| Project/Area Number |
05555239
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| Research Category |
Grant-in-Aid for Developmental Scientific Research (B)
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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 | Osaka University |
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Principal Investigator |
IKADA Isao Osaka University, Faculty of Engineering, Professor, 工学部, 教授 (70029049)
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| Co-Investigator(Kenkyū-buntansha) |
NOSE Shinji Daiso Co.&Ltd., Vicepresident, 取締役副社長, 研究員
HIRAO Toshikazu Osaka University, Faculty of Engineering, Professor, 工学部, 教授 (90116088)
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| Project Period (FY) |
1993 – 1994
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| Project Status |
Completed (Fiscal Year 1994)
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| Budget Amount *help |
¥8,200,000 (Direct Cost: ¥8,200,000)
Fiscal Year 1994: ¥800,000 (Direct Cost: ¥800,000)
Fiscal Year 1993: ¥7,400,000 (Direct Cost: ¥7,400,000)
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| Keywords | Acetonylation / Acetonylidenation / Palladium Catalyst / pi-Allyl Complex / Metalacyclobutanone / Cycloaddition / アセトニル化試剤 / α-フロロメチルエーテル / アセタール化合物 / エピクロロヒドリン / X線結晶解析 / オキソジメチレンメタン / [1+2]付加環化 |
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| Research Abstract |
Acetonylation and acetonylidenation are the very important reactions in organic synthetic reaction. By these reactions, a substituent of a 3-carbon chain having reactive sites including a carbonyl group is introduced, giving a chance to further versatile derivatization. In some cases of agricultual chemicals or medicines, the emergence or improvement of phamacological reactivity may be obtained by introduction of these substituents. Many kinds of reagents for these purposes have been developed. In the present research, 2-chloromethyl-3,5-dioxahex-1-ene, which can be synthesized from epichlorohydrin in high yield by a 2-step process, was developed for derivatizing with ease to acetonylation products in high yield. 3-Chloro-2- (2-pyranyloxy) propylene (1) and 3-chloro-2-(1-alkyloxyethyloxy)-propylene (2) were also developed for the purpose of acetonylation and acetonylidenation, in which cases the deprotection of acetal group in the intermediate can proceed only with a catalyc amount acid in non-aqueous solution. Alkyl carbonyl derivatives of 1 and 2 afforded metalacyclobutanones by only mixing with palladium (0) or platinum (0). By using this reaction, acetonylidenation of strained olefins such as norbornadiene with these carbonyl derivatives occurred in the presence of catalytic amount of palladium to offer cyclopropane derivatives.
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