CARBONYL COMPOUNDS (OR)

ALDEHYDES & KETONES

 It is polar due to high electronegativity of oxygen

SYNOPSIS
  
CO  C O
Aldehydes and Ketones
 General formula of both aldehydes and ketones
is Cn H 2 nO Nomenclature: Aldehydes
Common System
 Aldehydes and ketones are collectively called
carbonyl compounds because both have carbon  Aldehydes names are derived from
corresponding Carboxylic acids to which they
C  O ) called carbonyl are oxidised. The suffix ‘ic acid’ is replaced by
oxygen double bond (
aldehyde.
group In IUPAC system aldehydes are named as
 In aldehydes carbonyl group is linked to one Alkanals.
alkyl or aryl group and one H - atom.  The position of the substituents on the parent
chain is indicated by Greek letters
Aldehyde group is monovalent group and chain
 ,  ,  ...........etc. The  - carbon is linked
terminating group.
directly to CHO group and  -carbon is the
 In Ketones, Carbonyl group is joined to two next and so on.
alkyl groups or two aryl groups or one alkyl and Ketones
one aryl group.
In case of simple ketones they are named as
 Ketone group is bivalent and non chain dialkyl ketones.
terminating group. In case of mixed ketones - names of Alkyl groups
 If the two groups attached to carbonyl group are prefixed in alphabetical order.
are same then they are called simple ketones. In IUPAC system Ketones are named as
 If the two groups attached to carbonyl group Alkanones.
are different then they are called mixed ketones. Isomerism: Aldehydes (Mains)
Aldehydes show chain isomerism, funcitonal and
O O O Tautomerism. Ketones exhibit chain, position,
|| || || functional, metamerism and tautomerism.
R C  H R C  R (or) R  C  R1
aldehyde simple ketone mixed ketone Isomerism Minimum No. of carbons
STRUCTURE OF CARBONYL GROUP Aldehydes Ketones
Chain 4 5
 Carbonyl carbon is Sp 2 hybridised Position - 5
 It has 3Sp 2 hybrid orbitals and one unhybridised Functional 2 3
p-orbital. Metamerism - 5
Tautomerism 2 3
 It form 3 bonds .
 Bond angles are approximately 1200 .
 Shape is trigonal planar.
Common and IUPAC names of some aldehydes
Formula Common name IUPAC name
HCHO Formaldehyde Methanal
CH 3CHO Acetaldehyde Ethanal
CH 3CH 2CHO Propionaldehyde Propanal
CH 3 2 CHCHO Isobutyraldehyde 2-Methylpropanal
CH 3CH 2CH 2CH 2CHO Valeraldehyde Pentanal
CH 3  CH 2  CH  CH 2  CHO   Methyl valeraldehyde 3-Methyl pentanal
|
CH 3

CH 2  C H  CHO Acrolein Prop-2-enal

CH 3  CH  CH  CHO Crotonaldehyde 2-Butenal
Benzaldehyde Benzenecarbaldehyde

Cyclohexanecarbaldehyde Cyclohexanecarbaldehyde

p-Nitrobenzaldehyde 4-Nitrobenzenecarbaldehyde

Phthalaldehyde Benzene-1,2-dicarbaldehyde

Br   Bromobutyraldehyde. 3 – bromo butanal

|
CH 3  CH  CH 2  CHO
  
propane-1,2,3- propane-1,2,3-
tricarbaldehyde. tricarbaldehyde.

 -hydroxy 2-hydroxy cyclopentane

cyclopentane carbaldehyde
carbaldehyde

  methoxypropional 2 - methoxypropanal
dehyde

    - hydroxy 2 – hydroxyl butanal

CH 3  CH 2  CH  CHO butyraldehyde
|
OH
Common and IUPAC names of some ketones
Formula Common name IUPAC name
CH3COCH3 Dimethyl Ketone Propanone
CH3COCH2CH3 Ethyl Methyl Ketone Butanone-2
CH 3  CH  CO  CH  CH3 Di-isopropyl ketone 2,4-
| | Dimethylpentan-3-
CH 3 CH 3 one

CH 3  CO  CH 2  CH 2  CH 3 Methyl n-propyl ketone Pentan-2-one

 ,  ,   Trichlorodiethyl 2,2,4-
1
Cl
| ketone Trichloropentan-3-
CH 3  CH  CO  C  CH 3 one
| |
Cl Cl

 CH 3  2 C  CHCOCH3 Mesityl oxide 4-Methylpent-3-en-

2-one
Cl Cl  ,  1  dichlorodiethyl 1, 4 dichloro pent 3
| | – one
CH 3  CH  CO  CH 2  CH 2 ketone
  1 1
  methyl 3-methyl
cyclopentanone cyclopentanone

  oxovaleraldehyde 3-oxopentanal

Methyl phenyl ketone 1-phenyl ethanone

Or Acetophenone

Diphenyl ketone Benzophenone

Ethylbenzyl ketone 1-Phenylbutan-2-

one
Propiophenone or ethyl 1-Phenyl propan-1-
phenyl ketone one

COCH 3 Ortho fluoro 2 – fluoro

acetophenone acetophenone

F
 JEE MAINS - VOL - IX CARBONYL COMPOUNDS (OR) ALDEHYDES & KETONES
Chain Isomerism O
||
 Aldehydes and ketones exhibit chain isomerism CH 3  C  CH 3  CH 2  C  OH  CH 3
among themselves b.
CH 3
 keto form   enolform 
 Metamerism
CH 3CH 2CH 2CHO | Aldehydes do not exhibit metamerism because
CH 3  CH  CHO it is terminal functional group. Ketones being
Butanal
2  Methylpropanal bivalent exhibit metamerism.
O C2 H 5COC2 H 5 and C3 H 7COCH 3
||
CH 3  CH 2  CH 2  C  CH 3 3- pentanone 2-pentanone
2-pentanone Physical properties
 Physical State
CH 3
|
Formaldehyde is a gas while next 10 members
CH 3  CH  CO  CH 3 of aldehydes are colouless volatile liquids.
Ketones upto eleven carbon atoms are volatile
3-methyl 2-butanone liquids. The higher members are solids.
 Functional Isomerism Solubility
The functional isomers of the compound with  These are misible in organic solvents like benzene
ether, chloroform etc.
general formula Cn H 2 nO are Aldehydes,  The lower members containing upto 4 carbon
ketones, unsaturated alcohols, cyclic alcohol, atoms are soluble in water due to formation of
unsaturated ethers, cyclic ethers. hydrogen bond with water.
 The structural Isomers with the general  As the number of carbon atoms increases,
formula C3 H 6O solubility of aldehydes and ketones decreases.
Odour
1. CH 3CH 2CHO  propanal  Lower aldehydes have unpleasant sharp pungent
2. CH 3COCH 3  Acetone odour.
 As the number of carbon atoms increases, the
3. H 2C  CH  CH 2OH  prop 2-en-1-ol odour becomes less pungent and more fragrant,
4. CH 3  CH  CH  OH  -prop1-en-1-ol hence they are used in the blending of perfumes
and flavouring agents.
5. H 3C  C  OH   CH 2  prop-en-2-ol  Acetone is inflammable liquid.
OH Boiling points
 Aldehydes and ketones have higher Boiling points
 cyclopropanol
|
6. than ethers and alkanes of similar molecular mass
due to more dipole - dipole interactions in
7. O  methoxy ethene carbonyl coumpounds.
 Carbonyl compounds have lower Boiling points
8. O 1,3  Epoxy propane than alcohols of comparable masses due to
absence of intermolecular H - bonding in
O carbonyl compounds.
9. 1,2-epoxy propane
Ex: The B.P. order is
1 - Propanol (370K) > propanone (329K) >
Tautomerism: Aldehydes and ketones having propanal (322K) > methoxyethane (281K) >
 hydrogens exhibit tautomerism with Butane (273K)
unstaturated alcohol. Ex: the B.P. order of
CH 3  CH 2  CH 2  CH 2  OH 
O
||
CH 3  C  H  CH 2  CH  OH  CH 3  CH 2  CH 2  CHO 
a.
ethanal  keto form  ethenol  enolform  C2 H 5  O  C 2 H 5 
CH 3  CH 2  CH 2  CH 3
Ex: The boiling point order of
C2 H 5OH  CH 3CHO  CH 3OCH 3  C3 H 8
CARBONYL COMPOUNDS (OR) ALDEHYDES & KETONES JEE MAINS - VOL - IX
PREPARATIONS OF ALDEHYDES PREPARATIONS OF ALDEHYDES
1) By Partial oxidation of primary alcohols 1) By Partial oxidation of secondary alcohols
OH OH OH O
PDC or PCC
RCH2(O)
PDC or PCC
RCH RCR(O) RCR
CH2Cl2 CH2Cl2

Note: PCC does not attack double bond present H

in alcohols. Note: PCC is used in non aqueous medium
Primary alcohols on oxidation with PCC / PDC / Secondary alcohols on oxidation with PCC / PDC
Collins reagent gives aldehydes with same gives ketones with same number of carbons
number of carbons If strong oxidizing agents are used then carbonyl
PCC = Pyridiniumchlorochromate, compounds are further oxidized to carboxylic
(C5H5N+HCrO3Cl -) acids.
PDC=Pyridiumdichromate [(C5H5NH)2Cr2O7]
0
2) By dehydrogenation of 2) By dehydrogenation of 2 alcohols (Industrial
O method) O
Cu/Ag/300C Cu/Ag/300C
OH RCHH2 OH RCRH2

RCH O RCR O
Cu/Ag/air Cu/Ag/air
1 alchol RCHH2O 1 alcohol RCRH2O

Note: This method is best for volatile alcohols. Note: In this method there is no risk for further
oxidation of aldehydes and ketones
3) By the dry distillation of calcium salts 3) By the dry distillation of calcium salts
(ONLY MAINS) (ONLY MAINS)
(RCOO)2 Ca(HCOO)2 Ca Drystillation 2RCHO2CaCO3 (RCOO)2 Ca Drystillation RCORCaCO3
CalalkanoateCalformate Aldehyde Cal. alkanoate Ketone
Distillation
(HCOO)2 Ca HCHOCaCO3
Note: This is method is suitable for the
Note: This method is not suitable for the preparation of only symmetrical ketones.
preparation of aldehydes except formaldehyde Calcium salts of dicarboxylic acids produce 5 – 6
because we get mixture of carbonyl compounds. membered cyclic ketones.
4) By the reduction of Carboxylic acids (ONLY 4) By the reduction of Carboxylic acids (ONLY
MAINS) MAINS)
MnO2 MnO2
RCOO  HCOOH RCHOH2OCO2 RCOOH  R COOH
1
RCOR H2OCO2
1

Carboxylic Formic 300C Carboxylic Formic 300C

acid acid acid acid

MnO2 MnO2
CH3COOH  HCOOH CH3CHOH2OCO2 CH3COOH  C2H5COOH CH3COC2H5H2OCO2
acetic acid Formic acid 300C acetaldehyde acetic acid Propanoic acid 300C 2-butatone

Note: The number of carbon atoms in aldehyde Note: Mixture of fatty acid and formic acid
or ketone formed is equal to sum of the carbon vapours forms mixture of aldehydes and ketones.
atoms in two moles of acid
5) By the Hydrolysis of alkenes ( Wacker's 5) By the Hydrolysis of alkenes ( Wacker's
process) (ONLY MAINS) process) (ONLY MAINS)
CuCl2(or) CuCl2(or)
CH2=CH2+PdCl2  H2O CH3CHOPd2HCl Ch3CH=CH2PdCl2 H2O CH3COCH3Pd2HCl
CdCl2 CdCl2

Note: Ethene gives acetaldehyde Note: All alkenes except ethene gives ketones
JEE MAINS - VOL - IX CARBONYL COMPOUNDS (OR) ALDEHYDES & KETONES

6) Reductive ozonolysis of alkenes 6) Reductive ozonolysis of dialkyl substituted

alkenes
i.O3 i.O3
CH2=CH2 2HCHO R2C=CR2 2RCOR
ii.H2O/Zn ii.H2O/Zn
7) By the hydrolysis of alkynes (Kucherovs 7) By the hydrolysis of alkynes (Kucherovs
reaction) OH reaction )
HC  CH
40%H2SO4 tautomerism 40%H2SO4
1%HgSO46070c
CH3CHO CH2=C H RC  CH RCOCH3
1%HgSO46070c

Note: Only acetylene gives aldehyde Note: All alkynes except acetylene gives ketones.
Formaldehyde cannot be prepared by this Product formed is according to Markonikoff rule.
method.
8) Hydroboration Oxidation of terminal 8) Hydroboration Oxidation of non terminal
alkynes (ONLY MAINS) alkynes (ONLY MAINS)
i.BH3 / THF rearrangement i.BH3 / THF rearrangement
ii.H2O2 / OH  ii.H2O2 / OH


OH O OH O

Note: Disiamyl borane is better used in place of Note: product formed is according to Anti
B2H6 to avoid complications due to double markonikoff rule.
addition of diborane. Unsymmetrical nonterminal alkynes give
mixture of ketones.
9)By alkaline Hydrolysis of Terminal Gem 9)By alkaline Hydrolysis of Non terminal Gem
dihalides dihalides
X OH O X OH O
-2KX -H2O -2KX -H2O
RCH2KOH RCH RCH RCH2KOH RCR RCR

X OH X OH

Note: This method is not much used because the

aldehydes are affected by alkali and
Gemdihalides are usually prepared from
carbonyl compounds
CARBONYL COMPOUNDS (OR) ALDEHYDES & KETONES JEE MAINS - VOL - IX
Relative Reactivity of Carbonyl
Chemical properties Compounds
 Aldehydes and ketones both possess highly polar  Aldehydes are generally more reactive than
carbonyl group so they undergo similar chemical ketones in nucleophilic addition reactions due to
reactions. steric and electronic reasons.

