7.aldehydes and KetonesExercise

Chem i str y | 23.
35
Solved Examples
JEE Main/Boards
Example 1: Identify A to E in the following reactions:
COOH
Conc.HNO₃ SOCl₂ (i)NaBH₄

A B C
+Conc. H₂SO₄ (ii)H₃O+
SOCl₂
H₂-Pd/BaSO4
D E
+ S or quinoline
Sol: The First step is nitration, the reaction with SOCl2 forms an acid chloride derivative, which on Rosenmund
reduction forms a formyl group whereas the acid chloride derivative on reduction with NaBH4 gives an alcohol.
COOH COOH COCl
Conc. HNO₃ SOCl₂

+Conc. H₂SO₄ -SO₂, -HCl
(Nitration)
NO₂ NO₂
Benzoic acid m-Nitro- m-Nitrobenzoyl
benzoic acid (A) chloride (B)
-SO₂ SOCl₂ (i) NaBH₄

-HCl
(ii) H₃O+
COOH CHO CH₂OH
H₂-PdBaSO₄
+ S or quinoline
(Rosenmund NO₂
Benzoyl reduction) Benzaldehydro (E) m-Nitrobenzoyl
chloride (D) alcohol, (C)
Example 2: Identify A to E in the following series of reactions:
273-283 K H₃O+
CH₃+CrO₃+(CH₃CO)₂O A B
Conc. NaOH
KMnO₄,KOH
Heat COONa
H₃O+
D E C+
Sol: Toluene with KMnO4/KOH undergoes oxidation to form Benzoic acid. On the other side, toluene with chromium
oxide and acetyl acetate gives benzylidene acetate which on treatment with an acid gives aldehyde which on
reaction with a strong base undergoes the Cannizzaro reaction.
2 3 . 3 6 | Aldehydes and Ketones
OCOCH₃
CH₃ CH
273-283 K OCOCH₃
+CrO₃+(CH₃CO)₂O
Toluene Benzylidene
diacetate (A)
KMrO₄,KOH,
(Oxidation) H₃O+
COOK CHO
Pot. benzoate (D) Benzaldehyde (B)
Cone. NaOH
H₃O+
(Cannizzaro reaction)
CH₂OH COONa
COOH
Benzoic acid (E) Benzyl alcohol (C)
Example 3: Complete each synthesis by filling the missing starting materials, reagents or products (X, Y and Z).
NaOH
(a) C6H5CHO + CH3CH2CHO  →X
Y
(b) CH3CH2CH2CH2OH → CH3CH2CH2COOH
Z
(c) CH3 (CH2 )3 COOC2H5 → CH3 (CH2 )9 CHO
Sol: (a) The reaction is Claisen-Schmidt condensation.
O OH CH3 CH3
NaOH | | 3| 2
C6H5–C–H + CH3CH2CHO C6H5–CH–CH–CHO –H2O C6H5–CH=C–CHO
(Claisen Schmidt
Benzaldehyde Propanal condensation) 2-methyl-3-phenylprop-
2-en-1-al (X)
(b) Oxidation of alcohol to acid thus the reagent used must be KMnO4
(i) Alk.KMnO
4 → CH CH CH COOH
CH3CH2CH2OH  3 2 2
Butan−1−ol (ii) H+ ,H2O Butanoic acid
(i) DIBAL −H
(c) CH3 (CH2 )9 COOC2H5  → CH3 (CH2 )9 CHO
Ethyl undecanoate (ii) H2O Undecanal
Thus, Y = (i) Alk. KMnO4, (ii) H+, H2O

And Z = (i) DiBAL-H, (iii) H2O
Chem i str y | 23.37
Example 4: (a) Identity A, B and C in the following reaction

dil.H SO
dil.NaOH
2 4 → A → heat
HC ≡ CH  B  →C
HgSO 4
(b) Give reasons: (i) p-Nitrobenozoic acid has higher Ka value than benzoic acid
(ii) Acetone is highly soluble but benzophenone is not
Sol: (a) The first step is conversion of the alkyne to an unsaturated alcohol, which then tautomerises to form an
aldehyde. When this aldehyde is treated with dil NaOH and undergoes self-condensation, reaction known as aldol
which form β- hydroxyl carbonyl compound On heating it gives α,β unsaturated carbonyl compound.
2 4→ dil.H SO Tautomerises dil.NaOH

HC ≡ CH  =[H2C CHOH]  → CH3CHO →
Acetylene (Addional of H2O) Vinylalcohol Acetaldehyde(A) (Aldolcondensation)
heat
CH3 − CHOH − CH2 − CHO  → CH3 − =
CH CH − CHO
β−Hydroxybutyraldehyde)(B) Dehydration( −H2O) But −2 −en−1 −al(C)
(Analdol)
Sol: (b) (i) Higher the K a stronger is the acid.

p-nitrobenzoic acid is a stronger acid than benzoic acid. This is due to the following two reasons:
I. Due to -I-and - R-effect of the –NO2 group, the electron density in the O–H bond decreases. As a result, the O–H
bond becomes weak and hence p-nitrobenzoic acid more easily loses a proton than benzoic acid.
II. Due to -I and R-effect of the NO2 group, dispersal of the-ve charge occurs and hence
p-nitrobenzoate ion becomes more stable than the benzoate ion.
O O
O + -O +
N C O H N + C O H
-O -O
O + O -O + O O
N C - -O N C -O C -O
-O O
p-Nitrobenzoate ion (more stable) Benzoate ion (less stable)
(ii) This is because, the carbonyl group of Acetone easily forms Hydrogen bonds with water and hence acetone is
highly soluble in water.
However, in Benzophenone, the phenyl groups are larger and hence C = O group cannot form hydrogen bonds
with water due to steric crowding. Benzophenone is thus insoluble in water.
Example 5: Show how each of the following compounds could be converted to benzoic acid
(i) Ethylbenzene (ii) Acetophenone (iii) Bromobenzene (iv) Phenylethene (Styrene)
Sol: First step is oxidation with KMnO4 and KOH to for Potassium Benzoate followed by treatment. with acid.
(a) This can be achieved by treating it with KMnO4-KOH followed by treatment with acid.
CH₂CH₃ COO-K+ COOH
KMnO₄-KOH H₃O+

Ethylbenzene Pot. benzoate Benzoic acid
(b) COCH₃ COO-K+ COCH
KMnO₄-KOH H₃O+

Acetophenone Pot. benzoate Benzoic acid
COOH₃ COONa COOH
I₂-NaOH
(lodoform reaction) H₃O+
Alternatively,
-CH₃
Acetophenone Sod. benzoate Benzoic acid
(c) First of all we have to prepare the Grignard reagent. It is prepared by treating Bromobenzene with Mg in dry
ether. Now this Grignard reagent is treated with dry ice followed by hydrolysis to form Benzoic acid.
O
Br MgBr C
Mg O=C=O OMgBr H₃O+
Dry ether (dry ice) -Mg(OH)Br
Bromobenzene Phenylmag O
bromide
C
OH
Benzoic acid
(d) This can be achieved by following the same process of KMnO4-KOH and acid.
CH=CH₂ COO-K+
KMnO₄-KOH H₃O+
+ HCOO-K+
Pot. formate
Phenylethene Pot. benzoate
or styrene
COOH
+ HCOOH
Methanoic acid
Benzoic acid
Example 6: An organic compound A (molecular formula C8H16O2) was hydrolysed with dilute sulphuric acid to give
a carboxylic acid (B) and an alcohol (C) Oxidation of (C) with chromic acid produced (B). (C) on dehydration gives
but-1-ene. Write equations for the reactions involved.
Sol: (i) Since the organic compound (A) on hydrolysis with dil. H2SO4 gives carboxylic acid (B) and the alcohol (C)
therefore, (A) must be an ester. Further, since the oxidation of (C) with chromic acid produces the acid (B) therefore
both the carboxylic acid (B) and the alcohol (C) must contain the same number of carbon atoms.
(ii) Since the ester (A) contains eight carbon atoms, therefore both the carboxylic acid (B) and the alcohol (C) must
contain four carbon atoms each.
(iii) (C) on dehydration gives but-1-ene, therefore, (C) must be a straight chain alcohol. i.e. butan-1-ol.
(iv) If (C) is butan-1-ol, then acid (B) which is gives on oxidation must be butanoic acid and the ester (A) must be
butyl butanoate.
O O
Dil.H₂SO₄
CH₃CH₂CH₂ C OCH₂CH₂CH₂CH₃ CH₃CH₂CH₂ C OH + CH₃CH₂CH₂CH₂OH
Hydrolysis
Butyl butanoate (A) Butanoic acid (B) Butan-1-ol (C)
(M.F. = C₈H1₆O₂)
O
CrO₃H₂SO₄ Dehydration
CH₃CH₂CH₂ C OH CH₃CH₂CH₂CH₂OH CH₃CH₂CH=CH₂
Oxidation (-H₂O)
Butanoic acid (B) Butan-1-ol (C) But-1-ene
Example 7: How will you prepare the following compounds from benzene? You may use any inorganic reagent and
any organic reagent having not more than one carbon atom.
(a) Methyl benzoate (b) m-Nitrobenzoic acid (c) p-Nitrobenzoic acid
(d) phenyl acetic acid (e) p-Nitrobenzaldehyde.
Sol:
Br MgBr COOH
Br₂/FeBr₃ Mg/dry ether (i) Dry ice

(a) (Nuclear (Grignard (ii)H₃O+
bromination) reaction)
Bromo- Phenylmag.
benzene bromide
COOCH₃
CH₃OH (excess),
Conc. H₂SO₄,
(Esterification)
COOH COOH
Conc. HNO₃
As in (i) above + Conc. H₂SO₄,
(b)
(Nitration)
NO₂
Benzene Benzoic acid m-Nitrobenzoic acid
CH₃ CH₃ CH₃

Conc. HNO₃
CH₃Cl/Anhyd.AlCl₃ + Conc. H₂SO₄,
NO₂
(c) +
(F.C.alkylation) (Nitration)
Benzene Toluene o-Nitrotoluene

NO2 (solid)
p-Nitrotoluene (major product)
(solid)
(major product)
CH₃ COOH
Separate by (I) KMnO₄/KOH,
filtration (ii) Dil.H₂SO₄
NO2 NO₂
p-Nitrotoluene p-Nitrobenzoic acid
CH₃ CH₂Br
NBS , hv
(d) As in (iii) above or Br₂, and hv Alc. KCN,
(side chain, (Nucleophilic
bromination) substitution)
Benzene Toluene
CH₂CN CH₂COOH
+
H /H₂O
(Hydroliysis)
Benzyl cyanide Phenylacetic acid
CH₃ CHO
(i) CrO₂Cl₂/CS₂
As in (iii) or CrO₂/(CH₃CO)₂O
(e) above (ii) H₃O+
Benzene
NO₂ NO₂
p-Nitrotoluene p-Nitrobenzaldehyde
Example 8: An aromatic compound ‘A’ (Molecular formula C8H8O) gives positive 2, 4-DNP test. It gives a yellow
precipitate of compound ‘B’ on treatment with iodine and sodium hydroxide sol. Compound ‘A’ does not give
Tollen’s or Fehling’s test. On drastic oxidation with potassium permanganate is forms a carboxylic acid ‘C’ (Molecular
formula C7H6O2), which is also formed along with the yellow compound in the above reaction, Identify A, B and C
and all the reaction involved.
Sol: (i) From the given data we can see that aromatic compound ‘A’ (MFC8H8O) gives positive 2, 4-DNP test, thus it
must be an aldehyde or a ketone.
(ii) As compound ‘A’ does not give Tollen’s test or Fehling’s test, thus ‘A’ must be a ketone.
(iii) Compound ‘A’ on treatment with I2/NaOH, gives yellow precipitate of compound ‘B’ therefore, compound ‘B’
must be iodoform and the ketone A’ must be a methyl Ketone (Haloform reaction)
(iv) Since methyl ketone ‘A’ on drastic oxidation with KMnO4 gives a carboxylic acid ‘C’ (MFC7H6O2), therefore, ‘C’
must be benzoic acid and compound ‘A’ must be acetophonenone (C6H5COCH3).
Example 9: When liquid ‘A’ is treated a freshly prepared ammonical silver nitrate sol, it gives bright silver mirror.
The liquid forms a white crystalline solid on treatment with sodium hydrogensulphite. Liquid ‘B’ also forms a white
crystalline solid with sodium hydrogensulphite but it does not give test with ammoniacal silver nitrate. Which of
the two liquids is the aldehyde? Write the chemical equations of these reactions as well.
Sol: (i) As we can see, liquid ‘A’ forms a white crystalline solid on treatment with NaHSO3, thus it may be an aldehyde
or a methyl ketone. And also liquid ‘A’ forms a bright silver mirror on treatment with a freshly prepared ammoniacal
Sol of AgNO3. Therefore, liquid ‘A’ is an aldehyde. (Aldehyde gives positive silver mirror test)
(ii) On the other side, liquid ‘B’ forms a white crystalline solid on treatment with NaHSO3, it may be an aldehyde or
a methyl ketone. But liquid ‘B’ shows negative test with ammoniacal AgNO3 solution therefore, liquid ‘B’ must be
a methyl ketone.
Chemical equations for the reactions discussed are
R R SO₃Na
C=O + NaHSO₃ C
H H OH
Liquid ‘A’ White NaHSO₃ adduct
R R SO₃Na
C=O + NaHSO₃ C
CH₃ CH₃ OH
Liquid ‘B’ White NaHSO₃ adduct
+ - warm
RCOO- + 2 Ag

RCHO + 2 [Ag(NH₃)₂] + 3 OH + 4 NH₃ + 2 H₂O
Liquid ‘A’ Tollens reagent Carboxylate ion Silver
mirror
Tollens reagent
RCOCH₃ No silver mirror
Liquid ‘B’
Example 10: Give reasons for the following:

(a) Oximes are more acidic than hydroxylamines
(b) Iodoform is obtained by the reaction of acetone with hypoiodite but not with the iodide ion.
(c) Oxidation of toluene to benzaldehyde with CrO3 is carried out in presence of acetic anhydride and not in
presence of H2SO4.
Sol: (a) In case of oxime, on proton loss it gives a conjugate base which is stabilized by resonance but the conjugate
base of NH2OH is not.
C=N O H -H
+
C=N O-
-
C N O
Oxime Conjugate base (Stabilized by resonance)
+
-H
NH₂ O H NH₂ O (Not Stabilized by resonance)
Hydroxylamine Conjugate base
(b) During the course of reaction, I+ is required which is supplied by IO– ion but not by I– ion thus iodide ion is not
used. The reaction is as shown below:
CH₃ CO CH₂ H + O I CH₃COCH₂ + H O I

