《有机氟化学》课件.ppt

有机氟化学 12 138 30 11 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O Hagan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 Van tHoffinrecognitionoftheextraordinaryserviceshehasrenderedbythediscoveryofthelawsofchemicaldynamicsandosmoticpressureinsolutions 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 DavidO Hagan FLUORINATORX raystructureofoneofthefluorinaseenzyme stwotrimerswiththreeboundS adenosyl L methioninesubstratemolecules Theenzymeusesinorganicfluoridetoconvertthemoleculesto5 fluoro 5 deoxyadenosine BruceE Smart FluorineChemistry sUnchartedTerritory Coordinationormetathesispolymerizationmethods suchasZiegler Natta typereactionscarriedoutonethyleneandpropylene havebeenunsuccessfulWithfluoroolefins Smartsaid Thesefluorinatedmonomerstypicallyaretoounreactivebecausetheyhavehighlyelectron deficientdoublebonds Iftheydor