Amarta Kumar Pal

Babulal Das

Mithu Saha

Comptes Rendus Chimie

Greener Synthesis of Pyran derivatives under Ultrasound irradiation using Ni nanoparticles as reusable catalyst in aqueous mediumMithu Sahaa, Babulal Dasb , Amarta K. Pal*a  aDepartment of Chemistry, North Eastern Hill University, Mawlai  Campus, Shillong 793022, India.bDepartment of Chemistry, IIT Guwahati, IndiaCONTENT1.	Experimental---------------------------------------------------------22.	General Procedure--------------------------------------------------33.	Spectral data--------------------------------------------------------4-94.	Scanned spectra of 1H and 13C NMR----------------------------10-41GeneralExperimental Melting points were determined in open capillaries and are uncorrected. IR spectra were recorded on Spectrum BX FT-IR, Perkin Elmer (υmax in cm-1) on KBr disks. 1H NMR and 13C NMR (400 MHz and 100 MHz respectively) spectra were recorded on Bruker Avance II-400 spectrometer in CDCl3 (chemical shifts in δ with TMS as internal standard). Mass spectra were recorded on Waters ZQ-2695. Transmission Electron Microscope (TEM) was recorded on JEOL JSM 100CX. Scanning electron microscope (SEM) was recorded on JSM-6360 (JEOL). XRD was recorded on Bruker D8 XRD instrument SWAX .CHN were recorded on CHN-OS analyzer (Perkin Elmer 2400, Series II). Silica gel G (E-mark, India) was used for TLC. Hexane refers to the fraction boiling between 60 οC and 80 οC. Ultrasonication reaction was carried out in JAC 1500 (Made in Korea)X-ray crystallography: The X-ray diffraction data were collected at 296 K with Mo Kα radiation (λ = 0.71073 Å) using a Bruker Nonius SMART APEX II CCD diffractometer equipped with a graphite monochromator. Smart software was used for data collection and also for indexing the reflections and determining the unit cell parameters; the collected data were integrated using saint software. The structures were solved by direct methods and refined by full-matrix least-squares calculations using SHELXTL software. All the non-H atoms were refined in the anisotropic approximation. (CCDC 836545).General procedure for the synthesis of pyran derivatives A mixture of carbonyl compounds 1 (1 mmol), malononitrile 2 (1 mmol) and activated C-H compounds 3-5 (1 mmol) was taken in a round bottle flask to that nickel nanoparticles (10 mol %), water (2 mL) or water-ethanol mixture (1:1) (2 mL) [in case of 4-hydroxy coumarin 5] was added and irradiated in ultrasound for the time in mentioned in table 2. After completion (TLC), the reaction mixture was cooled, filtered and the solvent was removed under reduced pressure. The residue was extracted with ethyl acetate (3 × 10 mL) and the combined organic extract was washed with water (3 × 10 mL), brine (10 mL) and dried over anhydrous Na2SO4. After removing the solvent the crude product was purified by column chromatography over silica gel (60-120 mesh) using hexane-ethyl acetate as eluent to afford the pure products.SUPPORTING INFORMATION1.	Compound 6aIR (KBr): 3476, 3330, 2196, 1659 cm-1. 1H NMR (DMSO-d6, 400 MHz): δ = 1.76 (s, 3H), 3.27 (brs, 2H), 4.67 (s, 1H), 7.21-7.50 (m, 8H), 7.76 (d, J = 8.0 Hz, 2H). ESI-MS m/z 329 [M + H]+. Anal calcd for: C20H16N4O: C, 73.15; H, 4.91; N, 17.06. Found: C, 73.02; H, 4.82; N, 16.91.2.	Compound 6bIR (KBr): 3475, 3326, 2196, 1656 cm-1. 1H NMR (CDCl3+ DMSO-d6, 400 MHz): δ = 1.78 (s, 3H), 2.25 (s, 3H), 4.50 (s, 1H), 6.22 (s, 2H), 7.35 (t, J = 7.8 Hz, 5H), 7.65 (d, J = 8.4 Hz, 4H). 13 C NMR (CDCl3+ DMSO-d6, 100 MHz): δ = 12.4, 20.6, 36.6, 60.1, 98.1, 119.7, 120.2, 125.8, 127.3, 128.7, 128.8, 136.2, 137.3, 139.5, 143.6, 145.6, 158.9. ESI-MS m/z 343 [M + H]+. Anal calcd for C21H18N4O: C, 73.67; H, 5.30; N, 16.36. Found: C, 73.75; H, 5.36; N, 16.48.3.	Compound 6cIR (KBr): 3420, 3310, 2196, 1666 cm-1. 1H NMR (CDCl3+ DMSO-d6, 400 MHz): δ = 1.81 (S, 3H), 4.60 (s, 1H), 4.64 (brs, 2H), 6.95-7.42 (m, 7H), 7.56 (d, J = 8.0 Hz, 2H) . ESI-MS m/z 347 [M + H]+. Anal calcd for C20H15 FN4O: C, 69.37; H, 4.37; N, 16.18 Found: C, 69.29; H, 4.48; N, 16.04.4.	Compound 6dIR (KBr): 3400, 3320, 2230, 1658 cm-1. 1H NMR (CDCl3+ DMSO-d6, 400 MHz): δ = 1.78 (S, 3H), 4.74 (s, 1H), 6.89 (brs, 2H), 7.21 (t, J = 7.4 Hz, 1H), 7.38-7.45 (m, 4H), 7.70 (d, J = 8.0 Hz, 2H), 8.13 (d, J = 8.8 Hz, 2H). 13 C NMR (CDCl3+ DMSO-d6, 100 MHz): δ = 12.5, 36.8, 57.4, 96.9, 119.4, 120.1, 123.5, 125.9, 128.6, 128.8, 137.2, 143.9, 145.1, 146.5, 150.3, 159.5. ESI-MS m/z 374 [M + H]+. Anal calcd for C20H15N5O3: C, 64.08; H, 4.05; N, 18.76. Found: C, 64.23; H, 4.19; N, 18.67.5.	Compound 6eIR (KBr): 3456, 3330, 2196, 1666 cm-1. 