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What is Green Chemistry? Applying Green Chemistry to Undergraduate Research Baylis-Hillman Reaction Synthesis of TMS-PVK. TMS-PVK by Tandem Grignard- Oppenauer Oxidation Goal of research Potential Oxidizing agents Tandem Grignard- Oppenauer Oxidation with acetaldehyde. Tandem Grignard- Oppenauer Oxidation with Paraformaldehyde. Continuing Research Acknowledgements Questions
Doxsee, K.M. and Hutchison, J.E. Green Chemistry: Strategies, Tools, and Laboratory Experiments. Thomson, Brookes, and Cole. 2003.
Baylis-Hillman Reaction
O OR
+
R3N
RCHO OR NR3 R
O H OR
+
- R3N R
OH O OR
NR3
O R3N Si
O RCHO Ph R
O Si Ph
+
Si - R3N R
O Ph
NR3
NR3
Essentially eliminates head-to-tail dimerization of PVK under reaction conditions This methodology is allowing new applications of the Baylis-Hillman reaction to be developed
O PCC / SiO2TMS
TMS
Oxidation reactions are generally non-green due to their use of heavy metals and toxic reagents.
1. Mg Br 2. PhCHO
O Si
Mg Br
O Si
OH
Results
Si Br 1. Mg O Si
OH
80% yield of TMS-PVK 100% yield of benzyl alcohol Results demonstrate successful Grignard addition and complete oxidation Benefits
Reduced synthesis by one step and utilizes oxidizing potential of the magnesium alkoxide salt. Eliminated the use of PCC.
Greenest Route?
Replacement of 2nd equivalent of benzaldehyde with smaller ketones or aldehydes will improve atom economy. Additionally, use of small ketones or aldehydes would eliminate the need for column chromatography to separate the TMS-PVK from excess benzaldehyde.
Goal of Research
To find a greener oxidizing agent than the benzaldehyde. Find a reaction that is more atom economic.
acetone
isopropanol
H3C H3C
CH3 O Si CH2
OH
O H
acetaldehyde
Paraformaldehyde
Testing Paraformaldehyde the Tandem Grignard- Oppenauer Oxidation 1 equivalent of benzaldehyde was used as the electrophile in the Grignard reaction. 1 equivalent of paraformaldehyde was used as the oxidizing agent for the Oppenauer Oxidation. Aqueous workup removes methanol.
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Results
Preliminary results indicate that TMSPVK was synthesized, but some alcohol precursor still remained (~2:1 ratio) Excess paraformaldehyde may be needed.
Continuing Research
Trimer of acetaldehyde
Boiling point = 124C
O Allows for the oxidation with greater atom efficiency and a smaller waste product. Less volatile than the acetaldehyde. Preliminary results indicate formation of TMSPVK.
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Acknowledgements
Thanks to:
Dr. Carl Lecher Marian College Department of Natural and Behavioral Sciences
Questions?
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