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Organic compounds containing Oxygen :
CarboxyIicAcids:
General methods of preparation, properties,
reactions anduses.
Acidic strengthandfactors affectingit.
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JEE(NITs)_CarboxyIic Acids & Acid Derivatives - 1
Introduction :
The characteristic functional group in a carboxylic acid is the carboxyl group.
Carboxylic acid derivatives are compounds that can be hydrolyzed under acidic or basic conditions to give a
related carboxylic acid . All of them can be conceptually derived by replacing a small part of the carboxylic
acid structure with other groups.The most important acid derivatives are esters, amides, acid halides, anhy-
drides and nitriles.
O
R C X
acid halide
O O
R C O C R
anhydride
O
R C O R'
ester
O
R C NH
2
amide
R C N
nitrile
Carboxylic acids and their derivatives have not only structural similarities but also close relationships in their
chemistry. With the exception of nitriles, all carboxylic acid derivatives contain a carbonyl group. Many
important reactions of these compounds occur at the carbonyl group. Furthermore, the C N(cyano) group
of nitriles has reactivity that resembles that of a carbonyl group. Thus, the chemistry of carboxylic acid
derivatives, like that of aldehydes, ketones, and carboxylic acids, involves the chemistry of the carbonyl
group.
1. CarboxyIic acid :
PhysicaI properties of acids and acid derivatives :
PhysicaI state :
First three members are colourless pungent smelling liquid. The next three members are also colurless oily
liquid with unpleasant smell. Higher member (> 7) are colourless waxy solids.
BoiIing point :
The boiling point of carboxylic acids are higher than that of alcohols, ketones or aldehydes of similar
molecular weight.
CH C OH
acetic acid,
bp 118ºC
3
O
CH OH
1-propanol
bp 97ºC
3
CH CH
2 2
The high boiling points of carboxylic acids is the result of formation of a stable hydrogen-bonded dimer.
R C
C R
O ----- H O
O H ----- O
hydrogen bonded acid dimer
Esters and acid chlorides have boiling points near to those of the unbranched alkanes with similar molecular
weights.
Acids containing more than 8 carbon atoms are generally solids, unless they contain double bonds. The
presence of double bonds (especially cis double bond) in a long chain impedes the formation of a stable
crystal lattice resulting in a lower boiling point.
O
CH (CH ) C OH
3 2 16
Stearic acid, mp 70ºC
O
C = C
C = C
H
H H H
CH (CH )
3 2 4
CH
2
(CH ) C OH
2 7
linoleic acid mp 5ºC
JEE(NITs)_CarboxyIic Acids & Acid Derivatives - 2
MeIting point :
There is no regular pattern in melting point of carboxylic acid (up to 10 carbon atoms) having even number of
Catoms are higher than neighbouring members having odd number of Catoms because carboxylic acid and
methyl group in even members lie in opposite side of zig-zag carbon chain hence they fit better into crystal
lattice resulting in higher melting points.Vice-versa is observed in case of carboxylic acid having odd no. of
carbon atoms.
SoIubiIity:
Carboxylic acids form hydrogen bond with water and the lower molecular - weight carboxylic acids (upt o
4 carbon atoms) are miscible with water.
Acidderivatives (esters, acidchlorides, anhydrides, nitriles andamides) aresolubleincommon organic solvents
suchas alcohols, ethers, chlorinatedalkanes andaromatic hydrocarbons. Acidchlorides andanhydrides cannot
be used in nucleophilic solvents such as H
2
Oand alcohols, because they react with these solvents.
2. Methods of preparation of carboxyIic acids :
2.1 Oxidation of primary aIcohoIs with acidic or aIkaIine KMnO
4
or acidic K
2
Cr
2
O
7
:
R CH
2
OH + [O]
,
4 2 7 2 2
SO H / O Cr K
R COOH + H
2
O
2.2 By oxidation of aIkyIbenzenes - aromatic acids are produced :
O H / H ) ii (
¯ OH / KMnO
2
4
O H / H ) ii (
¯ OH / KMnO ) i (
2
4
4 2
7 2 2
SO H
O Cr K
2.3 Synthesis of CarboxyIic acids by the hydroIysis of nitriIes :
+ + H
+
heat
+
DMSO
NaCN
CH CN
2
Benzyl cyanide (92%)
CH COH
2
Phenylacetic acid (77%)
||
O
CH CCH CH CH
3 2 2 3
|
OH
|
CN
ile Ethanenitr
N C CH
3
+ 2H
2
O + HCl
acid Ethanoic
Cl NH COOH CH
4 3
le Benzonitri
N C H C
5 6
+ 2H
2
O + HCl
acid Benzoic
Cl NH COOH H C
4 5 6
JEE(NITs)_CarboxyIic Acids & Acid Derivatives - 3
Note: (1) Alkyl cyanides needed for the purpose can easily be prepared from the corresponding alkyl halides with
alcoholic KCNor NaCN.
R Cl + KCN R C N + KCl
(2) This reaction is used to ascend the series having one carbon atom more than the corresponding alkyl
halides which are prepared fromalcohol on treating with phosphorus halide.
ROH+ PX
5
R X + POX
3
+ HX
(3) This hydrolysis of alkyl cyanide provides a useful method to get carboxylic acid having one carbon atom
more than the original alkyl halide and alcohols.
Ex. Preparation of propanoic acid fromethyl alcohol follows :
CH
3
CH
2
OH
5
PCl
CH
3
CH
2
Cl
KCN
CH
3
CH
2
CN
H / O H
2
CH
3
CH
2
COOH
Ex. C
3
H
6
Cl
2
(A)
KCN
(B)
OH / O H
2
(C)
2
CO
2-Methylpropanoic acid
Cl
|
CH C CH
|
Cl
3 3
KCN
CN
|
CH C CH
|
CN
3 3
OH / O H
2
COOH
|
CH C CH
|
COOH
3 3
2
CO
2-Methylpropanoic acid
2.4 Synthesis of carboxyIic acids by the carboxyIation of grignard reagents :
RMgX + O = C = O
ether
Dry
OMgX C R
||
O
X ) OH ( Mg
O H / H
2
OH C R
||
O
e tan Chlorobu 2
Cl
|
CH CHCH CH
3 2 3
1. Mg / diethyl ether
2. CO
2
3. H O
3
+
%) 86 76 ( acid
oic tan Methylbu 2
H CO
|
CH CHCH CH
2
3 2 3
Ex.
