Carboxylic Acid and Its Derivative

1.
INTRODUCTION 2
2. METHOD OF PREPARATION OF CARBOXYLIC ACID 3
3. PHYSICALPROPERTIES OF CARBOXYLIC ACID 7
4. CHEMICAL PROPERTIES OF CARBOXYLIC ACID 7
5. ACID DERIVATIVES 11
6. METHOD OF PREPARATION OF ACID DERIVATIVES 12
7. PHYSICAL PROPERTIES OFACID DERIVATIVES 12
8. CHEMICAL PROPERTIES OFACID DERIVATIVES 15
9. ESTERS 15
10. METHOD OF PREPARATION OF ESTERS 15
11. CHEMICAL PROPERTIES OF ESTERS 16
12. ACID AMIDES 18
13. PHYSICALPROPERTIES OFACID AMIDES 18
1
CONTENTS
S.NO. TOPIC PAGE NO
Carboxylic Acid & It's Derivatives
1. INTRODUCTION :
The compounds containing C OH as the functional groups are called as carboxylic acids.
O
Carboxylic acids may be aliphatic or aromatic depending upon the group available on the carboxylic group.
R COOH
Aliphatic carboxylic acid
Aliphatic carboxylic acids :
Ar COOH
Aromatic carboxylic acid
These are further classified into mono, di, or tri carboyxlic acids depending upon the number of carboxylic
groups present.
(a) Monocarboxylic acids.
e.g. HCOOH,
CH
3
COOH
C
3
H
7
COOH
Dicarboxylic acid
COOH
Formic acid
Acetic acid
Butyric acid
Methanoic acid
Ethanoic acid
Butanoic acid
(b)
Oxalic acid
COOH
CH
2
COOH
COOH
COOH
COOH
Malonic acid
(CH
2
)
2
Succinic acid
CH
2
COOH
CH
2
Glutaric acid
CH
2
COOH
CH
2
COOH
CH
2
CH
2
Adipic acid
CH
2
COOH
COOH
(CH
2
)
5
COOH
CH
2
COOH
(CH
2
)
6
CH
2
COOH
CH
2
COOH
(CH
2
)
7
CH
2
COOH
COOH
(CH
2
)
8
COOH
Pimelic acid
Suberic acid
Azelaic acid
Sebacic acid
3
CARBOXYLICACID&IT'SDERIVATIVES
Aromatic acids :
(a) Monocarboxylic acids
COOH COOH COOH COOH
OH NH
2
CH
3
Benzoic acid
(b) Dicarboxylic acids
Salicylic acid Anthranillic acid Toluic acid
COOH
COOH
COOH
COOH
COOH
Isopthalic acid
COOH
Terpthalic acid
Pthelic acid
2. METHOD OF PREPARATION OF CARBOXYLICACID :
1. From Aldehydes and Ketones : Aldehydes and ketones are oxidised to carboxylic acids
RCHO + (O)
Aldehyde
RCOOH
R CH
2
C CH
2
R'
R CH
2
COOH + R'COOH
Mixture of carboxylic acids
O
Ketone
The oxidising agents which could be used are HNO
3
, acidic KMnO
4
, acidic K
2
Cr
2
O
7
, and
Mn(CH
3
COO)
2
, and mild oxidising agents for aldehydes only.
FromAlcohols : Alcohols can be oxidised to carboxylic acids using oxidising agents.
p-alcohols are oxidised to single carboxylic acids via aldehydes.
s-alcohols are oxidised to mixture of carboxylic acids via ketones.
K
2
Cr
2
O
7
+ H
2
SO
4
2.
CH
3
CH
2
OH +2 (O) CH
3
COOH
A
K
2
Cr
2
O
7
+ H
2
SO
4
A
CH
3
CH CH
2
CH
3
+ 4 (O) 2 CH
3
COOH
OH
CH
2
OH CHO COOH
K
2
Cr
2
O
7
+ H
2
SO
4
A
(O)
3. From the Hydrolysis of nitriles and isonitriles :
to formcarboxylic acids.
H
+
/H
2
O
Nitriles may be hydrolysed with acids or alkali
R C N
R C OH + NH
3
O
3
Mechanism :
H
+
From H
2
SO
4
+
R C NH
+
R C = NH
R C N: +
HSO
4
. .
R C = NH
R C = NH
OH
H O
2
+
O
H
H
H
+
From H SO
Tautomerisation +
R C NH
3
R C NH
2
2 4
O O
HSO
4
H
H
+
R C O R C OH
H O
2
O
H
+
/H
2
O
O
R NC
R NH + H COOH
2
Formic acid
4. From Hydrolysis of Acid Derivatives : All acid derivatives may be hydrolysed is the presence
of dilute acids or alkali to formcarboxylic acids.
H
2
O
+ H
+
(a)
R C X
RCOOH + HX
O
H
2
O
R C OR'
+ H
+
R COOH + R'OH (b)
O
R C NH
2
H O
+ H
+ 2
(c) RCOOH + NH
3
O
R C O C R
H
2
O
+ H
+
(d) RCOOH + RCOOH
O
For acid hydrolysis to take place the group must
O
Mechanism : have lone pair of electrons
. . . . . .
e.g. X
. .
:
O
.
R
.
' NH
2 , , etc.
H
+ H
+
R C OR'
R C O R'
+
O
O
+
R
+
C = O
+ R'OH
R C O R'
O H
H
2
O
HSO
4
R C = O
OH
+ H
2
SO
4
. R C = O
+
R C = O
+
O
H
H
+
= O is the criteria of reactivity of RCOOR' for acid hydrolysis. Hence stability of R C
R
R
R
R
So the reactivity towards acid hydrolysis is R CH
2
COOR' < CH COOR'
<
C COOR'
.
R
4
Base Hydrolysis
OH /H
2
O
R COO
+ HX
R C X
O
R C OR'
OH / H
2
O
R C O
+ R'OH
O
RCOO
+ NH
3
O
R C NH
2
OH / H
2
O
O
R C O C R
OH / H
2
O
R COO
+ RCOO
O O
Mechanism :
OH
R C OR'
O
+ OR
+ OH R C OH'
R C O R'
O O
Reactivity of esters towards base hydrolysis is increased by the presence of strong-I groups at the o-
positions.
CH
2
COOR'
Cl
CH
2
COOR'
NO
2
> CH
3
COOR'. >
The general reactivity of the acid derivatives for hydrolysis is
R C O C R R C OR R C NH
2 RCOX > > >
O O O O
This is because the leaving group ability order is
O C R
X > > OR' > NH
2
.
O
From Grignards Reagent :
CO
2
5.
H
+
/H
2
O
R C OMgX
RMgX RCOOH + MgXOH
Dry ether
O
O
COOH
C OMgX
CO
2
H
2
O/H
+
C
6
H
5
MgX
+ MgX (OH)
Dry ether
6. From Sodium Alkoxides :
Under presure
H
+
/H
2
O
RONa + CO RCOONa RCOOH + Na
and temperature
7. From Dicarboxylic Acids : When Dicarboxylic acids (geminal) are heated then they undergo
easy decarboxylation to form monocarboxylic acids.
A
A
COOH COOH
R CH COOH
HCOOH + CO
2
R CH
2
COOH + CO
2
COOH
5
Mechanism :
O
A R CH C O
R CH COOH
COOH
H
+
+
O C OH
O
R CH
H
+
R CH C OH C = O
H
+
R CH C OH +
Stablized due to resonance
O H
OH
R CH COOH
Z
CH
2
Z + CO
2
where Z = OH, NH
2
, C R, COOH,
Here it would be right to say that any molecule of the type would undergo
decarboxylation readily to form R
O
C H etc.
O
e.g. COOH CH
2
COOH
From Alkane :
CH
3
COOH + CO
2 A
8.
Mn (CH
3
COO)
2
underure
Mn (CH
3
COO)
2
underure
3
R CH
3
+
2
O
2
R COOH + H
2
O
3
CH
3
CH
3
+
2
O
2
CH
3
COOH + H
2
O
9. From Alkene : Alkenes when heated with carbon mono-oxide and water at 573 K with H
3
PO
4
as catalyst give carboxylic acid.
H
3
PO
4
(a) CH
2
= CH
2
+ CO + H
2
O CH
3
CH
2
COOH
CH
3
573 673 K
H
3
PO
4
CH COOH
CH
3
CH = CH
2
+ CO + H
2
O 573 673 K
CH
Under presure 3
(b) Alkenes on oxidation with hot KMnO
4
give carboxylic acids.
R CH = CH
2
+ Hot KMnO
4
Manufacture of HCOOH :
RCOOH + CO
2
+ H
2
O
A
Formic acid is manufactured by reacting sodium hydroxide and carbon monoxide at high prressure
and temperature.
O
+
H /H
2
O
6 - 10 atm
473 K
H C OH
O
NaOH + CO
H C ONa
Manufacture of CH
3
COOH :
(a) From Methanol : Methanol and carbon monoxide when heated in the presence of Rhodium gives
acetic acid.
CH
3
C O H
Rh
A
CH
3
OH + CO
O
(b) Ethanol is converted to acetic acid by acetobector.
Acetobactor
C
2
H
5
OH + O
2
CH
3
COOH + H
2
O
6
St
Preparation of Benzoic acid
COOH
CH
3
3 CoMn acetate
A
+
2
O
2
+ H
2
O
CCl
3
COOH
Ca (OH)
2
Fe
A
+ 3H
2
O + 3HCl
3. PHYSICALPROPERTIES OF CARBOXYLICACID :
1. The first three acids are colourless, pungent smelling liquids. The next four smell like bitter goats
butter where as higher members are colourless solids.
Solubility, the lower aliphatic carboxylic acids are soluble in water. While the higher members are
insoluble.
The boiling points of carboxylic acids is even more than alcohols.
The melting points of carboxylic acids show alteration effect or oscillation effect. The melting points
of even members is always higher than the next higher or lower odd number acid. This is because even
number acids is more symmetrical and fits well into the crystal lattice and more energy is required to
break them.
2.
3.
4.
CH
2
CH
2
COOH CH
