金属有机课件Class No. 1

基于金属有机化学的化学工艺
(1) 钯催化的从乙烯出发合成乙醛(Wacker process) (2) Ziegler-Natta催化剂催化烯烃聚合; (3) Rh催化的烯烃氢化； (4) 美国孟山都公司Rh催化从MeOH和CO出发制备醋酸的工艺 (5) 联合碳化公司的Rh催化的氢甲酰化生产醛的工艺; (6) 孟山都公司从合成气出发合成乙二醇的生产流程； (7) DuPont公司的尼龙-66前体合成工艺； (8) BASF、Rohm & Haas公司的丙烯酸酯生产工艺; (9) 日本高沙香料公司的薄荷醇的不对称合成 (10) 金属催化的不对称合成技术在药物合成工业的实际应用
为演示该理论，几位评委挑起了交换 舞伴的舞蹈
All life on Earth is based on these carbon compounds, but they can also be produced artificially through organic synthesis. The word metathesis means 'change-places'. In metathesis reactions, double bonds are broken and made between carbon atoms in ways that cause atom groups to change places. This happens with the assistance of special catalyst molecules. Metathesis can be compared to a dance in which the couples change partners.
2004年5月17日－19日，Grubbs作了题为“The Synthesis of Large and Small Molecules Using Olefin Metathesis”的报告
Metathesis – a change-your-partners dance
This year's Nobel Prize Laureates in chemistry have made metathesis into one of organic chemistry's most important reactions. Fantastic opportunities have been created for producing many new molecules – pharmaceuticals, for example. Imagination will soon be the only limit to what molecules can be built! Organic substances contain the element carbon. Carbon atoms can form long chains and rings, bind other elements such as hydrogen and oxygen, form double bonds, etc.
(6) The Nobel Prize in Chemistry 2001 "for their work on chirally catalysed hydrogenation reactions" William S. Knowles Ryoji Noyori St. Louis, MO, USA Nagoya University, Chikusa, Nagoya, Japan
在宣布仪式上，诺贝尔化学奖评委会主席佩尔 · 阿尔伯格 将烯烃复分解反应描述为“交换舞伴的舞蹈”。他亲 自走出讲台，邀请身边的皇家科学院教授和两位女工 作人员一起在会场中央为大家表演烯烃复分解反应的 含义。最初两位男士是一对舞伴，两位女士是一对舞 伴，在“加催化剂”的喊声中，他们交叉换位，转换 为两对男女舞伴，在场记者随即发出了笑声。
French chemist in full François-Auguste-Victor Grignard born May 6, 1871, Cherbourg, France died Dec. 13, 1935, Lyon French chemist and corecipient, with Paul Sabatier, of the 1912 Nobel Prize for Chemistry for his developmnet of the Grignard reaction. This work in organomagnesium compounds opened a broad area of organic synthesis. In 1898, while a student under Philippe Barbier at Lyon, Grignard began his prizewinning work with a study of the alkylzinc compounds developed earlier by Sir Edward Frankland. It was Barbier who had Grignard repeat some experiments on the preparation of a tertiary alcohol from a mixture of methyl heptyl ketone, magnesium, and methyl iodide. Grignard hit upon the idea of treating the iodide with the magnesium first and carried out the reaction in ether. This first of the Grignard reagents was a complete success. Grignard’s doctoral dissertation (1901) described the preparation of alcohols, acids, and hydrocarbons by means of reactions of organomagnesium compounds. He became a professor of chemistry at Nancy (1910) and at Lyon (1919). At the time of his death some 6,000 papers reporting applications of the Grignard reaction had been published.
1. Nickel oxide is reacted with Syngas at 200 °C to remove oxygen, leaving impure nickel. Impurities include iron and cobalt. NiO (s) + H2 (g) → Ni (s) + H2O (g) 2. The impure nickel is reacted with excess carbon monoxide at 50 - 60 °C to form nickel carbonyl. Ni (s) + 4 CO (g) → Ni(CO)4 (g) 3. The mixture of excess carbon monoxide and nickel carbonyl is heated to 220 - 250 °C. On heating, tetracarbonyl nickel decomposes to give nickel: Ni(CO)4 (g) → Ni (s) + 4 CO (g)
有机合成化学
C－C键的形成和断裂 C－X键的形成和断裂 导向有机合 成的金属 有机化学 金属 中间体 生成 金属中间体 相互转化 金属 中间体 淬灭
金 属 有 机 化 学
C－M (H－M) 键的形成
C－M (H－M) 键的断裂
金属有机化合物 的合成与表征
第一章 Introduction
# 1760 Cradle of organometallic chemistry Paris military pharmacy
www.nobel.se 1917 1938 "for his work on chirally catalysed oxidation reactions" K. Barry Sharpless 1941 The Scripps Research Institute La Jolla, CA, USA
<<金属参与的现代有机合成反应>> 广东科技出版社, 第二版, 2003
无机化学
有机化学
金属有机
Fra Baidu bibliotek
碳（氢)－金属键的形成和反应
金属元素占所有元素的约80％ 诺贝尔化学奖 (1) 1912年 V. Grignard (2) 1963年 Ziegler和Natta (3) 1973年 E. O. Fisher和G. Wilkinson (the chemistry of sandwich compounds) (4) 1976年 W. N. Lipscomb (5) 1979年 H. C. Brown 和 G. Wittig
# 1899 P. Barbier
H3C O H3C CH3
1. CH3I/Mg 2. H2O
H3C OH H3 C H 3C CH3
Barbier’s student: V. Grignard (starting from 1900-) (1912 Nobel prize)
Victor Grignard
(7) The Nobel Prize in Chemistry 2005
In 1971 Yves Chauvin was able to explain in detail how metatheses reactions function and what types of metal compound act as catalysts in the reactions. Now the "recipe" was known. The next step was, if possible, to develop the actual catalysts. Richard Schrock was the first to produce an efficient metal-compound catalyst for methasesis. This was in 1990. Two years later Robert Grubbs developed an even better catalyst, stable in air, that has found many applications. Metathesis is used daily in the chemical industry, mainly in the development of pharmaceuticals and of advanced plastic materials.
金属有机化学
--------- 金属参与的现代有机合成反应
王
磊
淮北师范大学
Definition of this course: C(H)-Metal bond is formed during/or after the reaction. Main Textbook: Prof. Ma Shengming (SIOC, AC, CN)
Dr Ludwig Mond (March 7, 1839 — December 11,
1909), was a German-born chemist and industrialist who took British nationality.
Mond discovered nickel carbonyl, a previously unknown compound, which could be easily decomposed to produce pure nickel from its ores through the Mond process:
# 1849 Frankland:
3 EtI + 3 Zn Et2Zn + EtZnI + ZnI2
Skill for the manipulation of air-sensitive compounds. He的发现者：searching for radical The most successful failure! # 1890 L. Mond: Ni(CO)4: used in a commercial process for refining nickel.
# 1827 Zeise (丹麦药剂师) Zeise’s salt: K[PtCl3C2H4] First olefin complex （乙醇＋氯铂酸盐）
(Wö hler 1828年合成尿素; 门及列夫1869年元素周期表)
Liebig: 空想！1868年：Birnbaum证实
Liebig是谁？ 蒸馏器的发明人 Justius Liebig’s Annalen 创始人 有机化学发展之父