2000 Fiscal Year Final Research Report Summary
Clarification of Reaction Routes and Synthetic Application regarding Specific Decarbonylative α-Arylation of Carboxylic Acids in Acidic Media
| Project/Area Number |
11640599
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| Research Category |
Grant-in-Aid for Scientific Research (C)
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| Allocation Type | Single-year Grants |
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| Section | 一般 |
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| Research Field |
物質変換
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| Research Institution | Tokyo University of Agriculture and Technology |
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Principal Investigator |
YONEZAWA Noriyuki Tokyo University of Agriculture & Technology. Department of Organic and Polymer Materials Chemistry, Associate Professor, 工学部, 助教授 (10167033)
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| Co-Investigator(Kenkyū-buntansha) |
MAEYAMA Katsuya Tokyo University of Agriculture & Technology. Department of Organic and Polymer Materials Chemistry, Research Associate, 工学部, 助手 (20311657)
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| Project Period (FY) |
1999 – 2000
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| Keywords | 2-Alkoxyalkanoic acid / 2-Oxocarboxylic acid / Electrophilic aromatic substitution / Decarbonylation / Decarbonylative arylation / Phosphoric petoxide / Methanesulfonic acid / Trifluoromethanesulfonic acid |
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| Research Abstract |
2-Methoxyalkanoic acids were found to undergo consecutive decarbonylative a, a-diarylation in P2O5-MsOH instead of Friedel-Crafts type arylation on the carbonyl carbon. The influences of the substituents of the arenes and the carboxylic acids in this reaction were elucidated on the basis of the reaction yields. The reaction behavior was found to be primarily governed by the electron-withdrawing/releasing property of the a-substituents on the carboxylic acids as well as the positive species-accepting ability of the arenes. The steric hindrance was shown to participate in determining the reaction feasibility as a secondary factor.
Elucidation of the exact reaction behaviors and clarification of reaction routes including rough reaction mechanism for decarbonylative a-arylation of a-ketocarboxylic acids were also performed. In addition, synthetic reaction of novel conjugated molecules from pyruvic acid was investigated.
Theme 1 : Clarification of structural requirements of carboxylic acid su
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bstrates for decarbonylative a-arylation. -Influence of the form of a-substituents on reaction behavior and steric and electric effects of the substituents on the aromatic ring were elucidated. Furthermore, semi-quantitative estimation of steric and electric effects of the a-alkyl (a-aryl) groups revealed that the reaction behaviors are divided into 4 types according to the feasibility of decarbonylation and the number of arylation. The relation between the type of the reaction and the structure of a-ketocarboxylic acids is clearly interpreted.
Theme 2 : Elucidation of the role of the hetero atoms in condensation mediators. - 2-Methoxypropanoic, methoxyacetic, and methoxyphenylacetic acids were allowed to react with arenes in the presence of phosphorus pentoxide (P2O5), polyphosphoric acid (PPA), methanesulfonic acid mixture (P2O5-MsOH), methanesulfonic acid (MsOH), trifluoromethanesulfonic acid (TfOH), Nafion-H, polyphosphoric acid ethyl ester, or polyphosphoric acid trimethylsilyl ester. As a result, the reaction behavior of decarbonylative a-arylation of a-methoxycarboxylic acids was proved to be strongly dependent on the nature of the acidic mediators. These behaviors were also shown to be characteristic for each mediator. Particularly, the relation between product distribution and the nature of the acidic mediator such as acidity function value evaluated for methoxyacetic acid showed more distinct dependence on the mediator than those of other carboxylic acids. However, general explanation for the whole reaction behavior has not been clarified yet.
Theme 3 : Determination of reaction routes and mechanism based on the model reaction of the intermediate candidates. - Clarification of the reaction route has been performed for the reaction of 2- methoxypropanoic acid. Contrarily, investigation on that for methoxyacetic acid revealed that the reaction propagates with different ways from those observed in the reaction of other a-methoxycarboxylic acids. In the reaction of methoxyacetic acid with TfOH, Friedel-Crafts acylation type reaction followed by rearrangement concurrently was observed to propagate along with decarbonylative a-arylation. Less
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Research Products
(10 results)
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[Publications] Yonezawa,N.,Hino,T.,Kinuno,T.,Matsuki,T.,Ikeda,T.: "ACID-MEDIATED SPECIFIC α,α-DIARYLATION AND α-MONOARYLATION REACTIONS OF PYRUVIC ACID WITH/WITHOUT DECARBONYLATION"Synth.Commun.. 29. 168-1695 (1999)
Description
「研究成果報告書概要(和文)」より
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[Publications] Yonezawa,N.,Hino,T.,Shimizu,M.,Matsuda,K.,Ikeda,T.,: "Reaction Routes of the Decarbonylative α,α-Diarylation of 2-Methoxypropanoic Acid and Related Compounds"J.Org.Chem.. 64. 4179-4182 (1999)
Description
「研究成果報告書概要(和文)」より
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[Publications] Yonezawa,N.,Hino,T.,Matsuda,K.,Matsuki,T.,Narushima,D.,Kobayashi,M.,Ikeda,T.: "Specific and Chemoselective Multi-α-Arylation Reaction of Benzoylformic Acid with/without Decarbonylation in P_2O_5-MsOH and Related Acidic Media."J.Org.Chem.. 65. 941-944 (2000)
Description
「研究成果報告書概要(和文)」より
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