Oxidation And Reduction

Lecture-05
 1. Oxidation
• Oxidation is a reaction, during which the
average oxidation value of a compound
increases
• This can undergo due to:
Withdrawal of electrons
Withdrawal of hydrogen =
Dehydrogenation
Insertion of oxygen
 2. Reduction
• Reduction is a reaction, during which
the average oxidation value of a
compound decreases
• This can undergo due to:
Insertion of electrons
Insertion of hydrogen = hydrogenation
Withdrawal of oxygen
3. The Oxidation Value in an Organic
Compound
• Determination of formal charge in three steps:
Step1: in a bond, all binding electrons are added to
more electronegative partner
Step 2: in a bond of two identical bond partners, a half
of the binding electrons are added to each bond
partner
Step 3: Compare the sum of outside electrons of an
atom in the compound with that of atom in question in
elemental state
(Vergleich dieser Anzahl an Außenelektronen am Atom in der
Verbindung mit der Anzahl der Außenelektronen des betreffenden
Atoms im elementaren Zustand)
Oxidation Values
Oxidation Values of C-Atoms in
Different Compounds
 4. Oxidability (Oxidierbarkeit)
• Oxidability is the ability of a substance or a
functional Group to be oxidized = Reduction ability
• A measure for the oxidability of functional group is the
ionization potential, which can be polarographically
determined (half wave potential). The measurement
of ionization potential should be carried out to
calculate the energy needed to abstract an electron
from a substance
• The oxidability is a property of a substance. It
depends not only from physical parameter, ionization
potential, but also from chemical behavior, i.e. the
reactivity against oxidizing agent
Voltammogram of Fe
 5. Oxidation Reaction
• Alcohol, Aldehyd, Carboxylic Acid
• Chromate as oxidizing agent: Chrom(VI)-
Compounds (Chromates) in different solvents are
used
• Examples:
I. HCrO4 - in H2O: preparation: dissolve CrO3 in
H2O
II. CrO3 in acetone: Jones-Reagenz. Reaction:
Jones-Oxidation.
The basic reaction mechanism in the oxidation of
alcohols or aldehyds are as follows:
Oxidation of an Alcohol to Aldehyd or
Keton
Oxidation of Aldehyd to Carboxylic
Acid
 Swern-Oxidation:
• The use of dimethylsulfoxide as Oxidizing
agent:

• The activation of DMSO:

Oxalylchloride Sulfonium-Ion Sulfonium-Ion

Sulfonium-ion A and B are strong electrophiles and react in
a substitution reaction with alcohol to produce Sulfuran C.

Sulfuran

Dissoziation to sulfonium-ion D:
Production of Sulfonium-Ylid E: CH acidity of Sulfonium-ion D

End step: Keton/Aldehid, under beta-elimination

via cyclic intermediate
 Oppenauer-Oxidation
• Application: oxidation of steroid
 Mechanism
1. Exchange of Ligand:

2. Reaction of Lewis Acid (Al-alcanolate) and Base

(Acetone), activated C-alpha:
3. Hyride Shifting: from alcohol to activated alpha-C:

4. Dissoziation: release of oxidation product:

 3. Oxidation of Diol and Olefin
1. Epoxidation (Prileschaew-Reaction): electrophilic
Addition
2. Lemieux-Johnson- und Malaprade-
Oxidation: Production of aldehyd from alkene

Mechanism of Lemieux-Johnson-Oxidation: 1. „Anlagerung“ of

osmium tetraoxide, 2. Hydrolisis
2. Malaprada Oxidation:
 4. Oxidation of Keton to Ester
Baeyer-Villiger-Oxidation: 1. Addition of percarboxylic acid
to double bond, 2. Oxidation via cyclic intermediate