Some Oxidising Agents in Organic Chemistry

Functional Groups Oxidising Agents

Dil. aq. alk. O3/Zn/H2O KMnO4/H+ CrO3/H+ (H2CrO4) CrO3/Anhy. Cu MnO2 Alkaline Tollen’s Fehling’s
O3/H2O PCC PDC HIO4 NaOH/I2
KMnO4 or O3/Me2S or K2Cr2O7/H+ or HNO3 e.g., pyridine at 300°C KMnO4 reagent reagent

〉C = C〈            1
  
C C            1
  2

—CH2OH           3
   4
 
〉CH—OH           3
  5
 4
 6
 6

C—OH             5
  
H
C=O
            5
 4
 
〉C = O             5
 4
 7
 7

O
C OH
    8
          8
 8

1. In combination with KMnO4, periodate (NaIO4) is used for oxidation of alkenes into carboxylic acids/ketones.

2. Terminal alkynes gives white ppt of silver alkynide with tollen’s reagent.

3. Allylic or benzylic alcohols are selectively oxidised into aldehydes/ketones with MnO2.

4. Ar/H/R directly attached to —CH(OH)X,—CH(OH)CH3, —COCH3, or their mono,di, tri-halogen derivatives are oxidised into corresponding carboxylic acid —COOH and CHX3.

5. >C(OH)—C(OH)< or >CO—CO< or >CH(OH)—CO— are cleaved by HIO4 into corresponding aldehydes/ketones/carboxylic acids.

6. Hemiacetals RCH(OH)(OR) are converted into parent aldehyde and hence give positive tollen’s test.

7. a-hydroxy ketones e.g. fructose give positive tollen’s test or fehling’s test.

8. Formic acid, HCOOH is oxidised by acidified KMnO4/K2Cr2O7 or tollen’s reagent/fehling’s reagent into CO2.
 [O]
 Ar—R Ar—COOH (R is aliphatic hydrocarbon derivative side chain having a hydrogen)
[O]
Ar—CMe3 No reaction
drastic
oxidation
Me3C—COOH

(1) CrO2Cl2/CS2
 Ar—CH3 Ar—CHO (Etard reaction)
(2) H2O

(1) CrO3/Ac2O
(2) H3O+

KMnO4
 R3C—H R3C—OH

–
H2O2/OH
 R3B R—OH + B(OH)3

Me
O2
 Ph—CHMe2 Ph—C—O—O—H

Me

O
Br2/water
 —CH O — C—OH

OH O
Cr2O2–
7 /H
+
 or H2CrO4
(Dark color)

O2/light
 CHCl3 COCl2
–HCl
 Some Reducing Agents in Organic Chemistry

Functional Groups Reducing Agents

–
LiAlH4 NaBH4 H2 + Catalyst H2 + Pd/BaSO4 Na + Liq. NH3 HI + Red P B2H6 DiBAL-H Zn-Hg/HCl N2H4,OH /glycol, D SnCl2/HCl Sn or Fe/HCl C2H5OH (Na)

〉C = C〈             
C C             
—X             
—OH             
H
C=O
            
〉C = O             
O
C OH
            
O
C Cl          — — — 
O O
C O C          — — — 
O
C OR
         — — — 
C N          —  — 
O
C NH2         — — — — 
NC       —  —  — — 
NO2             
+ – H3PO2 or EtOH
 Ar—N2 Cl Ar—H
(—H3PO3/—CH3CHO)
Zn
 Ar—OH Ar—H