Amines: Synthesis, Properties and Applications

379 Pages·2004·9.13 MB·English

by  Stephen A. Lawrence

Cambridge University Press
0521782848 - Amines: Synthesis, Properties and Applications
Stephen A. Lawrence
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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
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0521782848 - Amines: Synthesis, Properties and Applications
Stephen A. Lawrence
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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
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Firstpublished2004
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Lawrence,StephenA.,1960–
Amines:synthesis,properties,andapplications/StephenA.Lawrence.
p. cm.
Includesbibliographicalreferencesandindex.
ISBN0521782848
1.Amines. I.Title.
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0521782848 - Amines: Synthesis, Properties and Applications
Stephen A. Lawrence
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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
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0521782848 - Amines: Synthesis, Properties and Applications
Stephen A. Lawrence
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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
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0521782848 - Amines: Synthesis, Properties and Applications
Stephen A. Lawrence
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Contents vii
Appendix1 Molecularstructuresandisosurfaceelectronicchargesof
selectedamines 309
Appendix2 Physicalpropertiesofselectedamines 315
Appendix3 Namedreactionsinvolvingamines 317
Index 361
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0521782848 - Amines: Synthesis, Properties and Applications
Stephen A. Lawrence
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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
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0521782848 - Amines: Synthesis, Properties and Applications
Stephen A. Lawrence
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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.
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