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1. Alternative Solvents for Green Chemistry
RSC Green Chemistry Book SeriesSeries Editors: James H Clark, Department of Chemistry, University of York, York, UK George A Kraus, Department of Chemistry, Iowa State University, Iowa, USAGreen Chemistry is one of the most important and rapidly growing concepts inmodern chemistry. Through national awards and funding programmes,national and international courses, networks and conferences, and a dedicatedjournal, Green Chemistry is now widely recognised as being important in all ofthe chemical sciences and technologies, and in industry as well as in educationand research. The RSC Green Chemistry book series is a timely and uniqueventure aimed at providing high level research books at the cutting edge ofGreen Chemistry.Titles in the Series:Alternative Solvents for Green ChemistryBy Francesca M. Kerton, Department of Chemistry, Memorial University ofNewfoundland, St. John's, NL, CanadaThe Future of Glycerol: New Uses of a Versatile Raw MaterialBy Mario Pagliaro, CNR, Instiute of Nanostructured Materials and Institute forScientific Methodology, Palermo, Italy and Michele Rossi, Department ofInorganic Chemistry, University of Milan, Milan, ItalyVisit our website on www.rsc.org/booksFor further information please contact:Sales and Customer Care, Royal Society of Chemistry, Thomas Graham House,Science Park, Milton Road, Cambridge, CB4 0WF, UKTelephone: +44 (0)1223 432360, Fax: +44 (0)1223 426017, Email: email@example.com
Alternative Solvents for GreenChemistryFrancesca M. KertonDepartment of Chemistry, Memorial University of Newfoundland, St. John's,NL, Canada
ISBN: 978-0-85404-163-3A catalogue record for this book is available from the British Libraryr Francesca M. Kerton 2009All rights reservedApart from fair dealing for the purposes of research for non-commercial purposes or forprivate study, criticism or review, as permitted under the Copyright, Designs and PatentsAct 1988 and the Copyright and Related Rights Regulations 2003, this publication may notbe reproduced, stored or transmitted, in any form or by any means, without the priorpermission in writing of The Royal Society of Chemistry or the copyright owner, or inthe case of reproduction in accordance with the terms of licences issued by the CopyrightLicensing Agency in the UK, or in accordance with the terms of the licences issued by theappropriate Reproduction Rights Organization outside the UK. Enquiries concerningreproduction outside the terms stated here should be sent to The Royal Society ofChemistry at the address printed on this page.Published by The Royal Society of Chemistry,Thomas Graham House, Science Park, Milton Road,Cambridge CB4 0WF, UKRegistered Charity Number 207890For further information see our web site at www.rsc.org
PrefaceEveryone is becoming more environmentally conscious and therefore, chemi-cal processes are being developed with their environmental burden in mind.Of course, this also means that more traditional chemical methods are beingreplaced with new innovations. This includes new solvents. Solvents are everywhere, but should they be? They are used in most areasincluding synthetic chemistry, analytical chemistry, pharmaceutical productionand processing, the food and flavour industry and the materials and coatingssectors. But, the principles of green chemistry guide us to use less of them, or touse safer, more environmentally friendly solvents if they are essential. There-fore, we should always ask ourselves, do we really need a solvent? Chapter 2explains some of the challenges and successes in the field of solvent-freechemistry, and the answer becomes apparent: not always! In the introductory chapter, some of the hazards of conventional solvents(e.g. toxicity and flammability) and their significant contribution to wastestreams are highlighted. The general properties of solvents and why and wherethey are used are outlined. Additionally, EHS (Environmental, Health andSafety) assessments and life cycle analyses for traditional and alternative sol-vents are described. It becomes clear that often a less hazardous VOC isavailable and that although only ''light green'' (or at least ''less black'') incolour, they can be used as an interim measure until a more satisfying optionbecomes available. In each of the subsequent chapters, where possible, the useof an alternative solvent is described for a range of chemical applicationsincluding extractions, synthetic and materials chemistry. At the beginning ofeach of these chapters, some of the advantages and disadvantages of thatmedium are laid out. Water is often described as Nature's solvent; therefore Chapter 3 describesthe solvent properties of water. It is already used quite widely on an industrialscale, particularly in emulsion polymerization processes and hydrodistillations.However, some of the most exciting results have come in the field of syntheticRSC Green Chemistry Book SeriesAlternative Solvents for Green ChemistryBy Francesca M. Kertonr Francesca M. Kerton 2009Published by the Royal Society of Chemistry, www.rsc.org v
vi Prefacechemistry. Recently, 'on-water' reactions have shown that hydrophobic (waterinsoluble) compounds can achieve higher rates dispersed in water compared toreactions in conventional solvents or under solvent-free conditions. Water canalso be used at very high temperatures and under pressure in a near-critical orsupercritical state. Under these conditions, its properties are significantlyaltered and unusual chemistry can result. This is further discussed in Chapter 4,which describes supercritical fluids. The focus here is on the non-flammableoptions, that is, carbon dioxide and water. Modifications that are performed onsubstrates in order to make them soluble in supercritical carbon dioxide aredescribed. Additionally, the benefits of the poor solvating power of carbondioxide, e.g. selective extractions, are highlighted and its use in tuning reactivitythrough its variable density is described. In addition to water and carbon dioxide, there is an increasing availability ofsolvents sourced from renewable feedstocks including ethanol, ethyl lactate and2-methyl-tetrahydrofuran. The properties of these solvents and their potentialas replacements to petroleum-sourced solvents are discussed in Chapter 5.Renewable feedstocks and their transformations are a growing area of greenchemistry and they have significantly impacted the solvent choice arena. Inaddition to renewable VOC solvents, non-volatile ionic liquid and eutecticmixture solvents have been prepared from renewable feedstocks and arelooking to be very promising alternatives in terms of toxicity and degradation.These and other room temperature ionic liquids (RTILs) will be discussed inChapter 6. The field of RTILs has grown dramatically in the last ten years andthe range of anions/cations that can be used to make these non-volatile solventsis continually expanding. Although some of these media may be more expensivethan other alternatives, the chance to make task-specific solvents for particularprocesses is very exciting. RTILs, alongside fluorous solvents, have also made alarge impact in the area of recyclable homogeneous catalysts. Fluorous sol-vents, as described in Chapter 7, show interesting phase behaviour and allowthe benefits of a heterogeneous and homogeneous system to be employed byadjusting an external variable such as temperature. Recent advances in this areawill be discussed, for example, supported fluorous chemistry, which avoids theuse of large amounts of fluorous solvents and might be more amenable toindustrial scale processes. Possibly the least explored and newest options available to the green chemistare liquid polymer solvents (Chapter 8) and switchable and tunable solvents(Chapter 9). Unreactive low molecular weight polymers or those with low glasstransition temperatures can be used as non-volatile solvents. In particular,poly(ethyleneglycols) and poly(propyleneglycols) have been used recently in arange of applications. Probably the most important recent additions to ourtoolbox are switchable solvents. New molecular solvents have been discoveredthat can be switched from non-volatile to volatile or between polar and non-polar environments by the application of an external stimulus. Gas-expandedliquids will also be discussed in Chapter 9, as carbon dioxide can be used as asolubility switch and to reduce the environmental burden of conventionalsolvents.
