Green organic chemistry in lecture and laboratory

Sustainability: Contributions through Science and Technology Series Editor: Michael C Cann Green Organic Chemistry in Lecture and Laboratory Edited by Andrew P Dicks Green Organic Chemistry in Lecture and Laboratory Sustainability: Contributions through Science and Technology Series Editor: Michael C Cann, Ph.D Professor of Chemistry and Co-Director of Environmental Science University of Scranton, Pennsylvania Preface to the Series Sustainability is rapidly moving from the wings to center stage Overconsumption of nonrenewable and renewable resources, as well as the concomitant production of waste has brought the world to a crossroads Green chemistry, along with other green sciences technologies, must play a leading role in bringing about a sustainable society The Sustainability: Contributions through Science and Technology series focuses on the role science can play in developing technologies that lessen our environmental impact This highly interdisciplinary series discusses significant and timely topics ranging from energy research to the implementation of sustainable technologies Our intention is for scientists from a variety of disciplines to provide contributions that recognize how the development of green technologies affects the triple bottom line (society, economic, and environment) The series will be of interest to academics, researchers, professionals, business leaders, policy makers, and students, as well as individuals who want to know the basics of the science and technology of sustainability Michael C Cann Published Titles Microwave Heating as a Tool for Sustainable Chemistry Edited by Nicholas E Leadbeater, 2010 Green Chemistry for Environmental Sustainability Edited by Sanjay Kumar Sharma, Ackmez Mudhoo, 2010 Forthcoming Title A Novel Green Treatment for Textiles: Plasma Treatment as a Sustainable Technology C W Kan, 2012 Sustainability: Contributions through Science and Technology Series Editor: Michael Cann Green Organic Chemistry in Lecture and Laboratory Edited by Andrew P Dicks Boca Raton London New York CRC Press is an imprint of the Taylor & Francis Group, an informa business CRC Press Taylor & Francis Group 6000 Broken Sound Parkway NW, Suite 300 Boca Raton, FL 33487-2742 © 2012 by Taylor & Francis Group, LLC CRC Press is an imprint of Taylor & Francis Group, an Informa business No claim to original U.S Government works Version Date: 20110708 International Standard Book Number-13: 978-1-4398-4077-1 (eBook - PDF) This book contains information obtained from authentic and highly regarded sources Reasonable efforts have been made to publish reliable data and information, but the author and publisher cannot assume responsibility for the validity of all materials or the consequences of their use The authors and publishers have attempted to trace the copyright holders of all material reproduced in this publication and apologize to copyright holders if permission to publish in this form has not been obtained If any copyright material has not been acknowledged please write and let us know so we may rectify in any future reprint Except as permitted under U.S Copyright Law, no part of this book may be reprinted, reproduced, transmitted, or utilized in any form by any electronic, mechanical, or other means, now known or hereafter invented, including photocopying, microfilming, and recording, or in any information storage or retrieval system, without written permission from the publishers For permission to photocopy or use material electronically from this work, please access www.copyright.com (http://www.copyright.com/) or contact the Copyright Clearance Center, Inc (CCC), 222 Rosewood Drive, Danvers, MA 01923, 978-750-8400 CCC is a not-for-profit organization that provides licenses and registration for a variety of users For organizations that have been granted a photocopy license by the CCC, a separate system of payment has been arranged Trademark Notice: Product or corporate names may be trademarks or registered trademarks, and are used only for identification and explanation without intent to infringe Visit the Taylor & Francis Web site at http://www.taylorandfrancis.com and the CRC Press Web site at http://www.crcpress.com Contents Foreword vii Preface .ix About the Editor .xi Contributors xiii Chapter Introduction to Teaching Green Organic Chemistry Dr Sudhir B Abhyankar Chapter Designing a Green Organic Chemistry Lecture Course 29 Dr John Andraos Chapter Elimination of Solvents in the Organic Curriculum 69 Dr Andrew P Dicks Chapter Organic Reactions under Aqueous Conditions 103 Dr Effiette L O Sauer Chapter Organic Chemistry in Greener Nonaqueous Media 