   Bulky groups offer steric hindrance and decrease
C O
the reactivity towards nucleophilic addition.
CO    I effect decreases the positive charge on
carbonyl carbon and decreases the reactivity
 The carbonyl group has two active centres, the towards nucleophilic addition reactions.
positively charged carbon is readily attacked by   I effect increases the positive charge on
electron rich nucleophiles. The negatively charged carbonyl carbon and increases the reactivity
oxygen is attacked by electron defficient towards nucleophilic addition reactions.
electrophiles. However during addition reactions  Due to  R effect of benzene ring, the aromatic
nucleophilic attack produces the anion which is carbonyl group is less electrophilic and hence
more stable than the cation. Attack of nucleophile aromatic aldehydes and ketones are less reactive
on electrophile is rate determining step. Thus than corresponding aliphatic aldehydes and
carbonyl compounds undergo nucleophilic ketones.
addition reactions.  Ex.1. Order of reactivity in carbonyl compounds
 Nucleophilic addition mechanism is
 If the attacking nucleophile is strong, it will readily HCHO  CH 3CHO  C2 H 5CHO 
attack the carbonyl carbon. The resulting addition
product can be readily protonated by the solvent CH 3COCH 3  CH 3CH  CH 3  COCH 3 
(or) by the added acid.
O
||
 CH 3 2 CHCOCH  CH 3 2
R  C  H / R1  Z  :   Ex.2- Chloral is more reactive than acetaldehyde.
 Ex.3- Comparitive reactivity of
H

CHO  COCH 3  CO
 A poor nucleophile requires an acid catalyst to
make the nucleophilic reaction occur at a
reasonable rate. The acid protonates the  Ex. 4- Compare the reactivity of
carbonyl oxygen, thus increasing the susceptibility
of the carbonyl carbon to nucleophilic attack.


 H
  

 Z :
H 

 If the attacking atom of the nucleophile has a pair 4 1 2  3

Ex: 5 - Benzaldehyde < Propanal
of nonbonding electrons in the addition product, Ex.6 -Butanone < Propanone < Propanal <
water will be eliminated from the addition Ethanal
product. Hence the reaction is called as
nucleophilic addition - elimination reaction.

R  C  H / R1  H 2O
||
Z
JEE MAINS - VOL - IX CARBONYL COMPOUNDS (OR) ALDEHYDES & KETONES
PROPERTIES OF ALDEHYDES PROPERTIES OF KETONES

1. Addition of sodium bisulphite 1. Addition of sodium bisulphite

OH OH
NaHSO3 | |
 H
NaHSO3

CH 3CHO   
 
 
CH
 
  C 
CH 3COCH 3    
 
CH
 
 C  CH 3
dil H  3
| dil H  3 |
SO3Na SO3Na

Acetaldehyde sodiumbisulphite
Acetonesodium bisulphite
Note: This test is used for the separation and
purification of carbonyl compounds from Note: Among aromatic aldehydes and ketones,
noncarbonyl compounds. benzaldehyde forms a sodium bisulphite adduct
The addition product is white ppt and water but acetophenone does not due to steric reasons.
soluble it can be converted to the original
carbonyl compound by treating with dilute mineral
acids or alkali

2. Addition of hydrogen cyanide 2. Addition of hydrogen cyanide

OH OH
| |
3  C H
CH 3COCH 3  HCN  3  C  CH 3
Base
CH 3CHO  HCN   
Base
 
CH

 CH

| |
CN CN

acetaldehyde cyanohydrin acetone cyanohydrin

Note: It is a reversible reaction and forms Note: only unsymmetrical ketones with HCN
Racemic mixture. forms Racemic mixture.
This reaction occurs very slowly so catalysed by Cyanohydrins are important synthetic
base. CN  is a strong nucleophile substances since on hydrolysis they give

 HCN  OH 

carboxylic acids and on reduction forms 10
 H 2O  CN  . amines with same number of carbons.

3. Addition of Grignard Reagent 3. Addition of Grignard Reagent

OH OH
| |
CH 3  Mg  X / Hydrolysis
CH 3  Mg  X / Hydrolysis
CH 3CHO  CH 3  C  H CH 3COCH 3  CH 3  C  CH 3
|
| CH 3
CH 3
2- methyl 2 - propanol
Isopropylalcohol
Note: Ketones with grignard reagent forms
Note: Formaldehyde reacts with grignard reagent
addition compounds which on hydrolysis forms
and forms addition product which on hydrolysis
gives 10 alcohols. 30 alcohols.
Other aldehydes give 20 alcohols.
4. Addition of alcohols 4. Addition of alcohols
a. Catalysed by acid in 1:1
OH R CH 2OH
|
CH 3CHO  R OH 
 dry HCl
 C H CO 
dry HCl

  
1
dil . HCl
CH
 3 dil HCl
| CH 2OH
OR1
R
Unstable Hemiacetal ethylene glycol
CARBONYL COMPOUNDS (OR) ALDEHYDES & KETONES JEE MAINS - VOL - IX
b. Catalysed by acid in 1:2
O  CH 2
R
CH 3CHO  2 R OH 
dry HCl


1



dil . HCl
C
OR1
| R O  CH 2
CH 3  C  H  gem di alkoxyalcohol 
|
OR1
ethylene glycol ketal
stable acetal Note:1) Ketones do not ordinarily react with
1) Acetals and ketals are hydrolysed with monohydric alcohols but react with dihydric
alcohols to form cyclic ketals.
mineral acids to give corresponding aldehydes
and ketones respectively. 2) Dry HCl protonates oxygen of Carbonyl group
and increases the electrophilicity of the carbonyl
carbon thus facilitating nuclophilic attack.
5. Addition of ammonia
5. Addition of ammonia
H

CH 3  C  O  NH 3 
|
H CH 3  C  O  NH 3 
|
NH 2
CH 3
|
CH 3  C  OH 
H O
 CH 3  CH  NH NH 2
|
2
 CH 3  C  CH 3   NH
|
H CH 3  C  OH 
H O
| 2
acetaldehyde ammonia acetaldehydeimine CH 3

Note: (1) Formaldehyde reacts with ammonia to acetone ammonia acetoneimine

form Hexamethylenetetramine which is used as Note: Ketones give variable products with
urinary antiseptic under the name urotrophine. ammonia.
(2) Benzaldehyde reacts with NH 3 to form
hydrobenzamide.

6. Addition of amino alkane  R  NH 2  6. Addition of amino alkane  R  NH 2 

CH 3  C  O  H 2 NR  CH 3  C  NR CH 3  C  O  H 2 NR  CH 3  C  NR
| | | |
H H CH 3 CH 3
substituted acetaldehyde imine substituted acetone imine
7. Addition of hydroxyl amine  NH 2OH  7. Addition of hydroxyl amine  NH 2OH 

CH 3  C  O  H 2 NOH  CH 3  C  NOH CH 3  C  O  H 2 NOH  CH 3  C  NOH

| | | |
H H CH 3 CH 3

acetaldehyde oxime acetone oxime

8. Addition of hydrazine  H 2 N  NH 2  8. Addition of hydrazine  H 2 N  NH 2 

CH 3  C  O  H 2 N  NH 2  CH 3  C  N  NH 2 CH 3  C  O  H 2 N  NH 2  CH 3  C  N  NH 2
| | | |
CH 3 CH 3
H H

acetaldehyde hydrazone acetone hydrazone

JEE MAINS - VOL - IX CARBONYL COMPOUNDS (OR) ALDEHYDES & KETONES

9. Addition of phenyl hydrazine 9. Addition of phenyl hydrazine

 H 2 N  NHC6 H 5   H 2 N  NHC6 H 5 

CH 3  C  O  H 2 N  NHC6 H 5 CH 3  C  O  H 2 N  NHC6 H 5
| |
H CH 3

 CH 3  C  N  NHC6 H 5  CH 3  C  N  NHC6 H 5
| |
H CH 3

acetaldehyde phenyl hydrazone acetone phenyl hydrazone

10. Addition of 2, 4 – Di nitro phenyl hydrazine 10. Addition of 2, 4 – Di nitro phenyl hydrazine
(2, 4 DNP test) (2, 4 DNP test)
CH 3  C  O H 2 N  NH CH 3  C  O  H 2 N  NH
|
H NO2 |
CH 3 NO2

NO2
NO2

CH3 C  N  NH
|  CH 3  C  N  NH
H NO2 |
CH3 NO2

NO2 NO2
acetaldehyde2,4dinitro acetone 2,4dinitro
phenyl hydrazone phenyl hydrazone

Note: 2, 4 – DNP derivatives are yellow, orange Note: 2, 4 DNP is called Brady’s / Borsche’s
or red solids used for identification carbonyl reagent
compounds.

11. Addition of Semi Carbazide 11. Addition of Semi Carbazide

*
CH 3  C  O  H 2 N  NHCO N H 2
*
CH 3  C  O  H 2 N  NHCO N H 2
|
|
CH 3
H
* *
 CH 3  C  N  NHCO N H 2  CH 3  C  N  NHCO N H 2
| |
H CH 3

acetaldehyde semi carbazone acetone semi carbazone

*
NOTE: The hydrogen of NH group is involved
2
in resonance so does not undergo condensation.
CARBONYL COMPOUNDS (OR) ALDEHYDES & KETONES JEE MAINS - VOL - IX
12. Addition of X 2 and KOH or NaOX 12. Addition of X 2 and KOH or NaOX
(Iodoform reaction) (Iodoform reaction)
CH 3CHO  3I 2  4 KOH RCOCH 3  3I 2  4 KOH
 CHI 3  HCOOK  3KI  3H 2O  CHI 3  RCOOK  3KI  3H 2O
Iodoform pot. formate Iodoform pot.carboxylate
RCOCH 3 
NaOX

Note:1) Ethyl alcohol only among 10 alcohols,
|
RCOONa  CHX 3  X  Cl , Br , I 
CH 3 C H  OH  containing 20 alcohols and Note:1) In haloform reaction aldehydes and
ketones are oxidized by sodium hypohalite to
aldehyde and ketones containing CH 3CO group carboxylic acids with one carbon less.
give yellow coloured crystals of iodoform. 2) This test is used to distinguish methyl
2) Haloform reaction does not effect ketones from other ketones.

13. Addition of Cl2 and HCl (Chlorination) 13. Addition of Cl2 and HCl (Chlorination)
h
h
CH 3CHO  3Cl2   CCl3CHO  3HCl CH 3COCH 3  3Cl2   CCl3COCH 3  3HCl
chloralor Trichloro acetaldehyde Trichloro acetone
Note: With Br2 / CH 3COOH mono
Note:   Hydrogens are replaced by Chlorine halogenation takes place
atom.

14. Addition of PCl5 (ONLY MAINS) 14. Addition of PCl5 (ONLY MAINS)
O Cl
|| |
CH 3  C  H  PCl5  CH 3  C  H  POCl3 O
||
Cl
|
CH 3  C  CH 3  PCl5  CH 3  C  CH 3  POCl3
|
Cl
|
Cl
ethylidene chloride
propylidene chloride
15. Oxidation 15. Oxidation
a.With strong oxidizing agents a. With strong oxidizing agents
H 
/ KMnO4 or K 2Cr2O7 or HNO3  H 
/ KMnO4 or K 2Cr2O7 or HNO3 
CH 3CHO  CH 3COOH
S .O . A.
W .O . A. CH 3COCH 3 
S .O . A.
 CH 3COOH
Note: Aldehydes on oxidation gives carboxylic Ketones on oxidation gives carboxylic acids with
acids with same number of carbon atoms. less number of carbon atoms according to
b. On oxidation with weak oxidizing agents like Popoff’s Rule.
Bromine water, Tollen’s reagent, Fehlings POPOFF’S RULE
solution, Shiff’s reagent, Benedict’s solution, During oxidation of unsymmetrical ketones keto
aldehydes give carboxylic acids with same group will be retained with lower alkyl group.
number of carbon atoms.
O18
These reagents are used to distinguish aldehydes ||
and ketones CH 3  C  CH 2CH 2CH 3 
oxidation

