Structure-reactivity correlation for the kinetics of the formation reaction of 4-(substituted phenyl)-1,4-dihydropyridines
Korelacije strukture i reaktivnosti za kinetiku reakcije sinteze supstituisanih 4-fenil-1,4-dihidropiridina
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Quantitative structure-reactivity correlations for the kinetics of the Hantzsch synthesis of 4-(substituted phenyl)-1,4-dihydropyridines in the reaction between ethyl m- and p-substituted 2-benzylideneacetoacetate and the enamine (ethyl 3-aminocrotonate) was studied. The reaction kinetics was followed spectrophotometrically. It was found that the reaction correspond to second-order kinetics. Quantitative structure-reactivity correlations of log k were obtained with the corresponding substituent constants (s, s+, sI and s + ) using the Hammett and extended Hammett equation (dual substituent parameter, DSP, equation). They showed linear relationships with positive values of reaction constants (r). The obtained data were processed by linear regression analysis. It was confirmed that Michael addition of the enamine to benzylidene represented the slow step of the reaction with a high positive charge at the benzylidene molecule. MO calculations were performed and they were in agreement with ...the conclusions derived from the structure-reactivity correlations. .
Proučavan je kvantitativan odnos strukture i reaktivnosti za kinetiku Hančove sinteze supstituisanih 4-fenil-1,4-dihidropiridina u reakciji etil-m- i p-supstituisanih 2-benziliden-acetoacetata i enamina. Kinetika ispitivane reakcije je praćena spektrofotometrijskim metodom. Zapaženo je da je reč o reakciji drugog reda. Kvantitativne korelacije strukture i reaktivnosti koje izražavaju logaritam određene konstante brzine reakcije (log k) u zavisnosti od odgovarajućih konstanti supstituenata (s, s+,sI i s +) određene su za Hametovu (Hammett) i proširenu Hametovu jednačinu (DSP-jednačinu). Pokazale su linearnu zavisnost sa pozitivnim vrednostima nagiba, odnosno reakcione konstante (r). Time je potvrđeno da Majklova (Michael) adicija enamina na benziliden predstavlja spori stupanj u reakciji sa izraženim pozitivnim naelektrisanjem na molekulu benzilidena. MO proračuni su takođe urađeni i njihovi rezultati su bili u skladu sa zaključcima izvedenim iz korelacija strukture i reaktivnosti. .
Кључне речи:
1,4-dihydropyridines / Hantzsch synthesis / Michael addition / Hammet equation / extended Hammett equation / MO calculationsИзвор:
Journal of the Serbian Chemical Society, 2013, 78, 12, 1963-1973Издавач:
- Serbian Chemical Society, Belgrade
Финансирање / пројекти:
- Проучавање синтезе, структуре и активности органских једињења природног и синтетског порекла (RS-MESTD-Basic Research (BR or ON)-172013)
- Рационални дизајн и синтеза биолошки активних и координационих једињења и функционалних материјала, релевантних у (био)нанотехнологији (RS-MESTD-Basic Research (BR or ON)-172035)
Институција/група
Tehnološko-metalurški fakultetTY - JOUR AU - Urošević, Jovica V. AU - Drmanić, Saša AU - Nikolić, Jasmina AU - Juranić, Ivan AU - Jovanović, Bratislav Ž. PY - 2013 UR - http://TechnoRep.tmf.bg.ac.rs/handle/123456789/2347 AB - Quantitative structure-reactivity correlations for the kinetics of the Hantzsch synthesis of 4-(substituted phenyl)-1,4-dihydropyridines in the reaction between ethyl m- and p-substituted 2-benzylideneacetoacetate and the enamine (ethyl 3-aminocrotonate) was studied. The reaction kinetics was followed spectrophotometrically. It was found that the reaction correspond to second-order kinetics. Quantitative structure-reactivity correlations of log k were obtained with the corresponding substituent constants (s, s+, sI and s + ) using the Hammett and extended Hammett equation (dual substituent parameter, DSP, equation). They showed linear relationships with positive values of reaction constants (r). The obtained data were processed by linear regression analysis. It was confirmed that Michael addition of the enamine to benzylidene represented the slow step of the reaction with a high positive charge at the benzylidene molecule. MO calculations were performed and they were in agreement with the conclusions derived from the structure-reactivity correlations. . AB - Proučavan je kvantitativan odnos strukture i reaktivnosti za kinetiku Hančove sinteze supstituisanih 4-fenil-1,4-dihidropiridina u reakciji etil-m- i p-supstituisanih 2-benziliden-acetoacetata i enamina. Kinetika ispitivane reakcije je praćena spektrofotometrijskim metodom. Zapaženo je da je reč o reakciji drugog reda. Kvantitativne korelacije strukture i reaktivnosti koje izražavaju logaritam određene konstante brzine