Correlation analysis of IR, 1H- and 13C-NMR spectral data of N-alkyl and N-cycloalkyl cyanoacetamides
Korelaciona analiza IR, 1H- i 13C-NMR spektalnih podataka N-alkil- i N-cikloalkilcijanoacetamida
Abstract
Linear free energy relationships (LFER) were applied to the IR, 1H- and 13C- -NMR spectral data in N-alkyl and N-cycloalkyl cyanoacetamides. N-alkyl and N-cycloalkyl cyanocetamides were synthesized from corresponding amine and ethyl cyanoacetate. A number of substituents were employed for alkyl substitution, and fairly good correlations were obtained, using simple Hammett equation. In N-alkyl and N-cycloalkyl cyanoacetamides substituent cause SCS of N-H hydrogen primarily by steric interaction, polar subtituent effect influences SCS shift of C=O carbon, while steric effect of N-alkyl substituent causes IR stretching frequencies of N-H, C=O and CN group. The conformations of investigated compounds have been studied by the use of semiempirical PM6 method, and together with LFER analysis, give a better insight into the influence of such a structure on the transmission of electronic substituent effects. Negative ρ values for several correlations (reverse substituent effect) were found.
Principi linearnih korelacija slobodnih energija (LFER) su primenjeni na IR, 1H- i 13C-NMR spektralne podatke N-alkil i N-cikloalkilcijanoacetamida. Širok opseg alkil i cikloalkil suptituenata je korišćen pri sintezi N-alkil i N-cikloalkilcijanoacetamida sa ciljem ispitivanja uticaja njihovih elektronskih i sternih efekata na IR, 1H i 13C NMR spektralne podatke. Zadovoljavajuće korelacije su dobijene primenom proste Hammett-ove jednačine. Na osnovu korelacionih rezultata uočen je primaran uticaj sternih efekata supstituenata na SCS (supstituent indukovana hemijska pomeranja) vrednosti N-H vodonika ispitivanih jedinjenja, što je posledica blizine i različitih konformacija N-alkil i N-cikloalkil supstituenata. Takođe se uočava reversni efekat supstituenata na SCS pomeranja karbonilnog C=O ugljenika, kao posledica π-polarizacije. Indukovani dipol na N-alkil ili N-cikloalkil supstituentu izaziva povećanje elektronske gustine karbonilnog ugljenika iako elektron-akceptorski efekat supstituen...ta raste. Može se zaključiti da se efekat π-polarizacije odražava na veličinu rezonancionog efekta amidne grupe. Polarni efekat N-alkil ili N-cikloalkil supstituenata se primarno prenosi efektom polja kroz prostor. Uticaj efekata N-alkil ili N-cikloalkil supstituenata na IR vibracije istezanja N-H (simetrične i antisimetrične), C=O i CN veze je prevashodno određen konformacionim (sternim) efektom supstituenata koji utiče na jačinu veze, a time i na položaj trake u odgovarajućem spektru.