2
CH
2
Butanoic acid
CH
2
Pentanoic acid
CH
3
CH
3 COOH
Butanoic acid has higher melting point than pentanoic acid.
4. CHEMICALPROPERTIES OF CARBOXYLICACID :
(A) Reactions : Due to R C O H
breakage
O
1
R C ONa
1. RCOOH + Na +
2
H
2
O
2RCOOH + Zn
R C O
Zn + H
2
O
2
This shows the acidic character of RCOOH.
2. With NaOH
RCOOH + NaOH RCOONa + H
2
O
All carboxylic acids in alkali to formsalt of metal.
3. With Na
2
CO
3
and NaHCO
3
Carboxylic acids decompose carbonates and bicarbonates to carbondioxide
2RCOOH + Na
2
CO
3
2Na (COO R) + CO
2
+ H
2
O
RCOONa + H
2
O + CO
2
R C OH
+ NaHCO
3
O
7
(B) Reactions involving R C OH
breakage
O
1. Reactions with ammonia
O
A
H O
RCOOH + NH
3
RCOONH
4
R C NH
2
CH
3
C NH
2
2
CH
3
C ONH
4
CH
3
C OH + NH
3 A
O
O
2. Reactions with Alcohols
conc.H
2
SO
4
O
R C OH
+ R' OH
R C OR' + H
2
O
O O
Mechanism :
R C OH
OH
+ . .
R C OH
+ H
R C OH
+
O
+
R C OH
R C = O H
OH OH
+
OH
Resonance stablized
H R'
+
O
+
R C OH
+ R'OH
R C OH
OH OH
-
HSO
4
OH
OH
H
R'
H
2
O
R C OR'
R C OR' R C O + H
2
SO
4
+
O H O
OH
Hence the reactivity of ester depends upon the steric hindrance created by the alkyl group (R) in
R C
+
OH . Hence the reactivity of acids towards esterification reaction is
OH
R
R
R
CH COOH R
C COOH
R CH
2
COOH > >
R
While the reactivity order of alcohol towards esterification reaction is p- > s- > t-.
3. Reaction with P
4
O
10
When carboxylic acids are heated with phosphorus pentaoxide, then dehydration of carboxylic acids to
form carboxylic acid anhydride occurs.
R C OH R C OH R C O C R
P
4
O
10
A
+
O O O O
O O
COOH
P O
C O C
4 10
A
2
8
4. Reaction with PCl
5
, PBr
5
, PBr
3
or SOCl
2
When reacted with PCl
5
or SOCl
2
then carboxylic acids give acid chloride
R C OH R C Cl
+ PCl
5
+ HCl + POCl
3
A
O
R C OH
O
R C Cl
+ SOCl
2
+ SO
2
+ HCl
A
O
3 R C OH
O
R C Br
+ PBr
3
+ H
3
PO
3
A
O
(C) Reactions involving
O
R C OH
O
Decarboxylation Reactions : The removal of carboxylic acid is called decarboxylation. It can be
brought about by two methods.
(i) Chemical Decarboxylation : (Soda lime decarboxylation) Sodium or potassium salts of carboxylic
acids on heating with soda lime give alkane with one carbon atom less.
CaO
RCOONa + NaOH R H + Na CO .
2 3
A
(ii) Electrolytic Decarboxylation :
Electrolysis
RCOONa + 2H
2
O R R + 2CO
2
+ 2NaOH + H
2
.
Reaction to Alcohols :
All carboxylic acids are reduced to alcohols using copper chromite, or LiAlH
4
, or H
2
/Ni, or Pt or Pd, or
Na/EtOH.
CuO + CuCr
2
O
4
R C OH
RCH
2
OH
A
O
The catalyst copper chromite is called Adkins catalyst.
Reaction to Alkanes :
All carboxylic acids are converted to alkanes on heating wtih HI/Red P.
Red P
R C OH
+ 6HI R CH
3
+ 2H
2
O + 3I
2
473 K
O
Reactions corresponding to Alkyl Groups Hell Volhard Zelinsky Reaction (HVZ Reactions)
The carboxylic acids having o-H atoms on halogenation in the presence of red phosphorus forma- haloacids
Red P
A
R CH COOH
R CH
2
C OH
+ X
2
O
Mechanism 2P + 3X
2
3R CH
2
COOH +
X
2PX
3
PX
3
+ H
3
PO
3 3 R CH
2
C X
O
+ HX R CH
2
C X
+ X
2
R CH C X
O
O X
9
R CH C X + R CH
2
COOH R CH C OH + R CH
2
C X
O O
X O X
The compound
R CH
2
C X
proceeds through enolization of acid halide which undergoes easy
O
halogenation.
R CH
2
C X
R CH = C X
OH O
R
CH = C X
:OH
X
R CH C X
X
R CH C X
X X
O H
O-
O
X
This is a very important reaction because the X (Cl or Br) can easily be replaced by strong nucleophiles like
CN, NH
2
, etc, form substituted acids.
R CH COOH
X
+ NH
3
R CH COOH
NH
2
R CH COOH
X
+ aq.NaOH R CH COOH
OH
+ alc.KOH R CH = CH COOH R CH
2
CH COOH
X
KCN
R CH COOH
X
R CH COOH
CN
ARNDT EISTERT SYNTHESIS : - It is the conversion of lower carboxylic acids to higher carboxylic
acid
i) CH
3
NH
2
ii) H
2
O
PCl
5
R C OH R C Cl R CH
2
COOH
O O
Ex.1 Anester of molecular formula C H O onhydrolysis affords an acid (A) and an alcohol (B). Oxidation
8 16 2
of alcohol (B) with Na Cr O gives rise to an acid (C). Sodiumsalts of acids (A) and (C) on fusion with
2 2 7
solid NaOHyield propane in each case. What is the structural formula of the original
ester ?
O
CH CH CH C OCH CH CH CH
H
OH
CH CH CH COOH
Sol.
H
+
3 2 2 2 2 2 3 3 2 2
(A)
+ CH
3
CH
2
CH
2
CH
2
OH
(B)
Compound (A), C H Cl, reacts with alcoholic KOHto form(B), C H . Compound (B) discharges Ex.2
3 7 3 6
Br /CCl solution. Reactionof (A) with Mginether and subsequent treatment with CO and dilute acid
2 4 2
gives (C). whose molecular formula is C H O . When we add compound (C) to aqueous NaHCO
4 8 2
solution, bubbles are evolved. What are (A) to (C)
?
3
10
COOH
CH
CH
3
Cl
CH
CH
3
(A) =
H
3
C
(B) = H
3
C (C) = H
3
C CH
Sol.
CH
2
5. ACID DERIVATIVES :
General :
Afunctional derivative of a carboxylic acid is a compound formed by replacement of the hydroxyl group of the
acid by some other group, say Z, that can be hydrolysed back to the parent acid.
Members :
Four important classes of acid derivatives are
1.
2.
3.
4.
Esters
Acid anhydrides
Acid chlorides
Acid amides
RCOOR
RCOOCOR'
RCOCl
RCONH
2
Where R and R' stand alkyl or phenyl groups. All these compounds contain the acyl group (RCO) and hence
they are also known as acyl compounds.
Nucleophilic Acyl substitution :
The presence of the carbonyl group in the acid derivatives brings on these molecules certain characteristic
reactivity.
Thus the acyl compounds undergo nucleophillic substitution in which OHof the acid, Cl of the acidchloride,
OOCR of the acid anhydride, NH
2
of the amide and OR'. of the ester is replaced by some other basic
groups. This is possible only due to the presence of the carbonyl group because nucleophillic substitution does
not usually take place at a saturated carbon atom.
R C = O + Z
R C Z + Nu
Nu
O
Where Z stands for OH, Cl, OOCR, NH
2
or OR'.
The above nucleophilic acyl substitution proceeds by two steps :
Intermediate formation of a tetrahedral anion.
This step is affected by two factors :
(a) Favoured by electron-wtihdrawl which stabilizes the developing negative charge on the oxygen
atom.
(b) Steric hinderence by the presence of bulky groups which become crowded together in the transition
state.
Ejection of Z group and returning to a trigonal compound.
This step depends upon the basicity of the leaving group; Weaker the base, better the leaving group.
Non-Occurance of acyl nucleophillic substitution reactions in aldehydes and ketones.
Acid derivatives show acyl nucleophillic substitution reactions while aldehydes and ketones do not show these
reactions. This is explained on the basis of following two reasons :
(1)
(2)
11
(1) Stability of the intermediate tetrahedral anion :
The attack of the nucleophileon the acyl carbon atomof the acid derviatives produces a less stable intermediate
:Z:
(tetra hedral anion
R C O
due to the presence of an additional electron with drawing group Z, while the
-
Nu
R
intermediate obtained during such an attack on aldehydes and ketones (R C O
) where R and R' may be alkyl

