[Type text]

Solved Problems
OBJECTIVE

Problem 1: Which of the following will react with acetone to give a product containing
C=N–
(a) C6H5NH2 (b) (CH3)3N
(c) C6H5⋅NHC6H5 (d) C6H5NHNH2

Solution: H3C H3C

O + H2N NH 
→ N

H3C C 6 H5 H3C NH C 6H5

∴(d)

O
|| +
H3O
Problem 2: CH3 – C – Cl + R – MgX A; A is
(excess)
O O
|| ||
(a) R – C – CH3 (b) R – C – CH2Cl
OH O
| ||
(c) CH3 – H C − R (d) CH3 – C – H

Solution: (c)

Problem 3: In the reaction HO – CH2 – CHO 

dil . NaOH
→
how many distinct products (saturated) are possible ?
(a) 1 (b) 2
(c) 3 (d) 4

Solution: (d) Four possible products are

* *
HO – CH2 – CHO 
Aldol condensation
→ HO – CH2 C H(OH) C H(OH)CHO
Tetrose
It can be D, L-erythrose and D, L-threose.

Problem 4: Benzaldehyde on reaction with CH2 = CH – CH = PPh3 forms

CH3
CH2
(a) (b)
CH3
CH2
(c) (d)

Solution: Wittig reaction

[Type text]
[Type text]
O Ph
Ph
H5 C6 + P H5 C6 CH2 + POPh3
Ph
H

CH2
∴ (d)

Problem 5: What is A in the following reaction?

O

Cl O
t − BuOK
+ 
t − BuOH
→A

O
H5 C2
O O
H3C
O
(a) C 2 H5 (b)
C 2H 5

O
O
OH
(c) (d)
O
O C 2H5

O
Solution: Cl O Cl O
O -
O
t − BuOK
 → CH →
t − BuOH
Cl O
O O
Cl C 2 H5
H5C 2 H5C 2
-
Cl

O
O C 2 H5

∴ (c)

O
||
H3 O +
Problem 6: CH3MgBr + CH2 = CH – C – H  → product
H2C H3C
OH
(a) (b)
H3C
H CH3

H3C O

(c) (d) None is correct

OH

[Type text]
[Type text]

Solution: H2C
O is conjugate system O
OH
H

H  → H3C
+ tautomerises
hence I + CH 3 − Mg − Br 
H3 O
→ H3C H

∴ (d)
O
Problem 7:

CH3
is the final product obtained when one of the following is reacted with base.
O O O O

(a) (b)
H3C CH3 H3C CH3
O O
O O

(c) H3C (d)

H3C CH3
CH3
O
Solution: O O

CH3  →
Alkali
H3C ∆

CH3

∴ (a)
O
O C OH +
Problem 8: CH3 H
(A)
C C
CH3 H
The product (A) in the given reaction would be
O O OH
O
C O
C C (b)
(a) OH C C H
H3C C
CH3 H3C CH3
H
O O
H OH
CH3 C
(c) (d) C H
C H C C
CH3
CH3 CH3

[Type text]
[Type text]

O
O + O O
(c) CH3 C OH H CH3
Solution:
C C C C C O H
CH3 H CH3 H
unstable
+ CO2
H
H
H3C O H3C OH
C C C C
H H3C H
H3C
enol

Problem 9: End product of the following sequence of reactions is

+
CH ≡ CH 
CH3 MgBr
→ 
CO 2 / H 3O

→ 
HgSO 4 / H 2SO 4
→ 
Ag 2 O
∆
→
O O
H3C HO O
(a) OH
(b)
O OH
O O
H3C H O
(c) (d)
O OH
Solution: CH ≡ CH + CH3MgBr → CH ≡ C – MgBr
CO2/H3O+

– COOH is (EWG) CH ≡ C → COOH

HgSO4/H2SO4

OHC – CH2 – COOH

Ag2O

HOOC – CH2 – COOH

∴ (b)

Problem 10: In which of the following substrates, rate of Benzoin condensation will be
maximum ?