O18
||
CH 3  C  OH  CH 3CH 2COOH
JEE MAINS - VOL - IX CARBONYL COMPOUNDS (OR) ALDEHYDES & KETONES

c. Oxidation with SeO2 Note: Ketones are not oxidized by weak

oxidizing agents.
CH 3CHO 
SeO2
 CHO  CHO c. Oxidation with SeO2
Note: SeO2 oxidises alpha position in
CH 3COCH 3 
SeO2
 CH 3COCHO
cabonylcompounds to C  O group.
d. Oxidation with per acids (Baeyer villager Note: In this oxidation reactivity of CH 2 is more
oxidation) than CH 3 group.
RCHO 
 RCOOHper acid
d. Oxidation with per acids (Baeyer villager
Note: Per acids oxidize aldehydes to carboxylic oxidation)
acids
RCOR 
per acid
 RCOOR
Note: Per acids oxidize ketones to esters
16. Reductions 16. Reductions
a. with LiAlH 4 / H 2  Ni / NaBH 4 / Al a. with LiAlH 4 / H 2  Ni / NaBH 4 / Al
isopropoxide isopropoxide
O OH O OH
|| | || |
CH 3  C  H  CH 3  C  H
LiAlH 4
CH 3  C  CH 3 
LiAlH 4
CH 3  C  CH 3
| |
H H

ethylalcohol Iso propyl alcohol

Note: Aldehydes on reduction with LiAlH 4 gives Note: Ketones on reduction with LiAlH 4 with
primary alcohols gives secondary alcohols
LiAlH 4 can reduced acids, esters, amides and Reduction of ketones with Al isopropoxide is
nitriles called meerwein poundorfverley (MPV)
b. Clemmensons Reduction reduction which is the reverse of oppenauer
Zn  Amalgam
oxidation.
CH 3CHO 
Con. HCl
 CH 3CH 3 b. Clemmensons Reduction
Zn  Amalgam
Ethane CH 3COCH 3 
Con. HCl
 CH 3CH 2CH 3
NOTE: It is used for base sensitive carbonyl
compounds Propane
c. Wolf-Kishner Reduction c. Wolf-Kishner Reduction
H 2 N  NH 2
CH 3CHO  CH 3  CH  NNH
H 2 N  NH 2
CH 3COCH 3  CH 3  C  CH 3   NNH

 KOH
 CH 3CH 3  N 2  KOH
ethylene glycol .
 CH 3CH 2CH 3  N 2
ethylene glycol .
Propane
Ethane
NOTE: It is used for acid sensitive carbonyl
compounds d. with HI and Red phosphorous
d. with HI and Red phosphorous CH 3COCH 3 
HI/Red P
 CH 3CH 2CH 3
CH 3CHO 
HI /Red P
 CH 3CH 3 Propane
Ethane
NOTE: Carbonyl compounds on reduction with
HI and red P forms alkanes with same number
of carbons.
 CARBONYL COMPOUNDS (OR) ALDEHYDES & KETONES JEE MAINS - VOL - IX
17. Polymerization (ONLY MAINS) 17. Condensation (ONLY MAINS)
a. with con.H 2 SO4 at 300 C (Trimerization) a. with con.H 2 SO4

3CH 3CHO 

con. H 2 SO4
0   CH 3CHO 3 3CH 3COCH 3 
ConcH 2 SO4
 C6 H 3  CH 3 3
30 C

Paraldehyde  Hypnotic comp. Mesitylene

b. with HCl
b. with con.H 2 SO4 at 00 C (Tetramerization)
2CH 3COCH 3 
HCl
  CH 3 2 C  CHCOCH 3
4CH 3CHO   CH 3CHO 4con. H 2 SO4
Mesityl oxide
00 C
HCl
  CH 3 2 C  CHCOCH  C  CH 3 2
Metaldehyde  Solid fuel   CH COCH
3 3

Phorone

Preparations of Benzaldehyde 3. Gatterman - Koch reaction

1. Oxidation of methyl benzene Here benzene is treated with carbon
Strong oxidising agents oxidise toluene and its monoxide and HCl in the presence of
derivatives to benzoic acid. So to stop the anhydrous AlCl3 and Cu2Cl2
oxidation at aldehyde stage suitable reagents are
used.
a) ETARD reaction
With chromyl chloride followed by hydrolysis
CH 3 CH(OCrOHCl2)2 CHO

+ CrO 2Cl2
CS 2 H 3O + MECHANISM
 
Toluene Chromium complex Benzaldehyde

CuCl  CO + HCl+AlCl3 CHO  CuCl  AlCl4

 Brown 
O
H O

Note: Chromyl chloride  CrO2Cl2  oxidises methyl  HC O 

 
AlCl4
  HCl + AlCl3

group to a chromium complex, which on

hydrolysis gives corresponding benzaldehyde. 4. From benzoyl chloride (Rosenmund
b) With chromic oxide CrO3 in acetic anhydride reduction)
C6 H 5COCl  H2
Pd  BaSO4
 C6 H 5CHO
CH3 CH(OCOCH3) 2 CHO Benzoylchloride Benzaldehyde
  CH 3CO 2 O  CrO3
273 283 K  H 3O 

5. Duff Reaction (Mains)
Toluene benzylidene diacetate CHO

[O]
  N2 
2. By side chain chlorination followed by (CH ) N2 6 4
Hexamethyl tetraa min e
hydrolysis (Commericial Method)
Benzene Benz aldehyde

6. Gattermann aldehyde synthesis (Mains)

OH OH
CHO
 HCl  HCN 
 An ZnCl2
 JEE MAINS - VOL - IX CARBONYL COMPOUNDS (OR) ALDEHYDES & KETONES
PREPARAITON OFACETOPHENONE
Friedal Crafts Acylation:

   CH 3 2 C  CHCOCH 3
Mesityl oxide
COR
Mechanism
Generation of nucleophile
 RCOCl 
 An AlCl3
CH 3  CHO  OH   CH 2CHO  H 2O
Attack of nucleophile on carbonyl group
Note: Substituted Benzenes also give this
reaction CH 3  CHO  CH 2CHO 
 Electrophilic substitution reaction CH 3  CH  CH 2  CHO
Aromatic aldehydes and ketones undergo
electrophilic substitution at the ring in which the
carbonyl group acts as a deactivating and meta- O
directing group.
Hydrolysis
CHO CHO
CH 3  CH  CH 2CHO  H 2O 


HNO3 / H 2 SO4
273 283 K
 O
CH 3  CH (OH )  CH 2CHO  OH 
NO2
 Crossed aldol condensation If the aldol
condensation is between two different aldehydes
or ketones, it is called crossed aldol
OTHER REACTIONS
condensation. When both of them have
12. Aldol Condensation
  hydrogen, a mixture of four products are
Acidity of   hydrogens: The acidity of formed.
  hydrogen atoms of carbonyl compounds is due to ) NaOH , ii ) 
Eg : CH 3  CHO  CH 3  CH 2CHO i  
the strong electron with drawing effect of the carbonyl
group and resonance stabilisation of the conjugate base.
Carbonyl compounds with atleast one   hydrogen
undergo aldol / ketol condensation.
OH
|

2CH 3CHO  CH 3  CH  CH 2  CHO

dil . NaOH /
Na2 CO3

3-Hydroxy Butyraldehyde  Acetone may also be involved in cross

condensation

 CH 3CH  CHCHO
H O  OH  , 293K
2 C6 H 5CHO  CH 3  CO  C6 H 5   

Crotonaldehyde C6 H 5  CH  CHCO.C6 H 5
OH 1,3  diphenyl prop  2  en  1  one (benzal
|
OH  acetophenone)
2CH 3COCH 3   CH 3  C  CH 2COCH 3 Ex :
Ba ( OH )2 |
CH 3

Diacetone alcohol
CARBONYL COMPOUNDS (OR) ALDEHYDES & KETONES JEE MAINS - VOL - IX
conc.NaOH
Eg. 1) HCHO  HCHO  
CH3OH  HCOONa
CH O
conc.KOH
Eg. 2) C 6 H 5 CHO  C 6 H 5CHO  
 CH 3  CO  CH 3 
 Ba ( OH ) 2


C6 H5CH2 OH  C 6 H5COOK

Mechanistically, Cannizzaro reaction is a

characteristic reaction of aromatic aldehydes and
C H (O H )  C H 2C O C H 3 of aliphatic aldehydes without  -hydrogen. In
the presence of a strong base, such aldehydes
 undergo self-oxidation-reduction
 
(disproportionation or dismutation) yielding salt
of carboxylic acid and an alcohol.
CH3 CH3 CH3
O

2H3C HO
 H3C  H3C

CH  CHCOCH 3 O O CH3 OH
CH3 CH3
NaOH
2C6H5CHO   C6H5CH2OH  C6H5COONa
Benzaldehyde Benzyl Alcohol Sodiumbenzoate

Mechanism
Step – 1: Addition of hydroxide ion to carbonyl
 Claisen Schmidt Reaction group
The base catalysed cross aldol condensation
between an aromatic aldehyde and an aliphatic OH
aldehyde or a ketone is called claisen - schmidt 

condensation C6H5 C  OH
O  
C

 6H5 C O

C6 H 5CHO  CH 3CHO 

dil NaOH
 H H
Hydroxy alkoxide ion
 H 2O
C6 H 5CHOH  CH 2CHO  
Step – 2: Transfer of hydride ion directly to
C6 H 5CH  CHCHO another aldehyde molecule. This is rate
determining step
Cinnamaldehyde
OH O OH O
C6 H 5CHO  CH 3COCH 3 
 dil NaOH
 H 2O
C6H5 C O  C6H5 C 
 C6H5 C Slow
C6H5 C H
H O H
C6 H 5  CH  CH  COCH 3 Benzoic acid
Benzalacetone
Step – 3: Hydrolysis

 Cannizzaro’s reaction
Aldehydes that have no   hydrogen atom
undergo this reaction involving disproportionation
(self oxidation and reduction) on treating with
strong conc. alkali.
 JEE MAINS - VOL - IX CARBONYL COMPOUNDS (OR) ALDEHYDES & KETONES
CH 2 OH CH 2

O  O

C6H5 C H  H O  
H3 O
 
conc H 2 SO4
CO

2  C6H5 CH2 OH  OH (B)

COOH
(C)
H (III) Internal Crossed-Cannizzaro reaction
 Crossed cannizzaro’s reaction.  -Keto aldehydes in which keto group has no
Different aldehydes having no   hydrogen  - hydrogen also give Cannizzaro reaction
atoms undergo disproportionation on heating with known as internal Crossed- Cannizzaro reaction.
concentrated alkali to form alcohol and salt of In this case, aldehyde group undergoes oxidation
carboxylic acid. and keto group undergoes reduction
 O
 OH
EX. HCHO  C6H5CHO   HCOO
   C 6H5CH2OH

 Intermolecular cannizzaro reaction ( i ) conc. NaOH / 
C6 H 5  C  CHO  
( ii ) H 
(I) When both aldehydes are different :
case-I. When both aldehydes are different and C6 H 5  CH (OH )COOH
none is formaldehyde:  Distinction of aldehydes and ketones
C6 H 5  CHO  (CH 3 )3 CCHO 
 ( i ) NaOH / 
 Oxidation
( ii ) HOH / H 
 Tollen’s Reagent Test (Silver mirror test):
C6 H 5  CH 2OH  (CH 3 )3 CCH 2OH + Ammonical silver nitrate is called Tollen’s reagent.
C6 H 5  COOH  (CH 3 )3 CCOOH Aldehydes on heating with Tollen’s reagent
undergo oxidation to form carboxylic acid
Case-II. When both are different and one is
accompanied by the reduction of silver ion to
formaldehyde :
metallic silver.
( i ) conc NaOH / 
C 6 H 5  CHO  HCHO     
Re d
( ii ) HOH / H 
Oxi RCHO  2  Ag  NH 3  2  OH 

C 6 H 5  C H 2O H  H C O O H 2Ag  RCOONH 4  H 2O  NH 3
(II) Intramolecular Cannizzaro reaction Note : It is also given by terminal alkynes and HCOOH
This reaction is given by dialdehydes in which Fehling Solution
 -hydrogen is not present.  Fehling’s solution is an alkaline solution of copper
CHO CH2OH sulphate containing sodium potassium tartrate
(i)conc.NaOH /  (Rochelle salt) as the complexing agent.

