2005 Fiscal Year Final Research Report Summary
Development of a New Catalytic System for the Carbon Radical Generation and Its Application to Organic Syntheses.
| Project/Area Number |
13853008
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| Research Category |
Grant-in-Aid for Scientific Research (S)
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| Allocation Type | Single-year Grants |
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| Research Field |
有機工業化学
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| Research Institution | Kansai University |
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Principal Investigator |
ISHII Yasutaka Kansai University, Faculty of Engineering, Professor, 工学部, 教授 (50067675)
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| Co-Investigator(Kenkyū-buntansha) |
SAKAGUCHI Satoshi Kansai University, Faculty of Engineering, Lecturer, 工学部, 専任講師 (50278602)
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| Project Period (FY) |
2001 – 2005
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| Keywords | N-hydroxyphthalimide / molecular oxygen / catalysis / oxidation / hydrocarbon / alkyl radical / hydroperoxide / green chemistry |
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| Research Abstract |
The achievement of highly efficient and selective transformations of hydrocarbons to useful chemical substances is an ambitious goal in synthetic chemistry. It is interesting to open up a new vista in organic synthesis and to confirm the catalytic method for the carbon radical generation from a C-H bond of a wide variety of compounds by the use of N-hydroxyphthalimide (NHPI) which serves as a carbon radical producing catalyst (CRPC). By employing NHPI as the catalyst, a novel aerobic oxidation of alkanes, which surpasses the conventional autoxidations in conversion and selectivity, has been achieved under mild conditions. This oxidation method provides entry to a diverse array of significant oxygen-containing compounds. In particular, a success in the direct conversion of cyclohexane to adipic acid with dioxygen in high conversion and selectivity has greatly benefited the chemical industry as an environmentally benign process, because the current production of adipic acid via nitric acid oxidation causes the evolution of nitrogen oxides that are serious air-polluting materials. In addition, the NHPI catalyzes the aerobic oxidation of alkylbenzenes, thus various carboxylic acids were efficiently synthesized by this method. Caprolactone and caprolactam precursors were obtained through generation of alpha-hydroxyperoxides from KA-oil without formation of any wastes. This new methodology is applicable to the functionalization of alkanes to afford nitroalkanes by allowing them to react with NO_2. Finally, a new type of reaction for the concomitant introduction of alkanes and O_2 to alkenes, which is referred to as catalytic oxyalkylation of alkenes, has been established. α-Hydroxy-γ-lactones, which are very difficult to synthesize by conventional methods, are easily prepared by the reaction of alcohols, alkenes and O_2 under the influence of the NHPI catalyst. The NHPI can be used as a polarity-reversal catalyst for hydroacylation of alkenes with aldehydes.
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Research Products
(106 results)