Acetone
+
CH₃COCH₂ + I OH CH₃COCH₂I+OH
+
(Source of I )
+IO +IO OH
CH₃COCH₂I CH₃COCHI₂ CH₃COCl₃ CH₃l + CH₃COO
OH OH
1, 1, 1, -Tri-iodoacetone Iodoform Acetate ion
(c) This is because CrO3/H2SO4 is a powerful oxidizing agent. During the oxidation of toluene with CrO3/H2SO4 the
intermediate benzaldehyde formed readily undergoes oxidation to form benzoic acid due to the presence of H2O
in H2SO4.
CrO₃/H₂SO₄ H₂O CrO₃/H₂SO₄
C₆H₅ CH₃ C₆H₅ CHO C₆H₅CH(OH)₂ C₆H₅COOH

Toluene Benzaldehyde Benzaldehyde hydrate Benzoic acid
However, with CrO3 in (CH3CO)2 O, due to the absence of H2O as soon as benzaldehyde is formed, it reacts with
acetic anhydride to form benzylidene diacetate which does not undergo further oxidation. In this way, oxidation of
benzaldehyde to benzoic acid is prevented. The gem-diacetate this formed upon subsequent hydrolysis with alkali
or acid gives benzaldehyde.
CrO₃-(CH₃CO)₂O H₃O+
C₆H₅CH₃ C₆H₅CH(OCOCH₃)₂ C₆H₅CHO
273-283 K (Hydrolysis)
Toluene Benzylidene diacetate Benzaldehyde
(gem-diacetate)
JEE Advanced/Boards
Example 1: Complete the following reaction by identifying (A), (B) and (C)
Pd/BaSO
(a) A + H2 (g) 
4 →(CH ) CH − CHO
3 2
CH3
|
(b) CH3– C— C– CH3 +NaOl → B + C
| ||
CH3 O
Sol: (a) This is a well-known Rosenmund reduction reaction. The catalyst used is palladium poisoned with BaSO4
supported on carbon.
The reagent is specific and acts only upon acid chloride group. Since acid chlorides on Rosenmund reduction give
aldehydes, therefore, compound (A) must be an acid chloride, (CH3)2CH–COCl
CH₃ CH₃
Pd/BaSO₄
CH₃ CH COCl + H₂ (g) (Rosenmund reaction) CH₃ CH CHO + HCl
2-Methylpropanoyl 2-Methylpropanal
chloride (A)
(b) This is an example of an Iodoform reaction. A Ketone containing methyl group undergoes this reaction. This method
is used to identify methyl ketone specifically. Yellow precipitate of Iodoform confirms the presence of a methyl group.
Methyl ketone on oxidation with NaOI (I2 + NaOH) gives iodoform and the sodium salt of the acid. Thus,
CH₃ CH₃
NaOl
CH₃ C C CH₃ CH₃ C COONa + CHI₃
(Iodoform reaction)
CH₃ O CH₃
3,3-Dimethylbutan-2-one Sod. 2, 2-dimethylpropanoate (B) Iodoform (C)
Example 2: Suggest a sequence of reactions to carry out the following transformation, but one intermediate must
be an alkene.
N(CH₃)₂
O
OH from
Sol: Here we can apply new approach for the following transformation. i.e Retrosynthesis. This is achieved by
transforming a target molecule into simpler precursor structures without assumptions regarding starting materials.
There are many alkene reactions, so this is really not a significant restriction. The starting compound ketone
suggests that a Wittig route might be possible
Retro synthesis:
1. First locate the Bond which has been broken to form the end product.
2. Presence of two alkyl group and OH outside the Cyclohexane shows that it must be an Epoxy group.
3. Nucleophilic addition of (CH3)2NH open ups the ring.
4. Now we all know Epoxide is formed from a double bond so there must be a double bond outside the cyclohexane
ring. (We have satisfied the demand of the question that transformation should contains one alkene intermediate.)
5. As our starting material is a carbonyl group we can easily convert it into an alkene by a well-known wittig
reaction.
6. The Retrosynthetic approach for the above transformation can be written in form of reaction as follows:
Retrosynthesis:
(CH₃₃))₂₂N
(CH N
Nucleophilic addition
Nucleophilic addition
HN(CH
HN(CH₃₃))₂₂ Epoxidation
Epoxidation Witting
Witting
O
O
OH
OH O
O
Forward direction:
(CH₃₃))₂₂N
(CH N
+
+ -- CH
Ph₃P
Ph₃P CH₂
CH₂ CH₃₃CO
CO₃₃H
H (CH₃₃))₂₂NH
(CH NH
O
O CH₃OH
CH₃OH
O
O OH
OH
Example 3: Explain:
(a) α-Halocarbonyl compounds, even the 3° types like

( R
R
Cl (
CHO , do not undergo SN1 reaction.
(b) Which is more reactive: (i) PrCl or (ii) MeCOCH2Cl with Nal/acetone?
−
(c) Acetals and ketal are regenerated back to carbonyl, compounds with H3O⊕ but not with OH .
(d) Cyclohexanone is more reactive than cyclopentanonone with HCN.
Sol: (a) SN1 reaction involves formation of Carbocation, although it contains adjacent two alkyl group the carbocation
formed is unstable this is because of the presence of positive charges on adjacent C atoms.(Electron withdrawing
effect of chlorine makes two alkyl group slightly electron deficient)
(b) Both are Primary alkyl halide and undergo SN2 (Substitution nucleophilic bimolecular) reaction. Orde of reactivity
is (ii) >> (i).
The high reactivity of (ii) in SN2 reaction is due to the stabilizing effect produced in the transition state of ketone
by the overlap of adjacent π-bond with the p-orbital of the sp2-hybridised C atom. This type of overlap is also
responsible for the high reactivity of halides in SN2 reaction.
SN2 -
Cl I + Cl
i. Me Finkelstein reaction (F.R.) Me
-
I
O O
SN2 -
C Cl I + Cl
SN2 -
Cl I + Cl
i. Me Finkelstein reaction (F.R.) Me
2 3 . 4 4 | Aldehydes
I
- and Ketones
O O
SN2 -
C Cl I + Cl
CH₂ Me
ii. Me Finkelstein reaction (F.R.)
-
I
O
Me C l
C H
( Orbital diagram of the
intermediate transition state
of the ketone
(
H
Cl
Me Me Me
C O C O C O
l- CH₂ Cl l -
CH₂ Cl -
l -
CH₂ Cl -
Intermediate transition state
O
l + Cl
-
Me
(c) The formation of hemiacetal or half hydrate takes place in acid only. OH- is a weaker base than OR- It’s not
possible in base because a weaker base (OH− ) cannot displace stronger base (RO − ) . But the formation of acetal
from hemiacetal can take place by both acid and base. So the reverse process of hemiacetal to (C=O) compound
can occur only with acid but not with base.
(d) (i) Cyclopentanone suffers from ring strain. In Cyclopentanone, the hybridization of C atom of (C=O) group
changes from sp2 → sp3, and the adjacent hydrogen atoms are in eclipsed position which increases the strain due
to eclipsing interaction.
(ii) In cyclohexanone, the hybridization of C atom of (C=O) group changes from sp2 → sp3, the ring is free from strain
and after nucleophilic addition, all the adjacent H and OH atoms are in staggered position hence destabilization
effect is lost as there no eclipsing interaction.
H H H H
HCN OH
O sp² sp³ CN
H H H H
sp² sp³
All adjacent H atoms are in eclipsed
position : more strained and high energy.
H H
H HCN
H
H H
sp² sp³ CN
2
O H 1
H sp³
sp²
OH
( ((
Initially (C=O) is in
eclipsed position with the
adjacent equatorial H atoms
All adjacent H atoms and (OH)
are in staggered position (
(No eclipsing interaction
(
( (
High energy eclipsing (More stable)
interaction
(Less stable)
Example 4: Complete the following reaction

Me
(a) CH₃COOH (C) (b)
H₂O
(B) O (B) (C)
Me 700OC EtOH
(A) (D) (A) CH₃ COOH
PrOH
(D)
Ph
SO₂Cl₂
(c) O (B)
Me
(A) (C)
NBS
Sol: The formation of (B) in both (a) and (b) is industrial method for the preparation of ketone .
(a) O -
-
-
H OH
H₂C C -H₂O
H₂C C O
Ketene
H OH (B) CH₃ C O
- -
-
(A) PrO H
Acetic acid OH
CH₃ C O (C)
Acetic acid
Opr
Propylacetate
(D)
(b) H₃C - -
-
EtO H
C O 700 C
O CH₂ C O
H H₂C Ketene
(A) (B) CH₃ C O
Acetone - -
-
CH₃COO H OEt
O O (C)
Ethylacetate
CH₃ C O (or) CH₃ C O C CH₃
OCOCH₃
(D) (Acetic anhydride)
(Commercial method for the preparation
of acetic anhydride)
(c) Halogenation occurs at the α-position of the (C=O) group, via free radical mechanism. NBS (N-Bromosuccinimide)
is commonly used brominating agent.
Ph Ph
SO₂Cl₂
O O
Me Me Cl
H
H -Chlorobutan-2-one
Butan-2-one
(A) (B)
Ph
NBS O
Me
Br
-Bromobutan-2-one
(C)
Example 5: Complete the following reactions:

(a) HO Br (i) DIBAL-H
Product (B)
(ii) H₃O -
-
(A) ll
O (i) LiAlH (O- tBu)₃
Product (C)
(ii) H₃O -
-
(i) H₂+Pd+ BaSO₄

(ii) H₃O -
-
Product (D)
(b) Give the major products of the following

O
ll
1 1. LAH
2 (B)
-
l
-
2. H₃O
4 3
(C)
1. Sia₂BH
Me Me -
-
Me 2. H₃O
4-r-Butylcyclo
hexanone
(D)
H₂/Pr
Sol: (a) After looking at the question you will notice that all the three reagents, namely, DIBAL-H, LiAlH (O-t-But)3,
and (H2+Pd +BaSO4) (Rosenmund reduction ) are reducing agents.
Thus they will reduce the acid halides to aldehydes.
The products (B), (C), and (D) are same Hydroxyl aldehydes than undergo intramolecular reaction to give cyclic
hemiacetal. On reduction with all three reagents give (I) Hydroxyaldehyde anion, which undergoes ring closure. A
chiral center is formed during the ring closure reaction and as a result, two enantiomer forms are obtained and the
product is a racemic mixture. (Optically inactive)
[H] CH O -
-
H₃O
(A) All three -
reagents
O
(1) OH HO
- -
-
H H
O O
( - )or racemate
-
(b) Bulky-1-butyl group always occupies less hindered equatorial in cyclohexane.

(i) Sia2BH is a bulky group. Thus it approaches (C=O) from the less hindered equatorial side, pushing (OH) to axial
position which result in the formation of less stable cis-isomer.
(ii) Less bulky LAH approaches (C=O) from the more hindered axial side, pushing (OH) to equatorial position.
Resulting in the more stable trans-isomer.
(iii) With H2+Pt : Cis-alcohol is formed in major amount, because H2 is adsorbed on the surface of a finely divided
catalyst, and H approaches from the less hindered equatorial side and gives cis-alcohol as in (i)
Sia₂BH
H H
LAH
-
-
H₃ O
Me₃C 1 Me₃C OH
2
3 O
(A) H
LAH (B)
Sia₂BH
H - (trans-Alcohol)
-
H₃O
(trans-4-t-Butylcylohexanol)
Me₃C H (OH) and (t-Bu) gps, are in trans

trans-position (OH) in up ( ) and

(t-Bu) in down ( ) position

cis-Alcohol OH (more stable)
(C)
(cis-r--Butylcylohexanol)
Both (OH) and (t-Bu) gps, are in

cis position: both down ( ) position.

(Less stable)

(a) OTs Ph₃P (excess) 2 eq. of PhLi 2 eq. of
(B) (C) MeCHO
OTs
(D) + (E)
(b) I
Ac₂O + AlCl₃ 2 EtOH/HCl 1. Mg

(B) (C)
2. D₃O
-
-
(A) H₃O
(E) (D)
(c) Et O
-
O AlCl₃ NH₂NH₂/OH
+ (C) (D)
+H -
-
(i) EtMgl
O (G) (F) (E)
(ii) H₃O -
(A) -H₂O -
(B) O
Sc at 500 C
(Succinic anhydride)
(H)
(d) Br 1. Ph₂S NaH 1. NaOH
Br 1. Ph₂S (B) NaH (C) 1. NaOH (D)
I 2. AgBF₄ (B) (C) 2. Acetone (D)
I 2. AgBF₄ 2. Acetone
(A)
(A)
Me I
(e) Me I + Ph₂S PhLi PhCHO
Me PhLi (C) PhCHO (D) + (E)
Me + Ph₂S (C) (D) + (E)
(A) (B)
(A) (B)
Sol:
(a) - - -
-
-
PPh₃
( ( - 2 eq. of PPh₃
( -(
-
(B) - Li
-
- PPh₃ OTs PhLi

-
2 2
- PPh₃
2MeCH=O PPh₃ O HC Me
PPh₃ O CH Me
CH Me (C)
2Ph₃P O+
CH Me
(E)
(D)
(b) I I
O O
AlCl₃
+ Me O Me F.C. acylation
Acetic anhydride at para
(A) (Ac₂O)
O Me
(B)
D D I
H₃O -
-
Me EtOH + HCl
D₂O Ketal formation
+ Me O Me F.C. acylation
Acetic anhydride at para
(A) (Ac₂O)
2 3 . 4 8 | Aldehydes and Ketones Me
O
(B)
D D I
H₃O -
-
Me EtOH + HCl
D₂O Ketal formation
O Me EtO Me EtO Me
OEt EtO
(p-Deuterio-
acetophenone) (D) (C)
or
(p-d-acetophenone)
(E)
(c) First step is Friedal craft acylation that takes place at para position followed by Wolf kishner reduction. Further
steps involved are Grignard reaction and aromatization.
Et Et
O
AlCl3
O
F.C. acylation OH
(A) at para O
O
O
(B)
(C)
Et
NH2NH2 + OH
HF Wolff-Kishner
HO
-H2O (C=O) CH2
H O
O
Et (D) Et
EtMgl H
O Et
H2O -H2O
OH
Et Et
7
6 8
o
Sc at 500 C
5 Et Et
1
Aromatisation
4 2
3
(H) (G)
(1.7 Diethyl napthalene)
(d) It is a Wittig type reaction and proceeds via-sulphur ylide. Dihalide compound is treated with Ph2S in AgBF4
Followed by the treatment with a strong base to form Witting reagent. Now this Wittig reagent when treated with
KOH forms sulphurylide which reacts with carbonyl compound to form a Spiro compound.
Br Ph₂S Br -
- BF₄ + Agl
-
l AgBF₄ SPh₃
(A) I - is better leaving
( gp. than Br - ;
AgBF₄ - helps
in removal of I -
( (B)
- - -
-
-
-
Br
- Na NaH (H acts as base)
-
- SPh₂
- KOH
- Br
-
SPh₂
(C)
( Intermediate carbanion displaces
Br -and forms 4-membered ring. (
- --
-
SPh₂ Me₂C O - SPh₂

Me₂C O
-
(Sulphur ylide)
Ph₂S +
Me O
Me
(D)
(Spiro compound) (Spiranyl epoxide)
(e) It is a Wittig type reaction and proceeds via sulphur ylide, the product formed is a substituted epoxide ring.
-
-
Me I Me SPh₂
Me + Ph₂S Me
(A) (B)
PhLi
-
Me SPh₂
Me -
PhCH=O
(C)
-
-
SN2 Me SPh₂
-Ph₂S
Me CH Ph
-
Me O
Me Ph Me
-Ph₂S + Me
O O Ph
(E) (D)

O
CHO -
Me (i) OH
(a)
Give the number
+Me
(ii) H₃O -
of products
-
CHO (B)
(A)
(b)
Cl
H₃O -
-
KCN (i) NaOEt/EtOH
(B) (C)
-
(ii) PhCHO/OH
(i) SOCl₂
(A) (E) (D)
(ii) MeNH₂
(I)
(I) Moist
Moist Ag
Ag22O
(c) OHC COOH
O
(B)
(B)
OHC COOH
(ii)
(ii) Br
Br22/CCl
/CCl22D
D
(A)
(A)
COOH
COOH (i)
(i) Ba
Ba (OH)₂
(OH)₂
(d) (B)
(B)
COOH
COOH (ii)
(ii) Dry
Dry distillation
distillation
(A)
(A)
Sol: (a) In this reaction, 4 products are possible.