 
 Aldehydes on warming with this solution, give a
(ii) H
CHO COOH red precipitate of cuprous oxide.
( i ) conc .NaOH / 
Fehling’s reagent = Fehling’s solution (A) +
CHO  CHO   HOCH 2  COOH Fehling’s soluiton (B).
( ii ) H

CHO Fehling’s solution (A) = aqCuSO4


Fehling’s soluiton (B) = alkaline sodium potassium
Ex : conc
. (A) H
NaOH


3O
(B) concH
 (C)
2SO4
tartrate (Rochelle salt)
CHO

CHO
CH 2 OH RCHO2Cu(OH)2  NaOH
RCOONa  Cu2O 3H2O
Red precipitate

Sol : 
conc. NaOH

Note : Aromatic aldehydes donot give this test
COONa
CHO
(A) Benedict’s Solution
 CARBONYL COMPOUNDS (OR) ALDEHYDES & KETONES JEE MAINS - VOL - IX
 Benedict’s solution is alkaline copper sulphate camphor etc., are well knonw for their flavours.
containing citrate ions as complexing agent.  Acetone and ethyl methyl ketone are common
Aldehydes on warming with this solution, give industrial solvents.
brick red precipitates. OTHER REACTIONS FOR ADVANCE
2
RCHO  Cu (complex) 
 Cu 2 O  RCOOH Tischenko Reaction
Red precipitate All aldehydes (with or without  -hydrogen) can
Note :Benedict’s and Fehling solution oxidised be made to undergo cannizzaro reaction on
only aliphatic aldehydes and have no effect treatment with aluminium ethoxide. However
on any other functional group. under these conditions the alcohol and acid
Schiff’s Reagent produced as result of cannizzaro combine
 Schiff’s reagent is an aqueous solution of magenta together to form ester.
or pink coloured para rosaniline hydrochloride Al(OC2H5 )3
2CH3 CHO   CH3 COOCH2CH3
H2O
which has been decolourised by passing SO2. Ethyl acetate

When aldehydes are treated with decolourised Perkin Reaction

solution of Schiff’s reagent, its pink or magenta In Perkin reaction, condensation has been
colour is restored. This reaction is used as a test effected between aromatic aldehydes and
for aldehydes because ketones do not restore aliphatic acid anhydride in the presence of sodium
the pink colour of Schiff’s reagent. or potassium salt of the acid corresponding to
the anhydride, to yield  ,   unsaturated
aromatic acids.
The acid anhydride should have at least two  -H.
C6 H 5 CHO  (CH 3CO) 2 O 
AcONa
170 180 C, 5h
C6 H 5  CH  CH  COOH

Schmidt Reaction
This is the reaction between a carbonyl
compound and hydrazoic acid in the presence
of a strong acid concentrated sulphuric acid.
Aldehydes give a mixture of cyanide and formyl
derivatives of primary amines, where as ketones
give amides :
RCHO  HN 3 
H 2SO 4
 RCN  RNHCHO  N 2
 Tests for acetone
Uses of Carbonyl compounds:  Legal Test
 The 40% solution of formaldehyde (formalin) is CH3COCH3 +
used as disinfectant, germicide and antiseptic. It Sodium Nitroprusside+NaOH  Wine red
is used for the preservation of biological colour changes to yellow
specimens.  Indigo test
 It is used in making synthetic plastics like bakelite, Ortho nitro benzaldehyde
urea-formaldehyde resin and other polymeric
+2ml. of Acetone
products.
+ diluted with KOH gives blue colour of indigotin
 Many carbonyl compounds like vanillin (from
vanilla beans), salicyladehyde (from meadow OTHER USES
sweet) and cinnamaldehyde (from cinnamon) . Acetaldehyde
 Benzaldehyde, Butyraldehyde, acetophenone,  In the preparation of Acetic acid, Acetic
anhydride ethyl acetate, chloral, 1,3-butadiene
 JEE MAINS - VOL - IX CARBONYL COMPOUNDS (OR) ALDEHYDES & KETONES
(used in Rubber) dyes and drugs.
 Used as antiseptic inhalent in nose troubles.
 In the preparation of paraldehyde (hypnotic)
Metaldehyde (Solid fuel, for killing slugs & snails)
 Used in spirit lamp.
 In the preparation of acetaldehyde ammonia
O
(a rubber accelerator) O
Acetone C
C
 As a solvent for cellulose accetate, cellulose Cl 2  H   
Lindlars Catalyst

H
nitrate, celluloid, resins etc. 7.
 Used in storing of acetylene. BenzoylChloride
Benzaldehyde

 In the manufacture of Cordite - a smokeless

explosive. 8.  C6 H 5CH 2 2 Cd  2CH 3COCI 
 Used as nail polish remover.
O
 Used in the preparation of plexiglass ||
(unbreakable glass), Synthetic rubber. CH 2  C  CH 3
 Used in the prep. of chloroform, iodoform and
chloretone.
WORKED OUT EXAMPLES:
9. CH 3  CH 2  C  N  C6 H 5 MgBr
1. CH 2  CH  CH 2OH
Allyl alcohol NMgBr
P.C .C
 CH 2  CH  CHO
Propenal 
ether
 CH 3CH 2  C
2. CH 3  CH  CH  CH 3 C6 H 5
But-2-ene
O3 / H 2O  Zndust O

 2CH 3CHO

Ethanal 
H 3O
 C2 H 5 C
CH 2 CHO C6 H 5
3. 

1. B2 H 6 /THF
Propiophenone
2. H 2O2 / OH 

1-Phenylpropanone 
Hg 2 , H 2 SO4
H 3C  C  C  CH 3 

4. CH 3 MgX  H  C  N  H  C  NMgX
H 3CCH 2COCH 3 |
CH 3

CH 3C  CH 
40% H 2 SO4
 CH 3COCH 3 10. 
H 2O
H  C  O
5. 0 0

1% H g SO4 60  70 C  |
CH 3

C6 H 5 MgX  C2 H 5  C  N  C2 H 5  C  NMgX
|
6. C6 H 5

11. 
H 2O
 C2 H 5  C  O
|
C6 H 5
 CARBONYL COMPOUNDS (OR) ALDEHYDES & KETONES JEE MAINS - VOL - IX
DIBAL  H
12. CH 3CN   CH 3CHO
Ethane nitrile Ethanal
 i DIBAL  H
CH 3  CH  CH  CH 2  CH 2  CN 
 ii  H O

2
13.
CH 3  CH  CHCH 2CH 2CHO
 i DIBAL  H
14. CH 3COOC2 H 5 
 ii  H O
 CH 3CHO
2

15. CH 3  CH 2 9 COOC2 H 5  CH 3  CH 2 9 CHO

16. R  CH  CHCH  CHO 
O
|| 
NH 2  C  NH  NH 2 
H


R  CH  CH  CH  N  NH  CO  NH 2

COOH COCH 3
17. 
H 2CrO4
 
NaOH
I

2

COONa
CHI 3

CH 2  CHCH 2OH 

PCC
CH Cl

2 2
18.
Allyl alcohol
CH 2  CH  CHO
Acrolein
DiBAL  H
19. CH 3CN 
H O
 CH 3CHO
2

20. CH 3C  N  CH 3 MgBr 

H 2O

CH 3COCH 3  NH 3  MgBr  OH 
 9. Alkaline hydrolysis of gemdihalides gives
1) aldehydes only 2) ketones only
CONCEPTUAL 3) carbonyl compounds 4) Ethers
10. The first oxidation product of secondary
NOMENCLATURE & ISOMERISM alcohol is
1) acid 2) aldehyde
1. Which of the following is not a monovalent 3) ketone 4) ether
functional group. 11. Acetone can not be obtained from
1) Aldehydic 2) Ketonic 1) hydrolysis of isopropylidene chloride
3) Carboxylic 4) Hydroxy 2) hydration of propyne
2. IUPAC name of a
3)dehydrogenation of isopropyl alcohol
 -hydroxybutyraldehyde
1) 1-hydroxy butanal 2) 2-hydroxy butanol 4) hydrolysis of ester
3) 2-hydroxy butanal 12 Catalytic poison in Rosemunds reaction
4) 2-hydroxy butyraldehyde 1) Quinoline 2) H2
3. Vinylalcohol gets converted into 3) CH3COCl 4) CH3CHO
acetaldehyde by 13. Formaldehyde is treated with
1) oxidation 2) reduction methylmagnesium iodide in dry ether and
3) rearrangement 4) polymerization finally with water. The product obtained is
4. Arrange the following compounds in 1) Isopropyl alcohol 2) Ethyl alcohol
increasing order of their reactivity in 3) Methyl alcohol 4) n  propyl alcohol
nucleophilic addition reactions.
Ethyl alcohol  A B
Cu
Ethanal (I) Propanal(II) 14. 3000 C
Propanone(III) Butanone(IV) What are A & B
1) III<II<I<IV 2) II<I<III<IV 1) Acetaldehyde, Acetone
3) IV<III<II<I 4) I<II<III<IV 2) Acetone, Water
3) Acetaldehyde, H 2
PREPARATION
5. CH 3COCl  H 2 
Lindlar ' s
 CH 3CHO  HCl 4) Acetone, H 2 ,
catalyst

The above reaction is known as PROPERTIES

1) Aldol condensation OH  CH CH(OH)CH CHO
CH3CHO 
15. 3 2
2) Clemmenson’s reduction
3) Rosenmund’s reduction represents
4) Carbyl amine reaction 1) Cannizaro’s reaction
6. Stephens reaction is used in the preparation 2) Benzoin’s condensation
of 3) Aldol condensation
1) Carboxylic acids 2) Ketones 4) Perkin’s reaction
3) Alcohol 4) Aldehydes
ZnHg / conc.HCl.
7. Isopropyl alcohol on oxidation forms 16. R  CHO  4[ H ]  
1) Acetaldehyde 2) Ethylene
R-CH3+H2O is
3) Ether 4) Acetone
1) Wurtz’s reaction
8. The solvent used in Etard’s reaction during
the formation of benzaldehyde from toluene 2) Clemmenson reduction
is 3) Wolf-Kishner reduction
1) acetic acid 2) water 4) Friedel-Craft’s alkylation
3) liq.NH3 4) CS 2
 JEE MAINS - VOL - IX
17. The correct increasing order of boiling points USES
is 25. The percentage of formaldehyde in fomalin
is
(1) C3 H 7CHO  C4 H 9OH   C2 H 5  2 O  CH 3  CH 2 3 CH 3
1) 40% 2) 10%
(2) CH 3  CH 2 3 CH 3   C2 H 5  2 O  C3 H 7CHO  C4 H 9OH 3) 20% 4) 5%
26. Salicylaldehyde is extracted from
(3) C4 H 9OH   C2 H 5  2 O  C3 H 7CHO  CH 3  CH 2  3 CH 3
1) Meadow sweet 2) Meadow hot
(4) CH 3  CH 2 3 CH 3  C3 H 7CHO   C2 H 5  2 O  C4 H 9OH 3) Vanilla beans 4) Cinnamon
18. The reagent that gives an orange coloured 27. Formaldehyde is used as
ppt. with acetaldehyde 1) Disinfectant 2) germicide
3) Antiseptic 4) All
1) NH2OH 2) NaHSO3
3) Iodine 4) 2,4-DNP
KEY
19. Oxime is the product of the following
1) >C=O + hydrazine
CONCEPTUAL
2) >C=O + Phenylhydrazine
1) 2 2) 3 3) 3 4) 3 5) 3
O
||
3)  C  O H  S O C l 6) 4 7) 4 8) 4 9) 3 10) 3
2 11) 4 12) 1 13) 2 14) 3 15) 3
4) >CO + Hydroxylamine 16) 2 17) 2 18) 4 19) 4 20) 2
20. The molecular formula of acetaldehyde 21) 3 22) 1 23) 3 24) 4 25) 1
semicarbazone is 26) 1 27) 4
1) CH3-CH=N-CO-NH-NH2
2) CH3-CH=N-NH-CONH2 HINTS
3) CH3-CH=N-OH 4) CH3-CH=N-NH2
21. Haloform reaction is not given by CONCEPTUAL
1) CH3COCH3 2) CH3COC 2 H5 OH
3) C6 H5COC 2 H5 4) CH3CHOHCH3 2. |
CH3  CH2  CH  CHO
2-hydroxy butanal (IUPAC)
TESTS
22. Schiff’s reagnet is
1) P-Rosaniline hydrochloride decolourised by 3.
passing SO2 4. Reactivity decreases as the size and number of
2) P-Rosaniline hydrochloride decolourised by alkyl groups around CO group increases.
chlorine 7. CH 3 .CH(OH).CH 3 + [O] 
PCC

3) Acidic solution of phenolphthalein CH3COCH3 + H2O
4) Rochelle salt soltion CuSO4  NaOH 9. 1,1-dihalides produce aldehydes whereas 2,2-
23. Which of the following reagent is used to dihalides produce ketones
identify carbonyl group from other functional 10. 2° alcohols produce ketones on oxidation
groups
1) Schiff’s reagent 2) Fehling solution 11. Esters on hydrolysis produce acid and alcohol
3) 2, 4 dinitro phenyl hydrazine but not carbonyl compound.
4) Tollen’s reagent 12. Quinoline retards the activity of the catalyst ‘Pd’
24. Ethanal and propanone can be distinguished
13. RMgX reacts with formaldehyde and forms
by
1) Schiff’s reagent 2) Tollen’s reagent primary alcohols.
3) Fehling’s solution 4) All
14. Primary alcohols on dehydrogenation with 5. Addition of water to alkynes occurs in acidic
copper / 3000 C forms aldehydes with same medium and in the presence of Hg 2 ions
number of carbons. as a catalyst. Which of the following
17. Popoff’s rule products will be formed on addition of water
19. Carbonyl compound + NH2OH  oxime to but -1-yne under these conditions.
H O
20. CH 3 - C = O + H 2 N - NH - CO - NH 2  1)
CH 3  CH 2  CH 2  C  H
CH3 - CH = N - NH - CO - NH2
O O
21.
CH 3 - C - group is absent 2)
CH 3  CH 2  C  CH 3

O
LEVEL - I
CLASS WORK 3)
CH 3  CH 2  C  OH  CO2

PREPARATIONS O O
4)
1. The Alkene which on ozonolysis gives CH 3  C  OH  H  C  H
acetaldehyde and acetone is
6. When propyne is subjected to hydroboration
CH 3 reaction, it is converted to
1. |
CH 3  CH  C  CH 3 1) propanol 2) acetone
3) propanal 4) butanone
2. CH 3  CH  CH  CH 2  CH 3
PROPERTIES
3. CH 2  CH  CH 3 7. The formation of cyanohydrin from
4.  CH 3 2 C  C  CH 3 2 acetone is which type of reaction?
1) Electrophilic substitution
2. For the following conversion which reagent is 2) Electrophilic addition
used 3) Necleophilic addition
CH 2  CH  CH 2OH 4) Necleophilic substitution
8. The reaction in which >C = O group changes
?
 CH 2  CH  CHO t o > C H

