Synlett 2016; 27(06): 900-904
DOI: 10.1055/s-0035-1561292
letter
© Georg Thieme Verlag Stuttgart · New York

A Polymer Nanocomposite with CuNP Stabilized by 1-Vinyl-1,2,4-triazole and Acrylonitrile Copolymer

Alexander S. Pozdnyakov
A.E. Favorsky Irkutsk Institute of Chemistry, Siberian Branch of Russian Academy of Sciences, 1 Favorsky Street, Irkutsk 664033, Russian Federation   Email: omtrof@irioch.irk.ru
,
Artem I. Emel’yanov
A.E. Favorsky Irkutsk Institute of Chemistry, Siberian Branch of Russian Academy of Sciences, 1 Favorsky Street, Irkutsk 664033, Russian Federation   Email: omtrof@irioch.irk.ru
,
Nadezhda P. Kuznetsova
A.E. Favorsky Irkutsk Institute of Chemistry, Siberian Branch of Russian Academy of Sciences, 1 Favorsky Street, Irkutsk 664033, Russian Federation   Email: omtrof@irioch.irk.ru
,
Tamara G. Ermakova
A.E. Favorsky Irkutsk Institute of Chemistry, Siberian Branch of Russian Academy of Sciences, 1 Favorsky Street, Irkutsk 664033, Russian Federation   Email: omtrof@irioch.irk.ru
,
Yulia I. Bolgova
A.E. Favorsky Irkutsk Institute of Chemistry, Siberian Branch of Russian Academy of Sciences, 1 Favorsky Street, Irkutsk 664033, Russian Federation   Email: omtrof@irioch.irk.ru
,
Olga M. Trofimova*
A.E. Favorsky Irkutsk Institute of Chemistry, Siberian Branch of Russian Academy of Sciences, 1 Favorsky Street, Irkutsk 664033, Russian Federation   Email: omtrof@irioch.irk.ru
,
Alexander I. Albanov
A.E. Favorsky Irkutsk Institute of Chemistry, Siberian Branch of Russian Academy of Sciences, 1 Favorsky Street, Irkutsk 664033, Russian Federation   Email: omtrof@irioch.irk.ru
,
Tatyana N. Borodina
A.E. Favorsky Irkutsk Institute of Chemistry, Siberian Branch of Russian Academy of Sciences, 1 Favorsky Street, Irkutsk 664033, Russian Federation   Email: omtrof@irioch.irk.ru
,
Vladimir I. Smirnov
A.E. Favorsky Irkutsk Institute of Chemistry, Siberian Branch of Russian Academy of Sciences, 1 Favorsky Street, Irkutsk 664033, Russian Federation   Email: omtrof@irioch.irk.ru
,
Galina F. Prozorova
A.E. Favorsky Irkutsk Institute of Chemistry, Siberian Branch of Russian Academy of Sciences, 1 Favorsky Street, Irkutsk 664033, Russian Federation   Email: omtrof@irioch.irk.ru
› Author Affiliations
Further Information

Publication History

Received: 21 September 2015

Accepted after revision: 21 November 2015

Publication Date:
28 December 2015 (online)


Abstract

An insoluble nanocomposite with copper nanoparticles (CuNP) stabilized by 1-vinyl-1,2,4-triazole and acrylonitrile copolymer was synthesized and characterized by scanning electron microscopy, Fourier transform infrared spectroscopy, X-ray diffraction, and thermogravimetric data analysis. The nanocomposite showed high catalytic activity in the multicomponent synthesis of 1-benzyl-4-phenyl- and 1-benzyl-4-phenyl-5-(2-phenylethynyl)-1H-1,2,3-triazoles.

