IIT-JEE Chemistry by N.J.

Sir ORGANIC chemistry

Date: DPP NO- 04 Time: 15 minutes

KNOEVENAGEL REACTION :

Reaction of active methylene group with aldehyde and ketones is known as Knoevenagel reaction.
Z
Pyridine
RCHO + CH2  → RCH = C(COOR) 
( i ) H2O / H⊕
→ R – CH = CH – COOH
or piperidine 2
Z′ ( ii ) ∆,− CO2

Z can be
O
||
CHO, COOMe, COOH, CN, NO2, C – R ,SOR, SO2R, SO2OR etc.
Mechanism

IR
⊕ Θ
&& + H C(COOR)
R3N R3 NH + HC(COOR )2
2 2

O O O
+ OH
|| | R3NH |
R –C + CH (COOR)2 − H2O
R –C – CH (COOR)2 R –C – CH (COOR)2  →
|
H
S |
H
–R3N•• |
H

⊕
( i ) H2O / H
R –CH = C (COOR)2  → R – CH = CHCOOH
( ii ) ∆,−CO2
J.
High reactivity of the methylene group of the active methylene compound prevents
self-condensation of the aldehyde.
N.

(1) Pip
Q.1 CH3CHO + H2C (COOR)2  → A
( 2 ) H O⊕ / ∆
3

(1) Pip
Q.2 C6H5CHO + H2C(COOR)2  → B
( 2) H O⊕ / ∆
3

(1) Pip
Q.3 HOOC–CHO + H2C (COOR)2  → C
( 2) H O⊕ / ∆ 3

Glyoxalic acid

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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
O ||
|| C– Me
Et 2NH
Q.4 +
Ph – C – H CH2  → D
∆
C– OEt
||
O

O
||
Q.5 Ph – C – H + CH3 – NO2 nC5H11NH2 E
 →
∆

Me O
CN ||
C = O + CH2 CH3C– NH2
Q.6 F

IR
Me COOR CH3COOH, ∆

O
CN || NaOEt
Q.7 CH2 + Ph – C – H ∆→ G
NO2
S
J.
N.

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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