3
3
CH
|
MgBr CH CH
H / O H ) ii (
CO ) i (
2
2
) acid propanoic methyl 2 ( acid Ìsobutyric
CH
|
COOH CH CH
3
3
Ex. C
3
H
5
Cl (A)
dryether / Mg
(B)
H / O H ) ii (
CO ) i (
2
2
(C)
] O [
C
8
H
12
(D)
(A) = ; (B) = ; (C) = ; (D) =
2.5 By hydroIysis of acid derivatives :
+
Pyridine
+
+ + CH
3
COOH
JEE(NITs)_CarboxyIic Acids & Acid Derivatives - 4
Ester
' RCOOR
+ H
2
O
¯ OH or H
RCOOH + ROH
chloride Acid
O H RCOCl
2
¯ OH or H
RCOOH+ HCl
amide Acid
O H RCONH
2 2
¯ OH or H
RCOOH + NH
3
2.6 By hydroIysis of 1, 1, 1-trihaIides :
loride Benzotrich
KOH 3 CCl H C
3 5 6
KCl 3
) Unstable (
3 5 6
) OH ( C H C
O H
2
acid Benzoic
COOH H C
5 6
2.7 By oxidation of methyI ketones-(HaIoform) reaction :
one 2 tan Pen
COCH CH CH CH
3 2 2 3
O H / H ) ii (
NaOH / ) i (
2
2

acid oic tan Bu
CH COOH CH CH CH
3 2 2 3

2.8 From oIefins (CarboxyIation of AIkene) :
) steam ( Ethylene
O H CO CH CH
2 2 2
pressure under
K 673 573 , PO H
4 3
acid opionic Pr
COOH CH CH
2 3
3. ChemicaI Reactions of carboxyIic acid :
JEE(NITs)_CarboxyIic Acids & Acid Derivatives - 5
HVZ Reaction (HaIogenation of aIiphatic acids and substituted acids) :
Ìn the presence of a small amount of phosphorus, aliphatic carboxylic acids react smoothly with chlorine or
bromine to yield a compound in which -hydrogen has been replaced by halogen. This is the Hell-Volhard-
Zelinsky reaction. Because of its regioselectivity-only alpha halogenation takes place.
CH
3
COOH
P , Cl
2
ClCH
2
COOH
P , Cl
2
Cl
2
CHCOOH
P , Cl
2
Cl
3
CCOOH
CH
3
CH
2
COOH
P , Br
2
CH
3
CHBrCOOH
P , Br
2
CH
3
CBr
2
COOH
P , Br
2
nofurther substitution
The halogen of these halogenated acids ungergoes nucleophilic substitution and elimination much as it does
in the simpler alkyl halides. Halogenation is therefore the first step in the conversion of a carboxylic acid into
many important substituted carboxylic acids.
acid
enated log ha An
Br
|
RCHCOOH + large excess of NH
3
acid o min a An
NH
|
RCHCOOH
2
Br
|
NaOH RCHCOOH
OH
|
RCHCOONa
H
acid hydroxy An
OH
|
RCHCOOH
Br
|
) alc ( KOH CHCOOH RCH
2
RCH = CHCOO¯
H
acid d unsaturate , An
CHCOOH RCH
Conversion of acid into acid derivatives :
A carboxylic acid is converted directly into an ester when heated with an alcohol in the presence of a little
mineral acid, usually concentrated sulfuric acid or dry hydrogen chloride. This reaction is reversible, and
generally reaches equilibrium when there are appreciable quantities of both reactant and products present.
+ + H
2
O
JEE(NITs)_CarboxyIic Acids & Acid Derivatives - 6
4. DicarboxyIic acids :
Ìf the substituent is a second carboxyl group, we have a dicarboxylic acid. For example :
Few methods of preparation and properties :
Heating product of few dibasicacid :
(1) Malonic acid acetic acid (2) Glutaric acid Glutaricanhydride
(3) Adipic acid Cyclopentanone + CO
2
+ H
2
O (4) Pimelic acid Cyclohexane +CO
2
+H
2
O
JEE(NITs)_CarboxyIic Acids & Acid Derivatives - 7
5. Hydroxy acid (Preparation and heating product) :
5.1 -Hydroxy acid :
1.
2. R CH
2
COOH
P / Br
2
5.2 Hydroxy acid :
+
/ Zn
!!
O H
2
5.3 Hydroxy acid :
H / O H
2
O H
2
5.4 Hydroxy acid
H / O H
2
O H
2
Note : Other higher hydroxy acids on heating undergo intermolecular esterification to give linear polymer.
JEE(NITs)_CarboxyIic Acids & Acid Derivatives - 8
6. Acid Derivatives :
6.1 AcyI haIides :
Methods of preparation of AcyI haIides :
(i) RCOOH + PCl
5
RCOCl + POCl
3
+ HCl
3RCOOH+ PCl
3
3RCOCl + H
3
PO
3
RCOOH + SOCl
2
Pyridine
RCOCl + SO
2
+ HCl
(ii) 3CH
3
COONa + PCl
3
Distil
chloride Acetyl
3 3 3
PO Na COCl CH 3
benzoate . Sod
3 5 6
POCl COONa H C 2
Distil
chloride Benzoyl
NaPO NaCl COCl H C 2
3 5 6
ChemicaI reactions of acid haIides :
6.2 Acidanhydrides :
Methods of Preparation of acid anhydrides :
(i)
acid Acetic
HOOCCH COOH CH
3 3
,
5 2
O P
anhydride Acetic
O H CH . CO . O . CO CH
2 3 3
(ii) CH
3
COOH+ CH
3
COCl
Pyridine
CH
3
CO.O.COCH
3
+ HCl
(ii) CH
3
COCl + CH
3
COONa CH
3
CO.O.COCH
3
+NaCl
ChemicaI Reactions of acid anhydrides :
(1) FriedeI Craft reaction :
+ ArH +
(2) Reaction with aIcohoIs : Acid anhydrides react with alcohols to form esters. The reaction may be
carried out in the presence of pyridine or it may be catalysed by acids. Ìn the example shown, only one acyl
group of acetic anhydride becomes incorporated into the ester ; the other becomes the acyl group of an
acetic acid molecule.
+ +
JEE(NITs)_CarboxyIic Acids & Acid Derivatives - 9
+ + CH
3
COOH
(3) Reaction with ammonia and amines :
Acid anhydrides react with ammonia and amines to form amides. Two molar equivalents of amine are
required. Ìn the example shown, only one acyl group of acetic anhydride becomes incorporated into the
amide and the other becomes the acyl group of the amine salt of acetic acid.
+ +
+ + CH
3
COOH
(4) HydroIysis : Acid anhydrides react with water to yield two carboxylic acid functions. Cyclic anhydrides
yield dicarboxylic acids.
+ +
+
6.3 Esters :
Methods of Preparation of esters :
(i)
acid Acetic
OH H C COOH CH
5 2 3
H
O H H COOC CH
2 5 2 3
OH CH COOH H C
3 5 6
H
O H COOCH H C
2 3 5 6
(ii) Alcohols react with acyl chlorides by nucleophilic acyl substitution to yield esters. These reactions are
typically performed in the presence of a weak base such as pyridine.
