| Project/Area Number |
05650882
|
|---|
| Research Category |
Grant-in-Aid for General Scientific Research (C)
|
| Allocation Type | Single-year Grants |
|---|
| Research Field |
Synthetic chemistry
|
|---|
| Research Institution | Tottori University |
|---|
Principal Investigator |
OKANO Tamon Tottori University, Dpartment of Materials Science, Associate Professor, 工学部, 助教授 (20112104)
|
|---|
| Co-Investigator(Kenkyū-buntansha) |
KIJI Jitsuo Tottori University, Dpartment of Materials Science, Professor, 工学部, 教授 (60026002)
|
|---|
| Project Period (FY) |
1993 – 1994
|
| Project Status |
Completed (Fiscal Year 1994)
|
| Budget Amount *help |
¥1,800,000 (Direct Cost: ¥1,800,000)
Fiscal Year 1994: ¥400,000 (Direct Cost: ¥400,000)
Fiscal Year 1993: ¥1,400,000 (Direct Cost: ¥1,400,000)
|
|---|
| Keywords | Lanthanoid tri-2-propoxides / Ester interchangereaction / Acetalizatior / Ester exchange reaction / Lanthanoid trisulfonates / Michael addition / Aldol reaction / Robinson annellation / ランタノイドアルコキシド / ラクトン / ランタノイドトリトリフラート / オルソ蟻酸エステル |
|---|
| Research Abstract |
Lanthanoid tri-z-propoxides acted as catalysts for the ester interchange and esteralcohol exchange reaction under mind conditions. The catalytic activity of the lanthanoid catalysts was higher than those of aluminum and titanium alkoxides which are commonly used for these reactions. In these reactions, primary and secondary alcohols and their esters gave the desired esters in high yields. These reactions also exhibited high applicability to the esters having a long alky1 chain. However, the reactivity of the esters of tertiary alcohols was poor under these conditions. The ester exchange reaction was applicable to the ring-opening polymerization of 6-hexanolide which gave the polymer having high Mn and narrow Mw/Mn values.
Lanthanoid tri-2-propoxides also catalyzed the acetalization of carbony1 compounds with methy1 orthoformate. In this reaction however, lanthanoid trisulfonates were superior to the alkoxides in catalyticactivity. The acetalizationin the presence of the sulfonates was very fast and gave the acetals of various ketones and aldehydes in excellent yields.
The Michael reaction of alpha, beta-unsaturated aldehyde with ketones was unsuccessful but gave the corresponding aldol condensation products. The reaction of alpha, beta-unsaturated ketones gave Robinson adducts which were formed via Michael reaction and then aldol condensation. Though these reactions were not catalytic, the use of stoichiometric amounts of 2-propxides resulted in high yields.
Lanthanoid tri-2-propoxides were efficient catalysts for the aldol reaction of aldehydes and ketones. The reaction of cyclic ketones gave the condensation products in high yields, while that of noncyclic ketones produced the products in poor yields. The reaction of aldehydes formed beta-hydoxy aldehydes in good yields, whereas the reaction in 2-propanol at elevated temperatures formed 1,3-diol which were produced from Meerwein-Ponndorf-Verleyreduction of the aldols with 2-propanol as hydrogen donor.
|