Z
or hydrogen) is more stable. This results in the ejection of group Z to formstable trigonal compound.
(2) Basicity of the leaving group :
The ease with which a group is lost depends upon its basicity; the weaker the base, the better the leaving
group. The hydride ion (H
O-
) or alkiyde ion (R
O-
) are the leaving groups of aldehydes and ketones whereas
Cl
O-
, RCOO
, R O
O-
and NH
2
are the leaving groups of acid derivatives i.e., acid chlorides, anhydrides,
ester and amides respectively. Cl
, RCOO
etc, are comparatively weaker bases than H

O-
or R
O-
ions. Rather
H
O-
and R
O-
are the strongest bases of all. So aldehydes and ketones show nucleophillic addition reactions
instead.
The order of reactivity of the acid derivatives towards nucleophillic acyl substitution has been found to be :
RCOCl > RCOOCOR > RCOOR' > RCONH
2
.
AcidChlorides
6. METHOD OF PREPARATION OFACID DERIVATIVES :
(a) By the action of PCl
5
or PCl
3
on the carboxylic acids.
RCOOH + PCl
5
R C Cl + POCl
3
+ HCl
O
C
6
H
5
COCl + POCl
3
+ HCl
CH
3
C Cl +H
3
PO
3
.
C
6
H
5
COOH + PCl
5
CH
3
COOH + PCl
3
O
By the action of thionyl chloride on carboxylic acids.
CH
3
C Cl
(b)
CH
3
COOH + SOCl
2
+ SO
2
+ HCl
O
(c) From benzaldehyde : By passing chlorine through benzaldehdye .
CHO
COCl
+ Cl
2
+ HCl
7. PHYSICALPROPERTIES OFACID DERIVATIVES :
Hydrolysis :
Acid halides are hydrolysed by water to the parent acid.
R C Cl + H
2
O + HCl R C OH
O O
12
Aliphatic acid halides are hydrolysed in cold water but benzoyl halide is hydrolysed very slowly in cold water
in alkaline medium.
Alcoholysis :
Treatment of acid halides with alcohols, give esters.
Pyridine
R C Cl
e.g. + R'OH
R C OR' + HCl
O O
Pyridine
C OR' C Cl
+ R' OH + HCl
O
O
OH O
C Cl
aq.NaOH
C O
+ + HCl
O
The function of pyridine is to remove HCl.
Ammonolysis :
With ammonia acid halides give amides
R C NH
2 R C Cl + 2NH
3
+ NH
4
Cl
O
O
R C Cl R C NH R'
+ R'NH
2
+ NH
4
Cl
O O
NH
2
O O
C Cl C NH
+
In all these reaction aliphatic acid halides react faster than aromatic acid halides.
Reactions with carboxylic acid or sodium carboxylate.
Acid halides formanhydrides with carboxylic acids or sodiumcarboxylates.
R' C O C R' R C OH
+
R' C Cl Pyridine + HCl
O O O
O
R C ONa R C O C R'
+ R' C Cl + NaCl
O O O
Reaction with KCN :
O
Since cyanide ion is a strong nucleophile than water, therefore it reacts with acid chlorides to form alkanoyl
cyanides.
R C Cl R C CN
+ KCN + KCl
O O
The hydrolysis of alkanoyl cyanides give keto acids
H
+
/H
2
O
R C COOH R C CN
O O
13
Reaction reactions :
When reduced with hydrogen in the presence of finely-divided polladiumon BaSO
4
and sulphur acid chlorides
are reduced to aldehydes (Rosenmund Reaction)
Pd/BaSO
4
+ S
R C Cl
+ H
2
RCHO + HCl
A
O
CHO
COCl
Pd/BaSO
4
+ S
A
+ H
2
+ HCl
Reactions of Benzene ring in aromatic acid halides :
Since COOH, COCl, COOR', C O C C groups are all strong deactivating groups and electophillic
O O
substitution reactions take place at meta position.
AcidAnhydrides :
Acid anhydrides may be regarded as derived by the removal of one molecule of water fromtwo molecules of
carboxylic acids.
Preparation :
(a) Fromcarboxylic acids
R C OH
+ P
2
O
5
+ HPO
3
Metaphosphoric acid
R C O C R
O
O O
(b) From sodium carboxylate and acid chlorides
R C ONa
+ R' C Cl + NaCl
R C O C R'
O
From Acetylene
O
O O
(c)
O
O C R
O C R
HgSO
4
+ S
H C C H + 2 R COOH + CH CH
3
O
O
O C R
O C R
distill
CH
3
CHO +
R C O C R
CH
3
CH
O O
O
(d) From acetic acid and ketones:
AlPO
4
CH
3
COOH CH
2
= C = O + H
2
O
970 K
CH
3
C O C CH
3
CH
2
= C = O + CH
3
COOH
O O
14
8. CHEMICAL PROPERTIES OFACID DERIVATIVES :
(a) Hydrolysis :
All acid anhydrides undergo hydrolysis both acid catalysed and base catalysed to give acids. The base
catalysed hydrolysis is more rapid..
R C O C R
+ H
2
O RCOOH + RCOOH
O O
(b) Alcoholysis :
Acid anhydrides react with alcohols to form esters.
R C O R' R C O C R
+ R'OH + RCOOH
O O O
(c) With ammonia :
Acid anhydrides react with ammonia to form amides.
CH
3
C O C CH
3
+ NH
3
CH
3
C NH
2
O O O
acetamide
+
CH
3
C O NH
4
O
Ammonium acetate
(d) Friedal Crafts Acylation :
O
Anhyd.AlCl
3
A
C R
+
R C O C R
O O
9. ESTERS :
Nomenclature
O
Common name IUPAC name
Methyl formate Methylmethanoate
H C OCH
3
O
Ethyl acetate Ethylethanoate
H
3
C C OC
2
H
5
O
Methyl benzoate Methylbenzoate
C
6
H
5
C OCH
3
10. METHOD OF PREPARATION OF ESTERS :
(1) From diazomethane
Ether
N
2
RCOOH +
Carboxylic acid
CH
2
N
2
Diazomethane
RCOOCH
3
Methyl ester
CH
2
N
2
Diazomethane
H
3
CCOOH
Acetic acid
Ether
N
2
+
H
3
CCOOCH
3
Methyl acetate
15
(2) By Tischenko reaction
O
Ether
Aluminium
ethoxide
H
3
C CHO + CH
3
CHO
Acetaldehyde
(two molecules)
H C C OC H
3 2 5
H
2
O
Ethyl acetate
11.
(1)
CHEMICAL PROPERTIES OF ESTERS :
Hydrolysis : It is the reverse of esterification.
They undergo hydrolysis both in acidic as well as in basic medium.
O
O
H
+
R C OR' + H OH R C OH + R'OH
Alcohol
Ester Carboxylic acid
O
O
H
+
H C C OH + CH OH
H
3
C C OCH
3
+ H OH 3
Acetic acid
3
Methyl alcohol
Methyl acetate
(2) Ammonolysis : It leads to the formation of acid amides.
O
O
R C NH
2
Acid amide
+ R'OH
Alcohol
R C OR' + NH
3
NH
2
H
Ester
O
O
H
3
C C OC
2
H
5
+ H NH
2
Ethyl acetate
H
3
C C NH
2
+ C
2
H
5
OH
Acetamide
Ethyl alcohol
(3) Alcoholysis or trans-esterification
O O
+
H or
RO
Na
+
R C OR"
New Ester
+ R' OH
New Alcohol
R C OR'
Ester
+ H OR"
Alcohol
O
O
+
H
3
C C OC
2
H
5
+ H O C
4
H
9
H
H
3
C C OC
4
H
9
+ C
2
H
5
OH
n-Butyl alcohol Ethyl acetate
n-Butyl acetate
Ethyl alcohol
(4) Reaction with Grignards reagent : Esters, react with Grignards reagent to form alcohols,
16
H OH
OH
H
3
C C C
2
H
5
C
2
H
5
3-Methylpentan-3-ol
O MgI
H
2
O/H
+
Mg(OH)I
C
2
H
5
MgI
H C C C H
3 2 5
C
2
H
5
(5) Claisen condensation : Ester containing o-hydrogen atom undergo self-condensation in the presence
of strong bases such as sodium ethoxide to form |-ketoesters. This reaction is known as Claisen
condensation.
O O
O O
o
o
H C C CH C OC H C
2
H
5
ONa
C
2
H
5
OH
H
3
C C OC
2
H
5
+ H CH
2
C OC
2
H
5
3 2
Acetoacetic ester
(Ethyl acetoacetate)
2 5
Ethyl magnesium iodide
Ethyl acetate
Aceto-acetic ester shows
O
keto-enol tautomerism.
O OH
O
CH
3
C CH
2
C OC
2
H
5
(Keto-form)
CH
3
C = CH C OC
2
H
5
(Enol-form)
The keto-form structure is supported by the reactions of acetoacetic ester with HCN, NaHSO
3
, NH
2
OH and
phenyl hydrazine whereas the enol-form structure is supported by reactions with Na, PCl
5
, FeCl
3
and
decolourisation of Br
2
water.
Knorr (1911) isolated both the keto- and enol- forms of acetoacetic ester at low temperature. At room
temperature, the two form co-exist in dynamic equilibrium with 93% of the keto-form and 7% of the enol-
form.
It is a pleasant smelling liquid. Its synthetic utility depends upon the facts that it can formalkyl derivatives and
it can be hydrolysed in two ways.
O O O O
C
2
H
5
ONa
RI
C
2
H
5
ONa
RI
CH
3
C CH
2
C OC
2
H
5
CH
3
C CH C OC
2
H
5
R
O O
CH
3
C C C OC
2
H
5
R R'
Reaction :
(6)
O
H
R C OR' + 2H
2
R'OH + R CH
2
OH
Alcohol
Copper chromite
525 K, 200-300 atm
H-H H
Ester
17
This reaction is often referred to as hydrogenolysis, as it involves the cleavage of ester by hydrogen.
O
CH
3
OH
Methyl alcohol
+ H
3
C CH
2
OH
Ethyl alcohol
Copper chromite
(Adkin's Catalyst)
H
3
C C OCH
3
+ 2H
2
Methyl acetate
12. ACIDAMIDES :
Nomenclature Common name IUPAC name
O
Formamide Methanamide
H C NH
2
O
Acetamide Ethanamide
H
3
C C NH
2
O
Benzamide Benzamide
C
6
H
5
C NH
2
13. PHYSICALPROPERTIES OF ACIDAMIDES :
(1) Boiling Point. Due to strong intermolecular hydrogen bonding amides have quite high boiling points
among all the given organic compounds of comparable molecular masses.
------ H N C = O ------ H N C = O ------ H N C = O ------
H R H H R R
(2) Amphoteric nature : Acid amides are amphoteric in nature as they can behave as an acid as well as
a base.
(a) As base :
O O
H
3
C C NH
2
+ HCl H
3
C C NH
2
.HCl
Acetamide hydrochloride
(Salt)
Acetamide
(Base)
Acid
(b) As acid :
O
O
+
H
3
C C NH
2
+ Na
Acetamide
H
3
C C NHNa + 1/2 H
2
Sodium acetamide
(3) Hydrolysis : It leads to the formation of carboxylic acids.
O O
O O
H
+
H
+
H
3
C C NH
2
HO H
Acetamide
+ H
2
O R C OH,
Carboxylic acid
H
3
C C OH
Acetic acid
R C NH
2
+ H
2
O
Acid amide
NH
NH
3
3
18
(4) Dehydration :
O
P
2
O
5
/A
H
2
O
R C N
Alkyl cyanide
R C NH
2
Acid amide
O
P
2
O
5
/A
H
2
O
H C C N
3
H
3
C C NH
2
Ethane nitrile
Acetamide
O
P
2
O
5
/A
H O
C
6
H
5
C N
Benzene nitril
C
6
H
5
C NH
2
Benzamide
Reaction :
O
2
(5)
LiAlH
4
/ether
R CH
2
NH
2
1 Amine
R C NH
2
Acidamide
H
2
O
O
LiAlH
4
/ether
H
3
C CH
2
NH
2
Ethyl amine
H
3
C C NH
2
Acetamide
H O
2
19
Ex.1 Treatment of 2, 4-pentanedione with KCNand CH COOH, followed by hydrolysis yields two prod-
3
ucts, (A) and (B). Both (A) and (B) are dicarboxylic acids of formula C H O . (A) melts at 98C.
7 12 6
When heated,(B) gives first a lactonic acid (C H O ) and finally a dilactone (C H O ).
7 10 5 7 8 4
(a) What structure must (B) have that permits readyformation of both a monolactone and a dilactone?
(b) What is the structure of (A) ?
CH
3 CH
3 CH
3
CH
3
C O
HO C COOH
HO C COOH HOOC C OH
CH
2
(
i ) K
CN/
CH
3
COO
CH
2 CH CH
2 2
(ii )
H
3
O
+
C O
HO C COOH
HOOC C OH HO C COOH
Sol.
CH
3 CH
3
(A) Meso
CH
3
CH
3
Racemic
( B)
Compound (B) is a recemic modification. It gives monolactone (II), but the remaining OH and
COOHare cis; (II) can react further to formthe dilactone.
O
OH OH OH COOH
C
A
O C
CH
2
C O
CH
2
C O
H
3
C C CH
2
C CH
3
C
C C
H
2
O
COOH COOH
H
3
C
O
CH
3
H
3
C
O
CH
3
(B) (II) Monolactone Dilactone
(A) is the meso compound. It gives monolactone (III); here, the remaining OHand COOHare
trans, and further reaction is not possible.
OH COOH OH CH
3
CH
2
C O
H
2
O
H
3
C C CH
2
C COOH C C
COOH OH H
3
C
O
COOH
(A) Monolactone
Ex.2
Sol.
Acarboxylic acid does not formanoxime or phenyl hydrazone. Explain.
It is because, carboxylic group does not have a free carbonyl group. Actually carboxylic acids
undergoes resonance.
..
O:
..
:O:
..
+
R C = O H
R C O
..
H
Due to resonance bond of COOH group acquires partial double bond character and C = O
cannot showreactions with hydrazine, hydroxylamine etc.
20
SOLVEDEXAMPLE
The reaction between H
3
CCOOC
2
H
5
+ H
2
OCH
3
COOH+ C
2
H
5
OHis slowto start with, but
becomes fast later on. Why ?
Ex.3
Sol.
H
3
CCOOH + C
2
H
5
OH
Acetic acid Ethyl alcohol
H
3
C COOC
2
H
5
+ H
2
O
Ethyl acetate
CH
3
COO
+ H
+
H
2
CCOOH
Acetic acid produced in the above reaction, provides H+ions and catalyses the hydrolysis of
ester. This is an example of auto catalyst.
(a)Acid halides of formic acid are unstable. Why?
(b) Formic anhydride cannot be prepared by heating.
Ex.4
C O bond is a very stable bond due to large AH
f
of CO so the decomposition reaction
O
Sol. (a)
C O + HXis favoured. Formyl chloride is not stable above 60C. H C X
(b) This is because dehydration occurs intramolecularlyrather thanintermolecularly.
HCOOH CO + H
2
O
Ex.5 Anorganic compound (A) of formula C H Odecolourises Br /CCl colour but has no reaction with
6 10 2 4
ammonical cuprous chloride solution. (A) reacts with Schiffs reagent and also reduces Fehlings solu-
tion. (A) on treatment with silver oxide suspended in aqueous base gives compound (B). C H O ,
6 10 2
which evolves CO from aqueous NaHCO . (B) on ozonolysis yields one mole each of propanal
and
2
pyruvic acid. What are (A) and (B) ?
3
Sol. Compound (A) contains olefinic double bond as it discharges the redcolour of Br /CCl . It also contains
2 4
CHO group as it gives positive tests for this group. Since comound (B) liberates CO fromNaHCO
2 3
hence it contains COOHgroup. the structure of (B) is determined fromits products of ozonolysis as
follows :
H
H COOH
COOH
C
C
2
H
5
O + O C