2

A) Clemenson’s reduction
1) O 3 / H 3O 2) PCC B) Wolff - Kishner reduction
3) HgSO 4 / H  4) Lucas reagent C) Aldol condensation
D) Rosenmunds reduction
3. Grignard reagents do not give carbonyl 1) A & B only 2) B and C only
compounds with 3) A and D only 4) A, B, C, D
1) CO2 2) RCOCl 3) RCN 4) RCOOR 9. The correct order of reactivity of-
4. The medium in which ethanol is oxidised to I) Acetophenone II) p-Nitrobenzaldehyde.
ethanal using PCC or PDC is III)Benzaldehyde IV) p-Tolylaldehyde
1) any alcohol 2) Nitro benzene 1) I<IV<III<II 2) I<II<III<IV
3) Methylene dichloride 4) ether 3) I>IV>III<II 4) III<I<II<IV
 JEE MAINS - VOL - IX
10. Which of the products formed when acetone TESTS
reacts with barium hydroxide solution?
O CH3 15. An organic compound readily forms
|| |

1) CH 3  C  CH 2  C|  CH 3 cannizaro reaction but does not react with

OH Fehling’s solution
O
|| 1) HCHO 2) CH 3CHO
2) CH3  C  CH
|
 CH
|
 CH 3
CH3 OH 3) PhCHO 4) CH 3COCH 3
O
|| 16. An organic compound give    ve haloform test
3) CH3  C  CH
|
 CH
|
 CH 3
but does not react with tollen’s reagent.
OH CH3
1) Acetone 2) 2 - butanol
OH OH
| |
3) Both 4) 1 - Butanol
4) CH3  C|  C|  CH 3
CH3 CH3
17. An organic compound gives    ve 2, 4 - DNP
11. Which of the following compounds does not test but does not react with Fehling’s solution.
react with sodium bisulphite
1) PhCHO 2) PhCOCH 3
1) Benzaldehyde 2) Acetone
3) Acetophenone 4) Acetaldehyde 3) CH 3COCH 3 4) All
12. A mixture of Benzaldehyde and
Formaldehyde on heating with aqNaOH
solution gives
1) sodium benzoate and methyl alcohol KEY
2) sodium benzoate and ethyl alcohol LEVEL - I
3) benzyl alcohol and methyl alcohol 1) 1 2) 2 3) 1 4) 3 5) 2
4) benzyl alcohol sodium formate 6) 3 7) 3 8) 1 9) 1 10) 1
11) 3 12) 4 13) 3 14) 3 15) 3
13. Acetaldehyde and Acetone on reaction with 16) 3 17) 4
chlorine respectively gives
1) Mono chloro acetone, methane HINTS
2) Chloral and Dichloro acetone LEVEL - I
3) Chloral and Tri chloro acetone CLASS WORK
4) Tetra chloro Ethanal, Hexa chloro acetone 3. RMgX with CO2 gives carboxylic acid
14. Acetaldehyde forms white crystalline 5. Addition of water to unsymmetrical alkynes
precipitate on mixing with a ..........solution follows Markownikov’s rule
of ........ 6.
C H 3  C  C  H  H 2 O  HOB 
2H6
 C H 3  C H 2  C H O
1) Acidic Zn, Hg 2 /OH 
2

addition follows anti markownikov’s rule

2) Alcoholic Na 2 SO 3 9. Based on steric and electronic reasons
3) Saturated, aqueous NaHSO 3 11. Only acetophenone doesnot form adduct due to
steric effect
4) Aqueous NaCl 12. Crossed cannizzaro reaction
13.   halogenation
15. Aromatic aldehydes and aldehydes without  
Hydrogen atoms.
 1) CH 3  CH  CHCH 2CH 2COOH
2) CH 3  CH 2  CH 2CH 2CH 2CHO
LEVEL - I
3) CH 3  CH 2  CHCH 2CH 2CHO
HOME WORK
PREPARATIONS 4) CH 3  CH  OH   CH 2CH 2CH 2CHO
1. Oxidation of toluence with CrO3 in 5. Methyl cyanide reacts with ethyl
magnesium Bromide and forms an addition
presence of  CH 3CO  2 O gives a product compound which on hydrolysis forms a
(A) which on hydrolysis forms Benzaldehyde compound (A). The functional Isomer of (A)
A is _____ is
1) Chromium complex 1) Butanone 2) Propanone
2) Benzylidene diacetate 3) Butanal 4) Propanal
3) Benzophenone 6. Propanoyl chloride on reduction with
4) Benzal chloride Lindlar’s catalyst forms a compound (A).
Product (A) is
2. Which of the following alkene is most
1) Propanone 2) Propanoic acid
suitable for the preparation of butanone by
3) Propanol 4) Propanal
Ozonolysis
PROPERTIES
7. CH 3CHO  NH 2OH  X   H 2O
Y
1)
The number of  bonds,  bonds and lone
pairs of electrons in the compound ‘Y’ are
respectively
1. 9, 1, 4 2. 11, 1, 5
2)
3. 9, 2, 2 4. 8, 1, 3
8. A carbonyl compound reacts with hydrogen
cyanide to form cyanohydrin which on
hydrolysis forms a racemic mixture of
3)  -hydroxy acid. The carbonyl compound is
1) formaldehyde 2) acetaldehyde
3) acetone 4) diethyl ketone
9. The increasing order of the rate of HCN
4) addition to compound, A-D is
A) HCHO B) CH 3COCH 3
3. Which of the following on heating with
aq KOH produces butanal dehyde C) PhCOCH 3 D) PhCOPh
1) A<B<C<D 2) D<B<C<A
1) CH 3CH 2CH 2CH 2Cl 3) D<C<B<A 4) C<D<B<A
2) CCl3CH 2CH 2CH 3 10. Which of the following is reduced with zinc
and hydrochloric acid to give corresponding
3) CH 3CH 2CH 2CHCl2 hydrocarbon
4) CH 3CCl2CH 2CH 3 1) Ethyl acetate 2) Acetic acid
3) Acetamide 4) Butan-2-one
CH 3  CH  CH  CH 2 11. Iodoform test is not given by
 i DIBAL  H 1) 2-pentanone 2) 3-pentanone
 CH 2  CN 
 ii  H O
 3) ethanal 4) ethanol
4. 2
12. Aldol condensation does not occur between
CH 3  CH  CHCH 2CH 2CHO
 JEE MAINS - VOL - IX
1) a & b 2) b & c 3) only b 4) All
1) two different aldehydes
2) two different ketones
3) an aldehyde and a ketone KEY
4) an aldehyde and an ester LEVEL - I (H.W)
13. The reagent which gives the same reduction
product with propionaldehyde and acetone 1) 2 2) 1 3) 3 4) 3 5) 3 6) 4
is 7) 4 8) 2 9) 3 10) 4 11) 2 12) 4
1) LiAIH4 2) Na-Hg / H2O 13) 4 14) 4 15) 2 16) 1 17) 3 18) 4
19) 1
3) Ni / H2 4) Zn-Hg/Conc.HCl
14. Which of the following undergoes cannizaro HINTS
reaction? LEVEL - I (H.W)
A) HCHO B) C 6 H5CHO 3) Terminal gemdihalides give aldehydes
D)  CH 3 3 C  CHO
4) Double bond is not affected in stephens
C) Cl 3C  CHO
reduction.
1) Only A and B 2) Only B and C 5) Aldehydes and ketones are functional isomers
3) Only C and D 4) All A,B,D 8)   hydroxy acid formed must be chiral as it
forms racemic mixture. Only acetaldehyde
15. Which of the following does not undergo cyanohydrin forms acid with chiral carbon on
aldol condensation hydrolysis
1) ClCH 2CHO 2) CCl 3CHO 10) Only aldehydes and ketones
11) There is no CH 3CO group.
3) C 6H 5CH 2CHO 4) CH 3CHO 13) Clemmenson’s (or) Wolf - kishner reduction
16. Which of the following combination of 14) Aldehydes containing no   hydrogen undergo
aldehydes gives orange yellow ppt with 2,4 reaction except CCl3CHO and
-DNP
 C6 H 5 3 CHO
1) Carbonyl compounds
15) No   hydrogen atoms
2) Carboxylic acids 16) 2, 4 - DNP test is the identification test for
3) only aldehydes carbonyl compounds
4) only ketones
17. Di - Isobutyl alluminium hydride (DIBAL-
H) can be used to carry out which of the
following conversions,
1) Ester to aldehyde 2) Nitriles to imines
3) Both 1 & 2
4) Aldehyde to Carboxylic acids
18. Which of the following Tollen’s test
1) Acetylene and propyne
2) Formic acid
3) Acetaldehyde
4) All
19. Which of the following gives Fehlings test
a) HCHO b) RCHO
c) PhCHO d) RCOR
 3. ALDEHYDES, KETONES AND CARBOXYLIC ACIDS

ALDEHYDES AND KETONES

2) Aldol Condenation
3) Clemmenson reduction
4) Etard reaction
LEVEL - II 7. A Substance C4 H10O on oxidation yields
CLASS WORK
compound C4 H 8O . which gives an oxime
PREPARATION
and a positive iodoform test. The original
1. Two isomeric compounds ‘A’ and ‘B’ have substance on treatment with conc. H 2 SO4
the formula C3H6Cl2. With aq KOH solution gives C4 H 8 . The compound is
‘A’ gives propionaldehyde and ‘B’ gives
acetone. Then ‘A’ and ‘B’ are 1. CH 3CH 2CH 2CH 2OH
1) CH3-CCl2-CH3 and CH3-CH2-CHCl2 2. CH 3CHOHCH 2CH 3
2) CH3-CHCl-CHCl2 and CH3-CH2- CHCl2
3.  CH 3 3 COH
3) CH3-CH2-CHCl2 and CH3-CCl2-CH3
4) CH3-CHCl-CHCl2 and CH3-CCl2-CH3 4. CH 3CH 2  O  CH 2CH 3
8. Which of the following has the most acidic
PROPERTIES hydrogen?
1) 3 - Hexanone 2) 2, 4 - Hexanedione
2. A new C - C bond formation is possible in 3) 2, 5 - Hexanedione 4) 2, 3 - Hexanedione
9. What are the products of the following
1) Cannizaro reaction
crossed cannizaro reactions
2) Rosenmund’s reduction
3) Clemmenson’s reduction
4) Reimer - Tiemann reaction
3. The enol form of acetone, after treatment
with D 2 O finally gives 1) , CH 3OH

1) CH 3 - C = CH 2 2) CH 3 - C - CH 3
| || 2)
OD O
3) CH 3 = C - CH 2D 4) CD3 - C - CD3
| ||
OH O 3)
4. Reactivity of H C H O ( I ). C H 3 C H O ( II ) and
C 6 H 5 C H O (III ) is in order 4)
1) I > III > II 2) III > II > I 10. Identify the product of the following
3) I = II > III 4) I > II > III condensation reaction
5. A 
Cl2
 CCl3CHO 
NaOH
 B. In
this reaction A and B are
1) CH3CHO and CHCl3 1) 2)
2) CH3CHO and C2H5Cl
3) CH3CH2OH and CH3Cl
4) CH3OCH3 and CHCl3 3) 4)
 1CrO 2 Cl 2 /CS 2
  A    B

OH
6. C 6 H 5 CH 3  H O
3
11. By cannizaro reaction A changes to B and C
The Conversion of A to B is called as
1) Cannizaro reaction
 JEE MAINS - VOL - IX
as given. Identify ‘A’
A ¾ 5¾0 % ¾N a ¾
OH
¾® C O O N a C H 2O H
| + | 3) 4)
COONa COONa
(B ) (C )
CHO CHO 16. A compound ‘A’ has a molecular formula
1) | 2) | C 2 Cl 3 OH . It reduces Fehling solution and on
COOH CHO
oxidation produces a mono carboxylic acid
CH 2 OH CH 2 OH
3) | 4) | ‘B’. A can also be obtained by the action of
CHO CH 2 OH Cl 2 on ethanol ‘A’ is
1) Chloral 2) CHCl 3
12. Benzaldehyde and acetone are subjected to
aldol condensation in 2 : 1 molar ratio 3) CH 3 Cl 4) Chloroacetic acid
- 17. The major product obtained in the reaction
2 benzaldehyde +acetone ¾ -¾H ¾®
OH
O 2
¾ HCN
¾¾ ® X ¾ HH¾2OSO¾®
4
Y is
Product is 2 /D

1) C - OH 2) CN
1) 2) ||
O
H
3) | 4)
3) 4) C - NH 2

13. In the cannizaro reaction given below

- 18. On vigorous oxidation by permangnate
2Ph.CHO ¾ OH
¾¾ ® Ph.CH 2 OH + PhCO -2
The slowest step is solution (CH 3 )2 C = CH - CH 2 CHO gives
1) The attack of OH- at the carbonyl group.
2) The transfer of hydride to the carbonyl group 1) (CH 3 )2 CO and OHC - CH 2 - CHO
3) The abstraction of proton form the carboxylic 2) (CH 3 )2 - C - CH - CH 2 - CHO
group | |
4) Deprotonation of ph.CH 2 OH OH OH

