CAK – 1

ALDEHYDES AND KETONES

C1A Physical Properties :

It has high dipole moment

Boiling point are lower than alcohols due to their inability to form intermolecular H-bonding.
B.Pt. are higher than corresponding alkanes due to dipole-dipole interaction.
Carbonyl group can form H-bond with H2O hence they are soluble in water to varying extent.
C1B Method of Preparation :
1. Oxidation :

(a)

(b)

(c)

This oxidation is called as oppenauer oxidation.

2. Rossenmund Reduction :

3. [LiAlH (O-t-C4H9)3 or Lithium tri-t-butoxy Aluminium hydride]

4.
5. Hydrolysis of Gem-Dihalide

(a)

(b)

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 CAK – 2
Cl , heat H O
(c) ArCH 3 2  ArCHCl 2 
2
 ArCHO

6. Hydration of Alkynes : Hydration of alkynes gives ketones (except CH  CH which gives CH3CHO)


(a) H O, H H O, H 
CH  CH 2  CH 3 CHO (b) CH 3 C  CH 2  CH 3 COCH 3
HgSO 4 HgSO 4

7. Hydroboration Oxidation :
Hydroboration of a non-terminal alkyne followed by oxidation of the intermediate yields a ketone
but terminal alkyne yield aldehyde.

8. Use of Grignard Reagent :

(a) With HCN aldehyde is formed.

(b) With RCN a ketone is formed.

9. With Esters

(a)

(b)

10. Decarboxylation of calcium salts of carboxylic acids :

11. Oxo Process :

2 CH3CH = CH2 + CO + H2 CH3CH2CH2CHO +

[COH(CO)4] 
 Cobal + Carbonyl hydride
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12. Reduction of acid chloride with organocopper compounds :

13. Friedel-Crafts Acylation :

(a)

(b)

14. From Cadmium and Lithium Salts :

1. 2RMgX + CdCl2 
 R – Cd – R + MgCl2 + MgX2

R – Cd – R + R’COCl 
 RCOR’ + RCdCl

 should be 10 alkyl or aryl (–C6H5)

R 

15. Ozonylysis of Alkene (Zn/H+) 

 Aldehyde/Ketone

C2 Chemical Properties :
1. Nucleophilic Addition to the Carbon-Oxygen Double bond :
The most characteristic reaction of aldehyde and ketone is nucleophilic addition to the
carbon-oxygen double bond.

General Reaction :

Relative reactivity of Aldehydes versus Ketones :

Aldehydes are more reactive than Ketones. There are two reasons for this, they are as follows :
1. Steric Factor 2. Electronic factor
1. Steric Factor : With one group being the small hydrogen atom, the central carbon of the tetrahedral
product formed from the aldehyde is less crowded and the product is more stable.
With ketones two alkyl groups at the carbonyl carbon causes greater steric crowding in the
tetrahedral product and make it less stable. Therefore small concentration is present at equilibrium.
2. Electronic Factor : Because alkyl group are electron releasing therefore aldehydes are more reactive
on electronic grounds as well. Aldehyde have one electron releasing alkyl group to stablise the partial
positive charge on the carbon atom of the carbonyl group. Whereas ketones have two alkyl groups.

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(a) Addition of cyanide :

(b) Addition derivatives of ammonia :

(i)

(ii) HCHO reacts with NH3 differently forming UROTROPINE [hexamethylene tetraamine].

6HCHO + 4NH3  (CH2)6N4 + 4H2O

H2N – G Product

H2N – OH Hydroxylamine = N – OH oxime

H2N – NH2 Hydrazine = N – NH2 Hydrazone

H2N – NHC6H5 Phenylhydrazine = N – NHC6H5 Phenylhydrazone

H2N – NHCOCH2 Semicarbazine = NNHCOCH2 Semicarbazone

(c) Addition of Alcohols : Acetal Formation

(i)

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(ii)

Important :

(d) Addition of Grignard reagents :

Formaldehyde with Grignard Reagent gives 10alcohol, all higher aldehydes with grignard reagent
give 20 alcohol and ketones with grignard reagent gives the 30 alcohol.
C3 Other Reactions of Aldehyde and Ketones :
(a) Oxidation :

(i) RCHO or ArCHO

Aldehydes (except) benzaldehyde reduce “Fehling’s Solution” (Cu2+ reduced to Cu+) which is an
alkaline solution of Cu2+ ion complexed with tetrarate ion.
(ii) Example : Tollen’s Test :

CH 3 CHO  2Ag( NH 3 ) 2   3OH – 

 CH 3 COO   2Ag  4NH 3  2H 2 O
Colourless Silver
Solution mirror

Fehling Solution CH 3 CHO  2Cu 2   3OH  

 CH 3 COO   2Cu   2H 2O
Re d PPt .

