Wacker Olefin Oxidation

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Wacker Olefin Oxidation
Presented by
Kittichai Jinachai 4605121 Athikom
Prathumsuk 4605651
Department of Chemistry, Faculty of
Science, Chiang Mai University, Thailand
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Introduction

• The oxidation of ethylene to acetaldehyde
  by oxygen in water in the presence of a palladium
  tetrachloride catalyst.
• Produce aldehydes and ketones from a number
  of alkenes.
• An example of homogeneous catalysis.

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Reaction mechanism
The modern understanding of the reaction
mechanism for the Wacker process (olefin
oxidation via palladium(II) chloride) is
described below
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Reaction mechanism
The catalytic cycle can be described as follows
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Mechanism summary
The Wacker process is the migration of the
hydrogen from oxygen to chlorine and formation of
the C-O double bond. This step is generally
regarded to proceed through a so-called ß-hydride
elimination with a four-membered cyclic
transition state
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Mechanism summary
One in silico study argues that the
transition state for this reaction step is
unfavorable (activation energy 36.6 kcal/mole)
and proposes an alternative reductive elimination
reaction mechanism in which the proton directly
attaches itself to chlorine with an activation
energy of 18.8 kcal/mol. The proposed reaction
step gets assistance from a water molecule acting
as a catalyst.
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Mechanism summary
Wacker-Tsuji oxidation
The so-called Wacker-Tsuji oxidation is the
laboratory scale version of the above reaction,
for example the conversion of 1-decene to
2-decanone with palladium(II) chloride and
copper(II chloride in a water / dimethylformamide
solvent mixture in the presence of air .
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Reference

• Translated in part from deWacker-Verfahren.
• F.C. Phillips, Am. Chem. J., 1894, 16, 255-277.
• F.C. Phillips, Z. Anorg. Chem., 1894, 6, 213-228.
  
• J. Smidt, W. Hafner, R. Jira, J. Sedlmeier, R.
  Sieber, R. Rüttinger, and H. Kojer, Angew. Chem.,
  1959, 71, 176-182.
• W. Hafner, R. Jira, J. Sedlmeier, and J. Smidt,
  Chem. Ber., 1962, 95, 1575-1581.
• J. Smidt, W. Hafner, R. Jira, R. Sieber, J.
  Sedlmeier, and A. Sabel, Angew. Chem., Int. Ed.
  Engl., 1962, 1, 80-88.

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Thank you for your attention