有机氟化学Class 2005 中科院上海有机所吕龙研究员课堂讲义.ppt

有机氟化学,12/138:3011:30(第三教室),胡金波,12/13:全球氟化学领域回顾、展望12/20:氟化学反应中的反应机理（i）12/27:氟化学反应中的反应机理（ii）,课程安排,中国有机氟化学研究黄维垣主编,参考书：,氟元素:“化学元素中举足轻重的小个子”,尖端材料：在军用尖端材料中，含氟材料占近一半（由于其独特优异的稳定性和其它物理特性）；医药农药：最近报道，全球新注册的医药中10含有氟元素；新注册的农药中，40含有氟元素。,有机含氟材料（包括有机含氟化合物、调聚物、聚合物）的起源可以上溯到19世纪后期。1886年法国化学家moissan首次分离出了单质氟，随后经过了19世纪30年代的氟利昂的发现，40年代曼哈顿计划氟材料的大量使用，才在50年代以后逐渐发展成为既有浓厚学术性又有极强应用性的一门学科。经过了100多年的曲折发展道路，有机氟材料领域不断得到提高，深刻影响了全球经济发展和社会进步。,有机氟化学起源,氟化学发展中的里程碑,1886年moissan分离得到单质氟；1892年swarts发现了三氟化锑作用下的氯/氟卤素交换反应；1928年midgley发明了“氟利昂”;1938年plunkett发现了聚四氟乙烯，标志着含氟聚合物的诞生；1947年fowler发现了三氟化钴作用下的全氟化方法；1949年simons发现了电化学氟化方法；1954年fried对有机含氟物质在医学上的应用的研究；1962年georgeolah利用含氟物质首次发现稳定的碳正离子存在；1962年bartlett发现了惰性气体的氟化（xeptf6）；1974年molina和rowland对某些氟利昂破坏臭氧层的研究；1979年margraves发现了直接氟化；2003年ohagan分离出了第一个氟化酶。,j.fluorinechem.2005,henrimoissan(1852-1907),1906年度诺贝尔化学奖得主,1886年分离出f2,从100多年的诺贝尔化学奖看化学发展趋势,1901年j.h.vanthoffinrecognitionoftheextraordinaryserviceshehasrenderedbythediscoveryofthelawsofchemicaldynamicsandosmoticpressureinsolutions.1902年h.e.fischerinrecognitionoftheextraordinaryserviceshehasrenderedbyhisworkonsugarandpurinesyntheses.1903年s.a.arrheniusinrecognitionoftheextraordinaryserviceshehasrenderedtotheadvancementofchemistrybyhiselectrolytictheoryofdissociation.1904年w.ramsayinrecognitionofhisservicesinthediscoveryoftheinertgaseouselementsinair,andhisdeterminationoftheirplaceintheperiodicsystem.1905年j.f.w.a.v.baeyerinrecognitionofhisservicesintheadvancementoforganicchemistryandthechemicalindustry,throughhisworkonorganicdyesandhydroaromaticcompounds.1906年h.moissaninrecognitionofthegreatservicesrenderedbyhiminhisinvestigationandisolationoftheelementfluorine,andfortheadoptionintheserviceofscienceoftheelectricfurnacecalledafterhim.1907年e.buchnerforhisbiochemicalresearchesandhisdiscoveryofcellfreefermentation.1908年l.e.rutherfordforhisinvestigationsintothedisintegrationoftheelements,andthechemistryofradioactivesubstances.1909年w.ostwaldinrecognitionofhisworkoncatalysisandforhisinvestigationsintothefundamentalprinciplesgoverningchemicalequilibriaandratesofreaction.,1910年o.wallachinrecognitionofhisservicestoorganicchemistryandthechemicalindustrybyhispioneerworkinthefieldofalicycliccompounds.1911年m.curieinrecognitionofherservicestotheadvancementofchemistrybythediscoveryoftheelementsradiumandpolonium,bytheisolationofradiumandthestudyofthenatureandcompoundsofthisremarkableelement.1912年v.grignardforthediscoveryoftheso-calledgrignardreagent,whichinrecentyearshasgreatlyadvancedtheprogressoforganicchemistry.p.sabatierforhismethodofhydrogenatingorganiccompoundsinthepresenceoffinelydisintegratedmetalswherebytheprogressoforganicchemistryhasbeengreatlyadvancedinrecentyears.1913年a.wernerinrecognitionofhisworkonthelinkageofatomsinmoleculesbywhichhehasthrownnewlightonearlierinvestigationsandopenedupnewfieldsofresearchespeciallyininorganicchemistry.1914年t.w.richardsinrecognitionofhisaccuratedeterminationsoftheatomicweightofalargenumberofchemicalelements.1915年r.m.willstatterforhisresearchesonplantpigments,especiallychlorophyll.1918年f.haberforthesynthesisofammoniafromitselements.,1920年w.h.nernstinrecognitionofhisworkinthermochemistry.1921年f.soddyforhiscontributionstoourknowledgeofthechemistryofradioactivesubstances,andhisinvestigationsintotheoriginandnatureofisotopes.1922年f.w.astonforhisdiscovery,bymeansofhismassspectrograph,ofisotopes,inalargenumberofnon-radioactiveelements,andforhisenunciationofthewhole-numberrule.1923年f.preglforhisinventionofthemethodofmicro-analysisoforganicsubstances.1925年r.a.zsigmondyforhisdemonstrationoftheheterogenousnatureofcolloidsolutionsandforthemethodsheused,whichhavesincebecomefundamentalinmoderncolloidchemistry.1927年h.ottowielandforhisinvestigationsoftheconstitutionofthebileacidsandrelatedsubstances.1928年a.o.r.windausfortheservicesrenderedthroughhisresearchintotheconstitutionofthesterolsandtheirconnectionwiththevitamins.1929年a.hardenandh.k.a.s.v.euler-chelpinfortheirinvestigationsonthefermentationofsugarandfermentativeenzymes.,1930年h.fischerforhisresearchesintotheconstitutionofhaeminandchlorophyllandespeciallyforhissynthesisofhaemin.1931年c.boschandf.bergiusinrecognitionoftheircontributionstotheinventionanddevelopmentofchemicalhighpressuremethods.1932年i.langmuirforhisdiscoveriesandinvestigationsinsurfacechemistry.1934年h.c.ureyforhisdiscoveryofheavyhydrogen.1935年f.joliotandi.joliot-curieinrecognitionoftheirsynthesisofnewradioactiveelements.1936年p.debyeforhiscontributionstoourknowledgeofmolecularstructurethroughhisinvestigationsondipolemomentsandonthediffractionofx-raysandelectronsingases.1937年w.n.haworthforhisinvestigationsoncarbohydratesandvitaminc;p.karrerforhisinvestigationsoncarotenoids,flavinsandvitaminsaandb2.1938年r.kuhnforhisworkoncarotenoidsandvitamins.(causedbytheauthoritiesofhiscountrytodeclinetheawardbutlaterreceivedthediplomaandthemedal.)1939年a.butenandtforhisworkonsexhormones.(causedbytheauthoritiesofhiscountrytodeclinetheawardbutlaterreceivedthediplomaandthemedal);l.ruzickaforhisworkonpolymethylenesandhigherterpenes.,1943年ghevesyforhisworkontheuseofisotopesastracersinthestudyofchemicalprocesses.1944年o.hahnforhisdiscoveryofthefissionofheavynuclei.1945年a.i.virtanenforhisresearchandinventionsinagriculturalandnutritionchemistry,especiallyforhisfodderpreservationmethod.1946年j.b.sumnerforhisdiscoverythatenzymescanbecrystallized;j.northropandw.stanleyfortheirpreparationofenzymesandvirusproteinsinapureform.1947年r.robinsonforhisinvestigationsonplantproductsofbiologicalimportance,especiallythealkaloids.1948年a.tiseliusforhisresearchonelectrophoresisandadsorptionanalysis,especiallyforhisdiscoveriesconcerningthecomplexnatureoftheserumproteins.1949年w.f.giauqueforhiscontributionsinthefieldofchemicalthermodynamics,particularlyconcerningthebehaviourofsubstancesatextremelylowtemperatures.,1950年dielsandalderfortheirdiscoveryanddevelopmentofthedienesynthesis.1951年mcmillanandseaborgfortheirdiscoveriesinthechemistryofthetransuraniumelements.1952年martinandsyngefortheirinventionofpartitionchromatography.1953年h.staudingerforhisdiscoveriesinthefieldofmacromolecularchemistry.1954年l.c.paulingforhisresearchintothenatureofthechemicalbondanditsapplicationtotheelucidationofthestructureofcomplexsubstances.1955年vigneaudforhisworkonbiochemicallyimportantsulphurcompounds,especiallyforthefirstsynthesisofapolypeptidehormone.1956年hinshelwoodandsemenovfortheirresearchesintothemechanismofchemicalreactions.1957年toddforhisworkonnucleotidesandnucleotideco-enzymes.1958年f.sangerforhisworkonthestructureofproteins,especiallythatofinsulin.1959年j.heyrovskyforhisdiscoveryanddevelopmentofthepolarographicmethodsofanalysis.,1960年libbyforhismethodtousecarbon-14foragedeterminationinarchaeology,geology,geophysics,andotherbranchesofscience.1961年m.calvinforhisresearchonthecarbondioxideassimilationinplants.1962年perutzandkendrewfortheirstudiesofthestructuresofglobularproteins.1963年zieglerandnattafortheirdiscoveriesinthefieldofthechemistryandtechnologyofhighpolymers.1964年hodgkinforherdeterminationsbyx-raytechniquesofthestructuresofimportantbiochemicalsubstances.1965年robertwoodwardforhisoutstandingachievementsintheartoforganicsynthesis.1966年r.s.mullikenforhisfundamentalworkconcerningchemicalbondsandtheelectronicstructureofmoleculesbythemolecularorbitalmethod.1967年eigen,norrishandporterfortheirstudiesofextremelyfastchemicalreactions,effectedbydisturbingtheequlibriumbymeansofveryshortpulsesofenergy.1968年l.onsagerforthediscoveryofthereciprocalrelationsbearinghisname,whicharefundamentalforthethermodynamicsofirreversibleprocesses.1969年bartonandhasselfortheircontributionstothedevelopmentoftheconceptofconformationanditsapplicationinchemistry.,1970年l.f.leloirforhisdiscoveryofsugarnucleotidesandtheirroleinthebiosynthesisofcarbohydrates.1971年g.herzbergforhiscontributionstotheknowledgeofelectronicstructureandgeometryofmolecules,particularlyfreeradicals.1972年anfinsteinforhisworkonribonuclease,especiallyconcerningtheconnectionbetweentheaminoacidsequenceandthebiologicallyactiveconfirmation;mooreandsteinfortheircontributiontotheunderstandingoftheconnectionbetweenchemicalstructureandcatalyticactivityoftheactivecentreoftheribonucleasemolecule.1973年fischerandwilkinsonfortheirpioneeringwork,performedindependently,onthechemistryoftheorganometallic,socalledsandwichcompounds.1974年p.j.floryforhisfundamentalachievements,boththeoreticalandexperimental,inthephysicalchemistryofthemacromolecules.1975年cornforthforhisworkonthestereochemistryofenzyme-catalyzedreactions;prelogforhisresearchintothestereochemistryoforganicmoleculesandreactions.1976年lipscombforhisstudiesonthestructureofboranesilluminatingproblemsofchemicalbonding.1977年i.prigogineforhiscontributionstonon-equilibriumthermodynamics,particularlythetheoryofdissipativestructures.1978年mitchellforhiscontributiontotheunderstandingofbiologicalenergytransferthroughtheformulationofthechemiosmotictheory.1979年brownandwittigfortheirdevelopmentoftheuseofboron-andphosphorus-containingcompounds,respectively,intoimportantreagentsinorganicsynthesis.,1980年bergforhisfundamentalstudiesofthebiochemistryofnucleicacids,withparticularregardtorecombinant-dna;gilbertandsangerfortheircontributionsconcerningthedeterminationofbasesequencesinnucleicacids.1981年fukuiandhoffmannfortheirtheories,developedindependently,concerningthecourseofchemicalreactions.1982年klugforhisdevelopmentofcrystallographicelectronmicroscopyandhisstructuralelucidationofbiologicallyimportantnucleiacid-proteincomplexes.1983年henrytaubeforhisworkonthemechanismsofelectrontransferreactions,especiallyinmetalcomplexes.1984年merryfieldforhisdevelopmentofmethodologyforchemicalsynthesisonasolidmatrix.1985年hauptmanandkarlefortheiroutstandingachievementsinthedevelopmentofdirectmethodsforthedeterminationofcrystalstructures.1986年herschbach，李元哲andpolanyifortheircontributionsconcerningthedynamicsofchemicalelementaryprocesses.1987年cram，lehn，pedersenfortheirdevelopmentanduseofmoleculeswithstructure-specificinteractionsofhighselectivity.1988年deisenhofer，huber，michelforthedeterminationofthethree-dimensionalstructureofaphotosyntheticreactioncentre.1989年altman，cechfortheirdiscoveryofcatalyticpropertiesofrna.,1990年e.j.coreyforhisdevelopmentofthetheoryandmethodologyoforganicsynthesis.1991年r.r.ernstforhiscontributionstothedevelopmentofthemethodologyofhighresolutionnuclearmagneticresonance(nmr)spectroscopy.1992年r.a.marcusforhiscontributionstothetheoryofelectrontransferreactionsinchemicalsystems.1993年theprizewasawardedforcontributionstothedevelopmentsofmethodswithindna-basedchemistryequallybetween:mullisforhisinventionofthepolymerasechainreaction(pcr)method.smithforhisfundamentalcontributionstotheestablishmentofoligonucleiotide-based,site-directedmutagenesisanditsdevelopmentforproteinstudies.1994年georgea.olahforhiscontributiontocarbocationchemistry.1995年crutzen,molina,rowlandfortheirworkinatmosphericchemistry,particularlyconcerningtheformationanddecompositionofozone.1996年curl,kroto,smalleyfortheirdiscoveryoffullerenes.1997年boyer,walkerfortheirelucidationoftheenzymaticmechanismunderlyingthesynthesisofadenosinetriphosphate(atp);skouforthefirstdiscoveryofanion-transportingenzyme,na+,k+-atpase.1998年kohnforhisdevelopmentofthedensity-functionaltheory;popleforhisdevelopmentofcomputationalmethodsinquantumchemistry.1999年zewailforhisstudiesofthetransitionstatesofchemicalreactionsusingfemtosecondspectroscopy,2000年heeger,macdiarmid,shirakawaforthediscoveryanddevelopmentofconductivepolymers.2001年knowles,noyorifortheirworkonchirallycatalysedhydrogenationreactions;sharplessforhisworkonchirallycatalysedoxidationreactions.2002年fenn,tanakafortheirdevelopmentofsoftdesorptionionisationmethodsformassspectrometricanalysesofbiologicalmacromolecules;wuthrichforhisdevelopmentofnuclearmagneticresonancespectroscopyfordeterminingthethree-dimensionalstructureofbiologicalmacromoleculesinsolution.2003年theprizeisbeingawardedfordiscoveriesconcerningchannelsincellmembraneswithonehalfoftheprizeto:p.agreforthediscoveryofwaterchannels;r.mackinnonforstructuralandmechanisticstudiesofionchannels.2004年aaronciechanover,avramhershko,irwinroseforthediscoveryofubiquitin-mediatedproteindegradation.2005年yveschauvin,roberth.grubbs,richard,r.schrockforthedevelopmentofthemetathesismethodinorganicsynthesis.,上图为“极端化学（extremechemistry）大师”karlo.christe教授研究小组所使用的高危险反应（无水氟化氢、氟气、四氟化二氮等参与的反应）真空线、反应管道和实验人员安全保护装备。karlo.christe教授兼任美国edward空军基地高能爆炸物质研发部首席科学家，acs氟化学奖、moissan氟化学奖获得者。1999年该小组利用这类实验装置研究出了迄今为止所见爆炸力最强的高能物质(原子弹除外)：五氮正离子，被c&enews誉为该年度全球五大化学发现之一。,karlo.christe,davidohagan,fluorinatorx-raystructureofoneofthefluorinaseenzymestwotrimerswiththreebounds-adenosyl-l-methioninesubstratemolecules.theenzymeusesinorganicfluoridetoconvertthemoleculesto5-fluoro-5-deoxyadenosine.,brucee.smart,fluorinechemistrysunchartedterritory,coordinationormetathesispolymerizationmethods,suchasziegler-natta-typereactionscarriedoutonethyleneandpropylene,havebeenunsuccessfulwithfluoroolefins,smartsaid.thesefluorinatedmonomerstypicallyaretoounreactivebecausetheyhavehighlyelectron-deficientdoublebonds.iftheydoreact,metal