14. C3 H 8O 
O
K 2Cr2O7 / H 2 SO4
C3 H 6O 3) (CH 3 )2 CO and OHC - CH 2 - COOH

4) (CH 3 )2 CO and CH 2 (COOH )2

I 2 / alk
warm
 CHI 3
KMnO4 / H  / 
4 - heptanone 
In this reaction the first compound is 19.  A+B. Identify
1) CH 3 CH 2 CH 2 OH 2) CH 3 CH - CH 3 A and B
|
OH 1) Ethanoic acid pentanoic acid
3) CH 3 - O - CH 2 - CH 3 4) CH 3 CH 2 CHO 2) Ethanal and butanone
3) Butanoic acid and propanoic acid
4) Acetic acid and pentanoic acid
15. product is 20. Which of the following alkenes on reductive
ozonolysis will give a mixture of ketones
1) CH 3 CH = CHCH 3
1) 2) 2) (CH 3 )2 C = CHCH 3

47
 CH 3
identify the product formed
/
3) (CH 3 )2 C = C \ Ph  CH 2  CH  C  CHO
1) |
C2 H 5 Ph

2) Ph  Ph
4) (CH 3 )2 C = C (CH 3 )2

21. Compounds showing Cannizaro’s reaction Ph  CH 2  CH C  CHO

3) |
Ph
are
4) Ph  CHO
A) CH 3 CH 2 CHO B) CHCl2CHO
C) (CH 3 )3 C -

+
+
D)

H
C
O
O
K
CHO C 6 H 5 CHO

C
H
O
25. 
conc.
KOH
 CH 2 OH
1) A, B, C 2) C, D
3) A, C, D 4) A, B, C, D
X is _____
1) Formic acid 2) Formaldehyde
3) Acetaldehyde 4) Methanol
22.
KEY
Y is LEVEL - II
CLASS WORK
1) 2) 1) 3 2) 4 3)4 4) 4 5) 1
6) 1 7) 2 8) 2 9)4 10) 3
11) 1 12)3 13) 2 14) 2 15) 1
16) 1 17)1 18) 4 19) 3 20) 3
3) 4) 21) 2 22) 1 23) 3 24) 1 25) 2

HINTS
23. Identify “C” in the following LEVEL - II
O
( CLASS WORK )

1. Terminal geminal dihalides gives aldehydes and



OH

 A 

B that of other geminal dihalides give ketones with
aq.KOH
O Cl
|


NH  NH / Base
2 2
 C A) B) C  C|  C
Cl

2. In Reimer-Tiemann reaction a new C-C bond

O O formation is possible
æCH 3 - C = CH 2 ö÷
1 çç ÷
çç ÷
 2 3. The enolic form of acetone çè
|
OH
÷
÷
ø÷
HO contains active hydrogen, replaceable by
deuterium.
 4 Cl2 NaOH
 3 5. CH3CHO  Cl3C  CHO  CHCl3
OH 6. Aldehydes containing no  hydrogen undergo

cannizaro reaction
24. Ph  CH 2  CHO 
dilOH
H
 ‘X’  A to C is cannizaro reaction
 JEE MAINS - VOL - IX

10.

11.aldehyde with acidic group (hydroxyl) can give 20.

equation of fatty acid and alcohol.

O
||
12. C 6 H 5 - CH = O + H 2 CH - C - CH
22. Aldehyde containing no a - hydrogen atom
H 2 + O = CH - C 6 H 5 ¯ - H O / OH - gives cannizaro’s reaction (CH 3 )3 - C - CHO
2

and C 6 H 5 CHO do not have a - hydrogens

O
13.


14. CH 3 - CH - CH 3 ¾ K¾Cr¾O[ ¾]
¾ ¾®
O
2 2 7 + H 2 SO 4
23. 
OH

|
OH O
O
C3 H 6 O ¾ Iwarm
¾ ¾® CHI3
2 .alk


 
15. HO
O
16. CCl3CHO+ 2CuO ¾ ¾
® Cu2O+ CCl3COOH
Fehling
(B) NH 2  NH 2 / Base
  
Chloral Red ppt
solution

CH 3 CH 2 OH ¾ oxidation
¾Cl¾ 2
¾® CH 3 CHO ¾ Chlorination
¾ 3Cl
¾2 ¾®
Ethanol

CCl3CHO 25. Cannizaro reaction.

(A)
18. On vigorous oxidation by permangnate solution LEVEL-II
(CH 3 )2 C = CH - CH 2 CHO gives (CH 3 )2 CO HOME WORK
and CH 2 (COOH )2 . The C = C bond is cleared PREPARATIONS
and oxidised to - COOH , - CHO group is also 1. Identify A in the following
oxidised to - COOH .
CH
(CH 3 )2 C = ¾[ nO¾
] 2
CH - CH 2 CHO ¾ KM ®
O
4

COOH     A
1 .B2 H 6 /T H F

| 2.H O /O H 
2 2
(CH 3 )2 CO + CH 2 1) cyclo hexane
|
COOH 2) methyl cyclo hexene
19. Popoff rule 3) cyclo hexane carbaldehyde
4) methyl cyclo hexane carbaldehyde
2.  C 6 H 5C H 2  2 C d  2X 

49
 O 3) NaOH , I 2 / H 
||
CH 2  C  CH 3 4) Tollen’s reagent
8. (CH 3 )2C  CHCOCH 3 can be oxidised to
(CH 3 )2C  CHCOOH by
1) chromic acid 2) NaOI
Identify X
1) acetyl chloride 2) ethyl chloride 3) Cu at 3000 C 4) KMnO 4
3) vinyl chloride 4) methyl chloride 9. A compound ‘A’ has molecular formula
3. X  C H 3 M g B r  H2 O
 C 2Cl 3OH . It reduces Fehling’s solution
and on oxidation gives a monocarboxylic
CH 3COCH 3  NH 3  MgBr  OH  acid ‘B’. ‘A’ is obtained by the action of
Identify X Cl 2 on ethyl alcohol. ‘A’ is
1) ethyl cyanide 2) ethyl chloride
1) chloral 2) chloroform
3) ethane nitrile 4) methane nitrile
3) chloromethane 4) chloroacetic acid
COC6 H 5 10. The smallest ketone and its next
4 
C6 H 5COCl
 homologue are reacted with NH 2OH to
An AlCl 3
form oxime
Name of above reaction is 1) two different oximes are formed
1) Wurtz reaction 2) three different oximes are formed
2) Clemmenson reduction 3) two oximes are optically active
3) Wolf-Kishner reduction 4) all oximes are optically active
4) Friedel - Craft’s alkylation 11. O-Xylene on oxidation with alkaline
KMnO 4 followed by acidification with
5 A  Z O3

n /H 2O
 2 O
HCl gives
Identify A and name the reaction 1) benzaldehyde 2) benzonitrile
3) benzoic acid 4) phthalic acid
1) , reductive ozonolysis 12. If 3-hexanone is reacted with NaBH4
followed by hydrolysis with D2O, the
2) , reductive ozonolysis product will be
1) CH3CH2CH(OH)CH2CH2CH3
3) , oxidative ozonolysis 2) CH3CH2CD(OH)CH2CH2CH3
3) CH3CH2CH(OD)CH2CH2CH3
4) , oxidative ozonolysis 4) CH3CH2CD(OD)CH2CH2CH3
13. What will be the final product when
6. Which of the following on hydrolysis with cyclohex-2-enone is selectively reduced in
dilute alkali followed by acidification gives MPV reaction?
benzaldehyde. 1) Cyclohexanol 2) Cyclohex-2-enol
1) Benzotrichloride 2) Benzal chloride 3) Cyclohexanone 4) Benzene
3) Benzyl chloride 4) p-chlorotoluene 14. Aldol condensation, between which of the
following compounds followed by
PROPERTIES dehydration gives methyl vinyl ketone?
7. Butan-2-one can be converted to 1) Formaldehyde and acetone
propanoic acid by which of the following: 2) Formaldehyde and acetaldehyde
1) NaOH , Nal / H  3) Two molecules of acetaldehyde
2) Fehling’s solution 4) Two molecules of acetone
 JEE MAINS - VOL - IX
H CH 3 O
CH 3
NaOCl
CC  
2) C OK  CH 2OH
15. H 3C C
O
O        
3) KO C OK  KO OK
H CH 3
O
C C ONa  Z
   

H 3C C 4) C OK  OK
O
What is ‘Z’ in a above reaction 20. MATCHING
1) chloral 2) chloroform COLUMN - I
3) iodoform 4) chloro acetone

OH
P) PhMgBr   x  
H
10 alcohol
1
C6 H 5  C  CH 3 Can be prepared from 
16. 1 Q) PhMgBr   y  
H
 20 alcohol
C2 H 5

1) C6 H 5COCH 3 and C2 H 5 MgBr R) PhMgBr   z  
H
 30 alcohol

2) CH 3CH 2COCH 3 and C6 H 5 MgBr S) PhMgBr   w  
H
 Benzene
3) C6 H 5COC2 H 5 and CH 3 MgBr COLUMN - II
4) all of these 1) Formaldehyde
2) Propanal dehyde

17. CH3  CH2  OH 
PCC
A 
OH
B 3) Acetone
4) Ethylalcohol
Then ‘B’ is
P Q R S
1) CH2 = CH2 1) 1 2 4 3
2) CH3CHO 2) 1 4 2 3
3) 1 3 2 4
3) CH3-CH2-OH 4) 1 2 3 4
OH
|
KEY
4) CH 3  C|  CH 2  CHO
H LEVEL - II
18. CH 3  CHO 
LiAIH 4
 A 
PCl3
 B. 1) 3 2) 1 3) 3 4) 4 5) 1
Then ‘B’ is 6) 2 7) 3 8) 2 9) 1 10) 2
1) Ethyl alcohol 2) Acetic acid 11) 4 12) 3 13) 2 14) 1 15) 2
3) Ethyl chloride 4) Acetaldehyde 16) 4 17) 4 18) 3 19) 2 20) 4
19. Which product is formed when the compound
is reated with concentrated
CHO
LEVEL-II
HOME WORK
aqueous KOH solution?
HINTS
 
1) K O CHO
CHO
1.
51
2.  C6 H 5CH 2 2 Cd  2CH 3COCI  O
O3
 2 O ||
5. Zn / H 2O
H 3C  C  N  NH  C  NH 2
13. Reduction with aluminium isopropoxide in 4)
excess of isopropyl alcohol is called |
Meerwein Ponndorff Verley reduction CH 3
(MPV) .
PREVIOUS EAMCET QUESTIONS
2012 3. Match the following
List-I
1. Compound-A  C3 H 6 O  undergoes following A) Acetaidchyde, Vinyalcohol
reactions to form B and C. Identify A, B and C B) Eclipsed and staggered ethane
Zn  Hg / HCl
C   C3 H 6 O 
I 2 / NaOH
B C) (+)2-Butanol, (-) 2-Butanol
A B C D) Methyl-n-propylamine and Dicthylamine
List-II
O
I) Enantiomers
1) ||
CHI3 H3C  CH 2  CH 3 II) Tautomers
H3C  C  CH 3
III) Chain isomers
H 2 C  C  CH 2 OH IV) Conformational isomers
2) | CH 3 I H 3C  CH 2  CH 2  OH V) Metamers
H The correct answer is
1) A-II, B-IV, C-III, D-V
H 3C  CH  CH 3
2) A-II, B-IV, C-I, D-V
3) H 3C  CH 2  CHO CH 3 I |
3) A-V, B-I, C-IV, D-II
OH 4) A-V, B-I, C-III, D-II
H 3C  CH  CH 3 2010
O
|| | 4. Which one of the following gases yellow
4) CHI3 precipitate with iodine and NaOH solution?
H3C  C  CH 3 OH
2. What is the product obtained in the reaction of 1) CH 3  CHO 2) C6 H 5COC6 H 5
Acetaldehyde with semicarbazide? 3) HCHO 4) CH 3OH
O 2009
|| 5. What are X and Y in the following reaction
1) sequence
H3C  C(H)  N  NH  C NH2
C 2 H 5OH 
Cl2
X 
Cl2
Y
2) H 3C  CH  N  NH 2
1) C2 H 5Cl, CH 3CHO
3) H 3C  CH  N  OH
2) CH 3CHO, CH 3CO 2 H
3) CH 3CHO, CCl3CHO
4) C2 H 5Cl, CCl3CHO
6. What areA, B, C in the following reactions?
 JEE MAINS - VOL - IX
I)  CH3CO2 2 Ca 

A

II) CH 3CO 2 H  B

HI
Red P Above conversion can be acheived by :
1. Wolf-Kishner-reduction
III) 2CH 3CO 2 H 
P4 O10
C 2. Clemmensen reduction
A B C 3. , following by Raney
1) C2 H 6 CH 3COCH 3  CH3CO 2 O Ni
4. None of these
2)  CH3CO 2 O C2 H 6 CH 3COCH 3

3) CH 3COCH 3 C 2 H 6  CH3CO 2 O
 Zn Hg
4. 
Hcl 
;
4) CH 3COCH 3  CH3CO 2 O C2 H 6
7. The synthesis of crotonaldehyde from
acetaldehyde is an example of..........reaction Product of the Clemmensen reduction is;
1) Nucleophilic addition
2) Elimination
3) Electrophilic addition
4) Nucleophilic addition - elimination
PREVIOUS EAMCET QUESTIONS KEY 1. 2.
1) 1 2) 1 3) 2 4) 1
5) 4 6) 3 7) 4

LEVEL-III

3. 4.
1. " X " O3  
Zn / H 2 O
 CHO CHO
X is ___
1) 1-butene 2) Cyclo butene
3) Cyclo butyne 4) cyclo butane

  A ;
N H
5. 
2 4
HO  , 
2. (Wolf  Kishnerreduction )

Above conversion can be acheived by :

1. Wolf-Kishner-reduction
2. Clemmensen reduction
Product  A is ;
3. LiAiH 4 4. NaBH 4

3.