Keywords:
N-alkyl cyanoacetamides / N-cycloalkyl cyanoacetamide / LFER analysis / IR and NMR spectra / SCS shift / Hammett equation / N-alkilcijanoacetamidi / N-cikloalkilcijanoacetamidi / LFER analiza / IR i NMR spektri / SCS pomeraj / Hammett-ova jednačinaSource:
Chemical Industry & Chemical Engineering Quarterly, 2011, 17, 3, 307-314Publisher:
- Association of the Chemical Engineers of Serbia
Funding / projects:
- Study of the Synthesis, Structure and Activity of Natural and Synthetic Organic Compounds (RS-MESTD-Basic Research (BR or ON)-172013)
DOI: 10.2298/CICEQ110302016M
ISSN: 1451-9372
WoS: 000296947800007
Scopus: 2-s2.0-80052873985
Institution/Community
Tehnološko-metalurški fakultetTY - JOUR AU - Marinković, Aleksandar AU - Nedeljković, Jelena AU - Mijin, Dušan AU - Ilić, Nataša AU - Petrović, Slobodan PY - 2011 UR - http://TechnoRep.tmf.bg.ac.rs/handle/123456789/1847 AB - Linear free energy relationships (LFER) were applied to the IR, 1H- and 13C- -NMR spectral data in N-alkyl and N-cycloalkyl cyanoacetamides. N-alkyl and N-cycloalkyl cyanocetamides were synthesized from corresponding amine and ethyl cyanoacetate. A number of substituents were employed for alkyl substitution, and fairly good correlations were obtained, using simple Hammett equation. In N-alkyl and N-cycloalkyl cyanoacetamides substituent cause SCS of N-H hydrogen primarily by steric interaction, polar subtituent effect influences SCS shift of C=O carbon, while steric effect of N-alkyl substituent causes IR stretching frequencies of N-H, C=O and CN group. The conformations of investigated compounds have been studied by the use of semiempirical PM6 method, and together with LFER analysis, give a better insight into the influence of such a structure on the transmission of electronic substituent effects. Negative ρ values for several correlations (reverse substituent effect) were found. AB - Principi linearnih korelacija slobodnih energija (LFER) su primenjeni na IR, 1H- i 13C-NMR spektralne podatke N-alkil i N-cikloalkilcijanoacetamida. Širok opseg alkil i cikloalkil suptituenata je korišćen pri sintezi N-alkil i N-cikloalkilcijanoacetamida sa ciljem ispitivanja uticaja njihovih elektronskih i sternih efekata na IR, 1H i 13C NMR spektralne podatke. Zadovoljavajuće korelacije su dobijene primenom proste Hammett-ove jednačine. Na osnovu korelacionih rezultata uočen je primaran uticaj sternih efekata supstituenata na SCS (supstituent indukovana hemijska pomeranja) vrednosti N-H vodonika ispitivanih jedinjenja, što je posledica blizine i različitih konformacija N-alkil i N-cikloalkil supstituenata. Takođe se uočava reversni efekat supstituenata na SCS pomeranja karbonilnog C=O ugljenika, kao posledica π-polarizacije. Indukovani dipol na N-alkil ili N-cikloalkil supstituentu izaziva povećanje elektronske gustine karbonilnog ugljenika iako elektron-akceptorski efekat supstituenta raste. Može se zaključiti da se efekat π-polarizacije odražava na veličinu rezonancionog efekta amidne grupe. Polarni efekat N-alkil ili N-cikloalkil supstituenata se primarno prenosi efektom polja kroz prostor. Uticaj efekata N-alkil ili N-cikloalkil supstituenata na IR vibracije istezanja N-H (simetrične i antisimetrične), C=O i CN veze je prevashodno određen konformacionim (sternim) efektom supstituenata koji utiče na jačinu veze, a time i na položaj trake u odgovarajućem spektru. PB - Association of the Chemical Engineers of Serbia T2 - Chemical Industry & Chemical Engineering Quarterly T1 - Correlation analysis of IR, 1H- and 13C-NMR spectral data of N-alkyl and N-cycloalkyl cyanoacetamides T1 - Korelaciona analiza IR, 1H- i 13C-NMR spektalnih podataka N-alkil- i N-cikloalkilcijanoacetamida EP - 314 IS - 3 SP - 307 VL - 17 DO - 10.2298/CICEQ110302016M ER -
