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

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1、有机氟化学,12/13 8:3011:30(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

2、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

3、 Fried对有机含氟物质在医学上的应用的研究；1962年 George Olah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.Fluorine Chem.2005,Henri Moissan(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.Vant Hoff in recogn

4、ition of the extraordinary services he has rendered by the discovery of the laws of chemical dynamics and osmotic pressure in solutions.1902年 H.E.Fischer in recognition of the extraordinary services he has rendered by his work on sugar and purine syntheses.1903年 S.A.Arrhenius in recognition of the e

5、xtraordinary services he has rendered to the advancement of chemistry by his electrolytic theory of dissociation.1904年 W.Ramsay in recognition of his services in the discovery of the inert gaseous elements in air,and his determination of their place in the periodic system.1905年 J.F.W.A.V.Baeyer in r

6、ecognition of his services in the advancement of organic chemistry and the chemical industry,through his work on organic dyes and hydroaromatic compounds.1906年 H.Moissan in recognition of the great services rendered by him in his investigation and isolation of the element fluorine,and for the adopti

7、on in the service of science of the electric furnace called after him.1907年 E.Buchner for his biochemical researches and his discovery of cellfree fermentation.1908年 L.E.Rutherford for his investigations into the disintegration of the elements,and the chemistry of radioactive substances.1909年 W.Ostw

8、ald in recognition of his work on catalysis and for his investigations into the fundamental principles governing chemical equilibria and rates of reaction.,1910年 O.Wallach in recognition of his services to organic chemistry and the chemical industry by his pioneer work in the field of alicyclic comp

9、ounds.1911年 M.Curie in recognition of her services to the advancement of chemistry by the discovery of the elements radium and polonium,by the isolation of radium and the study of the nature and compounds of this remarkable element.1912年 V.Grignard for the discovery of the so-called Grignard reagent

10、,which in recent years has greatly advanced the progress of organic chemistry.P.Sabatier for his method of hydrogenating organic compounds in the presence of finely disintegrated metals whereby the progress of organic chemistry has been greatly advanced in recent years.1913年 A.Werner in recognition

11、of his work on the linkage of atoms in molecules by which he has thrown new light on earlier investigations and opened up new fields of research especially in inorganic chemistry.1914年 T.W.Richards in recognition of his accurate determinations of the atomic weight of a large number of chemical eleme

12、nts.1915年 R.M.Willstatter for his researches on plant pigments,especially chlorophyll.1918年 F.Haber for the synthesis of ammonia from its elements.,1920年 W.H.Nernst in recognition of his work in thermochemistry.1921年 F.Soddy for his contributions to our knowledge of the chemistry of radioactive subs

13、tances,and his investigations into the origin and nature of isotopes.1922年 F.W.Aston for his discovery,by means of his mass spectrograph,of isotopes,in a large number of non-radioactive elements,and for his enunciation of the whole-number rule.1923年 F.Pregl for his invention of the method of micro-a

14、nalysis of organic substances.1925年 R.A.Zsigmondy for his demonstration of the heterogenous nature of colloid solutions and for the methods he used,which have since become fundamental in modern colloid chemistry.1927年 H.Otto Wieland for his investigations of the constitution of the bile acids and re

15、lated substances.1928年 A.O.R.Windaus for the services rendered through his research into the constitution of the sterols and their connection with the vitamins.1929年 A.Harden and H.K.A.S.V.Euler-Chelpin for their investigations on the fermentation of sugar and fermentative enzymes.,1930年 H.Fischer f

16、or his researches into the constitution of haemin and chlorophyll and especially for his synthesis of haemin.1931年 C.Bosch and F.Bergius in recognition of their contributions to the invention and development of chemical high pressure methods.1932年 I.Langmuir for his discoveries and investigations in

17、 surface chemistry.1934年 H.C.Urey for his discovery of heavy hydrogen.1935年 F.Joliot and I.Joliot-Curie in recognition of their synthesis of new radioactive elements.1936年 P.Debye for his contributions to our knowledge of molecular structure through his investigations on dipole moments and on the di

18、ffraction of X-rays and electrons in gases.1937年 W.N.Haworth for his investigations on carbohydrates and vitamin C;P.Karrer for his investigations on carotenoids,flavins and vitamins A and B2.1938年 R.Kuhn for his work on carotenoids and vitamins.(Caused by the authorities of his country to decline t