Preface vii Although many advances in the area of alternative solvents have originatedin academia, many alternatives are already in use on an industrial scale. Forexample, supercritical carbon dioxide is used in coffee decaffeination and nat-ural product extractions, as an alternative solvent in dry-cleaning and as asolvent in continuous flow hydrogenation reactions. An overview of these andsome other industrial processes that use alternative solvents will be described inChapter 10. Unfortunately, as will become clear to readers, there is no universal greensolvent and users must ascertain their best options based on prior chemistry,cost, environmental benefits and other factors. It is important to try andminimize the number of solvent changes in a chemical process and therefore,the importance of solvents in product purification, extraction and separationtechnologies has been highlighted. There have been many in-depth books and reviews published in the area ofgreen solvents. Hopefully, readers will find this book a readable introduction tothe field. However, some cutting-edge results from the recent literature havebeen included in an attempt to give a clearer picture of where green solvents aretoday. For more comprehensive information on a particular solvent system,readers should look to the primary literature and the many excellent reviews ofrelevance to this field in journals such as Green Chemistry and ChemicalReviews. Certain solvent media can be fascinating in their own right, not just as 'green'solvent alternatives! Therefore, we must not be blind to our overall goal inreducing the environmental burden of a particular process. Hopefully, readersof this book will be able to make up their own minds about the vast array ofsolvents available for a greener process, or even come up with a new additionfor the green chemistry toolbox. Although many advances have been madeduring the past decade, the most exciting results are surely yet to come. I would like to thank the editors of the RSC Green Chemistry Series, JamesClark and George Kraus, for the opportunity to contribute a book to thisimportant group of books. Also, I would like to acknowledge Merlin Fox (thecommissioning editor) and the staff at RSC Publishing involved with this series,particularly, Annie Jacob, who has been advising and helping me all along theway. Finally, I would like to thank my husband, Chris Kozak, for his patience,support and motivational input during the writing of this book. Francesca Kerton St. John's, Newfoundland, Canada
ContentsChapter 1 Introduction 1.1 The Need for Alternative Solvents 1 1.2 Safety Considerations, Life Cycle Assessment and Green Metrics 4 1.2.1 Environmental, Health and Safety (EHS) Properties 4 1.2.2 Life Cycle Assessment (LCA) 5 1.2.3 Solvents in the Pharmaceutical Industry and Immediate Alternatives to Common Laboratory Solvents 12 1.3 Solvent Properties Including Polarity 14 1.4 Summary 20 References 21Chapter 2 'Solvent free' Chemistry 2.1 Introduction 23 2.2 Chemical Examples 25 2.2.1 Inorganic and Materials Synthesis 25 2.2.2 Organic Synthesis 27 188.8.131.52 Enantioselective Catalysis 36 220.127.116.11 Microwave assisted Reactions 39 126.96.36.199 Photoreactions 39 2.3 Summary and Outlook for the Future 39 References 41RSC Green Chemistry Book SeriesAlternative Solvents for Green ChemistryBy Francesca M. Kertonr Francesca M. Kerton 2009Published by the Royal Society of Chemistry, www.rsc.org ix
x ContentsChapter 3 Water 3.1 Introduction 44 3.1.1 Biphasic Systems 46 3.2 Chemical Examples 49 3.2.1 Extraction 49 3.2.2 Chemical Synthesis 51 126.96.36.199 Metal-mediated and Catalysed Reactions 54 22.214.171.124 Microwave Assisted Reactions 56 188.8.131.52 Biocatalysis 57 188.8.131.52 Carbon Dioxide Fixation 58 3.2.3 Materials Synthesis 60 3.3 High Temperature, Superheated or Near Critical Water 63 3.4 Summary and Outlook for the Future 64 References 65Chapter 4 Supercritical Fluids 4.1 Introduction 68 4.2 Chemical Examples 71 4.2.1 Supercritical and Liquid Carbon Dioxide 71 126.96.36.199 Solubility in Supercritical Carbon Dioxide 71 22.214.171.124 Extraction 74 126.96.36.199 Chemical Synthesis 76 126.96.36.199 Materials Synthesis and Modification 82 4.2.2 Supercritical Water and Near Critical Water 84 188.8.131.52 Extraction and Analytical Chemistry 84 184.108.40.206 Chemical Synthesis 86 18.104.22.168 Materials Synthesis 89 188.8.131.52 Supercritical Water Oxidation (SCWO) 90 4.3 Summary and Outlook for the Future 91 References 92Chapter 5 Renewable Solvents 5.1 Introduction 97 5.2 Chemical Examples 100 5.2.1 Alcohols including Glycerol 100 5.2.2 Esters 103 126.96.36.199 Biodiesel 105 5.2.3 2-Methyltetrahydrofuran (2-MeTHF) 108 5.2.4 Terpenes and Plant Oils 109 5.2.5 Renewable Alkanes 113
Contents xi 5.2.6Ionic Liquids and Eutectic Mixtures Prepared from Bio-Feedstocks 114 5.3 Summary and Outlook for the Future 115 References 116Chapter 6 Room Temperature Ionic Liquids and Eutectic Mixtures 6.1 Introduction 118 6.2 Chemical Examples 123 6.2.1 Extractions using RTILS 123 6.2.2 Electrochemistry in RTILS 125 6.2.3 Synthesis in RTILS 126 184.108.40.206 Biocatalysis in RTILs 131 220.127.116.11 Polymer Synthesis and Processing 132 6.2.4 Selected Unconventional Uses of RTILs 136 6.3 Summary and Outlook for the Future 138 References 138Chapter 7 Fluorous Solvents and Related Systems 7.1 Introduction 143 7.1.1 Overview of Fluorous Approach 143 7.1.2 Fluorous Solvent Polarity Data, Solubility and Miscibility Data 145 7.1.3 Fluorous Catalysts and Reagents 149 7.2 Chemical Examples 150 7.2.1 Fluorous Extractions and Fluorous Analytical Chemistry 150 7.2.2 Fluorous Reactions 152 7.2.3 Fluorous Biphase Catalysis 153 18.104.22.168 Continuous Fluorous Biphase Catalysis 160 7.2.4 Fluorous Biological Chemistry and Biocatalysis 162 7.2.5 Fluorous Combinatorial Chemistry 164 7.2.6 Fluorous Materials Chemistry 166 7.3 Summary and Outlook for the Future 167 References 167Chapter 8 Liquid Polymers 8.1 Introduction 170 8.1.1 Properties of Aqueous PEG Solutions 170 8.2 Chemical Examples 173 8.2.1 PEG and PPG as Non-volatile Reaction Media 173 22.214.171.124 PEG as a Reaction Solvent 174
xii Contents 8.2.2 Poly(dimethylsiloxane) as a Non-volatile Reaction Medium 182 8.3 Summary and Outlook for the Future 185 References 186Chapter 9 Tunable and Switchable Solvent Systems 9.1 Introduction 188 9.2 Chemical Examples 189 9.2.1 Gas Expanded Liquids 189 22.214.171.124 Solvent Properties of CXLs 190 18.104.22.168 Applications of CXLs 191 9.2.2 Solvents of Switchable Polarity 193 9.2.3 Switchable Surfactants 197 9.2.4 Solvents of Switchable Volatility 199 9.2.5 Thermomorphic and Related Biphasic Catalysis 201 9.3 Summary and Outlook for the Future 202 References 202Chapter 10 Industrial Case Studies 10.1 Introduction 204 10.2 Selected Applications: Examples 205 10.2.1 Water as a Solvent and Reaction Medium 206 10.2.2 Carbon Dioxide as a Solvent and Reaction Medium 210 10.2.3 RTILs in Industry 214 10.3 Summary and Outlook 215 References 216Subject Index 218
CHAPTER 1Introduction1.1 The Need for Alternative SolventsOne of the 12 principles of green chemistry asks us to 'use safer solvents andauxiliaries'.1–3 Solvent use also impacts some of the other principles andtherefore, it is not surprising that over the last 10 years, chemistry research intothe use of greener, alternative solvents has grown enormously.4–8 If possible, theuse of solvents should be avoided, or if they cannot be eliminated, we should tryto use innocuous substances instead. In some cases, particularly in the manu-facture of bulk chemicals, it is possible to use no added solvent—so-called'solvent free' conditions. Yet in most cases, including specialty and pharma-ceutical products, a solvent is required to assist in processing and transporting ofmaterials. Alternative solvents suitable for green chemistry are those that havelow toxicity, are easy to recycle, are inert and do not contaminate the product.There is no perfect green solvent that can apply to all situations and thereforedecisions have to be made. The choices available to an environmentally con-cerned chemist are outlined in the following chapters. However, we must firstconsider the uses, hazards and properties of solvents in general. Solvents are used in chemical processes to aid in mass and heat transfer, andto facilitate separations and purifications. They are also an important and oftenthe primary component in cleaning agents, adhesives and coatings (paints,varnishes and stains). Solvents are often volatile organic compounds (VOCs)and are therefore a major environmental concern as they are able to form low-level ozone and smog through free radical air oxidation processes.3 Also, theyare often highly flammable and can cause a number of adverse health effectsincluding eye irritation, headaches and allergic skin reactions to name justthree. Additionally, some VOCs are also known or suspected carcinogens. Forthese and many other reasons, legislation and voluntary control measures haveRSC Green Chemistry Book SeriesAlternative Solvents for Green ChemistryBy Francesca M. Kertonr Francesca M. Kerton 2009Published by the Royal Society of Chemistry, www.rsc.org 1
2 Chapter 1been introduced. For example, benzene is an excellent, unreactive solvent but itis genotoxic and a human carcinogen. In Europe, prior to 2000, gasoline(petrol) contained 5% benzene by volume but now the content is o1%.Dichloromethane or methylene chloride (CH2Cl2) is a suspected human car-cinogen but is widely used in research laboratories for syntheses and extrac-tions. It was previously used to extract caffeine from coffee, but nowdecaffeination is performed using supercritical carbon dioxide (scCO2).Perchoroethylene (CCl2CCl2) is also a suspected human carcinogen and is themain solvent used in dry cleaning processes (85% of all solvents). It is alsofound in printing inks, white-out correction fluid and shoe polish. ScCO2 andliquid carbon dioxide technologies have been developed for dry cleaning;however, such solvents could not be used in printing inks. Less toxic, renewableand biodegradable solvents such as ethyl lactate are therefore being consideredby ink manufacturers. Despite a stagnant period for the solvent industry during 1997–2002, worlddemand for solvents, including hydrocarbon and chlorinated types, is currentlygrowing at approximately 2.3% per year and approaching 20 million tonnesannually. However, when the less environmentally friendly hydrocarbon andchlorinated types are excluded, market growth is around 4% per year. There-fore, it is clear that demand for hydrocarbon and chlorinated solvents is on adownward trend as a result of environmental regulations, with oxygenated andgreen solvents replacing them to a large extent.9 It should be noted that thesestatistics exclude in-house recycled materials and these figures therefore justrepresent solvents new to the market; the real amount of solvent in useworldwide is far higher. It also means that annually a vast amount of solvent isreleased into the environment (atmosphere, water table or soil). Neverthelessthe situation is moving in a positive direction, as in the USA and WesternEurope environmental concerns have increased sales of water based paints andcoatings to levels almost equal to the solvent based market. Therefore, it is clearthat legislation and public interests are causing real changes in the world ofsolvents. The introduction of legislation by the United States Food and DrugAdministration (FDA) means that some solvents, e.g. benzene, are alreadybanned in the pharmaceutical industry and others should only be used ifunavoidable, e.g. toluene and hexane. FDA-preferred solvents include water,heptane, ethyl acetate, ethanol and tert-butyl methyl ether. Hexane, which isnot preferred and is a hazardous air pollutant, is used in the extraction of awide range of natural products and vegetable oils in the USA. According to theEPA Toxic Release Inventory, more than 20 million kg of hexane are releasedinto the atmosphere each year through these processes. It may seem straight-forward to substitute hexane by its higher homologue, heptane, when lookingat physical and safety data for solvents (Table 1.1). However, heptane is moreexpensive and has a higher boiling point than hexane, so economically and interms of energy consumption a switch is not that simple. Therefore, it is clearthat much needs to be done to encourage the development and implementationof greener solvents.