(a) O2N CHO (b) H3C CHO

(c) HO CHO (d) NH2 CHO

[Type text]
[Type text]

O O O O O O H
Solution: N C + CN N C H N C:
O H O O
C N C N
(I) (II) (III)
Benzoin condensation is due to stability of intermediate (III) when negative
charge on C is extensively delocalised in benzene ring, nitro and C ≡ N group. In
all other cases, such dispersal is not extensively possible. On the other hand,
NO2− is also creating a positive charge center on carbonyl carbon, making it more
susceptible to nucleophilic attack of CN−.

Write-up - I
Aldehydes and ketones show nucleophilic addition reactions. The α-hydrogens in aldehydes and
ketones are acidic. Therefore, aldehydes and ketones having at least one α-H undergo aldol
condensation in the presence of a base such as NaOH. Aldehydes having no α-hydrogen undergo
Cannizzaro reaction in the presence of concentrated alkali. The carbonyl group of aldehydes and
ketones can be reduced to methylene group by Clemmensen or Wolf Kishner reduction.
Aldehydes are easily oxidised to carboxylic acids by Tollen’s reagent and Fehling solution.
Functional derivatives of carboxylic acids undergo nucleophilic acyl substitution with
nucleophiles.

1. R O
+
O + H2N 
dil.H − H2O
→ A  →B
H NH
H2N
In the reaction correct statement(s) about A and B are:
I. A is optically active and dextrorotatory
II. A is racemic mixture and optically inactive
III. R
B is N
H NH
O NH2

IV. R
B is N O
H NH
NH2

(a) I and III (b) II and IV

(c) II and III (d) I and IV

[Type text]
[Type text]

2. The convert CH2 = CH – CH2CHO to CH2 = CH – CH2COOH best reagent will be

(a) KMnO4 (b) P.C.C.
(c) [Ag(NH3)2]OH (d) HIO4

3. The reactivity order of following toward nucleophilic substitution will be

O O O O O
|| || || || ||
R − C − OR ′ R − C − Cl R − C− O − C− R R − C − NH 2
(I) (II) (III) (IV)

(a) I > III > IV > II (b) II > III > I > IV
(c) III > IV > I > II (d) III > I > IV > II

4.

O
||
(a) COCl2 (b) CH3 − CH 2 − C − OEt
O
| |
(c) CH3 − CH 2 − C − CH 2 − CH3 (d) All

Solution:

1. (b) Attack is through more nucleophilic N atom and Nucleophile attack at planar
sp2 carbon to give racemic mixture.

2. (c) Tollen’s reagent is highly selective

3. (b) Weaker the base better is the leaving group. Leaving group ability has following
order.
Cl– > RCOO– > OR'– > NH −2
4. (d)

Write-up II

(Cannizzaro Reaction)
R2 O R2 R2

R1 C C H 
conc. NaOH
→ R1 C CH2OH + R C COO
1

R3 R3 R3
Mechanism

[Type text]
[Type text]

O O

i) R 3C C H + OH − R 3C C OH

H
O O

ii) R 3C C OH + OH − R 3C C O + H2O
H H
O O O

iii) R 3C C O + R 3C C H 
slow
step
→ R 3C C O + R 3C CH2O

H
iv) R 3C − CH 2 − O − + H 2 O →
fast
R 3C − CH 2 − OH + OH −
The following questions are based on given mechanism

1. Out of following which statement is incorrect about this mechanism.

(a) order of reaction is 3
(b) Molecularity of reaction is 2
(c) Hydride shift involves in rate determining step
(d) It is a disproportionation reaction

O O
2. Ph C C H reacts with conc. OH
(II) (I)

Out of following which statements are correct about this reaction. Select the correct
option.
1) Oxidation of carbon (I) take place 2) Reduction of carbon (II) take place
3) OH– first attack to carbon (I)
(a) 1, 2 and 3 (b) 1, 3
(c) 2, 3 (d) 1, 2

O O
O2 N

−
3. NO2 
OH
→?