131 Mr Leo Mui Chapter Environmentally Friendly Organic Reagents 165 Dr Loyd D Bastin Chapter Organic Waste Management and Recycling 199 Ms Amanda R Edward Chapter Greener Organic Reactions under Microwave Heating 225 Dr Marsha R Baar v Foreword If you not change direction, you may end up where you are heading —Lao Tzu, the founder of Taoism Although this quote is more than 2,000 years old, it is more appropriate now than ever before The direction that humankind is now moving is not sustainable We are rapidly being engulfed by a growing environmental, social, and economic storm The combination of our expanding world population, rising affluence, and technological advances has brought the world to the brink of environmental bankruptcy Our ecological footprint now significantly exceeds the carrying capacity of the earth Without serious mid-course corrections of our unsustainable lifestyles, humankind will face some very serious threats to world order Challenges include the following: How we feed, clothe, shelter, and provide potable water to the current billion people on the planet, and the billion that will inhabit the earth by mid-century? How we curb the threat of climate chaos, while meeting the demands of an increasingly affluent population whose energy demands are projected to increase by more than 30% through 2050? Just like information technology has swept the world by storm, sustainable technology will as of necessity be the next thunderbolt that encompasses all of humanity Novel scientific applications, along with conservation, offer a pathway to sustainability Education is, of course, the key to launching and maintaining a wholesale shift in the way we develop and enact technologies New approaches must efficiently and effectively utilize our natural resources in a cyclical manner, reduce our energy demands, and eliminate the use and production of toxic materials, all while utilizing renewable resources and energy “Green chemistry” or “sustainable chemistry” is at the heart of a revolution in the discipline that has the potential to all of these This book helps to bring the world of green chemistry to not only the scientists and engineers of the future, but also to our prospective political leaders, economists, business leaders, teachers, and world citizens The development and implementation of sustainable technology offers a mighty challenge to humankind, but it also provides a wonderful opportunity to those with the proper skills and knowledge The term green chemistry was coined in 1991, and significant educational endeavors have taken place since then, particularly in the venue of organic chemistry It is our understanding that these enterprises have never been reviewed, compiled, and presented in a single volume as in this work The editor and the chapter authors sincerely hope this book will excite and provoke the minds of those individuals who explore its pages, will sow the seeds for tomorrow’s sustainable applications, and will stimulate further pedagogical efforts in green chemistry Michael C Cann University of Scranton vii Preface We know of no published green experiments designed for use in the organic teaching laboratory —Scott Reed and Jim Hutchison, Journal of Chemical Education, Volume 77, December 2000, 1627–1629 How times have changed! Since these words were written ten years ago as part of an article describing the environmentally benign preparation of adipic acid, the volume of pedagogical green chemistry literature has grown to impressive proportions Much of the credit for this goes to Ken Doxsee and Jim Hutchison, who published their excellent, motivating textbook (Green Organic Chemistry: Strategies, Tools, and Laboratory Experiments) in 2004 The majority of the hands-on activities and lecture case studies have been designed for undergraduates taking organic courses at college or university There are, of course, many students worldwide who are enrolled in such offerings As we rapidly approach the 2011 International Year of Chemistry, the opportunity to teach future generations about green and sustainable principles has never been more important As part of the CRC Press book series “Sustainability: Contributions through Science and Technology,” this publication is unlike others in the realm of green chemical education It is primarily written for organic chemistry educators who are instructing at either introductory or advanced levels Faculty teaching first-year general chemistry will also find it useful, particularly if their course has even a small organic component to it As the title implies, the book is comprehensive in its coverage of teaching green organic chemistry from both practical and