1. Lecture 13 CATALYSIS – OXIDATION OF ALKENES
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2. ETHYLENE OXIDATION TO ACETALDEHYDE:
Acetaldehyde – of commercial importance - oxidation to acetic acid - dehydration to acetic anhydride Previous synthetic route: Today, Wacker process is used producing 4 million tons of acetaldehyde from ethylene.
ETHYLENE OXIDATION TO ACETALDEHYDE:
WACKER PROCESS

3. Net Reaction: WACKER PROCESS
CH2=CH2 + PdCl2 + H2O  CH3C(=O)H + Pd(0) + 2HCl
Pd(0) + 2 CuCl2  PdCl CuCl
2CuCl + 2HCl + 1/2O2  2CuCl H2O
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CH2=CH /2O2  CH3C(=O)H Ho = -243 kJ/mol
WACKER PROCESS

4. THE WACKER PROCESS

5. WACKER PROCESS

6. Step a Two Cl ions are displaced and substituted with alkene and H2O
WACKER PROCESS

7. Step b
Attack of a nucleophile (H2O) on the alkene
WACKER PROCESS

8. Step c Loss of Cl
WACKER PROCESS

9. ALKENE DIMERIZATION AND OLIGOMERIZATION
Step d -elimination
ALKENE DIMERIZATION AND OLIGOMERIZATION

10. ALKENE DIMERIZATION AND OLIGOMERIZATION
Step e
ALKENE DIMERIZATION AND OLIGOMERIZATION

11. ALKENE DIMERIZATION AND OLIGOMERIZATION
Step g Regeneration of Pd(II)
ALKENE DIMERIZATION AND OLIGOMERIZATION

12. EPOXIDATION OF ALKENES

13. EPOXIDATION OF ALKENES

14. Lecture 13 CATALYSIS – CARBONYLATION AND CARBOXYLATION REACTIONS
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15. CARBONYLATION and CARBOXYLATION
Main industrial processes using CO: Synthesis of methanol Fischer-Tropsch process Hydroformylation process Synthesis of acetic acid Production of formic acid Synthesis of dimethyl carbonate Synthesis of polyketones
CARBONYLATION and CARBOXYLATION

16. MONSANTO PROCESS

17. MONSANTO PROCESS

18. OLEFIN HYDROFORMYLATION : THE OXO PROCESS

19. CARBONYLATION OF ALKENES/ALKYNES : REPPE RXN

20. CARBONYLATION ALKENES AND ALKYNES
Production of methyl methacrylate (MMA) – an intermediate for the polymer synthesis of plexiglass.
CARBONYLATION ALKENES AND ALKYNES

21. CARBONYLATION OF ALKENES AND ALKYNES
Synthesis of ployketones: In the absence of methanol
CARBONYLATION OF ALKENES AND ALKYNES

22. CARBONYLATION OF ALKENES AND ALKYNES
Industrial application of the Reppe reaction using alkynes: Acrylic acid synthesis.
CARBONYLATION OF ALKENES AND ALKYNES

23. CARBOXYLATION