|
The Martinet dioxindole synthesis was first reported in 1913 by J. Marinet. It is a chemical reaction in which a primary or secondary aniline or substituted aromatic amine is condensed with ethyl or methyl ester of mesoxalic acid to make a dioxindole in the absence of oxygen. center ==Proposed mechanism== center In the first step, the amino group on the aniline (1) attacks the carbonyl of the ethyl oxomalonate (2). A proton from the nitrogen is extracted by the oxygen and an alcohol group forms (3). The carbonyl re-forms to make a keto group and an ethanol molecule leaves (4). Next, a ring closing reaction occurs by the bond from the aromatic benzene ring attacking the partially positive carbonyl to form a five-member ring (5). After a proton transfer (6), an isomerization or a () hydride shift occurs and aromaticity is restored to the six-membered ring (7). In the presence of base, the ester is hydrolyzed, ethanol is lost (8) and a decarboxylation occurs (9). The resulting product is the desired dioxindole (10). 〔Wang, Z. (2009) ''Comprehensive Organic Name Reactions and Reagents II''. John Wiley and Sons, Inc.: Hoboken, NJ, p. 1839, ISBN 0471704504.〕 In the presence of oxygen, dioxindole converts to isatin through oxidation.〔 center 抄文引用元・出典: フリー百科事典『 ウィキペディア（Wikipedia）』 ■ウィキペディアで「Martinet dioxindole synthesis」の詳細全文を読む スポンサード リンク
|
