An Example of Polynomial Expansion: The Reaction of 3(5)-Methyl-1<i>H</i>-Pyrazole with Chloroform and Characterization of the Four Isomers
The reaction in phase-transfer catalyzed conditions of 3(5)-methyl-1<i>H</i>-pyrazole with chloroform affords four isomers <b>333</b>, <b>335</b>, <b>355</b> and <b>555</b> in proportions corresponding to the polynomial expansion (a + b)<...
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MDPI AG
2019-02-01
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| Series: | Molecules |
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| Online Access: | https://www.mdpi.com/1420-3049/24/3/568 |
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| author | Vera L. M. Silva Artur M. S. Silva Rosa M. Claramunt Dionisia Sanz Lourdes Infantes Ángela Martínez-López Felipe Reviriego Ibon Alkorta José Elguero |
| author_facet | Vera L. M. Silva Artur M. S. Silva Rosa M. Claramunt Dionisia Sanz Lourdes Infantes Ángela Martínez-López Felipe Reviriego Ibon Alkorta José Elguero |
| author_sort | Vera L. M. Silva |
| collection | DOAJ |
| description | The reaction in phase-transfer catalyzed conditions of 3(5)-methyl-1<i>H</i>-pyrazole with chloroform affords four isomers <b>333</b>, <b>335</b>, <b>355</b> and <b>555</b> in proportions corresponding to the polynomial expansion (a + b)<sup>3</sup>, with a = 0.6 and b = 0.4, a and b being 3-methyl and 5-methyl proportions. The up (<i>u</i>) and down (<i>d</i>) conformation of the pyrazolyl rings with regard to the Csp<sup>3</sup>⁻H atom was established by X-ray crystallography and by <sup>1</sup>H-, <sup>13</sup>C- and <sup>15</sup>N-NMR in solution combined with gauge-including atomic orbitals (GIAO)/B3LYP/6-311++G(d,p) calculations. A comparison with other X-ray structures of tris-pyrazolylmethanes was carried out. |
| first_indexed | 2024-12-20T08:42:06Z |
| format | Article |
| id | doaj.art-61220bc4e72e43668e841d7624bf4ce5 |
| institution | Directory Open Access Journal |
| issn | 1420-3049 |
| language | English |
| last_indexed | 2024-12-20T08:42:06Z |
| publishDate | 2019-02-01 |
| publisher | MDPI AG |
| record_format | Article |
| series | Molecules |
| spelling | doaj.art-61220bc4e72e43668e841d7624bf4ce52022-12-21T19:46:22ZengMDPI AGMolecules1420-30492019-02-0124356810.3390/molecules24030568molecules24030568An Example of Polynomial Expansion: The Reaction of 3(5)-Methyl-1<i>H</i>-Pyrazole with Chloroform and Characterization of the Four IsomersVera L. M. Silva0Artur M. S. Silva1Rosa M. Claramunt2Dionisia Sanz3Lourdes Infantes4Ángela Martínez-López5Felipe Reviriego6Ibon Alkorta7José Elguero8Chemistry Department and QOPNA and LAQV-REQUIMTE, University of Aveiro, 3810-193 Aveiro, PortugalChemistry Department and QOPNA and LAQV-REQUIMTE, University of Aveiro, 3810-193 Aveiro, PortugalDepartamento de Química Orgánica y Bio-Orgánica, Facultad de Ciencias, UNED, Paseo Senda del Rey, 9, E-28040 Madrid, SpainDepartamento de Química Orgánica y Bio-Orgánica, Facultad de Ciencias, UNED, Paseo Senda del Rey, 9, E-28040 Madrid, SpainDepartamento de Cristalografía y Biología Estructural, Instituto de Química-Física Rocasolano, CSIC, Serrano, 119, E-28006 Madrid, SpainDepartamento de Cristalografía y Biología Estructural, Instituto de Química-Física Rocasolano, CSIC, Serrano, 119, E-28006 Madrid, SpainInstituto de Química Médica, CSIC, Juan de la Cierva, 3, E-28006 Madrid, SpainInstituto de Química Médica, CSIC, Juan de la Cierva, 3, E-28006 Madrid, SpainInstituto de Química Médica, CSIC, Juan de la Cierva, 3, E-28006 Madrid, SpainThe reaction in phase-transfer catalyzed conditions of 3(5)-methyl-1<i>H</i>-pyrazole with chloroform affords four isomers <b>333</b>, <b>335</b>, <b>355</b> and <b>555</b> in proportions corresponding to the polynomial expansion (a + b)<sup>3</sup>, with a = 0.6 and b = 0.4, a and b being 3-methyl and 5-methyl proportions. The up (<i>u</i>) and down (<i>d</i>) conformation of the pyrazolyl rings with regard to the Csp<sup>3</sup>⁻H atom was established by X-ray crystallography and by <sup>1</sup>H-, <sup>13</sup>C- and <sup>15</sup>N-NMR in solution combined with gauge-including atomic orbitals (GIAO)/B3LYP/6-311++G(d,p) calculations. A comparison with other X-ray structures of tris-pyrazolylmethanes was carried out.https://www.mdpi.com/1420-3049/24/3/568pyrazolespyrazolylmethanesphase transfer catalysisNMR spectroscopyX-ray crystallographytheoretical calculationsGIAO calculations |
| spellingShingle | Vera L. M. Silva Artur M. S. Silva Rosa M. Claramunt Dionisia Sanz Lourdes Infantes Ángela Martínez-López Felipe Reviriego Ibon Alkorta José Elguero An Example of Polynomial Expansion: The Reaction of 3(5)-Methyl-1<i>H</i>-Pyrazole with Chloroform and Characterization of the Four Isomers Molecules pyrazoles pyrazolylmethanes phase transfer catalysis NMR spectroscopy X-ray crystallography theoretical calculations GIAO calculations |
| title | An Example of Polynomial Expansion: The Reaction of 3(5)-Methyl-1<i>H</i>-Pyrazole with Chloroform and Characterization of the Four Isomers |
| title_full | An Example of Polynomial Expansion: The Reaction of 3(5)-Methyl-1<i>H</i>-Pyrazole with Chloroform and Characterization of the Four Isomers |
| title_fullStr | An Example of Polynomial Expansion: The Reaction of 3(5)-Methyl-1<i>H</i>-Pyrazole with Chloroform and Characterization of the Four Isomers |
| title_full_unstemmed | An Example of Polynomial Expansion: The Reaction of 3(5)-Methyl-1<i>H</i>-Pyrazole with Chloroform and Characterization of the Four Isomers |
| title_short | An Example of Polynomial Expansion: The Reaction of 3(5)-Methyl-1<i>H</i>-Pyrazole with Chloroform and Characterization of the Four Isomers |
| title_sort | example of polynomial expansion the reaction of 3 5 methyl 1 i h i pyrazole with chloroform and characterization of the four isomers |
| topic | pyrazoles pyrazolylmethanes phase transfer catalysis NMR spectroscopy X-ray crystallography theoretical calculations GIAO calculations |
| url | https://www.mdpi.com/1420-3049/24/3/568 |
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