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Synlett 2018; 29(13): 1776-1780
DOI: 10.1055/s-0037-1610183
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© Georg Thieme Verlag Stuttgart · New York

One-Pot Three-Component Synthesis of Bispyrazole-thiazole-pyran-2-one Heterocyclic Hybrids

Aicha Saidoun
a   Laboratoire de Chimie Organique Appliquée, Faculté de Chimie, Université des Sciences et de la Technologie Houari Boumediène, BP 32, El-Alia Bab-Ezzouar, 16111 Alger, Algeria   Email: yrachedi@gmail.com
,
Leila Boukenna
a   Laboratoire de Chimie Organique Appliquée, Faculté de Chimie, Université des Sciences et de la Technologie Houari Boumediène, BP 32, El-Alia Bab-Ezzouar, 16111 Alger, Algeria   Email: yrachedi@gmail.com
b   Centre de Recherche Scientifique et Technique en Analyses Physico-Chimiques (CRAPC), BP 384, Bou-Ismail, 42004 Tipaza, Algeria
,
Yahia Rachedi*
a   Laboratoire de Chimie Organique Appliquée, Faculté de Chimie, Université des Sciences et de la Technologie Houari Boumediène, BP 32, El-Alia Bab-Ezzouar, 16111 Alger, Algeria   Email: yrachedi@gmail.com
,
Oualid Talhi*
b   Centre de Recherche Scientifique et Technique en Analyses Physico-Chimiques (CRAPC), BP 384, Bou-Ismail, 42004 Tipaza, Algeria
c   QOPNA & Department of Chemistry, University of Aveiro, 3810-193 Aveiro, Portugal   Email: oualid.talhi@ua.pt   Email: artur.silva@ua.pt
,
Yacine Laichi
b   Centre de Recherche Scientifique et Technique en Analyses Physico-Chimiques (CRAPC), BP 384, Bou-Ismail, 42004 Tipaza, Algeria
,
Najet Lemouari
b   Centre de Recherche Scientifique et Technique en Analyses Physico-Chimiques (CRAPC), BP 384, Bou-Ismail, 42004 Tipaza, Algeria
,
Mohamed Trari
d   Laboratoire de Stockage et de Valorisation des Energies Renouvelables, Faculté de Chimie, Université des Sciences et de la Technologie Houari Boumediène BP 32, El-Alia Bab-Ezzouar, 16111 Alger, Algeria
,
Khaldoun Bachari
c   QOPNA & Department of Chemistry, University of Aveiro, 3810-193 Aveiro, Portugal   Email: oualid.talhi@ua.pt   Email: artur.silva@ua.pt
,
Artur M.S. Silva  *
c   QOPNA & Department of Chemistry, University of Aveiro, 3810-193 Aveiro, Portugal   Email: oualid.talhi@ua.pt   Email: artur.silva@ua.pt
› Author AffiliationsThanks are due to the University of Aveiro and FCT/MEC for financial support to the QOPNA research project (FCT UID/QUI/00062/2013), ­financed by national funds and, when appropriate, co-financed by FEDER under the PT2020 Partnership Agreement, as well as to the Portuguese NMR Network. We would also like to thank FCT/MEC and the General Directorate for Scientific Research and Technological ­Development – DGRSDT of Algeria and the Agence Thématique de ­Recherche en Sciences et Technologie ATRST for approving the co-­financed bilateral project PT-DZ/0005.
Further Information

Publication History

Received: 20 April 2018

Accepted after revision: 16 May 2018

Publication Date:
25 June 2018 (online)

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Abstract

A new series of some interesting bispyrazole-thiazole-pyran-2-one heterocyclic hybrids has been efficiently synthesized via a one-pot catalyst-free three-component reaction of α-bromoacetylated pyran-2-one derivatives, thiosemicarbazide, and polysubstituted-1-(1H-pyrazol-4-yl)butane-1,3-diones. This multicomponent procedure has been advantageously applied to prepare a structural diversity of hetero­cyclic hybrids characterized by extensive 1D and 2D NMR spectroscopic studies.

