Mechanistic investigation and DFT calculation of the new reaction between S-methylisothiosemicarbazide and methyl acetoacetate
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2013
Authors
Markovic, VioletaMarković, Svetlana
Janicijevic, Ana
Rodić, Marko V.
Leovac, Vukadin
Todorović, Nina
Trifunović, Snežana
Joksovic, Milan D.
Article (Published version)
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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.
Keywords:
Pyrazolone / Reaction mechanism / DFT / Thermodynamic and kinetic controlSource:
Structural Chemistry, 2013, 24, 6, 2127-2136Publisher:
- Springer/Plenum Publishers, New York
Funding / projects:
- Synthesis, modeling, physicochemical and biological properties of organic compounds and related metal complexes (RS-MESTD-Basic Research (BR or ON)-172016)
DOI: 10.1007/s11224-013-0223-3
ISSN: 1040-0400
WoS: 000328326800034
Scopus: 2-s2.0-84889098809
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IHTMTY - JOUR AU - Markovic, Violeta AU - Marković, Svetlana AU - Janicijevic, Ana AU - Rodić, Marko V. AU - Leovac, Vukadin AU - Todorović, Nina AU - Trifunović, Snežana AU - Joksovic, Milan D. PY - 2013 UR - https://cer.ihtm.bg.ac.rs/handle/123456789/1225 AB - 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. PB - Springer/Plenum Publishers, New York T2 - Structural Chemistry T1 - Mechanistic investigation and DFT calculation of the new reaction between S-methylisothiosemicarbazide and methyl acetoacetate VL - 24 IS - 6 SP - 2127 EP - 2136 DO - 10.1007/s11224-013-0223-3 ER -
@article{ author = "Markovic, Violeta and Marković, Svetlana and Janicijevic, Ana and Rodić, Marko V. and Leovac, Vukadin and Todorović, Nina and Trifunović, Snežana and Joksovic, Milan D.", year = "2013", 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.", publisher = "Springer/Plenum Publishers, New York", journal = "Structural Chemistry", title = "Mechanistic investigation and DFT calculation of the new reaction between S-methylisothiosemicarbazide and methyl acetoacetate", volume = "24", number = "6", pages = "2127-2136", doi = "10.1007/s11224-013-0223-3" }
Markovic, V., Marković, S., Janicijevic, A., Rodić, M. V., Leovac, V., Todorović, N., Trifunović, S.,& Joksovic, M. D.. (2013). Mechanistic investigation and DFT calculation of the new reaction between S-methylisothiosemicarbazide and methyl acetoacetate. in Structural Chemistry Springer/Plenum Publishers, New York., 24(6), 2127-2136. https://doi.org/10.1007/s11224-013-0223-3
Markovic V, Marković S, Janicijevic A, Rodić MV, Leovac V, Todorović N, Trifunović S, Joksovic MD. Mechanistic investigation and DFT calculation of the new reaction between S-methylisothiosemicarbazide and methyl acetoacetate. in Structural Chemistry. 2013;24(6):2127-2136. doi:10.1007/s11224-013-0223-3 .
Markovic, Violeta, Marković, Svetlana, Janicijevic, Ana, Rodić, Marko V., Leovac, Vukadin, Todorović, Nina, Trifunović, Snežana, Joksovic, Milan D., "Mechanistic investigation and DFT calculation of the new reaction between S-methylisothiosemicarbazide and methyl acetoacetate" in Structural Chemistry, 24, no. 6 (2013):2127-2136, https://doi.org/10.1007/s11224-013-0223-3 . .