@article{ author = "Marinković, Aleksandar and Nedeljković, Jelena and Mijin, Dušan and Ilić, Nataša and Petrović, Slobodan", year = "2011", abstract = "Linear free energy relationships (LFER) were applied to the IR, 1H- and 13C- -NMR spectral data in N-alkyl and N-cycloalkyl cyanoacetamides. N-alkyl and N-cycloalkyl cyanocetamides were synthesized from corresponding amine and ethyl cyanoacetate. A number of substituents were employed for alkyl substitution, and fairly good correlations were obtained, using simple Hammett equation. In N-alkyl and N-cycloalkyl cyanoacetamides substituent cause SCS of N-H hydrogen primarily by steric interaction, polar subtituent effect influences SCS shift of C=O carbon, while steric effect of N-alkyl substituent causes IR stretching frequencies of N-H, C=O and CN group. The conformations of investigated compounds have been studied by the use of semiempirical PM6 method, and together with LFER analysis, give a better insight into the influence of such a structure on the transmission of electronic substituent effects. Negative ρ values for several correlations (reverse substituent effect) were found., Principi linearnih korelacija slobodnih energija (LFER) su primenjeni na IR, 1H- i 13C-NMR spektralne podatke N-alkil i N-cikloalkilcijanoacetamida. Širok opseg alkil i cikloalkil suptituenata je korišćen pri sintezi N-alkil i N-cikloalkilcijanoacetamida sa ciljem ispitivanja uticaja njihovih elektronskih i sternih efekata na IR, 1H i 13C NMR spektralne podatke. Zadovoljavajuće korelacije su dobijene primenom proste Hammett-ove jednačine. Na osnovu korelacionih rezultata uočen je primaran uticaj sternih efekata supstituenata na SCS (supstituent indukovana hemijska pomeranja) vrednosti N-H vodonika ispitivanih jedinjenja, što je posledica blizine i različitih konformacija N-alkil i N-cikloalkil supstituenata. Takođe se uočava reversni efekat supstituenata na SCS pomeranja karbonilnog C=O ugljenika, kao posledica π-polarizacije. Indukovani dipol na N-alkil ili N-cikloalkil supstituentu izaziva povećanje elektronske gustine karbonilnog ugljenika iako elektron-akceptorski efekat supstituenta raste. Može se zaključiti da se efekat π-polarizacije odražava na veličinu rezonancionog efekta amidne grupe. Polarni efekat N-alkil ili N-cikloalkil supstituenata se primarno prenosi efektom polja kroz prostor. Uticaj efekata N-alkil ili N-cikloalkil supstituenata na IR vibracije istezanja N-H (simetrične i antisimetrične), C=O i CN veze je prevashodno određen konformacionim (sternim) efektom supstituenata koji utiče na jačinu veze, a time i na položaj trake u odgovarajućem spektru.", publisher = "Association of the Chemical Engineers of Serbia", journal = "Chemical Industry & Chemical Engineering Quarterly", title = "Correlation analysis of IR, 1H- and 13C-NMR spectral data of N-alkyl and N-cycloalkyl cyanoacetamides, Korelaciona analiza IR, 1H- i 13C-NMR spektalnih podataka N-alkil- i N-cikloalkilcijanoacetamida", pages = "314-307", number = "3", volume = "17", doi = "10.2298/CICEQ110302016M" }
Marinković, A., Nedeljković, J., Mijin, D., Ilić, N.,& Petrović, S.. (2011). Correlation analysis of IR, 1H- and 13C-NMR spectral data of N-alkyl and N-cycloalkyl cyanoacetamides. in Chemical Industry & Chemical Engineering Quarterly Association of the Chemical Engineers of Serbia., 17(3), 307-314. https://doi.org/10.2298/CICEQ110302016M
Marinković A, Nedeljković J, Mijin D, Ilić N, Petrović S. Correlation analysis of IR, 1H- and 13C-NMR spectral data of N-alkyl and N-cycloalkyl cyanoacetamides. in Chemical Industry & Chemical Engineering Quarterly. 2011;17(3):307-314. doi:10.2298/CICEQ110302016M .
Marinković, Aleksandar, Nedeljković, Jelena, Mijin, Dušan, Ilić, Nataša, Petrović, Slobodan, "Correlation analysis of IR, 1H- and 13C-NMR spectral data of N-alkyl and N-cycloalkyl cyanoacetamides" in Chemical Industry & Chemical Engineering Quarterly, 17, no. 3 (2011):307-314, https://doi.org/10.2298/CICEQ110302016M . .