Supporting Information

 
  • References and Notes

    • 2a Meldal M, Tornøe CW. Chem. Rev. 2008; 108: 2952
    • 2b Hein JE, Fokin VV. Chem. Soc. Rev. 2010; 39: 1302
    • 2c Aragão-Leoneti V, Campo VL, Gomes AS, Field RA, Carvalho I. Tetrahedron 2010; 66: 9475
    • 2d Liang L, Astruc D. Coord. Chem. Rev. 2011; 255: 2933
    • 2e Haldón E, Nicasio MC, Pérez PJ. Org. Biomol. Chem. 2015; 13: 9528
    • 3a Pozdnyakov AS, Emel'yanov AI, Ermakova TG, Prozorova GF. Polym. Sci., Ser. B 2014; 56: 238
    • 3b Myachina GF, Kon'kova TV, Korzhova SA, Ermakova TG, Pozdnyakov AS, Sukhov BG, Arsent'ev KY, Likhoshvai EV, Trofimov BA. Dokl. Chem. 2010; 431: 63
    • 3c Prozorova GF, Korzhova SA, Emel'yanov AI, Pozdnyakov AS, Khutsishvili SS, Vakul'skaya TI, Ermakova TG. Russ. J. Appl. Chem. 2013; 86: 1452
    • 3d Prozorova GF, Pozdnyakov AS, Kuznetsova NP, Korzhova SA, Emel'yanov AI, Ermakova TG, Fadeeva TV, Sosedova LM. Int. J. Nanomed. 2014; 9: 1883
    • 4a Jin T, Yan M, Yamamoto Y. ChemCatChem 2012; 4: 1217
    • 4b Alonso F, Moglie Y, Radivoy G, Yus M. Synlett 2012; 23: 2179
    • 4c Abdulkin P, Moglie Y, Knappett BR, Jefferson DA, Yus M, Alonso F, Wheatley AE. H. Nanoscale 2013; 5: 342
    • 4d Kaur S, Bhalla V, Kumar M. Chem. Commun. 2015; 51: 526
    • 4e Alonso F, Moglie Y, Radivoy G. Acc. Chem. Res. 2015; 48: 2516
  • 5 1-Vinyl-1,2,4-triazole was synthesized according to the previously reported procedure: Ermakova TG, Tatarova LA, Kuznetsova NP. Russ. J. Gen. Chem. 1997; 67: 805
  • 6 Copolymer VT–AN A mixture of 1-vinyl-1,2,4-triazole (1.28 g, 13.46 mmol), acrylonitrile (0.72 g, 13.57 mmol), and AIBN (0.01 g, 0.06 mmol) in DMF (1 mL) was sealed in a glass tube under argon and maintained at 80 °C for 0.5 h. After cooling to r.t., the resulting polymer was precipitated by addition into distilled H2O (500 mL), filtered, and washed several times with EtOH. Finally, the solid was dried under vacuum at 50 °C overnight until a constant weight was achieved to give the VT–AN copolymer (1.42 g, 71% yield).
  • 7 Nanocomposite with CuNP Stabilized by Copolymer VT–AN A solution of СuCl2·2H2O (0.3 g, 1.76 mmol) in HNO3 (6 mL, 37% concentration) was added to a solution of VT–AN prepared by dissolving the copolymer (0.5 g, 3.38 mmol) in HNO3 (10 mL) and stirring for 5 h. The HNO3 was evaporated at 90 °C, and the resulting complex was washed with distilled H2O and dried under vacuum at r.t. for 6 h to achieve a constant weight and was then kept at 210 °C for 1 h. Under these conditions, vigorous evolution of gas was observed, and the nanocomposite was observed to increase three- to fourfold in volume.
  • 9 Elemental analysis was performed with a Thermo Finnigan Flash EA 1112 microanalyzer. FTIR spectra were recorded on a Vertex 70 FTIR Spectrometer in the spectral range between 4000 and 400 cm–1, using KBr pellets. The SEM micrographs were recorded on a scanning electron microscope TM 3000 HITACHI. XRD measurements were performed using a BRUKER D8 ADVANCE powder diffractometer. Data were collected on a Bruker D8 Venture diffractometer with MoKα (λ = 0.71073 Å) using the φ and the ω scans. TGA was obtained with a 449C Jupiter from Netzsch with a heating rate of 10 °C/min. The 1H NMR and 13C NMR spectra were recorded on a Bruker DPX-400 spectrometer at r.t. Mass spectra were obtained with a GC–MS Agilent 5975C.
