有機(jī)氟化學(xué)1-PPT課件

1、有機(jī)氟化學(xué) 12/13 8:3011:30 (第三教室)胡金波12/13: 全球氟化學(xué)領(lǐng)域回顧、展望12/20: 氟化學(xué)反應(yīng)中的反應(yīng)機(jī)理 （I）12/27: 氟化學(xué)反應(yīng)中的反應(yīng)機(jī)理 （II）課程安排 中國有機(jī)氟化學(xué)研究黃維垣 主編參考書： 氟元素: “化學(xué)元素中舉足輕重的小個(gè)子”尖端材料：在軍用尖端材料中，含氟材料占近一半（由于其獨(dú)特優(yōu)異的穩(wěn)定性和其它物理特性）；醫(yī)藥農(nóng)藥：最近報(bào)道，全球新注冊的醫(yī)藥中10含有氟元素；新注冊的農(nóng)藥中，40含有氟元素。 原子電負(fù)性(Pauling)Pauling原子半徑 ()Bondi原子半徑 （)鍵能 (CH3-X)(kcal/mol)鍵長CH3-X()H2.1

2、1.201.20991.09F4.01.351.471161.39Cl3.01.801.75811.77Br2.81.951.85681.93O (OH)3.51.401.52861.43S (SH)2.51.851.80651.82 有機(jī)含氟材料（包括有機(jī)含氟化合物、調(diào)聚物、聚合物）的起源可以上溯到19世紀(jì)后期。1886年法國化學(xué)家Moissan首次分離出了單質(zhì)氟，隨后經(jīng)過了19世紀(jì)30年代的氟利昂的發(fā)現(xiàn)，40年代曼哈頓計(jì)劃氟材料的大量使用，才在50年代以后逐漸發(fā)展成為既有濃厚學(xué)術(shù)性又有極強(qiáng)應(yīng)用性的一門學(xué)科。經(jīng)過了100多年的曲折發(fā)展道路，有機(jī)氟材料領(lǐng)域不斷得到提高，深刻影響了全球經(jīng)濟(jì)發(fā)展和

3、社會進(jìn)步。 有機(jī)氟化學(xué)起源 氟化學(xué)發(fā)展中的里程碑 1886年 Moissan分離得到單質(zhì)氟； 1892年 Swarts發(fā)現(xiàn)了三氟化銻作用下的氯/氟鹵素交換反應(yīng)； 1928年 Midgley發(fā)明了“氟利昂”; 1938年 Plunkett發(fā)現(xiàn)了聚四氟乙烯，標(biāo)志著含氟聚合物的誕生； 1947年 Fowler發(fā)現(xiàn)了三氟化鈷作用下的全氟化方法； 1949年 Simons發(fā)現(xiàn)了電化學(xué)氟化方法； 1954年 Fried對有機(jī)含氟物質(zhì)在醫(yī)學(xué)上的應(yīng)用的研究； 1962年 George Olah利用含氟物質(zhì)首次發(fā)現(xiàn)穩(wěn)定的碳正離子存在； 1962年 Bartlett發(fā)現(xiàn)了惰性氣體的氟化（XePtF6）； 1974

4、年 Molina和Rowland對某些氟利昂破壞臭氧層的研究； 1979年 Margraves發(fā)現(xiàn)了直接氟化； 2019年 OHagan分離出了第一個(gè)氟化酶。 J. Fluorine Chem. 2019Henri Moissan (1852-1907)1906 年度諾貝爾化學(xué)獎(jiǎng)得主1886年分離出 F2 從100多年的諾貝爾化學(xué)獎(jiǎng)看化學(xué)發(fā)展趨勢 1901年 J. H. Vant Hoff in recognition of the extraordinary services he has rendered by the discovery of the laws of chemical d

5、ynamics 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 extraordinary services he has rendered to the advancement of chemistry by his electrolytic

6、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 recognition of his services in the advancement of organic chemistry and the chemical

7、 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 adoption in the service of science of the electric furnace called after him. 1907年 E.

