IIT-JEE Chemistry by N.J.

Sir ORGANIC chemistry

Date: DPP NO- 01 Time: 15 minutes

ALDOL CONDENSATION:
The α-hydrogen a carbonyl compound is acidic due to the fact that the anion (also known as the enolate anion)
is stabilized by resonance.

Θ
O O O
Θ
base
CH3 C CH2 C CH2 C
H H H
α- hydrogen (enolate anion)

In aqueous base, two acetaldehyde molecules react to form a β-hydroxy aldehyde called aldol. The reaction is
called Aldol condensation. The enolate ion is the intermediate in the aldol condensation of aldehyde and
ketone. Acetaldehyde for instance, forms a dimeric product aldol in presence of a dilute base ( ≈ 10% NaOH)

R
Θ
OH / HOH
2CH3CHO   → CH3 CH – CH2 – CHO ∆
→ CH3–CH = CH – CHO
5°C
SI OH
β-hydroxy butyraldehyde (Aldol)

Mechanism :

H
OH
CH2 – C – H CH2 – C – H + H2O
O O
J.
O O

CH3 – C – H + CH2 – C – H Slow CH3– C – CH2 – C – H

O H O
N.

O OH

CH3– C – CH2 – C – H + H – OH CH3– CH – CH2– C – H + OH

H O (aldol) O

Aldols are stable and may be isolated. They, however can be dehydrated easily by heating the basic reaction
mixture or by a separate acid catalyzed reaction. Thus if the above reaction is heated the product is dehydrated
to crotonaldehyde (2-butenal). In acid catalysed aldol condensation enol form of carbonyl is the nucleophile in
place of enolate.

Q.1 Write the product and mechanism for given reactions. [8]
CH3– CH2 – C – H  ∆
→ (A) →
(I) Dil.NaOH (B)
O

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IIT-JEE Chemistry by N.J. Sir
A-833, Indra Vihar, near IL back door,
Contact: 9414969800, 9549908816
web : symmetryiitjee.com
 O

(II) Dil.NaOH
 → (C)

Dil.NaOH
(III) C6H5 – CH2 – CHO 
→ (D)

(IV) Dil.NaOH ∆
→ (E) → (F)
 

(V) C 6H 5 – C –CH 3 
Dil.NaOH

∆
→ (G) → (H)
O

R
Q.2 Identify the intramolecular aldol product? [7]
O O
Dil.NaOH ∆
(I) → (A) → (B)
CH3 – C – CH2 – CH2 – C – CH3 

(II)
SI O O
→ (C)
CH3 – C – CH2 – CH2 – CH2 – CH2 –C – CH3 

O O
Dil.NaOH

Dil.NaOH
(III) CH3 – C – CH2 – CH2 – CH2 – C – CH3 
→ (D)

O
J.
Dil.NaOH
(IV)   → (E) →
∆ (F)
N.

O O
Dil.NaOH
(V) CH3 – C – CH2 – CH2 – CH2 – CH2 – CH2 – C – CH3  
∆

→ (G)

Q.3 Find out the total number of aldol products (including and excluding stereo products) and write the IUPAC
name of products. [10]
NaOH / HOH
(I) CH3 – CHO + CH3 – CH2 – CHO    →
5°C

NaOH / HOH
(II) C6H5 – CHO + CH3 – CHO    →
5°C

CH3 NaOH / HOH

CHO + CH3 – C –CH3 
(III)   →
5°C
O

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IIT-JEE Chemistry by N.J. Sir
A-833, Indra Vihar, near IL back door,
Contact: 9414969800, 9549908816
web : symmetryiitjee.com
 NaOH / HOH
(IV) CH3 CH = O + CH3 – CH2 – C – CH3    →
5°C
O

C6H5 NaOH / HOH

CHO + CH3 – CH2 – C – CH3 
(V)   →
5°C
O

Q.4 Identify the structure of substrate? [4]

Dil. NaOH
(I) A   
→ A=?
5°C
OH

R
OH
A Dil. NaOH
   → CH3 C –CH2 – C – CH3 A = ?
(II) (2 mole) 5°C
SI O CH3

Q.5 Complete reaction sequence : [7]

(i) O3 (i) OH
(a) (a) (B)
(ii) Zn/H2O (ii) ∆
J.
(i) OH
(b) (A)
(i) C6H5CHO
|| (iii) ∆
O
O OH
CH3 || |
N.

(i) OH CH – CH3
(c) (A) + (B)
(ii) ∆

O
||
Θ
(d) OH
(A)  →
CH3

OH

Θ
( i) OH
(e) [X]  →
( ii) ∆

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IIT-JEE Chemistry by N.J. Sir
A-833, Indra Vihar, near IL back door,
Contact: 9414969800, 9549908816
web : symmetryiitjee.com