Tollen’s test is cheifly given by aldehydes. Tollen’s reagent does not attack carbon-carbon double
bond. Aldehyde also reduce benedict’s solution (Cu2+ complexed with citrate ion) to Cu+
(b) (i) Ketones with strong oxidants and at high temperature undergo cleavage of C-C
bond on either side of carbonyl group.

Carbonyl Group after bond cleavage goes with that alkyl group which is of smaller
size.
(ii) Ketones are also oxidised from cleavage of bond by caro’s acid (H2SO5) or
peroxybenzoic acid (C6H5CO3H) to esters. RCOR  H SO 5
 RCOOR  [Bayer’ss
2 
[O ]

Villiger Oxidation]

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(c) Haloform Test :
(i) Methylketones :

(ii) Hypohalite NaOX (NaOH + X2) cannot only halogenate can also oxidise alcohols

(d) Reduction :

(a) Reduction to alcohol

(e) Reduction to hydrocarbons :

(f) Reductive Amination (Discussed under Amines)

(g) Cannizzaro reaction : In the presence of an concentrated base i.e. alkali, aldehydes
containing no -hydrogens undergo self oxidation and reduction to yield a mixture of an
alcohol.

(i)

(ii)

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(h) Crossed Cannizzaro reaction :

(i) Tischenko Reaction :

All aldehyde in presence of aluminium ethoxide, Al(OC2H5)3 can be simultaneously oxidised
(to acid) and reduced (to alcohols) to form ester. This is called Tischenko reaction and is
thus like cannizaro reaction.

(j) Distinction
Aldehyde and Ketones
S.No. Test RCHO RCOR
1. Schiffs magenta no. reaction
reagent colour restored by
RCHO
2. Tollen’s reagent is reduced by RCHO is not reduced
3. Fehling’s solution is reduced by RCHO is not reduced
(except C6H5CHO) -hydroxy, ketones
reudce Tollen’s re
agent and Fehling’s
solution

Practice Problems :
NaOH
1. Identify (Z) in the reaction series, CH 2  CH 2 HBr
 (X) Hydrolysis
  (Y) I ( Z)
2 ( excess )

(a) C2H 5I (b) C2H5OH (c) CHI3 (d) CH3CHO

2. A compound (X) of the formula C3H8O yields a compound C3H6O on oxidation. To which of the
following class of compounds could (X) belong
(a) aldehyde (b) secondard alcohol
(c) alkene (d) tert. alcohol
3. Which statement is incorrect in the case of acetaldehyde and acetone
(a) both react with hydroxylamine
(b) both react with NaHSO3

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 CAK – 8
(c) both react with hydrazine
(d) both reduce ammonical silver nitrate
4. Which of the following undergoes Cannizzaro’s reaction
(a) CH3CHO (b) CH3CH2CHO (c) (CH3)2CHCHO (d) HCHO
5. Urotropine is formed by the action of ammonia on
(a) acetaldehyde (b) formaldehyde (c) acetone (d) phenol
6. Hydrocarbons are formed when aldehydes and ketones are reacted with amalgamated zinc and
conc. HCl. The reaction is called
(a) Cannizzaro’s reaction (b) Clemmensen’s reduction
(c) Rosenmund’s reaction (d) Tischenko reaction
7. When acetaldehyde is treated with aluminium ethoxide, it forms
(a) ethyl acetate (b) ethyl alcohol
(c) acetic acid (d) methyl propionate
8. Chloretone is formed when chloroform reacts with
(a) formaldehyde (b) acetaldehyde (c) acetone (d) benzaldehyde
9. Which of the following reagent reacts differently with HCHO, CH3CHO and CH3COCH3
(a) HCN (b) NH2OH (c) C6H5NHNH2 (d) NH3
10. In the following sequence of reactions, the end product is
2
CaC2 H
2O
 (A) Hg
 / H 2SO 4
 (B) [
O]
((C) Ca
( OH
 )2
(D) heat
(E)
(a) acetaldehyde (b) formaldehyde (c) acetic acid (d) acetone
11. In the following sequence of reactions, the end product is
2
HC  CH Hg
 / H 2SO 4
 (A) CH
3MgX

 [O]
((B)  (C)
[ H 2O ]

(a) acetaldehyde (b) isopropyl alcohol

(c) acetone (d) ethyl alcohol
HCN H O
12. In the following sequence of reactions, the end product is CH 3CHO 
( A ) 