O O

[Type text]
[Type text]
COO COO CH2OH COO
O 2N O2 N

(a) NO2 (b) NO2

CH 2OH CH2OH CH2OH COO

COO CH2OH COO CH2OH
O2 N O2N

(c) NO2 (d) NO2

CH2OH COO COO CH2OH

Solution: 1. (a) 2. (a) 3. (d)

O
OH O
H O
2. −


SeO2
→ 
OH
→ Ph C C O
O H
H

SUBJECTIVE

Problem 1: Write down the product with appropriate mechanism for the following reaction:
O
-
OH
C CH2 CH2 C CH3 ?
O
O O
- O
OH
Solution: C CH2 CH2 C CH3 -
C C CH2 CH2 C CH3
O

O
O
H2O C
CH2
CH2
C
CH3 -
H3C O
Problem 2: Complete the following reactions:
O
(i) HCO3H, H3O+
O 2N C A

[Type text]
[Type text]

O
Solution: O 2N C O (A)

Problem 3: Suggest how you will carry out the following transformation
O

Solution: O3, Zn, H2O

dil NaOH
H3O+, warm

Problem 4: Conversion
O O

H O H C O
O C
(i) LiAlH4 Ozonolysis H C O dil. NaOH,
Solution: +
(ii) H

O CH2 CH2OH

H+ H2/Ni
Ozonolysis

(i) Ph CHO, OH
Problem 5: (A)
(ii) Zn - Hg, HCl
(iii) O3, Zn/H2O

What is A ?

H3C O CH3
O
(i) Ph CHO, OH
Solution:
(ii) Zn - Hg, HCl
(iii) O3, Zn/H2O
(A)

[Type text]
[Type text]

Problem 6: Write down the mechanism of following reaction:

CH3 CH3
+
H
H3C C C CH(CH3)2 H3C C C CH(CH3)2
OH O O OH

CH3 CH3 CH3

+
H +
Solution: H3C C C CH(CH3)2 H3C C C C H
OH O OH OH CH3

- CH3 shift

CH3 +
CH3
-H +
H3C C C CH(CH3)2 H3C C C CH(CH3)2
O OH OH OH

Problem 7: Predict the product

C6H5
Bayer's reagent HIO 4 dil. NaOH,
(A) (B) (C)
C6H5
C6H5 C O
C6H5
dil. NaOH,
H O
Solution: OH
O
OH (C)
(B)
(A)

Problem 8: An organic compound C6H8O3 (A) gives an acid C6H8O4 (B) with K2Cr2O7 in
acidic medium. Compound (A) gives yellow predicate with I2 and NaOH.
Compound (B) very easily gives C5H8O2 on heating. Identify the compound A, B
and C.

Solution: (A) gives acid on rxn with K2Cr2O7 i.e., it contains – CHO group and it give halo
form test, i.e., it has CH3 – C – group and as [B] releases CO2 on heating i.e, it is a
||
O
β - keto acid

[Type text]
[Type text]

∴ (A) is
K2Cr2O7
H3C C CH2 C CH2 CHO H3C C CH2 C CH2 COOH
+
H
O O O O
[A] [B]
-CO2

H3C C CH2 C CH3

O O
[C]
- -
OH, excess MeI OH
Problem 9: A + B CH3CHO C
Identify A, B and C with proper reasoning.