First of all it can undergo intermolecular Cannizzaro reactions. Other is it can undergo aldol condensation here 2
products are formed. And third is Claisen Schmidt reaction (Reaction between A and B)
(i) Intramolecular Cannizzaro reaction of (A):
CHO - COO -
(i) OH H₃O -
-
(ii) H₃O -
-
CHO CH₂OH
(not -H) O O
OH
O
OH
(I)
(ii) Aldol condensation of (B)

(1)
O
-
Me OH
Me O H₂ CH

Me
Me Me
Me O
(II)
(2) Me
Me -
OH Me
O H Me
Me Me
Me H Me O
O
(III)
1 Me
CH O H 5 -
(iii)
2
6 OH
H O
7
CH Seven C atom
3 O H₂ HC
4 side ring
1
2 3 Me
6
5 O
4 7
(IV)
( Numbering in accordance
with problem understanding (
(b) (i) First step is nucleophilic substitution.
(ii) Second step is hydrolysis, thus acid is formed(CN→COOH)
(iii) Third step is esterification using ethanol (COOH→COOC2H5)(protection of acid group)
(iv) Fourth step is Knoevenagel Condensation, product obtained is hydrolysized to obtain acid group.(Deprotection)
(v) Reaction with SOCl2 produces acid chloride group which on treatment with methyl amine gives the product.
CH2C N COOH
KCN
Hydrolysis in
basic medium

(B) Esterification with EtOH

O HO H O
H
Ph CH OEt OEt
H
H₃O -
-
PhCH O
- OH
(C)
PhCH (-H acidic)
CO OH
Ph CH C SOCl₂
Ph O
(D)
C Cl H- HN Me
Ph CH C
Ph O
Ph
NH Me
H Ph
(E)
(c) Moist Ag2O gives AgOH which acts as an oxidising agent and oxidises (–CHO) group to (–COOAg); the (COOH)
group also change to (–COOAg), which then undergoes Hunsdiecker reaction.
(d) First step is a simple acid base neutralization reaction forming a salt of Ba which on heating gives off BaCO3 and
bicyclic ketone as a final product.
2 O 2 2
( (
11
(A) Ba(OH)₂ 1
O
3
1 10
1
3 Numbering in
Ba accordance with
O -BaCO₃ 7 4
4 6 7 4 9 7 naming
Seven C atom 5 6 O 6 5 O
5 O 8
( (
side ring
Numbering in (Bicyelo-[5.4.0] undecan-4-one)
accordance with (B)
problem understanding
Example 8: Complete the following reaction:
CHO
H₂/Pd HCN Conc. HI or HBr Ac₂O + AcONa

(E) (D) (B) (C)
(Vanillin) or BBr₃/H₂O
OMe
OH
(A)
Sol:
OH O
OH CH H₂ HC COO COMe
NH₂ H C N Perkin reaction
H₂/Pt HCN (A) Hl
[(C NCH₂NH₂]
OH OH CH CH COOH
(E) OH
OH
Noradrenaline (B)
(an adrenal hormone) (D)
OH
OH (C)
Caffinic acid (found in coffee beans)
NH2OH,HCl H⊕
Example 9: (A) (C8H8O) (B) + (C)
Rearrangement
(B,C,D, E all are isomers of C8H9NO) (D) + (E)

Boiled with CH3COCl
(D) Alc.KOH
An oil (F) (C6H7N) (D)
(i) Alkali
(E) (ii) H⊕
(G) (C7H6O2) A white solid
Sol: Degree of unsaturation = 5° (aromatic and ketone), i.e. Beckmann rearrangement

Ph
NH2OH.HCl
C=O
CH3 (A)
Ph OH Ph
C=N + C=N
CH3 ( c) CH3 OH
(B)
B.R. B.R.
- -
-
H H
Ph C NH CH3 CH3 C NH Ph
O O
CH3COCl
Alkali, H -
-
Alc. KOH
PhCOOH + CH3NH2 CH3COOH + PhNH2

(G) (A white solid) (F) (An oil)
Example 10: Complete the following:

(a) 2PhCHO + NH2NH2 →
(b) Reduction of PhCHO with the following
(i) Tollens reagent (ii) Zn/HCl (iii) LAH (iv) Clemmensen’s reduction (Zn (Hg)/conc. HCl)
−
(v) Wolff-Kishner reduction (NH2NH2 + Glycol + OH ) vi. Two moles of PhCHO with Zn+HCl
Sol: (a) CH O + H₂ N.N H₂+O CH CH N N CH
Benzylidenazine (A)
(b) (i) with Tollen’s regent, it will form PhCOOH

(ii) Zn/HCl is a reducing agent so it will reduce the aldehyde in to primary alcohol, i.e. PhCH2OH
(iii) LAH is also a reducing agent thus it will form the same product, i.e. PhCH2OH
(iv) and (v) Wolf kishner reduction and Clemensen’s reduction-It will reduce the carbonyl group (CHO → CH2)
Thus hydrocarbon will be formed. i.e PhCH3
(vi) A pinacol will be formed.
Zn/ HCl
2 CHO + 2H CH CH
OH OH
(Pinacol) (Hydrobenzoin)
JEE Main/Boards
Exercise 1 Q.8 Write the names of the reagents and equations in

the conversion of
Q.1 Explain Knovengeal Reaction with mechanism? (i) Phenol to salicylaldehyde.
(ii) Anisole to p -methoxyacetophenone.
Q.2 Which of the following compounds would undergo
aldol condensation, which the Cannizzaro reaction and Q.9 Write one chemical reaction each to exemplify the
which neither? Write the structures of the expected following
products of aldol condensation and Cannizzaro
reaction. (i) Rosenmund reduction (ii) Tollens’ reagent
(i) Methanal (ii) 2-Methylpentanal

Q.10 Explain Pinacole-Pinacolone Rearrangement?
(iii) Benzaldehyde (iv) Benzophenone
(v) Cyclohexanone (vi) 1-Phenylpropanone Q.11 Write reactions for obtaining
(vii) Phenylacetaldehyde (i) Acetone from acetic acid.
(viii) Butan-1-ol (ii) Benzene from toluene.
(ix) 2,2-Dimethylbutanal
Q.12 a) How will you obtain an aldehyde by using
Q.3 How will you convert ethanal into the following following process
compounds? (i) Dehydrogenation (ii) Catalytic hydrogenation?
(i) Butane-1, 3-diol (ii) But-2-enal b) (i) Why do aldehydes behave like polar compounds?
(iii) But-2-enoic acid (ii) Why do aldehydes have lower boiling point than
corresponding alcohols?
Q.4 Write structural formulas and names of four
possible aldol condensation products from propanal Q.13 Explain witting reaction with mechanism?
and butanal. In each case, indicate whichaldehyde acts
as nucleophile and which as electrophile.
Q.14 Convert:
(i) Acetaldehyde to Acetone
Q.5 An organic compound with the molecular formula
C9H10O forms 2, 4-DNP derivative, reduces Tollens’ (ii) Acetone to Acetylene
reagent and undergoes Cannizzaro reaction. On
vigorous oxidation, it gives 1, 2-benzenedicarboxylic Q.15 An organic compound (A) (molecular formula
acid. Identity the compound. C8H16O2) was hydrolysed with dilute sulphuric acid to
give a carboxylic acid (B) and an alcohol (C). Oxidation of
Q.6 Describe the following reactions (C) with chromic acid produced (B). (C) on dehydration
gives but-I-ene. Write equations for the reactions
(i) Cannizzaro’s reaction
involved.
(ii) Cross aldol reaction
Q.16 Give simple chemical tests to distinguish between
Q.7 Give chemical tests to distinguish between the following pairs of compounds.
(i) Acetaldehyde and Benzaldehyde (i) Propanol and Propanone
(ii) Propanone and propanol. (ii) Acetophenone and Benzophenone
(iii) Phenol and Benzoic acid
Q.17 How will you bring about the following conversions (vi) CH3—CH—C—CH3
in not more than two steps? | ||
OH O
(i) Propanone to Propene
O
(ii) Ethanol to 3-Hydroxybutanal (vii) (viii) O OMe
(iii) Benzaldehyde to Benzophenone
Q.18 Give possible explaination for each of the

following:
Q.23 Which of the amino group in semi carbazide will
(i) Cyclohexanone forms cyanohydrin in good yield but react with Ph-CH = O carbonyl group?
2, 2, 6-trimethylcyclohexanone does not. O
(ii) There are two -NH; groups in semicarbazide. ||
H2N–C–NH–NH2
However, only one is involved in the formation of (1) (2) (3)
semicarbazones.
(iii) During the preparation of esters from a carboxylic acid Q.24 How many organic products are formed in good
and an alcohol in the presence of an acid catalyst, the water amount in above reaction?
or the ester should be removed as soon as it is formed.
Q.25 How many molecules of MeMgCl will be consumed
Q.19 An organic compound contains 69.77% carbon, for per molecule of phosgene
11.63% hydrogen and rest oxygen. The molecular mass Cl C Cl
of the compound is 86. It does not reduce Tollens’
reagent but forms an addition compound with sodium
hydrogensulphite and give positive iodoform test. On
O
vigorous oxidation it gives ethanoic and propanoic

acid. Write the possible structure of the compound.
Exercise 2
Q.20 Write the difference between aldol condensation
and cannizzaro reaction. Single Correct Choice Type
O
Q.21 A compound with molecular formula C8H18O4
does not give litmus test and does not give color C CH3
with 2, 4-DNP. It reacts with excess MeCOCl to give a
Q.1 (A) NaOH reactant (A) is
compound whose vapour density is 131. Compound A
contains how many hydroxy groups?
III
Q.22 Which of the following compounds will give (A) O O

Fehling’s test positive?
|| ||
CH3 –C–(CH2)5–C–CH3
CHO CHO
(i) (ii) (B) O O
|| ||
CH3 –C–(CH2)4–C–H
(C) O O
(iii) OH || ||
H –C–(CH2)5–C–H
CH2OH
O
(D) O
OH ||
OH
OH CH3 –C–(CH2)4–CH2–OH
(iv) HCOOH (v) CH3–C–C–CH3

|| ||
O O
Q.2 O Q.4 O O
||
CH3 –C–CH2–CH3
CH2N2 || ||
CH3–C–CH2–CH2–C–OC2H5
A(Major)
CH3CO 3H
B(Major) H O
| ||
Product B is CH3–C–CH2–CH2–C–OC2H5
|
(A) O OH
||
CH3–O–C–CH2–CH2–CH3 The conversion is carried out by using which of the
following
(B) O
(A) NaBH4 (B) LiAlH4 (C) Pd/H2 (D) Na-EtOH
||
CH3–C–O–CH2–CH2–CH3
Q.5 Which of the following compounds can undergo
(C) O
aldol condensation.
||
CH3–CH2–C–O–CH2–CH3 (A) Me3C–CHO (B) PhCHO
(D) O (C) MeCHO (D) HCHO
|| O
CH3–C–O–CH2–CH3
Q.6
Ba(OH)2
(X)
Q.3 The product Octalone is obtained by Michael
addition followed by aldol condensation of reactants R Major product (X) is

and S in presence of a base. S gives positive iodoform
O O
test.
O
(A) (B)
B
R+S
Octalone O O
R and S respectively.
(C) (D)
(A) O
Q.7 O
+ CH3 CH=O || NH2–CH3
CH3–C–CH3 ∆
(X) Major
(B) O
H3C
Major product (X) is
+ CH2 = CH C H
NH=CH2 NH
O | ||
O (A) CH3–CH–CH3 (B) CH3–C–CH3
(C)
+ CH2 = CH C CH3
N–CH3 NH–CH3
O || |
(C) CH3–C–CH3 (D) CH3–CH–CH3
O
(D)
+ CH3= CH2 C CH3
Q.8 O
O
CH3O OCH3 CH3O OCH3

Conversion can be achieved by (C) CH2–OH (D) CHO

| |
(A) Clemmenson reduction HO–CH2–C–CH2OH HO–CH2–C–CH2–CH2–OH
| |
(B) Wolf-Kishner reduction CHO CH2–OH
(C) Pd/BaSO4
Q.12 Principal product of following reaction is isolated
(D) Sn/HCl in form of CH2=C=O+H2S →?
Q.9 BuC CH
LiNH2 (i) PhCHO MnO2 (A) SH (B) O
(ii) H2O | ||
CH2=C CH3C–SH
|
A B C
SH
D
(C) CH3C–OH (D) OH
|| |
O CH2=C–SH
Compound D of the above reaction is -
Bu O
Q.13 ,
(A) (B)
N2H4 KOH/
COOH (X) (Y) + N2,
OH
Bu OH
COPh Bu
(D) the structures of (X) and (Y) are-

(B)
C-Ph OH
(A) and
O
Q.10 O
NHH2
EtONa
+ HCO2 Et (X)
(B) and
Identify unknown (X) in
O O O
(A) C O Et
(B) (C) and
NH2
CHO
O O
N
CH OH (D) and
(C) (D)
CO2Et
Q.11 OH O
Q.14 O O
| || HO⊕ || || KOH
CH3–CH–CH2–C–H (Retro aldol)
CH3–C–CH2–CH2–CH2–CH2–C–CH3 ∆
Na2CO3 Possible products are-

(A), 3HCHO+A (B)
40°C 82%
O
CH3
Product (B) of above reaction is -
(A) (B)
(A) CH2–OH (B) CH2–OH
| | CH3 C CH3
HO–CH2–C–CH2OH HO–CH2–C–CHO O
| |
CH2–OH CH2–OH
O O
CH3
(C) (D)
(A) (A) (B) (B)
CH CH C CHC3 CH3
2 3 . 5 8 | Aldehydes
3 and Ketones
3
O O
O O O O (C) 2.2, 2-Trichloropropanol