theoretical standpoints Previous titles have tended to focus on one or the other of these perspectives An instructor may wish to develop an upper-level stand-alone course in the subject, or to simply “green up” aspects of an existing syllabus Both approaches will be made much easier upon consultation of the experiments and case studies outlined within these pages Adding green components to a current program is often the route of choice, and incorporating even one element that showcases sustainability into a chemistry curriculum is a positive step forward Chapter 1, “Introduction to Teaching Green Organic Chemistry,” appropriately focuses on the twelve principles, and how they can be used to focus classroom and laboratory discussions Time is also taken to outline the plethora of resources available in the field The second chapter, “Designing a Green Organic Chemistry Lecture Course,” provides a fascinating firsthand account of the challenges and rewards an instructor may experience The remaining contributions are based upon areas where much didactic research has taken place during the last decade These are solventless and aqueous reactivity, greener reagents, greener nonaqueous solvents, waste management/recycling, and energy efficiency (microwave heating) Each of these ix Electrophilic addition Electrophilic addition Electrophilic addition Electrophilic addition Electrophilic addition Electrophilic addition Electrophilic addition Electrophilic addition Electrophilic addition Electrophilic addition/ nucleophilic addition Electrophilic addition/ pericyclic Electrophilic aromatic substitution Electrophilic aromatic substitution 10 12 13 11 Reaction Mechanism Entry Alkylation Acylation of ferrocene Hetero Diels-Alder reaction Halohydrin formation Iodolactonization Alkene epoxidation Alkene iodochlorination Alkene oxidation/cleavage Alkene chlorination Alkene epoxidation Alkene bromination Alkene bromination Alkene bromination Transformation JCE 2007, 84, 692–693 JCE 2008, 85, 261–262 JCE 2006, 83, 270–272 JCE 1985, 62, 638 JCE 2006, 83, 921–922 JCE 2004, 81, 1018–1019 JCE 2008, 85, 962–964 JCE 2000, 77, 1627–1629 JCE 2003, 80, 1319–1321 JCE 2004, 81, 1187–1190 GCLR 2010, 3, 39–47 JCE 2005, 82, 306–310 JCE 2005, 82, 306–310 Journal MI, MS, LE, LD, GF, RE, CC H, VF, RE MI, VF, LE, GF, LD, D/ RE H, VF, R MS, LE, LD, GF, RE MS, LE, LD, GF, RE H, LE, LD, GF, RE, VF MS, H, VF, R MS, LD, GF, RE MS, LE, LD, GF MS, VF, H, LE, LD, RE MS, H, VF, R MS, H, VF Techniques (continued) Catalytic, greener reagent, solvent-free, atom efficiency, microwave heating Catalytic, greener reagent, microwave heating Greener, recyclable reagent Safer reagent, alternative reaction solvent, product recycling Greener reagents, alternative reaction solvent, atom efficiency, product recycling Catalytic, greener reagent, aqueous solvent, atom efficiency Greener reagent Catalytic, greener reagent, alternative reaction solvent, atom efficiency Aqueous solvent Alternative reaction solvent Catalytic, greener reagent, aqueous solvent Aqueous solvent Aqueous solvent Greener Principles Appendix 259 Electrophilic aromatic substitution Electrophilic aromatic substitution Electrophilic aromatic substitution Electrophilic aromatic substitution Electrophilic aromatic substitution Electrophilic aromatic substitution Electrophilic aromatic substitution Electrophilic aromatic substitution Electrophilic substitution Electrophilic substitution/ nucleophilic acyl substitution Electrophilic substitution/ rearrangement/nucleophilic addition/decarboxylation Elimination Fermentation Ionic liquid formation 14 27 25 26 24 22 23 21 20 19 18 17 16 15 Reaction Mechanism Entry Journal Deep eutectic solvent synthesis Alcohol dehydration Alcohol production EC 2005, 42 (1), 12–15 JCE 1993, 70, 493–495 JCE 2010, 87, 708–710 JCE 1999, 76, 1717 JCE 2008, 85, 834–835 JCE 2010, 87, 190–193 α-Fluorination Haloform reaction Hofmann rearrangement GC 2001, 3, 267–270 GC 2001, 3, 267–270 JCE 2005, 82, 616–617 Porphyrin formation Porphyrin formation Nitration JCE 2008, 85, 1426–1428 JCE 1997, 74, 324 Fries rearrangement Iodination TCE 2001, 6, 25–27 JCE 2006, 83, 1665–1666 TCE 1998, 3, 1–6 Friedel-Crafts acylation Dipyrromethane formation Bromination Transformation Techniques ES, H H, LE, LD, GF H, D MS, H, VF, R MS, H, VF, RE MS, H, VF H, CC MI, LE, GF, RE, CC MS, H, VF, R ES, VF, R MI, LE, LD, GF, RE MS, LE, GF, SE MS, GF, LD, VF, LE, RE, D H, VF Catalytic, greener reagent Biocatalytic, greener reagent, renewable feedstock Greener product Greener reagent Greener reagent Aqueous solvent Solvent-free Aqueous solvent, renewable feedstock Solvent-free, microwave heating Recyclable reagent, microwave