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Green Chemistry

Green Chemistry

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Green Chemistry

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  1. Green Chemistry By Dr. Kandikere Ramaiah Prabhu Principal Research Scientist Department of Organic Chemistry Indian Institute of Science Bangalore – 560 012 October 23, 2010, Bangalore

  2. History….. Green Chemistry is born around 199o What is green chemistry or Sustainable Technology Traditionally - Chemical Yield was paramount Green Chemistry Focuses on - Process efficiency in terms of eliminating wastes at source and avoid using or generating toxic substances

  3. 12 Principals of green chemistry • PreventionIt is better to prevent waste than to treat or clean up waste after it has been created. • Atom EconomySynthetic methods should be designed to maximize the incorporation of all materials used in the process into the final product. • Less Hazardous Chemical SynthesesWherever practicable, synthetic methods should be designed to use and generate substances that possess little or no toxicity to human health and the environment. • Designing Safer ChemicalsChemical products should be designed to effect their desired function while minimizing their toxicity. • Safer Solvents and AuxiliariesThe use of auxiliary substances (e.g., solvents, separation agents, etc.) should be made unnecessary wherever possible and innocuous when used. • Design for Energy EfficiencyEnergy requirements of chemical processes should be recognized for their environmental and economic impacts and should be minimized. If possible, synthetic methods should be conducted at ambient temperature and pressure.

  4. Use of Renewable FeedstocksA raw material or feedstock should be renewable rather than depleting whenever technically and economically practicable. • Reduce DerivativesUnnecessary derivatization (use of blocking groups, protection/ deprotection, temporary modification of physical/chemical processes) should be minimized or avoided if possible, because such steps require additional reagents and can generate waste. • CatalysisCatalytic reagents (as selective as possible) are superior to stoichiometric reagents. • Design for DegradationChemical products should be designed so that at the end of their function they break down into innocuous degradation products and do not persist in the environment. • Real-time analysis for Pollution PreventionAnalytical methodologies need to be further developed to allow for real-time, in-process monitoring and control prior to the formation of hazardous substances. • Inherently Safer Chemistry for Accident PreventionSubstances and the form of a substance used in a chemical process should be chosen to minimize the potential for chemical accidents, including releases, explosions, and fires.

  5. E-Factor??? • Mass ratio of waste to desired product • Higher e-factor – more waste and –ve environmental impact • Raw Materials-Product output product The key to waste minimization is precision in organic synthesis, where every atom counts!!!

  6. Atom efficiency Molecular weight of the product Sum molecular weight of the all products formed Atom efficiency of stoichiometric versus catalytic oxidation of alcohols

  7. Additional questions!!?? Environmental impact of waste!! Waste can be an useful output What is the waste generated in manufacture of Organic compounds??? Fine chemicals and pharmaceuticals use stoichiometric amounts of reagents Reductions – Metal hydride Oxidations - CrO3, KMnO4,etc Sulfonation, Nitration, Friedel-Crafts reaction etc……!!!!

  8. The technologies used for the production of many substituted aromatic compounds have not changed in more than a century and are, therefore, ripe for substitution by catalytic, low-salt alternatives

  9. Two routes to hydroquinones

  10. Catalysts • Homogeneous catalyst & Heterogeneous catalysts • Organocatalyst • Biocatalysts

  11. Homogeneous catalyst & Heterogeneous catalysts • Organocatalyst

  12. Development Catalysis in Organic Synthesis

  13. If the solution to the waste problem in the fine chemicals industry is so obvious Replacement of classical stoichiometric reagents with cleaner, catalytic alternatives Why was it not applied in the past? There are several reasons for this.

  14. First, because of the smaller quantities compared with bulk chemicals, the need for waste reduction in fine chemicals was not widely appreciated. • A second, underlying, reason is the more or less separate evolution of organic chemistry and catalysis. • Fine chemicals and pharmaceuticals have remained primarily the domain of synthetic organic chemists who, generally speaking, have clung to the use of classical “stoichiometric” methodologies and have been reluctant to apply catalytic • alternatives. • A third reason, which partly explains the reluctance, is the pressure of time. Fine chemicals generally have a much shorter lifecycle than bulk chemicals and, especially in pharmaceuticals, ‘time to market’ is crucial.