1H NMR (CDCl3+ DMSO-d6, 400 MHz): δ = 1.81 (s, 3H), 4.55 (s, 2H), 5.96 (brs, 2H), 7.07 (d, J = 8.4 Hz, 2H), 7.21 (t, J = 7.2 Hz, 1H), 7.37-7.41 (m, 4H), 7.63 (d, J = 8.0 Hz, 2H). ESI-MS m/z 407, 409 [M + H]+. Anal calcd for C20H15 BrN4O: C, 58.98; H, 3.71; N, 13.76. Found: C, 59.06; H, 3.74; N, 13.78.6.	Compound 6fIR (KBr): 3456, 3370, 2230, 1660 cm-1. 1H NMR (CDCl3, 400 MHz): δ = 1.82 (s, 3H), 4.58 (s, 1H), 4.66 (brs, 2H), 7.12 (d, J = 8.4 Hz, 2H), 7.25 (d, J = 8.4 Hz, 2H), 7.38 (t, J = 7.4 Hz, 3H), 7.56 (d, J = 8.0 Hz, 2H). ESI-MS m/z 363, 365 [M + H]+. Anal calcd for C20H15ClN4O: C, 66.21; H, 4.17; N, 15.44. Found: C, 65.92; H, 4.24; N, 15.57.7.	 Compound 6gIR (KBr): 3429, 3400, 2369, 1653 cm-1. 1H NMR (CDCl3+ DMSO-d6, 400 MHz): δ = 1.81 (s, 3H), 4.67 (s, 1H), 4.74 (brs, 2H), 7.25-7.61 (m, 9H). ESI-MS m/z 354 [M + H]+. Anal calcd for C21H15N5O: C, 71.38; H, 4.28; N, 19.82. Found: C, 71.16; H, 4.44; N, 19.85.8.	Compound 6hIR (KBr): 3456, 3363, 2190, 1659 cm-1. 1H NMR (CDCl3+ DMSO-d6, 400 MHz): δ = 1.80 (s, 3H), 4.73 (s, 2H), 6.08 (brs, 2H),7.23-7.67 (m, 7H), 8.03-8.09 (m, 2H). ESI-MS m/z 374[M + H]+. Anal calcd for C20H15N5O3: C, 64.34; H, 4.05; N, 18.76. Found: C, 64.16; H, 3.93; N, 19.03.9.	Compound 6iIR (KBr): cm-1. 1H NMR (CDCl3,,400 MHz): δ = 1.81 (s, 3H), 4.67(brs, 2H), 5.23 (s, 1H), 7.12-7.41 (m, 7H), 7.56 (d, J = 8.0 Hz, 2H). ESI-MS m/z 363, 365 [M + H]+. Anal calcd for C20H15 ClN4O: C, 66.21; H, 4.17; N, 15.44. Found: C, 65.96; H, 4.06; N, 15.29.10.	Compound 7aIR (KBr): 3428, 3371, 2196, 1659, 1613 cm-1. 1H NMR (CDCl3, 400 MHz): δ = 7.23-7.10 (m, 5H), 4.47 (s, 2H), 4.33 (s, 1H), 2.38 (s, 2H), 2.10-2.20 (m, 2H), 1.04 (s, 3H), 0.97 (s, 3H). 13C NMR (CDCl3, 100 MHz): δ = 195.8, 161.5, 157.4, 143.1, 128.5, 127.5, 127.1, 118.6, 114.0, 63.5, 50.6, 40.6, 35.5, 32.2, 28.8, 27.6. ESI-MS m/z 295 [M + H]+. Anal calcd for C18H18N2O2: C, 73.45; H, 6.16; N, 9.52. Found: C, 73.34; H, 6.13; N, 9.64.11.	Compound 7bIR (KBr): 3429, 3330, 2395, 2190, 1679, 1600 cm-1. 1H NMR (CDCl3, 400 MHz): δ = 7.05-7.00 (m, 4H), 4.45 (s, 2H), 4.29 (s, 1H), 2.37 (s, 2H), 2.21 (s, 3H), 2.15 (d, J = 5.6 Hz, 2H), 1.03 (s, 3H), 0.97 (s, 3H).13C NMR (CDCl3, 100 MHz): δ = 196.0, 161.4, 157.3, 140.2, 136.7, 129.3, 127.3, 118.7, 114.1, 63.7, 50.6, 40.6, 35.1, 32.2, 28.9, 27.7, 21.0. ESI-MS m/z 309 [M + H]+. Anal calcd for C19H20N2O2: C, 74.00; H, 6.54; N, 9.08. Found: C, 73.70; H, 6.31; N, 9.02. 