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1、 本讲内容。 背景介绍。 含氟生理活性分子。 毛利昂。 高级灭火剂抗粘材料/氟碳涂料。 人造血液。 氟碳相。 氯在有机化学中的应用超酸新加)。 氟化学反应的基本原理和反应规律，。 参考文献 Is Fluorine a boring element 2 下Lorz12eFluorine was first identified by Karl W. Scheele in 1771 and first isolatedin 1886 by the French chemist Henri Moissan. Etch glass (HPF)Toothpaste (NaF: active ingred
2、ient, prevent cavity) Fluorined Molecules in Industry1，Material (Manhattan Project, for military use)2，Medicinal and Pharmaceutical Products3， Lubricator Teflon Rocket Nuclear WeaponPropellant solate uraniumArtificial blood 。 Ereon as Refrigerant 本Florus chemistry (CEF:CD) isotopes (UF4) Fluorine: S
3、ome FactsNatural abundanceEarth s crust: 950 ppm; Important minerals: Fluorspar CaF:; Apatite Cas(POJ)3EF;Cryolite NasAlFe (CI 130 ppm) ”冰晶石Ocean: 1.3 ppm (C1 18000 ppm)Essential element: 0.3-0.5 mg/day for humans;ahuman body (70 kg) contains 2.6 g fluorineBond distance to C: CH;-F 1.39A (CH;-C11.77
4、A)Bond dissociation energy from C: CHi-F 116 kcal/mol (CH3-C1 81 Kkcalmol)Fluorine forms the strongest single bond to carbon (and other elements1)Hammett a parameters到 ap0.06 :aum0.34 CEF;: ap054:am0.43SOCFi: ap0.96;am0.8318F: Tio=109.8 min; P* (1.655 MeV)Application in Positron Emission Tomography
5、(PET) Fluorine (2): Discovery, Manufacture, UsesAlandmark in the history of chemistryHenri Moissan first preparation of the elementfiuorine on June 26 1886 by electrolysis of a1 to 12 mixture of KF and HF in a U-shapedPt tube cooled at -23*C in a MeCl ba由Henri Moissan28.9.1852-20.2.1907Nobel prize i
6、mchemistry 1906 The principle of Moissan electrolytic preparation of fiuorineis stll in use for the industrial manufactureMain uses of F2 :UEF6 C35UP38U isotope separation by gas diffusion)SFE6 (very good insulator)CIF3. BrF3,IFS, SF4,etc (versatile fuorinating/etching agents)Direct perfiuorination
7、of organic materials The First Purely Chemical Synthesis of Fluorine“Theidea: Hish oxidation-state transition metal fiuorides, such as MnF, NiF, CuF, areunstable and can only be stabilized as hexafluoro metallates MFe. Hence, abstraction offluoride from such MEFs- complexes should generate species t
8、hat decompose siving fluorine 1The synthesis of the prectrsor does notuse F;50% HF2KMnO +2KF +10 HE +3 HIO， 人 2KMnF +8HO+30，The abstraction of fhuoride from KMnFs with SbF; leads to the formation of elemental fuorine150*C, lhKMnF。 + 2 SbFs KSbF。 + MnF， + 1/2F，The principle of this reaction has been
9、applied for the preparation of solid propellantfluorine generators (mixtures of ee. CsiCuFsand BiF to be heated at ca. 200*C) 2.器 K.O_ Christe，Jnorg. Chem. 1986, 25. 3722思 K.O_Christe, RD .Wilson, norg. Cheml. 1987, 26. 2555 一 一 Hydrogen Fluoride (HPF)AdvantagesCheapest form of fluorine”Most industrial fluorine compound made using HEFDisadvantagesHighly Corrosive, skin contact can be fatalReacts with glassGas (B.P 20 C) at room temperature