2
 ( B)
(a) CH3COOH (b) CH3CHOHCOOH
(c) CH3CH2NH2 (d) CH3CONH2
13. A compound, C5H10O, forms a phenyl hydrazone and gives negative Tollen’s and iodoform tests. The
compound on reduction gives n-pentane. The compound A is
(a) pentanal (b) pentanone-2 (c) pentanone-3 (d) amyl alcohol
14. The product Z in the series is
Na 2 CO 3
CH 2  CH 2 HBr
 X Hydrolysis
   Y I  Z
2 ( excess )

(a) C2H 5I (b) C2H5OH (c) CHI3 (d) CH3CHO

15. If formaldehyde and KOH are treated together, we get
(a) methane (b) methanol (c) ethyl acetate (d) acetylene
16. The correct order of reactivity in nucleophilic addition reaction CH3CHO, CH3COC2H5 and
CH3COCH3 is
(a) CH3CHO > CH3COCH3 > CH3COC2H5
(b) C2H5COCH3 > CH3COCH3 > CH3CHO
(c) CH3COCH3 > CH3CHO > C2H5COCH3
(d) CH3COCH3 > C2H5COCH3 > CH3CHO

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17. To distinguish between 2-pentanone and 3-pentanone which reagent can be used
(a) NaOH/I2 (b) Tollen’s reagent
(c) K 2Cr2O7/H +
(d) Zn–Hg, HCl
18. CH3CH = CHCHO is oxidised to CH3 – CH = CHCOOH, using oxidising agent as
(a) alkaline KMnO4 (b) K2Cr2O7/conc. H2SO4
(c) ammonical AgNO3 (d) dilute HNO3
19. m-chloro benzaldehyde on reaction with conc. KOH at room temperature gives
(a) potassium m-chloro benzoate and m-hydroxy benzaldehyde
(b) m-chloro benzyl alcohol and m-hydroxy benzaldehyde
(c) m-chloro benzyl alcohol and m-hydroxy benzyl alcohol
(d) m-chloro benzyl alcohol and potassium m-chloro benzoate
20. The reagent which can be used to distinguish acetophenone from benzophenone is :
(a) 2, 4-dinitrophenyl hydrazine (b) benedict reagent
(c) I2 and Na2CO3 (d) aqueous solution of NaHSO3
21. Best starting material to synthesize 2-methyl-2-butenoic acid is

(a) (b) CH3CH2CH2CHO

(c) (d)

22. X and Y can be distinguished by :

(a) silver-mirror test(b) iodoform test (c) both (d) none

23. Which of the following will give haloform test
O
||
(a) CH3  C CCl3 (b) CH 3  C  CH 2 I
|
OH
(c) CH 3  C CH 2Cl (d) all
||
O

[Answers : (1) c (2) b (3) d (4) d (5) b (6) b (7) a (8) c (9) d (10) d (11) c (12) b (13) c (14) c (15) b
(16) a (17) a (18) a (19) d (20) c (21) c (22) c (23) d]

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SINGLE CORRECT CHOICE TYPE
1. Which of the following reagent reacts differently 8. Formic acid and formaldehyde can be distinguished
with HCHO, CH3CHO and CH3COCH3 by treating with
(a) HCN (b) NH2OH (a) Benedict’s solution
(c) C6H5NHNH2 (d) NH3 (b) Tollen’s reagent
2. In the following sequence of reactions, the end (c) Fehling’s solution
product is
(d) NaHCO3
Condensati on Dehydratin g agent
CH 3CHO   
(A )    
(B) Al ( OC H )
mild alkali heat 9. 2CH3CHO  2  
5 3
 CH3COOCH2CH3. This
reaction is called
(a) aldol
(a) Cannizzaro’s reaction
(b) crotonaldehyde
(b) Aldol condensation
(c) paraldehyde
(c) Claisen’s reaction
(d) metaldehyde
(d) Tischenko reaction
3. Which of the following reaction is a condensation
reaction 10. The reaction involving condensation of acetic an-
hydride with an aromatic aldehyde by a carboxy-
(a) HCHO  Paraformaldehyde
late ion is an example of
(b) CH3CHO  Paraldehyde
(a) aldol condensation
(c) CH3COCH3  Mesityl oxide
(b) benzoin condensation
(d) CH2 = CH2  Polyethylene
(c) Perkin reaction
4. A compound A has molecular formula C2Cl3OH. It
(d) Wurtz reaction
reduces Fehling’s solution and on oxidation gives a
monocarboxylic acid. A is obtained by the action of 11. Benzaldehyde when refluxed with aqueous alcoholic
Cl2 on ethyl alcohol. The compound A is KCN forms
(a) chloroform (a) benzoin
(b) chloral (b) benzene
(c) trichloro ethanol (c) phenyl cyanide
(d) trichloro acetic acid (d) phenyl isocyanide
5. The product Z in the series is 12. Benzyl alcohol is obtained from benzaldehyde by
(a) Wurtz reaction
HBr Hydrolysis
CH 2  CH 2 
 X   Y (b) Cannizzaro’s reaction
(c) Perkin reaction
Na 2 CO 3
(d) Claisen reaction
I  Z
2 ( excess )
Anhyd .AlCl
13. C6H6 + CO + HCl   
3  (X) + HCl
(a) C2H 5I (b) C2H5OH
The compound (X) is
(c) CHI3 (d) CH3CHO
(a) C6H5CHO (b) C6H5COOH
6. Cyanohydrin of which of the following gives lactic
acid on hydrolysis (c) C6H5CH2Cl (d) C6H5CH3
(a) acetone (b) acetaldehyde 14. Which of the following is the weakest acid
(c) propanal (d) HCHO (a) benzene sulphonic acid
7. In the reaction CH3CHO + HCN  CH3CHOHCN, (b) benzoic acid
a chiral centre is produced. The product is (c) benzyl alcohol
(a) meso compound (d) phenol
(b) laevorotatory
(c) dextrorotatory
(d) racemic mixture

