Experimental, Spectroscopic, and Computational Insights into the Reactivity of “Methanal” with 2-Naphthylamines
The reactions of 2-naphthylamine and methyl 6-amino-2-naphthoate with formalin and paraformaldehyde were studied experimentally, spectrally, and by quantum chemical calculations. It was found that neither the corresponding aminals nor imines were formed under the described conditions but could be pr...
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MDPI AG
2023-02-01
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| Series: | Molecules |
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| Online Access: | https://www.mdpi.com/1420-3049/28/4/1549 |
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| author | Martin Havlík Tereza Navrátilová Michaela Drozdová Ameneh Tatar Priscila A. Lanza Diego Dusso Elizabeth Laura Moyano Carlos A. Chesta Domingo Mariano A. Vera Bohumil Dolenský |
| author_facet | Martin Havlík Tereza Navrátilová Michaela Drozdová Ameneh Tatar Priscila A. Lanza Diego Dusso Elizabeth Laura Moyano Carlos A. Chesta Domingo Mariano A. Vera Bohumil Dolenský |
| author_sort | Martin Havlík |
| collection | DOAJ |
| description | The reactions of 2-naphthylamine and methyl 6-amino-2-naphthoate with formalin and paraformaldehyde were studied experimentally, spectrally, and by quantum chemical calculations. It was found that neither the corresponding aminals nor imines were formed under the described conditions but could be prepared and spectrally characterized at least in situ under modified conditions. Several of the previously undescribed intermediates and by-products were isolated or at least spectrally characterized. First principle density functional theory (DFT) calculations were performed to shed light on the key aspects of the thermochemistry of decomposition and further condensation of the corresponding aminals and imines. The calculations also revealed that the electrophilicity of methanal was significantly greater than that of ordinary oxo-compounds, except for perfluorinated ones. In summary, methanal was not behaving as the simplest aldehyde but as a very electron-deficient oxo-compound. |
| first_indexed | 2024-03-11T08:22:03Z |
| format | Article |
| id | doaj.art-534c95dfcd46482ea146ed8ff638fc15 |
| institution | Directory Open Access Journal |
| issn | 1420-3049 |
| language | English |
| last_indexed | 2024-03-11T08:22:03Z |
| publishDate | 2023-02-01 |
| publisher | MDPI AG |
| record_format | Article |
| series | Molecules |
| spelling | doaj.art-534c95dfcd46482ea146ed8ff638fc152023-11-16T22:20:01ZengMDPI AGMolecules1420-30492023-02-01284154910.3390/molecules28041549Experimental, Spectroscopic, and Computational Insights into the Reactivity of “Methanal” with 2-NaphthylaminesMartin Havlík0Tereza Navrátilová1Michaela Drozdová2Ameneh Tatar3Priscila A. Lanza4Diego Dusso5Elizabeth Laura Moyano6Carlos A. Chesta7Domingo Mariano A. Vera8Bohumil Dolenský9Department of Analytical Chemistry, University of Chemistry and Technology Prague, Technická 5, 166 28 Praha, Czech RepublicDepartment of Analytical Chemistry, University of Chemistry and Technology Prague, Technická 5, 166 28 Praha, Czech RepublicDepartment of Analytical Chemistry, University of Chemistry and Technology Prague, Technická 5, 166 28 Praha, Czech RepublicDepartment of Analytical Chemistry, University of Chemistry and Technology Prague, Technická 5, 166 28 Praha, Czech RepublicQUIAMM-INBIOTEC, Department of Chemistry, Facultad de Ciencias Exactas y Naturales, Universidad Nacional de Mar del Plata, Mar del Plata B7602AYL, ArgentinaQUIAMM-INBIOTEC, Department of Chemistry, Facultad de Ciencias Exactas y Naturales, Universidad Nacional de Mar del Plata, Mar del Plata B7602AYL, ArgentinaINFIQC, Department of Organic Chemistry, Facultad de Ciencias Químicas, Universidad Nacional de Córdoba, Córdoba 5000, ArgentinaInstituto de Investigaciones en Tecnologías Energéticas y Materiales Avanzados (IITEMA), Universidad Nacional de Río Cuarto (UNRC), Consejo Nacional de Investigaciones Científicas y Tecnológicas (CONICET), Campus Universitario, Río Cuarto 5800, ArgentinaQUIAMM-INBIOTEC, Department of Chemistry, Facultad de Ciencias Exactas y Naturales, Universidad Nacional de Mar del Plata, Mar del Plata B7602AYL, ArgentinaDepartment of Analytical Chemistry, University of Chemistry and Technology Prague, Technická 5, 166 28 Praha, Czech RepublicThe reactions of 2-naphthylamine and methyl 6-amino-2-naphthoate with formalin and paraformaldehyde were studied experimentally, spectrally, and by quantum chemical calculations. It was found that neither the corresponding aminals nor imines were formed under the described conditions but could be prepared and spectrally characterized at least in situ under modified conditions. Several of the previously undescribed intermediates and by-products were isolated or at least spectrally characterized. First principle density functional theory (DFT) calculations were performed to shed light on the key aspects of the thermochemistry of decomposition and further condensation of the corresponding aminals and imines. The calculations also revealed that the electrophilicity of methanal was significantly greater than that of ordinary oxo-compounds, except for perfluorinated ones. In summary, methanal was not behaving as the simplest aldehyde but as a very electron-deficient oxo-compound.https://www.mdpi.com/1420-3049/28/4/1549methanalnaphthylaminequinazolineTröger’s basespiro-Tröger’s basemechanisms |
| spellingShingle | Martin Havlík Tereza Navrátilová Michaela Drozdová Ameneh Tatar Priscila A. Lanza Diego Dusso Elizabeth Laura Moyano Carlos A. Chesta Domingo Mariano A. Vera Bohumil Dolenský Experimental, Spectroscopic, and Computational Insights into the Reactivity of “Methanal” with 2-Naphthylamines Molecules methanal naphthylamine quinazoline Tröger’s base spiro-Tröger’s base mechanisms |
| title | Experimental, Spectroscopic, and Computational Insights into the Reactivity of “Methanal” with 2-Naphthylamines |
| title_full | Experimental, Spectroscopic, and Computational Insights into the Reactivity of “Methanal” with 2-Naphthylamines |
| title_fullStr | Experimental, Spectroscopic, and Computational Insights into the Reactivity of “Methanal” with 2-Naphthylamines |
| title_full_unstemmed | Experimental, Spectroscopic, and Computational Insights into the Reactivity of “Methanal” with 2-Naphthylamines |
| title_short | Experimental, Spectroscopic, and Computational Insights into the Reactivity of “Methanal” with 2-Naphthylamines |
| title_sort | experimental spectroscopic and computational insights into the reactivity of methanal with 2 naphthylamines |
| topic | methanal naphthylamine quinazoline Tröger’s base spiro-Tröger’s base mechanisms |
| url | https://www.mdpi.com/1420-3049/28/4/1549 |
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