heating Greener reagent Catalytic, greener reagent, aqueous solvent, atom efficiency Solvent-free Greener reagent Greener Principles 260 Appendix Metathesis Metathesis Metathesis Metathesis Metathesis Metathesis Nucleophilic acyl substitution Nucleophilic acyl substitution Nucleophilic acyl substitution Nucleophilic acyl substitution Nucleophilic acyl substitution Nucleophilic acyl substitution Nucleophilic acyl substitution Nucleophilic acyl substitution Nucleophilic acyl substitution Nucleophilic acyl substitution Nucleophilic acyl substitution Nucleophilic acyl substitution Nucleophilic acyl substitution 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 Esterification Esterification Phthalimide synthesis Diimide formation Ester hydrolysis Coffee ground degradation Ring-opening metathesis polymerization Amide formation Amide formation Amide hydrolysis Amine formylation Aspirin synthesis Aspirin, acetanilide, phenacetin, acetaminophen synthesis Claisen condensation Ring-closing metathesis Ring-closing metathesis Ring-opening metathesis polymerization Cross-metathesis Ring-closing metathesis JCE 1993, 70, 493–495 JCE 2009, 86, 227–229 JCE 1992, 69, 938–939 JCE 2008, 85, 1649–1651 JCE 2006, 83, 634–636 JCE 2001, 78, 1669–1671 JCE 2003, 80, 1446–1447 JCE 2003, 80, 1444–1445 JCE 2002, 79, 1344 JCE 2009, 86, 227–229 JCE 2009, 86, 227–229 JCE 2006, 83, 628–631 JCE 2000, 77, 356–357 JCE 1999, 76, 661–665 JCE 2010, 87, 721–723 JCE 2007, 84, 1998–2000 JCE 1993, 70, 165–167 JCE 2006, 83, 283–284 JCE 2007, 84, 1995–1997 SG, H, R MI, MS, LE, LD, GF, RE, R H, LE, LD, GF, D MI, MS, RE, LE, LD, GF SG, MI, VF, R H, LE, GF, LD, RE, T, R H, SX, RE VF MI, VF, R MI, MS, VF MI, MS, VF MI, ES, VF, R MI, VF, R MS, IA, VF, RE, VF MS, RE, CC, VF, R MS, H, VF, ST, IA, CC, RE MS, IA, GF, RE MS, H, RE, VF, IA H, VF (continued) Consumer product recycling, renewable feedstock Solvent-free Aqueous solvent, microwave heating Catalytic, greener reagent Catalytic, microwave heating Microwave heating Solvent-free Greener reagent Microwave heating Microwave heating Microwave heating Catalytic, microwave heating Catalytic, aqueous solvent, microwave heating Catalytic, greener reagent Catalytic, greener reagent Catalytic, greener reagent, aqueous solvent, renewable feedstock, product recycling Catalytic, greener reagent Catalytic, greener reagent Catalytic, greener reagent Appendix 261 Reaction Mechanism Nucleophilic acyl substitution Nucleophilic acyl substitution Nucleophilic acyl substitution Nucleophilic acyl substitution Nucleophilic acyl substitution Nucleophilic acyl substitution Nucleophilic acyl substitution Nucleophilic acyl substitution Nucleophilic acyl substitution Nucleophilic acyl substitution Nucleophilic acyl substitution Entry 47 48 49 50 51 52 53 54 55 56 57 Transesterification (biodiesel synthesis) Transesterification (biodiesel synthesis) Transesterification (biodiesel synthesis) Transesterification (biodiesel synthesis) Transesterification (biodiesel synthesis) Transesterification (biodiesel synthesis) Polyethylene terephthalate degradation Polyethylene terephthalate degradation Polyethylene terephthalate degradation Transesterification Polylactic acid degradation Transformation Journal JCE 2011, 88, 197–200 TCE 2009, 14, 98–104 JCE 2006, 83, 260–262 JCE 2006, 83, 257–259 JCE 2007, 84, 296–298 TCE 2005, 10, 130–132 JCE 2010, 87, 423–425 JCE 2010, 87, 519–521 JCE 1999, 76, 1525–1526 JCE 2003, 80, 79–82 JME 2008, 30, 257–280 Techniques MS, H ES, MI MS, H, LE MS, H, LE, LD MS, H, C MS, H, LE, VF MS, VF, RE, D MS, H, VF MS, H, LE, VF MS, H, VF, GF MS, H, RE Biocatalytic, greener reagent, low-solvent usage Consumer product recycling, renewable feedstock, greener product Consumer product recycling, renewable feedstock, greener product Consumer product recycling, renewable feedstock, greener product Consumer product recycling, renewable feedstock, greener product Consumer product recycling, renewable feedstock, microwave heating, greener product Consumer product recycling,renewable feedstock, greener product Consumer product recycling Consumer product recycling Consumer product recycling, renewable feedstock Consumer product recycling Greener Principles 262 Appendix Barbier (Grignard type) reaction Cannizzaro reaction Cannizzaro reaction Cellulose degradation Nucleophilic addition Nucleophilic addition Nucleophilic addition Nucleophilic addition Nucleophilic addition Nucleophilic addition 66 67 68 69 70 71 Cellulose degradation Aldol condensation Aldol condensation Nucleophilic addition 65 Aldehyde reduction Aldehyde reduction Aldehyde reduction Nucleophilic addition Nucleophilic addition Nucleophilic addition 62 63 64 61 Acetal formation