CH3 CH3 (D) Chloroform
(C) (C) (D) (D)
CH3 CH3
CH3 CH3 Q.4 In Cannizzaro reaction given below
−
OH
Q.15 The given reaction can not be performed by the 2PhCHO → PhCH2OH + PhCO2− the slowest step
is (2009)
use of which of the following reagents?
(A) The attack of at the carboxyl group
(B) The transfer of hydride to the carboxylic group
CHO COOH
O O (C) The abstraction of proton from the carboxylic group
(A) KMnO4/H2SO4 (B) K2Cr2O7/H2SO4 (D) The deprotonation of PhCH2OH
(C) Ag2O/NaOH (D) LiAlH4
Q.5 A mixture of benzaldehyde and formaldehyde on
heating with aqueous NaOH solution gives (2001)
Q.16 Citral can be converted into geraniol by the use of
(A) Benzyl alcohol and sodium formate
CH3 CH3
(B) Sodium benzoate and methyl alcohol
CHO CH2OH
(C) Sodium benzoate and sodium formate
(D) Benzyl alcohol and methyl alcohol
H3C CH3
Q.6 Which one of the following undergoes reaction
Which reagent with 50% sodium hydroxide solution to give the
corresponding alcohol and acid (2007)
(A) H2/Pd–C (B) LiAlH4
(A) Butanal (B) Benzaldehyde
(C) H2/Pd-BaSO4–CaCO3 (D) NaBH4
(C) Phenol (D) Benzoic acid
Q.7 The increasing order of the rate of HCN addition to

Previous Years’ Questions
compounds A-D is (2006)
Q.1 Which of the following on heating with aqueous (a) HCHO (b) CH3COCH3 (c) PhCOCH3 (d) PhCOPh
KOH produces acetaldehyde (2009)
(A) a < b < c < d (B) d < b < c < a
(A) CH3COCl (B) CH3CH2Cl
(C) d < c < b < a (D) c < d < b < a
(C) CH2ClCH2Cl (D) CH3CHCl2
Q.8 The pair of compounds in which both the compounds
Q.2 Ozonolysis of an organic compound gives give positive test with Tollen’s reagent is (2004)
formaldehyde as one of the products. This confirms the
(A) Glucose and Sucrose
presence of (2011)
(B) Fructose and Sucrose
(A) Two ethylenic double bonds
(C) Acetophenone and Hexanal
(B) A vinyl group
(D) Glucose and fructose
(C) An isopropyl group
(D) An acetylenic triple bond Q.9 In the given transformation which the following is
the most appropriate reagent (2012)
Q.3 Trichloroacetaldehyde was subjected Cannizzaro’s CH=CHCOCH3
reaction by using NaOH. The mixture of the products Reagent
contains sodium trichloroacetate ion and another
HO
compound. The other compound is (2001)
CH=CHCH2CH3
(A) 2.2, 2-Trichloroethanol
(B) Trichloromethanol HO
(C)
O
O
−
(A) NH2NH2 OH (B) Zn–Hg/HCl CH2OH HOH2C
(C) Na, Liq, NH3 (D) NaBH4

(D)
Q.10 Compound ‘A’ (molecular formula C3H5O) is treated

with acidified potassium dichromate to form a product CH2OH HOH2C
‘B’ (molecular formula C3H6O.) ‘B’ forms a shining silver
mirror on warming with ammonical silver nitrate. ‘B’ Q.12 The product of acid hydrolysis of P and Q can be
when treated with an aqueous Sol: of H2NCONHNH2. distinguished by (2003)
HCl and sodium acetate gives a product ‘C’. Identify the
OCOCH3 H3C
structure of ‘C (2002)
P=H2C Q=
(A) CH3CH2CH = NNHCONH2
CH3 OCOCH3
(B) CH CH = NNHCONH
3 2
| (A) Lucas Reagent (B) 2, 4-DNP
CH3
(C) Fehling’s solution (D) NaHSO3
(C) CH3CH = NCONHNH2

| Q.13 On vigorous oxidation by permanganate solution
CH3 (CH3)2C= CH –CH2CH2CH3 gives (2002)
(D) CH3CH2CH–NCONHNH2 OH OH
OH OH
(A) CH C CH CH2CH3
(A) CH33 C CH CH2CH3
Q.11 CHO OHC CH
CH33
(i) NaOH/100oC
CH3
(ii) H+/H2O CH3
(B) CHCO2H + CH3COOH
(B) CH CHCO2H + CH3COOH
CHO OHC CH33
Major product is. (2003) CH3

CH3
(C) CHOH + CH3CH2CH2OH
(C) CH CHOH + CH3CH2CH2OH
COOH HOOC CH33
CH3
(A) CH3
(D) C=O + CH3CH2COOH
(D) CH C=O + CH3CH2COOH
CH33
COOH HOOC
Q.14 Silver Mirror test is given by which one of the

OH HOOC following compounds (2011)
(A) Acetaldehyde (B) Acetone
(B)
(C) Formaldehyde (D) Benzophenone
COOH OH
Q.15 In the following sequence of reactions, the alkene
O affords the compound ‘B’
O O H O
CH 3 → A 
2 → B.
= 3CH CHCH3  Zn
(C) The compound B is (2008)
(A) CH3CH2CHO (B) CH3COCH3
O
O (C) CH3CH2COCH3 (D) CH3CHO
CH2OH HOH2C
(D)
Q.16 Which of the following on heating with aqueous Q.18 Which compound would give 5-keto
KOH, produces acetaldehyde? (2009) -2-methylhexanal upon ozonolysis. (2015)
(A) CH3COCl (B) CH3CH2Cl
CH3 CH3 CH3 CH3
(C) CH2ClCH2Cl (D) CH3CHCl2 CH3 H3C
(A) (B) (C) (D)
Q.17 In Cannizzaro reaction given below,

CH3 CH3 CH3
aqu.KOH
CH3CHCl2  → CH3CH(OH)2 → CH3CHO Q.19 Ozonolysis of an organic compound gives
−H O 2
formaldehyde as one of the product. This confirms the
the slowest step is:
presence of: (2011)
(−)
: OH
2PhCHO → PhCH2OH + PhCO2( − ) (2009) (A) A vinyl group

(B) An isopropyl group
(A) The attack of OH at the carboxyl group
(C) An acetylenic triple bond
(B) The transfer of hydride to the carbonyl group
(D) Two ethylenic double bonds
(C) The abstraction of proton from the carboxylic group
(D) The decomposition of CH2OH
JEE Advanced/Boards
Exercise 1 CCH
+
(i) HgSO4, H3O
Complete the following equations and identify the Q.6 ?
(ii) NH2OH
products A, B, C, D, E, F, G, H etc in the following
reactions
O
SOCl
Q.1 o − HOOC − C6H4 − CH2 − C6H5  →
Q.7 (i) MeMgBr
?
anhydrousZn − Hg
(ii) aq HCl
G  →H I OMe
AlCl3 HCl
CH3
CH3
Q.2 HBr
[E]
Perroxide Q.8 CH3 C CH2Br C2H5OH

CH3
H CrO CrO
Q.3 [J] ←
2 3 → CH CHO
4  [I] 
3 H2
H2O (Pyridine)
Q.9 CH3
Lindlar Catalyst
?
OH NaHSO
Q.4 Acetone (2mol.)  4
→[K] →[L]
F
O
Q.5 (i) Br2 (I equivalent) Q.10

NaOCH3
CH3
(ii) NaBH4
NO2
O moist 2 5
2 4 → B  H SO C H OH
Q.22 C2H5 I → A  →C
Ag2O 140°C
Q.11 N
Br2/Fe(aq)
X excess
Q.23 CH3COOH → ClCH2COOH  →Y
NH3
O
HgSO
Q.24 [A] or [B] + H2O 
(i) dil. alkali 4→
Q.12
(ii) Heat H2SO 4
O NaOI
CH3CH2 COCH3  → [C] + [D]
Boil.alkali
Q.13 H3C − CH2 − CHCl2 → ?
[A] C6H5 [C]
Q.25 CH4 CH2Br [B]
AlCl 3(anhy.)
KOH CHCl2
Q.14 H3CO CHO+HCHO CHCl2
| +
H2O,H sod. acetate (anhyd.)
[D] [E]
H2O.H [D] sod. acetate (anhyd.) [E]
+ acetic anhydride
Q.15 Br3/CCl4
A
Na/NH2 acetic anhydride
[F]
CH=NOH
HgSO4/H2SO4
B C
CH=NOH
C
NH2NHCONH2
D
|
NaOD/D2DO (excess)
D E
Q.26 Explain giving reasons
(i) Solubility of carbonyl compounds decreases with the
Q.16 COO
HNO3/H2SO4
? increase in their molecular masses.
(mononitration)
(ii) Sodium bisulphite is used for the purification of
aldehydes and ketones.
OH
(iii) Oxidation of toluene with chromium trioxide to
(CH3CO2)O
Q.17 ? benzaldehyde is carried out in presence of acetic
CH3COONa
CHO
anhydride.
(iv) Although aldehydes are easily oxidisable yet
propanal can conveniently be prepared by the oxidation
NaOH of propanol by acidic dichromate.
Q.18 A’ B’ CH=CH.CHO
(v) O part of the O group does not react with
|| ||
−C − −C − OH
Q.19 CH3COOH + NH3 → hydroxylamine hydrochloride.
heat C
A  → B  → CH3NH2
Q.27 Give Reason
(O) Cl (i) Me3CCH2COOH is more acidic than Me3SiCH2COOH.

Q.20 CH3CH2OH  2→
→ A 
(ii) The K2 for fumaric acid is greater than for maleic
B →
dil.NaOH acid.
CHCl3
(iii) Carbon oxygen bond lengths in formic acid are 1.23
P and Br2 Å and 1.36 Å and both the carbon oxygen bonds in
Q.21 CH3CH2 COOH  →A
sodium formate have the same value ie. 1.27 Å.

(i)alc.KOH(excess)
→B (iv) The reaction CH3COOC2H5 + H2O → CH3COOH +
C2H5OH is slow in the beginning but fast subsequently)
(v) Although both > C = O and > C = C < groupings (B) Me

have double bond, they exhibit different types of |
addition reaction. Me2C = CH–C–CHO
|
Q.28 An organic compound (A) C9H12O was subjected Me
to a series of tests in the laboratory. It was found that
this compound. (C) Me2CH–CH2–OH
(i) Rotates the plane of polarised light. (D) Me2CH–COOH
(ii) Evolves hydrogen with sodium.
(iii) Reacts with I2 and NaOH to produce a pale yellow Q.2 CH2 Cl
solid compound. O
(iv) Does not react with Br2/CCl4. Ph3P

(X)
Ph-Li
(Y)
H-C-H
(Z)
(v) Reacts with hot KMnO4 to form compound (B)
C7H6O2 which also be synthesised by the reaction of
benzene and carbonyl chloride followed by hydrolysis. End product (Z) in above reaction
(vi) Loss optical activity as a result of formation of CH= CH2

compound (C) on being heated with HI and P.
(vii) Reacts Lucas reagent in about 5 min. Give structure (A) (B)
of A and C with proper reasoning and draw Fischer
projections for (A). Give reactions for the steps wherever
possible. CH2 CH3
Q.29 When 0.0088 g of a compound (A) was dissolved (C) (D)

in 0.5 g of camphor, the melting point of camphor
was lowered by 8°C. Analysis of (A) gave 68.18% C
and 13.63% H. Compound (A) showed the following Q.3 If 3-hexanone is reacted with NaBH4 followed by
reactions: hydrolysis with D2O the product will be
(a) It reacted with acetyl chloride and evolved hydrogen
(A) CH3CH2CH(OD)CH2CH2CH3
with sodium.
(b) When reacted with HCl + ZnCl2, a dense oily layer (B) CH3CH2D(OH)CH2CH2CH3
separated out immediately. Compound (A) was passed (C) CH3CH2CH(OH)CH2CH2CH3
over Al2O3 at 350°C to give compound (B) which on
ozonolysis gives (C) and (D) which gave positive test (D) CH3CH2CD(OD)CH2CH2CH3
with carbonyl reagents but only (C) gave a positive test
with Fehling Sol: and resinous substance with NaOH. CHO
ldentify (A), (B), (C) and (D) with proper reasoning. Kf for Q.4 CH2
14 ZnHg
A
camphor = 40 K kg mol–1. HCl
CHO
Final major product of this reaction is
Exercise 2
14 14
(A) CH3 CH2 CH3 (B) CH3 CH2CH3
Single Correct Choice Type
14 14
NaOH (C) CH3 CH2 − CHO (D) CH3 − CH2 − CHO
Q.1 Me2CH − CHO 
→ Major products of this
∆
reaction is -
Q.5 SH
OH Me OH
| | dry HCl
(A) Me2CH –CH–C–CHO + Me2C=O A is?
| OH
Me
SH
SH OH
H3O
SH
SH Q.8 (A) + (B)
(A)
(A) O
OH
OH (A) + (B) formed can be distinguished by -
CMe2
CMe
(A) Iodoform (B) Fehling
2
S
(C) NaHSO3 (D) 2, 4-DNP
S Me
Me
(B)
(B) NaBH CN
O Me
Me Q.9 (X) + (Y) 
2 → C6H5CH2NHCH2CH3
O methanol
OH
OH
(A) C6H5CH2OH + C2H5NH2
SH
SH
Me (B) C6H6 + CH3 + NH CH2 CH3
O
O Me
((C))
C
O
O Me (C) C6H5 CHO+CH3 + NH CH2 CH3
Me
(D) C6H5CHO+C2H5NH2
CMe
CMe22
Me
(D)
OH
OH Me Q.10 OH OH
(D) H+
OH
OH Me
NaBH4 H+ (C)
Me (A) (B)

Q.6 Compound A (molecular formula C2H8O) is treated (Major). Product C is
with acidified potassium dichromate to form a product
B (molecular formula C3H6O). B forms a shining silver (B)
mirror on warming with ammoniacal silver nitrate, B (A)
when treated with an aqueous sol of NH2NHCONH2
and sodium acetate gives a product C.ldentify the
structure of C. (C) (D)
(A) CH3CH2CH=NNHCONH2
(B) CH3C = NHHCONH2 O
| Q.11
1
CH3 2
3
(C) CH3C = NCONHNH2
O
| Me
CH3
above compound is hydrated maximum at which
(D) CH2CH2CH=NCONHNH2
position?
(A) 1 (B) 2 (C) 3 (D) Equal
Q.7 When cyclohexanone is treated with Na2CO3 sol,
we getO O
O O Q.12 Et – C – Me is prepared as one of the products by
OH ||
(A) OH (B) O
(A) (B) OH dry distillation of calcium salt of which o the following
OH acids:
OH
OH OH (A) Ethanoic acid and methonoic acid
COOH
(C)
OH
(D) COOH (B) Propanoic acid and methonoic acid
(D) COOH
(C) COOH (C) Propanoic acid and ethanoic acid
(D) None of these
Q.13 Reagents A & B are Q.17 Major product of this reaction is