8、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. Ostwald in recognition of his work on catalysis and for his investigations int

9、o 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 compounds.1911年 M. Curie in recognition of her services to the advancement of

10、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, which in recent years has greatly advanced the progress of organic ch

11、emistry. 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 of his work on the linkage of atoms in molecules by which he has t

12、hrown 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 elements.1915年 R. M. Willstatter for his researches on plant pigments

13、, 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 substances, and his investigations into the origin and nature

14、 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-analysis of organic substances. 1925年 R. A. Zsig

15、mondy 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 related substances. 1928年 A. O. R. Windaus

16、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 for his researches into the co

17、nstitution 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 surface chemistry. 1934

18、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 diffraction of X-r

19、ays 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 the award

20、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 on

21、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 dis

22、covery 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

23、and adsorption 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

24、their discovery 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 chemis

25、try.1954年 L.C. Pauling 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 Hinsh

26、elwood and Semenov for 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 polarog

27、raphic methods of analysis. 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

28、of globular proteins. 1963年 Ziegler 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

29、the art of organic synthesis.1966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

30、by means of very short pulses of 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

31、application in chemistry. 1970年 L.F. Leloir 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

32、 on ribonuclease, especially concerning the 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 mol

33、ecule.1973年 Fischer and Wilkinson for their 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 Cor

34、nforth for his work on the stereochemistry of enzyme-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 contribution

35、s to non-equilibrium thermodynamics, particularly the theory 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 phos

36、phorus-containing compounds, respectively, into important reagents 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 i

37、n nucleic acids. 1981年 Fukui and Hoffmann for their theories, developed 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 Henr

38、y Taube for his work on the mechanisms of electron transfer reactions, 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 d

39、etermination of crystal structures. 1986年 Herschbach，李元哲 and Polanyi 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，Mi

40、chel for the determination of the three-dimensional structure of a 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 t

41、he development of the methodology of high resolution nuclear magnetic 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

42、chemistry equally between: Mullis for his invention of the polymerase chain 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 c

43、arbocation chemistry. 2019年 Crutzen, Molina, Rowland for their work in atmospheric chemistry, particularly concerning the formation and decomposition of ozone. 2019年 Curl, Kroto, Smalley for their discovery of fullerenes.2019年 Boyer, Walkerfor their elucidation of the enzymatic mechanism underlying

44、the synthesis of adenosine triphosphate (ATP); Skou for the first discovery of an ion-transporting enzyme, Na+, K+-ATPase.2019年 Kohn for his development of the density-functional theory; Pople for his development of computational methods in quantum chemistry. 2019年 Zewail for his studies of the tran

45、sition states of chemical reactions using femtosecond spectroscopy2000年 Heeger, MacDiarmid, Shirakawa for the discovery and development of conductive polymers.2019年 Knowles, Noyori for their work on chirally catalysed hydrogenation reactions; Sharpless for his work on chirally catalysed oxidation re

46、actions. 2019年 Fenn, Tanaka for their development of soft desorption ionisation methods for mass spectrometric analyses of biological macromolecules;Wuthrich for his development of nuclear magnetic resonance spectroscopy for determining the three-dimensional structure of biological macromolecules in

47、 solution. 2019年 The prize is being awarded for discoveries concerning channels in cell membranes with one half of the prize to: P. Agre for the discovery of water channels; R. Mackinnon for structural and mechanistic studies of ion channels. 2019年 Aaron Ciechanover, Avram Hershko, Irwin Rose for th

48、e discovery of ubiquitin-mediated protein degradation. 2019年 Yves Chauvin, Robert H. Grubbs, Richard, R. Schrock for the development of the metathesis method in organic synthesis. 上圖為“極端化學(xué)（extreme chemistry）大師”Karl O. Christe教授研究小組所使用的高危險(xiǎn)反應(yīng)（無水氟化氫、氟氣、四氟化二氮等參與的反應(yīng)）真空線、反應(yīng)管道和實(shí)驗(yàn)人員安全保護(hù)裝備。Karl O. Christe教授兼

49、任美國Edward空軍基地高能爆炸物質(zhì)研發(fā)部首席科學(xué)家，ACS氟化學(xué)獎(jiǎng)、Moissan氟化學(xué)獎(jiǎng)獲得者。2019年該小組利用這類實(shí)驗(yàn)裝置研究出了迄今為止所見爆炸力最強(qiáng)的高能物質(zhì)(原子彈除外)：五氮正離子，被C&E News譽(yù)為該年度全球五大化學(xué)發(fā)現(xiàn)之一。 Karl O. ChristeDavid OHaganFLUORINATOR X-ray structure of one of the fluorinase enzymes two trimers with three bound S-adenosyl-L-methionine substrate molecules. The enzyme

50、uses inorganic fluoride to convert the moleculesto 5-fluoro-5-deoxyadenosine.BIOCHEMICAL FLUORINE The biosynthetic pathway to fluoroacetate and 4-fluorothreonine in the bacterium S. cattleya involves a fluorinase-catalyzed CF bond formation in the first step shown here. The intermediate metabolites

51、shown have been identified, but in some cases (indicated by dashed arrows) the enzymes involved remain to be isolated.Bruce E. SmartFluorine Chemistrys Uncharted TerritoryCoordination 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 electr