Cu(II) phthalocyanine complex formation Pechmann condensation Nucleophilic acyl substitution/ dehydration Nucleophilic acyl substitution/ electrophilic aromatic substitution/dehydration Nucleophilic addition 59 60 Transesterification (biodiesel synthesis) Nucleophilic acyl substitution 58 TCE 2000, 5, 315–316 JCE 2008, 85, 546–548 JCE 2009, 86, 85–86 JCE 2004, 81, 1794–1795 JCE 1998, 75, 85 JCE 2006, 83, 1871–1872 JCE 2007, 84, 475–476 JCE 2006, 83, 285–286 JCE 2005, 82, 1674–1675 JCE 2011, 88, 322–324 JCE 2001, 78, 70–72 JCE 2011, 88, 319–321 JCE 2011, 88, 86–87 JCE 2011, 88, 201–203 H, VF SG, VF SG, H, LE, VF, GF, LD, RE H, VF, D MS, GF, LE, LD, RE MS, LE, LD, GF, RE MS, VF MS, VF MS, LE, LD, RE MS, H, LE, LD, RE MS, H, VF, R ES, H, VF, R SG, MI MS, H, LD, GF Consumer product recycling, renewable feedstock Consumer product recycling, renewable feedstock (continued) Solvent-free Solvent-free Consumer product recycling, renewable feedstock, greener product Solvent-free, catalytic, greener reagent, microwave heating Solvent-free, catalytic,greener reagent, recyclable reagent, atom efficiency Catalytic, greener reagent, aqueous solvent Aqueous solvent Greener reagent Catalytic, greener reagent, atom efficiency Catalytic, greener reagent, aqueous solvent, atom efficiency Catalytic, greener reagent, renewable feedstock, atom efficiency Aqueous solvent Appendix 263 Ketone reduction Ketone reduction Ketone reduction Mannich reaction Michael reaction Nucleophilic addition Nucleophilic addition Nucleophilic addition Nucleophilic addition Nucleophilic addition Nucleophilic addition Nucleophilic addition Nucleophilic addition Nucleophilic addition Nucleophilic addition Nucleophilic addition Nucleophilic addition Nucleophilic addition Nucleophilic addition 73 74 75 76 77 78 79 80 81 82 83 84 85 86 Michael reaction/alkene reduction Ketone reduction Ketone reduction Ketone reduction Ketone reduction Ketone reduction Horner–Wadsworth– Emmons reaction Ketone reduction Grignard reaction Creatine synthesis Nucleophilic addition 72 Transformation Reaction Mechanism Entry JCE 2011, 88, 322–324 JCE 2010, 87, 194–195 TCE 2008, 13, 344–347 GCLR 2008, 1, 149–154 JCE 1996, 73, A104-A105 JCE 2006, 83, 943–946 JCE 2002, 79, 727–728 JCE 2006, 83, 1049–1051 JCE 2005, 82, 1049–1050 JCE 1986, 63, 909 JCE 1998, 75, 630–631 JCE 2005, 82, 1055–1056 TCE 2005, 10, 300–302 JCE 2009, 86, 227–229 JCE 2006, 83, 1654–1657 Journal LE, LD, RE CC, RE, H, VF, R MS, H MS, H, D, GF, LD, RE MI, VF, R MS, H, VF, R, LE, RE MS, H, VF, LE, LD, RE, CC MS, GF, LE, LD, RE, CC H, VF, LE, LD, GF, RE SG, MI, LE, LD, GF, RE MS, LE, LD, GF, RE/D MS, GF, LD, RE, D MI, MS, LE, LD, GF, RE, R MS, H, VF, R MS, VF, R Techniques Biocatalytic, greener reagent, aqueous solvent Greener reagent Catalytic, greener reagent Microwave heating Alternative and recyclable reaction solvent, atom efficiency Catalytic, greener reagent, atom efficiency Catalytic, greener reagent Biocatalytic, greener reagent Biocatalytic, greener reagent Aqueous solvent Biocatalytic, greener reagent Solvent-free, microwave heating Aqueous solvent Catalytic, greener reagent, aqueous solvent, atom efficiency Microwave heating Greener Principles 264 Appendix 102 101 100 99 Nucleophilic addition/ dehydration Nucleophilic addition/ dehydration Nucleophilic addition/ dehydration Nucleophilic addition/ dehydration Nucleophilic addition/ dehydration 98 97 96 95 Coumarin formation Coumarin formation Biginelli reaction Aldol condensation Aldol condensation Aldol condensation Aldol condensation Aldol condensation Wittig reaction Wittig reaction Wittig reaction Wittig reaction Wittig reaction Knoevenagel condensation/ Michael addition/annulation Passerini reaction Nucleophilic addition Nucleophilic addition Nucleophilic addition Nucleophilic addition Nucleophilic addition Nucleophilic addition(s)/ dehydration(s)/decarboxylation Nucleophilic addition(s)/ nucleophilic acyl substitution Nucleophilic addition/ dehydration Nucleophilic addition/ dehydration Nucleophilic addition/ dehydration 88 89 90 91 92 93 94 Oxazolidinone formation Nucleophilic addition 87 PAC 2001, 73, 1257–1260; GC 2000, 2, 245–247 PAC 2001, 73, 1257–1260; GC 2000, 2, 245–247 JCE 2009, 86, 730–732 TCE 2011, 16, 23–25 JCE 2004, 81, 1345–1347 JCE 2007, 84, 475–476 JCE 1994, 71, A142, A144 JCE 2009, 86, 488–493 JCE 2009, 86, 1077–1079 JCE 2004, 81, 1492–1493 JCE 2007, 84, 119–121 JCE 2007, 84, 2004–2006 JCE 2007, 84, 119–121 JCE 1978, 55, 813 JCE 2007, 84, 1477–1479 JCE 2005, 82, 1229–1230 MS, VF SG, VF MS, H, SG, VF ES, VF, R SG, VF, R MS, H, VF MI, VF SG, T, VF, R SG, VF, R MS, GF, RE SG, MI, LE, RE, CC H, MS, GF, RE, R H, MS, GF, VF, R MI, MS, LE, LD, GF, RE MS, VF, R