Bio-Olefins prepared by acyclic diene metathesis

184 Pages·2003·7.4 MB·English

by  Hopkins, Timothy Edward

BIO-OLEFINSPREPAREDBYACYCLICDIENEMETATHESIS
By
TIMOTHYEDWARDHOPKINS
ADISSERTATIONPRESENTEDTOTHEGRADUATESCHOOL
OFTHEUNIVERSITYOFFLORIDAINPARTIALFULFILLMENT
OFTHEREQUIREMENTSFORTHEDEGREEOF
DOCTOROFPHILOSOPHY
UNIVERSITYOFFLORIDA
2003
Copyright2003
by
TimothyEdwardHopkins
ThisdocumentisdedicatedtomylovingandsupportiveparentsEdandPatriciaHopkins.
Also,IwouldliketoaddaspecialdedicationtomyfriendBobChristie,atruefriendwho
wasalwaystheretolistenandcheermeupduringthebadtimesandtojoinmein
celebrationduringthegoodtimes. Bob,Iwillalwaysmissyou.
ACKNOWLEDGMENTS
Iwouldliketoacknowledgemyadvisor,ProfessorKenWagener,forhisguidance
and friendship. His love ofpolymer chemistry and constant concern for his group
membershasmademytimeintheWagenergroupatrulyenjoyableexperience. Heisa
rolemodelforhowtobeasuccessfulprofessionalandagoodhumanbeing. Iwouldalso
liketoacknowledgeMrs.Wagenerforherkindnessthroughtheyears. Iwillalways
cherishthetimeIhavespentwithDr.andMrs.Wagener,whotreatedme,andallofthe
Wagenergroupmembers,asfamily.
IacknowledgeDr.andMrs.ButlerformakingpolymerchemistryattheUniversity
ofFloridaareality,andfortheirfriendship. Ithasbeenapleasuretogettoknowbothof
themduringmytimeattheUniversityofFlorida. Inaddition,Iwouldliketothankthem
personallyfortheButlerPolymerResearchAwardandfortheircontinuedsupportofthe
ButlerPolymerLaboratory.
I thank the members ofmy committee (Professors John R. Reynolds, J. Eric
Enholm,JonD.Stewart,andLaurieGower)fortheirhelpthroughoutmytenureatthe
UniversityofFlorida. Inaddition,IwanttothankMrs.LorraineWilliamsforallofher
help. Sheisadelightfulpersontoworkwithonadailybasis,andatrueblessingtothe
polymerfloor. Also,specialthanksgotoMrs.LorieClarkinthegraduateofficeforall
ofherhelpandadvice. Further,Iwouldliketothankalloftheexcellentemployeesin
thebusinessoffice,stockroom,glassshop,machineshop,andthemainofficeforallof
theirhelpandsupport.
IV
IhavehadthepleasureofworkingwithsomesuperbcolleaguesattheUniversity
ofFlorida. Specifically,Iwasblessedwithhavingprobablythebestlabmateanyone
could have, John Sworen. I will miss our late-night problem-solving sessions and
interestingdiscussions. IwouldalsoliketothankmyotherclassmateintheWagener
Group,EdLehman,forhisadviceandfriendshipthroughtheyears. Iwouldliketothank
Mrs.FlorenceCourchayandMr.PiotrMatlokafortheirfriendshipandforsynthesizing
thecatalystsusedinthiswork. Also,IwouldliketoacknowledgeMr.TravisBaughman
forhiseffortsinworkingoutthecarboxylicacidbranchedpremonomersyntheses,and
forbeingagoodfriendwithagreatinterestindiscussingchemistry. Inaddition,Iwould
like to acknowledge older group members (specifically Jason Smith, Jim Pawlow,
Cameron Church, Fernando Gomez, John Schwendeman, andPatrick O’Donnell) for
theirguidanceandfriendship. Inaddition,IthanktheentireWagenerResearchGroup,
whohaveprovedtobegreatcolleaguesandfriends.
IacknowledgepastandcurrentReynoldsGroupMembers(Dr.DeanWelsh,Dr.
CarlGaupp,Mr.BarryThompson,Dr.KyukwanZong,Dr.ShaneWaybright,andDr.
C.J. Dubois) for their friendship and help in countless ways on the polymer floor.
Further, I would like to thank Dr. Ravi Orogunti, Dr. Buck Batson, Dr. Claude
Robotham, Professor Dennis Wright, and Professor Eric Enholm for their helpful
discussionsandadvice.
IwouldliketothanktheWagenerGroupMemberswhowillbecontinuingthis
project. Mr. Joshua Priebe, Mr. James Leonard, and Mr. Giovanni Rojas will be
responsiblefortakingthisprojecttothenextlevel. Also,Iwouldliketoacknowledge
anothermemberofthebio-olefinproject,Mrs. VioletaPetkovska,whoisperforming
V
MALDIanalysesonthesepolymerswiththehelpofDr.DavePowell. Iwouldliketo
thankthemallforbeingexcellentcoworkers,andwishthemthebestofluckonthis
fruitfulproject.
Iwouldlike tothankourcollaborators. I am verygrateful to ProfessorTodd
Emrick, Chip Breitenkamp, and the entire Emrick research group fortheirhelp and