12.	Compound 7cIR (KBr): 3420, 3323, 2335, 2196, 1659, 1606 cm-1. 1H NMR (CDCl3, 400 MHz): δ = 7.09 (d, J = 8.0 Hz, 2H), 6.75 (d, J = 8.4 Hz, 2H), 4.49 (s, 2H), 4.28 (s, 1H), 3.69 (s, 3H), 2.38 (s, 2H), 2.19-2.09 (m, 2H) 1.03 (s, 3H), 0.96 (s, 3H). ESI-MS m/z 325 [M + H]+. Anal calcd for C19H20N2O3: C, 70.35; H, 6.21; N, 8.64. Found: C, 70.53; H, 6.09; N, 8.8013.	Compound 7dIR (KBr): 3421, 3363, 2316, 2196, 1653, 1600 cm-1. 1H NMR (CDCl3, 400 MHz): δ = 7.15-7.12 (m, 2H), 6.92-6.88 (m, 2H), 4.49 (s, 2H), 4.33 (s, 1H), 2.38 (s, 2H), 2.20-2.10 (m, 2H), 1.04 (s, 3H), 0.96 (s, 3H). ESI-MS m/z 313 [M + H]+. Anal calcd for C18H17FN2O2: C, 69.22; H, 5.49; N, 8.97. Found: C, 69.42; H, 5.42; N, 8.88. 14.	Compound 7eIR (KBr): 3396, 3323, 2448, 2196, 1666, 1600 cm-1. 1H NMR (CDCl3 + DMSO-d6, 400 MHz): δ = 8.07 (d, J = 8.4 Hz, 2H), 7.37 (d, J = 8.4 Hz, 2H), 6.31 (s, 2H), 4.38 (s, 1H), 2.44 (s, 2H), 2.21-2.07 (m, 2H), 1.05 (s, 3H), 0.95 (s, 3H). ESI-MS m/z 340 [M + H]+. Anal calcd for C18H17N3O4: C, 63.71; H, 5.05; N, 12.38. Found: C, 63.60; H, 5.18; N, 12.29. 15.	Compound 7fIR (KBr): 3390, 3371, 2475, 2196, 1659, 1613 cm-1. 1H NMR (CDCl3 + DMSO-d6, 400 MHz): δ = 7.32 (d, J = 8.4 Hz, 2H), 7.06 (d, J = 8.4 Hz, 2H), 6.14 (s, 2H), 4.21 (s, 1H), 2.40 (s, 2H), 2.19-2.06 (m, 2H), 1.03 (s, 3H), 0.94 (s, 3H). ESI-MS m/z 373, 375 [M + H]+. Anal calcd for C18H17BrN2O2: C, 57.92; H, 4.59; N, 7.51. Found: C, 58.11; H, 4.37; N, 7.78. 16.	Compound 7gIR (KBr): 3390, 3317, 2300, 2190, 1659, 1606 cm-1. 1H NMR (CDCl3, 400 MHz): δ =7.06 (d, J = 8.4 Hz, 2H), 6.71 (brs, 2H), 4.43 (s, 2H), 4.26 (s, 1H), 2.86 (s, 6H), 2.36 (s, 2H), 2.15 (d, J = 3.6 Hz, 2H), 1.03 (s, 3H), 0.97 (s, 3H). ESI-MS m/z 338 [M + H]+. Anal calcd for C20H23N3O2: C, 71.19; H, 6.87; N, 12.45. Found: C, 71.14; H, 7.02; N, 12.33. 17.	Compound 7hIR (KBr): 3356, 2236, 2196, 1679, 1606 cm-1. 1H NMR (CDCl3, 400 MHz): δ = 7.20 (d, J = 8.0 Hz, 2H), 7.11 (d, J = 8.4 Hz, 2H), 4.53 (s, 2H), 4.31 (s, 1H), 2.38 (s, 2H), 2.20-2.10 (m, 2H), 1.04 (s, 3H), 0.95 (s, 3H). ESI-MS m/z 329, 331 [M + H]+. Anal calcd for C18H17ClN2O2: C, 65.75; H, 5.21; N, 8.52. Found: C, 65.64; H, 5.23; N, 8.58. 18.	Compound 7iIR (KBr): 3390, 2350, 2190, 1672, 1639 cm-1. 