Key words

pyrazoles - thiazoles - pyran-2-ones - chromen-2-ones - three-component synthesis - 1D and 2D NMR

Supporting Information

    Supporting information for this article is available online at https://doi.org/10.1055/s-0037-1610183.
  • Supporting Information
 

  • References and Notes

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  • 15 General Procedure for the Synthesis of Bispyrazole-thiazole-pyran-2-one Hybrids 13a–d, 14, 15a-c, 15e and 16An equimolar mixture of the appropriate 3-(2-bromoacetyl)-pyran-2-one 10 or 12 (1 mmol), thiosemicarbazide 11 (91 mg, 1 mmol), and diketo-phenylpyrazoles (6a–e or 9, 1 mmol) was heated to reflux in absolute ethanol (10 mL) with vigorous stirring for 30–45 min. After completion of the reaction as indicated by TLC (using a 3:1 mixture of CHCl3/EtOH as eluent), the products were collected by filtration and then washed with hot ethanol to afford pure products.
  • 16 3-{2-[3′-(4-Chlorophenethyl)-5′-hydroxy-5-methyl-1′-phenyl-1′H,2H-(3,4′-bispyrazol)-2-yl]thiazol-4-yl}-4-hydroxy-6-methyl-2H-pyran-2-one (13b)C30H24ClN5O4S, white solid, 0.50 g (85%), mp 299–301 °C. 1H NMR (400 MHz, DMSO-d 6): δ = 2.21 (s, 3 H, 6-CH 3), 2.32 (s, 3 H, 5b-CH3), 2.76 (br s, 4 H, H-1c and H-2c), 5.97 (s, 1 H, H-5), 6.40 (s, 1 H, H-4b), 7.00 (d, J = 8.2 Hz, 2 H, H-2′′′,6′′′), 7.08 (d, J = 8.2 Hz, 2 H, H-3′′′,5′′′), 7.28–7.31 (m, 1 H, H-4′′), 7.45–7.49 (m, 2 H, H-3′′,5′′), 7.64–7.66 (m, 2 H, H-2′′,6′′), 7.90 (s, 1 H, H-5a), 11.53 (s, 1 H, 5′-OH), 12.53 (s, 1 H, 4-OH) ppm. 13C NMR (100 MHz, DMSO-d 6): δ = 13.8 (5b-CH3), 19.8 (6-CH3), 28.4 (C-1c), 33.2 (C-2c), 91.5 (C-4′), 94.5 (C-3), 101.1 (C-5), 111.5 (C-5a), 113.6 (C-4b), 122.8 (C-2′′,6′′), 126.5 (C-4′′), 128.2 (C-3′′′,5′′′), 129.2 (C-3′′,5′′), 130.4 (C-2′′′,6′′′), 130.8 (C-4′′′), 135.3 (C-3b), 138.8 (C-1′′), 140.3 (C-1′′′), 144.4 (C-4a), 149.7 (C-3′), 152.4 (C-5b), 160.6 (C-2a), 161.8 (C-2), 162.9 (C-6), 165.1 (C-5′), 168.3 (C-4) ppm. HRMS-ESI+: m/z calcd for [C30H24ClN5O4S + H]+: 586.1310; found: 586.1313.
  • 17 4-Hydroxy-3-{2-[5′-hydroxy-3′,5-dimethyl-1′-phenyl-1′H,2H-(3,4′-bispyrazol)-2-yl]thiazol-4-yl}-6-methyl-2H-pyran-2-one (14)C23H19N5O4S, white solid, 0.44 g (95%), mp 235–237 °C. 1H NMR (400 MHz, DMSO-d 6): δ = 2.07 (s, 3 H, 3′-CH3), 2.20 (s, 3 H, 6-CH3), 2.32 (s, 3 H, 5b-CH3), 6.01 (s, 1 H, H-5), 6.49 (s, 1 H, H-4b), 7.26–7.30 (m, 1 H, H-4′′), 7.44–7.48 (m, 2 H, H-3′′,5′′), 7.66–7.68 (m, 2 H, H-2′′,6′′), 7.94 (s, 1 H, H-5a), 11.55 (s, 1 H, 5-OH), 12.74 (s, 1 H, 4-OH) ppm. 13C NMR (100 MHz, DMSO-d 6): δ = 13.8 (5b-CH3and 3′-CH3), 19.8 (6-CH3), 91.8 (C-4′), 94.6 (C-3), 101.1 (C-5), 111.8 (C-5a), 113.2 (C-4b), 122.5 (C-2′′,6′′), 126.2 (C-4′′), 129.2 (C-3′′,5′′), 135.7 (C-3b), 138.9 (C-1′′), 144.4 (C-4a), 147.1 (C-3′), 152.5 (C-5b), 160.7 (C-2a), 161.8 (C-2), 162.9 (C-6), 165.3 (C-5′), 168.5 (C-4) ppm. HRMS-ESI+: m/z calcd for [C23H19N5O4S + H]+: 462.1231; found: 462.1230.
