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 acetylenedicarboxylate or 4-br...

Full description

Bibliographic Details
Main Authors: Chayanna Harish Chinthal, Hemmige S. Yathirajan, Nagaraja Manju, Balakrishna Kalluraya, Sabine Foro, Christopher Glidewell
Format: Article
Language:English
Published: International Union of Crystallography 2021-04-01
Series:Acta Crystallographica Section E: Crystallographic Communications
Subjects:
Online Access:http://scripts.iucr.org/cgi-bin/paper?S2056989021002310
_version_ 1818490692646731776
author Chayanna Harish Chinthal
Hemmige S. Yathirajan
Nagaraja Manju
Balakrishna Kalluraya
Sabine Foro
Christopher Glidewell
author_facet Chayanna Harish Chinthal
Hemmige S. Yathirajan
Nagaraja Manju
Balakrishna Kalluraya
Sabine Foro
Christopher Glidewell
author_sort Chayanna Harish Chinthal
collection DOAJ
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, C25H23N5OS2 (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, C24H19Cl2N5OS2·0.5H2O (Ib), and the independent components are linked into a chain of spiro-fused R44(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, C31H27N5O4S2 (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, C32H22BrCl2N5OS2 (III). Comparisons are made with the structures of some related compounds.
first_indexed 2024-12-10T17:20:23Z
format Article
id doaj.art-48d2314859034c6f809379d9e4030357
institution Directory Open Access Journal
issn 2056-9890
language English
last_indexed 2024-12-10T17:20:23Z
publishDate 2021-04-01
publisher International Union of Crystallography
record_format Article
series Acta Crystallographica Section E: Crystallographic Communications
spelling doaj.art-48d2314859034c6f809379d9e40303572022-12-22T01:39:59ZengInternational Union of CrystallographyActa Crystallographica Section E: Crystallographic Communications2056-98902021-04-0177433534010.1107/S2056989021002310dx2035Reduced 3,4′-bipyrazoles carrying thiophene and thiazole substituents: structures of two intermediates and two productsChayanna Harish Chinthal0Hemmige S. Yathirajan1Nagaraja Manju2Balakrishna Kalluraya3Sabine Foro4Christopher Glidewell5Department of Studies in Chemistry, University of Mysore, Manasagangotri, Mysuru-570 006, IndiaDepartment of Studies in Chemistry, University of Mysore, Manasagangotri, Mysuru-570 006, IndiaDepartment of Studies in Chemistry, Mangalore University, Mangalagangotri, Mangalore-574 199, IndiaDepartment of Studies in Chemistry, Mangalore University, Mangalagangotri, Mangalore-574 199, IndiaInstitute of Materials Science, Darmstadt University of Technology, Alarich-Weiss-Strasse 2, D-64287 Darmstadt, GermanySchool of Chemistry, University of St Andrews, St Andrews, Fife KY16 9ST, UKCycloaddition 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, C25H23N5OS2 (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, C24H19Cl2N5OS2·0.5H2O (Ib), and the independent components are linked into a chain of spiro-fused R44(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, C31H27N5O4S2 (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, C32H22BrCl2N5OS2 (III). Comparisons are made with the structures of some related compounds.http://scripts.iucr.org/cgi-bin/paper?S2056989021002310heterocyclic compoundsreduced bipyrazolessynthesiscrystal structureregiochemistryhydrogen bondingsupramolecular assembly
spellingShingle Chayanna Harish Chinthal
Hemmige S. Yathirajan
Nagaraja Manju
Balakrishna Kalluraya
Sabine Foro
Christopher Glidewell
Reduced 3,4′-bipyrazoles carrying thiophene and thiazole substituents: structures of two intermediates and two products
Acta Crystallographica Section E: Crystallographic Communications
heterocyclic compounds
reduced bipyrazoles
synthesis
crystal structure
regiochemistry
hydrogen bonding
supramolecular assembly
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 heterocyclic compounds
reduced bipyrazoles
synthesis
crystal structure
regiochemistry
hydrogen bonding
supramolecular assembly
url http://scripts.iucr.org/cgi-bin/paper?S2056989021002310
work_keys_str_mv AT chayannaharishchinthal reduced34bipyrazolescarryingthiopheneandthiazolesubstituentsstructuresoftwointermediatesandtwoproducts
AT hemmigesyathirajan reduced34bipyrazolescarryingthiopheneandthiazolesubstituentsstructuresoftwointermediatesandtwoproducts
AT nagarajamanju reduced34bipyrazolescarryingthiopheneandthiazolesubstituentsstructuresoftwointermediatesandtwoproducts
AT balakrishnakalluraya reduced34bipyrazolescarryingthiopheneandthiazolesubstituentsstructuresoftwointermediatesandtwoproducts
AT sabineforo reduced34bipyrazolescarryingthiopheneandthiazolesubstituentsstructuresoftwointermediatesandtwoproducts
AT christopherglidewell reduced34bipyrazolescarryingthiopheneandthiazolesubstituentsstructuresoftwointermediatesandtwoproducts