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

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.

Key words

click chemistry - cycloaddition - copper - nanoparticles - 1-vinyl-1,2,4-triazole

• References and Notes

• 1a Broz P. Polymer-Based Nanostructures: Medical Applications . RSC Publishing; Cambridge: 2010: 398
• 1b Schmidt G. Nanoparticles: From Theory to Application . Wiley-VCH; Weinheim: 2010: 533
• 1c Such GK, Johnston AP. R, Liang K, Caruso F. Progr. Polym. Sci. 2012; 37: 985
• 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.
• 8a Morgan P. Carbon Fibers and their Composites . Taylor and Francis; New York: 2005: 1200
• 8b Rahaman MS. A, Ismail AF, Mustafa A. Polym. Degrad. Stab. 2007; 92: 1421
• 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) ų, 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