Amines: Synthesis, Properties and Applications PDF
Preview Amines: Synthesis, Properties and Applications
Cambridge University Press 0521782848 - Amines: Synthesis, Properties and Applications Stephen A. Lawrence Frontmatter More information AMINES Synthesis,PropertiesandApplications The understanding of amine chemistry is of paramount importance to numerous chemicalindustries,aswellastoacademicresearch.Thisbookprovidesanauthor- itative account of the properties and applications of amines with respect to the characteristicsofbondedsubstituentsandthenatureoftheirchemicalandphysical environments. The synthesis of alkyl, aryl and heterocyclic amines and inorganic amines with a review of their typical reactions is comprehensively treated, whilst practical synthetic and analytical methods for laboratory preparation and detec- tionareprovided.Theimportanceofaminechemistryfromthenineteenthcentury to the modern day, with a brief history of the development of ammonia synthe- sis, is included. This book is an invaluable reference source for undergraduates, postgraduatesandchemicalresearchersworkinginindustry. StephenA.Lawrenceisaprofessionallyqualifiedchemistwithover20years’ experience in the pharmaceutical and fine-chemicals industries. He is currently DirectorofthechemicalconsultancyfirmMimasLtd. © Cambridge University Press www.cambridge.org Cambridge University Press 0521782848 - Amines: Synthesis, Properties and Applications Stephen A. Lawrence Frontmatter More information AMINES Synthesis, Properties and Applications STEPHEN A. LAWRENCE © Cambridge University Press www.cambridge.org Cambridge University Press 0521782848 - Amines: Synthesis, Properties and Applications Stephen A. Lawrence Frontmatter More information published by the press syndicate of the university of cambridge ThePittBuilding,TrumpingtonStreet,Cambridge,UnitedKingdom cambridge university press TheEdinburghBuilding,Cambridge,CB22RU,UK 40West20thStreet,NewYork,NY10011–4211,USA 477WilliamstownRoad,PortMelbourne,VIC3207,Australia RuizdeAlarco´n13,28014Madrid,Spain DockHouse,TheWaterfront,CapeTown8001,SouthAfrica http://www.cambridge.org (cid:1)C S.A.Lawrence2004 Thisbookisincopyright.Subjecttostatutoryexception andtotheprovisionsofrelevantcollectivelicensingagreements, noreproductionofanypartmaytakeplacewithout thewrittenpermissionofCambridgeUniversityPress. Firstpublished2004 PrintedintheUnitedKingdomattheUniversityPress,Cambridge TypefaceTimes11/14pt. SystemLATEX2ε [tb] AcataloguerecordforthisbookisavailablefromtheBritishLibrary LibraryofCongressCataloguinginPublicationdata Lawrence,StephenA.,1960– Amines:synthesis,properties,andapplications/StephenA.Lawrence. p. cm. Includesbibliographicalreferencesandindex. ISBN0521782848 1.Amines. I.Title. QD305.A8.L38 2004 547(cid:2).042–dc22 2003065415 ISBN0521782848hardback ThepublisherhasuseditsbestendeavourstoensurethattheURLsforexternalwebsitesreferredtointhisbook arecorrectandactiveatthetimeofgoingtopress.However,thepublisherhasnoresponsibilityforthewebsites andcanmakenoguaranteethatasitewillremainliveorthatthecontentisorwillremainappropriate. © Cambridge University Press www.cambridge.org Cambridge University Press 0521782848 - Amines: Synthesis, Properties and Applications Stephen A. Lawrence Frontmatter More information Contents Preface page ix 1 Anintroductiontotheamines 1 1.1 Introducton 1 1.2 Nitrogen 2 1.3 Thehistoryofammoniaanditsimportancetomankind 5 1.4 Thechemistryofammonia 18 References 23 2 Aliphatic,fattyandcyclicamines 25 2.1 Thephysicalpropertiesandgeometriesofamines 25 2.2 Aliphaticamines 33 2.3 Cyclicamines 55 2.4 Diaminesandpolyamines 62 References 68 3 Arylamines 71 3.1 Anintroductiontoarylamines 71 3.2 Synthesisof(mono)arylamines 74 3.3 Reactionsofarylamines 85 3.4 Aminophenols 100 3.5 Aryldiamines 104 3.6 Diarylamines 109 3.7 Triarylamines 116 References 117 4 Heterocyclicamines 119 4.1 Anintroductiontoheterocyclicamines 119 4.2 Azirine 122 4.3 Aziridine(ethyleneimine) 123 4.4 Diazirene 129 4.5 Azetidine 130 v © Cambridge University Press www.cambridge.org Cambridge University Press 0521782848 - Amines: Synthesis, Properties and Applications Stephen A. Lawrence Frontmatter More information vi Contents 4.6 Pyrrole 133 4.7 Pyrazoleandimidazole 139 4.8 Fusedfive-memberednitrogenheterocycles 144 4.9 Pyridine 150 4.10 Pyrimidine,pyrazineandpyridazine 157 4.11 Quinoline,isoquinolineandquinolizine 162 4.12 Nitrogen-containingheterocycleswithlargerings 164 References 167 5 Inorganicamines,hydrazine,hydroxylamineandamineligands 169 5.1 Introductiontotheinorganicchemistryoftheamines 169 5.2 Chloramine 171 5.3 Nitrogentrichloride 174 5.4 Hydrazine 176 5.5 Hydroxylamine 185 5.6 Nitrogen-containingdonorligands 188 5.7 Nitrogen-containingmacrocyclicligands 194 5.8 Sulphur–nitrogencompounds 202 References 204 6 Small-scalesynthesesandanalyticalmethodsforamines 205 6.1 Introduction 205 