURU
Here y can be substituents like
OH – diacid ; R – -keto acid
H –  aldehyde acid ; X –  halo acid

Br O Br O
KOH –CO2
Ph OH base Ph O Ph CH2 + CO2

This decarboxylation proceeds through elimination.

7. Heating of ,  and  Hydroxy Acid :

O
H3C CH3
2H3C  COOH O

(i)
OH O
H H
O
-hydroxy Acid Lactides

CH2
(ii) H3C––CH C=O  H3C O

OH OH OH
-hydroxy Acid Unsaturatd Carboxylic Acid

CH2·CH2
(iii) H3C––CH C=O  H

H3C O O
OH
.. OH

-hydroxy Acid 5-methyldihydrofuran-2-one

8. Reaction of ,  and  halo carboxylic acid with aq. NaOH :

H3C  COOH H3C COO

OH

Br OH

H
H3C  COO
OH
COOH E2
H3C
Br

CH2 Br
H2C CH2 OH CH2 SN2 (Br)

– O O
Br C=O O O
HO Cyclization of  haloacid
JEEMAIN.GURU

9. Heating of Dicarboxylic Acids :

CH2CH2
–H2O
O C C O
O O O
O O
H H
Succinic acid Succinic anhydride

(CH2)3
HOOC COOH O O O
Glutamic anhydride

10. Oxidat ion of Carboxylic acid at Alkyl Group :

Acid on treatment with mild oxidising agent such as H2O2, is oxidized at the  position.


H 2O2
CH 3 C H 2  C H 2 COOH  [O ]  H3C
COOH
OH
3-hydroxybutanoic acid

Oxidation can also occur at  carbon atom on treatment with oxidizing agent like selenium dioxide SeO2.

SeO
RCH2COOH + [O] 

2 R COOH + Se + H2O

O
Keto acid

 Abnormal Behav iour of Formic Acid :

The behaviour of formic acid is different from other carboxylic acid due to presence of aldehydic group.

O
Aldehydic Group Carboxylic Group
H––C––OH

 Reaction with :
(a) 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 + Ag2O  CO2 + H2O + 2Ag  Silver mirror
H–COOH + 2CuO  CO2 + H2O + Cu2O  Red ppt.
(b) Reaction with HgCl 2 : Formic acid forms white ppt. of Hg2Cl2 with HgCl2 which is converted to Grey
ppt of mercury.
2HCOOH + HgCl2  CO2 + Hg2Cl2  + 2HCl
white ppt.
JEEMAIN.GURU

Te st for HCOOH and CH 3 COOH

Te s t HCOOH C H 3C O O H
(i) Reducing character
Reducing agents -
Tollen reagent Silver mirror –
Fehling solution Cu 2O red –
HgCl 2 Hg 2 Cl 2 –
Corrosive sublimate Calomel –
K 2 Cr 2 O 7 Cr + 3 –
(ii) Decarboxylation. Na 2CO 3 + H 2 CH 4
(iii) Heating at 160 0 C CO 2 + H 2 –
(iv) Heating sodium COONa
salts of acids COONa –
at 360 0 C 
 HCl

COOH
+ NaCl
COOH

5. Conc.H 2 SO 4 CO + H 2 O Dissolve

6. P 2O 5 – Anhydride

7. Cl2 / P CO 2 + 2HCl Products are mono, di,

tri chloro acetic acid.
8. Ca salt heat H CH O CH 3 COCH 3

 Use s of Formic Acid :

(i) As an antiseptic
(ii) For preservation of fruits.
(iii) For leather tanning.
(iv) In dying wool and cotton fabrics.
(v) As a coagulating agent for rubber.
(vi) For hydrogenation of oil as Ni-formate.
 Uses of Acetic Acid :
(i) Vinegar (6 - 10% solution) used as table acid and manufacture of pickles.
(ii) In the form of salts, it is used in medicine and paints.
(iii) For manufacture of rubber from latex and casein from milk CH3COOH is used as coagulant.
(iv) Al and Cr acetates are used as mordants.
(v) In the manufacture of dyes and perfumes.
(vi) As a solvent and laboratory reagent.
JEEMAIN.GURU

BENZOIC ACID (C 6 H 5 COOH)

 General Met ho d of Preparat i on :

