1. APPLICATIONS IN FINE CHEMICALS AND PHARMACEUTICAL
INDUSTRY
Organic Electrochemistry
Organic Electrochemistry
Presented by
Dr. Narender Rao Somisetti

2. Electrochemical synthesis
Chloro-alkali process
The chlor-alkali process is an industrial process for the electrolysis of sodium chloride. It is the technology used to
produce chlorine and sodium hydroxide (lye/caustic soda).
2NaCl + 2H2O —> 2NaOH + Cl2 + H2
Aluminum production
ADP synthesis
2CH2 =CHCN + H2O → NC(CH2)4 CN +1/2O2
The most successful organic electro synthesis process that has been commercialized is the manufacture of
adiponitrile from acrylonitrile. Adiponitrile (ADP) is a key intermediate for the production of nylon 6, 6 polymers. It is
used for the synthesis of hexamethylene diamine (HMD). 33% of the world consumption is made through
electrochemical synthesis.

3. Organic Electrochemistry: What is it?

4. Organic Electrochemistry: Why?
Reaction economy
Direct control of electron energy via over potential
Electrons/protons are (typically) sole reagents

5. Organic Electrochemistry: Why?
Electrochemistry enables the generation reactive intermediates from simple and
ubiquitous functional groups.
The ability of electrochemistry to expediently invert the intrinsic polarity of common
structural motifs.
The exceptional mildness and selectivity of electrochemical reactions.
The scalability and robustness of electrochemistry.
Exquisite control of chemo selectivity by “dialing in” reaction potentials.
Electrochemistry proffers reactivities and selectivities not within the purview of most
chemical reagents.

6. Organic Electrochemistry: Why?
Synthetic utility
Umpolung chemistry
High, typically predictable, tolerance of functional groups

7. Organic Electrochemistry: Why?
Synthetic utility:
Umpolung chemistry
Umpolung: pole reversal; reversion of polarity; turn-over.
Eg. Benzoin condensation in which Cyanide ion catalyzed dimerization of aromatic and heterocyclic
aldehydes to form α-ketols

8. Umpolung chemistry
Michael Stetter Reaction

10. Organic Electrochemistry: Early Beginnings

11. Organic Electrochemistry: Early Beginnings

12. Examples of industrial organic electro synthesis
processes at commercial scale

13. Electrochemistry Basics

14. Electrochemical Cell Design

15. Electrochemical Cells

16. Organo Electrochemical reactions @ Lab scale
Undivided design Divided design

17. The main advantages of electrochemical processes
• Versatility: Direct or indirect oxidation and reduction, phase separation, concentration or dilution, biocide
functionality, applicability to a variety of media and pollutants in gases, liquids, and solids, and treatment of small to
large volumes from micro liters up to millions of liters.
• Energy efficiency: Lower temperature requirements than their non electrochemical Counterparts and side
reactions being minimized by optimization of electrode structure and cell design.
• Amenability to automation: The system inherent variables of electrochemical processes, for example,
electrode potential and cell current, are particularly suitable for facilitating process automation and control.
• Cost effectiveness: Cell constructions and peripheral equipment are generally simple and if properly designed,
also inexpensive. The backbone of any electrochemical technology is the electrochemical reactor, therefore the
perfect design and scale-up plays an important role in successful of this electrochemical technology.

18. Limitations and challenges
Use in industry still restricted by mechanics of
process – engineering problem
Initial set up costs
Few examples for enantioselective additions or cyclization –
general for radical chemistry

19. Curiosity
Chemistry
Creativity