OH Cl
O
O
A> O MeOK
O MeOH
O OH
H
O B>
OH OMe
O COOCH3
OH
(A) (B)
(A) H2/Pd & LiAlH4 (B) LiAlH4 & NaBH4
(C) NaBH4 & LiAlH4 (D) LiAlH4 & H2/Pd H
OMe Cl OMe
Q.14 The reagent used to distinguish ethanol & O
OH
acetone is
(C) (D)
(A) Schiff’s reagent (B) Fehling’s sol.
(C) Ceric ammonium nitrate (D) Iodine with NaOH
H H
Q.15 Which one of the following compounds is the

Q.18 In the given reaction
best candidate for being prepared by an efficient mixed
aldol addition reaction? OH OH
OH O CH2 CH CH CH CH
(A) CCH2 CH O O O O
C C
CH3
H3C CH3 H3C CH3
O (i) H3O
(ii) NaIO4(aq)
(B) CCHCH3
Product will be -
CH2OH (A) 1 mole HCOOH and 1 mole HCHO
(B) 2 mole HCOOH and 1 mole HCHO
O
(C) 2 mole HCHO and 1 mole HCOOH
(C) CH2CCHCH3
(D) 2 mole HCHO and 4 mole HCOOH
HO C CH3
Q.19 In the given reaction
CH3
Br O
| || NH2–NH2/alc.KOH
O O
CH3–CH2–CH–C–CH3 X
∆
(D) CCH2CCH3
[X] will be -
O Br
|| |
(A) CH3–CH=CH–C–CH3 (B) CH3–CH–CH2–CH2–CH3
Q.16 PhCHO and HCHO will behave differently with
which of the following reagents
(C) CH3–CH=CH–CH2–CH3 (D) CH3–CH2–CH2–CHO
(A) Tollen’s Reagent (B) Fehling’s sol.
(C) Schiffs reagent (D) NaBH4
Multiple Correct Choice Type H3O

Q.22 (A)++(B)(B)
(A) formed
formed
Q.20 Compound (X) C4H8O, which gives 2,
O
4-Dinitrophenyl hydrazine derivative (orange or red or
yellow colour) and negative haloform test. cannot be differentiated by
O (A) Iodoform (B) Fehling
||
(A) CH3–CH=CH–C–CH3 (B) CH3–CH–CHO (C) NaHSO3 (D) 2, 4-DNP
|
CH3 Comprehension Type
OH
(C) (D) CH3–CH2–CH2–CHO O
O
58%
(CH3)3C C CH3 (CH3)3C C CH2 Br
Q.21 Which of the following reaction is not representing (a)
major product - (b) 54%
OH + O
H O OH
(A) C=N
CH3 C NH CH3
:
CH3 68%
(CH3)3C C CH2 (CH3)3C C CH2 Br
H
14 OH 14
Ph-Li CH3
C=C CC
(B) Q.23 Suggest a reagent appropriate step (a) the
Cl
synthesis -
CH3 (A) HO– / Br2 (1 mole) (B) H+ / Br2 (1 mole)
O (C) Both (A) and (B) (D) None of these
Br2
(C) Ph C NH2 Ph NH2
KOH
Q.24 Yield of each step as actually carried out in laboratory
Hoffman Brommamide
is given each arrow. What is over all yield of the reaction ?
O :NH
(A) 60% (B) 21% (C) 40% (D) 68%
HN3
(D)
H2SO4
Q.25 Match the column
Column I Column II
O
(A) (A) HCN LiAlH4 NaNO2 (p) Formation of six member ring takes place
(A) (B) (C)
traces of KOH HCl
(B) NH2OH H+ LiAlH4

(B) (A)

(B) (C) (q) Final product is Ketone
O O
OH-
(C) CH3 C CH2 CH2 CH2 C (A)
(C)
(r) Final product will give positive Tollen’s test
Ph OH-
(D) (A)
(D) CH3
(s) Final product formed will react with 2, 4-DNP,
OH OH (2, 4-Di-nitrophenyl hydrazine)
Q.26 Match the column
Column I Column II
Me conc.H2SO4
(A) (A) C=N
Product (p) Carbene formation is involved
Et OH
(B) (B) MCPB A LiAlH NaNO2 (q) Nitrene formation is involved

Products (A) (B)
HCl
(C)
(C) (C) CH2 = CH2 + NH3

Product (r) Carbocation formation is involved
CHCl3
(D) (D) Product (s) Final product is a cyclic compound
KOH/excess
(t) Azonium ion formation is involved
Previous Years’ Questions Q.3 What is X? (2005)

CHO
Q.1 A mixture of benzaldehyde and formaldehyde on
+ (X)
heating with aqueous NaOH Solution gives (2001)
MeO
COOH
(A) Benzyl alcohol and sodium formate
(D) Sodium benzoate and methyl alcohol CH3COONa
(C) Sodium benzoate and sodium formate
MeO
(D) Benzyl alcohol and methyl alcohol
(A) CH3COOH (B) BrCH2COOH
(C) (CH3CO)2O (D) HOC–COOH
Q.2 The order of reactivity of phenyl magnesium
bromide with following compounds is (2004)
Q.4 Butan-2-one can be converted to propanoic acid
O O O by which of the following? (2006)
(A) NaOH, NaI/H+ (B) Fehling Sol:
H3C CH3 H3C H Ph Ph
(C) NaOH, I2/H+ (D) Tollen’s reagent
(I) (II) (III)
(A) II > III > I Q.5 The smallest ketone and its homologue are reacted
with NH2OH to form oxime (2006)
(B) I > III > II
(A) Two different oximes are formed
(C) II > I > III
(B) Three different oximes are formed
(D) All the above react with the same rate
(C) Two oximes are optically active
(D) All oximes.are optically active
Q.6 Cyclohexene on ozonolysis following reaction with

zinc dust and water gives compound. Compound E on
further treatment with aqueous KOH yields compound
F. Compound F is - (2007)
Q.10 The structure of the product Q and R, respectively,

CHO
(A) (B) CHO are
O
H
(C) CHO (D) (A) CH3 COCH3
COOH
H3C CH3 H3C CH3
Q.7 Among the following compounds, which will react
with acetone to give a product containing C=N– ? O
(2014)
H
(A) C6H5NH2 (B) (CH3)3N (B) CHO
(C) C6H5NHC6H5 (D)C6H5NHNH2 H3C CH3 H3C CH3
Q.8 A new carbon bond formation is possible is (1998) O

(A) Cannizzaro’s reaction
H
(B) Friedel-Craft’s reaction (C) CHO
(C) Clemmensen’s reduction Me Et Me Et

(D) Reimer-Tiemann reaction
O
Me
Paragraph 1
CH3
A corbonyl compound P, which gives positive iodoform
(D) CHO
test, undergoes reaction with MeMgBr followed by Me
dehydration to give an olelfin Q. Ozonolysis of Q Me Et
leads to a dicarbonyl compound R, which undergoes Q.11 The structure of the product S, is-
intramolecular aldol reaction to give predominantly S.
O
1.MeMgBr 3 2 O /Zn H O OH − (2009)
P  → Q → R S
2.H+ ⋅H2O heat (A) (B)
3.H2SO 4 /Heat
O
Me Me
Q.9 The structure of the carbonyl compound P, is Me
O O
(A) Me
(C) (D)
O CH3
CH3
Me Me
(B)
O CH3
Paragraph 2
Two alipbatic aldehydes P and Q react in the presence of
(C) aqueous K2CO3 to give compound R, which upon treatment
with HCN provides compound S. On acidification and
O C2H5 heating. S gives the product shown below: (2010)
O
H3C OH
(D)
H3C
C2H5 O O
O
H3C C
2 3 . 6 8 | Aldehydes and Ketones H
(B) C
H3C
H2C
Q.12 The compounds P and Q respectively are Q.14 The compound S is -
CN
CH3 CH3 CH3 CN

O
CH H H3C CH CH CH
(A) H C
H3C (A) H3C CH H (C) H3C CH H
C C
and
O O H2C H2C
CN OH
CH3
CH O CN
H H H
(B)
H3C C C C H3C CH
H3C OH
and H (D) C
(B) C H3C
O O H3C
H2C H2C
H3C CH2 H H3C H CN
CN
(C) CH C and C
CH3 CN
CH3 O O
Q.15 Match CHcompounds/ions
CH in column I with their
properties
(C) H3C / reactions
CH inHcolumn II. (2007)
H3C CH2
H H H ColumnHI2C Column II
CH C
(D) C and (A) C6H5CHO (p) OH gives precipitate with
CH3 O O 2,4-dinitrophenylhydrazine
CN
(B) CH3C≡CH (q) gives precipitate with AgNO3
Q.13 The compound R is - (C) CN

H3C– (r) is a nucleophile
CH
(D) C OH
(D) IH3C
–
(s) is involved in cyanohydrin formation
O
H2C
H3C C Q.16 In the scheme
CN given below, the total number of
H
(A)
H3C
C intramolecular aldol condensation products formed
H2C from ‘Y’ is: (2010)
OH
1. O3 1. NaOH(aq)
Y
O 2. Zn,H2O 2. heat
H3C C
(B) C H Paragraph for Questions 17 and 18
H3C
CH In the following reactions sequence, the compound J is
H3C OH an intermediate (2012)
3 (CH CO) O
2 2 (i) H ,Pd/C
CH3
O I →
CH COONa
J 
(ii)SOCl /Anhy.AlCl
→K
3 2 3
CH C
(C) H3C CH H J(C9H8O2)gives effervescences on treatment with
NaHCO3 and positive Baeyer’s test.
H2C
OH
Q.17 The compound K is
CH3
O
CH (A) (A)
(B) (B) (C) (C) (D) (D
C
(D) H3C CH H O O O O
O O
CH (A) (B) (C) (D) O
(A) (B) (C) (D) O
H2C OH
O OO O
O O
?
OH-
CH3 Chem i str y | 23.69
Q.18 The compound OH

I is O OH OH
OHC CHO CHO
H
O H OH O CH3 H
H
CH3 H3C CHCl2 H3C CHCl2
CH3
(A) (B) (C) (D)
P Q R S
(A) P(major) (B) Q(minor)

H
OH O CH3 H (C) R(minor) (D) S(major)
H
Q.22 After completion of the reactions (I and II), the

(C) (D)
organic compound(s) in the reaction mixtures is(are)
(2013)
Q.19 The number of aldol reaction(s) that occurs in the O

given transformation is (2012)
Reaction I : H C Br3(1.0 mol)
OH OH 3 CH3 aqueous/NaOH
conc.aq. NaOH (1.0 mol)

CH3CHO+4HCHO O
O
HO OH
Br3(1.0 mol) Reaction II : Br3(1.0 mol)
Reaction I : H C CH3 H3C CH3
3 aqueous/NaOH CH3COOH
(A) 1 (B) 2 (C) 3 (D) 4 (1.0 mol)
(1.0 mol)
O O O O O
Q.20 The major product H in the given reaction
sequenceReaction
is II :
(2012)
Br3(1.0 mol)
H3C CH3 H3C CH2Br H3C CBr3 Br3C CBr3 BrH3C CH
CH3COOH
95%
95% H
H22SO P Q R S
CH CH 95% HCN
2SO
SO44
2 CO CH3 4 G H
CN
CH333
H3 CH2 CO CH CHCN
2 COGCH3
(1.0 Gmol)
H Heat H
Heat Heat
O O O O O
(A) CH3 CH=C (A)

(A) CH
CH33 CH=C
COOH CH=C COOH
COOH CNCH
(B)
(B) CH3 CH=C (B) CH33 CH=C
CH=C CNCN
H3C CH3 CH2Br H3C CBr3 Br C CBr
CH BrH3C CH2Br H3C ONa CHBr3
CH3 CH3 CH3 3 CH333
P Q R S T U
OH OH
OH
(A) Reaction I: P and Reaction II : P
CH
CH33 CH22 C
(C)COOH CH C COOH (D) CHNH
COCH 3 CH=C CO NH
CO NH22
C) CH3 CH2 C(C) COOH (D) CH3 CH=C (D) 3 CH=C
(B) Reaction I: U, acetone and Reaction II:Q, acetone
2
CH CH CH
CH3
CH CH3
(C) Reaction I : T, U, acetone and Reaction II : P
3 3 3 3
(D) Reaction I : R, acetone and Reaction II : S, acetone

Q.21 In the following reaction, the product(s) formed is
OH
(are) (2013)
OH CHCl3 Q.23 The most suitable reagent for the conversion of
OH-
CHCl 3
? R-CH2-OH → R-CHO is: (2014)
?
OH- (A) KMnO4
CH3
(B) K2Cr2O7
CH3
(C) CrO3
OH O OH OH
OHC OH CHO O OH
(D) PCC (Pyridinium
OH
chlorochromate)
CHO
OHC CHO CHO
CH3 H3C CHCl2 H3C CHCl2

CH3
CH H3C CHCl2 H3C CHCl2
P 3 Q R CH
S 3
P Q R S
Q.24 Among the following, the number of reaction(s) Q.27 Reagents which can be used to bring about the
that produce(s) benzaldehyde is (2015) following transformation is (2016)
CO, HCl
(A) Anhydrous AlCl3/CuCl O O O O
C O C O
H OH
CHCl2
O O
H2O COOH COOH
(B) o
100 C
(A) LiAlH4 in (C2H5)2O
COCl (B) BH3 in THF
(C) NaBH4 in C2H5OH
H2
(C)
Pd-BaSO4
(D) Raney Ni/H2 in THF
CO2Me
DIBAL-H Q.28 (2016)
(D) o
Toluene, -78 C
H2O OO
i) i)HCHO
HCHO(excess)/NaOH, heat
(excess)/NaOH, heat
Q.25 The major product of the following reaction is ii) HCHO/H+ +
(catalytic amount)
(2015) ii) HCHO/H (catalytic amount)
O
O O O O O OH
i. KOH, H2O O O O O O OH
CH3 ii. H+ , heat i) HCHO (excess)/NaOH, heat
(A) (B)
i) HCHO (excess)/NaOH, heat
(A) (B)
O ii) HCHO/H+ (catalytic amount)
ii) HCHO/H+ (catalytic amount)
O OH
CH3 CH3 O O
HO O OH
O O
O O O O O HOO O OH
O O (D) O O OH
(C)
(A) i) HCHO (excess)/NaOH, heat (D)
(C)
(A) (B) (B)
(A)
ii) HCHO/H+ (catalytic amount) (B) OH
O OH
CH3 O OH
O O O OH
O HO O O
CH3 O O HO O O OH
(C) (D) (D)
(C) (D)
(C)
(A) (B)
OH
OH
Q.26 Positive test is observed for O O (2016) O OH
HO
H O
H O CHO (D)
(C) CHO
(A) H (B)
(A) H H (B)
H OH
H
H
OH O
OH O
(C) Ph (D) Ph Ph
(C) Ph Ph (D) Ph Ph
Ph
O
O
MASTERJEE Essential Questions
JEE Main/Boards JEE Advanced/Boards