Me Me O
- -
- HO HO
Solution: Me C CH2OH + Me C C O
excess MeI
CH3CHO

Me Me H3C CH CH CHO
(A) (B)
(C)

Problem 10: Convert Cl O into HO

HO O

Solution: CH3 H2C


2C2 H5 OH
→ Cl O →
KOH (alc.)
O
Cl O HCl − KCl
− H2O
H5 C 2 O C2H5
O

CH3
HO O C 2 H5 HO OH HO
− H 2O
 →
+

Alkaline
→ 
2H2 O / H

→
KMnO 4 −2C H OH
H2 O + (O) 2 5

HO O HO OH HO O

H5C 2

Problem 11: a) Cyclopentene on treatment with aqueous dilute KMnO4 yields a dihydroxy
compound (A) which reacts with propanone in the presence of dry HCl to
yield a compound (B), C8H14O2, which is resistant to boiling alkali, but
which is readily converted into the compound (A) by aqueous acids. What
are (A) and (B)?
b) Cyclopentene on treatment with performic acid yields a dihydroxy
compound (A) which does not react with acetone to form (B). How do you
account for this fact?

[Type text]
[Type text]

Solution: The hydroxylation by aqueous KMnO4 and performic acid is stereospecific; the
former yields a cis-diol while the latter, a trans-diol.
a) H3C
O
H3C

aq. KMnO4

→ 
dry HCl-H O
→ H H →
NaOH
No effect
H O + (O) 2 Boiling
2
H
O O
cyclopentene HO HO H
cyclopentane-1,2-diol H3C CH3 (B)
(A)
dil. acid/boil

H3C
+ O
H
HO OH H3C
H
(A)
b)

HCO3H
→ 
CH3COCH3
→ no reaction
H O+ Dry HCl
3
H
cyclopentene HO HO H
cyclopentane-1,2-diol
(A)
Since the two –OH groups in the trans isomer are too far apart from the cyclic
structure to form.

Problem 12: Write the products of the following reaction sequence:

2RCH 2 CHO 
OH
H O
→(A) 
HA
−H O
→(B) 
H2
Pd.C
→(C)
2 2

LiAlH 4

(D)
Solution: R O R O

A= B=
HO R R
R O R OH

C= D=
R R

Problem 13: Suggest a mechanism for the following reaction:

CH3

H3C O + H3 O+ 
→
OH
CH3 CH3
H3C OH
CH3

Solution: The protonated aldehyde is an electrophile, the double bond is a nucleophile, the
reaction between two function closes the ring, hydration of the resulting
carbonium ion produces a diol.

[Type text]
[Type text]

CH3 CH3 CH3 CH3

+ H+ →
Ringcolour

H 2O
− H+
→
H H H H
+
O OH OH OH
H3C CH3
H3C CH3 H3C CH3 H3C CH3
OH
Protonated aldehyde t-carbonium ion

Problem 14: What products are formed when acetaldehyde reacts with acetone in presence of
a dilute alkali solution? What happens when each of these is dehydrated with
sulphuric acid?

Solution: Here crossed aldol condensation as well as pure aldol condensation occurs giving
four different aldols.
a) H3C
+

2CH 3CHO 

OH
→
−

∆
H
→ H3C O
− H2 O
Crotonaldehyde
HO O
b) O OH H3C
OH − H+
2 H3C 
→ H3C 
− H2 O
→
CH3 CH3 CH3 H3C CH3
O O
Diacetone alcohol
c) O H3C
α − +
H3C + H3C 
OH
→ 
H
−H O
→ H3C O
2

O CH3 HO CH3
O CH3
OH
d) H 3C H 3C
α − +
O + H 3C  O
H

→ H 3C  −
H
→
H O2

H 3C O CH3 O H 3C O

Problem 15: H 3C O CH3 O

and H 3C
CH3
H 3C CH3 CH3
H 3C
H 3C CH3

although contain carbonyl group, though do not form bisulphite addition

compounds, why? Explain

Solution: Owing to steric effect of bulky isopropyl and t-butyl groups and carbonyl group is
protected, hence these ketones do not form addition compounds with NaHSO3.