53
 A
CHO LiAH
8. 
or N 
4
aBH 
4
Ph

1. 2. CH2OH
1)
Ph
CH2OH
2)
Ph
CHO
3)
3. 4. Ph
CH 3
4)
Ph

9. A  B 
dil OH
Ph  CH  CH  CO  CH 3
Ca OH 
 A 
 B,
HNO  2
6. 
3
identify A & B in the above reaction
1) Acetophenone, Acetone
2) Acetophenone, Acetaldehyde
Product (B) in this reaction is ; 3) Acetone, Benzaldehyde
4) Acetaldehyde, Benzoic acid
10. OH  B
 O 
A
 OH
A and B respectively are
1) H 2 / Pt , LiAlH 4 / H 2O
1. 2.
2) H 2 / Pt , H 2 / Pt
3) LiAlH 4 / H 2O, LiAlH 4 / H 2O
4) LiAlH 4 / H 2O, H 2 / Pt

 CH 3 3 CCHO 

11. conc .OH
 X Y
3. 4.
X and Y are
1)  CH 3 3 CCOO  ,  CH 3 3 CCH 2OH
2)  CH 3 2 CHCOOH ,  CH 3 2 CHCH 2OH
A

CHO 
LiAH
or N 
4
7. aBH
3)  CH 3 3 COOH , CH 3CH 2OH
4
H 3C

identity (A ) in the above reaction 4) C2 H 5COOH , CH 3CH 2OH

1) Butanol 2) 2-butanol
3) But-2-en-1-ol 4) But-2-en-2-ol
 JEE MAINS - VOL - IX

O CHO CHO

1) 2)
Zn  Hg
12.  product
HCl
COOH CHO
OH
3) 4)
O

1) 2) 16. In the given reaction sequence

Cl
Cl 
Br2 / CH3COOH
X
CH 3CH 2 C|| CH 2CH 3
O 
Br2 / NaOH
 Y
x,y respectively are
3) 4) 1) CH3CH2COCHBrCH3 & CH 3CH 2COCBr2 CH 3
OH OH 2) CH 3CH 2COCBr2CH3 & CH 3CH 2COCHBrCH 3
3) CH3CH 2COCBr2CH3 & CH 3CH 2COCBr2CH 3
4) CH 3CH 2COCHBrCH 3 & CH 3CH 2COCHBrCH 3
17. In the reaction
13. Which statement about the aldol
condensation is correct ? CH 3CHO 
3 HCHO ,
dil . Na2CO3
 X . X is
1) A Lewis acid is commonly used as a catalyst
1) HO CH 2 CH 2 CHO
2) The initial step is probably the formation of a
carbanion 2)  HO CH 2 2 CH  CHO
3) A Lewis base is employed to induce
carbocation formation 3)  HO CH 2 3 C  CHO
4) C  CH 2OH 4
4) The carbon chain is lengthened through the
elimination of 1 mole of water
14. A compound gives a positive test with 18. C2 H 2 
HOCl
excess
A 
Cl2
B
I 2 / NaOH and is extracted from benzene by

NaOH
aq
C 
Conc
HNO3
D
saturated NaHSO3 . It may be : Identify A,B,C and D
1) CH 3  CH 2 4 CHO 1) CHCl3 , CHCl2CHO, CCl3 CHO , CCl3 NO2
2) CH 3  CH 2 3 COCH 3 2) Cl2CHCHO, CCl3 CHO , CHCl3 , CCl3 NO2
3) CH 3CH 2COCH 2CH 3 3) CH 3CH Cl2 , CH 3 CO CCl3 , CHCl3 , CCl3 NO2
4) CH 3  CH 2 4 CH 2OH 4) CH Cl3 , CCl3 CHO, CHCl2 CHO, CCl4

15. 
NBS
 
Mg / Ether
 
HcN / H 3O
X 19. Identify the product C in the series
CH 3CN Na / C H OH
2 5
 A 
HNO
2
 B 
PDC
C
1) CH 3COOH 2) CH 3CH 2 NH 2
3) CH 3CONH 2 4) CH 3CHO
20. In which of the following product will be

55
 aldehyde CHO O
1) (CH 3 ) 2 C  C (CH 3 ) 2 
( i )03
( ii ) Zn / H 2O
3) 4)
2) CH 3CH  CH 2 
CO / H 2
 C  C  Bu
 , Co  CO 8  C  C  Bu

3) CH 3CH  CH 2 
Pdcl2 , H 2O
CuCl2
 25. CH 2  CHO 
SeO2
 X 
KOH
Y
Identify the final product
4) CH 3  C  CH  
HgSO4
H 2 SO4 / H 2O

21. The product B in the reaction sequence is OH O

| ||
1)
(CH 3COO ) 2 Ca 
A distillation
Ph  CH  C  OK
Zn  Hg  HCl O
 B ||
2) Ph  CH  C  OH
1) (CH3)2CHOH 2)CH3-CH2-CH3 2

3) CH3CHO 4) CH3-CH2CH2OH O O
|| ||
3)
Ph  C  C  H
22. Select the compounds which can undergo
O
intramolecular cannizaro reaction in basic
medium 4)
CHO Ph OH
P hC O C H C l2 |
(A ) CHO
(B )

CHO
|
C H 3C O C H O
(C ) C H 2O H 26. In the following sequence
  i     ii 
(D )
1) A, B, D 2) B, C, D 3) A, B, C 4) B, C CH 3CH 2Cl 
NaCN Ni / H 2


acetic
  iii 
O anhydride

23. 
dil KoH
  A : Product (A) is 1) CH 3CH 2CH 2 NH 2
2) CH 3CH 2CONHCH 3
O 3) CH 3CH 2CH 2 NHCOCH 3
O
4) CH 3CH 2CH 2CONHCOCH 3
1) 2)
KEY
LEVEL - III
3) Both 1 & 2 4) None
1)2 2) 2 3) 3 4) 3 5) 2
24) Bu  C  CH  NaNH 2
6) 3 7) 3 8) 2 9) 3 10) 4
Ph CHO
H O
 
MnO2
X 11) 1 12) 1 13) 2 14) 2 15) 4
2
16)1 17) 3 18) 2 19) 4 20) 2
CHO CHO 21) 2 22) 3 23) 2 24) 2 25) 1
1) C  C  Bu 2)
26) 3
C  C  Bu
HINTS
 JEE MAINS - VOL - IX
13. Enolate ion formed is first step.
LEVEL - III 14. Methyl ketone give positive NaHSO3 test
(acidic)
2. We cannot use Wolf-kishner reduction because 15. NBS - Allylic substitution
in Wolf-Kinshner reduction due to basic medium
19. CH 3CN  4 H 
 CH 3  CH 2  NH 2
elimination take place.

 N , H O  CH 3CH 2  OH 
HONO
2 2 CH Cl  CH 3CHO
PDC
2 2

20. Oxo process or hydroformylation of alkene.

Alkene with water gas at high T & P in the
presence of cobalt carbonyl forms aldehyde.
21. Distillation of calcium salts forms carbonyl
compounds.
22. Alcohols cannot involve in intra molecular
cannizaro reaction and terminal gem dihalides on
basic hydrolysis gives aldehydes.
23. Aldol product
24. Bu  C  CNa; Nu  addition to aldehyde
3. Epoxide is unstable in acidic and basic medium group followed by oxidation to form ketone.
5. In basic medium halide undergo elimination
SeO2 oxidises   position in carbonyl
reaction ( E2 elimanation bimolecular)
compounds to  C  O  group.
O O
|| ||
25. followed by cannizaro
X  Ph  C  C  H
6. reaction.
26.  i  CH 3  CH 2  CN
 ii  CH 3  CH 2  CH 2  NH 2
conc.HNO Ca (OH ) 2
3  Adipic acid   iii  CH 3  CH 2  CH 2  NH  CO  CH 3
 
PREVIOUS MAINS QUESTIONS
2008
7. NaBH 4 and LiAlH 4 reduces carbonyl 1. In the following sequence of reactions, the alkene
compounds, carboxylic acid without effecting affords the compound ‘B’
C C . CH 3CH  CHCH 3 
O3
 A 
H2O
Zn
B
8. NaBH 4 and LiAlH 4 reduces C = C when The compound B is
phenyl group is present at  position. 1) CH 3CH 2 CHO 2) CH 3COCH 3
9. Aldol condensation
11. Cannizaro reaction 3) CH 3CH 2 COCH 3 4) CH 3CHO
12. Clemmensons reduction

2009
2. Which of the following on heating with aqueous
KOH, produces acetaldehyde ?

57
 1) CH3COCl 2) CH 3CH 2 Cl
3) CH 2ClCH 2Cl 4) CH 3CHCl2
3. In Cannizzaro reaction given below

the slowest 1)

step is :
 
1) the attack of OH at the carboxyl group
2)
2) the transfer of hydride to the carbonyl group
3) the abstraction of proton from the carboxylic 3) Hydride transfer is the slowest step
group 
4) 2CCl3CHO 
OH
 CCl3COONa  CCl3CH 2OH
4) the deprotonation of CH 2OH
Cannizaro reaction is a disproportionation
reaction
2011 One aldehyde molecule is oxidized to salt of the car-
4. Trichloroacetaldehyde was subjected to boxylic Acid, other one is reduced to
Cannizzaro’s reaction by using NaOH. The
Alcohol. So the compound is CCl3CH 2 OH
mixture of the products contains sodium
trichloroacetate and another compound. The IUPAC Name is 2, 2, 2, - Trichloro ethanol
other compound is : 5) Formaldehyde and Acetaldehyde can be oxi-
1) Trichloromethanol dized by tollen’s reagent to give silver mirror.
2) 2, 2, 2-Trichloropropanol 6) Iodoform is given by
3) Chloroform 1 ) m e t h y l k e t o n e s R - C O - C H

4) 2, 2, 2-Trichloroethanol 2) alcohols of the type R-CH(OH)CH3

5. Silver Mirror test is given by which one of the where R can be hydrogen also
following compounds ?
1) Acetone 2) Formaldehyde
3) Benzophenone 4) Acetaldehyde

2012
6. Iodoform can be prepared from all except :
1) Ethyl methyl ketone
2) Isopropyl alcohol
3) 3–Methyl – 2– butanone
4) Isobutyl alcohol