  15. Major points to be addressed • Catalysts • Solvents • Renewable Raw Materials – White biotechnology • Risky Reagents • Process integration and catalytic cascades

  16. Catalysts Acid base catalyst Heterogeneous catalysts Homogeneous catalyst Solid catalysts Bio catalyst Organo catalysts

  17. Acid base catalyst Montmorillonite clays

  18. Zeolites

  19. Reductions Catalytic reductions Hydrogen gas Hydrogenation catalysts Selectivity in hydrogenation Chiral reductions

  20. oxidations

  21. Biocatalysts Egs: Yeast-ADH as alcohol dehydrogenase Horse liver-ADH

  22. Organocatalysis Proline-catalyzed aldol reaction

  23. Oxidation Our Research…!!!! X XO MReduced M Oxidized XO X Reduction Transition Metal oxides Chemical transformations Academia & Industry. Metal-oxo complexes Oxidations & reductions processes.

  24. Oxygen is transformed from Molecular Oxygen M. Maddani, K. R. Prabhu, Tetrahedron Lett., 2008, 49, 4526

  25. Oxidation of Alcohols to Carbonyls Catalysed by Molybdenum Xanthate No reaction Liquid phases Heterogeneous catalysts Recovery, recycling and Stability.

  26. Efficiency of the catalyst M. Maddani, K. R. Prabhu, Unpublished Results

  27. Convert surplus high energy materials to safer products II • Disposal or decomposition protocols for hydrazine and its derivatives by using user friendly protocols

  28. R.A. BACK, Reviews of Chemical Intermediates, 5 (1984) 293—323 C.Willis, R.A.Back, International Journal of chemical kinetics, 1977, 9, 787

  29. In search of catalyst for hydrogenation using hydrazine hydrate

  30. Method for the Aerobic Hydrogenation of Olefins Method for the generation of diimide • using metal Catalyst H2NNH2, CuSO4, air H2NNH2, CuSO4, H2O2 H2NNH2, CuSO4, O2 Metals such as mercuric oxide and Hexacyanoferrate(III) are also used along with hydrazine hydrate E.J. Corey, W.L. Mock .D.J. Pasto Tetrahedron Lett. 1961, 347-352 S. Huitig, H. R. Miiller, W. Thier, TetrahedronLett.1961, 353.

  31. From Azodicarboxylates (acid catalyzed hydrolysis) • Thermal decomposition of arenesulfonyl hydrazides E. E. van Tamelen, R. S. Dewey, J. Am. Chem. Soc. 196183 3729 . E.J. Corey, W.L. Mock .D.J. Pasto Tetrahedron Letters 1961, 347-352

  32. Flavin-Catalyzed Generation of Diimide Y. Imada, H. Iida, T. Naota, J. Am. Chem. Soc. 2005, 127, 14544-14545 • Reduction of Carbon-Carbon Double Bonds • Using Diimidegenearted by using C. Smit, M. W. Fraaije, A. J. Minnaard, J. Org. Chem. 2008, 73, 9482–9485

  33. Flavin-Catalyzed Generation of Diimide Y. Imada, H. Iida, T. Naota, J. Am. Chem. Soc. 2005, 127, 14544-14545 Reduction of Carbon-Carbon Double Bonds Using diamide generated by an Organocatalyst C. Smit, M. W. Fraaije, A. J. Minnaard, J. Org. Chem. 2008, 73, 9482–9485

  34. Mechanism For oxidative cleavage of Hydrazine hydrate using Flavin Catalyst Y. Imada, H. Iida, T. Naota, J. Am Chem. Soc. 2005, 127, 14544-14545

  35. Environmentally Benign Method for the Aerobic Hydrogenation of Olefins

  36. Reduction of alkenes and alkynes

  37. Drugs with chiral methyl group

  38. Synthetic scheme