1. A) Industrial internship at Kodak
Microreactor study of the Wittig reaction and
Organic synthesis of porphyrin tapes
Supervisor : Dr Newington
Kodak, R&D department
Harrow, United Kingdom
September June 2003
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2. Microreactor study of the Wittig reaction
Contents
Microreactor study of the Wittig reaction
2) Organic synthesis of porphyrin tapes
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3. What is a microreactor and how it works ?
A microreactor is a network of micron sized interconnecting channels (rectangular cross-section, depths : m, widths : m)
Each reagent are dissolved in a specific solvent and introduced in a reservoir at the end of each channels.
The mobility of solutions is allowed thanks to Electro-osmotic flow.
The speed is directly proportional to the applied potentials between each reservoir and the terminal one.
Reagent A
Reagent B
Reagent C
Solvent
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4. Study of Wittig reaction in microreactor
All reagent are dissolved in methanol (50 L )
=> Optimization of the yield
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5. Full factorial experimental plan
T(terminal reservoir) = 0V
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6. Conclusion : Wittig reaction in microreactor
Results of the work :
The product is obtained and the yield depends on the applied potential
The results was optimized due to statistical plan
Advantages :
Very small amount of starting material (toxic, expensive…)
Very fast syntheses and easy to optimize
Good spatial and temporal control of reagents.
Possible to run continuously
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7. Organic synthesis of porphyrin tapes
Target molecule : monomer, dimer and trimer of porphyrin
0, 1, 2,…
R = alkyl chain
Strategy : 1) Synthesis of ballast group and of dipyrromethanes
2) Formation of porphyrines monomer with metal
3) Coupling reaction
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8. The interest of the porphyrin Tapes
Porphyrin arrays display extremely red-shifted absorption bands in the nm region
It enables to tune their optical and electronic properties in a predictable manner through the length of the arrays.
The change of ballast groups in the meso-positions must be achieved in order to improve the solubility.
Main properties :
Intense electronic absorption and emission ( Small HOMO-LUMO energy gap)
Flexible tunability of their optical and redox properties by appropriate metallation
Problems :
Poor solubility
Difficult separations
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9. 1) Synthesis of the ballast group
R = Alkyl chain
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10. 1) Synthesis of dipyrromethanes
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11. 2) Indirect synthesis of porphyrin monomer
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12. 2) Direct synthesis of porphyrin monomer
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13. 3) Coupling reactions of porphyrins
Poor yield
76%
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14. 3) Coupling reactions of porphyrins
99%
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15. 3) Coupling reactions of porphyrins
X= Br or I
Ar = 3,5-dialkyloxyphenyl-
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16. 3) Coupling reactions of porphyrins
X= Br or I
Ar = 3,5-dialkyloxyphenyl-
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17. 3) Synthesis of porphyrin tapes
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18. Conclusion on porphyrin tapes
Targeted molecules were obtained but the yield need to be optimized
IR spectra need to be recorded
This project was carried on by the next trainee but it has been given up six month later !!!
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