+ + +
JEE(NITs)_CarboxyIic Acids & Acid Derivatives - 10
CH
3
COCl + C
2
H
5
OH
Pyridine
CH
3
COOC
2
H
5
+ HCl
C
6
H
5
COCl + CH
3
CH
2
OH
NaOH
C
6
H
5
COOCH
2
CH
3
+HCl
+
(iii) (CH
3
CO)
2
O+C
2
H
5
OH
H
CH
3
COOC
2
H
5
+CH
3
COOH
(iv) RCOOH +
2
H C
N N
2 3
N RCOOCH
(v)
CHO RCH 2
2
3 5 2
) H OC ( Al
R CH COOCH RCH
2 2 2
(Tischenko reaction)
ChemicaI Reactions of ester :
6.4 Acidamides:
Methods of preparation of acid amides :
Reaction of esters with ammonia and amines :
+ +
Ammonia is more nucleophilic than water, making it possible to carry out this reaction using aqueous
ammonia.
Methyl 2-methylpropenoate
H C = C COCH
2 3
|
||
CH
3
O
+
2-Methylpropenamide
(75%)
H C= C CNH
2 2
|
||
CH
3
O
+
+ +
JEE(NITs)_CarboxyIic Acids & Acid Derivatives - 11
+ +
(i) RCOCl + 2NH
3
RCONH
2
+NH
4
Cl
(RCO)
2
O+ 2NH
3
RCONH
2
+RCOONH
4
RCOOR +NH
3
RCONH
2
+R OH
(ii) RCOONH
4
RCONH
2
+ H
2
O
4 3
COONH CH
2 3
CONH CH
(iii) R C N + H
2
O
NaOH O H or
HCl . Conc
2 2
R CONH
2
O H N C CH
2 3
4 2
SO H . Conc
2 3
CONH CH
+
ChemicaI Reactions of amides :
Ex. Write the structures of (A) C
3
H
7
NO which on acid hydrolysis gives acid (B) and amines (C). Acid (B) gives
(+)ve silver mirror test.
Ans. A = or
JEE(NITs)_CarboxyIic Acids & Acid Derivatives - 12
Hofmann bromamide reaction :
Ìt is used for preparation of 1º amine as well as aniline. Here amide is converted into amine on treating with
Br
2
in base (NaOH, KOH). During the reaction C is removed as carbonate ion hence this reaction is used to
descend the series. Also alkylisocyanate is obtained as an intermediate product.
R C NH
2
||
O
+Br
2
+ 4 KOH RNH
2
+ K
2
CO
3
+ 2KBr + 2H
2
O
Ìn the reaction R may be CH
3
, CH
2
CH
3
, , C
6
H
5
etc.
Mechanismof reaction proceeds through the following steps
2NaOH + Br
2
R C NH
2
||
O
OBr
Alkanamide
||
O
R C NH Br
OH
R N = C = O RNH
2
+ CO
2
+ H
2
O
JEE(NITs)_CarboxyIic Acids & Acid Derivatives - 13
JEE(NITs)_CarboxyIic Acids & Acid Derivatives - 14
OBJECTIVE PROBLEMS (JEE-MAIN)
Section (A) : Prepartion of CarboxyIic Acid
A-1. Acetic acid is obtained when
(1) Methyl alcohol is oxidised with potassium permanganate
(2) Formaldehyde is oxidised with potassium dichromate and sulphuric acid
(3) Acetonitrile is hydrolysed with a dilute mineral acid
(4) Glycerol is heated with sulphuric acid.
A-2. Ìn the following reaction sequence
C
2
H
5
Br
KCN
X
Boil
SO H . Dil
4 2
Y
Product Y is
(1) Ethanol (2) Ethanal (3) Propanoic acid (4) Ethanenitrile
A-3. Ìn the following reaction final product is :
C
6
H
5
MgBr + CO
2
Ether
H
(1) Benzoic acid (2) Benzaldehyde (3) Benzamide (4) Benzene
A-4. The acid Dobtained through the following sequence of reactions is
C
2
H
5
Br
KOH . Alc
A
4
2
CCl
Br
B
) excess (
KCN
C
O H
3
D
(1) Succinic acid (2) Malonic acid (3) Maleic acid (4) Oxalic acid
A-5. Which of the following does not give benzoic acid on hydrolysis ?
(1) Phenyl cyanide (2) Benzoyl chloride
(3) Benzyl chloride (4) Methyl benzoate
A-6. (Acetic anhydride) on hydrolysis gives :
(1) CH
3
COOC
2
H
5
(2) CH
3
COOH (3) C
2
H
5
OH (4) none of these
A-7. Ìn which of the following reaction the final product is neither an acid nor an acid salt.
(1) Ph CHO
reagent s ' Tollen
(2) CH
3
CH
2
OH
H O / KMnO
4
(3) Ph CHO
solution Fehling
(4) Ph CH
2
OH
H / O Cr K
7 2 2
Section (B) : ChemicaI reactions of CarboxyIic Acid
B-1. When excess of chlorine is passed through acetic acid in presence of red phosphorus, it forms
(1) Acetic anhydride (2) Chloral
(3) Trichloroacetic acid (4) Methyl chloride.
B-2. Which of the following will not undergo Hell-Volhard Zelinsky (HVZ) reaction ?
(1) HCOOH (2) CH
3
COOH (3) CH
3
CH
2
COOH (4) CH
3
CHBrCOOH.
B-3. Ìdentify Z in the following reaction sequence
l CH
3
Ether
Mg
X
O H ) ii (
ice Dry ) i (
3
Y
P d Re
Cl
2
Z
(1) CH
3
COOH (2) CH
3
Mgl (3) CH
3
COCl (4) ClCH
2
COOH.
JEE(NITs)_CarboxyIic Acids & Acid Derivatives - 15
B-4. The reaction : RCOOAg + Br
2
Reflux , CCl
4 R Br +AgBr + CO
2
is called
(1) Wurtz reaction (2) Hunsdiecker reaction
(3) Friedel-Crafts reaction (4) Kolbe's reaction
B-5. The reaction, CH
3
COOH+ CH
3
OH
H
CH
3
COOCH
3
+ H
2
Ois called
(1) Acidification reaction (2) Dehydration reaction
(3) Dehydrogenation reaction (4) Esterification reaction
B-6. Ìt is difficult to esterify R
3
C COOH because of
(1) Steric hindrance (2) Delocalization
(3) Ìnductive effect of the Rgroup (4) Hyperconjugation of the alkyl groups
B-7. Which of the following is correct order of esterification of following acids with CH
3
OH:
HCOOH , CH
3
COOH , CH
3
CH
2
COOH ,
   
(1)     (2)     (3)     (4)   
B-8. The product of the following reaction is :
(1) (2) (3) (4)
B-9. Which of the following methods is not used for the conversion of carboxylic acids into acid halides ?