2[ O
C
C
2
H
5
C
CH
3
CH
3
(A)
Pyruvic acid Propanal
Since (B) is obtained by the oxidation of (A) hence (A) is :
H CHO
C
C
2
H
5
C
CH
3
Ex.6 Asalt (A) of the formula C H OAg onrefluxing with bromine gives (B), C H Br. Compound (B) on
4 5 2 3 5
heating with alcoholic KOHyields (C), C H , which decolourises Br /CCl and cold dilute KMnO
3 4 2 4 4
solution, but does not react with ammonicalAgNO or Cu Cl . (C) on ozonolysis gives (D), C H O ,
3 2 2 3 4 4
which on heating eliminates CO to give acetic acid. What are (A) to (D) ?
2
H
2
C H
2
C
KOH
Br
2
CH COOAg CH Br
Sol.
C
2
H
5
OH
Reflux
H
2
C H
2
C
(A) (B)
H
2
C
COOH
A
(i ) O
H
2
C CH
3
COOH
CH CO
2 (ii) H
2
O
Acetic acid
COOH
HC
(C) (D)
21
Ex.7 Fluorine is more electronegative than chlorine even then, p-fluorobenzoic acid is a weaker acid than
p-chlorobenzoic acid. Explain.
Since the compound are more electronegative than carbon and also possesses lone pairs of electrons,
therefore, they exert both I and +Reffects. Nowin F, the lone of electrons are present in 2p-orbitals
but in Cl, they are present in 3p orbitals. Since 2p-orbitals of Fand Care of almost equal size, therefore,
the +Reffect is more pronounced in p-Fluorobenzoic acid thanin p-Chlorobenzoic acid.
Sol.
2p 2p
2p 3p
COOH COOH F Cl
Stronger +R-effect Weaker +R-effect
Thus inp-Fluorobenzoic acid +Reffect outweighs the I effect but inp-Chlorobenzoic acid, it is the I
effect whichout weighs the +Reffect. Hence p-Fluorobenzoic acid is weaker thanp-Chlorobenzoic
acid.
Benzamide is less easilyhydrolysed than methyl benzoate. Why?
..

Ex.8
..
O:
:
O
:
.. +
NH
2
C
6
H
5
C
Sol. C
6
H
5
C NH
2
(I)
(II)
Resonating structures of Benzamide
..
..
O:
:
O
:
.. +
C
6
H
5
C O
..
CH
3
C
6
H
5
C O
..
CH
3
(III) (IV)
Resonating structures of methyl benzoate
Since Nis less electronegative thanoxygen, therefore, Ncan donate a pair of electrons more readily
than oxygen. Therefore, magnitude of positive charge on carbonyl carbon in benzamide is less than in
methyl benzoate. Thus during hydrolysis, attack of OH
ion on carbonyl carbon in benzamide is difficult

thaninmethyl benzoate.
An organic acid (A) on heating with AlPO
4
at 700Cforms (B). Compound (B) also reacts with(A), to
give (C). Compound (C) on reaction with 1, 3, 5-trimethyl benzene in presence of AlCl
3
gives a ketone
(D) and CH
3
COOH. (D) on treatment with Na(Hg)/HCl gives an aromatic
hydrocarbon E. Give structures of (A) to (E) with proper reasoning.
Ex.9
Sol. (a) The reaction of compound (B) with (C) to forma ketone (D) and acetic acid is an example
of Friedal Craft acylation. Hence (C) should be an acyl chloride or an acid anhydride.
Since CH
3
COOH ia also formed in the reaction (C) must be acetic anhydride. Had these
been acetyl chloride or any other acid chloride HCl should have been there instead to
CH
3
COOH.
So the reaction can be represented as under.
CH
3
(b)
CH
3
AlCl
3
H
3
C CH
3 + (CH
3
CO)
2
O + CH
3
COOH
COCH
3
(D)
H
3
C CH
3
22
CH
3
Na(Hg)/HCl
CH
3
H
3
C
CH
2
CH
3
(E)
(c) Cis acetic anhydride, the organic acid is acetic acid.
CH
3
CO
CH CO
AlPO
4
700C
CH
3
COOH
CH
3
COOH
(A)
H
2
C = C = O
Ketene (B)
O
3
(C)
Ex.10 Aneutral liquid of formula C H O is hydrolysed to an acid (A), and an alcohol (B). Acid (A) has a
7 14 2
neutralization equivalent of 84.Alcohol (B) is not oxidized with anacid solution of Na Cr O . What is
2 2 7
the formula and name of the original compound?
O
CH
3
CH
3 C
OH
H
3
C CH
2
COOH + H
3
C C OH H
3
C O CH
3
Sol.
CH CH
3 3
CH
3
Na
2
Cr
2
O
No oxidation
H
3
C C OH
Dil. H SO
2 4
CH
3
23
Q.1 Two isomeric carboxylic acids Hand I, C H O , react with H /Pd giving compounds C H O . Hgives
9 8 2 2 9 10 2
a resolvable product and I gives a nonresolvable product. Bothisomers can be oxidized to CH COOH.
6 5
Give the structure of Hand I.
Identify the products (A), (B), (C) and (D) in the following sequence :
C
15
H
31
COOH (A) (B)
(
ii )
O
(C) (D)
Q.2
LiAlH
4 KMnO
4
+conc.H
2
SO
4
HCl (i )Mg , ether
Q.3 Aneutral liquid (Y) has the molecular formula C H O . On hydrolysis it yields an acid (A) and an
6 12 2
alcohol (B). Compound (A) has a neutralization equivalent of 60. Alcohol (B) is not oxidized byacidified
KMnO , but gives cloudiness immediately with Lucas reagent. What are (Y), (A) and (B) ?
4
Esterification does not take place inthe presence of ethyl alcohol andexcess of concentrated HSO at Q.4
2 4
170C. Explain.
Why does carboxylic acid functions as bases though weak ones?
Which ketone of the formula C H Owill yield an acid onhaloformreaction?
Q.5
Q.6
Q.7
Q.8
Q.9
Q.10
Q.11
5 10
Highly branched carboxylic acids are less acidic thanunbranched acids. Why?
Acarboxylic acid does not forman oxime or phenyl hydrazone. Why?
Formic acid reduce Tollens reagent. Why?
The K for fumaric acid is greater thanmaleic acid. Why.
2
Identify the final product inthe following sequence of reaction.
O
H2C CH2
CH
3
CH
2
MgBr X
H
3
O
+
Y

K
Mn
O
4
Q.12 What is (Z) in the following sequence of reactions ?
(i ) NaOH /
r
2
(ii ) H
3
O
+
(
i ) 2
NaN
H
2
(ii) 2CH
3
I

HgSO
(Y)
HCCH (X)
(Z)
H
2
SO
4
Q.13
Q.14
Acetic acid has a molecular weight of 120 inbenzene solution why ?
Place the following in the correct order of acidity
CHCCOOH;
(I)
CH
2
=CHCOOH;
(II)
CH
3
CH
2
COOH
(III)
Q.15
Q.16
Q.17
Phenol is a weaker acid than acetic acid why ?
Which acid derivative showmost vigorous alkaline hydrolysis ?
59 g of amide obtained fromthe carboxylic acid RCOOH, onheating with alkali gave 17g of ammonia.
What is the formula of acid ?
Which carboxylic acid (X) of equivalent mass of 52g / eq loses CO
2
whenheated to give anacid (Y) of
equivalent mass of 60g/eq.
Which of the reagent reacts with C
6
H
5
CH
2
CONH
2
to formC
6
H
5
CH
2
CN.
Consider the following ester
Q.18
Q.19
Q.20
(I) MeCH COOH (II) Me CHCOOH
2
(III) Me CCOOH
2
(IV) Et CCOOH
3 3
Correct order of the rate of esterification
24
EXERCISE-I
Q.21 Anorganic compound (A) on treatment with ethyl alcohol gives a carboxylic acid (B) and compound
(C). Hydrolysis of (C) under acidic conditions gives (B) and (D). Oxidation of (D) withKMnO also
4
gives (B). (B) on heating withCa(OH) gives (E) (Molecular formula C H O) (E) doesnot gives Tollens
2 3 6
test and does not reduce Fehling solution but forms 2, 4dinitrophenylhydrazone. Identify (A) to (E).
Two mole of an ester (A) are condensed in presence of sodium et ho xide to give a
B -keto ester (B) and ethanol. On heating in an acidic solution (B ) gives ethanol and a|-keto acid (C).
On decarboxylation (C) gives 3-pentanone. Identify (A), (B) and (C) with proper reasoning and give
reactions.
Compound (A) (C H O ) onReaction with LiAlH yielded two compounds (B) and (C). The com-
Q.22
Q.23
6 12 2 4
pound (B) on oxidation gave (D) 2 moles of (B) on treatment with alkali (aqueous) and subsequent
heating furnished (E). The later oncatalytic hydrogenation gave (C). The compound (D) was oxidized
further to give (F) whichwas found to be monobasic acid (m.wt.60.0). Deduce structures of (A) to (E).
Compound (A) C H O liberated CO on reaction with sodiumbicarbonate. It exists in two forms Q.24
5 8 2 2
neither of which is optically active. It yielded compound (B). C H O on hydrogenation. Compound
5 10 2
(B) canbe separated into enantimorphs. Write structures of (A) and (B).
The sodiumsalt of a carboxylic acid, (A) was produced by passing a gas (B) into aqueous solution of
caustic alkali at an elevated temperature and pressure (A) on heating in presence of sodiumhydroxide
followed by treatment with sulphuric acid gave a dibasic acid (C). Asample of 0.4g of (C) on combus-
tion gave 0.08 g of H Oand 0.39 g of CO . The silver salt of the acid, weighing 1.0 g, onignition yielded
Q.25
2 2
0.71 g ofAg as residue. Identify (A), (B) and (C).
An organic compound (A) on treatment with acetic acid in presence of sulphuric acid produces an ester
(B). (A) on mkild oxidation gives (C). (C) with 50%KOHfollowed by acidification with dilute HCl
generates (A) and(D). (D)_ withPCl followed byreaction withammonia gives (E). (E) ondehydration
Q.26
5
produces hydrocyanic acid. Identify (A) to (E).
Acetophenone onreactionwith hydroxylamine-hydrochloride can produce twoisomeric oximes. Write
structures of the oximes.
Anacidic compound (A), C H Oloses its optical activity onstrong heating yielding (B). C H O which
Q.27
Q.28
4 8 4 6 2
reacts readily with KMnO . (B) forms a derivative (C) with SOCl , whichon reaction with (CH NH
4 2 32
gives (D). The compound (A) on oxidation with dilute chromic acid gives an unstable compound (E)
which decarboxylates readily to give (F), C H O. The compound (F) gives a hydrocarbon (G) on
3 6
treatment withamalgamated Zn and HCl. Give structures of (A) to (G) with proper reasoning.
An organic acid (A), C H O reacts withBr inthe presence of phosphorus to give (B). Compound (B) Q.29
5 10 2 2
contains an asymmetric carbon atomand yields (C) ondehydrobromination. Compound (C) does not
show geometric isomerism and on decarboxylation gives an alkene (D) which on ozonolysis gives (E)
and (F). Compound (E) gives a positive Schiffs test but (F) does not. Give structures of (A) to (F) with
reasons.
An liquid (X) having molecular formula C H O is hydrolysed withwater in presence of anacid to give Q.30
6 12 2
a carboxylic acid (Y) and an alcohol (Z). Oxidation of (Z) with chromic acid gives (Y). What are (X),
(Y) and (Z) ?
25
Q.1 (a) Give the structures of the four optically-active isomers of C H O (Dthrough G) that evolve CO
4 8 3 2
with aq. NaHCO .
3
(b) Find the structure of (D), the isomer that reacts withLiAlH to give anachiral product.
4
(c) Give chemical reactions to distinguish among (E), (F) and (G).
Complete the following equation:
CH
3
Q.2
+
HCl Mg CO
2
H
2
O/ H
? ? ? ?
Peroxide Ether
H
3
C C CH
2
Q.3 Give structures of compounds:
+
(G)
C
O
2
(H)
H
3
O
( I)
Acetylene + CH MgBr
(C H O )
3 CH
4
3 2 2
H
2
O
, H
2
S
O
4
(J) (C H O )
K
Mn
O
4
CH (COOH)
HgSO
4 2 2 3 4 3
Q.4 Anester C H O was hydrolysed with water anacid (A), and analcohol (B), were obtained. Oxidation
6 12 2
of (B) with chromic acid producedA. what is the structure of the original ester? Write equations for all
the reactions.
Complete the following equation :
RCO
2
H ? ?
(
inert
solv
ent )
? ?
Acid halides of formic acid are unstable. Why?
What is the product of the following reaction?
Q.5
SOCl
2
NaN
3 D Hydrolysis
Q.6
Q.7
CHO
H
i ) Silver
oxide in a.q. ba
se
?
C C
(ii ) H
CH
3 H
3
C
2-Methyl-2-pentenal
Q.8 Anunsaturated acid (A) of molecular formula C H O eliminates CO easilyand gives another unsatur-
5 6 4 2
ated acid (B) of formula C H O . Bysaturation with H /Pt (B) gives butanoic acid. Neither (A) nor (B)
4 6 2
shows cis-trans isomerism. What are (A) and (B)?
2
Q.9 Anorganic compound Aon treatment with ethyl alcohol gives a carboxylic acid Band compound
C, Hydrolysis of Cunder acidic conditions gives Band DOxidation of D, with KMnO also
4
gives B. Bon heating with Ca(OH) gives E(molecular formula C H O). Edoes not give Tollens
2 3 6
test anddoes not reduce Fehlings solution but forms a 2,4-dinitrophenyl hydrazine. Identify A. BC
Dand E.
Two moles of an ester (A) are condensed in the presence of sodium ethoxide to give a |-keto ester (B)
and ethanol. On heating in an acidic solution (B) gives ethanol and |-keto acid (C). On decarboxylation
(C) gives 3-pentanone. Identify (A), (B) and (C) with proper reasoning. Name the reaction involved in
the conversion of (A) to (B).
Analkali salt of palmitic acid is known as ?
O
||
Acid do not react with sodium bisulphite though they have
C
group why ?
Q.10
Q.11
Q.12
26
EXERCISE-II
In the reaction sequence
X

