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 2002 - June 2003 BASF-14-12-2007

Microreactor study of the Wittig reaction Contents Microreactor study of the Wittig reaction 2) Organic synthesis of porphyrin tapes BASF-14-12-2007

What is a microreactor and how it works ? A microreactor is a network of micron sized interconnecting channels (rectangular cross-section, depths : 10-200 m, widths : 50-200 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 BASF-14-12-2007

Study of Wittig reaction in microreactor All reagent are dissolved in methanol (50 L ) => Optimization of the yield BASF-14-12-2007

Full factorial experimental plan T(terminal reservoir) = 0V BASF-14-12-2007

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 BASF-14-12-2007

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 BASF-14-12-2007

The interest of the porphyrin Tapes Porphyrin arrays display extremely red-shifted absorption bands in the 1400-1500 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 BASF-14-12-2007

1) Synthesis of the ballast group R = Alkyl chain BASF-14-12-2007

1) Synthesis of dipyrromethanes BASF-14-12-2007

2) Indirect synthesis of porphyrin monomer BASF-14-12-2007

2) Direct synthesis of porphyrin monomer BASF-14-12-2007

3) Coupling reactions of porphyrins Poor yield 76% BASF-14-12-2007

3) Coupling reactions of porphyrins 99% BASF-14-12-2007

3) Coupling reactions of porphyrins X= Br or I Ar = 3,5-dialkyloxyphenyl- BASF-14-12-2007

3) Coupling reactions of porphyrins X= Br or I Ar = 3,5-dialkyloxyphenyl- BASF-14-12-2007

3) Synthesis of porphyrin tapes BASF-14-12-2007

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 !!! BASF-14-12-2007