Novel Derivatives of Phenylisoxazole-3/5-Carbaldehyde Semicarbazone: Synthesis, Characterization, and Computational Studies
Six novel phenylisoxazole semicarbazone derivatives 1–6 were synthesized by reaction of the corresponding phenylisoxazole-3/5-carbaldehyde derivatives with semicarbazide hydrochloride. The synthesized compounds were characterized by ESI-MS, FT-IR, and NMR (1H, 13C) spectroscopic techniques. The two-...
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| Format: | Article |
| Language: | English |
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Wiley
2024-01-01
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| Series: | Journal of Chemistry |
| Online Access: | http://dx.doi.org/10.1155/2024/8891272 |
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| author | Fernando Carrasco Wilfredo Hernández Oscar Chupayo Rodolfo Pumachagua Evgenia Spodine Jackeline Mosquera Olivio N. Castro Jesus M. Rodilla Celedonio M. Álvarez Juan Z. Dávalos |
| author_facet | Fernando Carrasco Wilfredo Hernández Oscar Chupayo Rodolfo Pumachagua Evgenia Spodine Jackeline Mosquera Olivio N. Castro Jesus M. Rodilla Celedonio M. Álvarez Juan Z. Dávalos |
| author_sort | Fernando Carrasco |
| collection | DOAJ |
| description | Six novel phenylisoxazole semicarbazone derivatives 1–6 were synthesized by reaction of the corresponding phenylisoxazole-3/5-carbaldehyde derivatives with semicarbazide hydrochloride. The synthesized compounds were characterized by ESI-MS, FT-IR, and NMR (1H, 13C) spectroscopic techniques. The two-dimensional 1H-1H NOESY NMR (in acetone-d6) data revealed that compound 1 exists in the E isomeric form. The computational study of the energetic, structural, and electronic properties, carried out at B3LYP/6-311G++(d,p) level of theory, showed that the most stable conformer for the all synthesized compounds, in both gas and liquid (acetone and DMSO) phases, has a cisE geometrical configuration. This evidence found is in good agreement with the spectrometric results. The geometrical parameters, frontier molecular orbital (FMO), molecular electrostatic potential (MEP), Mulliken atomic charges, and natural bonding orbital (NBO) analysis were also performed at the same level of theory. Taking into account the relative enthalpies ΔH computed, we can establish for tautomeric structures of each of the compounds, the following stability order: I (cisE) > II (E′E) > III (cisE). The MEP descriptors indicate that the oxygen atom of the carbonyl group C=O is susceptible to electrophilic attack, while the hydrogen atoms of the amide and hydrazone fragments are sensitive to nucleophilic attack. The calculated HOMO-LUMO gap energies Eg indicate that 5 (in gas phase) and 6 (in liquid phase) are the most stable and less reactive compounds, while 1 is the less stable and the most reactive compound. From the NBO analysis, it becomes evident that the presence of the hydrazone fragment produces stabilizing effects due to hyperconjugative interactions. |
| format | Article |
| id | doaj-art-34928171c2cd4c9ea685dd5a6beafad0 |
| institution | Kabale University |
| issn | 2090-9071 |
| language | English |
| publishDate | 2024-01-01 |
| publisher | Wiley |
| record_format | Article |
| series | Journal of Chemistry |
| spelling | doaj-art-34928171c2cd4c9ea685dd5a6beafad02025-01-02T22:41:03ZengWileyJournal of Chemistry2090-90712024-01-01202410.1155/2024/8891272Novel Derivatives of Phenylisoxazole-3/5-Carbaldehyde Semicarbazone: Synthesis, Characterization, and Computational StudiesFernando Carrasco0Wilfredo Hernández1Oscar Chupayo2Rodolfo Pumachagua3Evgenia Spodine4Jackeline Mosquera5Olivio N. Castro6Jesus M. Rodilla7Celedonio M. Álvarez8Juan Z. Dávalos9Facultad de IngenieríaFacultad de IngenieríaFacultad de Ciencias Naturales y MatematicaFacultad de Ciencias Naturales y MatematicaFacultad de Ciencias Químicas y FarmacéuticasFacultad de CienciasFacultad de Química e Ingeniería QuímicaFaculdade de CiênciasFacultad de CienciasInstituto de Química-Física Blas CabreraSix novel phenylisoxazole semicarbazone derivatives 1–6 were synthesized by reaction of the corresponding phenylisoxazole-3/5-carbaldehyde derivatives with semicarbazide hydrochloride. The synthesized compounds were characterized by ESI-MS, FT-IR, and NMR (1H, 13C) spectroscopic techniques. The two-dimensional 1H-1H NOESY NMR (in acetone-d6) data revealed that compound 1 exists in the E isomeric form. The computational study of the energetic, structural, and electronic properties, carried out at B3LYP/6-311G++(d,p) level of theory, showed that the most stable conformer for the all synthesized compounds, in both gas and liquid (acetone and DMSO) phases, has a cisE geometrical configuration. This evidence found is in good agreement with the spectrometric results. The geometrical parameters, frontier molecular orbital (FMO), molecular electrostatic potential (MEP), Mulliken atomic charges, and natural bonding orbital (NBO) analysis were also performed at the same level of theory. Taking into account the relative enthalpies ΔH computed, we can establish for tautomeric structures of each of the compounds, the following stability order: I (cisE) > II (E′E) > III (cisE). The MEP descriptors indicate that the oxygen atom of the carbonyl group C=O is susceptible to electrophilic attack, while the hydrogen atoms of the amide and hydrazone fragments are sensitive to nucleophilic attack. The calculated HOMO-LUMO gap energies Eg indicate that 5 (in gas phase) and 6 (in liquid phase) are the most stable and less reactive compounds, while 1 is the less stable and the most reactive compound. From the NBO analysis, it becomes evident that the presence of the hydrazone fragment produces stabilizing effects due to hyperconjugative interactions.http://dx.doi.org/10.1155/2024/8891272 |
| spellingShingle | Fernando Carrasco Wilfredo Hernández Oscar Chupayo Rodolfo Pumachagua Evgenia Spodine Jackeline Mosquera Olivio N. Castro Jesus M. Rodilla Celedonio M. Álvarez Juan Z. Dávalos Novel Derivatives of Phenylisoxazole-3/5-Carbaldehyde Semicarbazone: Synthesis, Characterization, and Computational Studies Journal of Chemistry |
| title | Novel Derivatives of Phenylisoxazole-3/5-Carbaldehyde Semicarbazone: Synthesis, Characterization, and Computational Studies |
| title_full | Novel Derivatives of Phenylisoxazole-3/5-Carbaldehyde Semicarbazone: Synthesis, Characterization, and Computational Studies |
| title_fullStr | Novel Derivatives of Phenylisoxazole-3/5-Carbaldehyde Semicarbazone: Synthesis, Characterization, and Computational Studies |
| title_full_unstemmed | Novel Derivatives of Phenylisoxazole-3/5-Carbaldehyde Semicarbazone: Synthesis, Characterization, and Computational Studies |
| title_short | Novel Derivatives of Phenylisoxazole-3/5-Carbaldehyde Semicarbazone: Synthesis, Characterization, and Computational Studies |
| title_sort | novel derivatives of phenylisoxazole 3 5 carbaldehyde semicarbazone synthesis characterization and computational studies |
| url | http://dx.doi.org/10.1155/2024/8891272 |
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