| Project/Area Number |
04650762
|
|---|
| Research Category |
Grant-in-Aid for General Scientific Research (C)
|
| Allocation Type | Single-year Grants |
|---|
| Research Field |
有機工業化学
|
|---|
| Research Institution | Faculty of Science and Engineering, Kinki University |
|---|
Principal Investigator |
MATSUBARA Yoshio Faculty of Science and Engineering, Kinki University, Associate Professor, 理工学部, 助教授 (80088450)
|
|---|
| Project Period (FY) |
1992 – 1993
|
| Project Status |
Completed (Fiscal Year 1993)
|
| Budget Amount *help |
¥1,300,000 (Direct Cost: ¥1,300,000)
Fiscal Year 1993: ¥600,000 (Direct Cost: ¥600,000)
Fiscal Year 1992: ¥700,000 (Direct Cost: ¥700,000)
|
|---|
| Keywords | Catalytic synthesis / Allyl derivatives / Copper(I) Complexies / Enzymimic Function / Heterogeneous catalytic reaction Polymer supported copper(I) / Optical Active 1-Buten-3-ol / Asymmetric Hydroxylation Catalyst / 二酸化炭素固定 / アスコルビン酸 / アリルハライド / 水酸化反応 / pi-アリル銅ハライド |
|---|
| Research Abstract |
This study was investigated on the catalytic synthesis of allyl derivatives using copper(I) complexies having enzymimic function.
Heterogeneous catalytic reactions of allyl cholrides(1-chloro-2-propene, 1-chloro-2-butene, 3-chloro-1-butene, and cinnamyl chloride) were carried out with ascorbic acid polymer(poly(methyl methacrylate), polyacrylonitrile, ion exchange resin and chelate resin)-supported copper(I) as a polymeric catalyst(having enzymimic function)in the presence of corresponding nucleophiles under an argon atmosphere at 30ﾟC.These catalytic systems showed very high activity and the reactions proceed easily to give the corresponding allyl derivatives with catalytic amount of polymer-supported Cu(I) and ascorbic acid(1/100 mol based on subsurate)as compared with that in the absence of the polymeric supports. And also heterogeneous asymmetric hydroxylation of 1-chloro-2-butene was carried out with ascorbic acid and optical active polymers such as poly(l-menthyl methacrylate)(PMnMA) and poly((-)-bornyl methacrylate)(PBoMA) which supported coppre(I) as an asymmetric polymer catalyst in aqueous acetone at pH 4.0 under an argon atmosphere at 30ﾟC, and to give optical active 1-buten-3-ol. The polymeric cactalyst systems showed fairly high asymmetric induce as compared with that in the absence of the polymeric supports. This phenomenon was explained in terms of an increase stabilized interaction between reaction substrate and optical active ligand by the hydrophobic micro atmosphere on the surface of the polymeric support and also of the via pi-allyl copper chloride intermediate formation.
These background informations indicate a high utility method for synthesis of allyl derivatives on chemical industrially process.
|