Table 1.1 Properties of some volatile organic solvents, and some possible alternatives. IntroductionSolvent Boiling point/1C Flash point/1C TLV–TWAa/ppm Hazards Green?Methanol 64 12 200 Toxic, flammable Can be renewableEthanol 78 16 1000 Irritant, flammable Can be renewableIsopropanol 96 15 400 Irritant, flammable1-Butanol 117 12 100 Harmful, flammableEthyl acetate 76 À2 400 Harmful, flammableEthyl lactate 154 46 Not yet Irritant, flammable Renewable establishedTHF 65 À17 200 Irritant, flammable2-MeTHF 80 À11 Not yet Irritant, flammable Renewable established2-Butanone 80 À3 200 Irritant, flammableDichloromethane 40 none 100 Toxic, harmful, suspected carcinogenChloroform 61 none 10 Possible carcinogenToluene 110 4 50 Irritant, teratogen, flammableHexane 68 À26 50 Irritant, reproductive hazard, flammableHeptane 98 À4 400 Irritant, flammableWater 100 none Not applicable Renewable, non-flammable, cheapCarbon dioxide Not applicable none 5000 Compressed gas Renewable, non-flammable, cheapPEG-1000 Not applicable none Not applicable Non-toxic, non-volatile[Bmim] [PF6] Not applicable none Not yet established Non-volatileaTLV–TWA: threshold limit value—time weighted average in vapour. 3
4 Chapter 11.2 Safety Considerations, Life Cycle Assessment and Green MetricsIn recent years, efforts have been made to quantify or qualify the 'greenness' of awide range of solvents; both green and common organic media were con-sidered.10,11 In deciding which solvent to use, a wide range of factors should beconsidered. Some are not directly related to a specific application, such as costand safety, and these will generally rule out some options. For example, roomtemperature ionic liquids (RTILs) are much more expensive than water and theyare therefore more likely to find applications in high value added areas such aspharmaceuticals or electronics than in the realm of bulk or commodity chemicals.However, a more detailed assessment of additional factors should be performedincluding a life cycle assessment, energy requirements and waste generation. A computer-aided method of organic solvent selection for reactions has beendeveloped.12 In this collaborative study between chemical engineers and pro-cess chemists in the pharmaceutical industry, the solvents are selected using arules based procedure where the estimated reaction–solvent properties and thesolvent–environmental properties are used to guide the decision making processfor organic reactions occurring in the liquid phase. These rules (Table 1.2) ,whether computer-aided or not, could also be more widely used by all chemistsin deciding whether to use a solvent and which solvents to try first. The technique was used in four case studies; including the replacement ofdichloromethane as a solvent in oxidation reactions of alcohols, which is animportant area of green chemistry. 2-Pentanone, other ketones and some esterswere suggested as suitable replacement solvents. At this point, the programmewas not able to assess the effects of non-organic solvents because of a lack ofavailable data. However, this approach holds promise for reactions where a VOCcould be replaced with a far less hazardous, less toxic or bio-sourced option.1.2.1 Environmental, Health and Safety (EHS) PropertiesThe EHS properties of a solvent include its ozone depletion potential, biode-gradability, toxicity and flammability. Fischer and co-workers have developedTable 1.2 Rules used in computer-aided solvent selection for organic reactions.Establish need for solventsLiquid phase reactionsThe solvent must be liquid at room temperatureNeed for solvent as carrier; if one or more reactants are solidsNeed for solvents to remove reactants or products; if one or more products are solidsNeed for phase splitMatching of solubility parameters of solute and solvent; within Æ5% of the key reactant or productNeutrality of solventsAssociation/dissociation properties of solventsEHS property constraints (based on up to 10 EHS parameters)
Introduction 5 Table 1.3 Categories used in EHS assess- ment of solvents. Release potential Chronic toxicity Fire/explosion Persistency Reaction/decomposition Air hazard Acute toxicity Water hazard IrritationFigure 1.1 Results of an environmental, health and safety (EHS) assessment for 26 common solvents. [Reprinted with permission from Green Chem., 2007, 9, 927–934. Copyright 2007 The Royal Society of Chemistry.]a chemical (and therefore, solvent) assessment method based on EHS criteria.10It is available at http://www.sust-chem.ethz.ch/tools/ehs/. They have demon-strated its use on 26 organic solvents in common use within the chemicalindustry. The substances were assessed based on their performance in ninecategories (Table 1.3). Using this EHS method, formaldehyde, dioxane, formic acid, acetonitrileand acetic acid have high (environmentally poor) scores (Figure 1.1). For-maldehyde has acute and chronic toxicity, dioxane is persistent and the acidsare irritants. Methyl acetate, ethanol and methanol have low scores, indicatinga lower hazard rating.1.2.2 Life Cycle Assessment (LCA)The function of life cycle assessment (LCA) is to evaluate environmentalburdens of a product, process, or activity; quantify resource use and emissions;assess the environmental and human health impact; and evaluate and
6 Chapter 1 13implement opportunities for improvements. It is important to realize thatwhile this book focuses on solvents, VOC 'free' paints and other 'green' con-sumer items may not be entirely green or entirely VOC free when the whole lifecycle is considered. For example, a VOC may be used in the preparation of apigment or another paint component, which is then incorporated into the finalnon-VOC (e.g. aqueous) formulation. The same can also be said for manysynthetic procedures which are reported to be 'solvent free'. The reaction maybe performed between neat reagents; however, a solvent is used in purifying,isolating and analysing the product. Chemists should be aware of this andavoid over-interpreting what authors are describing. Fischer and co-workers undertook a LCA of the 26 organic solvents which theyhad already assessed in terms of EHS criteria (see above).10 They used the Eco-solvent software tool (http://www.sust-chem.ethz.ch/tools/ecosolvent/), which onthe basis of industrial data considers the 'birth' of the solvent (its petrochemicalproduction) and its 'death' by either a distillation process or treatment in ahazardous waste incineration plant. For both types of end-of-life treatment,'environmental credits' were granted where appropriate, e.g. solvent recovery andreuse upon distillation. The results of this assessment are shown in Figure 1.2.From an LCA perspective, tetrahydrofuran (THF), butyl acetate, cyclohexanoneand 1-propanol are not good solvents. This is primarily due to the environmentalFigure 1.2 Life cycle assessment of the treatment options (incineration and distilla- tion) for 26 common laboratory solvents. [Reprinted with permission from Green Chem., 2007, 9, 927–934. Copyright 2007 The Royal Society of Chemistry.]
Introduction 7Figure 1.3 Combined EHS and LCA method for assessing 'greenness' of solvents. [Reprinted with permission from Green Chem., 2007, 9, 927–934. Copy- right 2007 The Royal Society of Chemistry.]impact of their petrochemical production and their LCA would therefore bebetter if they came from a different source. For example, 1-propanol may one daybecome available through selective dehydration and hydrogenation of glycerol(a renewable feedstock). At the other end of this scale, diethyl ether, hexane andheptane are considered favourable solvents. However, the reader should alreadybe aware that diethyl ether is extremely hazardous in terms of flammability, lowflash point and explosion risk through peroxide contamination. Therefore, theresults from the EHS assessment and LCA were combined in an attempt toprovide the whole picture (Figure 1.3). It is evident from Figure 1.3 that formaldehyde, dioxane, organic acids,acetonitrile and THF are not desirable solvents. THF and formaldehyde aresignificant outliers on this last graph because of their particularly poor per-formance under one of the assessment methods. Methanol, ethanol and methylacetate are preferred solvents based on their EHS assessment. Heptane, hexaneand diethyl ether are preferred based on LCA. However, it must be noted thatthe LCA was performed based on petrochemical production of the solvents andif the first group of solvents was bio-sourced, perhaps these three solvents
8 Chapter 1Figure 1.4 Life cycle flow chart for solvent usage. Primary life cycle stages are represented by rectangles. [Reprinted with permission from Org. Proc. Dev., 2007, 11, 149–155. Copyright 2007 American Chemical Society.]would be the outright winners! Unfortunately, assessment tools used in thisstudy could not be applied to many currently favoured alternative solventtechnologies such as supercritical fluids and RTILs as there is a lack of avail-able data at this time to quantify them fully. However, a more qualitative LCA approach has been used by Clark andTavener to assess the neoteric solvents described in this book (Figure 1.4).11The solvent must first be manufactured, usually from petroleum. This is rela-tively straightforward for simple and aromatic hydrocarbons that are obtained
Introduction 9through cracking and distillation of crude oil. However, for other chemicalsmore complex synthetic routes are needed, e.g. to introduce heteroatoms suchas halogens. Yet others, such as acetone, are produced as by-products in themanufacture of some chemicals. In terms of the alternative solvents describedin this book, fluorous solvents and RTILs typically require multistage synth-eses. Carbon dioxide and water do not need preparation but do need pur-ification prior to use. Other renewable solvents, such as ethanol and esters,require separation or extraction and purification before use. A step oftenoverlooked in LCA of chemicals is their distribution. Carbon dioxide and waterare available globally and can therefore be sourced close to their point of use.Bioethanol would be a good solvent to use in Brazil but may not be readilyavailable in other areas of the world. Therefore, the authors suggested alabelling system, similar to the 'food miles' being introduced at supermarkets,enabling chemists to find out where their compounds or solvents weremanufactured. The third primary stage in the life cycle of a solvent is its use. Solvents areused in many areas and not just as media for reactions (Table 1.4). The choiceTable 1.4 Some solvent applications.Application DescriptionSolvent extraction In hydrometallurgy to recover metals from ores In nuclear fuel reprocessing In waste water treatment To recover natural products from plants or from fermen- tation liquors In organic synthesis and analytical chemistry As a degreaser and cleaning agentAnalytical chemistry and Eluant in analytical and preparative chromatography, and electrochemistry in other separation techniques Dissolving the electrolyte to permit current to flow between the electrodes, without being oxidized or reduced itself As an oxidant or a reductantOrganic chemistry As a reaction medium and diluent In separations and purification As a dehydrator (also in materials chemistry)Polymer and materials As a dispersant chemistry As a plasticizer As a blowing agent to create porosity As a binder to achieve cohesiveness in composite materials Production of powders, coatings, films, etc. As a developer in photoresist materialsHousehold and others Fuels and lubricants Paints, varnishes, adhesives, dyes, etc. Antifreeze Cleaning fluids As a humectant (hydrating material) and in emulsions within cosmetics and pharmaceuticals
