IIT-JEE Chemistry by N.J.

Sir ORGANIC chemistry

Date: DPP NO-06 Time: 15 minutes

CANNIZARO REACTION :
This reaction is given by aldehyde having no α- hydrogens in the presence of conc. NaOH/∆ or KOH/∆.
O O
KOH
H– C – H → H – C – O + CH3OH
∆
Mechanism of the reaction is

O O O O O
HO || ||
H–C–H H–C–H C CH3– O + H – C – O H CH3OH + H – C – O
OH H H r.d.s.

In the presence of a very strong concentration of alkali, aldehyde first forms a doubly charged anion (I) from

IR
which a hydride anion is transferred to the second molecule of the aldehyde to form acid and an alkoxide ion.
Subsequently, the alkoxide ion acquires a proton from the solvent.

O O O
|| OH | OH |
H C H C H H C H
| | | (I)
S H H O

O H O H
| | | |
H C H + C O → H C +H C O
J.
| (I) | || |
O H O H

H2O
HCH 2O HCH2OH + OH
From
N.

solvent
Q.1 Which of the following will not undergo Cannizaro reaction.

CHO
CHO
(A) (B) (C) (D) Cl3C – CHO
CHO Cl
O

O
|| H2 HCHO
Q.2 →
Ph – C – Cl Pd (A)  → (C) + (D)
−BaSO 4 ∆,KOH
Product (C) and (D) are-
(A) Ph –CO2H, Ph– OH (B) Ph –CO2, HCO2
(C) Ph –CH2OH, H – CO2– (D) Ph – CO2–, CH3OH

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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
 CHO
Q.3 | Conc .NaOH H+
  → (A) → (B)
CHO ∆

Product (B) is

O
||
O C
(A) H2C = CH– CO2H (B) CH2 CH2
C O
||
O

O
||
CH2– O – C

IR
(C) | | (D) H2C = C= O
CH2– O – C
||
O

NaOD
Q.4 (i) HCHO  →
∆
S
(ii) DCHO
NaOD
 →
∆

KOH
Q.5 (i) Ph–CHO + HCHO →
∆

Ph – C – C – H KOH
J.
(ii) →
∆
O O
KOH
Q.6 (i) MeCH2 – CHO →
∆

KOH
N.

(ii) Me2CH– CHO →

∆

Q.7 (i) KOH

Me– NO2 + HCHO (excess) →
(ii) KOH
Me– CHO + HCHO (excess) →

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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