Problem 16: Complete the following reactions:

O
− NH3 H3 O+ dil. H2SO4 (B)
(i) + H—C≡C Na+ (A)
−33OC Hg2+

[Type text]
[Type text]

(−H2O) 1. OsO4
(C) (D)
2. HIO4
Give the IUPAC nomenclature of (D).
O
NaOH
(ii) (A)
H2O, 100oC
O
Solution: i) OH OH
≡ C−CH3 C −CH3
O
O
(A) (B) (C)
ii) O
(D)
OHC
O
6,7-dioxooctanal
O
iii)

(A)

[Type text]
[Type text]

KVPY
1. The main product III obtained in the following reaction sequence is (2007)

2. The reaction between p-methylbenzaldehyde and NaOH is an example of (2008)

(A) Aldol condensation reaction (B) Cannizzarro reaction
(C) Disproportionation reaction (D) Hydrolysis reaction

3. X and Y in the following reactions, respectively are (2008)

(A) (B)

(C) (D)

4. A compound that shows positive iodoform test is (2011)

(A) 2-pentanone (B) 3-pentanone (C) 3-pentanol (D) 1-pentanol

5. The molecule having a formyl group is (2013)

(A) Acetone (B) acetaldehyde (C) Acetic acid (D) Acetic
anhydride

ANSWER KEYS:

1:D 2:B 3:A 4:A 5:B

[Type text]
[Type text]

Assignments
SECTION – I Single Choice Questions

Level - I

1. Which of the following reacts with water to form very stable product?
(a) CH3Cl (b) CCl4
(c) CCl3CHO (d) CH2ClCH2Cl

2. End products of the following sequence of reaction is

O
i) NaOI, ∆

ii) H + , ∆
→ A+B
CH3

O
A & B are
I CO2H I O
I and
(a) CH3 (b) I and
I
I O
O
I O I O
(c) I and (d) I and
I CO2H I

3. Compound A, C5H10O forms a phenyl hydrazone and give negative Tollen’s & iodoform
tests, compound A, on reduction gives n-pentane. A is
(a) A primary alcohol (b) A secondary alcohol
(c) An aldehyde (d) A ketone

4. Which of the following compound on treatment with LiAlH4 will give a product that will
give positive iodoform test?
(a) CH3CH2CHO (b) CH3CH2CO2CH3
(c) CH3CH2OCH2CH3 (d) CH3COCH3

5. Which of the following has the most acidic proton?

(a) CH3COCH3 (b) (CH3)2C = CH2
(c) CH3COCH2COCH3 (d) CH3CHO

6. The product obtained by reaction of PhCHO & MeCHO are

OH OH

(a) Ph O and Me O

CH3

[Type text]
[Type text]

OH OH

(b) Ph O and Ph O
Ph

OH OH

(c)
Ph OH and Me O
(d) None of these

7. CH3CHO + NH2OH → CH3CH = N – OH

The above reaction is carried out at
(a) pH = 1 (b) pH = 4.5
(c) pH = 12 (d) pH = 14

8. The reagent with which both acetaldehyde and acetone react easily is
(a) Fehling’s reagent (b) Grignard reagent
(c) Schiff’s reagent (d) Tollens reagent

9. The compound that gives a positive iodoform test is

(a) 1-pentanol (b) 2-pentanone
(c) 3-pentanone (d) pentanal

10. Which of the following does not undergo aldol condensation?

(a) HCHO (b) CH3CHO
(c) CH3COCH3 (d) CH3CH2CHO

11. Cannizzaro reaction is not given by

(a) Trimethylacetaldehyde (b) Acetaldehyde
(c) Benzaldehyde (d) Formaldehyde

12. The formation of cyanohydrin from a ketone is an example of

(a) electrophilic addition (b) nucleophilic addition
(c) nucleophilic substitution (d) electrophilic substitution

13. Which of the following statements regarding aldehydes is not correct?

(a) the carbonyl functional group is planar
(b) The boiling points of aldehydes is greater than those of alkanes of comparable molar
masses
(c) The boiling points of aldeydes is greater than those of alcohols of comparable molar
masses
(d) Formaldehyde is gas at room temperature

