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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

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2011
1451-93721100016M.pdf (339.0Kb)
Authors
Marinković, Aleksandar
Nedeljković, Jelena
Mijin, Dušan
Ilić, Nataša
Petrović, Slobodan
Article (Published version)
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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 jednačina
Source:
Chemical Industry & Chemical Engineering Quarterly, 2011, 17, 3, 307-314
Publisher:
  • Association of the Chemical Engineers of Serbia
Funding / projects:
  • Study of the Synthesis, Structure and Activity of Natural and Synthetic Organic Compounds (RS-172013)

DOI: 10.2298/CICEQ110302016M

ISSN: 1451-9372

WoS: 000296947800007

Scopus: 2-s2.0-80052873985
[ Google Scholar ]
2
2
URI
http://TechnoRep.tmf.bg.ac.rs/handle/123456789/1847
Collections
  • Radovi istraživača / Researchers’ publications (TMF)
Institution/Community
Tehnološko-metalurški fakultet
TY  - 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 . .

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