[O]
C6H5CHO
H+ /KMnO4
C6H5CH3
H3O+
C6H5CN
aq. KOH
C6H5CCl3
(i) Co2 (ii) H2O
C6H5MgBr
Zn
C6HCOOH
5
H O C6H4COOH

(o, m, p)

H2O
C6H5COCl
H2O
C6H5COOR
(i) COCl2/AlCl3
C6H6
H2O

 Chemical proper t i e s :

NaOH Ca Salt
C6H5COONa C6H5COC6H5


NaHCO3 CH2OH
C6H5COONa + H2O + CO2
reduction
Na/amyl alcohol
C2H5OH
C6H5COOC2H5
H2SO4
COOH
PCl5
C6H5COCl + POCl3 + HCl conc. HNO3/H2SO4

NO2
SOCl2
C6H5COCl + SO2 + HCl
COOH
P2O5 C6H5COOH Fumming
(C6H5CO)2O H2SO4
SO3H
Soda
C6H6 COOH
lime

Cl2/FeCl3
N3H
C6H5NH2 Cl
H2SO4


C6H5Br Neutral FeCl3
Hunsdiker buff coloured ppt.
(test)

LiAlH4
C6H5CH2OH

C6H5CONH2 (i) NH3

(ii) 
JEEMAIN.GURU

ACID DERIVATIVES
 Derivatives of Carboxylic Acid
The –OH of an acid can be replaced by –Cl, –OR, or –NH2 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
–OH
R C OH 
+Z R C Z
Acid Acid derivative
O
R C is Acyl group and Z is nucleophile Cl  , CH 3 COO  , C 2 H 5 O  , NH 2 etc.

O
–OH
+X
R Acyl halide
X
O
–OH
R Amide
O +NH2
NH2
R
OH O
–OH Ester
R
+ OR
OR

–OH
R O R Anhydride
–RCOO

O O
 Characterist ic react ion for acid derivat ive s is nucleoph i lic subst itut ion react ion :
Mechanism :
..
O O:
.. O
..
CH3 C + Nu  CH3 C Nu CH3 C Nu + Z
Z Z
sp2 hybrid C - atom sp3 hybrid C - atom
In this reaction Z is leaving group. Weak bases are good leaving groups.
Reactivity order - depends on the basic Character of Z

basicity : Cl – < CH 3 COO – < C 2 H 5 O – < NH 2–

–
In the given groups Cl is the weakest base so it is best leaving group.

 React ivi lt y order : CH 3 COCl > CH 3 COOCOCH 3 > CH 2 COOC 2 H 5 > CH 3 CONH 2
– –
In acid derivatives the carbonyl group > C O is attached to highly electronegative Cl , CH3COO , NH2– etc.
group due to electron withdrawing effect of these groups, the electron density on the carbonyl carbon is
 
reduced further. Thus acetyl group is readily attacked by Nu shows nucleophilic substitution reaction.
 Basicit y of leav i ng 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.
JEEMAIN.GURU
H2N – > RO – > RCOO – > Cl –
Basicity  
Ractivity 
R R 
O O
 Re sona nce Effect : L: L
Resonating 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 becasuse the protonation of the acyl compound
would facillitate 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.
 Met ho d of Preparat ion :
Carboxylic acid chloride can be prepared by the reaction of carboxylic acid with PCl5 or SOCl2 of PCl3 or SO2Cl2.
PCl5
RCOCl + HCl + POCl3
C5H5N

PCl5
RCOCl + H3PO3
C5H5N
R––COOH
SOCl2
RCOCl + SO2 + HCl
C5H5N
SO2Cl2
RCOCl + SO3 + HCl
C5H5N
 Chemical Proper t ie s :
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
CH3NH2
R––C––Cl R––C––NH––CH3
N-methylacetamide
O
(R)2NH R
R––C––N
R
N, N-dimethylacetamide
O
H2O (water)
R––C––OH
O
OH(aq.)base
R––C––O+ Cl
JEEMAIN.GURU

2. Ac ylat ion of aromat ic compound [Friedel Craft's react ion] :

R O

anhy. AlCl3
+ RCOCl + HCl

R
+ CH3COCl Acetophenone

+ C6H5COCl benzophenone

3. Cataly t ic hydrogenat ion (Rosenmund's React ion) :

O
Pd
R––C––Cl + H2 BaSO4
RCHO + HCl

LiAlH 4 or NaBH 4
RCOCl + 4H 
or C 2 H 5 OH  Na
 R–CH OH + HCl
2

Mechanism :