6.2 Syntheticmethodsforalkylandarylamines 205 6.3 Amino-acidprotection 215 6.4 Thesynthesisofheterocyclicamines 216 6.5 Analyticalmethodsforamines 220 References 234 7 Amineprotection,amineoxidesandaminoacids 235 7.1 Amineprotection 235 7.2 Amineoxides 245 7.3 Aminesandaminoacids 252 References 262 8 Selectedcommercialapplicationsofamines 265 8.1 Aminesascorrosioninhibitors 265 8.2 Aminesinpharmaceuticals 269 8.3 Aminesasanti-canceragentsandDNAalkylators 274 8.4 Aminesinthecosmeticsandtoiletriesindustries 278 8.5 Theapplicationsofaminesincolourreprography 284 8.6 Theapplicationsofhydrazines 288 8.7 Theapplicationsofaminesinagrochemicals 290 8.8 Azineandazodyes 300 8.9 Indigodyes 305 References 306 © Cambridge University Press www.cambridge.org Cambridge University Press 0521782848 - Amines: Synthesis, Properties and Applications Stephen A. Lawrence Frontmatter More information Contents vii Appendix1 Molecularstructuresandisosurfaceelectronicchargesof selectedamines 309 Appendix2 Physicalpropertiesofselectedamines 315 Appendix3 Namedreactionsinvolvingamines 317 Index 361 © Cambridge University Press www.cambridge.org Cambridge University Press 0521782848 - Amines: Synthesis, Properties and Applications Stephen A. Lawrence Frontmatter More information Preface Muchofthechemistryoftheamineswasdiscoveredinthenineteenthcenturyby pioneering chemists such as Hofmann, Leuckart, Gabriel and Knoll. The intro- ductionoftheCyanamideProcessandElectricArcProcessatthebeginingofthe twentiethcenturymadeaminescommerciallyavailableforthefirsttimeatlowcost andnolongeranacademiccuriosityorrestrictedforuseonlyinhigh-valueprod- ucts.However,theimplementationoftheHaber–BoschProcessatLeunainEastern Germanyin1917marksthebeginningofthemodernageofaminechemistry. Having worked with amines for many years, both on a small scale in the lab- oratory producing gram quantities of novel amines and also on a larger scale on full-sizedmanufacturingplantsproducingseveralhundredtonnesperyearofamine- basedpharmaceuticalintermediates,ithasalwaysbeenaproblemformethatIcould neverfindasingle,up-to-date,resourcebookspecificallydedicatedtothesynthesis, propertiesandreactionsofamines.ThemostrecentexamplesthatIwasabletofind that cover the whole area of amine chemistry were David Ginsburg’s Concerning Amines, which dates from 1968, and the third edition of Neville Sidgwick’s The OrganicChemistryofNitrogen(firstpublishedin1910butrevisedin1966byI.T. MillerandH.D.Springham),althoughmostgeneralorganicchemistrybookscon- tain a chapter or two on amines. Eventually I decided that the best way to rectify thissituationwouldbeformetowritesuchabook,andsothiswasmyreasonfor approaching Cambridge University Press, who agreed to my proposal. It is my hopethatthereadersofthisbookwillfindthatitcontainstheanswerstomanyof theirunansweredquestionsaboutaminesandalsoprovidessuitablereferencesfor furtherstudy. This book contains eight chapters and three appendices. Chapter 1 reviews the history and properties of ammonia and nitrogen. Chapters 2 and 3 are concerned withtheproperties,synthesesandreactionsofalkylandarylaminesrespectively. Heterocyclic amines are found in Chapter 4; inorganic amines including macro- cyclicligandsarethesubjectofChapter5,andChapter6containssomelaboratory ix © Cambridge University Press www.cambridge.org Cambridge University Press 0521782848 - Amines: Synthesis, Properties and Applications Stephen A. Lawrence Frontmatter More information x Preface syntheticroutestoaminesandalsodetailsofanalyticalprocedures.Amineoxides, protectedaminesandaminoacidsarereviewedinChapter7,andChapter8covers the applications and commercial uses of amines. At the end of the text there are threeappendices,whichshownthestructuresandisosurfaceelectronicchargesof some amines (Appendix 1), a table of the physical properties of selected amines (Appendix2)andthenamedreactionsandnamedsynthesesofamines(Appendix3). The reader’s attention is drawn to the safety advice given in, for example, Section 6.1. Some of the chemicals mentioned in this book are dangerous, and althoughtheauthorcanvouchthattheexperimentsdescribeddowork,ifproperly conducted, neither he nor the publisher will be liable for accidents that may take placeinthecourseofexperimentation! I would like to thank Frau Urte Thiele and Dr Klaus Baehr of Chemtec Leuna forthephotographsoftheplantatLeuna,andalsoInegardRafnandKaiEvensen of Norsk Hydro for the photographs of the plant and laboratories at Notodden in Norway. IwouldlikealsotothankTimFishlock,SimonCapelin,MichelleCarey,Robert Whitelock, Jayne Aldhouse and Emily Yossarian at Cambridge University Press fortheirencouragementandpatiencewhileIproducedthetypescript. FinallyIwouldliketothankmywifeBeverleyforhersupportduringthewriting processwhilstthisbookcametofruition. © Cambridge University Press www.cambridge.org
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