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15. In the Cannizzaro’s reaction given below 20. Which of the following will give haloform test
O
||
OH  
2Ph  CHO 
 Ph  CH 2 OH  PhCO 2
(a) CH3  C CCl3
the slowest step is
(b) CH 3  C  CH 2 I
(a) attack of OH— at the carbonyl group |
OH
(b) the transfer of hydride to the carbonyl
group (c) CH 3  C CH 2Cl
(c) the abstraction of proton from the ||
O
carboxylic acid
(d) the deprotonation of Ph–CH2OH (d) all

16. The reagent(s) which can be used to distinguish

acetophenone from benzophenone is (are) :
cannizzaro
21.     X and Y
(a) 2, 4-dinitrophenyl hydrazine
(Y is alcohol, D is deuterium)
(b) benedict reagent
X and Y will have structure :
(c) I2 and Na2CO3
(d) aqueous solution of NaHSO3
17. m-chloro benzaldehyde on reaction with conc. KOH
at room temperature gives (a)

(a) potassium m-chloro benzoate and

m-hydroxy benzaldehyde
(b) m-chloro benzyl alcohol and
m-hydroxy benzaldehyde
(b)
(c) m-chloro benzyl alcohol and m-hydroxy
benzyl alcohol
(d) m-chloro benzyl alcohol and potassium
m-chloro benzoate
18. A natural compound (X), C4H8O2, reduces Fehling’s
solution, liberates hydrogen when treated with (c)
sodium metal and gives a positive iodoform test.
The structure of (X) is
(a) CH3CHOHCH2CHO (d) none is correct
(b) HOCH2CH2CHO
(c) CH3COCH2CHO
22. NaOH
 A
(d) CH3COCH2CH2OH 

A is :

(a)
19.

X and Y can be distinguished by : (b)

(a) silver-mirror test(b) iodoform test
(c) both (d) none (c)

(d) none is correct

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23. A carbonyl compound with molecular weight 86, ANSWERS (SINGLE CORRECT
does not reduce Fehling’s solution but forms
crystalline bisulphite derivatives and gives CHOICE TYPE)
iodoform test. The possible compounds can be
(a) 2-pentanone and 3-pentanone 1. d 11. a 21. a
(b) 2-pentanone and 3-methyl-2-butanone 2. b 12. b 22. a
(c) 2-pentanone and pentanal 3. c 13. a 23. b
(d) 3-pentanone and 3-methyl-2-butanone 4. b 14. c 24. b
24. In the Cannizzaro’s reaction given below, 5. c 15. b

6. b 16. c
2Ph  CHO OH
 PhCH 2 OH  PhCOO 7. d 17. d
the slowest step is 8. d 18. a
(a) the attack of OH— at the carbonyl group
9. d 19. c
(b) the transfer of hydride to the carbonyl
group 10. c 20. d
(c) the abstraction of proton from the
carboxylic acid
(d) the deprotonation of Ph–CH2OH

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EXCERCISE BASED ON NEW PATTERN
COMPREHENSION TYPE 4. Structure of K formed is
Comprehension-1
H CrO (a)
Cyclohexanol 2 4  A(C 6 H10O)
acetone