MS, LE, LD, GF, RE Catalytic, greener reagent, solvent-free, improved energy efficiency, atom efficiency Catalytic, greener reagent, solvent-free Catalytic, greener reagent, aqueous solvent (continued) Aqueous solvent, renewable feedstock Solvent-free Solvent-free Solvent-free, microwave heating Solvent-free Aqueous solvent Aqueous/greener solvent, microwave heating Aqueous solvent, atom efficiency Catalytic, greener reagent, solvent-free, atom efficiency Microwave heating, atom efficiency Catalytic, greener reagent, aqueous solvent, atom efficiency Catalytic, greener reagent, solvent-free, atom efficiency Solvent-free, atom efficiency Appendix 265 Nucleophilic addition/ dehydration Nucleophilic addition/ dehydration Nucleophilic addition/ dehydration Nucleophilic addition/ dehydration Nucleophilic addition/ dehydration Nucleophilic addition/ dehydration 103 105 113 112 Heterocyclic syntheses (e.g., benzimidazole, phthalimide) Heterocyclic syntheses (e.g., pyrrole, oxazoline, thiazoline, indole) Aldol condensation/Michael reaction Semicarbazone formation Nucleophilic addition/ dehydration Nucleophilic addition/ dehydration or nucleophilic acyl substitution/dehydration Nucleophilic addition/ dehydration or nucleophilic acyl substitution/dehydration Nucleophilic addition/ dehydration/nucleophilic addition 110 111 Knoevenagel condensation Nucleophilic addition/ dehydration Knoevenagel condensation Imine formation Imine formation Imidazole synthesis Hantzsch reaction Dioxolanone synthesis Transformation 109 108 107 106 104 Reaction Mechanism Entry JCE 2005, 82, 468–469 JCE 2006, 83, 634–636 JCE 2006, 83, 632–633 JCE 2004, 81, 108 JCE 2009, 86, 227–229 TCE 2007, 12, 324–326 JCE 2006, 83, 1221–1224 JCE 2006, 83, 929–930 JCE 2006, 83, 1658–1660 JCE 2010, 87, 628–630 TCE 2003, 8, 33–36 Journal SG, MS, H, VF MI, MS, LE, LD, GF, RE, R, CC SG, MI, VF, R SG, VF, R MI, MS, VF MS, VF VF, MS, H, VD SG, R MI, VF, R MS, H, SG, VF, R MI, CC, RE Techniques Solvent-free, renewable feedstock, atom efficiency Solvent-free, microwave heating Solvent-free, atom efficiency, microwave heating Alternative reaction solvent, atom efficiency, microwave heating Solvent-free Alternative reaction solvent, atom efficiency Catalytic, greener reagent, aqueous solvent, atom efficiency Solvent-free, atom efficiency Low-solvent usage, improved energy efficiency, atom efficiency Microwave heating Microwave heating Greener Principles 266 Appendix 127 126 125 124 123 122 121 120 119 118 117 116 115 114 Nucleophilic addition/ dehydration/nucleophilic addition/hydrolysis Nucleophilic addition/ electrophilic addition Nucleophilic addition/ elimination Nucleophilic addition/ elimination Nucleophilic addition/ elimination Nucleophilic addition/ elimination Nucleophilic addition/ elimination Nucleophilic addition/ elimination Nucleophilic addition/ elimination Nucleophilic addition/ elimination Nucleophilic addition/ elimination Nucleophilic addition/ elimination Nucleophilic addition/ elimination Nucleophilic addition/ elimination JCE 1980, 57, 438 JCE 1987, 64, 371–372 Alcohol oxidation JCE 1991, 68, 1048–1049 QN 2009, 32, 1667–1669 JCE 1985, 62, 519–521 JCE 1982, 59, 981 JCE 1982, 59, 862 JCE 1981, 58, 824 Alcohol oxidation Alcohol oxidation Alcohol oxidation Alcohol oxidation Alcohol oxidation Alcohol oxidation Alcohol oxidation TCE 2010, 15, 115–116 JCE 2001, 78, 66–67 Alcohol oxidation Alcohol oxidation TCE 2004, 9, 30–31 Alcohol oxidation JCE 2003, 80, 907–908 JCE 2011, 88, 322–324 Alkene epoxidation Alcohol oxidation JCE 2004, 81, 874–876 Coumarin formation MS, VF, H, GF, RE, R MS, VF, H, GF, RE, R MS, LE, LD, RE, R MS, H, LE, LD, RE D, LE, LD MS, H, D, LE, LD D MS, H, D, LE, LD MS, LE, LD, GF, R MS, H, LE, LD, RE SG, H, LE, VF, LD, GF, RE SG, H, LE, LD, GF, RE MS, LE, LD, GF, RE MS, H, VF, R Greener reagent, recyclable reagent Greener reagent, recyclable reagent (continued) Catalytic, greener reagent Greener reagent Greener reagent Greener reagent Greener reagent Greener reagent Catalytic, greener reagent, aqueous solvent Product recycling Solvent-free Catalytic, greener reagent, aqueous solvent, atom efficiency Catalytic, greener reagent, atom efficiency Solvent-free Appendix 267 Nucleophilic addition/ elimination Nucleophilic addition/ elimination Nucleophilic addition/ elimination Nucleophilic addition/ elimination Nucleophilic addition/ elimination Nucleophilic addition/ elimination Nucleophilic addition/ elimination Nucleophilic addition/ elimination Nucleophilic addition/ elimination Nucleophilic addition/ elimination Nucleophilic addition/ nucleophilic acyl substitution Nucleophilic addition/ rearrangement Nucleophilic addition/ rearrangement 128 