O O O OH
LiAlH4 
–Cl LiAlH4
R––C––Cl H
R––C––Cl R––C R––CH2

H H
intermediate aldehyde Alcohol

4. Reaction with KCN :

O O O

H3 O
R––C––Cl + KCN R—C––CN R—C––COOH
keto acid(Pyruvic acid)

5. Reaction with AgNO 3 :

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 AgNO 3.
JEEMAIN.GURU
6. Reaction of acyl chloride with diazomethane in presence of Ag2O and water. (Arndt – Eistert synthesis).
This reaction convert acyl chloride to carboxylic acid with one carbon atom more :
O O
 
R––C––Cl + 2CH2N2 R—C––CH–N2 + CH3Cl + N2

O
  Ag H2O
R––C––CH—N2 –N2 R––CH=C=O R––CH2––COOH
ketene

ACID ANHYDRIDES (RCOOCOR)

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
two molecules of the acid.
O
O
R––C
2R––C––OH O + H2O
R––C
carboxylic acid
O
acetic anhydride
 Met ho d of preparat ion :
1. Acylation : Carboxylic acid reacts with acyl chloride in the presence of pyridine to give carboxylic acid anhydride.

O O O O

2R––C––OH + R'––C––Cl + R––C––O––C––OR + Cl

N N


2. So dium salt of carboxylic acids also react w it h ac yl chloride s to give :

O O O O
  
2R––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.

O O
CH2–––––OH CH2
300°C
O + H2O
CH2–––––OH CH2
O O
succinic acid
O O

––C––OH 230°C
O + H2O
––C––OH

O O
pthalic acid pthalic anhydride
JEEMAIN.GURU
4. Chemical Proper t ie s :
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
NH3
O O R––C––NH2 + R'––C––NH2
R––C––O––C––R O O
H2O
R––C––OH + R'––C––OH
hydrolysis

O O

OH/H2O  
R––C––O + R'––C––O

ESTERS (RCOOR)

Ester are the derivative 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.
 Met ho d of Preparat ion :
By reaction of acids wth alcohol or diazomethane in presence of ether.

H / H2 O
RCOOH + C 2H 5OH   R––COOC 2H 5 + H 2 O


ether
R––COOH + CH2N2  RC O O CH 3  N 2
Ester

O O
C5H5N
R––C––Cl + C2H5OH R––C––OC2H5 + HCl

O O
C H N
R––C––O O + C2H5OH 5 5
  R––C––OR' + R––COOH
2

 Chemical Proper t ie s :
1. Conversion to other e sters : 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"
JEEMAIN.GURU
3. React ion w it h Grignard Reagent :

O OMgX OH
diethylether 
H
R––C––OR + 2R"MgX R––C––R" R––C––R" + R'OMgX

R" R"
3° alcohol
4. Reduction of ester :

Na/Mg
MeCH(OH)CH2CO2C2H5
MeCOCH2COOC2H5
LiAlH4
MeCH(OH)CH2––CH2OH + C2H5OH
O
C CH2OH
LiAlH4
O
C CH2OH
O
Phthalic anhydride

5. Reaction of NH 3 with keto ester :

R–CO–CH2CO2C2H5 + NH3  R––C=CHCO2C2H5 + H2O

NH2

Mechanism :

O O OH

H –H2O
R––C––CH2.COOC2H5 R––C––CH2.COOC2H5 R––C––CH2.COOC2H5 R–C=CH–CO2C2H5

:NH3 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
Na/Xylene
2R––C R––C=O
OR
R––CH––OH
-hydroxyl ketone
Mechanism :
It is the intermolecular, sodium promoted condensation of two moles of ester or the intra molecular condesation
of a ester to -hydroxy ketone (acyloin).
OR OR
Na • –2OR 2Na
2R—C––OR 2R––C––OR 2R––C––C––R R––C––C––R
Electron dimerisation
donation   O O O O
O ONa  

• • 2H tautomerisation
R––C––C––R R––C C––R R––C C––R R––C––CHR

Na O
 O Na O O OH OH O OH
   
acyloin
JEEMAIN.GURU
 Hydrolysis of Ac yl Derivat ive s :

Ester hydrolysis can be carried out in mechanistic pathways A AC 1 , A AC 2 , A AL1 , B AC 2 .