10 Chapter 1of the right solvent can have significant effects on energy consumption and theE-factor of a process. Solvent effects can lead to different reaction pathways fora number of reasons;14 some of these effects will be briefly discussed later in thischapter. The E-factor is the mass ratio of waste to desired product.15 If thewrong solvent is chosen, it can significantly affect the yield of a process (99% inthe 'right' solvent compared to 30% in the 'wrong' one). For this reason, it isnot surprising to find tables in journal articles showing the conversions or yieldsfor a range of solvents. Clearly, in process development laboratories worldwidea significant amount of time and effort is spent optimizing the reaction con-ditions and the solvent choice to optimize this part of the LCA. Often thephysical properties of the solvent play a significant role here; the boiling pointand melting point, viscosity, volatility and density must all be consideredalongside the safety issues such as flash point, reactivity and corrosiveness thatwere discussed earlier. At this stage in the process and the life cycle, biphasicsystems and processes can be considered as these usually lead to reduced energyand increased efficiency.11 Fluorous solvents can be advantageous for thisreason. However, all alternative solvents have advantages and disadvantages.Unfortunately, in the chemical literature, most authors are biased and aretrying to 'sell' their chosen reaction medium. For example, the pressuresinvolved with supercritical fluids are a disadvantage, but the facile removal ofthe fluid at the end of a process is an advantage. Therefore, Clark and Tavenerused a scoring system to grade the solvents (Table 1.5) in an attempt to qualifythe general level of 'greenness' of a range of alternative solvents. It becomesapparent that all the solvents have some drawbacks and therefore solvent freeapproaches should attract greater attention. If a solvent is used, water shouldbe considered first, and then carbon dioxide. They also suggest that it isunrealistic to think that all VOCs can be replaced in every application andtherefore there is a growing role for VOCs derived from renewable resources inthe alternative solvent field. In all areas, we need to balance the technicaladvantages of a particular solvent with any environmental, cost or other dis-advantages.3 For example, in the coatings industry, a reduction in the amountof VOC in paints may lead to a range of problems, including the stability of theformulation, longer drying times, a lower gloss and a less hard-wearing finish.However, aqueous emulsion paint has notable EHS advantages, includingreduced VOC emissions, reduced user exposure and less hazardous wasteproduction. Manufacturers and consumers need to decide if the advantagesoutweigh the disadvantages. At the end of their life, solvents can often be reused or recycled by a range ofrecovery methods including distillation or biphasic separation. An environ-mental assessment of waste solvent distillation was recently reported and tookinto account a range of inputs and outputs including electricity consumption,cooling water, amount of recovered distillate and waste.16 On average per kg ofwaste solvent processed, 0.71 kg of solvent is recovered, 1.4 kg steam, 0.03 kW helectricity, 1.5 Â 10À3 m3 nitrogen gas and 2.7 Â 10À2 m3 cooling waterused. Steam is used for heating the waste solvent and nitrogen is used to avoidthe formation of explosive vapour. Despite extensive recycling of solvents
Table 1.5 Advantages and disadvantages for alternative solvents, grades 1 (poor) and 5 (very good) for five different categories to give a maximum overall score of 25.11 Ease of separation Cradle-to-grave envir- OverallKey solvent properties and reuse Health and safety Cost of use onmental impact score /25 IntroductionscCO2Poor solvent for many Excellent: facile, Non-toxic; high- Energy cost is high; spe- Sustainable and glob- 18 compounds; may be efficient, and selec- pressure reactors cial reactors; CO2 is ally available; no sig- improved with co-solvents tive (5) required (4) cheap and abundant (3) nificant end-of-life or surfactants (1) concerns (5)RTILsDesigner/tailor-made prop- Easy to remove Limited data avail- Expensive; but low-cost Mainly sourced from 13 erties; always polar (4) volatile products; able; some are versions may become petroleum but some others may be dif- flammable and/or available in time (2) sustainable variants ficult; reuse may toxic (2) exist; synthesis may be depend on purity wasteful and energy (2) intensive; environ- mental fate not well understood (3)Fluorous mediaVery non-polar solutes only; Readily forms Bioaccumulative, Very expensive (1) Very resource demand- 12 best used in biphasic sys- biphases; may be greenhouse gases; ing; may persist in tems (3) distilled and reused perfluoropoly- environment (4) ethers thought to be less proble- matic (2)WaterPossible to dissolve at least May be separated Non-toxic, non- Very low cost; energy Sustainable and safe to 19 very small quantities of from most organ- flammable and costs high (4) the environment; may many compounds; gen- ics; purification safe to handle (5) need purification (4) erally poor for non-polar may be energy (3) demanding (3)Bio-sourced solventsWide range: ethers, esters, May be distilled (4) Generally low toxi- Mixed costs; will decrease Sustainable resources, 19 11 alcohols and acids are city, can be flam- with greater market biodegradable, VOCs available (4) mable (4) volume and through will cause problems biotech advances (4) (3)
12 Chapter 1within the chemical industry, ultimately the solvent will likely be incinerated atthe end of its life (Figure 1.4). Incineration can generate valuable energy but theexhaust gases from the incineration plant also need treating. Unfortunately, accidents happen; solvents can leak or spill and may notmake it through to the normal end of their life cycle. Therefore, this possibilityof release into the environment must also be taken into consideration whenperforming LCA. In these end-of-life scenarios, carbon dioxide has littleenvironmental impact but other green solvents do. Water can become con-taminated and must be treated prior to release. Fluorous solvents are difficultto incinerate and may form dangerous acidic by-products, and they are alsopersistent in the environment. However, perfluoroalkyl ether compounds,which have many similar properties to perfluorocarbons, are more short-livedin the environment and are therefore better solvents in terms of LCA forfluorous biphasic approaches. Unsurprisingly, new RTILs are being developedthat take into account this part of a LCA and they are being designed withbiodegradation in mind.17,181.2.3 Solvents in the Pharmaceutical Industry and Immediate Alternatives to Common Laboratory SolventsThe pharmaceutical industry is playing an active role in the development ofgreen chemistry. In this industry solvents are a major concern and can havesignificant effects on the outcomes of complicated, multi-step synthetic proce-dures.19–22 Although because of the smaller scale of pharmaceutical manu-facturing—typically only 10–1000 tonnes of a product per year—the absoluteamount of waste formed is quite low. Nonetheless, on a per kg basis theenvironmental burden of pharmaceutical synthesis is very high, as can be seenfrom the average E-factors (Table 1.6). Therefore, important advances havebeen made by this sector to employ the principles of green chemistry, and at thesame time this reduces costs and increases profits for particular processes. Solvent use accounts for 80–90% of mass utilization in a typical pharma-ceutical batch chemical operation.20 Additionally, solvents play a dominant rolein the overall toxicity profile of most processes and are therefore the chemicals ofgreatest concern to many process development chemists. Table 1.7 lists thetypical solvents used in a pharmaceutical process. It should also be noted thatbecause of the multi-step procedures involved, an average of six different sol-vents are used in the manufacture of one bioactive compound. The avoidance ofsuch multi-solvent approaches can have a significant impact on the amount ofwaste generated and overall productivity. For example, when the pharmaceuticalcompany Pfizer redesigned their manufacturing process for the antidepressantdrug sertraline, a three-step sequence was streamlined to a single step usingethanol as the only solvent.23 This eliminated the need for dichloromethane,THF, toluene and hexane which had been used in the original process. The table of solvents recently used by GlaxoSmithKline (GSK) shows adownward trend in the use of THF, toluene and dichloromethane. Additionally,
Introduction 13 15Table 1.6 E-factors in the chemical industry.Industry segment Product tonnage E-factor (kg waste : kg product)Oil refining 106–108 o0.1Bulk chemicals 104–108 o1–5Fine chemicals 102–104 5–50Pharmaceuticals 10–103 25–100Table 1.7 Comparison of solvent use in GlaxoSmithKline Pharmaceuticals (GSK) over the last 15 years.20 2005 ranka 1990–2000 rank2-Propanol 1 5Ethyl acetate 2 4Methanol 3 6Denatured ethanol 4 8n-Heptane 5 12THF 6 2Toluene 7 1Dichloromethane 8 3Acetic acid 9 11Acetonitrile 10 14aTop 10 solvents used in GSK pilot plant processes during 2005.it is reported that dichloromethane is the largest contributor to GSK materialsof concern and there is an urgent need to develop alternatives for this solvent, orto develop different styles of reactor (not conventional batch reactors) whichcould reduce the amount of solvent required. Pfizer have developed a solvent selection tool, which has been used to educateresearchers about solvent replacement and has resulted in reduced amounts ofchlorinated and ethereal solvents being used in their research labs.19 A reducedavailability of less desirable solvents also encouraged the uptake of alternatives.For example, hexane was replaced by heptane in stockrooms. The chart shownin Figure 1.5 could be applied to other industries and is easily used in academicresearch labs. It has been modified to take into account the findings of Fischerand co-workers, and as a result acetonitrile and THF have been transferredfrom usable to undesirable based on their performance in LCA. The solvents in the 'black' category are there for a number of reasons: pentaneand diethyl ether because of their low flash points; the chlorinated solvents,pyridine and benzene because they are carcinogens; and the polar aprotic sol-vents dimethylamine (DMA), N,N-dimethylformamide (DMF) and N-methylpyrolidin-2-one (NMP) because they are toxic. Alternatives for many of these arereadily available in most laboratories and some of them are listed in Table 1.8. Unfortunately, no truly suitable alternatives to DMF, NMP and DMA areavailable at this time. Acetonitrile can be used in some cases but is not an idealreplacement.