  • 18 3-{2-[5′-Hydroxy-3′-(4-methoxyphenethyl)-5-methyl-1′-phenyl-1′H,2H-(3,4′-bispyrazol)-2-yl]thiazol-4-yl}-2H-chromen-2-one (15e)C34H27N5O4S, white solid, 0.36 g (60%), mp 265–267 °C. 1H NMR (400 MHz, DMSO-d 6): δ = 2.34 (s, 3 H, 5b-CH3), 2.71 (br s, 4 H, H-1c and H-2c), 3.51 (s, 3 H, 4′′′-OCH3), 6.42 (br s, 2 H, H-5 and H-4b), 6.56 (d, J = 8.5 Hz, 2 H, H-3′′′,5′′′), 6.91 (d, J = 8.4 Hz, H-2′′′,6′′′), 7.06–7.09 (m, 1 H, H-6), 7.28–7.32 (m, 1 H, H-4′′), 7.38–7.40 (m, 1 H, H-8), 7.45–7.49 (m, 2 H, H-3′′,5′′), 7.53–7.57 (m, 1 H, H-7), 7.86–7.88 (m, 2 H, H-2′′,6′′), 7.96 (s, 1 H, H-4), 8.09 (s, 1 H, H-5a), 11.68 (s, 1 H, 5′-OH) ppm. 13C NMR (100 MHz, DMSO-d 6): δ = 13.9 (5b-CH3), 29.7 (C-1c), 33.2 (C-2c), 55.1 (4′′′-OCH3), 92.2 (C-4′), 112.8 (C-4b), 113.8 (C-3′′′,5′′′), 116.4 (C-8), 116.8 (C-5a), 119.1 (C-4a), 120.7 (C-3), 121.2 (C-2′′,6′′), 124.9 (C-6), 125.8 (C-4′′), 128.5 (C-5), 129.5 (C-2′′′,6′′′), 129.6 (C-3′′,5′′), 132.3 (C-7), 133.5 (C-1′′′), 135.3 (C-3b), 139.3 (C-4), 139.4 (C-1′′), 144.8 (C-4a), 150.9 (C-3′), 151.7 (C-5b), 152.8 (C-8a), 157.7 (C-4′′′), 159.0 (C-2), 160.3 (C-2a), 161.7 (C-5′) ppm. HRMS-ESI+: m/z calcd for [C34H27N5O4S + H]+: 602.1857; found: 602.1858.
  • 19 3-{2-[5′-Hydroxy-3′,5-dimethyl-1′-phenyl-1′H,2H-(3,4′-bispyrazol)-2-yl]thiazol-4-yl}-2H-chromen-2-one (16)C26H19N5O3S, white solid, 0.35 g (72%), mp 248–250 °C. 1H NMR (400 MHz, DMSO-d 6): δ = 2.09 (s, 3 H, 3′-CH3), 2.34 (s, 3 H, 5b-CH3), 6.42 (br s, 1 H, H-5), 6.50 (s, 1 H, H-4b), 7.06–7.10 (m, 1 H, H-6), 7.32 (s, 1 H, H-4′′), 7.37–7.39 (m, 1 H, H-8), 7.47–751 (m, 2 H, H-3′′,5′′), 7.52–7.56 (m, 1 H, H-7), 7.89–7.91 (m, 2 H, H-2′′,6′′), 8.06 (s, 1 H, H-4), 8.11 (s, 1 H, H-5a), 11.72 (s, 1 H, 5′-OH) ppm. 13C NMR (100 MHz, DMSO-d 6): δ = 13.8 (5b-CH3and 3′-CH3), 91.9 (C-4′), 112.7 (C-4b), 116.4 (C-8), 116.9 (C-5a), 119.1 (C-4a), 120.8 (C-3), 121.1 (C-2′′,6′′), 124.9 (C-6), 125.9 (C-4′′), 128.4 (C-5), 129.7 (C-3′′,5′′), 132.4 (C-7), 135.4 (C-3b), 139.2 (C-4), 139.5 (C-1′′), 144.8 (C-4a), 149.3 (C-3′), 151.7 (C-5b), 152.8 (C-8a), 159.0 (C-2), 160.60 (C-2a), 162.0 (C-5′) ppm. HRMS-ESI+: m/z calcd for [C26H19N5O3S + H]+: 482.1281; found: 482.1274.