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Nobel化学奖(1911-2000:合成有机化学)

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2012/12/19 4:28:46LV.排长

http://www.nobel.se/chemistry/articles/malmstrom/index.html

The Nobel Prize in Chemistry:
The Development of Modern Chemistry
by Bo G. Malmstr?m
First published December 1999


3.8. Preparative Organic Chemistry 
One of the chief goals of the organic chemist is to be able to synthesize 
increasingly complex compounds of carbon in combination with various other 
elements, such as hydrogen, oxygen, nitrogen, sulfur and phosphorus. The 
first Nobel Prize for Chemistry recognizing pioneering work in preparative 
organic chemistry was that to Victor Grignard (1871-1935) in Nancy and 
Paul Sabatier (1854-1941) from Toulouse in 1912. Grignard had discovered 
that organic halides can form compounds with magnesium. These compounds, 
now generally called Grignard reagents, are very reactive, and they are 
consequently widely used for synthetic purposes. Sabatier was given the 
prize for developing a method to hydrogenate organic compounds in the 
presence of metallic catalysts. With his method oils can be converted to 
saturated fats, and it is, for example, used for margarine production and 
other industrial processes.

The prize in 1950 was presented to Otto Diels (1876-1954) from Kiel and 
Kurt Alder (1902-1958) from Cologne "for their discovery and development 
of the diene synthesis", also called the Diels-Alder reaction. In this 
reaction, which was developed already in 1928, organic compounds 
containing two double bonds ("dienes") can effect the syntheses of many 
cyclic organic substances. During the decades following the original work 
several industrial applications of the Diels-Alder reaction have been 
found, for example, in the production of plastics, which may explain the 
lateness of the prize.

The German organic chemist Hans Fischer (1881-1945) from Munich had 
already done significant work on the structure of hemin, the organic 
pigment in hemoglobin, when he synthesized it from simpler organic 
molecules in 1928. He also contributed much to the elucidation of the 
structure of chlorophyll, and for these important achievements he was 
awarded the Nobel Prize for Chemistry in 1930 (cf. Section 3.5). He 
finished his determination of the structure of chlorophyll in 1935, and by 
the time of his death he had almost completed its synthesis as well.

Robert Burns Woodward (1917-1979) from Harvard is rightly considered the 
founder of the most advanced, modern art of organic synthesis. He designed 
methods for the total synthesis of a large number of complicated natural 
products, for example, cholesterol, chlorophyll and vitamin B12. He 
received the Nobel Prize for Chemistry in 1965, and he would probably have 
received a second chemistry prize in 1981 for his part in the formulation 
of the Woodward-Hoffmann rules (see Section 3.4), had it not been for his 
early death. Work in synthetic organic chemistry was also recognized in 
1979 with the prize to Herbert C. Brown (1912- ) of Purdue University and 
Georg Wittig (1897-1987) from Heidelberg, who had developed the use of 
boron- and phosphorus-containing compounds, respectively, into important 
reagents in organic synthesis. Another master in chemical synthesis is 
Elias James Corey (1928- ) from Harvard, who received the prize in 1990. 
He had made a brilliant analysis of the theory of organic synthesis, which 
permitted him to synthesize biologically active compounds of a complexity 
earlier considered impossible.

The Nobel Prize for Chemistry in 1984 was given to Robert Bruce Merrifield 
(1921- ) of Rockefeller University "for his development of methodology for 
chemical synthesis on a solid matrix". Specifically, Merrifield applied 
this ingenious idea to the synthesis of large peptides and small proteins, 
for example, ribonuclease (cf. Section 3.12), but the principle has later 
also been applied to nucleic acid chemistry. In earlier methods each 
intermediate in the synthesis had to be isolated, which resulted in a 
drastic drop in yield in syntheses involving a large number of consecutive 
steps. In Merrifield's method these isolation steps are replaced by a 
simple washing procedure, which removes by-products as well as remaining 
starting materials, and in this way substantial losses are avoided.

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