Here A or B stand for acid or base catalysed and Ac and Al stand for acyl oxygen and alkyl oxygen cleavage and
1 or 2 stands for unimolecular or bimolecular.

A AC1 :

CH3 CH3 CH3

O H O CH3
Fast  slow  ..
H3C H3C O H3C C=O + CH3OH
H
OCH3
CH3 CH3 CH3

CH3

H3C CO

CH3

CH3 CH3
OH
 ..
H3C C=O +H2O H3C C=O + H
..

CH3 CH3

A AC 2 :


O OH OH ..
Fast H Slow H2O
H3C––C––OC2H5 H3C––C––OC2H5 H3C––C––OC2H5



OH O H O

H3C––C––OC2H5 H3C––C––OC2H5 + C2H5OH + H

 H3C OH
H––OH O––H

A AL1 :


O OH OH CH3 CH3
CH3 CH3
Fast H H3C––C––O–––––CH3 + H3C––C
H3C––C––O––C––CH3 H3C––C––O–––––CH3 
CH3 CH3 CH3 CH3
H2O

CH3
O
H3C––C––OH
H3C––C––OH CH3
JEEMAIN.GURU
B AC 2 :


O O
 O
OH Fast

H3C H3C––C––OH H3C + OC2H5
OC2H5 OH
OC2H5
proton exchange


O O
H3C H3C + C2H5OH

O O

AMIDES (RCONH 2 )
O
R––C––NH2
 Met ho d of Preparat ion :
1. Amide s from Ac yl 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.

R––COCl + RNH2  R––C––NH2 + NH4Cl

R––COCl + RR'NH  RCON(R)R' + RR'N +H 2Cl –

N, N-disubstituted amide

2. Amide s from acid a nhydride :

O
O 
O + 2NH3 R––C––NH2 + RCOO NH4
R––C–– 2
O
O 
O + 2R' ––NH2 R––C––NHR' + R––COONH3R'
R––C–– 2
O O O

C C––NH2 C––NH2
H2O H/H2O
O + 2NH3
 
C C––ONH4 C––OH
O O O
Phthalamic acid
both amide and acid
3. From Ester s (Ammonolysis) :
Ester undergoes nucleophilic substitution at their acyl carbon by nucleophilic ammonia or its derivative

O O
.. R' .. R'
R––C––OR + H––N R––C––N + R'OH
R" R"
JEEMAIN.GURU
4. By par t ial hydrolysis of alkyl nitri le s :

H or
R––CN + H2O 
OH  R––CO––NH2

 Physical Proper t ie s :
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 Proper t ie s :
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=NH2
(I) (II)

(i) Acidic character : Due to structure II amide can act as acid.

CH3––C––NH2 + CaO (CH3CONH)2Ca + H2O

As acid
1
CH 3 CONH 2  Na  CH3CONH–Na + H
Acid 2 2

(ii) Basic Character : Due to structure I having lone pair of electrons on N atom it acts as base.
CH3CONH2 + HCl      CH3CONH2+HCl–
As base Acid Salt
2. React ion w it h nitrous acid :
R––CONH2 + HONO  R––COOH + N2 + H 2O
The reaction proceeds via the attack of electrophilic species NO+ generated from HNO3.
3. Hoffma nn's Bromide React ion :
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––NH2 + Br2 + KOH  RNH2 + K2CO3 + 2KBr + 2H2O

CONH2 NH2

+ Br2+ 4KOH + K2CO3+ 2KBr + 2H2O

Mechanism :
2NaOH + Br2  NaOBr + NaBr + H2O
JEEMAIN.GURU

O O
–
(i) R––C––NH2 + OBr R––C––N––Br + OH

H
N-bromoacetamide

O H O
Rearrangement H2O
(ii) R––C––N––Br + OH R––C––N––Br R––N=C=O R––NH2+CO2
–H2O .. slow –OH