19、he award but later received the diploma and the medal.)1939年 A.Butenandt for his work on sex hormones.(Caused by the authorities of his country to decline the award but later received the diploma and the medal);L.Ruzicka for his work on polymethylenes and higher terpenes.,1943年 G Hevesy for his work

20、 on the use of isotopes as tracers in the study of chemical processes.1944年 O.Hahn for his discovery of the fission of heavy nuclei.1945年 A.I.Virtanen for his research and inventions in agricultural and nutrition chemistry,especially for his fodder preservation method.1946年 J.B.Sumner for his discov

21、ery that enzymes can be crystallized;J.Northrop and W.Stanley for their preparation of enzymes and virus proteins in a pure form.1947年 R.Robinson for his investigations on plant products of biological importance,especially the alkaloids.1948年 A.Tiselius for his research on electrophoresis and adsorp

22、tion analysis,especially for hisdiscoveries concerning the complex nature of the serum proteins.1949年 W.F.Giauque for his contributions in the field of chemical thermodynamics,particularly concerning the behaviour of substances at extremely low temperatures.,1950年 Diels and Alder for their discovery

23、 and development of the diene synthesis.1951年 McMillan and Seaborg for their discoveries in the chemistry of the transuranium elements.1952年 Martin and Synge for their invention of partition chromatography.1953年 H.Staudinger for his discoveries in the field of macromolecular chemistry.1954年 L.C.Paul

24、ing for his research into the nature of the chemical bond and its application to the elucidation of the structure of complex substances.1955年 Vigneaud for his work on biochemically important sulphur compounds,especially for the first synthesis of a polypeptide hormone.1956年 Hinshelwood and Semenov f

25、or their researches into the mechanism of chemical reactions.1957年 Todd for his work on nucleotides and nucleotide co-enzymes.1958年 F.Sanger for his work on the structure of proteins,especially that of insulin.1959年 J.Heyrovsky for his discovery and development of the polarographic methods of analys

26、is.,1960年 Libby for his method to use carbon-14 for age determination in archaeology,geology,geophysics,and other branches of science.1961年 M.Calvin for his research on the carbon dioxide assimilation in plants.1962年 Perutz and Kendrew for their studies of the structures of globular proteins.1963年 Z

27、iegler and Natta for their discoveries in the field of the chemistry and technology of high polymers.1964年 Hodgkin for her determinations by X-ray techniques of the structures of important biochemical substances.1965年 Robert Woodward for his outstanding achievements in the art of organic synthesis.1

28、966年 R.S.Mulliken for his fundamental work concerning chemical bonds and the electronic structure of molecules by the molecular orbital method.1967年 Eigen,Norrish and Porter for their studies of extremely fast chemical reactions,effected by disturbing the equlibrium by means of very short pulses of

29、energy.1968年 L.Onsager for the discovery of the reciprocal relations bearing his name,which are fundamental for the thermodynamics of irreversible processes.1969年 Barton and Hassel for their contributions to the development of the concept of conformation and its application in chemistry.,1970年 L.F.L

30、eloir for his discovery of sugar nucleotides and their role in the biosynthesis of carbohydrates.1971年 G.Herzberg for his contributions to the knowledge of electronic structure and geometry of molecules,particularly free radicals.1972年 Anfinstein for his work on ribonuclease,especially concerning th

31、e connection between the amino acid sequence and the biologically active confirmation;Moore and Stein for their contribution to the understanding of the connection between chemical structure and catalytic activity of the active centre of the ribonuclease molecule.1973年 Fischer and Wilkinson for thei

32、r pioneering work,performed independently,on the chemistry of the organometallic,so called sandwich compounds.1974年 P.J.Flory for his fundamental achievements,both theoretical and experimental,in the physical chemistry of the macromolecules.1975年 Cornforth for his work on the stereochemistry of enzy

33、me-catalyzed reactions;Prelog for his research into the stereochemistry of organic molecules and reactions.1976年 Lipscomb for his studies on the structure of boranes illuminating problems of chemical bonding.1977年 I.Prigogine for his contributions to non-equilibrium thermodynamics,particularly the t

34、heory of dissipative structures.1978年 Mitchell for his contribution to the understanding of biological energy transfer through the formulation of the chemiosmotic theory.1979年 Brown and Wittig for their development of the use of boron-and phosphorus-containing compounds,respectively,into important r

