Potassium permanganate/ carboxylic acid/ organic solvent: a powerful reagent for c-c bond formation, aryl coupling reactions and enone oxidation ipso-nitration of arylboronic acids with silver nitrite/ tmscl

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2009

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Fındık, Hamide

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The first part of the thesis presents the KMnO4/ carboxylic acid/ organic solvent which is a powerful reagent for C-C bond formation, aryl coupling reactions and enone oxidation. The a¢-acetoxylation of enones and the a-acetoxylation of aromatic ketones were carried out with potassium permanganate and acetic acid, in which acetoxylation products were obtained in 74-96% yields. The same reaction was carried out with carboxylic acids other than acetic acid, which furnished corresponding acyloxy ketones with the same regioselectivity. For the first time, formyloxylation products were synthesized in a 61-85% yield by using formic acid. The potassium permanganate and acetic acid method was also used for aryl coupling reactions. The reaction of arylboronic acids and aryl hydrazines in benzene with potassium permanganate and acetic acid in turn furnished biaryls in a 85-96% yield. We showed that potassium permanganate/carboxylic acid/organic solvent behaves as manganese(III) acetate. In the second part of the thesis, ipso-nitration of arylboronic acids with AgNO2/ TMSCl was performed. Nitration of aromatic compounds is one of the most extensively studied reactions, and nitroaryl moieties play key roles in the physical and chemical properties of many target molecules in organic synthesis. For electrophilic nitration of aromatic compounds, a wide variety of reagents are available to date. Most of them are very strong nitrating agents and often lead to further nitration and mixture of isomers. Since most nitrating agents are oxidants, oxidation of other functional groups can also occur, giving a mixture of products. Thus, a search for milder and selective nitrating agents is a good research goal. In this work, we aimed to apply AgNO2/ TMSCl system to ipso nitration of arylboronic acids.

Subject Keywords

Chemistry, Organic, Dihydrofurane derivative.

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http://etd.lib.metu.edu.tr/upload/12610472/index.pdf
https://hdl.handle.net/11511/18503

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Graduate School of Natural and Applied Sciences, Thesis

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Citation Formats

H. Fındık, “Potassium permanganate/ carboxylic acid/ organic solvent: a powerful reagent for c-c bond formation, aryl coupling reactions and enone oxidation ipso-nitration of arylboronic acids with silver nitrite/ tmscl,” Ph.D. - Doctoral Program, Middle East Technical University, 2009.