Separation and recycling of phosphane ligands from homogeneously catalyzed processes / von László Majoros. 2006
Content
- 1 Introduction
- 2 General Part
- 2.1 Influence of the chirality on the behavior of the compounds
- 2.2 Enantiomerically pure compounds
- 2.3 Catalysis
- 2.4 Asymmetric reduction
- 2.4.1 Enantioselective hydrogenation
- 2.4.2 Mechanism of the asymmertric hydrogenation
- 2.4.3 Asymmetric homogeneous hydrogenation using metal-catalyst in industrial application
- 2.4.4 Chiral Cl-MeO-Biphep ligand
- 2.5 Palladium catalyzed C-N bond-forming process
- 2.5.1 General Buchwald-Hartwig amination reaction [61]
- 2.5.2 Proposed Mechanism of the amination reaction
- 2.5.3 Dave-Phos and X-Phos ligands applied in C-N formation
- 2.6 Biphasic systems for reuse and recycling of the catalyst complexes
- 2.6.1 Immobilization by aqueous catalysts
- 2.6.2 Immobilization by nonaqueous biphasic systems
- 2.6.3 Immobilization and fixation to supported organic and inorganic polymers or matrices
- 3 Results and Discussion
- 3.1 Aims and Scopes
- 3.2 Asymmetric hydrogenation with different conditions and solvents using Cl-MeO-Biphep and BINAP ligands
- 3.2.1 Comparison of the two biaryl type phosphine ligands 3 and 11
- 3.2.2 Use of different solvents for the reduction of 1
- 3.2.3 Applying IL as a medium for the enantioselective hydrogenation of 1
- 3.2.4 Investigation of σ-ability of Cl-MeO-Biphep (3)
- 3.2.5 Scale up reaction for asymmetric hydrogenation in the research laboratory of Lanxess FC
- 3.2.6 Further improvement of asymmetric hydrogenation for the industrial applications with the view of costs
- 3.3 Derivatization of Cl-MeO-Biphep ligand (3)
- 3.4 Optimization of the recycling procedure of Cl-MeO-Biphep ligand via oxide derivative 3a and its scale up
- 3.4.1 Designing a separation and recycling cycle to demonstrate the steps of the complete procedure
- 3.4.2 Optimization of the reduction step using the standard oxide 3a
- 3.4.3 Optimization of the recovery cycle
- 3.4.4 Modeling of the recycling procedure as an industrial process
- 3.5 Results of Buchwald-Hartwig amination and the recycling process applying Dave-Phos and X-Phos ligands
- 4 Summary and Outlook
- 5 Experimental Part
- 5.1 General Technique
- 5.2 Characterisation and use of ligand 3 in asymmetric hydrogenation
- 5.3 Derivatization of ligand 3
- 5.4 Optimization of the recycling cycle for ligand 3
- 5.5 Amination reaction using Dave-Phos (7) and X-Phos (8) ligand
- 6 Spectra
- 7 Literature