1H NMR (CDCl3, 400 MHz): δ =7.54 (d, J = 8.0 Hz, 2H), 7.30 (d, J = 8.0 Hz, 2H), 4.61 (s, 2H), 4.38 (s, 1H), 2.40 (s, 2H), 2.21-2.10 (m, 2H), 1.05 (s, 3H), 0.95 (s, 3H). ESI-MS m/z 320 [M + H]+. Anal calcd for C19H17N3O2: C, 71.46; H, 5.37; N, 13.16. Found: C, 71.65; H, 5.40; N, 13.37.19.	Compound 7j IR (KBr): cm-1. 1H NMR (CDCl3, 400 MHz): δ = 7.26-7.05 (m, 4H), 4.78 (s, 1H), 4.56 (s, 2H), 2.38 (s, 2H), 2.19-2.05 (m, 2H), 1.04 (s, 3H), 0.99 (s, 3H). ESI-MS m/z 329, 331 [M + H]+. Anal calcd for C18H17ClN2O2: C, 65.75; H, 5.21; N, 8.52. Found: C, 65.57; H, 5.46; N, 8.45.20.	Compound 7kIR (KBr): 3317, 2380, 2183, 1659, 1593 cm-1. 1H NMR (CDCl3, 400 MHz): δ = 8.31(d, J = 8.4 Hz, 1H), 7.76 (d, J = 8.0 Hz, 1H), 7.65 (d, J = 8.4 Hz, 1H), 7.51 (t, J = 7.6 Hz, 1H), 7.42 (t, J = 7.4 Hz, 1H), 7.33 (t, J = 7.8 Hz, 1H), 7.17 (t, J = 7.2 Hz, 1H), 5.19 (s, 1H), 4.46 (s, 2H), 2.50-2.39 (m, 2H), 2.18-2.07 (m, 2H), 1.05 (s, 3H), 0.99 (s, 3H). ESI-MS m/z 345 [M + H]+. Anal calcd for C22H20N2O2: C, 76.72; H, 5.85; N, 8.13. Found: C, 76.64; H, 5.91; N, 7.96.21.	Compound 7lIR (KBr): 3310, 2909, 1719, 1679, 1613 cm-1. 1H NMR (DMSO-d6, 400 MHz): δ = 10.35 (s, 1H), 7.19 (s, 2H), 7.09-6.73 (m, 4H), 2.52 (m, 2H), 2.15 (d, J = 16.0 Hz, 1H), 2.06 (d, J = 16.0 Hz, 1H), 1.01 s, (3H), 0.98 (s, 3H). ESI-MS m/z 336 [M + H]+. Anal Calcd for: C19H17N3O3: C, 68.05; H, 5.11; N, 12.53. Found: C, 67.93; H, 5.26; N, 12.61.22.	Compound 8aIR (KBr): 3328, 2196, 1712, 1672, 1613 cm-1. 1H NMR (CDCl3 + DMSO-d6, 400 MHz): δ = 7.88-7.11 (m, 9H), 4.43 (s, 1H), 3.22 (brs, 2H). ESI-MS m/z 317 [M + H]+. Anal calcd for: C19H12N2O3: C, 72.15; H, 3.82; N, 8.86. Found: C, 72.04; H, 3.68; N, 8.80.23.	Compound 8bIR (KBr): 3396, 2203, 1712, 1606 cm-1. 1H NMR (CDCl3 + DMSO-d6, 400 MHz): δ = 7.85-6.99 (m, 8H), 4.40 (s, 1H), 3.20 (brs, 2H), 2.20 (s, 3H). ESI-MS m/z 331 [M + H]+. Anal calcd for: C20H14N2O3: C, 72.72; H, 4.27; N, 8.48. Found: C, 72.91; H, 4.36; N, 8.7524.	Compound 8cIR (KBr): 3476, 2196, 1719, 1613 cm-1. 1H NMR (CDCl3 + DMSO-d6, 400 MHz): δ = 8.07-7.23 (m, 8H), 4.60 (s, 1H), 3.11 (brs, 2H). 13C NMR (CDCl3 + DMSO-d6, 100 MHz): δ = 164.9, 163.3, 159.1, 157.3, 154.7, 151.7, 137.8, 133.7, 129.5, 128.5, 127.7, 123.6, 121.4, 117.7, 107.9, 62.5, 41.9. ESI-MS m/z 362 [M + H]+. Anal calcd for: C19H11N3O5: C, 63.16; H, 3.07; N, 11.63. Found: C, 62.87; H, 2.93; N, 11.54.25.	Compound 8d IR (KBr): 3396, 2196, 1710, 1605 cm-1. 