14 Chapter 1Figure 1.5 Modified solvent selection guide.Table 1.8 Possible alternatives for some 'blacklisted' solvents.19Undesirable solvent AlternativePentane or hexane(s) HeptaneEthers 2-MeTHF or methyl t-butyl ether (MTBE)Dichloromethane (extractions) Ethyl acetate, MTBE, toluene, 2-MeTHFDichloromethane (chromatography) Ethyl acetate–heptane mixture In 2005, the American Chemical Society Green Chemistry Institute (ACSGCI) Pharmaceutical Roundtable was established to encourage innovation andthe uptake of green chemistry principles in this industry. It developed a list ofkey research areas, several of which were directly related to solvents.21 Theseincluded solventless reactor cleaning, replacements for polar aprotic solvents(including NMP and DMF) and alternatives to chlorinated solvents for oxida-tions or epoxidations. The need to replace polar aprotic solvents is due to theirdesignation as reproductive toxins and the resulting legislation that is cominginto force.20 Also, the mixed organic–aqueous waste that results from processesusing these solvents is difficult to purify or incinerate.1.3 Solvent Properties Including PolaritySolvents can have a significant effect on the outcome of chemical reactions andphysical chemical processes including extractions and crystallizations. Both themacroscopic (boiling point, density) and microscopic (dipole moment, hydro-gen bonding ability) properties of the solvent affect its influence on such pro-cesses and the choice of solvent for a chemical system. For most paints and inks
Introduction 15a volatile solvent is required, so a solvent is chosen with a relatively low boilingpoint and high vapour pressure. In reaction chemistry, the solvent plays manyroles; it can act solely as the medium or it can participate in the reaction itself.For example, it can stabilize intermediates and increase rates of reaction; it cancause a shift in the equilibrium of a process; it can act as an acid or a base.There are many ways that a solvent can be involved in a process beyondsolubilizing species. This has led to many investigations into the role of solventsin chemical reactions and further information can be found in textbookspublished in that field.14,24 A short review and introduction to solvents andsolvent effects is also available.25 Although solvents are used as dispersing agents and in the formation ofemulsions, they are generally used to dissolve materials. Whether this is to cleana surface or a reaction vessel, or to act as a heat transfer medium in a reaction,we need to consider the question—'Why do things dissolve?' Generally, thereasons are thermodynamic, in that if the dissolution process is energeticallyfavourable it will occur. However, kinetics can also play a role and solutes thatare poorly soluble at room temperature can be heated to increase solubility, atechnique that is widely employed in recrystallizations. Ionic compounds will dissolve in water if the Gibbs energy of solution (DGs)is negative. As enthalpies of solution (DHs) are usually negative and DGs ¼ DHs– TDSs, most ionic species will dissolve. However, this does not mean thatentropy of solution does not take a role. For non-ionic compounds to dissolvein a solvent, the Gibbs energy of mixing (DGmix) must be negative (Figure 1.6).This can be encouraged by (1) the formation of strong intermolecularFigure 1.6 Simplified thermodynamic cycle for the dissolution of a compound (Â) in a solvent (J).
16 Chapter 1interactions between the solute and the solvent, such as dipole–dipole inter-actions, or (2) the presence of very weak intermolecular forces in the solventand/or solute itself. Further explanation of this can be found in Chapter 4,where the importance of such effects is crucial in utilizing the relatively poorsolvent power of supercritical carbon dioxide (scCO2). In general, one can use the rule 'like dissolves like' to qualitatively understandsolubility and solvent miscibility. Ionic compounds do not dissolve well in non-polar solvents such as hydrocarbons, but generally will dissolve in many ionicliquids. Ethanol, which is a polar molecule and capable of hydrogen bonding, ismiscible with water whereas hydrocarbons are immiscible. In fact, many of themacroscopic physical properties of the solvent are dependent on the molecularstructure of the solvent molecules. For example, hydrogen bonding solventsoften have high heat capacities and this can be useful in the role of the solvent asa heat transfer medium. Halogenated solvents typically have high densities andthis means they are useful in separations of aqueous–organic mixtures.Throughout this book, selected physical parameters are given for some solvents.However, further data can be found in the CRC Handbook and on materialssafety data sheets (MSDS) for most compounds. There are many parameters that have been used to describe the attractiveforces (dispersive, dipolar and hydrogen bonding) present within a solvent orliquid. However, Hildebrand's solubility parameter (d) is probably the mostcommonly used. In general, two liquids are miscible if the difference in d is lessthan 3.4 units. Also, if a solid (e.g. a polymer) has a d similar to the solvent, itwill dissolve. However, there are exceptions to this rule especially with polarsolvents and solutes. Therefore, it is often worth testing solubility or solventmiscibility on a small scale even if data are available. 'Polarity' is often used to predict the solubility of compounds, but unfortu-nately the concept is not straightforward. We all know that water and alcoholsare more polar solvents than hydrocarbons such as toluene and hexane.However, we would not feel so confident describing the differences betweenhalogenated solvents and ethers in terms of polarity. This is because polarity isactually described by several parameters and whether one solvent is more polarthan another often depends on which scale or parameter you are using. Solventpolarity might best be defined as the solvation power of a solvent. It depends onthe interplay of electrostatic, inductive, dispersive, charge-transfer and hydro-gen bonding forces.4 The terms polar, apolar and dipolar are often used to describe solvents andother molecules, but there is a certain amount of confusion and inconsistency intheir application. Dipolar is used to describe molecules with a permanent dipolemoment, e.g. ethanol and chloroform. Apolar should be used rarely and only todescribe solvents with a spherical charge distribution such as supercriticalxenon. All other solvents should, strictly speaking, be considered polar!Therefore, hexane is polar because it is not spherical and may be polarized in anelectric field. This polarizability is important when explaining the properties ofsuch solvents, which do not have a permanent dipole and give low values onmost polarity scales. Therefore, they are widely termed non-polar and, although
Introduction 17misleading, this term is useful in distinguishing solvents of low polarity fromthose with permanent dipoles.4 Solvents that are able to donate an acidichydrogen to form a hydrogen bond are termed protic (e.g. alcohols) and thosethat cannot are called aprotic (e.g. dimethyl sulfoxide). Despite the problems of quantifying solvent polarity, numerous methodshave been devised to assess polarity based on various physical and chemicalproperties. These include dielectric constant, electron pair acceptor and donorability, and the ability to stabilize charge separation in an indicator dye. Manystudies have been performed to assess the polarity of alternative solvents forgreen chemistry. The results are summarized in Figure 1.7.11 In addition to the terms defined in Table 1.9, empirical polarity scales havebeen developed based on solvatochroism. The most common solvatochromicdye used in these experiments is Reichardt's betaine dye (Figure 1.8). The UV-Vis spectrum of a solvatochromic dye changes in different solvents. In somecases, the dyes are modified to increase solubility for experiments in lowerpolarity media or alternative solvents. The p-p* transition for this dye varies between 810 nm (147 kJ molÀ1) and453 nm (264 kJ molÀ1) on going from non-polar diphenyl ether to polar water.Polar solvents stabilize the zwitterionic ground state of the dye. This increasesthe energy difference between the p and p* energy levels and leads to a higherenergy (shorter wavelength) absorption. Values from these experiments arereported on a ET(30) scale, which reports the energy in kcal molÀ1, or on a ENTFigure 1.7 Typical polarity and volatility characteristics of alternative reaction media. [Reprinted with modifications and permission from Org. Proc. Dev., 2007, 11, 149–155. Copyright 2007 American Chemical Society.]