  • 10 1-Benzyl-4-phenyl-1H-1,2,3-triazoles 1 To a solution of NaN3 (0.2 g, 3.12 mmol) in MeOH (20 mL) was added BnCl (0.36 mL, 3.12 mmol), PhC≡CH (0.32 mL, 3.12 mmol), and CuNP nanocomposite (0.027 g, 0.1 mmol). The reaction mixture was stirred at r.t. for 14 h and then filtered to remove the catalyst. The solvent was partially removed on a rotary evaporator, and the precipitated NaCl was filtered off. The filtrate was left at r.t. overnight. Compound 1 was obtained as colorless crystals; yield: 92%; mp 130–132 °C. 1H NMR (400.13 MHz, CDCl3): δ = 5.53 (s, 2 Н, CH2Ph), 7.26–7.38 (m, 8 Н, Н m , Н p Ph and Н m , Н р , Н о CH2Ph), 7.63 (s, 1 Н, Н-5), 7.77 (m, 2 Н, Н о Ph). 13C NMR (100.62 MHz, CDCl3): δ = 54.28 (СН2N), 119.58 (C-5), 125.77 (C m Ph), 128.87 (C o Ph), 128.12 (C o CH2Ph), 129.22 (C m CH2Ph), 128.22 (C p Ph), 128.84 (C p CH2Ph), 130.65 (C i Ph), 134.79 (C i CH2Ph), 148.29 (C-4). MS: m/z (%) = 235 (26) [М+], 206 (100), 180 (25), 116 (100), 91 (100). Anal. Calcd for C15H13N3: С, 76.57; H, 5.57; N, 17.86. Found: C, 76.35; H, 5.68; N, 17.98. 1-Benzyl-4-phenyl-5-(2-phenylethynyl)-1H-1,2,3-triazoles 2 To a solution of NaN3 (0.2 g, 3.12 mmol) in MeOH (20 mL) was added PhCH2Cl (0.36 mL, 3.12 mmol), PhC≡CH (0.64 mL, 6.24 mmol), and CuNP nanocomposite (0.027 g, 0.1 mmol). The reaction mixture was stirred at r.t. for 14 h and then filtered to remove the catalyst. The solvent was partially removed on a rotary evaporator, and the precipitated NaCl was filtered off. The filtrate was left at r.t. overnight. Compound 2 was obtained as colorless crystals; yield: 89%; mp 90–92 °C. 1H NMR (400.13 MHz, CDCl3): δ = 5.66 (s, 2 Н, CH2Ph), 7.33–7.49 (m, 13 Н, Н m , Н p Ph and Н m , Н р , Н о CH2Ph and C≡CPh), 8.17 (m, 2 Н, Н о Ph). 13C NMR (100.62 MHz, CDCl3): δ = 53.07 (СН2N), 75.71 (≡С-triazole), 102.42 (≡СPh); 117.32 (С-5), 121.56 (С i PhC≡C), 126.30 (C m Ph), 128.18 (C m C≡CPh), 128.58 (C p Ph), 128.67 (C p CH2Ph), 128.75 (C o Ph and CH2Ph), 128.97 (C m CH2Ph), 129.77 (C p C≡CPh), 130.41 (C i Ph), 131.65 (C o C≡CPh), 134.84 (C i CH2Ph), 148.23 (C-4). MS: m/z (%) = 335 (26) [М+], 216 (45), 91 (54). Anal. Calcd for C23H17N3: С, 82.36; H, 5.11; N, 12.53. Found: C, 82.26; H, 5.15; N, 12.61.
    • 11a Kidwai M, Bansal V, Kumar Mishra N, Kumar A, Mozumdar S. Synlett 2007; 1581
    • 11b Albaladejo MJ, Alonso F, Moglie Y, Yus M. Eur. J. Org. Chem. 2012; 16: 3093
  • 12 Crystal Data for C23H17N3 M r = 335.39, monoclinic, space group P 21/c, a = 19.081(5) Å, b = 5.5653(17) Å, c = 17.947(5) Å, α = 90, β = 109.617(9), γ = 90, V = 1795.2(9) Å3, Z = 4, T = 296.0 K, μ(MoKα) = 0.074 mm–1, D calcd = 1.241 g/cm3, 4263 reflections measured (4.82 ≤ 2Θ ≤ 60.3), 3133 unique (R int = 0.0680, R σ = 0.0278) which were used in all calculations. The final R 1 was 0.0579 (I > 2σ(I)) and wR 2 was 0.1728 (all data). The structure was solved and refined by direct methods, and nonhydrogen atoms were refined anisotropically using SHELX.14 The coordinates of the hydrogen atoms were calculated from geometrical positions. Crystallographic data for compound 2 have been deposited with the accession number CCDC 976226 and can be obtained free of charge from the ­Cambridge Crystallographic Data Centre via www.ccdc.cam.ac.uk/data_request/cif.
  • 13 Raghavendra MS, Lam Y. Tetrahedron Lett. 2004; 45: 6129
  • 14 Sheldrick GM. Acta Crystallogr., Sect. A: Found. Advances 2008; 64: 112