Biphasic Chemistry and The Solvent Case

Jean-Philippe Goddard is Professor of Molecular Chemistry at the University of Upper Alsace, France, and Deputy Director of LIMA (Laboratory of Molecular Innovation and Applications), Strasbourg, France.Max Malacria is Emeritus Professor at Sorbonne University, Paris, France, where his research deals with catalysis, radical chemistry and aromaticity.Cyril Ollivier is a CNRS Research Director at the IPCM (Parisian Institute of Molecular Chemistry) at Sorbonne University.

• Chapter 1. Solid-phase Supported Chemistry 1Géraldine GOUHIER1.1. Introduction 11.2. Principle of solid-phase chemistry 21.3. Advantages 41.4. Safety and environment 41.5. Disadvantages and limitations 51.6. Evolution 61.7. Supports: linear skeletons 61.8. Three-dimensional resins 71.8.1. Macroporous resins 71.8.2. Gel resins 81.9. Characteristics of gel supports 101.9.1. Functionalization rate 101.9.2. Swelling properties 101.9.3. Size of the beads 121.9.4. Influence of cross-linking on swelling 121.9.5. Diffusion effect 131.9.6. Influence of cross-linking on diffusion 131.9.7. Influence of steric bulk 141.9.8. Influence of agitation 141.9.9. Proximity and pseudodilution effects 141.9.10. Proximity effect 151.9.11. Pseudodilution effect 151.9.12. Availability and costs 161.10. Functionalization of the solid support 171.10.1. Spacer arms 171.10.2. Linkers 181.10.3. Influence of functionalization 191.11. Analytical methods and reaction monitoring 201.11.1. Centesimal analyses 201.11.2. Colorimetric dosages 221.11.3. Indirect analyses 231.11.4. Infrared spectroscopy 231.11.5. Nuclear magnetic resonance spectrometry 241.11.6. Mass spectrometry 291.12. Solid-phase syntheses 291.12.1. Supported reagents 291.12.2. Supported chiral catalysts 321.12.3. Scavengers 341.13. Innovative applications and processes 351.13.1. Examples 351.13.2. Parallel syntheses on a solid support 371.14. Activation on solid phase 401.14.1. Microwave reactions 401.14.2. Reactions under high pressure 421.14.3. Reactions under ultrasound 421.14.4. Supported electrochemical reactions 431.14.5. Reactions in ionic liquid 431.15. Industrial applications and prospects 451.16. Conclusion 451.17. References 45Chapter 2. Fluorous Tags and Phases for Synthesis and Catalysis 57Jean-Marc VINCENT2.1. Introduction 572.2. Structures and properties of fluorous tags and phases 582.2.1. History of fluorous chemistry 582.2.2. Fluorous tags 592.2.3. Fluorous solvents 602.2.4. Solid fluorous phases 622.3. Separation/recycling methodologies using fluorous tags and phases 642.3.1. Application for catalysis 642.3.2. Application for synthesis 752.4. Conclusion 902.5. References 90Chapter 3. Chemistry In and On Water 99Marie-Christine SCHERRMANN3.1. Introduction 993.1.1. Presentation and history 993.1.2. Position in the context of green chemistry 1003.2. General: origin of reactivity in and on water 1003.2.1. Water structure and properties 1003.2.2. Chemistry in water: the hydrophobic effect 1023.2.3. Origin of reactivity on water 1063.3. Limitations of the method 1073.4. Reactivity in and on water 1073.4.1. Pericyclic reactions 1073.4.2. Addition reactions of carbonyl derivatives 1213.4.3. Coupling reactions catalyzed by transition metals 1273.4.4. Radical reactions 1353.4.5. Oxidation and reduction reactions 1363.5. Multistep syntheses 1423.6. Industrial applications 1433.7. Conclusion 1443.8. References 145Chapter 4. Solvent-free Chemistry 169Thomas-Xavier MÉTRO, Xavier BANTREIL, Jean MARTINEZ and Frédéric LAMATY4.1. Introduction 1694.2. General information on solvent-free synthesis: why use a solvent? 1704.3. Working without solvents 1704.4. Limitations of the technique 1714.5. In practice: methods and reactivity 1724.5.1. Methods and equipment. 1724.5.2. Examples 1724.5.3. Scaling up: industrial applications 1734.6. Mortar and pestle 1764.6.1. Methods and equipment 1764.6.2. Examples 1764.6.3. Scaling up: industrial applications 1774.7. Ball-mills 1784.7.1. Methods and equipment 1784.7.2. Examples 1804.7.3. Scaling up: industrial applications 1854.8. Extruders 1904.8.1. Methods and equipment 1904.8.2. Examples 1914.9. Microwave irradiation 1924.9.1. Methods and equipment 1924.9.2. Examples 1944.9.3. Scaling up: industrial applications 1964.10. Photochemistry 1984.10.1. Methods and equipment 1984.10.2. Examples 1994.10.3. Scaling up: industrial applications 2014.11. Comparison of techniques 2044.12. Conclusion 2064.13. References 206List of Authors 217Index 219