18 Chapter 1Table 1.9 Terms related to solvent polarity.Term Meaning/DefinitionDipole moment Possessed by any compound with a non-symmetrical distribu- tion of charge or electron density. Symmetrical molecules have no permanent dipole moment.Dispersive forces Weak intermolecular attractions as a result of instantaneous dipole–instantaneous dipole interactions.Dielectric constant Also known as relative permittivity, as it is measured relative to (er) a vacuum. Measured by applying an electric field across the solvent (or vacuum) within a capacitor which induces a dipole in the solvent molecules and, therefore, takes into account polarizability. H2O, 78.3; EtOH, 24.6; acetone, 20.6; toluene, 2.4; hexane, 1.9Donor number Measure of the Lewis basicity of a solvent. (DN) H2O, 1.46; EtOH, 0.82; acetone, 0.44; toluene, o0.01; hexane, 0Acceptor number Measure of the Lewis acidity of a solvent. (AN) H2O, 54.8; EtOH, 37.9; acetone, 12.5; hexane, 0Figure 1.8 Negatively solvatochromic standard pyridinium-N-phenolate betaine dye, known as Reichardt's dye.scale, which is normalized to reflect SI units (Table 1.10). On this scale, tet-ramethylsilane has a ENT value of 0.000 and water a value of 1.000. However,there are limitations to this procedure, as the dye molecule used is onlyreflecting limited types of molecular interaction based on its own structure. Toovercome these limitations, the Kamlet–Taft parameters (a, b and p*) wereintroduced and used for a series of seven different dyes. For each solvent, a isthe hydrogen bond donor (HBD) ability, b is the hydrogen bond acceptor
Introduction 19Table 1.10 Polarity measurements for some solvents.Solvent ET(30)/kcal molÀ1 ENT a b p*Water 63.1 1.000 (defined) 1.17 0.47 1.09Methanol 55.4 0.762 0.98 0.66 0.60Ethanol 51.9 0.654 0.86 0.75 0.54Acetone 42.2 0.355 0.08 0.43 0.71Ethyl acetate 38.1 0.228 0.00 0.45 0.55THF 37.4 0.207 0.00 0.55 0.58Toluene 33.9 0.099 0.00 0.11 0.54Hexane 31.0 0.009 0.00 0.00 –0.04Figure 1.9 Solvent polarity effect on a keto–enol tautomerization.(HBA) ability, and p* is a measure of general polarity or polarizability(excluding hydrogen bonding effects). Obviously, to obtain this level of infor-mation involves a more complex procedure and Kamlet–Taft values aretherefore often unavailable for alternative solvents. The effect of solvent polarity on chemical systems including reaction ratesand equilibria can be quite significant. In general, it is necessary to consider therelative polarities of the reactants and products. In equilibria, a polar solventwill favour the more polar species. A good example is the keto–enol tauto-merization of ethyl acetoacetate shown in Figure 1.9. The keto tautomer ismore polar than the enol tautomer and therefore the equilibrium lies to the leftin polar media such as water Table 1.11. A classic example of solvent polarity effects on reaction rates can be seen bycomparing SN1 and SN2 nucleophilic substitution reactions. In an SN1 reaction,an uncharged reactant (e.g. haloalkane) proceeds to a charged transition stateand this will be stabilized by a more polar solvent, which will lead to a loweringof the activation energy and a faster reaction in a more polar solvent. However,in an SN2 reaction the nucleophile is already charged and reacts with anuncharged substrate to give a transition state where the intermediate has adelocalized charge. This means that a polar solvent will stabilize the original,highly charged nucleophile and SN2 reactions typically proceed more slowly ina more polar solvent than in a non-polar one. This is because of an increase in
20 Chapter 1Table 1.11 Some typical hydrogen bond donor (HBD) and hydrogen bond acceptor (HBA) solvents.HBD solvents HBA solventsWater AcetonitrileAcetic acid THFMethanol PyridineEthanol Acetonen-Propanol (Water and alcohols)the activation energy caused by stabilizing the reactant. In contrast, neutralreactants that pass through neutral intermediates on their way to neutralproducts generally show little change in reaction rate with changes in solventpolarity. However, as you will see later in this book, these are generalizationsand sometimes enhanced reaction rates can occur unexpectedly when onlyneutral species are present throughout the whole reaction.1.4 SummaryGreen chemistry and the use of alternative solvents are intertwined. This is inpart due to the hazards of many conventional solvents (e.g. toxicity, flamm-ability) and the significant contribution that solvents make to the waste gen-erated in any chemical process. Few solvents are inherently green, despite somemisleading assertions in the literature. Although certain organic solvents areundesirable from both health and environmental points of view, most organicsolvents can be handled safely in well designed plants with good recovery andrecycle facilities. These plants should be able to adopt the new classes of bio-VOC solvents (Chapter 5) quite easily. However, increasingly, data and tools(from computer aids to simple tables or lists) are also available to ensure that ifa VOC is chosen, it can be one with lower risks associated with it, e.g. heptanerather than hexane. Nevertheless, there are many alternatives to VOCs andalthough recent life cycle analyses suggest that some are greener than others,the choice of solvent really depends on the applications. New, often tailor-mademedia are being discovered on a regular basis which may be suitable, e.g.switchable solvents (Chapter 9). Alternative solvents have been developed andused for a wide range of properties. For example, in terms of volatility, we canchoose from the most volatile supercritical carbon dioxide (scCO2) to the leastvolatile polymeric and ionic liquid solvents. Volatility may be desirable in greenchemistry in order to reduce the amount of residual solvent, or it may beundesirable with regard to atmospheric pollution. In terms of polarity, we canchoose from polar aqueous phases to non-polar fluorous media. Accordingly,there should be a 'greener' solvent available for nearly every imaginable processand if there is not, it is just a matter of discovering it! A wide range of reactions have been studied in many of the green alternativesolvents that will be outlined in the following chapters. These can act as
Introduction 21benchmarks for comparisons between solvent systems and include Diels–Alder(and retro-Diels–Alder) reactions, hydrogenations, hydroformylations, oxida-tions, carbon–carbon bond formations, polymerizations and metathesis reac-tions. However, surely the most exciting results are still to come in themanufacture of new 'benign-by-design' chemical products and materials whichare yet to be imagined. Beyond reaction chemistry, there is even more to bediscovered in the realm of alternative solvents. The application of greenchemistry beyond the reaction (e.g. in analytical chemistry) is at a youngerstage, so even more avenues are open for new, greener discoveries.References 1. P. T. Anastas and J. C. Warner, Green Chemistry: Theory and Practice, Oxford University Press, New York, 1998. 2. J. H. Clark and D. J. Macquarrie, Handbook of Green Chemistry and Technology, Blackwell Science, London, 2002. 3. M. Lancaster, Green Chemistry: An Introductory Text, Royal Society of Chemistry, Cambridge, UK, 2002. 4. D. J. Adams, P. J. Dyson and S. J. Taverner, Chemistry in Alternative Reaction Media, John Wiley & Sons Ltd, Chichester, 2004. 5. K. Mikami, in Green Reaction Media in Organic Synthesis, Wiley-Black- well, Oxford, 2005. 6. W. M. Nelson, Green Solvents for Chemistry: Perspective and Practice, Oxford University Press, Oxford, 2003. 7. D. Clarke, M. A. Ali, A. A. Clifford, A. Parratt, P. Rose, D. Schwinn, W. Bannwarth and C. M. Rayner, Curr. Top. Med. Chem., 2004, 4, 729. 8. R. A. Sheldon, Green Chem., 2005, 7, 267. 9. R. Hofer and J. Bigorra, Green Chem., 2007, 9, 203.10. C. Capello, U. Fischer and K. Hungerbuhler, Green Chem., 2007, 9, 927.11. J. H. Clark and S. J. Tavener, Org. Process Res. Dev., 2007, 11, 149.12. R. Gani, C. Jimenez-Gonzalez and D. J. C. Constable, Comput. Chem. Eng., 2005, 29, 1661.13. R. L. Lankey and P. T. Anastas, Ind. Eng. Chem. Res., 2002, 41, 4498.14. C. Reichardt, Solvents and Solvent Effects in Organic Chemistry, Wiley- VCH, Weinheim, 2003.15. R. A. Sheldon, Green Chem., 2007, 9, 1273.16. C. Capello, S. Hellweg, B. Badertscher and K. Hungerbuhler, Environ. Sci. Technol., 2005, 39, 5885.17. S. Bouquillon, T. Courant, D. Dean, N. Gathergood, S. Morrissey, B. Pegot, P. J. Scammells and R. D. Singer, Aust. J. Chem., 2007, 60, 843.18. J. R. Harjani, R. D. Singer, M. T. Garcia and P. J. Scammells, Green Chem., 2008, 10, 436.19. K. Alfonsi, J. Colberg, P. J. Dunn, T. Fevig, S. Jennings, T. A. Johnson, H. P. Kleine, C. Knight, M. A. Nagy, D. A. Perry and M. Stefaniak, Green Chem., 2008, 10, 31.
22 Chapter 120. D. J. C. Constable, C. Jimenez-Gonzalez and R. K. Henderson, Org. Process Res. Dev., 2007, 11, 133.21. D. J. C. Constable, P. J. Dunn, J. D. Hayler, G. R. Humphrey, J. L. Leazer, R. J. Linderman, K. Lorenz, J. Manley, B. A. Pearlman, A. Wells, A. Zaks and T. Y. Zhang, Green Chem., 2007, 9, 411.22. A. M. Rouhi, Chem. Eng. News, 2002, 80, 30.23. G. P. Taber, D. M. Pfisterer and J. C. Colberg, Org. Process Res. Dev., 2004, 8, 385.24. E. Buncel, R. Stairs and H. Wilson, The Role of the Solvent in Chemical Reactions, Oxford University Press, Oxford, 2003.25. C. Reichardt, Org. Process Res. Dev., 2007, 11, 105.