14. Which of the following statements regarding CO group is not correct?

(a) The carbon atom of CO group in aldehydes is sp2 hybridized
(b) The carbon atom of CO group in the transition state formed during the addition
reaction across CO group is sp3 hybridized

[Type text]
[Type text]

(c) The aryl group in aromatic aldehydes speeds up the addition reaction across the CO
group
(d) An aryl group stabilizes an aldehyde more than the transition state

15. Which of the following compounds undergoes the Cannizzaro reaction?

(a) Acetaldehyde (b) Benzaldehyde
(c) Acetone (d) Propanal

16. Which of the following compound does not undergo aldol condensation?
(a) C6H5CH2CHO (b) C6H5CHO
(c) CH3COCH3 (d) CH3CH2CHO

17. Among the given compounds, the most susceptible to nucleophilic attack at the carbonyl
group is
(a) CH3COCl (b) CH3CHO
(c) CH3COOCH3 (d) CH3COOCOCH3

18. Which of the following does not give iodoform reaction?

(a) CH3CH2OH (b) CH3OH
(c) CH3CHO (d) PhCOCH3

19. The compound that will not give iodoform on treatment with alkali and iodine is
(a) acetone (b) ethanol
(c) diethyl ketone (d) isopropyl alcohol

20. Which of the following compounds undergo periodic oxidation

O
O OCH3
O
(a) (b)
OH HO
OH OH
(c) CH CH CH3
OH OH (d) all of these

Level - II

1. O
Ph
−
Ph 
OH
→ A. A is

[Type text]
[Type text]
OH
OH
Ph Ph
(a) (b)
O CO2
Ph
Ph
Ph
(c) Ph (d) None
O OH

2. In the reaction sequence, [X] is ketone :

CH3
KMnO 4/OH/
[X] HOOC(CH2)3 CH COOH
[X] will be
O O
CH3
(a) (b)

O O
CH3 (d) H3C CH3
(c)

3. The reagent(s) which can be used to distinguish acetophenone from benzophenone is (are)
(a) 2, 4-dinitrophenylhydrazine (b) aqueous solution of NaHSO3
(c) Benedict reagent (d) I2 and Na2CO3

4. In the given reaction

O
CH3
(i) NaH/ dry ether
[X]
(ii) CH3 - I
[X] will be :
O O
CH3 CH3
(a) CH3 (a) CH3

O
H3C CH3 HO CH3
(c) (d)

5. In the reaction:
O OH/
+ O [X]
[X] will be:

[Type text]
[Type text]
OH O OH OH

(a) (b)

OH O O

(c) (d)

6. The product of the reaction:

C6H5CH2COONa/
O 2N CHO + (C6H5CH2CO)2O [X]
will be
(b) O2N CH CH COOH
(a) C6H5 – CH = CH – COOH
(c) C6H5 CH C COOH

(d) O2N CH CH COOH

NO2 C6H5

7. In the reaction
CH2 Cl (i) (C6H5)3P
[X]
(i) CH3Li/
CH2 Cl CHO
(iii)
CHO
[X] will be:
CH CH CH CH
(a) (b)
CH2Cl OHC CH CH
CH
(d)
(c) Mixture of (a) and (b) CH

8. In the given reaction:

NaBH4
H2C O (A)
(i) BH3
(ii) H2O2/OH

(B)
(A) and (B) are :

[Type text]
[Type text]

(a) CH2 OH and HOCH2 O (b) CH3 OH and HOH2C O

(c) CH2 (d) CH3 OH and CH3 O

and HOH2C O
HO

9. In the Cannizzaro reaction given below,

−
2Ph—CHO  OH
→ Ph − CH 2 OH + PhCO−2
the slowest step is
(a) the attack of –OH at the carbonyl group
(b) the transfer of hydride to the carbonyl group
(c) the abstraction of proton from the carboxylic acid
(d) the deprotonation of Ph—CH2OH