( 1) CH MgI HA
 3

 B(C 7 H 14 O ) 
 C(C 7 H 12 )
( 2 ) H 3O heat
(b)
(1 ) O 3 (1) Ag 2O , OH 
 D(C 7 H 12O 2 )    

 E(C 7 H 12O 3 )
( 2 ) Zn , HOAc ( 2 ) H 3O

1. The structure of compound B formed is (c)

(a) (b)
(d)
5. Thus L is

(c) (d)
(a)
2. The D formed in the above sequence is

(b)
(a) (c) CH3CH = CHCO2Et

(b) (d)
(c) 6. Thus M is
(d) HOOC(CH2)4COOH (a) CH3CH2CH2CO2Et
–
3. D on treatment with Ag 2 O, OH and upon
acidification forms
(b)

(a)
(c)
(d) CH3CH2COOH
(b)
Comprehension-3
(c)
(d) HOOC(CH2)4COOH
A B
Comprehension-2  
The following reaction sequence shows how the
carbon chain of an aldehyde may be lengthened by
two carbon atoms.
( i ) NaOH
(1) BrCH CO Et , Zn
Ethanal   2 2  K (C 6 H 12 O 3 )  
HA , heat   
 Product(s) ?
( 2 ) H 3O ( ii ) H

H , Pt ( 1) DIBAL  H 7. The missing reagent A is

L(C 6 H 10O 2 ) 2  M(C 6 H 12O 2 )    
( 2 ) H 2O (a) OsO4, NaHSO3 (b) dilute KMnO4
butanal (c) any one of these (d) O3/H2O2
8. The missing reagent B is
(a) HIO4 (b) NaIO4
(c) any one of these (d) None
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9. The product(s) formed is/are (c) 2-Methyl propionaldehyde
(d) 2, 2-Dimethyl-propionaldehyde
8. On heating which of the following get
(a) (b) decarboxylated ?
(a) Methylmalonic acid
(b) succinic acid
(c) both of these (d) none
(c) 2, 2-Dimethyl acetoacetic acid
MULTIPLE CORRECT CHOICE TYPE
(d) Maliec acid
1. A new carbon-carbon bond formation is possible
in 9. Cannizaro reaction will be given by
(a) Cannizoro reaction
(a) (b)
(b) Friedal-craft reaction
(c) Clemensen reduction
(c) (d) CCl3 CHO
(d) Reimen-Tiemann reaction
2. Which of the following undergoes Aldol 10. Which of the following is/are correct about an
Condensation acetal ?
(a) Acetaldehyde (a) it is a condensation product of two
molecules of aldehyde
(b) propionaldehyde
(b) it is the condensation product of two
(c) Benzaldehyde molecules of ketones
(d) Trideuteroacetaldehyde (c) it is the condensation product of one
3. Which of the following on reduction with LiAlH4 molecular of aldehyde two molecules of
with give ethyl alcohol ? Alcohols
(a) (CH3CO)2O (b) CH3COCl (d) it is a diether
(c) CH3CO NH2 (d) CH3COOC2H5 Assertion-Reason Type
4. Acetophenone is obtained when Each question contains STATEMENT-1 (Assertion)
(a) Benzoylchloride treated with dimethyl and STATEMENT-2 (Reason). Each question has
cadmium 4 choices (A), (B), (C) and (D) out of which ONLY
ONE is correct.
(b) Acetylchloride is treated with dimethyl
cadmium (A) Statement-1 is True, Statement-2 is True;
Statement-2 is a correct explanation
(c) Acetyl chloride is treated with benzene
for Statement-1
in presence of anhydrous AlCl3
(B) Statement-1 is True, Statement-2 is True;
(d) Benzoyl chloride is reduced with H2 in
Statement-2 is NOT a correct
presence of Lindar’s catalyst
explanation for Statement-1
5. Which of the following on oxidation with alk.
(C) Statement-1 is True, Statement-2 is False
KMnO4 followed by acidification with HCl gives
benzoic acid (D) Statement-1 is False, Statement-2 is True
(a) Methyl benzene (b) Ethyl benzene 1. STATEMENT-1 : H2CO is a planar molecule.
(c) O-xylene (d) p-xylene STATEMENT-2 : In H2CO, C is sp2 hybridised
6. Which of the following statements about 2. STATEMENT-1 : H 2 + PhCH 2 CH 2 COCl
Benzaldehyde is/are true ? Pd / C
S   Ph CH2CH2CHO
(a) Reduces Tollen’s reagent or quinoline

(b) Undergoes Aldol condensation above reaction is correct.

