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Synthesis and Self-Assemblies of Bithiophene Functionalized 1H-Pyrazole Derivatives

  • Park, Jung Su (Department of Chemistry, Sookmyung Women's University)
  • Received : 2013.11.04
  • Accepted : 2013.12.11
  • Published : 2014.04.20
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Abstract

Keywords

Experimental

All reactions were carried out under an inert atmosphere of argon. THF was distilled from sodium with benzophen-one. Dichloromethane and DMF were distilled over CaH2. Pd(PPh3)4 and CuI were purchased from Aldrich and used without further purification. The compounds, 2,2'-bithiophen-5-yltributylstannane, tert-butyl 4-iodo-1H-pyrazole-1-carbox-ylate, tert-butyl 4-iodo-3,5-dimethyl-1H-pyrazole-1-carboxylate, and tert-butyl 4-iodo-3,5-diphenyl-1H-pyrazole-1-carboxylate were synthesized according to the reported pro-cedures.25,26 NMR spectra were recorded on a Varian Inova 400 MHz FT-NMR spectrometer at ambient temperature.

Synthesis of 4-([2,2'-Bithiophen]-5-yl)-1H-pyrazole (1). A mixture of 2,2'-bithiophen-5-yltributylstannane (5.02 g, 11 mmol), tert-butyl 4-iodo-1H-pyrazole-1-carboxylate (2.94 g, 10 mmol), Pd(PPh3)4 (0.58 g, 0.5 mmol), and CuI (0.19 g, 1 mmol) in 50 mL of THF was stirred for 24 h under reflux condition and then cooled to room temperature. The solvent removed by vacuum and the residue was heated for 30 minutes under vacuum at 180 °C. After cooling at room temperature, purification of the product by flash column chromatography (SiO2: n-hexanes/DCM) provided the corre-sponding product 1 in 65% yield. 1H NMR (400 MHz, DMSO-d6) δ 13.09 (s, 1H), δ 7.97 (br s, 2H), δ 7.45 (dd, J = 5.1, 1.1 Hz, 1H), δ 7.24 (dd, J = 3.6, 1.1 Hz, 1H), δ 7.21 (d, J = 3.7 Hz, 1H), δ 7.16 (d, J = 3.7 Hz, 1H), δ 7.06 (dd, J = 5.1, 3.6 Hz, 1H); 13C NMR (101 MHz, DMSO) δ 136.7, 134.5, 133.3, 128.3, 124.9, 124.6, 123.5, 123.2, 115.0; HRMS (ESI) m/z calcd. for C11H8N2S2 [MH]+ 233.0207; found 233.0096.

Synthesis of 4-([2,2'-Bithiophen]-5-yl)-3,5-dimethyl-1H-pyrazole (2). The reaction procedures was similar to the preparation of compound 1 except using tert-butyl 4-iodo-3,5-dimethyl-1H-pyrazole-1-carboxylate instead of tert-butyl 4-iodo-1H-pyrazole-1-carboxylate. (Yield 59%) 1H NMR (400 MHz, DMSO-d6) δ 12.49 (s, 1H), δ 7.46 (dd, J = 5.1, 1.0 Hz, 1H), δ 7.30-7.22 (m, 2H), δ 7.07 (dd, J = 5.1, 3.6 Hz, 1H), δ 6.94 (d, J = 3.7 Hz, 1H), δ 2.30 (s, 6H); 13C NMR (101 MHz, DMSO-d6) δ 145.4, 136.6, 135.0, 134.01, 128.3, 124.9, 124.9, 124.3, 123.5, 110.1, 13.4, 10.5; HRMS (ESI) m/z calcd. for C13H12N2S2 [MH]+ 261.0520; found 261.0408.

Table 1.Crystallographic data for 1 and 3

Synthesis of 4-([2,2'-Bithiophen]-5-yl)-3,5-diphenyl-1H-pyrazole (3). The reaction procedure was similar to the preparation of compound 1 except using tert-butyl 4-iodo-3,5-diphenyl-1H-pyrazole-1-carboxylate instead of tert-butyl 4-iodo-1H-pyrazole-1-carboxylate. (Yield 49%) 1H NMR (400 MHz, DMSO-d6) δ 13.59 (s, 1H), δ 7.52 (m, 4H), δ 7.46 (dd, J = 5.1, 0.9 Hz, 1H), δ 7.37 (m, 6H), δ 7.26 (d, J = 3.6 Hz, 1H), δ 7.24 (dd, J = 3.6, 0.9 Hz, 1H), ä 7.04 (dd, J = 5.1 , 3.6 Hz, 1H), δ 6.92 (d, J = 3.7 Hz, 1H); 13C NMR (101 MHz, DMSO-d6) δ 137.3, 136.4, 133.5, 129.8, 129.0-128.4 (br), 128.3, 127.4, 125.3, 125.1, 124.2, 123.9, 108.3, 99.6; HRMS (ESI) m/z calcd. for C23H16N2S2 [MH]+ 385.0833; found 385.0685.

X-ray Crystallography. All X-ray crystallographic data were collected on a Nonius Kappa CCD diffractometer using a graphite monochromator with MoKα radiation (λ = 0.71073 Å). The data were collected at 153 K using an Oxford Cryostream low temperature device. Details of crystal data, data collection and structure refinement are listed in Table 1. Data reductions were performed using DENZO-SMN.27 The structure was solved by direct methods and refined by full-matrix least-squares on F2 with anisotropic displacement parameters for the non-H atoms using SHELXL-97.28 The hydrogen atoms were calculated in ideal positions with isotropic displacement parameters set to 1.2xUeq of the attached atom (1.5 × Ueq for methyl hydrogen atoms). All the calculations were carried out with the SHELXTL pro-gram.29

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  2. ChemInform Abstract: Synthesis and Self‐Assemblies of Bithiophene Functionalized 1H‐Pyrazole Derivatives. vol.45, pp.39, 2014, https://doi.org/10.1002/chin.201439139