133 136 140 139 138 137 135 134 132 131 130 129 Reaction Mechanism Entry JCE 2005, 82, 1837–1838 JCE 2008, 85, 1274–1275 Epoxide rearrangement JCE 2010, 87, 640–642 JCE 1997, 74, 1225 JCE 2010, 87, 190–193 TCE 2004, 9, 370–373 JCE 2004, 81, 388–390 JCE 2007, 84, 852–854 Baeyer-Villiger reaction Hydantoin synthesis Wolff-Kischner reaction Ketone oxidation Ketone oxidation Benzylic oxidation Aldehyde oxidation JCE 2011, 88, 652–656 JCE 2009, 86, 227–229 Alcohol oxidation Alcohol oxidation JCE 2010, 87, 981–984 JCE 2001, 78, 951–952 Alcohol oxidation Alcohol oxidation JCE 2006, 83, 268–269 Journal Alcohol oxidation Transformation MS LE, LD, GF, RE, VF, R MI, VF, LE, LD, GF, RE, R MI, GF, RE MS, H, VF MS, H, VF, R MS, VF, CC MS, H, VF, R MS, H, LE, LD, RE, CC, IA, VF MI, MS, GF, LE, LD, RE MS, LE, LD, GF, RE, SB MS, VF, RE, CC MS, H, VF, RE, R Techniques Catalytic, greener reagent, atom efficiency Solvent-free Greener reagent, aqueous solvent Microwave heating, alternative reaction solvent Microwave heating Greener reagent Catalytic, greener reagent Greener reagent, recyclable reagent Catalytic, greener reagent, microwave heating Catalytic, greener reagents, alternative reaction solvent, renewable feedstock Aqueous solvent Greener reagent, recyclable reagent Greener reagent Greener Principles 268 Appendix Nucleophilic substitution Nucleophilic substitution Nucleophilic substitution Nucleophilic substitution Nucleophilic substitution(s) Oxidative addition/reductive elimination Oxidative addition/syn addition/β-hydride elimination/reductive elimination Oxidative addition/ transmetallation/reductive elimination Oxidative addition/ transmetallation/reductive elimination 148 149 150 151 152 153 156 155 154 Ionic liquid synthesis Williamson ether synthesis Williamson ether synthesis Nucleophilic substitution Nucleophilic substitution Nucleophilic substitution 145 146 147 Suzuki reaction JCE 2008, 85, 555–557 JCE 1999, 76, 74–75 TCE 2007, 12, 77–79 Heck reaction Sonogashira reaction JCE 2011,88, 331–333 JCE 2010, 87, 84–86 JCE 2010, 87, 84–86 JCE 2010, 87, 623–624 JCE 2009, 86, 850–852 JCE 2006, 83, 634–636 JCE 2006, 83, 943–946 JCE 2005, 82, 1839–1840 JCE 1980, 57, 822 JCE 2010, 87, 1233–1235 JCE 2006, 83, 285–286 JCE 2009, 86, 856–858 JCE 2010, 87, 196–201 Williamson ether synthesis Wittig salt synthesis Diazotization, alcohol formation Ullmann coupling Williamson ether synthesis Williamson ether synthesis Ether synthesis Ether synthesis Ionic liquid synthesis Ionic liquid synthesis Nucleophilic substitution Nucleophilic substitution Nucleophilic substitution Nucleophilic substitution 141 142 143 144 MS, H, VF, GF, R MS, H, SE, CC, RE, R MS, H, GF, VF, R SG, VF, CC, RE MS, H, LE, LD, GF, RE SG, H, VF, SB MS, H, LE, LD, D/RE, D H, VF MI, MS, LE, LD, GF, RE MI, MS, ES, VF, R MI, MS, VF MS, VF, R MS, RE, H, GP MS, H, GF, RE H, LE, LD, GF, D MS, MI, LE, RE (continued) Catalytic, greener reagent, aqueous solvent Catalytic, greener reagent, alternative reaction solvent Microwave heating Microwave heating Renewable feedstock, aqueous solvent Solvent-free, catalytic, greener reagent Catalytic, greener reagent, aqueous solvent Greener reagent Catalytic, greener reagent Aqueous solvent Greener products, microwave heating Greener products Solvent-free Catalytic, greener reagent, aqueous solvent Alternative reaction solvent Microwave heating Appendix 269 Oxidative addition/ transmetallation/reductive elimination Oxidative addition/ transmetallation/reductive elimination Pericyclic Pericyclic Pericyclic Pericyclic Pericyclic Pericyclic Pericyclic Pericyclic Pericyclic Pericyclic 157 160 161 162 163 164 165 166 167 168 159 158 Reaction Mechanism Entry Hetero Diels-Alder reaction Diels-Alder reaction Hetero Diels-Alder reaction Diels-Alder reaction Diels-Alder reaction Diels-Alder reaction Diels-Alder reaction Diels-Alder reaction Diels-Alder reaction JCE 2008, 85, 1538–1540 TCE 2010, 15, 28–31 JCE 1998, 75, 1285–1287 JCE 2010, 87, 84–86 JCE 1992, 69, 938–939 JCE 2005, 82, 625–629 JCE 2006, 83, 634–636 JCE 2009, 86, 488–493 JCE 2009, 86, 488–493 JCE 2005, 82, 1833–1836 TCE 2009, 14, 258–260 Suzuki reaction 1,3-Dipolar cycloaddition TCE 2007, 12, 414–418 Journal Suzuki reaction Transformation MI, VF, R D, MS, H, LE, LD, GF, RE, VF MS, H, LE, LD, GF, RE MI, MS, VF SG, MI, VF MI, VF, R MI, MS, RE, R MS, H, VF MS, H, VF, LE, LD, GF, RE MS, MI, VF, R MS, H, LE, LD, GF, RE, CC, R MI, VF, LD, GF, RE, CC Techniques Alternative reaction solvent, microwave heating, atom efficiency Microwave heating Aqueous solvent, atom efficiency Aqueous solvent, atom efficiency Catalytic, greener reagent, atom efficiency Alternative reaction solvent, atom efficiency, microwave