(c) Undergoes cannizaro’s reaction STATEMENT-2 : The reduction stops at the
(d) Does not form an addition compound aldehyde stage because the catalyst is poinsoned
with NaHSO3 by adding quinoline.
7. Base-catalysed Aldol condensation occurs with
(a) propionaldehyde
(b) Benzaldehyde

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 CAK – 15
8. STATEMENT-1 : Aldehydes are more reactive
3. STATEMENT-1 : H
SO

 than carboxyl group.
2 4
STATEMENT-2 : Carbonyl compounds cannot
form hydrogen bonding with H2O.
9. STATEMENT-1 : Boiling points of carbonyl
compounds are higher than those of alkanes.
STATEMENT-2 : Boiling points of carbonyl
The above reaction is pinacol-pinacolone compound are higher because of hydrogen-
rearrangement. bonding.
STATEMENT-2 : In Pinacol-pinacolone 10. STATEMENT-1 : The reaction of aldehydes and
rearrangement formation of the cyclopbtyl C+ is ketones with LiAlH4 and NaBH4 is uncleophilic
unlikely because the ring strain decreases. addition reaction.
4. STATEMENT-1 : When C 6 H 6 react with STATEMENT-2 : Aldol condensation reaction is
CO + HCl in the presence of CuCl/AlCl3, it form not given by C6H5CHO.
C6H5CHO.
STATEMENT-2 : The electrophilic aromatic
substitution take place in above reaction.
5. STATEMENT-1 : Under wollff-kishner reduction
RCHO reduce to CH4.
STATEMENT-2 : Under Clemmenson reduction
pHCH2CHO reduce to pHCH2CH3
6. STATEMENT-1 : H2CO is always oxidised in the
crossed cannizzaro reaction.
STATEMENT-2 : H 2CO is the most reactive
aldehyde, it exists in aqueous OH– solution mainly
as the conjugate base of its hydrate, H2C(OH)O–.
7. STATEMENT-1 : PCC oxidises 1 0 alcohol to
aldehyde and 20 alcohol to ketone.
STATEMENT-2 : Cu dehydrates 30 alcohol to
alkene.

(Answers) EXCERCISE BASED ON NEW PATTERN

COMPREHENSION TYPE
1. a 2. b 3. a 4. c 5. c 6. a
7. c 8. c 9. c
MULTIPLE CORRECT CHOICE TYPE
1. b, d 2. a, b, d 3. a, b, d 4. a, c 5. a, b 6. a, c
7. a, c 8. a, c 9. b, c, d 10. c, d
ASSERTION-REASON TYPE
1. B 2. A 3. C 4. A 5. D 6. A
7. B 8. C 9. C 10. B

Einstein Classes, Unit No. 102, 103, Vardhman Ring Road Plaza, Vikas Puri Extn., Outer Ring Road
New Delhi – 110 018, Ph. : 9312629035, 8527112111
 CAK – 16
INITIAL STEP EXERCISE
(SUBJECTIVE)
1. Complete the following equations and write down 7. A ketone (A) which undergoes haloform reaction
the names of the products : gives compound (B) on reduction. (B) on heating
with sulphuric acid gives compound (C), which
forms monozonide (D). (D) on hydrolysis in
(i) =O 1
. KCN / H 2SO 4
  ? presence of zinc dust gives only acetaldehyde.
2. LiAlH 4
Identify (A), (B) and (C). Write down the reactions
involved.
(ii) CH 3CH 2 C  CH (
i ) BD 3 ,THF
  ?
( ii ) H 2 O 2 , OH 8. Show, by equations, how acetaldehyde may be
converted into :
2. Identify the (A), (B), (C) and (D) in the following
reactions sequence : (i) EtOH; (ii) CH3COCl; (iii) CHI3; (iv) MeCOEt;
(v) CH3CO2Et; (vi) CH3CHOHCO2H; (vii) EtNH2;
(viii) CH3CHBrCHBrCO2H.
(i) CH 3  CH  CH  CHO NaBH
4 (
9. Convert ClCH2CH2CHO into HOCH2CHOHCHO.
10. Compound (A) and (B) on reaction in ether
HCl
(A) ZnCl
2 (B) 
 (C) KCN medium and subsequent acidification and

H oxidation give 2, 5-dimethyl 3-hexanone. What are
(A) and(B) ?
11. Identify (A) to (E) as reactant, reagent, product or
(ii) CH 3CH 2CH 2 Br KOH
 ( alc.) Br2
(A)  ( name of the reaction in following :