(1) RCOOH+ SOCl
2
(2) RCOOH+ PCl
5
(3) RCOOH+ Cl
2
(4) RCOOH+ PCl
3
Section (C) : Preparation of Acid derivatives
C-1. A fruity smell is produced by the reaction of C
2
H
5
OH with :
(1) CH
3
COCH
3
(2) CH
3
COOH (3) PCl
5
(4) CH
3
CHO
C-2. Benzoyl chloride on treatment with ammonia gives
(1) Benzamide (2) Acetamide (3) Benzylamine (4) Benzoic acid
C-3. Acetic anhydride is prepared in the laboratory by heating sodium acetate with
(1) ethyl chloride (2) acetyl chloride (3) conc. H
2
SO
4
(4) zinc dust
C-4. Synthesis of an ester involves the reaction of alcohols with
(1) a ketone (2) an amide (3) CH
3
MgBr (4) RCOCl
C-5. Diazomethane reacts with carboxylic acids to form
(1) Amines (2) Methyl esters (3) Alcohols (4) Aldehydes.
C-6. What product is formed when acetic acid reacts with P
2
O
5
.
(1) Acetyl chloride (2) Trichloro acetic acid (3) Acetic anhydride (4) Di-chloro acetic acid
JEE(NITs)_CarboxyIic Acids & Acid Derivatives - 16
C-7. The reagent which does not give acid chloride on treating with a carboxylic acid is :
(1) PCl
5
(2) Cl
2
(3) SOCl
2
(4) PCl
3
Section (D) : ChemicaI reaction of Acid derivatives
D-1. The decreasing order of reactivity towards nucleophilic acyl substitution is
(i) CH
3
COCl (ii) CH
3
COOC
2
H
5
, (iii) CH
3
CONH
2
(iv) (CH
3
CO)
2
O
(1) (i) > (iv) > (iii) > (ii) (2) (i) > (iv) > (ii) > (iii) (3) (iv) > (iii) > (i) > (ii) (4) (iii) > (i) > (iv) > (ii)
D-2. An anhydride R COOCORon reduction with LiAlH
4
will give
(1) RCH
2
OHandR OH (2) RCH
2
OHandROH
(3) RCH
2
OHandRCH
2
OH (4) R OHand ROH.
D-3. CH
3
CH
2
CH
2
CONH
2
is boiledwith aqueous NaOH, thenthereaction mixture is acidifiedwithHCl. The products
obtainedare
(1) CH
3
CH
2
CH
2
COO +NH
3
(2) CH
3
CH
2
CH
2
COONa+NH
3
(3) CH
3
CH
2
CH
2
COOH+NH
4
Cl (4) CH
3
CH
2
CH
2
COO +NH
4
Cl.
D-4. Acetamide and ethyl acetate can be distinguished by reacting with
(1) Aqueous HCl and heat (2) Aqueous NaOHand heat
(3) Acidified KMnO
4
(4) Bromine water.
D-5. A compound with molecular formula C
4
H
10
O
4
on acylation with acetic anhydride gives a compound with
molecular formula C
12
H
18
O
8
. Howmany hydroxyl groups are present in the compound ?
(1) one (2) Two (3) Three (4) Four
D-6. The product formed by the reaction of acetamide with Br
2
in presence of NaOH is :
(1) CH
3
CN (2) CH
3
CHO (3) CH
3
CH
2
OH (4) CH
3
NH
2
OBJECTIVE PROBLEMS (JEE-ADVANCE)
SingIe choice type
1. Hydrolysis of hydrogen cyanide results in the formation of
(1) Formic acid (2) Acetic acid (3) Formaldehyde (4) Acetaldehyde.
2. The final product in the following reaction is :
(1) (2) R CH
2
COOH (3) (4) 1 and 2 both
3. Which of the following does not give benzoic acid salt on oxidation with hot alkaline KMnO
4
.
(1) Ph CH
3
(2) Ph CH=CH CH
3
(3) Ph C C CH
3
(4) Ph C(CH
3
)
3
4. Ìn Hunsdiecker reaction
(1) Number of carbon atoms decreased. (2) Number of carbon atoms increased
(3) Number of carbon atoms remains same (4) May be increase or decrease
5. An optically active compound (X) has molecular formula C
4
H
8
O
3
. Ìt evolves CO
2
with NaHCO
3
. (X) reacts
with LiAlH
4
to give an achiral compound. Structure of (X) is.
(1) CH
3
CH
2
COOH (2) CH
3
COOH
(3) (4)
JEE(NITs)_CarboxyIic Acids & Acid Derivatives - 17
6. Ìdentify final product in the following reaction
product.
(1) (2) CH
2
=CH COOH
(3) (4) CH
3
CH
2
OH
7. + 3 NaOH (Q) + salt of fatty acid.
Product (Q) of the reaction is
(1) Ethylene glycol (2) Glycerol
(3) Glyceryl tri nitrate (explosive) (4) Cumene hydrogen peroxides
8. Give the order of ease of the esterification of the following acid
(1) Ì > ÌÌ > ÌÌÌ > ÌV (2) ÌV > ÌÌÌ > ÌÌ > Ì
(3) ÌÌ > Ì > ÌV > ÌÌÌ (4) Ì > ÌÌ > ÌÌÌ > ÌV
9. Ìn the following reaction, C
2
H
5
OH acts as :
C
2
H
5
OH+CH
3
COOH
O H
SO H . Conc
2
4 2
CH
3
COOC
2
H
5
(1) electrophilie (2) nucleophile
(3) dehydrating agent (4) All of the above
10. Acetic acid reacts separately with the following phenols. The rate of esterification is highest for -
(1) (2) (3) (4)
JEE(NITs)_CarboxyIic Acids & Acid Derivatives - 18
11. Which of the following reaction represents incorrect product.
(1) (2) + H
2
O
(3) CH
3
COOH+ CO
2
(4) CH
2
=CH COOH + CO
2
12. (A) would be :
(1)
O O
|| ||
CH C O C CH
3 3
(2) CH
3
COOH
(3) CH
3
COCl (4) CH
3
CONH
2
13. Starting frompropanoic acid, the following reactions were carried out
Propanoic acid
2
SOCl
X
3
NH
Y KOH Br
2 Z
What is the compound Z
(1) CH
3
CH
2
Br (2) CH
3
CH
2
NH
2
(3) (4) CH
3
CH
2
CH
2
NH
2
14. (A)
3
NH
(B)
O H
NaOH
2
(C)
KOH Br
2
(D)
HCl
(E)
Ìn this reaction the product (E) is
(1) o-nitrobenzoic acid (2) Salicylic acid
(3) anthranilic acid (4) Crotonic acid
15.