C
a(O
)
2
Y
Q.13
dry conc
Acetone

H
2
SO
4
Z
distillation
X, Yand Z are ?
o]
Q.14 CH
3
CH
2
COOH X, Product Xis
SeO
2
Q.15
Q.16
Which of the reagent attack onlythe carbonyl group of a fatty acid ?
In the sequence
CH
3
CH
3 CH
|| | | |
Z X Y
CH CHO COOH CH
4
The reagent X, Y, and Zare
In the reaction sequence Q.17
NH Br
2
Z

CH
3
NH
2
X

H
3
O
A
KOH
X, Yand Z are ?
An acid Xreact with PCl
5
to forma compound (Y). Xalso react with NaOHto forma compound (Z).
Both Yand Z react together and from(E), Ereact with a reagent (F) to give back compound (Y) what
are X, Y, Z, E and F ?
Howwill you synthesise ?
(A)Acetyl chloride frommethyl chloride
(B)Acetamide fromethyl alcohol
(C) Ethyl acetate fromacetic acid
Complete the following reaction ?
Q.18
Q.19
Q.20
O O
CH
3
(a) X +
CH3
O NH
Y
O
+ Z
NH O
O O
NH
2
(b)
O
+ E F + C
2
H
5
OH
P
l
3
NH2
NH
2
(c) X +
O

H
Cl
Y Z
H
2
NH2
Resin
rea
Q.21 Complete the following equations:

+
(i) CH CH CH CH Br

C
N
?
H
2
O
/ H
?
3 2 2 2
CH
3
+ CN ? ?
H
OH
?
H
2
SO
4
old
conc
OC
l
2
?
Mg
?

(
i ) C
O
2
H
3
C C Br
?
(ii)
(ii ) H
+
Ether
CH
3
Identify the compounds:
1, 4-Cyclohexadiene + CHBr
t
Bu
OK
(D) (C H Br )
K
Mn
O
4
(E) (C H Br O )
H
Q.22
7 8 2 7 8 2 4 Ni 3
(F) (C H O ).
7 10 4
27
Q.23 Compound(A) C H O liberated carbon dioxide on reaction with sodiumbicarbonate. It exists in two
5 8 2
forms neither of which is optically active. It yields compound (B) C H O on hydrogenation.
5 10 2
Compound(B) can be separated into two enantiomorphs. Write the structural formulae of (A) and (B)
givingreason.
An acidic compound (A), C H O loses its optical activity onstrong heating yielding (B), C H O which Q.24
4 8 3 4 6 2
reacts readily with KMnO . (B) forms a derivative (C) withSOCl , which on reaction with (CH ) NH
4 2 3 2
gives (D). The compound (A) on oxidation with dilute chromic acid gives an unstable compound (E)
which decarboxylates readily to give (F), C H O. The compound (F) gives a hydrocarbon (G) on
3 6
treatment withamalgamated Zn and HCl. Give structures of (A) to (G) with proper reasoning.
Apleasant smelling optically active ester (F) has M.W. = 186. It does not react with Br in CCl . Q.25
2 4
Hydrolysis of (F) gives two optically active compounds, (G) soluble in NaOH and (H). (H) gives a
positive iodoformtest and onwarming with conc. HSO gives (I) (Saytzeff-product) withno geometri-
2 4
cal isomers. (H) ontreatment with benzene sulfonyl chloride gives (J), which on treatment with NaBr
gives optically active (K). When theAg
+
salt of (G) is treated with Br racemic (K) is formed. Give
2
structures of (F) to (K) and explain your choices.
Q.26 Compound(A), M.FC H O reduces ammoniacal silver nitrate to metallic silver and loses its optical
6 12 2
activityon strong heating yielding (B), C H Owhich readilyreacts with dilute KMnO. (A) on oxida-
6 10 4
tionwithKMnO gives (C) having M.FC H O whichdecarboxylates readilyon heating to 3-pentanone.
4 6 10 3
The compound (A) can be synthesized froma carbonyl compound having M.F. C H Oon treatment
3 6
withdilute NaOH. Oxidationof (B) withammonical silver nitrate followed byacidificationgives (D). (D)
forms a derivative (E) with SOCl which onreaction with H CNHCH CH yields (F). Identify (A) to
2 3 2 3
(F) giving proper reaction sequences. What is the name of the reaction involved in the conversion of
C H Oto (A)? Give the IUPACnomenclature of compounds (A) to (F).
3 6
Asolid organic compound (A), C H O is insoluble indilute NaHCO. It produces a dibromoderivative Q.27
9 6 2 3
(B), C H O Br on treatment with Br /CS . Prolongedboiling of (A) withconcentrated KOHsolution
9 6 2 2 2 2
followed by acidification gives a compound (C), C H O . The compound (C) gives effervescence with
9 8 3
aqueous NaHCO . Treatment of (C) with equimolar amount of Me SO /NaOHgives (D), C H O .
3 2 4 10 10 3
The compound (D) is identical with the compound prepared fromortho-methoxy benzaldehyde by
condensation with acetic anhydride in the presence of sodiumacetate. Treatment of (C) with alkaline
C H SO Cl produces (E) which on vigorous oxidation with KMnO gives (F). Hydrolysis of (F) gives
6 5 2 4
a steamvolatile compound (G) having M.F. C H O . Give the structures of (A) to (G) giving the proper
7 6 3
reaction sequences.
Q.28 Aneutral compound (A) C H O on refluxing with dilute alkali followed by acidification yields (B)
9 16 2
C H O and (C) C H O. (B) liberates CO frombicarbonate solution. (C) on dehydration yields
5 8 2 4 10 2
2-butene as the major product. Bontreatment with OsO followed by reactive hydrolysis gives (D)
4
C H O (D) when treated with leadtetraacetate furnishes acetone and (E) C H O . (E) is acidic and
5 10 4. 2 2 3
reduces Tollens reagent. Identify (A), (B), (C), (D) and(E) and write the reactions involved.
Anorganic compoundAon treatment with ethyl alcohol gives a carboxylic acid Band compound C.
Hydrolysis of Cunder acidic conditions gives Band D. Oxidation of Dwith KMnO also gives B. The
Q.29
4
compound Bonheating with Ca(OH) gives E(molecular formula C H O). Edoes not giveTollens test
2 3 6
and does not reduce Fehlings solutionbut forms a 2, 4-dinitrophenylhydrazone. IdentifyA, B, C, Dand
E.
An aqueous alcoholic solution of acetoacetic ester imparts a blue colour with a solution of FeCl . To this Q.30
3
solution if bromine solution is added carefully, the initial colour disappears and the brown colour of
bromine appears, which fades soon andthe solution after remaining colourless for some time regains
the blue violet colour. Explain.
28
EtO
O
H
3
O
Zn(Hg)
(X)
Q.1
A
HCl
Product (X) of above reaction is:
(A) (B) (C) (D)
Q.2 Correct order of reactivityof following acid derivatives is
MeCOCl
I
MeCON
3
MeCOOCOMe
III
(C) I > III > II
II
(A) I > II > III (B) II > I > III (D) II > III > I
H
3
O
+
aO
Et
I
EtOH
Q.3 CH (COOEt) + (CH ) Br II
2
II is:
2 2 3 2
(A) (B) (C) (D)
Q.4 Find the reagent used to bringabout following conversions.
(A) ClCOCH
2
CH
2
COCl
(C) CH
3
COCl
(B) CH
3
COOCOCH
3
(D) ClCO COCl
i) C
H
2
N
2
(
4m
le )
(A), Product (A) of reaction is ? Q.5
(ii ) Ag
2
O; A / MeOH
(A) (B)
(C) (D)
29
EXERCISE-III
Q.6 X. Xwill be
(A) (B) (C) (D) None
O
||
18
dil.H SO
Q.7 Me
3
C C O CMe
3

2
Product of this reaction and the mechanismis:

O
18
O
||
(A) Me
3
C C OH
O
||
(C) Me
3
C C OH
Guess the product
||
Me
3
C C OH
O
18
+ Me
3
C OH , A
1
AC
(B) + Me
3
COH, A
1
AL
||
18
+ Me
3
C OH ,
18
A
2
AC
A
2
AL
(D) Me
3
C C OH + Me
3
COH,
Q.8
PCl
CH
3
CH
2
CONH
2
(A) CH
3
CH
2
CN
?
A
(B) CH
3
CH
2
COCl
(C) CH
3
CCl
2
CONH
2
(D) CH
3
CH
2
CONHCl
Q.9 End product due to hydrolysis of (A) andsubsequent heating is
(A) (B) (C) (D)
O
||