Exercise 1 Exercise 1
Q.1 Q.3 Q.9 Q.11 Q.12 Q.15
Q.10 Q.16 Q.22 Q.25 Q.26 (4) Q.27 (3)
Q.28 (5-i)
Exercise 2 Exercise 2
Q.3 Q.8 Q.12 Q.2 Q.6 Q.8
Q.15 Q.9 Q.17 Q.18
Q.25
Previous Years’ Questions Previous Years’ Questions

Q.2 Q.7 Q.8 Q.9 Q.14
Q.12
Answer Key
JEE Main/Boards
Exercise 2
Q.1 B Q.2 B Q.3 C Q.4 A Q.5 C Q.6 A

Q.7 C Q.8 B Q.9 D Q.10 C Q.11 C Q.12 C
Q.13 B Q.14 B Q.15 D Q.16 D

Q.1 D Q.2 B Q.3 A Q.4 B Q.5 A Q.6 B
Q.7 C Q.8 D Q.9 A Q.10 A Q.11 B Q.12 C
Q.13 D Q.14 A, C Q.15 D Q.16 D Q.17 A Q.18 B
Q.19 A
JEE Advanced/Boards
Exercise 2
Q.1 C Q.2 C Q.3 A Q.4 B Q.5 B Q.6 A Q.7 C

Q.8 A Q.9 D Q.10 C Q.11 B Q.12 C Q.13 C Q.14 C
Q.15 B Q.16 B Q.17 B Q.18 D Q.19 C
Multiple Correct Choice Type

Q.20 B, D Q.21 A, B, D Q.22 B, C, D
Comprehension Type
Q.23 C Q.24 B
Match the Columns

Q.25 A → p, q, s; B → p; C→ p, q, s; D → p, q, s; Q.26 A → r; B → r, s; C → q, s; D → p

Q.1 A Q.2 C Q.3 C Q.4 C Q.5 B Q.6 A Q.7 A, D
Q.8 B, D Q.9 B Q.10 A Q.11 B Q.12 B Q.13 A Q.14 D
Q.15 A → p, q, s; B → q, r; C → q, r, s; D → q, r Q.16 1 Q.17 C Q.18 A Q.19 C
Q.20 B Q.21 B, D Q.22 C Q.23 D Q.24 A, B, C, D Q.25 A Q.26 A, B, C
Q.27 C Q.28 A
Solutions
JEE Main/Boards CN
or CH2
CN
CH2
COOH CN
Exercise 1
Mechanism
Sol 1: Knovengeal reaction COOH COOH
CH2
CH + H
It is the condensation of any carbonyl compounds with COOH COOH
compounds containing in active methylene compound O OH
in the presence of pyridine || COOH | COOH
H–C–CH H–C–CH
CHO CH=CH–COOH COOH COOH
COOH
Pyridine
2 + CH2 OH
H2 O, CO2
COOH | COOH
H–C–CH CH=CH–CH–COOH
COOH COOH
Instead of CH2 we can also use (–H2O)
COOH (–CO2)
OH (vii) 2Ph–CH2–CH=O 

Dil. NaOH
→ Ph–CH–CH=O
CN Pyridine | ∆
|
CH3–C–H + CH2 CH–C–CH–CN
|| COOH | | CH–CH2–Ph
O H COOH |
OH
(viii) 2CH3–CH2–CH2–CH2–OH →
OH
| –H2O It will not undergo any reaction
CH3–C–CH–CN CH3–CH=CH–CN
–CO2
| | CH3 O
H COOH | ||
(ix) 2H3C – H2C – C – CH 
Conc. NaOH
→
∆
|
Sol 2: (i) CH2 = O it will undergo cannizzaro reaction : CH3
Conc. NaOH CH3

2CH2= O → HCOONa + CH3OH |
∆
CH3 – CH2 – C – COONa +
(ii) Aldol condensation |
O CH3
|| CH3
Dil. NaOH
H–C–CH–CH2–CH2–CH3  → |
| ∆
CH3
CH3 – CH2 – C – CH2 – OH
|
OH CH3 CH3
| |
H – C – CH – CH2 – CH2 – CH3 Sol 3:
O
O
|| ||
H–C–C–CH2–CH2–CH3 (i) CH3 – C – H  → CH2 – CH2 – CH – CH3
| | |
CH3 OH OH
O
Cannizzaro reaction ||
Dil. NaOH
(iii) Benzaldehyde CH3 – C – H  →
∆
O O
H O
|| ||
| || H2/Pd
C–H C–ONa CH2–OH CH3 – C – CH2 – C – H CH3–CH–CH2–CH2–OH
| |
Conc. NaOH OH OH
2 +
O

||
(iv) Benzophenone (ii) CH3 – C – H → H – C – C = C – CH3
O || | |
|| O H H
C
O H O
|| | ||
Dil. NaOH
CH3 – C – H  → CH3 – C – CH2 – C – H
It will not undergo aldol or cannizzaro reaction ∆
|
O OH
O Aldol OH H O
| ||
HCl
(v) 2 Dil NaOH
 → CH3 – C = C – C – H

|
H
O H O Sol 5: C9H10O → gives +ve tollen's test

|| | ||
⇒ It is a aldehyde → undergoes cannizzaro
(iii) CH3 – C – H → CH3–C–CH2–C–H
Dil. NaOH
∆
| ⇒ α hydrogens not present → vigorous oxidation →
OH
COOH
H O COOH
| ||
HCl
 → CH3 – C = C – C – H
|
H ⇒ C9H10O has two groups attached at neighbouring
O positions
||
CrO3/H2O/Acetone ⇒ 1 group is aldehyde with no α-hydrogen
CH3–CH=CH–C–OH
⇒ 2nd group is ethyl group
CHO
Sol 4: CH3–CH2–CHO CH2–CH3
Aldol
+  → So C9H10O is
CH3–CH2–CH2–CHO
(1) CH3–CH–CHO Sol 6: (i) Refer page-23.15 Section-6 in the sheet

|
CH–CH2–CH3 (ii) When the condensation is between two different
| carbonyl compounds, it is called crossed aldol condensation.
OH For example.
Θ
CH3–CH2–CHO is nucleophile OH
(a) R3C – CHO + CH3CHO  →
CH3–CH2–CHO is electrophile
R3C – CH(OH) – CH2 – CHO crossed product
O
(2) CH3–CH2–CH2–CH–CH–CH2–CH3 ||
| | OH–
(b) CH3CHO + CH3C – CH3
OH CHO
CH3 – CH(OH) – CH2 – COCH3
CH3–CH2–CH2–CHO is nucleophile
4-Hydroxypentan-2- one (crossed product)
CH3–CH2–CH2–CHO is electrophile
OH–
(c) C6H5CHO + CH3COCH3
(3) CH3–CH2–CH–CH–CH2–CH3
| | C6H5 – CH = CH – CO – CH3
OH CHO
Sol 7: (i) Fehling’s Test, (ii) 2, 4 DNP Test
CH3–CH2–CHO is electrophile
CH3–CH2–CH2–CHO is nucleophile OH OH O
CHO Sol 8: (i) CHCl3 H

3KOH
|
(4) CH3–CH2–CH2–CH–CH–CH3 Reimer – Tiemann reaction
|
OH (ii) OCH3 OCH3
CH3–CH2–CH2–CHO is electrophile
CH3–CH2–CHO is nucleophile
O
Friedel
Friedel Craft Acylation
– Crafts Acylation
Sol 9: (i) Rosenmund Reduction Sol 12: (a)

O O Catalytic
CH3COOCH3 + 2H2 CH3CH2OH + CH3OH
H2 hydrogenation
CH3 Cl Pd-BaSO4 CH3 H
Dehydrogenation
(ii) Tollen’s Reagent
CH3CHO + 2[Ag(NH3)2]+ + 3OH– → RCOO– + 2Ag +
2H2O + 4NH3 CH3CHO + HCHO
(b) (i) Due to the presence of 0 group with is

C =O
Sol 10: The pinacol-pinacolone rearrangement is a polar
method for converting a 1, 2- dial to a carbonyl compound
in organic chemistry. This 1, 2-rearrangement takes place (ii) Aldehydes have lower boiling points as they are not
under acidic conditions. The name of the reaction comes associated with intermolecular
from the rearrangement of pinacole to pinacolone.
H-bonding whereas alcohols are associated with
H H+ H H + H H intermolecular H-bonding. Aldehydes have lower B. P.
O O O O
Sol 13: Refer theory.
H3C CH3 CH3 CH3
CH3 CH3 CH3 CH3 Sol 14: (i)
pinacol LiAH4 SO2Cl2

CH3CHO CH3 CH2 OH CH3 CH2 Cl
H2O
H H
O O Alcoholic
H3C H3C KCN
CH3 CH3
H3C H3C hydrolysis
CH3 CH3
O LiAH4
H3C CH3 CH=CH2 dehydrate CH3 CH2 CH2 Cl CH3 CH2 COOH
H2O
H3C CH3
CH3
H2O
pinacolone
CrO2
CH3 CH CH3 CH3 CH CH3
Sol 11: (i)
OH O
LiAlH4 SO2Cl2
CH3COOH CH 3–CH2OH CH3–CH2–Cl
H2O (ii)
Alcoholic
bleach H3O+
KCN CH3–C–CH3 CH3COO–+CHCl3 CH3COOH
NaOH
||
dehydrate LiAlH4 O
CH3 –CH=CH2 CH3 –CH2 – CH2 – OH CH3 –CH2 –COOH
H2O
Br2 H2SO4 LiAlH4
H2O BrCH2–CH2Br CH2=CH2 CH3CH2OH
ether
CrO3
CH3–CH–CH3 CH3–C–CH3 alc. KOH
H+/H2O
| ||
OH O
acetylene
(ii) Friedel – Craft reaction
CH Cl+FeCl
Benzene 
3 3→ Toluene + HCl + FeCl3
H SO (ii) Semicarbazide has two –NH2 groups. The attachment

2 4 →B + C
Sol 15: A C8H16O2  of the two –NH2 groups on the
hydrolysis
C = O is different one –NH2 is directly attached to

C 
Chromic acid
→B C = O while the other –NH2 is not directly attached out
dehydration
attached through –NH. Therefore due to resonance
C  → but-1-ene the electron density on this –NH2 group decrease and
therefore cannot act as a nucleophile. The lone pair of
⇒ C = CH3CH2CH2CH2OH
electrons in –NH2 which is attached through –NH is
⇒ B → CH3CH2CH2CH2COOH not involved in resonance and therefore is available for
nucleophilic attack on the C = O.
⇒ A → CH3–CH2CH2 COOCH2CH2CH2CH3
(iii) The reaction between carboxylic acid and alcohol
is a reversible reaction. The ester and the water which
Sol 16: (i) 2-4 DNP test is formed as a product of can again react to form
Only carbonyl compounds give positive test carboxylic acid and alcohol so for a reaction to proced
in the forward direction in a reversible reaction, one
(ii) Acetophenone - It give iodoform test of the product should be removed. That is the reason
Benzophenone-It doesn’t give Iodoform test during the preparation of esters form a carboxylic acid
and an alcohol in the presence of an acid catalyst, the
(iii) Phenol - It give violet colour with FeCl3 test.
water on the ester should be removed as soon as it is
Benzoic acid-It doesn’t give violet colour with FeCl3 formed.
Sol 17: (i) Sol 19: Calculation of molecular formula :-

LiAlH4 H2SO4 % of C = 69. 77
CH3–C–CH3 CH3–CH–CH3 CH3CH=CH2
|| | % of H = 11.63
O OH % of O = 100 – (69. 77 + 11.63) = 18. 6%
Ratio of C = 69. 77 / 12 = 5. 88
(ii) CH3CH2OH Reduction
Cu Ratio of H = 11.63 / 1 = 11 63
Ethanol
Ratio of O = 18.6 / 16 = 1. 16
CH3CHO+NaOH → CH3–CH–CH2CHO smallest ratio
|
C = 5. 88/1. 16 = 5
OH
3-Hydroxybutanal H = 11.63/1. 16 = 10
O = 1. 16/1. 16 = 1
(iii) CHO CHOHC6H5 Empirical formula = C5H10O1
H+/H2O Mol mass = 86

+ C6H5–MgBr
n = molecular mass/Empirical formula mass = 86/86 = 1
COC6H5 MF = C5H10O
Reductions Since the compound forms on addition compounds
+ CH2Cl2
C6H5NH+Cl-/CrO3 with sodium hydrogensulphite, the said compound
should be ketone as aldehyde.
Since the compound does not reduce Tollen’s reagent,
Sol 18: (i) 2, 2, 6-trimethyl cyclohexanone has three therefore it is a ketone. Since the compound gives
methyl group at the alpha position. There is a lot positive iodoforms test, the compound should be
of steric hindrance in this molecule. Due to steric methyl ketone. On vigorous oxidation it gives ethanoic
hindrance the CN ion do not attack the molecule. These and propanoic acid therefore the given compound
is not steric hindrance in cyclohexanone. Therefore its should be pentan-2-one.
forms cyanohydrin in good percentage.
The structure is Sol 25:

O
|| Cl–C–Cl
MeMgCl
Me–C–Cl
MeMgCl
Me–C–Me
CH3–C–CH2–CH2–CH3 || || ||
O O O
Mg
Sol 20: Aldol takes place in the presence of α-hydrogen
and cannizzaro takes place in the absence of
MeMgCl
α-hydrogen.
Sol 21: A does not give litmus test ⇒ A does not Me

contain –COOH group. |
Me–C–Me
A does not give 2, 4-DNP test ⇒ A does not contain |
C = O group OH
A + MeCOCl → B So 3 moles of MeMgCl required for 1 mole Cl–C–Cl

262 ||
Initial mass = 178 O
Final mass = 262 difference is 84 O Exercise 2

||
Now A has lost hydrogen and gained (Me–C–) group Single Correct Choice Type
so change in mass corespnding to
Sol 1: (B)
1(–OH) group 43 – 1 = 42
84
So no of hydroxy groups = =2
42
Sol 22: (i) (3) (4) will give positive fehling test as they
are aldehydes (6) will give positive Fehling test as it has
α-hydroxy ketone.
Sol 23: 3 nitrogen will give reaction with C=O

because it has maximum electron density. The other
O
||
two nitrogens are in conjugation with (–C–) group so
they are loss electron density.
Sol 24: 2 products are formed in good amount 1 with Sol 2: (B)
1st nitrogen O O
H O ||
CH2N2
||
| || CH3–C–CH2–CH3 CH3–C–CH2–CH2–CH3
Ph–C=N–C–NH–NH2 (A)
(1) (2) (3)
CH3CO3H
1 with 3rd nitrogen
H O O
| || ||
Ph–C=N–NH–C–NH2 CH3–C–O–CH2–CH2–CH3
(3) (2) (1)
(Bayer villiger)
Sol 3: (C) Sol 7: (C)
O O CH2=CH–C–CH3 O O
|| H || || NH2–CH3
B
O CH3–C–CH3 CH3–C–CH3
, –H
NH–CH3
O O
||

OH2
H2O
CH3–C–CH3 CH3–C–CH3
O
||
OO O N–CH3 NH–CH3
O O O
|| ||
B
Sol 8: (B) O
H2O H2N NH2

+ N2
O H3C O OCH3 H3C O OCH3
Octane Wolf-kishner
Walf kisher --reduction
reduction
In clemmension reduction HCl will break ether bonds.