heating Aqueous solvent, atom efficiency Microwave heating, atom efficiency Microwave heating, atom efficiency Microwave heating, atom efficiency Catalytic, greener reagent, aqueous solvent, microwave heating Catalytic, greener reagent, aqueous solvent Greener Principles 270 Appendix Pericyclic/elimination Pericyclic/nucleophilic acyl substitution Polymerization Polymerization Polymerization Radical Radical Radical Radical 170 171 172 173 174 175 176 177 178 Bromination Biaryl formation JCE 2005, 82, 120–121 JCE 2010, 87, 526–527 JCE 2008, 85, 411–412 JCE 2004, 81, 1636–1640 JCE 2008, 85, 258–260 JCE 2005, 82, 1380–1381 Polylactic acid formation Polysuccinimide formation Biaryl formation Biaryl formation JCE 2008, 85, 972–975 JCE 2009, 86, 488–493 JCE 1994, 71, A142–144 JCE 2005, 82, 1679–1681 Adhesive synthesis Diels-Alder reaction Photochemical + cycloaddition Diels-Alder reaction H, VI MS, H, VF MS, H, VF, LE, LD, GF, RE, R MS, H, VF MS, H, RE H, VF MS, H, VF ES H, GF, VF, SG, VI, LE, LD, RE MI, VF, R Catalytic, aqueous solvent, greener reagent, atom efficiency Alternative reaction solvent Renewable feedstock, greener product Greener product Solvent-free, renewable feedstock, greener product Aqueous solvent Aqueous solvent Solvent-free, sunlight irradiation, atom efficiency Microwave heating, atom efficiency Solvent-free, atom efficiency Journal abbreviations: EC = Education in Chemistry, GC = Green Chemistry, GCLR = Green Chemistry Letters and Reviews, JCE = Journal of Chemical Education, JME = Journal of Materials Education, PAC = Pure and Applied Chemistry, QN = Quimica Nova, TCE = The Chemical Educator Experimental technique abbreviations: C = centrifugation, CC = column chromatography, D = distillation, ES = experimenter stirring, GF = gravity filtration, GP = gas phase reactivity, H = heating, IA = inert atmosphere, LD = liquid drying, LE = liquid extraction, MI = microwave irradiation, MS = magnetic stirring, R = recrystallization, RE = rotary evaporation, SB = sublimation, SE = steam bath evaporation, SG = solid grinding, ST = Schlenk techniques, SX = Soxhlet extraction, T = trituration, VD = vacuum distillation, VF = vacuum filtration, VI = visible light irradiation Pericyclic 169 Appendix 271 GENERAL CHEMISTRY Green Organic Chemistry in Lecture and Laboratory The last decade has seen a huge interest in green organic chemistry, particularly as chemical educators look to “green” their undergraduate curricula Detailing published laboratory experiments and proven case studies, this book discusses concrete examples of green organic chemistry teaching approaches from both lecture/seminar and practical perspectives The experienced contributors address such topics as the elimination of solvents in the organic laboratory, organic reactions under aqueous conditions, organic reactions in non-aqueous media, greener organic reagents, waste management/recycling strategies, and microwave technology as a greener heating tool This reference allows instructors to directly incorporate material presented in the text into their courses Encouraging a stimulating organic chemistry experience, the text emphasizes the need for undergraduate education to: • Focus on teaching sustainability principles throughout the curriculum • Be flexible in the teaching of green chemistry, from modification of an existing laboratory experiment to development of a brand-new course • Reflect modern green research areas such as microwave reactivity, • alternative reaction solvents, solvent-free chemistry, environmentally friendly reagents, and waste disposal Train students in the “green chemistry decision-making” process Integrating recent research advances with the Twelve Principles of Green Chemistry into lecture and laboratory environments, Green Organic Chemistry in Lecture and Laboratory highlights smaller, more cost effective experiments with minimized waste disposal and reduced reaction times This approach develops a fascinating and relevant undergraduate organic laboratory experience while focusing on real-world applications and problem-solving K11889 ... this mandate by integrating advances in green chemistry research into the teaching of green organic chemistry in both lecture and laboratory environments Some of the chapters that follow outline... term green chemistry was coined at the U.S EPA In one of the earliest publications about introducing green principles in teaching and research, Collins described a lecture course entitled “Introduction... Chapter Introduction to Teaching Green Organic Chemistry Dr Sudhir B Abhyankar Chapter Designing a Green Organic Chemistry Lecture Course 29 Dr John Andraos Chapter Elimination of Solvents in