reakcije (log k) u zavisnosti od odgovarajućih konstanti supstituenata (s, s+,sI i s +) određene su za Hametovu (Hammett) i proširenu Hametovu jednačinu (DSP-jednačinu). Pokazale su linearnu zavisnost sa pozitivnim vrednostima nagiba, odnosno reakcione konstante (r). Time je potvrđeno da Majklova (Michael) adicija enamina na benziliden predstavlja spori stupanj u reakciji sa izraženim pozitivnim naelektrisanjem na molekulu benzilidena. MO proračuni su takođe urađeni i njihovi rezultati su bili u skladu sa zaključcima izvedenim iz korelacija strukture i reaktivnosti. . PB - Serbian Chemical Society, Belgrade T2 - Journal of the Serbian Chemical Society T1 - Structure-reactivity correlation for the kinetics of the formation reaction of 4-(substituted phenyl)-1,4-dihydropyridines T1 - Korelacije strukture i reaktivnosti za kinetiku reakcije sinteze supstituisanih 4-fenil-1,4-dihidropiridina EP - 1973 IS - 12 SP - 1963 VL - 78 UR - https://hdl.handle.net/21.15107/rcub_technorep_2347 ER -
@article{ author = "Urošević, Jovica V. and Drmanić, Saša and Nikolić, Jasmina and Juranić, Ivan and Jovanović, Bratislav Ž.", year = "2013", abstract = "Quantitative structure-reactivity correlations for the kinetics of the Hantzsch synthesis of 4-(substituted phenyl)-1,4-dihydropyridines in the reaction between ethyl m- and p-substituted 2-benzylideneacetoacetate and the enamine (ethyl 3-aminocrotonate) was studied. The reaction kinetics was followed spectrophotometrically. It was found that the reaction correspond to second-order kinetics. Quantitative structure-reactivity correlations of log k were obtained with the corresponding substituent constants (s, s+, sI and s + ) using the Hammett and extended Hammett equation (dual substituent parameter, DSP, equation). They showed linear relationships with positive values of reaction constants (r). The obtained data were processed by linear regression analysis. It was confirmed that Michael addition of the enamine to benzylidene represented the slow step of the reaction with a high positive charge at the benzylidene molecule. MO calculations were performed and they were in agreement with the conclusions derived from the structure-reactivity correlations. ., Proučavan je kvantitativan odnos strukture i reaktivnosti za kinetiku Hančove sinteze supstituisanih 4-fenil-1,4-dihidropiridina u reakciji etil-m- i p-supstituisanih 2-benziliden-acetoacetata i enamina. Kinetika ispitivane reakcije je praćena spektrofotometrijskim metodom. Zapaženo je da je reč o reakciji drugog reda. Kvantitativne korelacije strukture i reaktivnosti koje izražavaju logaritam određene konstante brzine reakcije (log k) u zavisnosti od odgovarajućih konstanti supstituenata (s, s+,sI i s +) određene su za Hametovu (Hammett) i proširenu Hametovu jednačinu (DSP-jednačinu). Pokazale su linearnu zavisnost sa pozitivnim vrednostima nagiba, odnosno reakcione konstante (r). Time je potvrđeno da Majklova (Michael) adicija enamina na benziliden predstavlja spori stupanj u reakciji sa izraženim pozitivnim naelektrisanjem na molekulu benzilidena. MO proračuni su takođe urađeni i njihovi rezultati su bili u skladu sa zaključcima izvedenim iz korelacija strukture i reaktivnosti. .", publisher = "Serbian Chemical Society, Belgrade", journal = "Journal of the Serbian Chemical Society", title = "Structure-reactivity correlation for the kinetics of the formation reaction of 4-(substituted phenyl)-1,4-dihydropyridines, Korelacije strukture i reaktivnosti za kinetiku reakcije sinteze supstituisanih 4-fenil-1,4-dihidropiridina", pages = "1973-1963", number = "12", volume = "78", url = "https://hdl.handle.net/21.15107/rcub_technorep_2347" }
Urošević, J. V., Drmanić, S., Nikolić, J., Juranić, I.,& Jovanović, B. Ž.. (2013). Structure-reactivity correlation for the kinetics of the formation reaction of 4-(substituted phenyl)-1,4-dihydropyridines. in Journal of the Serbian Chemical Society Serbian Chemical Society, Belgrade., 78(12), 1963-1973. https://hdl.handle.net/21.15107/rcub_technorep_2347
Urošević JV, Drmanić S, Nikolić J, Juranić I, Jovanović BŽ. Structure-reactivity correlation for the kinetics of the formation reaction of 4-(substituted phenyl)-1,4-dihydropyridines. in Journal of the Serbian Chemical Society. 2013;78(12):1963-1973. https://hdl.handle.net/21.15107/rcub_technorep_2347 .
Urošević, Jovica V., Drmanić, Saša, Nikolić, Jasmina, Juranić, Ivan, Jovanović, Bratislav Ž., "Structure-reactivity correlation for the kinetics of the formation reaction of 4-(substituted phenyl)-1,4-dihydropyridines" in Journal of the Serbian Chemical Society, 78, no. 12 (2013):1963-1973, https://hdl.handle.net/21.15107/rcub_technorep_2347 .