Q.10

N
aO
Q, Q is
?
Me COCH CH NH
2 2 3
O
||
(B) Me C NH CH
2
CH
2
OH
O
||
Me C O CH
2
CH
2
NH
2
(A)
(C) (D) MeCOONa + HOCH
2
CH
2
NH
2
30
(i) LAH
(Y)
(
ii ) H
3
O
(Z)
(iii ) dil OH
OC
l
2
Q.11 4-Pentenoic acid (X)

Identify final (major) product:
O
||
(A) CH
2
= CH CH
2
CH
2
C
N
OH
(B) CH
2
=CHCH
2
CH
2
CH
2
N
|
CH
2
= CH
2
CH
2
CH
2
CH
N
(C) (D) CH
3
CH
2
CH
2
CH
2
CH
2
OH
O O
|| ||
A
Q.12 H
2
N C CH
2
CH
2
C
N
3
P; Pis
(A) (B) (C) (D)
aN
O
2
(S)
+HCl
2
O
(R)
(P)
A
2
O
(Q)
A
Q.13

N
N
3
Identify (S) major product:

(A) (B) (C) (D)
Q.14 Which of the following given two alcohol when it reacts with
LiAlH
4
.
O O O
||
CH
3
C O CH
3
O
||
CH
3
CH C O CH
2
CH
3
|
CH
3
|| ||
(A) (B) CH
3
C O C CH
2
CH
3
(C) (D)All
Q.15 In which of following reaction CO
2
gas will be
evolved. O O
CO
2
H
|| ||
CO
2
H
(A) (B)
Ph CCH COH
A A
2
CO
2
H
aH
O
3
A
(C) (D)All
31
Q.16 Which of the following pair will formsame osazone whenit reacts phenyl hydrazine.
CHO
|
H C OH
|
H C OH
(A) |
H C OH
|
H C OH
|
CH
2
OH
D allose
CHO
|
H C OH
|
HOC H
|
H C OH
|
H C OH
|
CH
2
OH
D glucose
CHO
|
H C OH
|
HOC H
|
H C OH
|
H C OH
|
CH
2
OH
D glucose
CHO
|
HO C H
|
HO C H
|
H C OH
|
H C OH
|
CH
2
OH
D mannose
and (B) and
CHO
|
HCOH
|
HCOH
|
HOCH
|
HCOH
|
CH
2
OH
Dgulose
CHO
|
H C OH
|
HOC H
|
H C OH
|
H C OH
|
CH
2
OH
D glucose
O
CHO
|
H C OH
|
H C OH
|
H C OH
|
H C OH
|
CH OH
CHO
|
HCOH
| HOC
H
| HOC
H
|
HCOH
|
CH OH
(C) and (D) and
2
2
D allose
Dgalactose
18
+ HO
||
Ph CO H

H
Cl
(X) Q.17
A
Major product (X) is.
O
18
O O
(C)
PhCO
18
(A) PhCO
(B)
PhCO (D) PhO
COOEt
tO
Na
H
3
O
/ A
Q.18 (P)
COOEt
Select incorrect statement.
(A) Pcanturn blue litmus red
(C) It is Dieckmann condensation
(B) Pcan not give effervescence of CO
2
with NaHCO
3
.
(D) Product is a bicylo compound
EtO
O
H O
B
Z
n(
g)
C
Q.19
A HCl
Cis:
(A) (B) (C) (D)
32
O
||
C NH
2
Product is:
O
(i) CH MgBr
i) I
2
+C
a(O
)
2
(ii ) A
P O
5
A
3
B
(ii ) H
3
O
+
Q.20 C
O
||
COH
||
C CH
3
(A) (B)
C CH
2
CH
3
||
O
(C) C
||
O
(D)
Q.21
A
(
i) I
2
+ O
H
B
B
r
2
+
2
O
C
(ii ) H
3
O
+
'C' formwhite precipitate compound 'C' is:
(A) (B) (C) (D)
Q.22 Which of the following esters cannot under go self claisen condensation
(A) CH
3
CH
2
CH
2
CH
2
CO
2
C
2
H
5
(C) C
6
H
5
CH
2
CO
2
C
2
H
5
18
(B) C
6
H
5
CO
2
C
2
H
5
(D) CH
3
CH
2
CO
2
C
2
H
5
onc
.H
2
SO
4
OH
Q.23
P.
+
COOH
18
CO
O
CO
O
(A) (B)
18
CO
O
CO
O
(C) (D)
Q.24 Method to distinguished RNH
2
&R
2
NH
(A) NaNO
2
/ HCl
(C) Hinsberg test
(B) Hoffmann's musturd oil reaction
(D)All of the above
33
O
2
, N
aH
CO
OH
Q.25 Product.
Major Product is
I
I
O
I
O O
(A) (B)
OH
I
O I
O
I
O
(C) (D)
ONa
Q.26 Which molecule will give the following dicarboxylic acid on heating with acidic solution of KMnO
4
?
O
||
O
CH
2
COOH
HOOC
(A) (B) (C) (D)
O O O
i ) H
2
O
(ii ) A
O O Q.27 Product:
O
O
O
O
O O
COOH
COOH
(A) (B) (C) (D)
COOH COOH
lC
l
3
[X]
H
+
/ H
2
O
Q.28 +
Z
n /
Hg
/ H
Cl
[Y]

H
[Z]. The structure of [Z] is

(A) (B) (C) (D) none
34
Q.29 + P(Product). Pis:
(A) (B) (C) (D)
Q.30 Which will elimination CO
2
only on
heating
(A) Me C CH
2
COOH
(B) Ph C CH
2
SO
2
H
||
O
||
O
OH
COOH
(C) (D) CH
2
= CHCH
2
COOH
Q.31 Methanoic acid and Ethanoic acid can be differentiated by:
(A) Fehling test (B) Iodoformtest
Assertion and Reason :
(C) Shiff's test (D) NaHCO
3
test
Q.32 Statement-1 : is opticallyinactive, it is taken ina glass container and plane polarized light
(PPL) is passed through it after heating it for several minutes. The PPLshows significant optical rotation.
Statement-2 : Like |-keto acid, gemdicarboxylic acid eliminates CO
2
on heating.
(A) Statement-1 is true, statement-2 is true and statement-2 is correct explanation for statement-1.
(B) Statement-1is true, statement-2 istrue andstatement-2 isNOTthe correct explanationfor statement-
1. (C) Statement-1 is true, statement-2 is false.
(D) Statement-1 is false, statement-2 is true.
Comprehension 1:
An unknown compound having molecular formula C
8
H
4
O
2
Cl
2
can give following set of reactions.
C
8
H
4
O
2
Cl
2
A
C
8
H
4
O
2
Cl
2
B
MgX
H
3
A
(C H O N)
C
8
H
6
O
4
C
C H O N

R
gX
8 5 2
D
8 4 2
E
CH
5
N
G
+ C
8
H
6
O
4
C
H O
C
9
H
7
O
2
N
F
3
35
Q.33 What could be the structure ofA:
(A) (B) (C) (D)
Q.34 What could be the structure of B
(A) (B) (C) (D)
Q.35 Structure of Dis (stable one)
(A) (B) (C) (D)
Comprehension 2 :
Ozonolysis of a compoundAgathene dicarboxylic acid gives following compounds:
HCHO, CHO
|
COOH
&
On complete Reaction by Na-EtOHAgathene dicarboxylic acid give hydrocarbon C
20
H
38
which have
5 chiral carbon in it.
Q.36 The structure ofAgathene dicarboxylic acid is
(A) (B)
(C) (D)
36
Q.37 Howmany chiral carbon are present inAgathene dicarboxylic acid:
(A) 2 (B) 3 (C) 4 (D) 5
Q.38 Total stereoisomers possible forAgathene dicarboxylic acid are:
(A) 16 (B) 18 (C) 32 (D) 64
Q.39 Structure of product formed whenAgathene dicarboxylic acid is heated with soda lime is:
(A) (B) (C) (D)
Comprehension 3 :
18
OMe
( i ) O
3
A + B
OH/A
(ii) H
2
O /Zn
+
H / H
2
O
E
C + D
+
H / A
F
Q.40 Product Cand Dare
O O
|| ||
O O
|| ||
18
(A)
HCCOH
O O
|| ||
HCCOH
+ MeOH (B) HCCOH
O O
+ MeOH
|| ||
HOCCOH
18
+ MeOH
18
+ MeOH (C) (D)
Q.41 Mechanismfor hydrolysis ofAwill be
(A) A (B) (C) (D) A
2
AL
A A
2 1 1
AC AL AC
Q.42 F is
(A) (B) H C C OH
|| ||
H C CH C CH
|| | || ||
O O O OH O O
O
O
O
(C) (D)
C
O
O
O
37
Comprehension 4 :
O
||
H C O CH = CH
2
KOH
3
O
A+
B
?
MnO
A
Red
KOH
C
?
A
Q.43 Mechanismof formation ofAand Bis
(A) A
2
AC
(B) A
1
AC
(C) (D) A
2
AL
A
1
AL
Q.44 Select true statement:
(A) Both Band Cgive same name reaction withKOH (B) Both
Band Cgive iodoformtest
(C) Both Band C give chiral product with PhMgCl followed by NH
4
Cl
(D) Both Band Care redox reaction
Best method out of the given to prepare Bis Q.45
O
||
H C Cl

M
e
2
Cd
O
O
||
HCCl
O
eM
Br
(A) (B)
||
(D) H C OMe

M
e
2
Cd
||
H COMe

M
eM
Cl
(C)
Match the Column:
Q.46 Match reactions givenin column I withnames in II.
ColumnI
COOEt
ColumnII
(A)

E
tO
Na
O
(P) Knovenagel reaction
COOEt
i) E
tO
( ii) H O
,A
(B) CH
2
(COOEt)
2
+
Br
(Q) Perkinreaction
3
O
i)
Zn
(C)
O
(R) Reformatskyrecation
(ii) H
3
O
O
O
MeO
(D)

M
eO
(S) Dieckmann's condensation

OEt
O
ColumnI Q.47 ColumnII
(Product differentiate by)
O
3
Zn
(A) CH
3
CH=CH
2
CH
3
(U) + (V) (P) ByHaloformtest
|
CH
3
C = CH CH
3
O
O
3
(B) (W) + (X) (Q) ByFehling test
Zn
||
Ph C O Ph

(C)

H
3
O
(Y) + (Z)
(R)
(S)
By aq. NaHCO
3
ByTollenTest
38
Q.48 (Reactions)
CH
3
CH = CH
2
+ HCl
CN
(Type of reaction)
Regioselective (A) (P)
(B)