CHAPTER 2'Solvent free' Chemistry2.1 IntroductionThe greenest solvent, in terms of reducing waste, is no solvent.1,2 Many industrialreactions are performed in the gas phase or without any solvent added. Similarly,many materials can be prepared without solvents via solid-state syntheticapproaches. In addition to the term 'solvent free', the term 'solventless' is used inthe literature to describe these reaction conditions. However, both these terms aresomewhat misleading in many instances,3 and the word 'neat' might be a betterdescription to explain the highly concentrated nature of the reagents and lack ofadditional solvent. A solution is defined as a liquid mixture where the solute isuniformly distributed throughout the solvent. Therefore, whenever a solution ispresent, a solvent is also present. In many solvent free reactions (as this seems tobe the most widely used term at this time) one of the reagents is a liquid and issometimes present in excess. This liquid is often acting as the solvent and yieldinga homogeneous reaction solution. In other solvent free reactions, there may be aliquid, e.g. water, formed during the course of the reaction and this liquid assiststhe reaction at the interface between the reagents and acts like a solvent. To add tothe confusion, many reagents are commonly used in aqueous solution, e.g. 30%hydrogen peroxide. If no solvent is added to an oxidation reaction where theoxidant is aqueous hydrogen peroxide, is that an aqueous reaction or a solventfree reaction? If the reaction mixture is an emulsion or suspension of organicreagents in an aqueous phase, then the reaction is solvent free. However, if thereaction is occurring as a homogeneous solution, it is aqueous. Unfortunately,the situation is far more complex than this and is probably somewhere betweenthe two extremes as many organic compounds are slightly miscible with water—even if only at a concentration of 0.1–1.0% by volume. Finally, in many solventfree approaches, VOCs are used to extract and purify the product, so although thereaction may be solvent free often the process as a whole does use solvents.RSC Green Chemistry Book SeriesAlternative Solvents for Green ChemistryBy Francesca M. Kertonr Francesca M. Kerton 2009Published by the Royal Society of Chemistry, www.rsc.org 23
24 Chapter 2Although a solvent is used in most of these 'solvent free' procedures, the amountof solvent required is dramatically reduced compared to conventional approachesand therefore these methods are generally very green. It should also be noted thatsome solvent free approaches lead to highly viscous solutions or indeed solidformation, in these cases, the technology may not be readily amenable forindustrial development. However, recent results using ball mills for solvent freereactions are very promising. In this approach, a ball bearing is placed inside avessel that is being shaken at high speeds. However, there are many variants ofthis approach, which are detailed in the introduction of a recent review.4 The termmechanochemistry is sometimes used to describe this synthetic approach. It hasalready been successfully used for kilogram scale reactions, and details can befound in the recent review by Kaupp.5 Industrially, similar results could possiblybe achieved using cement mill technologies. It should be noted that the cementmanufacturing is one of the largest scale chemical processes being conductedworldwide and that pilot-plant cement mills would normally be of a large enoughscale and sufficiently well-engineered for many other chemical procedures. On asmaller scale in a research laboratory, solvent free procedures (unless otherwiseindicated) use a mortar and pestle to grind the solid reagents together. Solvent freemethods have also been very successfully utilized in combination with microwaveheating.6,7 In some solvent free reactions, where the reaction involves a liquid, theprocess is similar to a conventional one except the conditions are highly con-centrated. However, it should be noted that kinetic energy is supplied duringthe grinding of solid reagents and this can have several effects including heatingand formation of surface defects.8 Grinding also provides mass transfer andcan prevent exothermic reactions forming hot spots, which would lead todecomposition. Mechanisms have been proposed, partially derived fromatomic force microscopy data, regarding how solid–solid reactions of this kindproceed.9 Initially, reagent molecules (A) migrate into cleavage planes orchannels within the structure of the other reagent (B). The product (C) starts toform at the interface further distorting the crystalline structures, and a mixedA–B–C phase forms. Next, as the concentration of the product (C) increases,crystals of C begin to form within the A–B–C phase. In turn, the presence ofgrowing amounts of C causes the mixed A–B–C phase to disintegrate and formnew particles, which reveal fresh surfaces for further reaction. Most of the recent literature in this field is concerned with synthetic organicreactions, supramolecular chemistry and crystal engineering. However, solventfree approaches can also be used in the extraction of natural products, althoughless information is available in the mainstream literature. Juice extractors canbe used to afford aqueous solutions of biologically active compounds fromundried plant material. An extract of Capsicum annum L. was recently preparedin this way, and then used in the green synthesis of silver nanoparticles.10 Theactual synthesis of the nanoparticles was conducted in the aqueous phase andtherefore this work will not be discussed further here. However, this solvent freeapproach to extraction is probably worthy of greater representation in thegreen chemistry literature.
'Solvent free' Chemistry 25 In the rest of this chapter, selected examples will be described and discussed;however, solvent free organic synthesis is a rapidly growing field and moreexamples can be found in recent reviews and a book on the subject.1–2,4,6–8 Inreaction schemes within this chapter, room temperature means the temperature atwhich the solventless procedure was set up. During the course of solvent freereactions (particularly in ball mills) heat is generated and therefore the reactionmight proceed at a higher temperature even though no external heat is applied.2.2 Chemical Examples2.2.1 Inorganic and Materials SynthesisIn the area of renewable materials, bulk oxypropylation of chitin and chitosanhas been performed.11 Chitin and chitosan are abundant natural polymersobtained from shellfish, such as crab shell or shrimp shell. This solvent freereaction yields viscous polyols. Unfortunately, propylene oxide homopolymeris formed as a by-product but is easily separated. It should be noted that carewas taken to minimize the risk involved in the use of toxic, flammable pro-pylene oxide (the reagent in this process). In the field of nanotechnology, limited solvents were recently employed in themicrowave assisted synthesis of nickel–graphitic shell nanocrystals (Figure 2.1).12Nickel nanoparticles were blended with poly(styrene) (PS) using ethyl acetateand a sonicator. The solvent was removed under vacuum to yield a nickel-containing PS phase. When this was heated in a microwave under solvent freeconditions, nickel–graphitic shell nanocrystals were formed. The nickel corescould be dissolved using 1 M hydrochloric acid and ultrasound to give hollowcarbon nanospheres. Given this initial study, there is probably a lot of potentialfor solvent free microwave synthesis in the preparation of new nanomaterials. Solvent free methods have been used extensively in supramolecular chem-istry, coordination chemistry and the formation of transition metal clusters andpolymers.8 Reactions range from very simple ligand substitution reactions forsalts of labile metal ions13 to more complex procedures, some of which areoutlined below. Calix[4]resorcinarenes, which can be used as supramolecular building blocks,have been prepared in high yields and purity using a solvent free approach.14Equimolar quantities of the benzaldehyde and resorcinol, in the presenceof p-toluenesulfonic acid, were ground together using a mortar and pestleFigure 2.1 Preparation of graphitic carbon nanostructures using a microwave induced solid state process.
26 Chapter 2Figure 2.2 Solvent free synthesis of calix[4]resorcinarene.(Figure 2.2). The reaction occurs between the two mutually dissolved reagentsto afford a viscous paste that becomes red in colour upon standing for 1 h. Theproducts could be easily purified using water to remove the acid and hotmethanol for recrystallization. Supramolecular self-assembly has been found to be dramatically acceleratedin some cases, and this is perhaps the reason why solventless reactions havebeen rapidly adopted by coordination chemists. For example, the formation ofa platinum-containing square is dramatically accelerated compared with thesame reaction in water (Figure 2.3).15 In water, the reaction needed to be heatedat 100 1C for 4 weeks. In a solvent free approach, approximately the same yieldwas achieved in 10 min at room temperature. Water and ethanol were the onlysolvents used in the work up of the reaction. This approach was then extendedto bowl-shaped and helical supramolecular structures. One-dimensional coordination polymers of copper, zinc and silver have alsobeen prepared using solvent free techniques (Figure 2.4).16–18 This was achievedby grinding the ligand (DABCO or trans-1,4-diaminocyclohexane) with the metalprecursor for 5 min, followed by recrystallization in water–methanol. No yieldsare reported for many of these reactions because of the small scale on which theywere conducted. However, in some cases, different structures are reported whenthe reaction is conducted in solution compared with the solid state. A reversible solid-state HCl elimination reaction from a Cu(II) pyridiniumcoordination complex has been reported.19 The reaction proceeds with a colourchange from yellow (pyridinium complex) to blue (pyridine complex). Thisreaction suggests that other protic ligands may successfully be coordinated tometals using a solvent free approach in the future. In an interesting twist on the solvent free reaction, Petrukhina and co-workers co-sublimed a volatile metal complex, [Rh2(CF3CO2)4], and arenemolecules including paracyclophanes to yield organometallic coordinationpolymers.20,21 Moderate yields of crystalline products were obtained (35–70%),
'Solvent free' Chemistry 27Figure 2.3 Solvent free supramolecular self assembly of a metallo-square.and because of the highly porous structure of the material these may findapplications in gas recognition and sorption. Therefore, the formation ofinteresting transition metal complexes is not restricted to solid–solid grindingprocedures. The use of solvent free conditions is also not limited to the preparation ofcomplexes and materials containing transition metals. Molecular inorganicmolecules containing main-group elements have also been prepared in this way,e.g. iodination of ortho-carboranes (Figure 2.5).22 Yields are significantlyhigher than in procedures performed using chlorinated solvents. The gaseoushydrogen iodide by-product is removed by evaporation and the excess iodine(required to get near quantitative yields of the desired product) can be removedby sublimation. Pure tetraiodinated carborane, with potential uses as anradiographic contrast agent, can be obtained by recrystallization from ethanol–water. The use of solvent free procedures is becoming commonplace for manysmall-molecule main-group reagents that are prepared and used industrially,such as chlorosilanes, but there is still probably extensive scope for expandingthe use of solvent free approaches in this field.2.2.2 Organic SynthesisDespite recent interest in solvent free procedures within inorganic and materialschemistry, most of the reactions studied in this way have been organic. Reac-tions that have been studied fall into two main classes: thermal and photo-chemical.2 Thermal solvent free reactions to date include oxidations,reductions, isomerizations, additions, eliminations, substitutions, carbon–carbon couplings (including cycloadditions, condensations, Reformatsky,Wittig), pinacol couplings, phenol couplings, oxidative couplings (Glaser) and