Sol 4: (A) It is carried out using NaBH4 as NaBH4 will
not reduce ester and reduces only carbonyl part.
Sol 9: (D)
LiNH2 (i)HCHO
Sol 5: (C) MeCHO can undergo aldel condensation as Bu–CCH Bu–CCH Bu–CC–C–Ph
(ii)H2O
its has more than 1 α hydrogen present.
OH
Sol 6: (A)
O MnO2
O O
Bu Bu
Ba(OH)2
Bu–CC–C–Ph

C–Ph C–Ph O
O O
O O
O
O O
Sol 10: (C) H O
O EtoNa H–C–OEt
O
H H–C–OEt
H2O, EtoNa
O
O
O O
C–H O C–H
O O
C–H OH C–H
OH
Sol 11: (C) Sol 15: (D) KMnO4 / H2SO4 ; K2Cr2O7 / H2SO4 ; Ag2O /
NaOH will oxidise – CHO → –COOH but LiAlH4 is a strong
O OH O
reducing reagent so it will reduce –CHO.
Aldol
2CH3–C–H CH3–CH–CH2–C–H
(A) Sol 16: (D) H2 / Pd–C will reduce –C= C and –CHO. H2/
Pd – BaSO4 – CaCO3 will reduce only –C ≡ C– LiAlH4 and
NaBH4 will reduce –CHO to –CH2OH.
O CH2–OH
Aldol
CH3–C–H + 3HCHO HOH2C–CH2–OH Previous Years’ Questions
CHO
Sol 1: (D)
Sol 12: (C) CH2 = C = O + H2S
Cl OH
KOH
CH3–CH CH3–CH
H+
HS Cl

OH
CH2=C=O CH2=C=OH CH2=C–OH
HS –H2O
CH3CHO
H O H
CH2–C–OH Sol 2: (B) CH2 = C O3
H–C +O=C
R H R
S Presence of one vinyl group gives formaldehyde as one
Sol 13: (B) of the product in ozonolysis
O NNH2
Sol 3: (A) The cannizzaro product of given reaction
N2H4 KOH/s yields 2, 2, 2-trichloroethanol.
OH Cl Cl Cl OH
| O | O | |
OH Cl–C–C
NaOH
Cl–C–C + Cl–C–CH2
| H | O– |
(x) (Y) Cl Cl Cl
Sol 4: (B)
Wolf kishner reaction O
O O ||
|| fast | Ph–C–H
Sol 14: (B) Ph–C–H+OH Ph–C–H R.D.S
|
Br2 OH
CH3–C–CH2–CH2–CH2–CH2–C–CH3
KOH O O
|| + ||
O O Ph–C–OH+Ph –CH2O
H
Ph–C–O+Ph –CH2–OH
exchange
Intramolecular aldol condensation will take place.
O
Sol 5: (A) Crossed aldol reaction gives benzyl alcohol
CH3
and sodium formate.
+
NaOH(aq)
C–CH3 CH3 C6H5CHO+ HCHO  →
Bezaldehyde Formaldehyde
O C6H5CH2OH+ HCOONa
Benzylalcohol Sod. formate
CHO CHO
OH/100°C
Intra molecular
Cannizzaro reaction
Sol 6: (B) Benzaldehyde will undergo Cannizzaro’s COO– CH2OH

reaction on treatment with 50% NaOH to produce
benzyl alcohol and benzoic acid as it does not contain +
H /H2O
α-hydrogen
CHO CH2OH CHO

| | | CHO OOC
50% NaOH COOH CH2OH

+
Benzaldehyde Benzyl alcohol Sodium benzoate
Sol 7: (C) It is a nucleophilic addition whose reactivity CH2OH COOH

depends upon the electrophilic character of carbonyl
carbon and steric hindrance only, So. the ease of the
reaction would be HCHO > CH3COCH3 > PhCOCH3 >
PhCOPh Sol 12: (C)
OH
Sol 8: (D) Tollen’s reagent oxidizes the compound +
H2O/H O
having aldehyde group like glucose and also oxidizes P H2C H3C—
α-hydroxy ketone having –COCH2OH group as in CH3 CH3
fructose - H2O/H
+
Q H3C
H3C—
Sol 9: (A) OH
CHO
CH=CHCOCH3
Sol 13: (D) CH3

–
NH2NH2/OH
KMnO4
HO
Wolf-kishner Reduction C= CHCH2CH2CH3
CH3
CH3
CH=CH–CH2CH3 C= O+HOOCCH2CH3
CH3
HO
Sol 14: (A, C)
–OH group and alkene are acid sensitive groups so O +
O
clemensen reduction can not be used. CH3–C
(Ag(NH3)2)
CH3–C +Ag
H O
(O)
Sol 10: (A) CH3 CH2 CH2OH  → CH3 CH2 − CHO O
(A) (B) O
|| (Ag(NH3)2)
–
H–C–H H–C +Ag

Sol 11: (B) CHO CHO O
CHO CHO
OH/100°C
Intra molecular
Cannizzaro reaction
COO– CH2OH
+
H /H2O
Sol 15: (D) CH3 CH3

O HBr
Sol 2: Peroxide
H3C CH CH CH3 CH3 H3C CH CH CH CH3 Br
(A)
O O HBr/Peroxide → Anti-Markownikoff’s Addition.
H2O/Zn
O Sol 3:
H2CrO4 CrO3
C [J] [I] CH3–CHO
H3 C H H2O (Pyridine)
(B)
Sol 16: (D)
Strong oxidizing Weak oxidising agent
aqu.KOH agent
CH3CHCl2  → CH3CH(OH)2 →
−H O
CH3CHO
2
J → CH3COOH I → CH3 CH2–OH

Sol 17: (A) In Cannizzaro reaction given below, the
slowest step is the attack of OH at the carboxyl group Θ
OHΘ HSO4
Sol 4: Acetone (2 mol) [K] [L]
Sol 18 : (B) The first reaction. Aldol condensation.
O OH
CH3
CH3
C dil OH C O
CH3 C CH2 CH2 CH CHO ∴ 2 CH3 CH3 CH3
CH3 O CH3 CH3 C
CH3
(5-keto-2-methyl hexanal)
(5-keto-2-methyl hexanal)
Thus, K is
Sol 19: (A) Vinyl group ( CH=2 CH − ) on ozonolysis

OH
|
O
||
give formaldehyde CH3 – C – CH2 – C – CH3
|
CH3
JEE Advanced/Boards
Exercise 1
HSO4 (H )
OH2 H O
Sol 1: Chlorination
| | ||
O CH3 – C – CH – C – CH3
|| |
COOH C–Cl
CH3
CH2–Ph CH2–Ph (a) O
SOCl2
||
L is CH3 – C = CH – C – CH3
Anhydrous
AlCl3 CH3
O
||
Sol 5:
Zn–Hg O O
HCl || ||
(H) C – CH3 C–CH2–Br
Br2 (1 eq,)
As only 1 equivalent is used, Br will be added to the Sol 9:

alkyl group otherwise the phenyl ring also would have CH3
be substituted. [H2/indlar’s catalyst
is addition of H2]
[NaBH4 → weak reducing agent. ] H
H
O OH
|| |
C – CH2Br CH2–CH2–Br Sol 10:
NaBH4
F F OCH3 OCH3
Na OCH3
HgSO4/H ⊕ –F
Sol 6: R–C≡CH R–C–CHO
O NO2 NO2 NO2
||
CCH CH2–C–H
HgSO4/H This is ArSN
Aromatic Substitution
O R
R–C + NH2OH C=N
| R’ OH2 Sol 11: O
R’ ||
C
Fe/Br2
Ph–CH2 N
CH2–CHO
C=N
+ NH2–OH H OH
This ring is This is
deactivated activated
(geometrical isomer)
O
Sol 7: O ||
||
(i) Me MgBr N Br
(ii) aq. HCl
OMe
Sol 12:
Me MgBr [Gignards Reagent] O
O
|| ||
dil alkali
|| ||
Me OMg Br Me OH
O O
HCl
O
|| O
OMe OMe ||
Sol 8:
Et–OH
O O

Br
H
O O
(Carbocation
Rearrangement)

(Elimination) OH
H
Sol 13: R D
D2O
R–CC–H C=C
Cl OH NaOD
Boil/alkali :OD H
CH3–CH2–CH CH3–CH2–CH D
Cl OH
R C H
C
two OH groups on same C, || D
unstable hence dehydration O
D2O
CH3–CH2–CHO
D
D R
R R D C H
Sol 14: C D D2O C
C D C D || D
KOH || DO
CH3O CHO + HCHO O OD
(Cannizaro Reaction)
Sol 16:
O O
MeO CH2OH + HCOOH || .. HNO3/H2SO4
||
CO CO NO2
(mono)
Here, alcohol is formed on the phenyl ring
Note :- as the (MeO –) group. Favours +ve charge Deactivated Activated
(stabilizes) O O
|| .. ||

CO
HNO3/H2SO4
CO NO2
(mono)
Sol 15:
Br
Deactivated Activated
Sol 17:
Br2/CCl4 Br NaNH2
OH
(trans addition) |
OH COOH
O ( NH2 - Nuclophile) (CH3CO)2O

|| NaOD/D2O
CH3COONa
CHO
HgSO4/H2SO4 (excess)
This is a very standard example of Perkin’s condensation
O
|| {If possible remember it}
NH2 – C – NH–NH2
O Sol 18:
|| D
NH NaOH
NH NH2 A+B C=CCHO
D
D | |
O H H
Mechanism with NaOD/D2O (excess) {Aldol condensation}

CHO
+ CH3CHO
(Desired product)
Sol 19: Sol 23:

O red P/Cl2
|| CH3–COOH ClCH2–COOH
(1 eq.)
CH3–COOH + NH3 CH3–C–NH2
(excess) NH3
(HVZ reaction)
Br2/KOH
CH3–CH2–NH2 CH3–CN O
Step 1 is : Nucleophilic substitution of –OH by –NH2 ||
CH2–C–NH2
Step 2 is : Clearly dehydration |
Step 3: Hoffman Bromanide Reaction (through the NH2
intermediate R–N=C=O)
( NH2 is a nucleophile)
Sol 20: CH3–CH2–OH
(O)
CH3–CH=O
Sol 24:
(i) Cl2
HCOOH
(ii) dil NaOH O O
+ CHCl3 (A)
HgSO4 NaOI
[Chloroform reaction]
H2SO4
OH
Iodoform → presence of α-hydrogen (B)
+ CHI3
Br
Sol 21: |
P and Br2
CH3–CH2–COOH CH3–CH–COOH
Br
| (Iodoform Reaction)
P and Br2
CH3–CH2–COOH CH3–CH–COOH
Br
| Sol 25:
Br
OH H
| CH3
alc. KOH Br2/Hv
CH3–C–COOH
OH CH4 CH3 Br
| (A) AlCl3 (anhyd) (C)
alc. KOH
CH3–C–COOH
OH (B) Cl2/hv
| (2 eq.)
OH
CHO OH Cl
dehydration CH CH
OH H2O/H Cl
dehydration
CH3–C–COOH (D)
||
CH3–C–COOH
O
CHO COOH
|| CH3COONa (anhy.)
red P/Br2 → Hell – Volhard Zelinski
O Reaction (HVZ)
[α - bromination]
(CH3CO)2O
[Perkin]
Moist H2SO4 C2H5OH C2H5OH
Sol I AgCO2H5CI 2Moist
C2H522: H5OHC2H5OHCHH22=CH
SO4
2 2=CH2
CH
2 Ag2O 140°C 140°C (D)
(A) (A) (B) (B)
..
.. .. NH2OH N
C2H5–OH C
2H5–OH

CH2 = CHCH
2 2 = CH2 CH2 – CHCH
2 –2 O – C22H
– CH – 5O – C2H5 (F) H OH
| |
H H (Mechanism)
C2H5–O–C H55–O–C2H5
C22H
∴ (C) → Et – O – Et
Perkins O
|| ..
CHO O (iii) In formic acid H–C–O–H
.. (I)
O O
| O O
C O || ||
C C
CH3 CH3 O CH3 O–
|
+ H–C=O–H (II)
COOH CH3COO
Structure (I) is more stable than structure (II)
OH O
COOH
| || So C=O bond length will be less than C–O in (I)
H O
+ ()
But in sodium formate resonance is equivalent
O O–
|| |
Sol 26: (i) Higher carbonyl compounds aare insoluble H–C–O H–C=O
in water due to more covalent character.
(iv) Because in the first step cleavage of ester is done
(ii) Bisulphites of O are soluble in water which is diffcult to do.
(v) Because in addition reaction, electron donating
∴ Carbonyl compounds form solid additive products
with NaHSO3 which are separated out. The solid tendency of C=O and C=C are different
bisulphites of carbonyl compounds on hydrolysis by dil.
acid regenerate original carbonyl compound. C=C is better than C=O
(iii) Oxidation of toluene with chromium trioxide to
benzaldehyde is carried out in presence of acetic
anhydride because it converts benzaldehyde into its Sol 28: (A) C9H12O
diacetate so preventing its further oxidation to acid form. (i) Optically active
(iv) This is because aldehyde is more volatile than (ii) acidic hydrogen –OH
corresponding acid or alcohol.
O
(v) In a carboxylic acid, there is a pair of electrons on
(iii) –C–CH3 group
the oxygen in conjugation with carbonyl oxygen. This
prevents the creation of a positive centre at carboxyl
carbon. Therefore nucleophilic addition of phenyl (iv) C==C do not present
hydrazine to give phenyl hydrazine is not possible.
hot H+
O (v) (A) (B) ←
|| KMnO 4 C7H6O2
Sol 27: (i) OH is more acidic than O

O ||
|| + Cl – C – Cl
Si
OH because Si has empty orbital so can do
backbonding and by this decreases the acidity.
P
(ii) After first ionisation maleic acid ion is stabilised by (vi) (A) →
HI
(e)
Optically
hydrogen bonding but there is no such stabilisation in inactive compound
fumeric acid.
O (vii) 2 alcohol
O
C O– OH
O– C
H H
C O C O H CH3
||
O O (A)
(A) →
Mallic fumaric
acid
H Sol 3: (A)
Sol 29: × 40 = 8 H
−4
5 × 10
NaBH4
moles
DT = kg m O
H–
O-
mass in kg
0.088 H
= 10−6
M D2O
mass = 88 OD
68.18
carbon atom = ≈ 12 Sol 4: (B)
12
O OH+ OH
oxygen = 1