A
(Q) Stereoselective +
CN
Cl
CH
2
D
(C) (R) Stereospecific
H
HCl
(D) (S) Diastereomers CH
2
CMe
3
H
(T) Cyclic addition
ColumnII Q.49 ColumnI
i) A
l(O
Et )
,A
(ii) H
3
O
(A) CH
3
C H Products (P) One of the organic product
||
O
formed will decolourise
bromine water
COOMe
i) M
eO
(ii) H
3
O / A
CH + CH
2
(B) Product(s) (Q) One of the organic product
COOMe
O
formed will give brisk
effervescence with NaHCO
3
One of the organic product
(C) PhMgCl
(
i) C
O
2
Products
(ii ) H
(iii )SOCl
2
(iv) MeMgCl
(R)
formed will give haloformtest.
One of the organic product
formed will give 2,4 DNPtest
(S)
Q.50 (Reaction)
R C OR'
||
O
(Product obtained byreaction)
i) L
(ii ) H
2
O
(A) (P) R'CH
3
(i) LAH
(ii ) H
2
O
(B) R'C OH
||
O
R'CH
2
Br
(Q) R'OH
(C)
(D)
(R)
(S)
R'CH
2
OH
R'H R'C H
||
O
BH
/ E
tO
(E) R C OR'
||
O

R
e d
P/
HI
(T) RCH
3
39
ANSWERKEY
EXERCISE -I
Q.1 The uptake of 2 Hatoms shows the presence of one >C= C<along with CH andCOOH, which
6 5
accounts for the 6 unsaturation. Furthermore Hand I are monosubstituted benzene derivatives. His
*
H
3
C.CHC
6
H
5
COOH
C H C(COOH) = CH giving with one asymmetric carbon atom. I is
6 5 2
C H CH= CH.COOH, giving C H CH CH COOHwith no asymmetric carbon.
6 5 6 5 2 2
CH
2
CH
2
COOH
CH CH.COOH
Pd
(I)
Q.2 (A) = C H CH OH, (B) = C H CH Cl, (C) = C H CH CH CH OH,
15 31 2
(D) = C H CH CH COOH.
15 31 2 15 31 2 2 2
15 31 2 2
(Y) is an ester because it is hydrolysed to acid and alcohol. Since the alcohol is not oxidized by acidified
KMnO and gives cloudiness at once withLucas reagent, hence it is a t-alcohol.
Q.3
4
CH
3
O O CH
3
OH
+ H
3
C C OH
H C C OH H C C O C CH
3 3 3
(A)
CH
3
(B)
CH
3
(Y)
Q.4 This is because C H OHundergoes dehydration to formC H at 170Cin presence of excess of conc.
2 5 2 4
H SO .
2 4
H
2
SO
4
(conc.)
CH
3
CH
2
OH
1
70C
H
2
O + CH
2
= CH
2
Q.5 In the presence of strong acids, the
H
is captured by the carboxylic acid and the following equilibrium

is established:
OH
O
+ H
2
SO
4 + H
2
SO
4
R C
R C
OH
OH
O
H
3
C CH
2
CH
2
C CH
3 Q.6
Q.7 It is because the carboxylate group (COO
) of the branched acid is more shielded fromthe solvent

molecules, therefore, it cannot be stabilized effectivelyby salvation.
40
Q.8 It is because carboxylic group does not have a true carbonyl group due to resonance.
O O
R C O H
R C OH
Due to resonance >C= Obond of COOHdevelops partial double bond character and cannot show
reactions with hydroxylamine, phenyl hydrazine, etc.
It is because formic acid combines the properties of both an aldehyde and an acid. Q.9
Aldehyde
H C
OH
Hence it has reducing character of aldehydes.
HCOOH + 2[Ag(NH
3
)
2
] OH HCOONH
4
+ 3NH
3
+ H
2
O + 2Ag +
or HCOOH + Ag
2
O CO
2
+ H
2
O + 2Ag +
Q.10 Both these unsaturated acids have two ionisable hydogens. After the release of first hydrogen, second
hydrogen of maleiate ionis involved inH-bonding, whereas no H-bonding is possible infumarate ion.
+ A
O H
O

C
`
O
)
H C C
O
H
C
H-bond
OH
H C C OH
O
(Maleiate ion)
O
(Fumarate ion)
(H-bond not possible)
Due to the formation of H-bond in maleiate ion more enegy is required to remove
H
fromit than from

fumarate ion, inwhich
H
release is easycomparatively. Thus, K

2
for fumaric acid is more than maleic
acid.
O
CH
3
CH
2
MgBr
H2C CH2
Q.11
O
+
H
CH
3
CH
2
CH
2
CH
2
O
MgBr

3
(X)
CH
3
CH
2
CH
2
CH
2
OH
(Y)
CH
3
CH
2
CH
2
COOH
(Z) Butanoic acid
Mn
41
O
Q.12 HCCH

NaN
NaCCNa

2 CH
3
I
CH
3
C C CH
3
2
S
O
4
CH
3
C = CH CH
3
|
(X) HgSO
4
OH
O
Tautomerises
CH
3
||
CH
2
CH
3
C
(Y)
Na+O
O
CH NaOH/ Br
||
Haloform reaction CH
C 2 3
H
3
O
+
CH CH COOH
3 2
(Z)
O-------H O
C CH
3
Q.13

(Dimmer)
CH3 C
O H ------O
Dimerization of acetic acid occur in benzene via intermolecular Hbonding. Hydrogen bond is a special
type of dipole dipole attraction.
Sp hybridized carbon of C C of acid (I) and SP
2
hybridized carbon of C = C of acid (II)
attract the bonded electron more than do the SP
3
hybridzed carbon atoms. Consequently CC and
C=C are acid strengthening EWGs [Electronwithdrawing group, stabilizes anion, thus stengthens
acid] This makes CH
3
CH
2
COOHweakest of all these threeacids since CCis moreacid strengthining
group than C=C group. This make acid (I) stranger than acid (II)
Q.14
Q.15
The electron charge incarboxylate ionis more dispersed incomparision to phenoxide ion, since there
are two electro negative oxygen carboxylate ion as compared to oxygen atomin phenoxide ion.
CH
3
COCl will after least stearic hinderance hence it hydrolysis will be more vigrous.
Amide = CH
3
CONH
2
Therefore acid is CH
3
COOH
Acid (Y) obtained after decarboxylation must be mono carboxylic acid thus molecular weight =
Equiva
lent weight
The acid must be (COOH45g / mol)
Given mass = 60g
= 60 45 = 15g/mol
Which is definetely due to CH
3
Hence Yis CH
3
COOH
Carboxylic acid (X) has second COOHreplacing H of CH
3
COOH
COOH
Q.16
Q.17
Q.18
So(X) is malonic acid
H
2
C
of molecular mass 60 + 44 = 104
COOH
Since it has two COOHgroup so its equivalent mass = 104/2 =52 g/eq.
42
Q.19 Dehydration occur withall the three reagent
C
6
H
5
CH
2
CONH
2

P
O
5
C H CH CN + H O
6 5 2 2
C H CH CONH C
6
H
5
CH
2
CN + 2HCl + SO
2
SOCl
2
6 5 2
OC
l
3
Or
C
6
H
5
CH
2
CONH
2
C H CH CN+H O
6 5 2 2 PCl
5
Q.20 The mechanismof esterification
OH
|
R'O
R C OH
OH
| H
+
+
R C OH2
|
OR'
Slow
O
||
R C OR'
O
||
R C OR'
H
+
2
O

As the size of the substituent ono carbon increases, the tetrahedral bonded intermediate become
more crowded. The greater the crowding the slower is the r reaction
(A) (CH CO) O (Acetic anhydride) Q.21
3 2
(B) CH COOH (Ethanoic acid)
3
(C) CH COOC H (Ethyl ethanoate)
3 2 5
(D) C H OH(Ethanol)
3 5
(E) CH COCH
3 3
Q.22 (A) CH CH COOC H (Ethyl propanonate)
3 2 2 5
(B)
CH
3
.CH
2
.CO.CH.COOC
2
H
5
(Ethyl (2-methyl, 3-ketopentanoate)
CH
3
(C) CH3.CH2.CO.CH.COOC2H5 (2-methyl, 3-ketopentanoic acid)
CH3
Q.23 (A) CH .CH .CH .CH COOCH .CH or CH COOCH CH CH CH
3 2 2 2
(B) C H OH
2 3 3 2 2 2 3
2 5
(C) CH .CH .CH
.
CH OH
3 2 2 2
(D) CH CHO
3
(E) CH CH==CH.CHO
3
(F) CH COOH
3
CH3CCOOH
Q.24 (A)
CH3CCOOH
CH3CH
Cis
HCCH3
Trans
H
(B) CH
3
.CH
2
.C*COOH (2-methylbutanoic acid)
CH
3
Q.25 (A) HCOOH (B) CO (C) COOH.COOH
43
Q.26 A
B
C
D
E
=
=
=
=
=
CH OH (Methanol)
(Methyl ethanoate)
(Methanal)
(Methanoic acid)
(Formamide or methanamide)
3
CH COCH
3
HCHO
HCOOH
HCONH
3
2
Q.27
OH
Q.28 A= B = H
2
C O HO OH
CH
3
CH
3
O
D =
H
2
C N
C =
H
2
C Cl
CH
3
O
O
E =
H
3
C OH
F = H
3
C CH
3
O O
O
G = H
3
C
CH
3
Q.29
H
3
C
H
3
C
O
O
Q.30 X =
H
3
C
Y=
CH
3
HO
propionic acid
O
propyl propionate
H
3
C
H
3
C
Z = D =
CH
2
OH
propan-1-ol H
3
C
44
EXERCISE - II
Q.1 (a) The isomers have 1 of unsaturation that must be due to COOH, since CO is evolved on
2
adding NaHCO . The remaining oxygen may be present as OHor OR.
3
COOH COOH
CH
2
COOH COOH
H
3
C CH
CH
2
OH
H
3
C CH
OCH
3
(G)
H
3
C CH
OH
(E)
H
2
CH
3
C CH
OH
(D)
(F)
(b) LiAlH converts COOHto CH OH. Only(D) is reduced to an achiral product.
4 2
Not chiral
COOH
CH
2
OH
H C CH
H
3
C CH
L
iAlH
3
HO
(D)
HO
(c) The ether (G) differs from(E) and (F) in that it is inert to oxidation by KMnO or CrO . (E) gives a
4 3
positive iodoformtest.
CH
3
CH
3
CH
3
CH
3
CO
2
Cl H
3
C
Ether
Mg
C MgCl H
3
C H
3
C
Peroxide
HCl
C C COOMgCl H
3
C C
Q.2
CH
3 CH
2
CH
3
CH
3
CH
3
+
H
2
O / H
H
3
C C COOH
Mg( OH) Cl
CH
3
CO
HC CH+CH MgBr HC CMgBr
2
HC C.COOMgBr
Q.3
3 CH
4
(G) (H)
+
H
H C CCOOH
H
gSO
4
/ H
2
SO
4
H C C COOH
T
auto
mer
ism
H
2
O
(I)
OH H
COOH
Mn
O4
H
2
C
H C
CH
2
COOH
(O)
COOH
O
(J)
O
C OCH CH
Q.4 CH
H
2
O
CH CH COOH + CH CH CH OH
CH CH
3 2 2 2 3 H
+
3 2
(A)
3 2 2
(B)
OH
C
hro
mic a
cid
CH
CH CHO
(
O)
CH CH COOH CH CH CH
3 2 2 (O) 3 2 3 2
(A)
45
SOCl
2
NaN
3 D HYdrolysis
Q.5
Q.6
RCO
2
H RCOCl RCON
3
RNCO RNH
2
bond is very stable due to large AH
f
of CO; so the decomposition reaction
C O
O
H C Cl C O+ HCl
is favoured. Formly chloride is not stable above 60C.
Q.7 An extremelymild but selective oxidizing agent for aldehydes is silver oxide suspended inaqueous base.
Anunsaturated acid is obtained with this reagent because the >C=C<remains untaouched by this
reagent.
COOH CHO
H H
C C
H
2
CH
3
C
C C
CH
3
CH
3
H
2
CH
3
C
Q.8
C H O
A
C H O
H
2
CH CH CH COOH
5 6 4
4 6 2
(B)
3 2 2 CO
2
COOH
A
CH = CH CH COOH
H
2
/ N
i
CH CH CH COOH
H
2
C CHHC 2 2 3 2 2 CO
2
COOH
(B)
Q.9 (A) (CH CO) O (B) CH COOH (C) CH COOC H (D) C H OH
3 2 3 3 2 5 2 5
(E) CH COCH
3 3
Q.10 (A) C H COOC H (B) C H COCH(CH )COOC H
2 5 2 5 2 5 3 2 5
(C) C H COCH(CH )COOH
2 5 3
Q.11 Analkali salt of palmitic acid is known as soap. The general formula of palmitic acid C
15
H
31
COOH.
Which onhydrolysis in presence of alkali give soap (C
15
H
31
COONa) and glycerol as by product.
Acids do not reacts withNaHSO
3
thoughtheyhave >C=Ogroup because of resonance stabilization. Q.12
The resonance take place as follows.
Q.13 CH
3
COOH
(X)
Acetic acid
CH
3
(CH
3
COO)
2
Ca
(Y)
Cal. acetate
a(O
)
2
ry
distillati on
C = O Conc. H SO
2 4
CH
3
Acetone
CH3
CH
3
(Z) Mesitylene
CH3
[o]
Q.14 CH
3
CH
2
COOH
CH CO COOH+H O
3
2 SeO
2
Propionic acid Pyruvic acid
46
Q.15 Acid are directlyreduced to the corresponding primaryalcohol withpowerful reactant like LiAlH
4
. It
attack onlyonthe carbonyl group of a fatty acid.
O
||
R C OH
+4H
L
iAl
H
4
RCH
2
OH + H
2
O
Alkanol
CH
3
|
CHO
CH
||
CH
2+ + 2
H
/ H
2
S
O
4
(x)