10. In a Cannizaro reaction, the intermediate that will be the best hydride donor is
O H
O

(a) OH (b) O

H H
O O

(c) O (d) O

CH3 O O 2N

11. Which one of the following will most readily bedehydrated in acidic condition?
O OH OH
(a) (b)
O O

(c) (d)
OH OH

SECTION – II More then one Choice Questions

1. Base catalysed aldol condensation occurs with

(a) propanal (b) benzaldehyde
(c) 2-methylpropanal (d) 2, 2-dimethylpropanal

2. Which of the following compounds will give a yellow precipitate with iodine and alkali?
(a) 2-Hydroxypropane (b) Acetophenone
(c) Methylacetate (d) Acetamide

3. A new carbon-carbon bond formation is possible in

(a) Cannizzaro reaction (b) Friedel-Craftsalkylation
(c) Clemmensen reduction (d) Reimer-Tiemann reaction

[Type text]
[Type text]

4. Which of the following will undergo aldol condensation?

(a) Acetaldehyde (b) Propanaldehyde
(c) Benzaldehyde (d) Trideuteroacetaldehyde

5. Which of the possible compound will be formed in the following sequence of reaction.
HBr Hydrolysis Na 2 CO 3
CH2=CH2  → X     → Y   → Z
I2 excess
(a) C2H5I (b) C2H5OH
(c) CHI3 (d) CH3CHO
6. Which of the following compounds will react with ethanolic KCN?
(a) Ethyl chloride (b) Acetyl chloride
(c) Chlorobenzene (d) benzaldehyde

7. Which of the following are the examples of aldol condensation?

(a) OH
2CH 3CHO 
dil. NaOH
→ CHO
H3C
(b) CH3

2CH 3COCH 3 

dil. NaOH
→ H3C CH2COCH3

OH
(c) 2HCHO  → CH3OH dil. NaOH

(d) C6H5CHO + HCHO 

dil. NaOH
→ C6H5CH2OH

8. Which of the following statements are correct?

(a) Benzaldehyde reduces Fehling’s solution
(b) C6 H 5CHO + C6 H5 CHO  NaOH
→ C6 H 5CH = CHC6 H5 + O 2 is a Claisen-Schmidt
reaction.
(c) pKa (formic acid) is less than pKa (acetic acid)
O OH
NaOH
(d) CH3CCH3 + CH3CHO CH3 C CH2CHO is an example of aldol condensation.
CH3

9. CH3 − CHO →

OH
CH3CH(OH)CH 2 CHO
In the aldol condensation of acetaldehyde represented above, which of the following
intermediate species are obtained?
-
O O
-
(a) H2C (b) H2C
H H
- -
O O
(c) H3C (d) H3C O
H O H CH2

[Type text]
[Type text]

10. Which of the following compounds will give a red precipitate on being heated with
Fehling’s solution.
(a) C6H5CHO (b) CH3CHO
(c) CH3COCH3 (d) C6H5CH2CHO

[Type text]
[Type text]

SECTION – III Comprehension Type Questions

Write-up I
The reaction is self oxidation – reduction type and takes place in presence of 50%
aqueous or ethanolic alkali. One molecule of the aldehyde (missing of α-hydrogen atom)
oxidizes the other molecule of it to corresponding carboxylic acid and the self being
reduced to the corresponding alcohol.
R2 R2 OH R2 H
H
R1 → R1 OH
Ethanol
+ R1
O R3 O R3 OH
R3
Mechanism: The mechanism involves two distinct steps Nucleophilic attack and hydride
ion transfer.
O

H H HO OH
H R
− -
O 
OH
→ OH → O + H O
- slow
R O R H

H2 O

O
OH + R
R OH

1. O


CH 2 O
OH(conc.)
→

O
H3C
OH O OH

(a) (b)

O O
H3C H3C
O O OH

(c) (d)

OH OH

[Type text]
[Type text]