28 Chapter 2Figure 2.4 Some 1D-coordination polymers formed using solvent free methods: Zn(II)-DABCO (left) and Ag(I)-trans-1,4-diaminocyclohexane (right).polymerizations. Photoreactions include dimerization, polymerization, cycliza-tion, isomerization, decarbonylation and addition. Therefore, many solventfree reactions have been studied (Figure 2.6) and reactions are perhaps moreamenable for study in this way than many of us would at first realize. Forinstance, reactions are definitely more amenable to study under solvent freeconditions than in supercritical carbon dioxide. However, some organic reac-tions proceed explosively in the solid state or under neat liquid conditions.In those cases, a solvent is required to mediate the reaction. However, as thelong list of reactions that have been studied demonstrates, many reactionsproceed moderately in the absence of solvent or in a water suspension and
'Solvent free' Chemistry 29Figure 2.5 Solvent free iodination of ortho-carboranes. Oxidation O O m-CPBA yield after 24h: O solid state = 85% solid state CHCl3 = 13% or in CHCl3 Reduction O OH NaBH4 yield after 5d: 100% Michael Addition O O Ph O Ph KOt Bu H Ph n-Bu4NBr Ph + Ph solvent-free COPh 99%de Photoaddition Ph Ph H N Ph N yield after 20h: hν + solid 25% PhFigure 2.6 Some synthetic organic reactions that have used solvent free conditions.therefore solvent free conditions should be employed wherever possible in anaim to reduce solvent usage and waste. Dihydropyrimidinones, which have promising biological activities as anti-hypertensive and anticancer drugs, can be prepared through a solvent free
30 Chapter 2Figure 2.7 Solvent and catalyst free Biginelli condensation of a 1,3-dicarbonyl com- pound, an aldehyde and urea.Figure 2.8 Solvent free hafnium chloride catalysed Diels–Alder cycloaddition of an ethoxycarbonylcoumarin with 1,3-diene.Biginelli reaction (Figure 2.7).23 The 1,3-dicarbonyl compound, aldehyde andurea are heated to around 100 1C for 1 h without any need for solvent orcatalyst and yield the dihydropyrimidone in good to excellent yields. Per-forming the same reaction in refluxing VOCs did not yield any product, indi-cating a special advantage for a solventless procedure in this case. The reactionhas been scaled up successfully to the 1 kg level and the only additional solventsrequired to work up the product effectively are water and ethanol. Diels–Alder cycloadditions can be catalysed by HfCl4 Á 2THF in air andunder solvent free conditions (Figure 2.8).24 3-Ethoxycarbonylcoumarins weresuccessfully reacted with 1,3-butadienes to afford the cycloadduct in excellentyield. The tetrahydrobenzo[c]chromenone moiety of the product occurs inmany natural products and therefore this reaction is of interest for the synthesisof biologically active compounds. Significantly, the yields are much higherunder solvent free conditions than in conventional reaction media (Table 2.1).Reactions performed in water or in a typical ionic liquid were also less effective.It should also be noted that one of the reagents, isoprene (2-methyl-1,3-buta-diene), is a liquid at room temperature and used in excess, so it may be playing asolvation role in this reaction. Additionally, ethyl acetate and petroleum ether
'Solvent free' Chemistry 31 Table 2.1 Conversions for hafnium chloride catalysed cycloaddition reactions in different reaction media.24 Reaction medium Conversion % Solvent-free 98 Nitromethane 50 Dichloromethane 40 Acetonitrile 10 THF 2 H2O (pH 1.6) o1 [Bmim][PF6] 35Figure 2.9 Base catalysed Baylis–Hillman reaction under solvent free conditions and using an HSBM.were used to purify the product by column chromatography. Therefore,although reduced in solvent demand this reaction is not entirely solvent free. Another atom-efficient process that has been studied solvent free is the Baylis–Hillman reaction.25 This reaction affords useful multifunctional products froman addition reaction between an electrophile (often an aldehyde) and an elec-tron-deficient olefin. Unfortunately, under most conditions it has the significantdrawback of a slow rate of reaction. However, this has been overcome through asolvent free approach that uses a high-speed ball mill (HSBM) (Figure 2.9).Previous solvent free studies of this reaction took 3–4 days to achieve comple-tion. In contrast, using an HSBM, the reaction is complete in 30 min. Unfor-tunately, a chlorinated solvent was chosen for reaction work up; clearly, itwould be desirable to use a less hazardous VOC here. Ball mills have been used for many carbon–carbon bond-forming reactionsand this field was recently reviewed.4 Reactions studied include catalyst-freeprocesses such as Knoevenagel condensations, organic- and base catalysedreactions including the Baylis–Hillman reaction discussed above and asym-metric aldol reactions discussed below, and metal-mediated or catalysed reac-tions including the Suzuki and Heck reactions. In a ball mill, the reactionmixtures are known to heat up and generate a considerable pressure; thereforefor the Heck reaction an attempt was made to ascertain the influence of boththese parameters. Although conversions were obtained by compressing the


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TFN Interview:
Empire And Rebellion: Razor's Edge
Author Martha Wells
Posted by
September 9, 2013
at 11:07 AM CST |
With the September 24th release of
Star Wars: Empire and Rebellion: Razor's Edge
fast approaching, TFN got in touch with first-time
Star Wars
author Martha Wells for a brief Q&A.
When did you first see a Star Wars film? Which one is your favorite?
When A New Hope first came out in 1977, when I was 13. For a long time, A New Hope was my favorite, but after some years I got over the trauma of the cliffhanger ending of The Empire Strikes Back, and now it's my favorite.
Who is your favorite Star Wars character?
I think it's Leia first, then Han, but I also like Chewie and Luke a lot.
Do you think Star Wars needs more books starring female characters?
Yes, I do.
Between Leia, Luke, and Han, whose voice was the most challenging to capture?
I didn't find any of them all that challenging, mostly because their voices are so familiar to me from growing up with the movies, and from seeing the movies so often.
Which one was the most fun to write?
I really had the most fun with Leia.
I thought you did a great job capturing Leia's occasional exasperation and sarcasm. Did you re-watch the movies to get a feel for her personality?
I've re-watched the whole first trilogy pretty frequently over the years, so the only one I watched again before I started writing was A New Hope.
After you wrote this book, with all of Leia and Han's internal monologues reflecting on their strange relationship, did it make you look at the movies in a new light?
Not really. The way I wrote their relationship was how I always saw it. When the trilogy was first coming out, I saw them as having a connection that started with the shared danger of the escape from the Death Star, and that managed to grow into a friendship despite the fact that they had conflicts. (I think everybody has that friend who you really love, and whose opinion you respect and value, but who still irritates the crap out of you sometimes and you know the feeling is often mutual.)
You explore the fact that Leia's role in the Rebellion is partly functional and partly symbolic. How do you think her status as a figurehead complicates her other responsibilities?
Having to present a certain image, and having to be very aware of how people perceive her as a symbol would make it very difficult. I think she's good at making the hard decisions, but being able to carry them out while also trying to fulfill these expectations could be very tricky, and probably take an emotional toll on her.
Thanks to Martha Wells for taking time out of her busy schedule to answer a few questions for us here at TFN!
Razor's Edge
will be released by Del Rey Books on September 24.
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We had a leisurely 15 km walk today. Conditions were cloudy to begin with but brightened over the morning as the cloud broke up into beautiful balls of cotton. We started with a climb up Round Hill, the penultimate C2C climb. Once we reached the summit we again had beautiful views across to the east and back at yesterday's path over the 3 hills. The rest of the walk was along an easy plateau. Since entering the North Yorkshire Moors the the quality of the paths ...
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We our day was rounded off with a late lunch in a posh Italian(?) restaurant housed in a colonnaded Romanesque building. We ate pizza because we didn't want to afford anything else...but enjoyed the cool ambience.
Coast to Coast
... was about 2 1/2 hours and there were no hold ups anywhere so we were there just after midday. We collected our possessions and then headed east once again.
About an hour later, we stopped at a little town called Kirby Lonsdale where we had a light lunch and purchased a couple of items. All was going well until then.
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Beautiful York, England
... Bessemer invented a quick and cheap process for turning molten pig iron into steel in the 1850s.
The first church built here was a wooden affair in the 680s before the arrival of the Vikings. The York "Minster" was the title given to churches established during the Anglo-Saxon period as missionary teaching churches. After the collapse of Rome, it was the Irish monks, St. Patrick most notable among them, who "Christianized" England and large parts ...


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Ohio's 'kissing cop' files discrimination complaint
A fired female deputy says she was unjustly fired, sexually harassed
By Allison Manning
The Columbus Dispatch
DELAWARE, Ohio — A fired female deputy who was linked to the former sheriff has filed a discrimination complaint against the county sheriff's office.
Janine Senanayake claims she was sexually harassed and then unjustly fired from her road-deputy job last month by the acting sheriff, said her Cleveland-based attorney, Avery Friedman.
Acting Sheriff Scott Vance said in the termination letter that she failed to satisfactorily complete her probationary period. In a separate matter concluded the same day, he issued her a one-day suspension for failing to show up at two hearings in municipal court in February.
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- 5 Wis. trooper killed ambusher before dying


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Getting more bang for your buck
Good news:
GrabOne's Voucher Guarantee means missing out on claiming your deal in time no longer means losing out altogether!
How does it work?
- A voucher is valid up to and including the expiry date stated.
- If you don't use your voucher before that date for whatever reason, it can still be used towards that service with that business for an additional 30 days.
For example, if you buy a bungy jump deal but don't use it before the expiry date, you can still use the amount you paid for the voucher towards a bungy jump, for another 30 days.
A few things to note:
- The GrabOne Voucher Guarantee does not apply to product deals, travel and accommodation-related deals, or time-dependent event deals.
- It's always best to use your voucher before the expiry date, so you get the most value for your money. And if you're a bit forgetful, we now automatically remind you if your vouchers are about to expire.
- During the extended Voucher Guarantee period, your voucher can only be put towards the service stated on the voucher.
- If the offer is seasonal, like a seasonal menu or chimney sweep service, the Voucher Guarantee can be put towards a similar offer at the merchant's discretion.
- The conditions on your voucher still apply during the Voucher Guarantee period.