Al2 O3
(A) O3
(B) (C) + (D) C–H C–H C–H

350C 802 H O 14 H 14 14
CH2 CH2 CH2
–OH
Group C–H C–H C–H
Present
O O O
C5H12O
Zn
fehling
test
OH OH
H
OH
OH C C–H
14
HCl 14 14
CH3–C–C–H CH2 C–H : CH2
(D) O
O H O O– C–H
||
(A) (B) (C) CH3–CH By O
Further Reduction
14
CH3–CH2–CH3
Exercise 2
Single Correct Choice Type Sol 5: (B)
SH S
NaOH
Sol 1: (C) 2 MeCH–CHO MeCH–CH2– OH OH
∆ dry
OH + MeCH–COONa HCl
O
Cannizzaro reaction OH OH
Sol 2: (C)
S S
CH2–Cl
O
PPh3 Ph–Li O OH
Ph3P–CH2Cl Ph3P–CH
OH –OH OH
Ph
H+
O Ph3P=CH Sol 6: (A) CH3–CH2–CH2OH CH3–CH2–CHO
K2Cr2O7
+ (A) (B)
H–C–H
+ Ph3–P=O + LiBr
B forms a shining silver mirron on wesming
NH2 NH CONH2 Sol 11: (B) Hydration will occur at position 2 as carbon
CH3–CH2–CHO at positive 2 has maximum δ+ charge due to –I effect of
(B) other carbonyl groups.
CH3CH2CH=N NH CO NH2
Sol 12: (C) CH3–CH2–COOH + CH3–COOH
Ca
O O CH3–CH2–C–CH3
OH distillation
Na2 CO3 O
Sol 7: (C)
Sol 13: (C) NaBH4 is weak reducing agent. So it will
aldol condensation will occur as Na2CO3 is a base. reduce only the ketone but LiAlH4 is strong reducing so
it will reduce both ester and ketone.
Sol 8: (A) O
H O
H3O Sol 14: (C) CH3–CH2–OH & CH3–C–CH3
O H
LAN oxidises alcohol to aldehyde or ketone so only
CH3–CH2–OH will give positive test.
It will not
Give iodoform Sol 15: (B)
test O
O
–C–CH2–CH3 + CH2=O
+
H O
It will give positive –C–CH–CH3

iodoform test
CH2–OH
Sol 9: (D)
best
N–C2H5 NH–C2H5
most reactive carbonion C=O
CHO C–H CH2
group
–
H O
+ C2H5NH2

–C–CH–CH3
Sol 10: (C)

H2O
+ Sol 16: (B) Aromatic aldehydes do not give positive
OH OH
OH test with Fehling’s solution.
OH

Sol 17: (B)
+
H
O
H O C
MeO
OH OH COOMe
+
H NaBH4

Sol 18: (D) O

OH OH Br2
(C) Ph–C–NH2 Ph–NH2
NaIO4 KOH
CH2–CH–CH–CH–CH–CH2 2HCHO + 4HCOOH
OH OH OH OH Hoffmann
Brommamide
Sol 19: (D)
O NH
Br O
N2H4/KOH HN3
CH3–CH2–CH–C–CH3 (D)
H2SO4
Br
Sol 22: (B, C, D)
CH3–CH2–CH–CH2–CH3
(A) H
KOH/ O
(B) CH–CH3
CH3–CH=CH–CH2–CH3
O
So only Iodoform can distinguish between them.
Multiple Correct Choice Type
Sol 20: (B, D) Aldehydes gives 2, 4-DNP test so (x) Comprehension Type
should have aldehyde x gives negative Iodoform ⇒ Sol 23: (C)
–C–CH3 group is absent so possible structure of (x) are O O

OH
(CH3)3–C–CH2 (CH3)3–C–CH2
O
Br–Br
CH3–CH–CHO & CH3–CH2–CH2–CHO H OH
O
CH3
(CH3)3–C–CH2Br
Sol 21: (A, B, D)
O OH
O
(A) OH
H+ (CH3)3–C–CH3 (CH3)3–C=CH2
C=N C–NH–CH3

Br–Br
CH3
OH
(B)
14 H R–C–CH2Br + HBr
Ph–Li
C=C
Cl
CH3 O
14
CC CH R–C–CH2–Br
Sol 24: (B) Overall yield = 0. 58 × 0. 54 × 0. 68 Sol 26: A → r; B → r, s; C → q, s; D → p

Overall yield = 0. 21 = 21% O
Me Conc. H2SO4
(A) C=N Me–NH–C–Et
Sol 25: A → p, q, s; B → p; C → p, q, s; D → p, q, s Et
OH
(A) O
O
O OH
MCPBA O
CN (B)
HCN LiAlH4

traces of KOH +
+ N3H N3
(C) +
H HN3 +
-H
OH
CH2–NH2
NaNO2 (D) CHI3
Carbene
HCl KOH (excess)
formation
O OH OH OH
⊕ ⊕ Previous Years’ Questions
⊕
O
||
Sol 1: (A) CHO + H – C–H
O N–OH
NaOH
–CH2OH+H–COONa
H2O
+
NH2OH H
(B)
This is an example of cross Cannizzaro reaction in which
formaldehyde is always oxidized.
OH
O Sol 2: (C) The reactivity of carbonyl compound towards
CH2
nucleophilic addition of Grignard’s reagent depends on
NH LAH NH extent of steric hindrance at α-carbon. Greater the steric
hindrance smaller the reactivity. Hence. reactivity order is
O CH3CHO>CHl3–CO–CH3>Ph –CO–Ph
OH– II I III
(C) CH3–C–CH2–CH2–CH2–C–H
O O Sol 3: (C) X is (CH3CO)2 O and it is an example of Perkins

reaction.
(D) Ph H Ph CH3 NaOH
CH3 CH3 I2/H2O
Sol 4: (C) H3C ||
OH OH OH O
+
H
CHI3 + CH3CH2COONa CH3CH2COOH
Ph
Ph
CH3
O CH3
OH
Sol 5: H Comprehension 1 (Questions 9 to 11)

H2C = O + H2N–OH C=N–OH (Single)
H Sol: Q.9 B, Q.10 A and Q.11 B

O
|| CH3
AlCl 3
CH3–C–H+H2NOH + CH3Cl
CH3 OH H3C (two)

C=N + C=N Friedel -Crafts alkylation
H H OH
CH3
CH3MgBr
Sol 6:
O O CH3
COOH || H P
CH3
Zn–H2O H || +
H /H2O
O CH3
CH3
KOH Q
H2O (gives possible iodoform test)
intramolecular aldol condension CHO

CH3
reaction O3
Q
Zn-H2O
Sol 7: O
H3 C CH3
H3C H3C
R
O + C6H5NH2 C=N–C6H5
H3C H3C
–
H3C OH
aldol
C=N–C6H5 + C6H5NHNH2 O
H3C S
H3C OH
|
C=N–NHC6H5
H3C + CHCl3 + NaOH
OH
Sol 8: In both Friedel-Crafts reaction and Reimer- |
CHO
Tiemann’s reaction new carbon-carbon bond is formed. H+
CH3
AlCl 3
+ CH3Cl Reimer-Tiemann's reaction
All those carbonyl compounds containing α-H to sp2

Friedel -Crafts alkylation carbon show keto-enol tautomerism.
Comprehension 2 (Questions 12 to 14)
Sol: Q.12 B Q.13 A and Q.14 D

The given product an ester, obtained by condensation
of a hydroxy acid obtained through hydrolysis of a
cyanohydrin –
CH3 OH S is obtained by nucleophile addition of HCN on R,

hence R is
CH3 —C—CH
+
H3 C OH CH3 O CH3 OH
H
CH2 C=O
H3 C
H3C —C—CH—H+HCN H3C —C—CH—CN
HO
OH O O CH2OH CH2OH
R S
Acid above is obtained by acid hydrolysis of cyanohydrin
S as R is obtained by treatment of P and Q aqueous K2CO3
CH3 OH CH3 OH Through aldol condensation reaction as
+
H
H3C —C—CH—CN H3C —C—CH—COOH CH3 O CH3
H2O
–
OH
CH2OH CH2OH CH3–CH–CHO+H–C–H OHC–C–CH2OH
S
P+Q CH3
R
Sol 15: A → p, q; B → q, r; C → q, r, s; D → q, r
NO2 O2N
(A)
PhCHO+O2N NH NH2 PhHC=N NH NO2

(ppt.)
NH3
PhCHO+Ag2O PhCOO- + Ag
(white ppt.)
CN
KCH
PhCHO Ph C O-
H
Ammonical AgNO
(B) CH3C ≡ CH 
3 → CH C ≡ C − Ag+
3
White ppt
CN
KCH
(C) PhCHO Ph C O-
(D) AgNO3 + CN− → AgCN ↓

AgNO3 + I − → AgI ↓
Sol 16: (1)

O
I) O3 O NaOH
O
II) Zn3/H2O
Sol 17 and 18: (C) and (A)
CHO CH=CH-COOH CH2-CH2-COOH

(CH3CO)2O H2-Pd/C
CH3COONa
I J
CH2 CH2 C Cl
SOCl2 AlCl3
O
K O
Sol 19: (C)
OH
O CH2
(i) OH- (i) OH-
H3C C H HO CH2 CH2 CH=O HO CH2 C CH=O
(ii) H-CH-O (ii) H-CH-O
(aldol) (aldol) H O
-
(i) OH (ii) H-C-H
(aldol)
OH
O OH OH
CH2
H C O + Conc. NaOH+HCHO
HO CH2 C CH=O
Crossed Cannizzaro reaction
HO OH CH2
OH
Sol 20: (B)
CN
CN- 95% H2SO4
HCN
O OH CN
(G)
Sol 21: (B, D)

OH O OH
CHO
CHCl3
OH
CH3 H3C CHCl2 CH3 (Mnjor)

(Minor)
CHCl3+OH : CCl2+H2O+Cl-
OH O-
+ OH + H2O
CH3 CH3
O- O O- OH
CCl2 CHCl2 CHO
+ :CCl2 OH
H
CH3 CH3 CH3 CH3(Major)
O- O O
H2O
CH3 :CCl2 H3C CCl2 H3C CHCl2(Minor)
Sol 22: (C) Solve as per law of limiting reagent.
OH OH
O +
C -H+ C
C + H+ H3C CH3 H2C CH3
H3C CH3
O
Br2
Br-+BrCH2 C CH3
Sol 23: (D) PCC (Pyridinium chlorochromate) is a mild oxidising agent. It oxidises alcohol to aldehyde.
Sol 24: (A, B, C, D)

CHO
CO, HCl
(I) Anhydrous AlCl3/CuCl
CHCl2 CHO
H2O
(II) o
100 C
COCl CHO
H2
(III) Pd-BaSO4
CO2Me CHO
DIBAL-H
(IV)
Toluene, -78oC
H2O
Sol 25: (A)
O O
OH
CH2 CH
CH3 CH3
O O
H2O
CH3 CH3
OH
O O
H+ , H2O/
Sol 26: (A, B, C)
CHO OH
Ph
CH2 = CH CHO, and Ph
O
Gives positive test with Tollen’s reagent.
Sol 27: (C) NaBH4 in C2H5OH selectively reduces aldehydic group.
Sol 28 : (A)
CH3
O CH3
CH3 C CH
O C CH
C CH CH3 CH3
CH3 O CH2 OH O
CH3 CH2OH
CH3 C CH
C CH CH3
O O CH2 O
CH3
CH2OH

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Chem i str y | 23.

Conc.HNO₃ SOCl₂ (i)NaBH₄

Conc. HNO₃ SOCl₂

-SO₂ SOCl₂ (i) NaBH₄

COOH CHO CH₂OH

Example 2: Identify A to E in the following series of reactions:

Pot. benzoate (D) Benzaldehyde (B)

Benzoic acid (E) Benzyl alcohol (C)

Sol: (a) The reaction is Claisen-Schmidt condensation.

Thus, Y = (i) Alk. KMnO4, (ii) H+, H2O

Example 4: (a) Identity A, B and C in the following reaction

2 4→ dil.H SO Tautomerises dil.NaOH

Sol: (b) (i) Higher the K a stronger is the acid.

CH₂CH₃ COO-K+ COOH

(b) COCH₃ COO-K+ COCH

Br₂/FeBr₃ Mg/dry ether (i) Dry ice

CH₃ CH₃ CH₃

Benzene Toluene o-Nitrotoluene

Separate by (I) KMnO₄/KOH,

filtration (ii) Dil.H₂SO₄

Benzyl cyanide Phenylacetic acid

Example 10: Give reasons for the following:

Hydroxylamine Conjugate base

CH₃ CO CH₂ H + O I CH₃COCH₂ + H O I

(a) α-Halocarbonyl compounds, even the 3° types like

Example 4: Complete the following reaction

Example 5: Complete the following reactions:

(i) H₂+Pd+ BaSO₄

(b) Give the major products of the following

(b) Bulky-1-butyl group always occupies less hindered equatorial in cyclohexane.

Me₃C H (OH) and (t-Bu) gps, are in trans

trans-position (OH) in up ( ) and

(t-Bu) in down ( ) position

cis position: both down ( ) position.

Example 6: Complete the following reactions:

Ac₂O + AlCl₃ 2 EtOH/HCl 1. Mg

- PPh₃ OTs PhLi

SPh₂ Me₂C O - SPh₂

Example 7: Complete the following reactions:

Sol: (a) In this reaction, 4 products are possible.

(ii) Aldol condensation of (B)

(B) Esterification with EtOH

Example 8: Complete the following reaction:

H₂/Pd HCN Conc. HI or HBr Ac₂O + AcONa

(B,C,D, E all are isomers of C8H9NO) (D) + (E)

Sol: Degree of unsaturation = 5° (aromatic and ketone), i.e. Beckmann rearrangement

PhCOOH + CH3NH2 CH3COOH + PhNH2

Example 10: Complete the following:

Sol: (a) CH O + H₂ N.N H₂+O CH CH N N CH

(b) (i) with Tollen’s regent, it will form PhCOOH

Exercise 1 Q.8 Write the names of the reagents and equations in

(i) Methanal (ii) 2-Methylpentanal

(iii) Benzaldehyde to Benzophenone

Q.18 Give possible explaination for each of the

vigorous oxidation it gives ethanoic and propanoic

Q.22 Which of the following compounds will give (A) O O

(iv) HCOOH (v) CH3–C–C–CH3

addition followed by aldol condensation of reactants R Major product (X) is

CH3O OCH3 CH3O OCH3

Separate by (I) KMnO₄/KOH,

Major product is. (2003) CH3

Previous Years’ Questions Q.3 What is X? (2005)

Q.8 A new carbon bond formation is possible is (1998) O