4. Reaction with PCl 5 , PCl 3 or SOCl 2 :

O
PCl5 or PCl3
R––C––NH2 or SOCl2
RCN + H2O

O O
PCl5 –HCl 
R—C––NH2 R––C––NH PCl4 R––C=N––PCl3 R––C––N=PCl3 R––CN+POCl3
HCl
O O


5. Reduction :

O
Na/C2H5OH
R––C––NH2 R––CH2NH2 + H2O

O
 
Li AlH4
R––C––NH2 R––CH2––NH2

Mechanism :

–
H––AlH3 H
..  LiAlH4
R––C––NH2 R––C––NH2 R––CH=NH2 R––CH2––NH2
–
O O––AlH3
Aldehyde-ammonia state
JEEMAIN.GURU

SOLVED EXA MPLES

O
(i) NaBH 4
1. End product of this conversion CH 3 — C—CH 2 —CH 2 —CO 2 H 
(ii ) H 2 O,H 
 is ?

H3C
O
(A) O (B) O
H3C O

OH O
(C) O (D)
O H3C H

Sol. (A)
NaBH 4 reduces reactant to

CH 3 — CH—CH 2 —CH 2 —CH 2 —CO 2H which forms e ster..

OH

2. When acetic acid reacts with ketene, product formed is :

(A) ethyl acetate (B) aceto-acetic ester (C) acetic anhydride (D) no reaction
Sol. (C)

CH 3 COOH + CH 2  C  O  acetc anhydride

Ketene

3. R—CH 2 —CH 2 OH can be converted in R—CH 2 CH 2 COOH. The correct sequence of reagents is :
(A) PBr 3 , KCN, H  (B) PBr 3 , KCN, H 2 (C) KCN, H  (D) HCN, PBr 3 , H 
Sol. (A)
PBr3
RCH 2 CH 2 OH   RCH 2 CH 2 Br 
KCN H2O / H 
 RCH 2 CH 2 CN   RCH 2 CH 2 COOH
4. Which of the following compound would be expected to decarboxylate when heated :

O O O O
(A) (B)
H3C OH H3C CH3

O O O O
CH3 OH
(C) H3C (D) H3C
O CH2
Sol. (A)

O O O

H3C OH H3C CH3

In case of -keto acid, the decarboxylation occurs radily due to 6-membered low energy transition state
formation.
JEEMAIN.GURU
O
5. CH3OH A ; A is ?
O

CH2—CH2 CH2—CH2
(A) (B) (C) both are correct (D) None is correct
OH COOCH3 COOH OCH3

Sol. (A)

O O O
 CH3OH OCH3
This bond breaks hence intermediate is
O O OH


6. End product of the following sequence of reaction is :

O
(i) I2+ NaOH, 
C—CH3 (ii) H, 

O O
(A) Yellow ppt. of CHI 3, (B) Yellow ppt. of CHI 3,
COOH CHO

O
COOH
(C) Yellow ppt. of CHI 3 , (D) Yellow ppt. of CHI 3, COOH

Sol. (C)

O
Intermediate is ; which loses CO 2 on heating (-keto acid)
COOH

7. The final product obtained in the reaction :


CH 2 =CHCH 2 CH 2 CO 2 H 
Br2 / OH


(A) BrCH 2 — CH—CH 2 CH 2 CO 2 H (B) HOCH 2 —CH 2 CH 2 CH 2 CO 2 H

OH

(C) BrCH2— C=O (D) C=O

O O
Sol. (C)

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) (CH 3 ) 2 C=CH—CH 2 COOH (B) (CH 3 ) 2 CH—COOH
(C) (CH 3 ) 2 C=CH—COOH (D) (CH 3 ) 2 C=CH—CO—COOH
Sol. (C)
JEEMAIN.GURU

O O
CH3 CH3
NaOH/I2
C=CH—C—CH3 C=CH—C—OH+CHI3
C3H7 mesityl oxide CH3

9. The ease of alkaline hydrolysis is more for :

COOCH3 COOCH3 COOCH3 COOCH3

(A) (B) (C) (D)

NO2 Cl OCH3
Sol. (A)

COOCH3

There is more electron deficiency on carbonyl carbon.

NO2

10. Which of the following does not undergo Hell-volhard Zelinsky reaction ?
(A) HCOOH (B) CCl3 COOH (C) C 6 H 5 COOH (D) All
Sol. (D) None of these contain alpha H-atom.