hospitalityduringthesynthesisoftheGRGDsequence. Also,ClayBohnandProfessor
AnthonyBrennanareacknowledgedfortheirhelpinobtainingmaterialpropertydataon
thesebio-olefins. IwouldliketothankDr.KimChaffinandProfessorFrankBatesfor
theircollaborationontheX-rayanalysisofthepolymers. Inaddition,Iwouldliketo
thankProf.ShunsakuKimura&Mr.ShigekatsuFujiifortheirhelpinobtainingsurface
information on the peptide-branched polymers; and finally Professor Sinskey, for
agreeingtohelpdeterminethebiologicalactivityoftheGRGD-branchedpolymer.
Inaddition,IwouldespeciallyliketoacknowledgeProfessorSeiichiTokuraforthe
creative ability to coin the title of this dissertation and the generic term for these
polymers:bio-olefins.
MygratitudegoestotheNationalScienceFoundation,theArmyResearchOffice,
andtheUniversityofFloridaDissertationEnhancementFellowshipprogramforfinancial
support. I havetrulybeenblessedto have fundingthatenabledmethefreedomof
exploringmyinterestsinthisresearch.
Iwouldliketoacknowledgemypastprofessorswhohelpedmerealizemyinterest
inchemistry. Specifically,IwouldliketothankProfessorRezaHeratiforshowingme
howmuchfunresearchcanbeandfortakingthetimetoteachmehowtobeasynthetic
VI
chemist. IwouldalsoliketothankCoachDaleSpragueforhiscontinuedguidanceand
friendshipthroughtheyears.
Finally,Icouldnothavesucceededwithoutthesupportofmyfamilyandfriends.
Myparents,EdandPatriciaHopkins,havealwaysbeensupportiveofmyendeavors. I
amtrulythankfulfortheirlove,patience,andsupport,whichhashelpedtoguideme
throughthetoughtimes. Theyhavealwayssacrificedthemselvesformysisterandme.
Thesesacrificeshaveenabledustohaveeverypossibleadvantagetosucceed,andIknow
thatthebestgiftIcangivethemistobesuccessfulnotonlyinacareerbutinlife. Iwill
alwayscherishtheprideontheirfacesformyaccomplishmentsandhopetheyrealizethat
theyhavemadethisallpossible.
vii
11
TABLEOFCONTENTS
page
ACKNOWLEDGMENTS iv
LISTOFTABLES x
LISTOFFIGURES xi
ABSTRACT xv
CHAPTER
1 BACKGROUNDONCHIRALPOLYOLEFINS 1
Introduction 1
Hydrocarbon-BasedChiralPolyolefins 3
ChiralVinylHydrocarbonPolymers 3
ChiralVinylEtherPolymerswithHydrocarbonChirality 7
ChiralVinylKetone,Acetamide,andAcrylatePolymerswithHydrocarbon
Chirality 8
ChiralPolyolefinsfromAchiralMonomers 9
ChiralPolyolefinswithAromaticSideChains 11
PolystyreneDerivatives 1
BulkyChiralAromaticSubstituents 14
ChiralAromaticChromophoreSubstituents 16
ChiralPolyolefinsBearingBranchedAminoAcids 19
ApplyingADMETtowardstheSynthesisofBio-Olefins 28
2 INTERNALAMINOALCOHOL-BASEDBIO-OLEFINS 3
Introduction 31
Experimental 32
Chemicals 32
Instrumentation 33
MonomerSynthesis 34
PolymerSynthesis 36
ResultsandDiscussion 39
MonomerSynthesis 39
PolymerSynthesis 39
ThermalProperties 46
Conclusion 47
viii
3 “C-TERMINUS”BIO-OLEFINS .48
Introduction 48
Experimental 50
Chemicals 50
Instrumentation 51
Characterization 52
MonomerSynthesis 52
PolymerSynthesis 62
ResultsandDiscussion 66
MonomerSynthesis 66
PolymerSynthesis 73
HydrogenationandDeprotectionofBio-olefins 80
ThermalCharacterization 82
InitialWAXDandSAXDResults 85
InitialSurfaceExamination 88
InitialInstronResults 91
Conclusions 91
4 ‘W-TERMINUS”ADMETBIO-OLEFINS 93
Introduction 93
Experimental 94
Chemicals 94
Instrumentation 95
Characterization 96
MonomerSynthesis 96
PolymerSynthesis 108
ResultsandDiscussion 113
MonomerSynthesis 113
PolymerSynthesis 121
ThermalCharacterization 127
InitialX-RayScatteringData 131
InitialInstronTestingData 132
InitialSurfaceCharacterization 134
WorkinProgresstoPrepareaBiologicallyActiveBio-olefin 137
Conclusions 144
DissertationOverviewandFuturePerspective 145
APPENDIX WAXDandSAXDDATA 147
LISTOFREFERENCES 155
BIOGRAPHICALSKETCH 165
IX
2-
3- LISTOFTABLES
3-
page
4-
1 Selectedcharacterizationdataforpolymers5b,6b,6c,and7b 44
1 TheGPCandDSCdataforthe“C-terminus”polymers 76
2 Comparisonofthemolecularweightsobtainedfor10a,11a,and12ausing
catalystsCl,C2,andC3 78
1 TheGPCandDSCdataforthe‘W-terminus”bio-olefins 121
X