Determination of protonation constants and structural correlations for some tertiary formamides and acetamides in sulfuric acid with UV spectroscopy
The protonation of ten aliphatic amides in sulfuric acid media was studied by UV spectroscopy. The pKBH+ values and solvation parameters were calculated using Yates and McClelland Method, Excess Acidity Method and Bunnett and Olsen Method. pKBH+ values were –1.44, –1.15, –0.80, –0.32, –1.13 and –0.8...
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| Format: | Article |
| Language: | English |
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Society of Chemists and Technologists of Macedonia
2015-11-01
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| Series: | Macedonian Journal of Chemistry and Chemical Engineering |
| Subjects: | |
| Online Access: | https://mjcce.org.mk/index.php/MJCCE/article/view/702 |
| _version_ | 1818926253772636160 |
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| author | Goran Stojković Elizabeta Dimitrieska-Stojković Emil Popovski |
| author_facet | Goran Stojković Elizabeta Dimitrieska-Stojković Emil Popovski |
| author_sort | Goran Stojković |
| collection | DOAJ |
| description | The protonation of ten aliphatic amides in sulfuric acid media was studied by UV spectroscopy. The pKBH+ values and solvation parameters were calculated using Yates and McClelland Method, Excess Acidity Method and Bunnett and Olsen Method. pKBH+ values were –1.44, –1.15, –0.80, –0.32, –1.13 and –0.80 for formamide, dimethylformamide, diethylformamide, diisopropylformamide, diisobutylformamide and dibutylformamide, respectively. According to the pKBH+ values obtained for acetamide, dimethylacetamide, diethylacetamide and diisopropylacetamide (–0.57, –0.29, –0.32 and 0.36, respectively), analogous acetamides were more basic than formamides. Applying the Hammett’s equation, satisfactory correlation could be gained only for some formamides, the basicities of which increased linearly with the inductive effect of the electron donating groups. From Taft’s approach, it can be concluded that the polar effect slightly dominates over the steric one. Excellent correlation between pKBH+ and solvation parameters m* was achieved for formamide, dimethylformamide and diethylformamide. At half- and full-protonation, better correlation was obtained for formamides than for acetamides. |
| first_indexed | 2024-12-20T02:54:11Z |
| format | Article |
| id | doaj.art-b83820939d2742f69278ed6700905709 |
| institution | Directory Open Access Journal |
| issn | 1857-5552 1857-5625 |
| language | English |
| last_indexed | 2024-12-20T02:54:11Z |
| publishDate | 2015-11-01 |
| publisher | Society of Chemists and Technologists of Macedonia |
| record_format | Article |
| series | Macedonian Journal of Chemistry and Chemical Engineering |
| spelling | doaj.art-b83820939d2742f69278ed67009057092022-12-21T19:55:57ZengSociety of Chemists and Technologists of MacedoniaMacedonian Journal of Chemistry and Chemical Engineering1857-55521857-56252015-11-0134225526510.20450/mjcce.2015.702283Determination of protonation constants and structural correlations for some tertiary formamides and acetamides in sulfuric acid with UV spectroscopyGoran Stojković0Elizabeta Dimitrieska-Stojković1Emil Popovski2Institute of Chemistry, Faculty of Science, Ss. Cyril and Methodius University, SkopjeInstitute for Food, Faculty of Veterinary Medicine, Ss. Cyril and Methodius University, SkopjeInstitute of Chemistry, Faculty of Science, Ss. Cyril and Methodius University, SkopjeThe protonation of ten aliphatic amides in sulfuric acid media was studied by UV spectroscopy. The pKBH+ values and solvation parameters were calculated using Yates and McClelland Method, Excess Acidity Method and Bunnett and Olsen Method. pKBH+ values were –1.44, –1.15, –0.80, –0.32, –1.13 and –0.80 for formamide, dimethylformamide, diethylformamide, diisopropylformamide, diisobutylformamide and dibutylformamide, respectively. According to the pKBH+ values obtained for acetamide, dimethylacetamide, diethylacetamide and diisopropylacetamide (–0.57, –0.29, –0.32 and 0.36, respectively), analogous acetamides were more basic than formamides. Applying the Hammett’s equation, satisfactory correlation could be gained only for some formamides, the basicities of which increased linearly with the inductive effect of the electron donating groups. From Taft’s approach, it can be concluded that the polar effect slightly dominates over the steric one. Excellent correlation between pKBH+ and solvation parameters m* was achieved for formamide, dimethylformamide and diethylformamide. At half- and full-protonation, better correlation was obtained for formamides than for acetamides.https://mjcce.org.mk/index.php/MJCCE/article/view/702uv spectroscopyformamidesacetamidesprotonation constantshammett-taft correlations |
| spellingShingle | Goran Stojković Elizabeta Dimitrieska-Stojković Emil Popovski Determination of protonation constants and structural correlations for some tertiary formamides and acetamides in sulfuric acid with UV spectroscopy Macedonian Journal of Chemistry and Chemical Engineering uv spectroscopy formamides acetamides protonation constants hammett-taft correlations |
| title | Determination of protonation constants and structural correlations for some tertiary formamides and acetamides in sulfuric acid with UV spectroscopy |
| title_full | Determination of protonation constants and structural correlations for some tertiary formamides and acetamides in sulfuric acid with UV spectroscopy |
| title_fullStr | Determination of protonation constants and structural correlations for some tertiary formamides and acetamides in sulfuric acid with UV spectroscopy |
| title_full_unstemmed | Determination of protonation constants and structural correlations for some tertiary formamides and acetamides in sulfuric acid with UV spectroscopy |
| title_short | Determination of protonation constants and structural correlations for some tertiary formamides and acetamides in sulfuric acid with UV spectroscopy |
| title_sort | determination of protonation constants and structural correlations for some tertiary formamides and acetamides in sulfuric acid with uv spectroscopy |
| topic | uv spectroscopy formamides acetamides protonation constants hammett-taft correlations |
| url | https://mjcce.org.mk/index.php/MJCCE/article/view/702 |
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