KOH ( alc.) Hg 2 (i) 3(CH 3 ) 2 C  O (

A)
( B)
(B) followed
 by NaNH
2 (C) H (D)
2SO 4 ( dil.) Aldol condensation
(C)
Ag 2 O PCl5
(ii) CH 3COCl  H 2  (D)
(iii) CH 3CHO 
(A) 
(B) Rosenmund’s reaction
NH 2 NH 2
H2
CH 3 MgBr (iii) ( E ) C  CH 3CH 2 CH 3 (F)
Pd
/ BaSO
4 (C)  

(D) 2 H 5 ONa
H 2O / H
12. Write the structural formula of the main organic
3. What happens when (Give equation only) Chloral prudent formed when : the compound obtained by
is heated with aqueous sodium hydroxide. the hydration of ethyne is treated with dilute
4. How will you differentiate between alkali.
(i) Acetaldehyde and Acetone. 13. How can we convert PhCH = CHCOCH3 to
5. How would you bring the following conversions : (a) PhCH = CHCOOH
(a) Acetone from acetaldehyde. (b) PhCH = CHCHOHCH3
(b) Methanal to ethanal (not more than (c) PhCH2CH2COCH3
3 steps) (d) PhCH = CHCH2CH3
(c) Acetone from methane. (e) Ph(CH2)3CH3
(d) 2-Butanone from ethyl alcohol. 14. An organic compound (A) contains 40% carbon
(e) 3-Hexanone from n-propyl alcohol. and 6.7% hydrogen. Its V.D. is 15. On reaction with
a conc. solution of KOH, it gives two compounds
6. Arrange the following :
(B) and (C). When (B) is oxidised, the original com-
(i) CH3CHO, CH3COCH3, HCHO, pound (A) is obtained. (C) give effervecence with
C2H5COCH3 in decreasing order of NaHCO3. Write the structures of A, B, C and D and
nucleophilic addition. explain the reactions.
(ii) CH3COCH2CHO,CH3COCH3, 15. An organic compound (A), C4H9Cl on reacting with
CH3CHO, CH3COCH2COCH3 in aqueous KOH gives (B) and on reaction alc. KOH
increasing order of expected enol content. gives (C) which is also formed on passing the
vapours of (B) over heated copper. The compound

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New Delhi – 110 018, Ph. : 9312629035, 8527112111

(C) readily decolourizes bromine water. Ozonoly-
sis of (C) gives two compounds (D) and (E). Com-
pound (D) reacts with NH2OH to give (F) and the
compound (E) reacts with NaOH to give an alcohol
(G) and sod. salt (H) of an acid. (D) can also be
prepared from propyne on treatment with water in
presence of Hg++ and H2SO4. Identify (A) to (H) with
proper reasoning.
16. How would you convert :
CAK – 17
18. A certain hydrocarbon A was found to contain
85.7% C and 14.3 % H. This compound consumes
1 molar equivalent of hydrogen to give a saturated
hydrocarbon B. 1.0 g of hydrocarbon A just
decolourised 38.05 of a 5 percent s o l u t i o n
(by weight) of Br 2 in CCl 4 . Compound A on
oxidation with concentrated KMnO 4 gave
compound C (molecular formulae C4H 8O) and
acetic acid. Compound C could easily be prepared
by action of acidic aqueous HgSO4 on 2-Butyne.
Determine the molecular formula of A and deduce
the structure of A, B and C

17. An organic compound A, C8H6, on treatment with

dilute H2SO4 containing HgSO4 gives a compound
B which can also be obtained from the reaction of
benzene with an acid chloride in the presence of
anhydrous AlCl3. The compound B when treated
with iodine and aq. KOH, yields C and a yellow
compound D. Identify A, B, C and D with
justification. Show how C and D is formed.