2 2
2 2
CONH CH
|
CONH CH
5 2
O P
(P)
O H
3
(Q)
The product (Q) is
(1) CH
3
CH
2
COOH (2)
COOH CH
|
COOH CH
2
2
(3) (4) CH
3
COOH
16. Which of the following reactions of alkanols does not involve C O bond breaking
(1) CH
3
CH
2
OH+ SOCl
2
(2) CH
3
CH(OH)CH
3
+ PBr
3
(3) CH
3
CH
2
OH+CH
3
COOH (4) ROH+ HX
JEE(NITs)_CarboxyIic Acids & Acid Derivatives - 19
MISCELLANEOUS PROBLEMS
Assertion / Reason
This section contains reasoning type questions. Each question has 4 choices (1), (2), (3) and (4), out of
which ONLY ONE is correct.
(1) Ìf both assertion and reason are true and reason is a correct explanation of assertion.
(2) Ìf both assertion and reason are true but reason is not a correct explanation of assertion.
(3) Ìf assertion is true but reason is false.
(4) Ìf assertion and reason both are false.
1. Assertion : 1º Amides react with Br
2
in presence of NaOH to form1º-amine having one carbon atom less
than amide.
Reason : Ìt is degradative reduction involving N-bromoalkanamide intermediate.
2. Assertion : Acetic acid does not give haloformreaction.
Reason : Acetic acid has no -hydrogen.
3. Assertion : Formic acid reduces mercuric chloride.
Reason : Formic acid has reducing aldehydic group.
4. Assertion : Carboxylic acids have a carbonyl group but they do not give the test of carbonyl group.
Reason : Due to resonance, the double bond character of carbonyl group is greatly reduced.
5. Assertion : Ethanamide (CH
3
CONH
2
) undergoes dehydration by heating with P
2
O
5
.
Reason : Ethanamide undergoes dehydration to give nitro compound.
6. Assertion: Pure acetic acid is converted into ice like solid called galcial acetic acid.
Reason : Acetic acid is stronger than formic acid.
7. Assertion : The order of base catalysed hydrolysis of ester is
(1) CH
3
COOCH
3
>CH
3
COOC
2
H
5
>CH
3
COOCH(CH
3
)
2
.
(2) > > >
Reason : S
N
2 Th is sterically as well as electronically controlled reaction.
8. Assertion : Acid catalysed hydrolysis of ester is reversible while base catalysed hydrolysis is irreversible.
Reason: Ìn acid catalysed ester hydrolysis carboxylic acid is formed on which nucleophilic attack of alcohol
is possible but in base catalysed ester hydrolysis carboxylate anion is formed on which nucleophilic attack
is not possible.
9. Assertion : Acetate ion is more basic than the methoxide ion.
Reason : The methoxide ion is resonance stabilized.
10. Assertion : p-Hydroxybenzoic acid has a lower boiling point than o-hydroxybenzoic acid.
Reason : o-Hydroxybenzoic acid has intermolecular hydrogen bonding.
JEE(NITs)_CarboxyIic Acids & Acid Derivatives - 20
Comprehenison # 1
Ìn general, the reactivity of acid derivatives follows the order :
> > >
The above order of reactivity can be explained in terms of the :
(i) Basicity of leaving group (ii) Resonance effect (iii) inductive effect
Weaker is the basic character of leaving group, more is the reactivityof acid derivative. Ìn general, all the acid
derivatives showresonance as follows:
More is the stabilization, lesser is the reactivity and vice-versa
Answer the following questions :
11. Which among the following anions is the most basic ?
(1)
2
H N
(2) R O (3) O CO R (4) Cl
12. Acid derivatives although contain group, yet do not undergo the usual properties of carbonyl group. Ìt is
mainly due to :
(1) Ìnductive effect (2) Resonance (3) Electromeric effect (4) All of these
13. Which of the following compound will be hydrolysed most easily ?
(1) Acid halide (2) Acid amide (3) Ester (4) Acid anhydride
Comprehension # 2
+ (Q)
) aldol cross (
CO K . aq
3 2
HCN
tion esterifica ular Ìntramolec
(T)
14. The compound Q is :
(1) (2)
(3) (4)
JEE(NITs)_CarboxyIic Acids & Acid Derivatives - 21
15. Conversion of (R) to (S) is an example of
(1) Nucleophilic addition reaction (2) Electrophilic addition reaction
(3) Nucleophilic substitution (4) Elimination reaction
16. The structure of compound (T) is :
(1) (2)
(3) (4)
LEVEL -1 : PREVIOUS YEARS AIEEE PROBLEMS (JEE-MAIN)
1. CompoundAgiven belowis : [AIEEE-2002]
OCOCH
3
COOH
(1) antiseptic (2) antibiotic (3) analgesic (4) pesticide
2. End product of the following reaction is : [AIEEE-2002]
CH
3
CH
2
COOH
P red
Cl
2
KOH alcoholic
(1)
OH
|
CHCOOH CH
3 (2)
OH
|
COOH CH CH
2 2
(3) CH
2
=CHCOOH (4)
OH Cl
| |
CHCOOH CH
2
3. Rate of the reaction is fastest when Z is : [AIEEE-2004]
R C
Z
O
+ Nu R C
Nu
O
+ Z
(1) Cl (2) OCOCH
3
(3) OC
2
H
5
(4) NH
2
4. Consider the acidity of the carboxylic acids : [AIEEE-2004]
(a) PhCOOH (b) o-NO
2
C
6
H
4
COOH
(c) p-NO
2
C
6
H
4
COOH (d) m-NO
2
C
6
H
4
COOH
which of the following order is correct ?
(1) a > b > c > d (2) b > c > d > a (3) b > d > a > c (4) b > d > c > a
JEE(NITs)_CarboxyIic Acids & Acid Derivatives - 22
5. On mixing ethyl acetate with aqueous sodium chloride, the composition of the resultant solution is :
[AIEEE-2004]
(1) CH
3
COOC
2
H
6
+NaCl (2) CH
3
Cl +C
2
H
5
COONa
(3) CH
3
COCl + C
2
H
5
OH+ NaOH (4) CH
3
COONa+C
2
H
5
OH
6. p-cresol reacts with chloroformin alkaline medium to give the compoundAwhich adds hydrogen cyanide to
form, the compound B. The latter on acidic hydrolysis gives chiral carboxylic acid. The structure of the
carboxylic acid is : [AIEEE-2005]
(1)
OH
CH
3
CH COOH
2
(2)
OH
CH
3
CH COOH
2
(3)
OH
CH
3
CH(OH)COOH
(4)
OH
CH
3
CH(OH)COOH
7. An organic compound having molecular mass 60 is found to to contain C= 20%, H= 6.67%and N= 46.67%
while rest is oxygen. On heating it gives NH
3
along with a solid residue. The solid residue give violet colour
with alkaline copper sulphate solution. The compound is : [AIEEE-2005]
(1) CH
3
CH
2
CONH
2
(2) (NH
2
)
2
CO (3) CH
3
CONH
2
(4) CH
3
NCO
8. Aliquid was mixed with ethanol and a drop of concentrated H
2
SO
4
was added. Acompound with a fruity smell
was formed. The liquid was : [AIEEE-2009]
(1) HCHO (2) CH
3
COCH
3
(3) CH
3
COOH (4) CH
3
OH
9. Sodiumethoxide has reacted with ethanoyl chloride. The compoundthat is produced in the above reaction is :
[AIEEE-2011]
(1) Diethyl ether (2) 2-Butanone (3) Ethyl chloride (4) Ethyl ethanoate
LEVEL - 2 : PREVIOUS YEARS JEE PROBLEMS (JEE-ADVANCE)
* Marked Questions are having more than one correct option.
