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Published on: January 19, 2016
Michael-type addition of azoles of broad-scale acidity to methyl acrylate
Sławomir Boncel1, Kinga Saletra, Barbara Hefczyc
1Silesian University of Technology, Department of Organic Chemistry, Bioorganic Chemistry and Biotechnology, Krzywoustego 4, 44-100 Gliwice, Poland, Tel.: +48 32 237 1792.
Abstract:
An optimisation of Michael-type addition of azole derivatives of broad-scale acidity - ranging from 5.20 to 15.00 pK(a) units - namely 4-nitropyrazole, 3,5-dimethyl-4-nitropyrazole, 4(5)-nitroimidazole, 4,5-diphenylimidazole, 4,5-dicyanoimidazole, 2-methyl-4(5)-nitroimidazole, 5(4)-bromo-2-methyl-4(5)-nitroimidazole and 3-nitro-1,2,4-triazole to methyl acrylate as an acceptor was carried out. The optimisation process involved the use of an appropriate basic catalyst (DBU, DIPEA, NaOH, NaH, TEDA), a donor/base/acceptor ratio and the reaction temperature. The reactions were performed in DMF as solvent. Target Michael adducts were obtained in medium to excellent yields. Importantly, for imidazole and 1,2,4-triazole derivatives, no corresponding regioisomers were obtained.
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