H
/
Cr
2
(Y)
Q.16
Acetylene
CH3
aO
CaO
||
COOH
CH
4
Ethanoic acid Methane
CH
3
CN
CH
3
COOH
O
+
H NH
Q.17

3
Ethane nitrile
(X)
CH
3
COONH
4
Ethanoic acid
(Y)
A

CH
3
CONH
2
Ammoniumethanoate Ethanamide
Br
2
/ KOH
CH NH
3 2
Amino methane
Q.18 CH
3
COONa
(Z)
PCl
5
CH
3
COOH
N
aOH
(X)
CH
3
COCl
(Y)
CH
3
COCl
(Y)
O
+ CH
3
COONa
(Z)
O
O
|| || ||
CH
3
C
O
C
CH
3
2CH
3

C
Cl
(E)
(a) CH
3
Cl
(Y)
Q.19 CH
3
COCl
Methyl chloride Acetyl chloride

CH
3
Cl

M
CH
3
MgCl
Methyl chloride
CO
2
+
H
2
O / H
CH
3
COOH CH
3
COCl
OC
l
2
Acetyl chloride
CH
3
CONH
2
(b) C
2
H
5
OH

Ethyl alcohol Acetamide
[O]
+ CH CH
3
OH + CHO

[
O]
3
K
2
Cr
2
O
7
/ H
Methyl alcohol
CH
3
COOH CH
3
COCl
S
OC
l
2
CH
3
CONH
2
Acetamide
H
3
47
(c) CH
3
COOH
Acetic acid
CH
3
COOH
Acetic acid
CH
3
COOC
2
H
5
Ethyl acetate
CH
3
CH
2
OH
LiA
IH
CH
3
COOC
2
H
5
Ethyl acetate
O
CH COOH / H
+
||
NHH CH3CH2OC
CH
2 + O = C
Q.20 (a)
NHH CH3CH2 OC
||
O
(X) Urea
O
||
NH C
l
3
O =
C
(Y)
CH
2
+2C
2
H
5
OH
NH C
||
O
(Z) Ethanol
NHH
C2H5 O C = O
|
+
C H = O C = O
(b)
O = C
2 5
NHH
Urea (E) Diethyl oxalate
NH C = O
|
NH C = O
l
3
O =
C
+ 2C
2
H
5
OH
(F) Parabanic acid
(Oxalyl urea)
NH
2
Cl
(c) CH
2
=O +
O = C
NH
2
Formaldehyde (X) Urea
CH
2
(OH) NH CONH
2
C
H
2
Monomethylol urea
CH
2
(OH)NHCONH (OH) CH
2
rea
Resin
Dimethylol urea ureaformaldehyde
(i) CH CH CH CH Br
CN
CH CH CH CH CN
Q.21
3 2 2 2 Br
3 2 2 2
+
HO
H/ H
CH CH CH CH COOH
3 2 2 2
nPen tanoic acid
CH
3
CH
3
CH
3
(ii)
H
3
C C Br
H
2
SO
4
H C
MR 3
CN
H C C HSO
4

H
OH
C
HCN 3
Br
CH
3
CH
3
CH
2
48
CH
3
CH
3
CH
3
CH
3
H
3
C C OH
S
OCl
2

Ether
Mg
MgCl
(i ) C
O
2
H
3
C C COOH H C C Cl H C C
3 3
(ii ) H O
+
3
CH
3
CH
3
CH
3
CH
3
H H
HOOCCH
2
HOOCCH
2
HOOCCH
2
HOOCCH
2
Br
Q.22

2
H
CH
2 C
2
Ni
Br
H
F
Meso compound
H
E
Meso compound
CH3 CH3
and
CH
3 COOH
C = C C = C
Q.23
H
COOH
H
CH
3
( A) Geometrical isomers
CH3 CH3
C2H5CCOOH HOOCCC2H5 or
H H
B
Q.24 (A) CH CHOHCH COOH (B) CH CH=CHCOOH
3 2 3
(D) CH CH = HCON(CH ) (C) CH CH = CHCOCl
3
(E) CH COCH COOH
3
(F) CH COCH
3 2
3 2 3 3
(G) CH CH CH
3 2 3
Q.25 is a saturated monoester with M.W= 186
CH
3
O CH
3 CH
3
O
CH
3 H
H
3
C O
F = G =
H
3
C O
CH
3
CH
3 CH
3
OH
CH
3
H =
H
3
C
I =
CH
3
OSO
2
C
6
H
5 Br
CH
3
CH
3
H
3
C H
3
C
J = K =
CH
3
CH
3
49
CH
3
CH
3 O
Q.26 A=
H
3
C
B = O
H
3
C
OH
CH
3
CH
3
O
O
H
3
C
H H
3
C H
C = D =
O O O
CH
3
CH
3 CH
3
N
Cl
H
3
C
E =
H
3
C
F =
O CH
3 O
Q.27
CH
3
CH3
Q.28
A
C = CHCOCHCH
2
CH
3
;
or C = CHCOCH2CH2CH2CH3
O
H
3
C
CH
3
O
CH3
CH
3
H
3
C
CH
3
CHCH
2
CH
3
OH
CH
3
CH
2
CH
2
CH
2
OH;
Dehydration
B C = CHCO
2
H ;
C
2 - Butene
CH
3
H
3
C
D O=CHCO
2
H
MF : C
2
H
2
O
3
CCHCO
2
H ;
E
OH OH
M.F C
5
H
10
O
4
50
Q.29 The given reactions are as follows.
C
2
H
5
O
B
A + C
(Carboxylic acid)
+
H
B
C + D
KMnO4
Ca(
OH
)
2
C H
O
B
3 6
(E)
A
The compound Emust be ketonic compound as it does not give Tollens test and does not rce
Fehlings solutionbut forms a 2, 4-dinitrophenyl-hydrazone. Therefore, its structure would be CHCOCH
3 3
(acetone).
Since E is obtained by heating Bwith Ca(OH) , the compound Bmust be CH COOH(acetic acid).
2 3
Since Bis obtained byoxidation of Dwith KMnO, the compound Dmust be analcohol with molecular
4
formula CH CH OH(ethanol).
3 2
Since Band Dare obtained byacid hydrolysis of C, the compound Cmust be an ester CHCOOC H
3 2 5
(ethyl acetate).
Since the compounds B(acetic acid) and C(ethyl acetate) are obtained by treatingAwith ethanol, the
compoundAmust be an anhydride (CH CO) O(acetic anhydride).
3 2
The givenreactions are
(CH
3
CO)
2
O
C
2
H
5
O
H
` CH
3
COOH + CH
3
COOC
2
H
5
acetic anhydride
(A)
acetic acid
(B)
ethyl acetate
(C)
H
+
CH
3
COCH
3
acetone
(E)
CH
3
COOH + C
2
H
5
OH
eth anol
(D)
acetic acid
(B)
KMnO
4
Q.30 Acetoacetic ester shows tautomerism and the two forms are called as keto and enol forms.
OH O
O O
C
2
H
5
C
2
H
5
H
3
C O
H
3
C O
Keto form Enol form
OH
)gives blue-violet colour with FeCl
3
solution. When Br
2
is added,
of the enol form.
The enol (
H
3
C C CH
it reacts at once with
Br
OH O
HO
C
2
H
5
C
2
H
5 + Br
2
O
H
3
C O H
3
C
Br
O
51
Ca( OH)
2
As soon as enol formis consumed, its colouration with FeCl disappears and excess of bromine gives
3
brown colour.Asketo and enol forms are inequilibrium, whenenol formis used, the equilibriumshifts to
right hand side to give more enol formwhich discharges the colour of excess of Br and gives blue violet
2
colour with excess of FeCl present in the reaction mixture.
3
EXERCISE - III
Q.1
Q.8
Q.15
Q.22
Q.29
Q.36
Q.43
Q.46
Q.48
Q.50
B
A
D
B
A
A
A
Q.2
Q.9
Q.16
Q.23
Q.30
Q.37
Q.44
A
B
B
B
A,C,D
C
D
Q.3
Q.10
Q.17
Q.24
Q.31
Q.38
Q.45
D
B
A
D
A,C
C
B
Q.4
Q.11
Q.18
Q.25
Q.32
Q.39
D
B
B
A
D
A
Q.5
Q.12
Q.19
Q.26
Q.33
Q.40
B
C
C
D
C
C
Q.6
Q.13
Q.20
Q.27
Q.34
Q.41
C
B
C
C
C
A
Q.7
Q.14
Q.21
Q.28
Q.35
Q.42
B
D
C
D
B
D
(A) S, (B) P, (C) R, (D) S
(A) P, (B) Q,R,T(C) P,S (D) P,Q,S
(A) QR(B) R(C) P(D) R (E) ST
Q.47
Q.49
(A) P, (B) Q,S (C) R
(A) Q,R(B) P,Q(C) R,S
52

Carboxylic Acid and Its Derivative

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Carboxylic Acid and Its Derivative

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1.

) where R and R' may be alkyl

etc, are comparatively weaker bases than H

ion on carbonyl carbon in benzamide is difficult

Q.12 What is (Z) in the following sequence of reactions ?

Q.21 Complete the following equations:

Product of this reaction and the mechanismis:

Q.11 4-Pentenoic acid (X)

Identify (S) major product:

[Z]. The structure of [Z] is

(S) Dieckmann's condensation

is captured by the carboxylic acid and the following equilibrium

) of the branched acid is more shielded fromthe solvent

fromit than from

release is easycomparatively. Thus, K

Methyl chloride Acetyl chloride

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