1H NMR (CDCl3 + DMSO-d6, 400 MHz): δ = 7.87-6.72 (m, 8H), 6.62 (brs, 2H), 4.42 (s, 1H), 3.69 (s, 3H). ESI-MS m/z 347 [M + H]+. Anal calcd for: C20H14N2O4: C, 69.36; H, 4.07; N, 8.09. Found: C, 69.55; H, 4.10; N, 8.30.26.	Compound 8eIR (KBr): 3421, 2201, 1712, 1614 cm-1. 1H NMR (CDCl3 + DMSO-d6, 400 MHz): δ = 7.89- 7.26 (m, 8H), 6.92 (brs, 2H), 4.56(s, 1H). ESI-MS m/z 342 [M + H]+. Anal calcd for: C20H11N3O3: C, 70.38; H, 3.25; N, 12.31. Found: C, 70.33; H, 3.37; N, 12.47.27.	Compound 8f IR (KBr): 3317, 2203, 1712, 1533 cm-1. 1H NMR (DMSO-d6, 400 MHz): δ = 10.64 (s, 1H), 7.19 (d, J = 7.2 Hz, 1H), 7.74 (t, J = 7.0 Hz, 1H), 7.63 (brs, 2H), 7.52 (t, J = 7.6 Hz, 1H), 7.46 (d, J = 8.0 Hz, 1H), 7.19 (t, J = 6.8 Hz, 2H), 6.91 (t, J = 7.8 Hz, 1H), 6.82 (d, J = 8.0  Hz, 1H),. ESI-MS: m/z 358 [M + H]+. Anal Calcd for: C20H11N3O4: C, 67.23; H, 3.10; N, 11.76. Found: C, 67.12; H, 3.90; N, 11.66.1.	Compound 6a 1H NMR Spectra2.	Compound 6b 1H NMR Spectra3.	Compound 6b 1H NMR Spectra4.	Compound 6c 1H NMR Spectra5.	Compound 6d 1H NMR Spectra1H NMR Spectra6.	Compound 6d  13C NMR Spectra13C NMR Spectra7.	Compound 6e 1H NMR Spectra8.	Compound 6f 1H NMR Spectra9.	Compound6g1H NMR Spectra10.	Compound 6h 1H NMR Spectra11.	Compound 6i 1H NMR Spectra12.	Compound 7a 1H NMR Spectra13.	Compound 7a  13C NMR Spectra14.	Compound 7b  1H NMR Spectra15.	Compound 7b  13C NMR Spectra16.	Compound 7c   1H NMR Spectra17.	Compound 7d  1H NMR Spectra18.	  Compound 7e  1H NMR Spectra19.	 Compound 7f  1H NMR Spectra20.	 Compound 7g  1H NMR Spectra21.	 Compound 7h  1H NMR Spectra22.	 Compound 7i  1H NMR Spectra23.	 Compound 7j  1H NMR Spectra24.	Compound 7k 1H NMR Spectra25.	 Compound 7l  1H NMR Spectra26.	Compound 8a   1H NMR Spectra27.	Compound 8b    1H NMR Spectra28.	Compound 8c    1H NMR Spectra29.	Compound 8c    1H NMR Spectra30.	Compound 8d    1 H NMR Spectra31.	Compound 8e    1H NMR Spectra32.	 Compound 8f    1H NMR Spectra1

Synthesis of pyran derivatives under ultrasound irradiation using Ni nanoparticles as reusable catalysts in aqueous medium

https://comptes-rendus.academie-sciences.fr/chimie/article/10.1016/j.crci.2013.05.012/file/attach/mmc1.doc

Synthesis of pyran derivatives under ultrasound irradiation using Ni nanoparticles as reusable catalysts in aqueous medium

Abstract

Similar works

Full text

Available Versions

Comptes Rendus Chimie