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Reduced 3,4′-bipyrazoles carrying thiophene and thiazole substituents: structures of two intermediates and two products
Cycloaddition reactions between 3-(5-aryloxy-3-methyl-1-phenyl-1H-pyrazol-4-yl)-1-(thiophen-2-yl)prop-2-en-1-ones and thiosemicarbazide leads to the formation of reduced 3,4′-bipyrazole-2-carbothioamides. Further cycloaddition of these intermediates with either diethyl acetylenedicarboxyl...
Autores principales: | , , , , , |
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Formato: | Online Artículo Texto |
Lenguaje: | English |
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International Union of Crystallography
2021
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Materias: | |
Acceso en línea: | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC8025870/ https://www.ncbi.nlm.nih.gov/pubmed/33936753 http://dx.doi.org/10.1107/S2056989021002310 |
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author | Harish Chinthal, Chayanna Yathirajan, Hemmige S. Manju, Nagaraja Kalluraya, Balakrishna Foro, Sabine Glidewell, Christopher |
author_facet | Harish Chinthal, Chayanna Yathirajan, Hemmige S. Manju, Nagaraja Kalluraya, Balakrishna Foro, Sabine Glidewell, Christopher |
author_sort | Harish Chinthal, Chayanna |
collection | PubMed |
description | Cycloaddition reactions between 3-(5-aryloxy-3-methyl-1-phenyl-1H-pyrazol-4-yl)-1-(thiophen-2-yl)prop-2-en-1-ones and thiosemicarbazide leads to the formation of reduced 3,4′-bipyrazole-2-carbothioamides. Further cycloaddition of these intermediates with either diethyl acetylenedicarboxylate or 4-bromophenacyl bromide leads to reduced 3,4′-bipyrazoles carrying oxothiazole or thiazole substituents, respectively. The structures of two representative intermediates and two representative products established unambiguously the regiochemistry of the cycloaddition reactions. The molecules of 3′-methyl-5′-(2-methylphenoxy)-1′-phenyl-5-(thiophen-2-yl)-3,4-dihydro-1′H,2H-3,4′-bipyrazole-2-carbothioamide, C(25)H(23)N(5)OS(2) (Ia), are linked by N—H⋯N hydrogen bonds to form simple C(8) chains. The analogous compound 5′-(2,4-dichlorophenoxy)-3′-methyl-1′-phenyl-5-(thiophen-2-yl)-3,4-dihydro-1′H,2H-3,4′-bipyrazole-2-carbothioamide hemihydrate crystallizes as a hemihydrate, C(24)H(19)Cl(2)N(5)OS(2)·0.5H(2)O (Ib), and the independent components are linked into a chain of spiro-fused R (4) (4)(20) rings by a combination of O—H⋯N and N—H⋯O hydrogen bonds. In the structure of ethyl (Z)-2-{2-[3′-methyl-1′-phenyl-5-(thiophen-2-yl)-5′-(2-methylphenoxy)-3,4-dihydro-1′H,2H-3,4′-bipyrazole-2-yl]-4-oxo-4,5-dihydrothiazol-5-ylidene}acetate, C(31)H(27)N(5)O(4)S(2) (II), inversion-related pairs of molecules are linked by paired C—H⋯π(arene) hydrogen bonds to form cyclic centrosymmetric dimers, but there are no direction-specific intermolecular interactions in 4-(4-bromophenyl)-2-[5′-(2,4-dichlorophenoxy)-3′-methyl-1′-phenyl-5-(thiophen-2-yl)-3,4-dihydro-1′H,2H-3,4′-bipyrazole-2-yl]-4-thiazole, C(32)H(22)BrCl(2)N(5)OS(2) (III). Comparisons are made with the structures of some related compounds. |
format | Online Article Text |
id | pubmed-8025870 |
institution | National Center for Biotechnology Information |
language | English |
publishDate | 2021 |
publisher | International Union of Crystallography |
record_format | MEDLINE/PubMed |
