有机化学双语版++organometallics.ppt

What' s Organometallic Compounds?,A carbon-metal bond,Sodium acetylide,Sodium ethoxide,The natures of C－M bonds,The electronegativity of the metal,Depend on,Carbanions (负碳离子),10.2 Preparation of Organolithium and Organomagnesium compounds,Alkyl halide,Tetrahydrofuran THF (四氢呋喃),Anhydrous!,Butyl bromide,Butyllithium (80% -90%),Diethyl ether Et2O,Grignard reagents: Alkylmagnesium Halides,Phenyl bromide,Characteristics of the reactions: Alkyl groups: 1°, 2 °, 3 ° alkyl, cycloalkyl alkenyl, aryl,2. Reactivity:,4. Exothermic,3. Without substitutes:,V. Grignard and P. Sabatier 1912 Nobel Prize,Alkyl Alkenyl or Aryl RI RBr RCl RF,Phenylmagnesium Bromide (95%),P223,7.4 Ch.P185(3),Grignard found that, in the presence of ether, magnesium reacts with alkyl and aryl halides at room temperature to form organo- magnesium compounds. These solutions,called “Grignard reagents“ react with most functional groups in a synthetically useful way. For this discovery, tremendously useful in laboratory and industrial synthesis, he was awarded the 1912 Nobel Prize in Chemistry(shared with Paul Sabatier,discoverer of catalytic hydrogenation).,François Auguste Victor Grignard,1871-1935,http://www.nobel.se/chemistry/laureates/1912/grignard-bio.html,Acidity of hydrocarbon:,,The stronger the acid is, the weaker the conjugate base is.,10.3 Carbanions as Brøsted bases:,Basicity of anions:,Carey(4th): 547,Organolithium compounds and Grignard reagents as base:,R－M reacts with much weaker acid than H2O,Ch. P186,10.4.1 Synthesis of alcohols using Grignard reagents,Reactions with carbonyl compounds:,Grignard reagents react with Formaldehyde(甲醛 ) — Primary alcohols:,B. Grignard reagents react with higher aldehydes— secondary alcohols:,P296, 9.10,,Example:,Synthesis of Acetylenic alcohols (炔基醇):,C. Grignard reagents react with ketones — Tertiary alcohols:,10.4.2 Retrosynthetic analysis (逆合成分析),Target Molecule,,Precursors,n-BuMgX + CH3COCH3,,,,n-BuBr + Mg,,Elias James Corey 1928-,which changed the way organic chemists undertake the synthesis of complex natural products, the synthesis of longifolene, maytansine, the ginkolides, prostaglandins and leukotrienes, the development of new synthetic methods, particularly using chiral catalysts, and the application of computers to synthesis design are among his most notable achievements. Corey has received many honors, including the Wolf Prize (1986), the National Medal of Science (1988), the Japan Prize in Medicinal Science (1989) and the Nobel Prize in Chemistry (1990). Born in Massachusetts, Corey obtained the Ph.D. at M.I.T. (1951), was on the faculty at the University of Illinois (1951-59) where he became full professor at the early age of 27, and since 1959 he has been professor at Harvard. His research associates (graduate students and postdoctoral fellows) number over 500 and populate the academic and industrial laboratories of Europe, Asia and the Americas.,Professor Corey (to collea- Gues and friends, E.J.) is known for his many spectacular contributions to synthetic organic chemistry. The concept of “retrosynthetic analysis“,,Preparation of lithium dialkylcuprate reagents:,Coupling reactions of Organocoppers with Alkylhalides,Ch.P185 (3),10.4.3 Alkanes synthesis by using organocopper reagents,Characteristics of the reaction:,SN2 reaction The order of the reactivity : CH3 1° 2° 3° I Br Cl F,2. To alkyl halides, R: primary,vinyl and aryl groups. To Lithium dialkylcuprate, R’: primary group or -CH3.,12.44 Ziegle-Natta Catalysis of Alkene Polymerization,Ziegle catalyst: TiCl4-Et2AlCl,Ethylene Ethylene oligomers,Characteristics of the products: Ethylene oligomers with 6-18 carbons High-density,G. Natta’s contributions:,Isotactic polypropylene 等规 (立构) 的聚丙烯,Carey:P567 14.15,Coordination polymerization 配位络合聚合,Polypropylene industry was started,K. Ziegle and G. Natta shared the 1963 Nobel Prize in Chemistry,Problems: Carey(4th)P573,14.15 (b), (d) 14.17 (h), (m), (n) 14.18 (d), (e) 14.19 ((b), (f) 14.20 (d), (e) 14.21 (a)-(c) 14.22 (b), (f), (g) 14.23 14.25 14.26*（选作） 14.27,14.28 (b) 14.29,。