1. Which of the following acids has the smallest dissociation constant ? [JEE 2002, 1/35]
(A) CH
3
CHFCOOH (B) FCH
2
CH
2
COOH (C) BrCH
2
CH
2
COOH (D) CH
3
CHBrCOOH
2. There is a solution of p-hydroxy benzoic acid and p-amino benzoic acid. Discuss one method by which we
can separate them and also write down the confirmatory test of the functional groups present.
[JEE-2003, 4/60]
3. Statement-1 : Acetate ion is more basic than the methoxide ion.
Statement-2 : The acetate ion is resonance stabilized. [JEE-2004, 3/84]
(A) Statement-1 is True, Statement-2 is True; Statement-2 is a correct explanation for Statement-1.
(B) Statement-1 is True, Statement-2 is True; Statement-2 is NOT a correct explanation for Statement-1
(C) Statement-1 is True, Statement-2 is False
(D) Statement-1 is False, Statement-2 is True
4. Ìn conversion of 2-butanone to propanoic acid which reagent is used. [JEE-2005, 3/84]
(A) NaOH, Na / (B) Fehling solution (C) NaOH, 
2
/ (D) Tollen's reagent
JEE(NITs)_CarboxyIic Acids & Acid Derivatives - 23
Passage
X
5. Which reagent (X) is used to convert  to  [JEE2006, 5/184]
(A) KBr / NaOH (B) Br
2
/ NaOH (C) NaHCO
3
(D) N-Bromo succinamide
6. Which step is rate determining step [JEE2006, 5/184]
(A) Formation of  (B) Formation of  (C) Formation of  (D) Formation of 
7. + under Hofmann conditions will give : [JEE2006, 5/184]
(A) + (B) +
(C) + (D) +
8. Statement-1 : p-Hydroxybenzoic acid has a lower boiling point that o-hydroxybenzoic acid.
Statement-2 : o-Hydroxybenzoic acid has intramolecular hydrogen bonding. [JEE2007,3/162]
(A) Statement-1 is True, Statement-2 is True; Statement-2 is a correct explanation for Statement-1.
(B) Statement-1 is True, Statement-2 is True; Statement-2 is NOT a correct explanation for Statement-1
(C) Statement-1 is True, Statement-2 is False
(D) Statement-1 is False, Statement-2 is True.
9. Ìn the reaction T, the strucutre of the Product T is :
[JEE-2010,3/163]
(A) (B)
(C) (D)
JEE(NITs)_CarboxyIic Acids & Acid Derivatives - 24
10. The major product of the following reaction is : [JEE-2011,3/160]
(A) (B)
(C) (D)
11. The compound that undergoes decarboxlylation most readily under mild condition is [JEE-2012, 3,/136]
(A) (B)
(C) (D)
12. With reference to the scheme given, which of the given statments(s) about T, U, V and W is (are) correct?
[JEE-2012, 4/136]
(A) T is soluble in hot aqueous NaOH
(B) U is optically active
(C) Molecular formula of W is C
10
H
18
O
4
(D) Vgives effervescence on treatment with aqueous NaHCO
3
.
JEE(NITs)_CarboxyIic Acids & Acid Derivatives - 25
EXERCISE # 1
A-1. 3 A-2. 3 A-3. 1 A-4. 1 A-5. 3
A-6. 2 A-7. 3 B-1. 3 B-2. 1 B-3. 4
B-4. 2 B-5. 4 B-6. 1 B-7. 2 B-8. 2
B-9. 3 C-1. 2 C-2. 1 C-3. 2 C-4. 4
C-5. 2 C-6. 3 C-7. 2 D-1. 2 D-2. 3
D-3. 3 D-4. 2 D-5. 4 D-6. 4
EXERCISE # 2
1. 1 2. 2 3. 4 4. 1 5. 3
6. 1 7. 2 8. 1 9. 2 10. 2
11. 4 12. 2 13. 2 14. 3 15. 3
16. 3
EXERCISE # 3
1. 1 2. 3 3. 1 4. 1 5. 3
6. 3 7. 1 8. 1 9. 4 10. 4
11. 1 12. 2 13. 1 14. 2 15. 1
16. 4
EXERCISE # 4
LeveI-1
1. 3 2. 3 3. 1 4. 2 5. 1
6. 3 7. 2 8. 3 9. 4
LeveI-2
1. C
2. +
These can be separated by aq. HCl.
Test (1) :
3
FeCl Neutral
Violet blue ppt.
Test (2) :
KOH / Naphthol HCl / NaNO
2
Red Orange dye.
3. D 4. C 5. B 6. D 7. A
8. D 9. C 10. A 11. B 12. ACD
JEE(NITs)_CarboxyIic Acids & Acid Derivatives - 26
SingIe choice type
1. Ìdentify the final product in the following sequence of reaction.
2
SOCl
3
NH
5 2
O P
(1) (2) (3) (4)
2. Which of the following acids remains unaffected on heating
(1) Malonic acid (2) Malic acid (3) Fumaric acid (4) Succinic acid
3. Ìdentify the final product in the following sequence of reaction.
h / Br
2 AA
O H ) 2 (
KCN ) 1 (
3
(1) (2) (3) (4)
4. Ìdentify (Z) in following sequence of reaction
CH
3
CH
2
CH
2
Br
NaCN
(X)
heat
O H
3
(Y)
H
OH CH CH
2 3
(Z)
(1) CH
3
CH=CH COOH (2) CH
3
CH
2
CH
2
CH( OCH
2
CH
3
)
2
(3) CH
3
CH
2
CH
2
O CH
2
CH
3
(4) CH
3
CH
2
CH
2
CH(OCH
2
CH
3
)
2
5. Esterification of the acid (P) with the alcohol (Q) will gives
+
(R configuration) (±)
(1) only one enantiomer (2) a mixture of diastereomer
(3) a mixture of enantiomer (4) only one fraction on fractional distillation
6. What makes a lemon sour ?
(1) Tartaric acid (2) Oxalic acid (3) Citric acid (4) Hydrochloric acid
7. Vinegar contains
(1) 10 20% Acetic acid (2) 50%Acetic acid (3) 7 8% Acetic acid (4) 100%Acetic acid
8. Methanoic acid is manufactred by the reaction of carbon monoxide and 
(1) NaOH (2) dil HCl (3) conc. H
2
SO
4
(4) PCl
5
9. CH
3
CH
2
CH
2
COOH
2
Br P d Re
Br
|
COOH CH CH CH
2 3
This reaction is called
(1) Cannizzaro reaction (2) Schmit reaction
(3) Hell Volhard Zelinsky reaction (4) Reimer tiemann reaction
JEE(NITs)_CarboxyIic Acids & Acid Derivatives - 27
10.