spelling | pubmed-80258702021-04-30 Reduced 3,4′-bipyrazoles carrying thiophene and thiazole substituents: structures of two intermediates and two products Harish Chinthal, Chayanna Yathirajan, Hemmige S. Manju, Nagaraja Kalluraya, Balakrishna Foro, Sabine Glidewell, Christopher Acta Crystallogr E Crystallogr Commun Research Communications Cycloaddition reactions between 3-(5-aryloxy-3-methyl-1-phenyl-1H-pyrazol-4-yl)-1-(thiophen-2-yl)prop-2-en-1-ones and thiosemicarbazide leads to the formation of reduced 3,4′-bipyrazole-2-carbothioamides. Further cycloaddition of these intermediates with either diethyl acetylenedicarboxylate or 4-bromophenacyl bromide leads to reduced 3,4′-bipyrazoles carrying oxothiazole or thiazole substituents, respectively. The structures of two representative intermediates and two representative products established unambiguously the regiochemistry of the cycloaddition reactions. The molecules of 3′-methyl-5′-(2-methylphenoxy)-1′-phenyl-5-(thiophen-2-yl)-3,4-dihydro-1′H,2H-3,4′-bipyrazole-2-carbothioamide, C(25)H(23)N(5)OS(2) (Ia), are linked by N—H⋯N hydrogen bonds to form simple C(8) chains. The analogous compound 5′-(2,4-dichlorophenoxy)-3′-methyl-1′-phenyl-5-(thiophen-2-yl)-3,4-dihydro-1′H,2H-3,4′-bipyrazole-2-carbothioamide hemihydrate crystallizes as a hemihydrate, C(24)H(19)Cl(2)N(5)OS(2)·0.5H(2)O (Ib), and the independent components are linked into a chain of spiro-fused R (4) (4)(20) rings by a combination of O—H⋯N and N—H⋯O hydrogen bonds. In the structure of ethyl (Z)-2-{2-[3′-methyl-1′-phenyl-5-(thiophen-2-yl)-5′-(2-methylphenoxy)-3,4-dihydro-1′H,2H-3,4′-bipyrazole-2-yl]-4-oxo-4,5-dihydrothiazol-5-ylidene}acetate, C(31)H(27)N(5)O(4)S(2) (II), inversion-related pairs of molecules are linked by paired C—H⋯π(arene) hydrogen bonds to form cyclic centrosymmetric dimers, but there are no direction-specific intermolecular interactions in 4-(4-bromophenyl)-2-[5′-(2,4-dichlorophenoxy)-3′-methyl-1′-phenyl-5-(thiophen-2-yl)-3,4-dihydro-1′H,2H-3,4′-bipyrazole-2-yl]-4-thiazole, C(32)H(22)BrCl(2)N(5)OS(2) (III). Comparisons are made with the structures of some related compounds. International Union of Crystallography 2021-03-05 /pmc/articles/PMC8025870/ /pubmed/33936753 http://dx.doi.org/10.1107/S2056989021002310 Text en © Harish Chinthal et al. 2021 http://creativecommons.org/licenses/by/4.0/ This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.http://creativecommons.org/licenses/by/4.0/ |
spellingShingle | Research Communications Harish Chinthal, Chayanna Yathirajan, Hemmige S. Manju, Nagaraja Kalluraya, Balakrishna Foro, Sabine Glidewell, Christopher Reduced 3,4′-bipyrazoles carrying thiophene and thiazole substituents: structures of two intermediates and two products |
title | Reduced 3,4′-bipyrazoles carrying thiophene and thiazole substituents: structures of two intermediates and two products |
title_full | Reduced 3,4′-bipyrazoles carrying thiophene and thiazole substituents: structures of two intermediates and two products |
title_fullStr | Reduced 3,4′-bipyrazoles carrying thiophene and thiazole substituents: structures of two intermediates and two products |
title_full_unstemmed | Reduced 3,4′-bipyrazoles carrying thiophene and thiazole substituents: structures of two intermediates and two products |
title_short | Reduced 3,4′-bipyrazoles carrying thiophene and thiazole substituents: structures of two intermediates and two products |
title_sort | reduced 3,4′-bipyrazoles carrying thiophene and thiazole substituents: structures of two intermediates and two products |
topic | Research Communications |
url | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC8025870/ https://www.ncbi.nlm.nih.gov/pubmed/33936753 http://dx.doi.org/10.1107/S2056989021002310 |
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