KEY
1) 4 2) 4 3) 2 4) 4
5) 2,4 6) 4

HINTS STATEMENT TYPE

 JEE MAINS - VOL - IX
1.Both the statements are true and statement- gives benzyl alcohol and formate ion.
II is the correct explanation of statement-I. Statement- II: Formaldehyde is a better
2. Both statements are true but statement-II hydride donor than benzaldehyde.
is not the correct explanation of statement-I. 10. Statement- I: Carbonyl compounds take part
3. Statement-I is true but statement-II is false in nucleophilic addition reactions.
4. Statement-I is false but statement-II is true. Statement- II: These reactions are initiated
1. Statement- I : HCHO and HCOOH can be by nucelophilic attack at the electron
distinguished by Tollen’s test. deficient carbon atom.
Statement-II: Silver mirror is formed when 11. Statement- I: Secondary alcohols can be
ammonical AgNO3 is reduced. easily oxidised to aldehydes.
2. Statement- I: CH3COCH2COCH3 does not Statement- II: Aldehydes are prone to
respond to the iodoform test with I2/OH-. further oxidation to carboxylic acids.
Statement- II Presence of active methylene
12. Statement- I: The addition of ammonia
group attracts the base.
derivatives on carbonyl compound is carried
3. Statement- I Acrolein containing aldehyde
in weakly acidic medium.
group undergoes aldol condensation with
alkali. Statement- II : In weakly acidic
Statement- II The double bond breaks when medium attacking nuclephile is also
treated with NaOH. protonated.
13. Statement- I: Fehling’s reagent is a test for
H 2 C = CH  CHO 
 HCHO + CH 3CHO
NaOH
all aliphatic aldehydes.
4. Statement- I: (CH 3 ) 2 CHCHO mainly Statement- II : Aliphatic aldehydes can be
undergoes Cannizzaro reaction when heated easily oxidised even with mild oxidising
with strong alkali. agents.
Statement- II : Steric hindrance prevents 14. Statement- I: Propanal undergoes
aldol Cannizzaro’s reaction.
condensation. Statement- II: It has an α - hydrogen atom.
5. Statement- I: The acetal formation with
ketones does not respond to base catalysis. PROPERTIES
Statement- II: The dehydration 15. Statement- I: Formaldehyde is a planar
step has to be acid catalysed. molecule.
6. Statement- I: (CH 3)3CCOC(CH 3)3 and
Statement- II: Carbon atom in
acetone can be distinguished by the reaction 2
with NaHSO3. formaldehyde is sp -hybridized.
16. Statement- I: Nitromethane can give aldol
Statement- II: SO32  is the nucleophile in condensation.
bisulphate addition. Statement- II: α - hydrogen of nitromethane
7. Statement- I: 2, 2-Dimethylpropanal is acidic.
undergoes Cannizzaro reaction with conc.
NaOH. 17. Statement- I: Chloral hydrate is stable.
Statement- II: Cannizzaro is a Statement- II: It is stable due to its high
disproportionation molecular weight.
reaction. 18. Statement- I: Acetaldehyde does not show
8. Statement- I: Aldol condensation can be aldol condensation.
catalysed both by acids and bases. Statement- II: Compounds having at least
Statement- II: β - Hydroxyaldehydes or one α - hydrogen give aldol condensation.
19. Statement- I: Lower aldehydes and ketones
ketones readily undergoes acid-catalysed
are soluble in water. The solubility
dehydration.
decreases as the molecular mass increases.
Statement- II: Distinction between
9. Statement- I: Crossed Cannizzaro reaction aldehydes and ketones can made by Tollen’s
between formaldehyde and benzaldehyde reagent.
59
20. Statement : 1 : CH3CHO on reaction with attack on sterically hindered ketones.
dil NaOH forms Aldol 7. Aldehydes not containing alpha hydrogens
Statement-II : Aldehydes and Ketones undergo cannizaro reaction.
having ‘  ’ hydrogen undergo Aldol
8. Both Carbanion (formed in presence of base)
condensation.
and enol form (formed in presence of acid) act
21. Statement : 1 :Acetaldehyde on reaction with
as nucleophiles and hence add on the carbonyl
H2SO4 at room temp forms a solidfuel
Statement : II :(CH3CHO)4 acts as a solid carbon.
fuel 11. Primary alcohols should carefully be oxidised to
22. Statement : 1 : Benzaldehyde undergoes aldehydes. Otherwise they oxidise directly to
aldol condensation. carboxylic acids.
Statement : II : It does not contain any 12. In strong acidic medium only protonation takes
 - hydrogen atom. place.
23. Statement : 1 : CH3CHO is more reactive
14. 2-methyl propanal has an ‘ α - hydrogen’. Hence
than CH3COCH3
if does not undergo cannizaro’s reaction.
Statement : II :The >C=0 group in CH3CHO
experiences more steric hinderance 17. Intermolecular hydrogen bond makes chloral
24. Statement : 1 : The solubility of aldehydes hydrate stable
and ketones in water decreases with 18. Acetaldehyde has α - hydrogens. It undergoes
increase of size of the alkyl group aldol condensation.
Statement : II :Alkyl groups are electron
releasing groups LEVEL-IV
25. Statement : 1 : The B.P’s aldehydes and
ketones are higher than those of ethers of
PASSAGE - 1
comparable molecular masses. Aldehydes containing no α - hydrogen atom,
Statement : II : Aldehydes and ketones when treated with concentrated alkali
undergo intermolecular association due to (aqueous or alcoholic), undergo self
dipole-dipole interactions. oxidation-reduction to yield a mixture of an
KEY alcohol and a salt of a carboxylic acid. This
01) 4 02) 1 03) 4 04) 1 reaction, known as Cannizzaro reaction, is
05) 1 06) 2 07) 2 08) 2 carried out at room temperature.
09) 1 10) 1 11) 4 12) 3 Cannizzaro reaction may be crossed, e.g.
13) 1 14) 4 15) 1 16) 1
C 6 H 5 CHO + HCHO  conc.
 NaOH
 
17) 3 18) 4 19) 2 20) 1
21) 4 22) 4 23) 3 24) 2 C 6 H 5 CH 2 OH + HCOONa
25) 1 Further, Cannizzaro reaction may be
HINTS internal too.
Aldehydes, having α - hydrogen atom,
1. HCHO and HCOOH respond positively to the
Tollen’s test. undergo reaction in different way.
OH
2. CH 3 COCH 2 COCH 3  OH

I2
 
2CH 3 CHO  OH
  CH 3 CHCH 2 CHO
CH 3 COCI 2 COCH 3
1. Which of the following statement is correct?
3. H 2 C = CH  CHO  
 OH 
1. Different behaviour of CH3CHO and HCHO
HCHO + CH 3CHO is due to difference in their acidic character.
4. 2.Both reactions (Cannizzaro reaction and

(CH 3 ) 2 CHCHO  OH
  aldol condensation) involve in nucleophilic
(CH 3 ) 2 CHCH 2 OH + (CH 3 ) 2 CHCOO  addition
3.Both 1 & 2 are correct
6. SO32- is a bulky nucleophile, hence, cannot 4.None is correct.
 JEE MAINS - VOL - IX
2. Which of the following can undergo
O
Cannizzaro reaction?
1. C6H5CHO 3. CH 3 - C - CH 3 undergoes nucleophilic
2. CHO.CHO O
O
addition, while CH 3 - C - CX 3 undergoes
3. C 6 H 5 CCHO nucleophilic substitution
4. All the above 4. Size of bromine is more than that of H
3. When (CH3)3CCHO and C6H5CHO are 6. Halogen reaction can be used for preparing
treated with aq. NaOH, the possible number -COOH from methyl ketones, which halogen
of products are is best suited for this purpose?
1. 1 2. 2 3. 3 4. 4 1.Cl2 2. Br2
PASSAGE - 2 3. either of the two 4. I2
When methyl ketones react with halogens PASSAGE - 3
in the presence of a base, all α - hydrogen A chemist treated a compound X with NaOH
atoms are replaced by halogens, one after in presence of acetone as solvent. However,
the other. it recovered the starting material as such,
and instead isolated a small amount of the
O O product A. the product A was shown to have
-
X2, OH C, H and O and it had a molecular weight of
CH3 - C - CH3 CH3 - C - CH3
Trihaloketone 116 g/mol. It gave a positive iodoform test
O and was found to be identical with a
compound obtained by the aldol self
X3C - C - CX3 condensation of acetone.
Although the product A did not discharge
The trihaloketone also undergoes
colour of bromine in CCl4, its dehydration
hydrolysis in presence of OH - forming
product B with hot sulphuric acid discharged
haloform.
bromine dissolved in CCl4.
7. What is the molecular weight of a compound
that undergoes an aldol self condensation
reaction and whose dehydrated product has
4. During formation of trihaloketone, which a molecular weight of 70?
halogen is introduced most easily? 1. 35 2. 44 3. 49 4. 58
1. First 2. Second 8. The aldol self condensation of acetone is in
3. Third 4. All at the same rate equilibrium that favours acetone over its
5. Acetone as well as trihaloacetone, both corresponding product. Which of the
contain C = O group, only the latter is following conditions is most likely to shift
hydrolysed by alkali while the former does the position of equilibrium toward product
not undergo hydrolysis. this is because. A?
1. By using a catalytic amount of NaOH
O
2. By using only a catalytic amount of acetone
1. CH 3 - C - CH 3 is stable, while 3. By removing product A as soon as it is formed
4.By increasing reaction temperature
9. Which of the following compounds will give
is unstable. a positive iodoform test?
A. C2 H 5OH B. CH 3CHO
2. -CX3 is stable while -CH3 is unstable.
C. CH 3OH D. HCHO

61
 1. Only compound A 2. Only compound B 11. Which one is most reactive for addition of
3. Both A and B 4.Only compound Z alcohol on carbonyl group?
PASSAGE - 4 1. C6H5CHO 2. HCHO
Aldehydes and ketones are polar molecules. 3. H C 4. CH3CH2CHO
3 CH CH 2 3
Nucleophiles usually attack C = O at
carbon (positively charged) and are attacked
by oxygen. The characteristic reaction of O
aldehyde and ketone is nucleophilic addition
12. How many aldol products can be formed
to the carbon of the group.
when 2-butanone and propionaldehyde
δ δ+ δ  O
δ+
O +H  A   H
reacts in presence of dilute base?
  A
1. 4 2. 5 3. 6 4. 7
H 13. Match the following
O
H
-  
O
A) Grignard reagent 1) H2 /Pd  BaSO 4
H + HO  R + H 2O
H
R
base enola te B) Clemmenson 2) N 2 H 4 /KOH /
reduction CH 2 OH  CH 2 OH

O O OH O C) Rosenmund’s 3) CH3MgX
O
O   H2O reduction
+   H H
H + R
R R R R D) Wolf-Kishner 4) Zn  Hg/Conc.HCl
R al dol
reduction
The reactivity of carbonyl compounds for
5) H 2 /Ni
nucleophilic addition reaction is inversely
proportional to electron releasing effects A B C D
(+I, +M) of the groups attached to the 1. 3 4 2 1
carbonyl carbon. 2. 3 4 1 2
10. Which of the following undergoes aldol 3. 2 1 4 5
condensation? 4. 5 3 2 1
H 14. Match the following
1. H Name of the reaction Reagent used
H 5C 6 1. Rosenmund’s reduction A. Zn-Hg/ConHCl
O 2. Wacker’s Process B.NH2-NH2+KOH
C 6H 5
+ (CH2OH)2
2. 3. Clemensons reduction C.PdCl2+CuCl2/H+
Cl
H 4. Wolff- kishner reduction D.Pd-BaSO 4/Qunoline
Cl 1) 1-D, 2-C, 3-A, 4-B
O 2) 1-B, 2-D, 3-C, 4-A
Cl
3) 1-A, 2-C, 3-B, 4-D
3. H
4) 1-C, 2-B, 3-A, 4-D
O
15. Match the reactions given in Column I with the
suitable reagents given in Column II.
4. CH 3 Column I Column II
i) Benzophenone
CHO
 Diphenylmethane a) LiAlH 4
 JEE MAINS - VOL - IX
ii) Benzaldehyde 
1-Phenylethanol b) DIBAL-H
iii) Cyclohexanone 4.
 Cyclohexanol c) Zn  Hg  / Conc.HCl
iv) Phenyl benzoate
 Benzaldehyde d) CH 3 MgBr 18.
1) i - (c) ii - (d) iii- (a) iv - (b)
  X    Y  (Major) ;
CH N CF CO H
2) i - (d) ii - (c) iii- (a) iv - (b) 
2 2 3 3

3) i - (a) ii - (d) iii- (c) iv - (b) Product (Y) is ;

4) i - (c) ii - (d) iii- (b) iv - (a)

16. In the given reaction 1)

OH OH
1 1
CH 3 C  C (CH 3 ) 2 
HIO4
 A B
(A) and (B) respectively are 2)
1) CH 3CHO, CH 3CHO
2) CH 3COCH 3 , CH 3CHO
3) CH 3COCH 3 , CH 3COCH 3 3)
4) CH 3COOH , CH 3COCH 3
4)
19. (CH3)2 C = CHCOCH3  (CH3 )2 CO
HCl
 ’X’. Here
‘X’ is
17. 1) Mesityl oxide 2) Phorone
3) Acetic acid 4) Mesitylene
20. 2CH3COCH3 'X'. ‘X’ is
dryHCl
Product (C) of 1) Mesityl oxide 2) Diacetone alcohol
above reaction; 3) Acetic acid 4) Mesitylene
21. Metaldehyde is the product of the following
1.
1) 4CH 3  CHO  
O
Conc.H 2SO4 , 0 C

O
||
2) CH  C  CH 
Conc.H 2SO 4 , roomtemp.

3 3

2.
3) 3CH 3CHO 
Conc.H 2SO 4 , roomtemp.

4) C 6 H 5  CHO  
Conc.H 2SO 4

22. Acetaldehyde when treated with
3. Conc.H 2SO 4 at room temp. undergoes
trimerisation and forms
1) Metaldehyde 2) Aldol
3) Paraldehyde 4) Acetaldoxime
23. Acetone is distilled with concentrated
H2SO4. The resultant product obtained is

63
 Molecular weight of the parent compound
88
1) 2) =  44
2
8. Removal of product A will favour the conversion
of acetol to product A to maintain equilibrium.
10. Aldehydes with atleast one α -H atom may
3) 4) undergo aldol condensation.
11. HCHO is highly reactive towards nucleophilic
additions.
17. PhCOCH 3 
NaNo2
PhCOCH 2 NO
KEY HCl

LEVEL-IV  PhCOCH  NOH 

Ac2O

H O 2
1) 3 2) 4 3) 4 4) 3 5) 2 
6)3 7) 2 8) 3 9)3 10) 1 PhCOCN  H 3O
 PhCOCO2 H
11)2 12)3 13) 2 14) 1 15)1 18. Bayer villeger oxidation
16) 2 17) 2 18) 2 19) 2 20) 1
21) 1 22) 3 23) 4

HINTS
LEVEL-IV

1. Aldol condensation is due to acidic behaviour of

α - H of carbonyl Compounds. Since HCHO
has no such ‘H’, it can not undergo aldol
condensation. Both reactions involve the attack
of nucleophile, OH- in Cannizaro reaction and
carbanion in aldol condensation as the Carbonyl
group.
2. All the three undergo Cannizaro reaction because
of absence α - ‘H’
3. Either of the compounds can undergo oxidation
as well as reduction. So, the total number of
Products will be four.
4. Introduction of the first halogen is slowest, while
that of the last, i.e., third is fastest because
introduction of the halogen increases the acidity
of the remaining α - hydrogens.
5. : CX 3 is a better leaving group and stabilised due
to the dispersal of the negative charge by three
halogens.
6. Since chloroform and bromoform are water
immiscible liquids, they can easily be separated
from the aqueous solution of the carboxylate
anion.
7 Molecular weight of dehydrated product = 70
Molecular weight of hydrated compound
(product of aldol self condensation)
= 70 + 18 = 88