O O
|| ||
OEt C CH CH C CH
2 2 3
O OH
|| |
OEt C CH CH CH CH
2 2 3
The above conversion is carried out by
(1) NaBH
4
(2) LiAlH
4
(3) Na / EtOH (4) DÌBAL
11. Which of the following compound takes maximum time for hydrolysis reaction.
(1)
O
||
Cl C CH
3
(2)
O O
|| ||
CH C O C CH
3 3
(3)
O
||
OEt C CH
3
(4)
O
||
NH C CH
2 3
12. Give the order of ease of decarboxylation of the following acids
(1) Ì > ÌÌ > ÌÌÌ > ÌV (2) ÌÌÌ > ÌV > ÌÌ > Ì (3) ÌV > ÌÌÌ > ÌÌ > Ì (4) Ì > ÌÌÌ > ÌÌ > ÌV
13. (A)
4
NaBH
H
Ether / LiAlH
4
(B)
(A) and (B) are
(1) , (2) ,
(3) , (4) Both are
14. Which of the following ester have most acidic -hydrogen atom.
(1) CH
3
COOC
2
H
5
(2)
O
||
H OC C CH N O
5 2 2 2
(3)
O
||
H OC C CH NC
5 2 2
(4)
O O
|| ||
H OC C CH C CH
5 2 2 3
15. List the following esters in order of decreasing reactivity in the second step of a nucleophilic acyl substitution
reaction .
(1) ÌV > Ì > ÌÌÌ > ÌÌ (2) ÌV > ÌÌÌ > Ì > ÌÌ (3) ÌÌÌ > ÌV > Ì > ÌÌ (4) ÌÌ > Ì > ÌÌÌ > ÌV
JEE(NITs)_CarboxyIic Acids & Acid Derivatives - 28
16.
O H ) 2 (
PhMgBr excess ) 1 (
2
X, X is :
(1) (2) (3) (4)
17.
CN ) CH ( C O H C
||
O
2 2 5 2
) excess (
LiAlH
4
X, X is :
(1) (2) (3) (4)
18.
10 4
O P
P
O H
MeMgBr
3
Q
2 2
Ì , ) OH ( Ca
R, compound R is :
(1) (2) (3) (4)
19.
O H
3
[X]
Select the correct statement.
(1) Xgives effervescence of CO
2
withNaHCO
3
(2) Xwill produce alkane when treated with Zn-Hg/HCl
(3) X will produce symmetrical diketone when treated with sodalime
(4) All of these
20. The compound (A) in the following sequence of reactions is a silver salt of
A
4
CCl
Br
2
B
EtOH
KOH
propene
(1) Propanoic acid (2) Butyric acid (3) isobutyric acid (4) Both (2) and (3)
21. The reaction, RCOOR + R OH(excess)
OH or H
RCOOR + R OHis called.
(1) Esterification (2) Trans-esterification (3) Saponification (4) Hydrolysis
22. The correct acidity order is :
(1) Ì > ÌÌ > ÌÌÌ (2) ÌÌ > ÌÌÌ > Ì (3) ÌÌÌ > ÌÌ > Ì (4) ÌÌ > Ì> ÌÌÌ
JEE(NITs)_CarboxyIic Acids & Acid Derivatives - 29
23. The correct acidity order is :
) P (
COOH CH CH N O
2 2 2
) Q (
F
|
COOH CH CH
3
) R (
COOH CH CH
2 3
(1) P > Q > R (2) Q > P > R (3) R > P > Q (4) Q > R > P
24. Ethanol on heating with acetic acid in the presence of a few drops of sulphuric acid gives the smell of
(1) Oil of wintergreen (2) Oil of mustard (3) Fruity smell (4) Oil of bitter almonds
25. Acetamide is amphoteric in character because it can react with
(1) Conc. HCl (2) HgO (3) Conc. HCl and HgO (4) NaOH
26. Among the following, the acid which undergoes fastest decarboxylation is
(1) (2) (3) PhCOOH (4) Ph COOH.
27. Which of the following reaction will not give cyclic products upon heating.
(1) (2)
(3) (4)
More than one choice type
28. Which reactions gives ester as final product.
(1) CH
3
COOAg + Br
2
4
CCl
(2) CH
3
COOH+CH
3
OH
H
(3) CH
3
OH +
O
||
Cl C CH
3
(4) CH
3
COOH + HCl
29. Consider the following reaction sequence.
CH
3
CH
2
CH
2
OH
4
KMnO
(B)
O H
Br P d Re
2
2
(C)
Which statement (s) is /are correct.
(1) (A) is more acidic than (B) (2) (C) is more acidic than (A) and (B)
(3) (C) is -Bromo acid (4) B is more acidic than (A) and (C)
30. Acetic anhydride can be prepared by
(1)
O
||
Cl C CH
3
+ CH
3
COO Na (2) CH
3
COOH
5 2
O P
(3)
OH CH
|
OH CH
2
2
+
COOH
|
COOH
H
(4) CH
3
COOC
2
H
5
+CH
3
OH
H
31. Which of the following can be used for the synthesis of benzyl acetate
(1) C
6
H
5
CH
2
OH +
O O
|| ||
CH C O C CH
3 3
base
(2) C
6
H
5
CH
2
OH +
O
||
OH C CH
3
H
(3) C
6
H
5
CH
2
OH +
O
||
Cl C CH
3
base
(4) C
6
H
5
CH
2
OH + CH
3
COOH
NaOH
JEE(NITs)_CarboxyIic Acids & Acid Derivatives - 30
32. Ìn which of the following reactions benzoic acid is the major product it
(1) C
6
H
5
CH
2
OH
O H ) 2 (
OH , KMnO ) 1 (
3
4
(2)
O
||
CH C H C
3 5 6
O H ) 2 (
NaOH , Cl ) 1 (
3
2
(3) Ph Mg Br
O H ) 2 (
CO ) 1 (
3
2
(4) Ph CH
3
O H
O , KMnO
3
4
33. Acid anhydride can be prepared by
(1) C
6
H
5
COOH+CH
3
COCl
pyridine
(2) C
6
H
5
COO Na
+
+
O
||
Cl C H C
5 6
(3)
O
||
NH C CH
2 3
+ C
6
H
5
COO Na
+
(4)
34. Ìn the esterification of propanoic acid with methanol in the presence of a mineral acid, which of the following
are intermediate species
(1) OH C H C
||
H O
5 2
(2)
OH
|
OH C H C
5 2
(3)
3
2 5 2
OCH
|
H O C H C
|
OH
(4)