35、eagents in organic synthesis.,1980年 Berg for his fundamental studies of the biochemistry of nucleic acids,with particular regard to recombinant-DNA;Gilbert and Sanger for their contributions concerning the determination of base sequences in nucleic acids.1981年 Fukui and Hoffmann for their theories,d

36、eveloped independently,concerning the course of chemical reactions.1982年 Klug for his development of crystallographic electron microscopy and his structural elucidation of biologically important nuclei acid-protein complexes.1983年 Henry Taube for his work on the mechanisms of electron transfer react

37、ions,especially in metal complexes.1984年 Merryfield for his development of methodology for chemical synthesis on a solid matrix.1985年 Hauptman and Karle for their outstanding achievements in the development of direct methods for the determination of crystal structures.1986年 Herschbach，李元哲 and Polany

38、i for their contributions concerning the dynamics ofchemical elementary processes.1987年 Cram，Lehn，Pedersen for their development and use of molecules with structure-specific interactions of high selectivity.1988年 Deisenhofer，Huber，Michel for the determination of the three-dimensional structure of a

39、photosynthetic reaction centre.1989年 Altman，Cech for their discovery of catalytic properties of RNA.,1990年 E.J.Corey for his development of the theory and methodology of organic synthesis.1991年 R.R.Ernst for his contributions to the development of the methodology of high resolution nuclear magnetic

40、resonance(NMR)spectroscopy.1992年 R.A.Marcus for his contributions to the theory of electron transfer reactions in chemical systems.1993年 The prize was awarded for contributions to the developments of methods within DNA-based chemistry equally between:Mullis for his invention of the polymerase chain

41、reaction(PCR)method.Smith for his fundamental contributions to the establishment of oligonucleiotide-based,site-directed mutagenesis and its development for protein studies.1994年 George A.Olah for his contribution to carbocation chemistry.1995年 Crutzen,Molina,Rowland for their work in atmospheric ch

42、emistry,particularly concerning the formation and decomposition of ozone.1996年 Curl,Kroto,Smalley for their discovery of fullerenes.1997年 Boyer,Walkerfor their elucidation of the enzymatic mechanism underlying the synthesis of adenosine triphosphate(ATP);Skou for the first discovery of an ion-transp

43、orting enzyme,Na+,K+-ATPase.1998年 Kohn for his development of the density-functional theory;Pople for his development of computational methods in quantum chemistry.1999年 Zewail for his studies of the transition states of chemical reactions using femtosecond spectroscopy,2000年 Heeger,MacDiarmid,Shira

44、kawa for the discovery and development of conductive polymers.2001年 Knowles,Noyori for their work on chirally catalysed hydrogenation reactions;Sharpless for his work on chirally catalysed oxidation reactions.2002年 Fenn,Tanaka for their development of soft desorption ionisation methods for mass spec

45、trometric analyses of biological macromolecules;Wuthrich for his development of nuclear magnetic resonance spectroscopy for determining the three-dimensional structure of biological macromolecules in solution.2003年 The prize is being awarded for discoveries concerning channels in cell membranes with

46、 one half of the prize to:P.Agre for the discovery of water channels;R.Mackinnon for structural and mechanistic studies of ion channels.2004年 Aaron Ciechanover,Avram Hershko,Irwin Rose for the discovery of ubiquitin-mediated protein degradation.2005年 Yves Chauvin,Robert H.Grubbs,Richard,R.Schrock fo

47、r the development of the metathesis method in organic synthesis.,上图为“极端化学（extreme chemistry）大师”Karl O.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。Karl O.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&E News誉为该年度全球

48、五大化学发现之一。,Karl O.Christe,David OHagan,FLUORINATOR X-ray structure of one of the fluorinase enzymes two trimers with three bound S-adenosyl-L-methionine substrate molecules.The enzyme uses inorganic fluoride to convert the moleculesto 5-fluoro-5-deoxyadenosine.,Bruce E.Smart,Fluorine Chemistrys Uncha

49、rted Territory,Coordination or metathesis polymerization methods,such as Ziegler-Natta-type reactions carried out on ethylene and propylene,have been unsuccessful With fluoroolefins,Smart said.These fluorinated monomers typically are too unreactive because they have highly electron-deficient double

50、bonds.If they do react,metal fluoride elimination is a problem.These circumstances have limited commercial polymerizations to free-radical processes.Its also difficult to tailor high-molecular-weight block copolymer structures with fluoroolefins,he added.,(2)Fluoroolefin polymerization is still base