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Mechanistic investigation and DFT calculation of the new reaction between S-methylisothiosemicarbazide and methyl acetoacetate |
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| Authors: | Violeta Markovi? Svetlana Markovi? Ana Jani?ijevi? Marko V Rodi? Vukadin M Leovac Nina Todorovi? Sne?ana Trifunovi? Milan D Joksovi? |
| Institution: | 1. Department of Chemistry, Faculty of Science, University of Kragujevac, R. Domanovica 12, 34000, Kragujevac, Serbia 2. Department of Chemistry Biochemistry and Environmental Protection, Faculty of Science, University of Novi Sad, Trg D. Obradovi?a 3, 21000, Novi Sad, Serbia 3. Institute for Chemistry, Technology and Metallurgy, Njego?eva 12, 11000, Belgrade, Serbia 4. Faculty of Chemistry, University of Belgrade, Studentski trg 16, P.O. Box 158, 11000, Belgrade, Serbia |
| Abstract: | A study on the synthesis and mechanistical aspects of formation of 3-methyl-5-oxo-3-pyrazolin-1-carboxamide (MOPC) starting from S-methylisothiosemicarbazide hydrogen iodide and methyl acetoacetate was performed. In the alkaline aqueous solution, the intermediate methyl acetoacetate S-methylisothiosemicarbazone undergoes substitution of CH3S? anion by hydroxide anion, cyclization, carbanion formation, and elimination of methanol, thus yielding corresponding Na-enolate salt of pyrazol-5-one derivative. The structure of the compound obtained after protonation of the formed enolate salt was determined by means of spectroscopic techniques and single-crystal X-ray diffraction analysis. The mechanism of conversion of methyl acetoacetate S-methylisothiosemicarbazone into MOPC was investigated by means of the B3LYP functional, and it was found that the reaction is thermodynamically controlled. |
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