O
||
C H C
5 2
35. Which of the following methods is/are used for the conversion of carboxylic acids into acid halides.
(1) RCOOH+ SOCl
2
(2) RCOOH+ PCl
5
(3) RCOOH+ Cl
2
(4) RCOOH+ PCl
3
MATCH THE COLUMN :
36. CoIumn I CoIumn II
(1) R CONH
2
(p) Most reactive towards acyl substitution
(2) R COOR (q) reduces HgCl
2
(3) HCOOH (r) High boiling point
(4) RCOCl (s) Fruity smell
37. CoIoumn I CoIoumn II
(1)
OH
R NH
2
(p) Curtius reaction
(2)
O H . 2
/ NaN . 1
2
3
R NH
2
(q) Hoffmann's reaction
(3) + Br
2
O H . 2
H O . 1
2
R NH
2
(r) Schmidt reaction
(4) + N
3
H
O H
2
R NH
2
(s) Lossen rearrangement
JEE(NITs)_CarboxyIic Acids & Acid Derivatives - 31
1. 3 2. 3 3. 4 4. 3 5. 2
6. 3 7. 3 8. 1 9. 3 10. 1
11. 4 12. 3 13. 3 14. 2 15. 1
16. 3 17. 4 18. 2 19. 2 20. 4
21. 2 22. 1 23. 2 24. 3 25. 3
26. 2 27. 3 28. 2,3 29. 2,3 30. 1,2
31. 1,2,3 32. 1,2,3,4 33. 2,4 34. 1,2,3 35. 1,2,4
36. (1) (r) ; (2) (s) ; (3) (q) ; (4) (p) 37. (1) (s) ; (2) (p) ; (3) (q) ; (4) (r)
1. 2
SOCl
3
H N
. .
5 2
O P
2. Ìn fumaric acid both COOHgroups are present on opposite side so it is unaffected on heating.
3.
h / Br
2
O H ) 2 (
KCN ) 1 (
3
4. CH
3
CH
2
CH
2
Br
NaCN
CH
3
CH
2
CH
2
CN
heat
O H
3
CH
3
CH
2
CH
2
COOH
H
OH CH CH
2 3
CH
3
CH
2
CH
2
O CH
2
CH
3
5. + (Diastereomers)
+
6. Citric acid makes a lemon sour.
7. Vinegar contains 7 8% acetic acid.
8. CO
2
+ NaOH HCOONa
H
HCOOH
9. Ìt is Hell Volhard Zelinsky reaction.
CH
3
CH
2
CH
2
COOH
2
Br P d Re
Br
|
COOH CH CH CH
2 3
10. NaBH
4
does not reduce ester functional group.
11. Rate of hydrolysis partial positive charge on
>
C= O groups.
JEE(NITs)_CarboxyIic Acids & Acid Derivatives - 32
12. Rate of decarboxylation stability of anion.
13. NaBH
4
cannot reduce ester group but LiAlH
4
can reduce ester as well as ketonic group.
14. Acidic strength
15. Rate
group leaving of basicity
1
16.
PhMgBr
Ph
OMgBr H O
2
Ph
OH
Ph
OH
17.
18. X
10 4
O P
O H
MeMgBr
3 2
2
Ì
) OH ( Ca
19.
O H
3
HCl / Hg Zn
20. (1)
AgBr
CO
CCl
2
4
CH
3
CH
2
Br
EtOH
KOH
CH
2
== CH
2
ethene
(2)
AgBr
CO
CCl
2
4
CH
3
CH
2
CH
2
Br
EtOH
KOH
(3)
AgBr
CO
CCl
2
4
EtOH
KOH
21. When an ester converts into another ester, it is called trans esterification.
22. Ì and M group increases acidic strength.
23. Ì and M group increases acidic strength.
24. CH
3
COOH + C
2
H
5
OH
H
CH
3
COOC
2
H
5
(ester)
25. Ìt can act as reducing as well as oxidising agent.
26. -Keto acid decarboxylates faster through 6 member cyclic transition state.
JEE(NITs)_CarboxyIic Acids & Acid Derivatives - 33
27. (1)
O H
2
(2)
O H
2
(3) CH
3
CH=CH COOH (4)
28. CH
3
COOH + CH
3
OH
H
CH
3
COOH
3
CH
3
OH +
O
||
Cl C CH
3
O
||
OCH C CH
3 3
29. CH
3
CH
2
CH
2
OH
4
KMnO
CH
3
CH
2
COOH
O H
Br P d Re
2
2
Br
|
COOH CH CH
3
-Bromo acid
30.
O
||
Cl C CH
3
Na COO CH
3
O O
|| ||
CH C O C CH
3 3
CH
3
COOH
5 2
O P
O O
|| ||
CH C O C CH
3 3
OH CH
|
OH CH
2
2
+
COOH
|
COOH
H
O
||
C O CH
| |
C O CH
||
O
2
2
CH
3
COOC
2
H
5
+CH
3
OH
H
CH
3
COOCH
3
(Trans esterfication)
31. (1) C
6
H
5
CH
2
OH
base
C
6
H
5
CH
2
O
(2) C
6
H
5
CH
2
OH +
O
||
OH C CH
3
H
(3) C
6
H
5
CH
2
OH +
O
||
Cl C CH
3
base
JEE(NITs)_CarboxyIic Acids & Acid Derivatives - 34
32. C
6
H
5
CH
2
OH
O H ) 2 (
OH , KMnO ) 1 (
3
4
PhCOOH
O
||
CH C H C
3 5 6
O H ) 2 (
NaOH , Cl ) 1 (
3
2
PhCOOH+CHCl
3
Ph Mg Br
O H ) 2 (
CO ) 1 (
3
2
PhCOOH
Ph CH
3
O H
O , KMnO
3
4
PhCOOH
33. C
6
H
5
COO Na
+
+
O
||
Cl C H C
5 6
34. OH C H C
||
O
5 2
H
OH C H C
||
H O
5 2
OH
|
OH C H C
5 2
OH CH
3
3
2 5 2
OCH
|
H O C H C
|
OH
35. RCOOH+ SOCl
2
RCOCl + SO
2
+ HCl
RCOOH+ PCl
5
RCOCl + POCl
3
RCOOH+ PCl
3
RCOCl + H
3
PO
3
36. Amide have high boiling point due to H-bonding .
Esters have fruity smell
Formic acid reduces HgCl
2
Acid halide is more reactive towards acyl substitution.
37. (1)
OH
reaction Lossen
R N=C=O
(2)
reaction Curtius
/ NaN ) i (
3
R N=C=O
(3)
Hoffman
OH / Br
2
OH
R N=C=O
(4) + N
3
H
reaction Schimdt
R N=C=O