UNIVERSITY INSTITUTE OF SCIENCES

DIVISION-CHEMISTRY
Masters Of Sciences (Chemistry)
Advance Organic Chemistry
Subject Code: 22SHT701

By: Pankaj Kumar

UID: 22MSC10065 DISCOVER . LEARN . EMPOWER
To: Dr. Harvinder Singh
 Manganese Oxidants
Manganese oxidants refer to compounds or substances that contain manganese
and are used as oxidizing agents in chemical reactions.

Examples:
1. Manganese dioxide (MnO2)
2. Potassium permanganate (KMnO4)
3. Manganese(II) acetate [Mn(OAc)2]
4. Manganese(II) oxide (MnO)

2
Manganese dioxide (MnO2):

• It is a weak oxidizing agent.

• It is selective.
• Only oxidizes allylic and benzylic alcohols.
• Convert allylic and benzylic alcohols to aldehydes and ketones (1o alcohols to
aldehydes and 2o alcohols to ketones)
• Order of reactivity:

>
(Benzylic) (Allylic)
Reactions:

Prop-2-en-1-ol Prop-2-en-1-al
(Acrolein)

But-3-en-2-ol But-3-en-2-one
Reactions:

Phenylmethanol Benzaldehyde

Phenylethanol Acetophenone
Mechanism:

1o alcohol

aldehyde
Reactions:

Allylic alcohol α-β-unsaturated Ketone

Benzylic alcohol aldehyde

Solvent: Neutral solvent like acetone/ CH2Cl2

Potassium permanganate (KMnO 4)

• Alkanes:
1. Usually dose not react or oxidize alkanes at normal conditions.
2. But when hot vapours of 3o alkane passes through solid KMnO4 then 3o alkane
converted into 3o alcohol.
Potassium permanganate (KMnO4)

• Alkenes:
Case 1- Cold diluted alkaline KMnO4 (Beyer’s Reagent)

Alkene Syn diol

Case 2- Hot concentrated acidic KMnO4 (in presence of H2SO4)

Potassium permanganate (KMnO 4)

• Case 1- Alkaline KMnO4 (Beyer’s Reagent)

K+
Potassium permanganate (KMnO4)
• Case 2- Hot concentrated acidic KMnO4 (in presence of H2SO4)

Mechanism:
Potassium permanganate (KMnO4)

• Alkynes:

KMnO4 ,H2O
Potassium permanganate (KMnO4)

• Terminal Alkynes:

KMnO4,H2O

• Aromatic side chain:

KMnO4,H2SO4

• Amino compounds:
Manganese(II) acetate [Mn(OAc)2]
• Ethane in presence of Manganese acetate gives acetic acid:

[Mn(OAc)2]

Ethane Acetic acid

• Mn(CH3COO)2 + 3H2O2 2MnO2 + 4CH3COOH + 2H2O

 Manganese(II) oxide (MnO):
• Aldehydes: By passing a mixture of the vapours of formic acid and any one of its
homologues over Manganous oxide at 300oC:

MnO
RCOOH + HCOOH RCHO + CO2 + H2O

• Ketones: By Passing the vapours of any monocarboxylic acid other than formic acid
over Manganous oxide at 300oC:

MnO
2RCOOH R2CO + CO2 + H2O
THANK YOU