Linear Free Energy Relationships of the C-13 NMR chemical shifts in 5-(3-and 4-substituted arylazo)-4,6-dimethyl-3-cyano-2-pyridones
Apstrakt
The C-13 NMR chemical shifts of the C2 carbon atom in the heteroaromatic nuclei of seventeen 5-(3- and 4-substituted arylazo)-4,6-dimethyl-3-cyano-2-pyridones were determined in deuterated DMSO solution. For quantitative assessment of the substituent effects on the C-13 NMR chemical shifts simple and extended Hammett equations and Swain-Lupton equation were used. The mode of transmission of substituent effects have been discussed in a relation to the geometry of investigated molecules. The geometry data were obtained using semiempirical MNDO-PM6 energy calculations. The observed C-13 NMR substituent chemical shifts were correlated with literature C-13 NMR data for the corresponding 3- and 4-substituted- 2',6'-dimethylazobenzenes and 3- and 4-substituted azobenzenes. A good linear dependence obtained in this way, provided a basis to discuss the influence of the ortho-methyl groups on the degree of coplanarity of azobenzene and pyridone systems, and on the efficiency of transmission of e...lectronic substituent effect from one ring to the other one.
Ključne reči:
LFER models / arylazo pyridone dyes / substituent effects / azo linking group / MNDO-PM6 and DFT-ab initio calculationsIzvor:
Arkivoc, 2009, 227-240Izdavač:
- Arkat Usa Inc, Gainesville
Finansiranje / projekti:
- Proučavanje sinteze, strukture i aktivnosti organskih jedinjenja prirodnog i sintetskog porekla (RS-MESTD-MPN2006-2010-142063)
- Sinteza, karakterizacija i aktivnost organskih i koordinacionih jedinjenja i njihova primena u (bio)nanotehnologiji (RS-MESTD-MPN2006-2010-142010)
DOI: 10.3998/ark.5550190.0010.d20
ISSN: 1551-7004
WoS: 000277913200020
Scopus: 2-s2.0-77953199233
Institucija/grupa
Tehnološko-metalurški fakultetTY - JOUR AU - Valentić, Nataša AU - Vitnik, Željko AU - Mijin, Dušan AU - Ušćumlić, Gordana AU - Todorović, Nina AU - Juranić, Ivan PY - 2009 UR - http://TechnoRep.tmf.bg.ac.rs/handle/123456789/1532 AB - The C-13 NMR chemical shifts of the C2 carbon atom in the heteroaromatic nuclei of seventeen 5-(3- and 4-substituted arylazo)-4,6-dimethyl-3-cyano-2-pyridones were determined in deuterated DMSO solution. For quantitative assessment of the substituent effects on the C-13 NMR chemical shifts simple and extended Hammett equations and Swain-Lupton equation were used. The mode of transmission of substituent effects have been discussed in a relation to the geometry of investigated molecules. The geometry data were obtained using semiempirical MNDO-PM6 energy calculations. The observed C-13 NMR substituent chemical shifts were correlated with literature C-13 NMR data for the corresponding 3- and 4-substituted- 2',6'-dimethylazobenzenes and 3- and 4-substituted azobenzenes. A good linear dependence obtained in this way, provided a basis to discuss the influence of the ortho-methyl groups on the degree of coplanarity of azobenzene and pyridone systems, and on the efficiency of transmission of electronic substituent effect from one ring to the other one. PB - Arkat Usa Inc, Gainesville T2 - Arkivoc T1 - Linear Free Energy Relationships of the C-13 NMR chemical shifts in 5-(3-and 4-substituted arylazo)-4,6-dimethyl-3-cyano-2-pyridones EP - 240 SP - 227 DO - 10.3998/ark.5550190.0010.d20 ER -
@article{ author = "Valentić, Nataša and Vitnik, Željko and Mijin, Dušan and Ušćumlić, Gordana and Todorović, Nina and Juranić, Ivan", year = "2009", abstract = "The C-13 NMR chemical shifts of the C2 carbon atom in the heteroaromatic nuclei of seventeen 5-(3- and 4-substituted arylazo)-4,6-dimethyl-3-cyano-2-pyridones were determined in deuterated DMSO solution. For quantitative assessment of the substituent effects on the C-13 NMR chemical shifts simple and extended Hammett equations and Swain-Lupton equation were used. The mode of transmission of substituent effects have been discussed in a relation to the geometry of investigated molecules. The geometry data were obtained using semiempirical MNDO-PM6 energy calculations. The observed C-13 NMR substituent chemical shifts were correlated with literature C-13 NMR data for the corresponding 3- and 4-substituted- 2',6'-dimethylazobenzenes and 3- and 4-substituted azobenzenes. A good linear dependence obtained in this way, provided a basis to discuss the influence of the ortho-methyl groups on the degree of coplanarity of azobenzene and pyridone systems, and on the efficiency of transmission of electronic substituent effect from one ring to the other one.", publisher = "Arkat Usa Inc, Gainesville", journal = "Arkivoc", title = "Linear Free Energy Relationships of the C-13 NMR chemical shifts in 5-(3-and 4-substituted arylazo)-4,6-dimethyl-3-cyano-2-pyridones", pages = "240-227", doi = "10.3998/ark.5550190.0010.d20" }
Valentić, N., Vitnik, Ž., Mijin, D., Ušćumlić, G., Todorović, N.,& Juranić, I.. (2009). Linear Free Energy Relationships of the C-13 NMR chemical shifts in 5-(3-and 4-substituted arylazo)-4,6-dimethyl-3-cyano-2-pyridones. in Arkivoc Arkat Usa Inc, Gainesville., 227-240. https://doi.org/10.3998/ark.5550190.0010.d20
Valentić N, Vitnik Ž, Mijin D, Ušćumlić G, Todorović N, Juranić I. Linear Free Energy Relationships of the C-13 NMR chemical shifts in 5-(3-and 4-substituted arylazo)-4,6-dimethyl-3-cyano-2-pyridones. in Arkivoc. 2009;:227-240. doi:10.3998/ark.5550190.0010.d20 .
Valentić, Nataša, Vitnik, Željko, Mijin, Dušan, Ušćumlić, Gordana, Todorović, Nina, Juranić, Ivan, "Linear Free Energy Relationships of the C-13 NMR chemical shifts in 5-(3-and 4-substituted arylazo)-4,6-dimethyl-3-cyano-2-pyridones" in Arkivoc (2009):227-240, https://doi.org/10.3998/ark.5550190.0010.d20 . .