−
2. C8 H 6 O 2 →
CH 2 O / OH
EtOH
C8 H10 O 2 
PBr3
→ C8 H8 Br2 . Identify A, B and C.
(A) (B) (C)
OH Br
CHO
OH Br CHO
, , OH Br
(a) CHO
(b) , ,
CHO
OH Br
OH Br
Br
OH
CHO CH3
Br
(c) , ,
(d) All of the above
CHO CH3
OH

3. O
H −

OH
EtOH
→ A. The A is
O
Ph
(a) Lactic acid (b) Mandelic acid
(c) Salicylic acid (d) Malonic acid

Write-up II
Aldehyde, ketone, acid and acid derivatives contain C = O group. Aldehyde and ketones
give nucleophilic addition reactions where as acid and acid derivatives give nucleophilic
addition followed by elimination reactions. Nucleophilic addition reactions followed by
elimination of acid derivatives is known as acyl substitution reaction. This substitution
reaction takes place by formation of tetrahedral intermediate.

4. For the given reaction

O O
L +Nu 
→ Nu + L
R R
which of these is correct?
(a) L must be better leaving group than Nu
(b) Nu− must be strong enough nucleophile to attack carbonyl carbon
(c) Carbonyl carbon must be enough electrophilic to react with Nu−
(d) all of these

5. Which one of the following compounds has very poor leaving group?
O O
(a) R (b) R
H Cl
O O
(c) R (d) R
OH OR'

[Type text]
[Type text]

6. Which one of the following is least reactive compound for nulceophilic acyl substitution.
O
O
H3C
(a) H3C (b) NH
Cl
H3C
O
O
H3C
H3C
NH
NH
(c) (d)

O2N

Write-up III

Aldehydes and ketones are amphoteric. Thus they can react both as acids and bases.
Under acidic conditions, the carbon of the protonated carbonyl group is much more
electrophilic, reacting even with weak nucleophile. Carbonyl compound gives
nucleophilic addition reaction. In this reaction the nucleophilic attack precedes the
electrophilic attack.

7. Which of these statements are correct?

(a) Carbonyl compound is amphoteric in character
(b) Acid catalyst makes the carbonyl carbon more electrophilic
(c) basic catalyst makes the nucleophile more nucleophilic
(d) All of these

8. Which of the statemetns are/is correct?

(a) The rate determining step of addition reaction is the addition of nucleophile
(b) The rate-determining step is addition of electrophile
(c) The reaction intermeidate of the reaction is alkoxide ion
(d) both (a) and (c)

9. Which one of the carbonyl compounds is more reactive towards NaCN/H+?

O H3C
(a) H5 C6 (b) O CHO
H
O O
(c) H3C (d) NC
H

10. Carbonyl compounds gives nucleophilic addition with

(a) carbon nucleophile (b) oxygen nucleophile
(c) Nitrogen nucleophile (d) All of these

[Type text]
[Type text]

Answers to Assignments
SECTION - I

Level - I
1. (c) 2. (d) 3. (d) 4. (d)
5. (c) 6. (d) 7. (b) 8. (b)
9. (b) 10. (a) 11. (b) 12. (b)
13. (c) 14. (c) 15. (b) 16. (b)
17. (a) 18. (b) 19. (c) 20. (d)

Level - II
1. (b) 2. (b) 3. (d) 4. (a) 5. (d)

6. (d) 7. (b) 8. (a) 9. (b) 10. (c) 11. (a)

SECTION - II

1. (a, c) 2. (a, b) 3. (b, d) 4. (a, b, d) 5. (b, c, d)

6. (a, d) 7. (a, b) 8. (c, d) 9. (a, b, c) 10. (b, d)

SECTION –III

1. (a) 2. (a) 3. (b) 4. (d) 5. (a)

6. (b) 7. (d) 8. (d) 9. (d) 10. (d)

[Type text]
[Type text]

[Type text]