FINAL STEP EXERCISE

(SUBJECTIVE)
1. How would you bring the following conversions : H 
(ii) PhMeC(OH)C(OH)MePh  ?
(a) Ethanal to 2-hydroxy-3-butenoic acid.
5. Compound (A), C10H12O gives off hydrogen on
treatment with sodium metal and also decolourises
(b) Propanal to
Br2 in CCl4 to give (B), C10H12OBr2. (A) on treat-
ment with I2 in NaOH gives iodoform and an acid
2. Convert : (i) n-butanol into 2-ethylhexan-1-ol; (C) after acidification. Give structures of (A) to (C)
(ii) bromocyclohexane into cyclopentancarboxylic and also of all the geometrical and optical isomers
acid. of (A).
3. Suggest what compounds the letters stand for in 6. A organic compound (A), C9H12O was subjected in
the following equations : a series of test in the laboratory. It was found that
(i) this compound
MeCOMe  CH  CH (
i ) NaNH 2
 B (i) Rotates the plane of polarised light.
( ii ) A
(ii) Evolves hydrogen with sodium
(ii) (iii) Reacts with NaOH and I2 to produce a
PhCOMe  ClCH 2 CO 2 Et  C NaNH 2 pale yellow solid compound.
(iv) Does not react with Br2/CCl4.
(iii)
(v) Reacts with hot KMnO4 to form
compound (B) C7H6O2 which can also be
synthesised by the reaction of benzene
and carbonyl chloride followed by
 ClCH 2 CO 2 Et t
 BuOK
 D hydrolysis.
t  BuOH
(vi) looses optical activity as a result of
formation of compound (C) on being
heated with HI and P.
4. Complete the following equations and give reasons
for your answer. (vii) Reacts with Lucas reagent in about 5 min.
Give structures of (A) to (C) with proper

(i) H
Me 2 C(OH)CH 2OH  ? reasoning and draw fischer projections
for (A). Give reactions for the steps
wherever possible.
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New Delhi – 110 018, Ph. : 9312629035, 8527112111
 CAK – 18
7. A neutral organic compound (A) on analysis gave
C = 52.17%; H = 13.04%. On mild oxidation (A) 11.
gave (B) which on treatment with dilute NaOH gave
another neutral compound (C) with double the
molecular mass. Compound (C) readily loses
water on heating to form (D) which on oxidation
gave CH3CH = CHCOOH (crotonic acid). Identify
(A), (B), (C) and (D) and explain the reactions.
8. (a) Identify A, B, in the following set up


O3
A  B OH



(b) An alkyne with 5 carbon atoms per

molecule when passed through dilute
sulphuric acid containing mercuric
sulphate gives a compound which forms
an oxime, but has no effect on Fehling’s
solution. The compound on oxidation
gives dimethyl acetic acid. It reacts with
sodamide to forms a hydrocarbon. What
is the structure of the alkyne ?
9. When 0.0088 g of compound (A) was dissolved in
0.50 g. of camphor, the melting point of camphor
was lowered by 80C. Analysis of (A) gave 68.18% C
and 13.16% H. Compound (A) showed the
following reactions : (i) It reacted with acetyl
chloride and evolved hydrogen with sodium, (ii)
When reacted with HCl + ZnCl2, a dense oily layer
separated out immediately. Compound (A) was
passed over Al2O3 at 3500C to give compound (B).
(B) on ozonolysis followed by hydrolysis gave two
neutral compounds (C) and (D) which gave
positive tests with carboyl reagents but only (C)
gave a positive test with Fehling solution. Identify
(A), (B), (C) and (D) with proper reasoning. Kf for
camphor = 40 mol–1 kg–1.
Identify A to G.
12. Wolff-Kishner reduction of the compound shown
gave compound A. Treatment of compound A with
m-chloroperoxy benzoic acid gave B which on
reduction with LiAlH 4 gave C. Oxidation of
compound C with chromic acid gave compound D
(C9H14O). Identify A, B, C and D.
13. An optically active alkyne A contains 89.52% C and
10.48 % H. After hydrogenation over a Pd catalyst
it is converted to 1-Methyl-4-propyl cyclohexane.
When compound A reacts with CH3MgBr no gas
is liberated. Hydrogenation of A over Lindlar
catalyst, followed by ozonylysis and reaction with
KMnO4 gives product B. Product B reacts with
I2/NaOH and gives a yellow precipitate, which is
filtered off. Acidification of the filterate gives an
optically active product C. Give the structures of
A, B and C and account for all observations.

10. Suggest the appropriate structures for the missing 14. Give the structure for compounds A – F :
compound. (The number of carbon atoms remain
the same throughout the reactions) C 6 H12 O H  B 1
2 CrO 4 . CH 3 MgI
 
 C HA
 /

A acetone 2. H 3 O


D 1
.O3
 E Ag
2O
,OH


F
2. Zn / CH 3COOH 2. H 3 O

15. C6H12O 6 can be glucose or fructose. To decide

nature, one can carry out following steps :

dil
. KMnO
4  A HIO
4  B HO
 C 
 H
C6 H12O 6 HCN 3O
 P
/ HI
 ?
What can be the end product starting with glucose
and fructose ?

Einstein Classes, Unit No. 102, 103, Vardhman Ring Road Plaza, Vikas Puri Extn., Outer Ring Road
New Delhi – 110 018, Ph. : 9312629035, 8527112111