1、S1 Supplementary Material An Efficient One-pot Synthesis of Symmetrical Diselenides or Ditellurides from Halides with CuO nanopowder/Se0 or Te0/Base Devender Singh, Anna M. Deobald, Leandro R. S. Camargo, Greice Tabarelli, Oscar E. D. Rodrigues,* and Antonio L. Braga,* Departamento de Qumica, Univer
2、sidade Federal de Santa Maria, 97105-900, Santa Maria, RS, Brazil Departamento de Qumica, Universidade Federal de Santa Catarina, 88040-970, Florianpolis, SC, Brazil e-mail: albragaqmc.ufsc.br, rodriguesoedsmail.ufsm.br S2 Contents General InformationS3 General procedure for the synthesis of Diselen
3、ides and ditelluridesS3 Spectroscopic Data .S4 Copies of 1H NMR , 13C NMR and mass spectrum of CompoundsS9 77Se NMR spetra of diselenides.S33 Mass spectra of selected dichalcogenides.S48 References.S51 S3 General Information: CuO nano particles (mean particle size, 33 nm, surface area, 29 m2/g and p
4、urity, 99.99%) were purchased from Sigma Aldrich. 1H and 13C NMR spectra were recorded at 400 and 100 MHz respectively with tetramethylsilane as internal standard. 77Se NMR were recorded at 76.28 MHZ respectively with diphenyl diselenide as a 77Se external reference (463.15 ppm). Column chromatograp
5、hy was performed using Merck Silica Gel (230-400 mesh). Thin layer chromatography (TLC) was performed using Merck Silica Gel GF254, 0.25 mm thickness. For visualization, TLC plates were either placed under ultraviolet light, or stained with iodine vapor, or acidic vanillin. All reagents used were pu
6、rchased from Sigma Aldrich. 1H and 13C NMR spectral data of the compounds are identical to those reported. High resolution ESI mass spectra were obtained from a Fourier transform ion cyclotron resonance (FT-ICR) mass spectrometer, an RF-only hexapole ion guide and an external electrospray ion source
7、. General Procedure for the Synthesis of Diselenides: To a stirred solution of Se0 metal (2.0 mmol) and halides (1.0 mmol) in dry DMSO (2.0 mL) was added CuO nanoparticles (10.0 mol %) followed by KOH (2.0 equiv) under nitrogen atmosphere at 90 0C. The progress of the reaction was monitored by TLC.
8、After the reaction was complete, the reaction mixture was allowed to cool, which was subjected to column chromatographic separation to give pure Diselenides. The identity and purity of the product was confirmed by 1H and 13C NMR spectroscopic analysis. The same procedure was followed for the synthes
9、is of Ditellurides. S4 Spectroscopic Data 1, 2-diphenyldiselenide (2a):1, 7 Yield: 96%; 1H NMR (CDCl3, 200 MHz): = 7.61 7.57 (m, 2H), 7.25 7.21 (m, 3H); 13C NMR (CDCl3, 50 MHz); 77Se NMR (CDCl3, 76.28 MHz) = 463.1; IR (KBr), (cm-1): 3040, 1585, 1475, 790. 1, 2-dip-tolyldiselenide (2b):1,7 Yield: 96%
10、; 1H NMR (CDCl3, 200 MHz): = 7.47 (d, J= 8.4 Hz, 2H), 7.04 (d, J= 8.4 Hz, 2H), 2.30 (s, 3H); 13C NMR (CDCl3, 50 MHz) = 139.32, 133.20, 130.51, 127.41, 22.80; 77Se NMR (CDCl3, 76.28 MHz) = 409.6; IR (KBr), (cm-1): 2916, 1627, 1396, 802. 1, 2-dio-tolyldiselenide (2c):5 Yield: 90%; 1H NMR (CDCl3, 200 M
11、Hz): = 7.61 (d, J= 7.2 Hz, 1H), 7.17 6.99 (m, 3H), 2.40 (s, 3H); 13C NMR (CDCl3, 50 MHz) = 138.69, 132.57, 130.81, 129.88, 127.91, 126.78, 22.17; 77Se NMR (CDCl3, 76.28 MHz) = 405.2; IR (KBr), (cm-1): 2908, 1581, 1288, 817. 1, 2-bis (4-chlorophenyl)diselenide (2d):1 Yield: 86%; 1H NMR (CDCl3, 200 MH
12、z): = 7.47 (d, J= 8.6 Hz, 2H), 7.20 (d, J= 8.6 Hz, 2H); 13C NMR (CDCl3, 50 MHz) = 134.19, 133.16, 129.53, 129.27; 77Se NMR (CDCl3, 76.28 MHz) = 449.3; IR (KBr), (cm-1): 3070, 1465, 1002, 810. S5 1, 2-bis (2-chlorophenyl)diselenide (2e):6 Yield: 90%; 1H NMR (CDCl3, 200 MHz): = 7.59 7.54 (m, 1H), 7.30
13、 7.24 (m, 1H), 7.15 7.06 (m, 2H); 13C NMR (CDCl3, 50 MHz) = 134.04, 133.06, 130.52, 129.15, 128.23, 127.78; 77Se NMR (CDCl3, 76.28 MHz) = 476.9; IR (KBr), (cm-1): 3070, 1465, 1080, 810. 2,2-diselenidediyldiphenol (2f):11 Yield: 72%; 1H NMR (CDCl3, 200 MHz): = 7.41 7.36 (m, 1H), 7.28 7.19 (m, 1H), 6.
14、97 6.92 (m, 1H), 6.87 6.78 (m, 1H), 1.67 (br, 1H);13C NMR (CDCl3, 50 MHz) = 155.48, 135.36, 130.79, 121.64, 115.68, 115.30; 77Se NMR (CDCl3, 76.28 MHz) = 329.1; IR (KBr), (cm-1): 3425, 1411, 1041, 902. 1,2-bis(4-bromophenyl)diselenide (2g):1,7 Yield: 89%; 1H NMR (CDCl3, 200 MHz): = 7.44 7.35 (m, 4H)
15、; 13C NMR (CDCl3, 50 MHz) = 134.49, 133.31, 132.48, 132.23; 77Se NMR (CDCl3, 76.28 MHz) = 457.6; IR (KBr), (cm-1): 3040, 1465, 1010, 810. 1,2-bis(4-methoxyphenyl)diselenide (2h):1, 7 Yield: 86%; 1H NMR (CDCl3, 200 MHz): = 7.53 (d, J= 8.8 Hz, 2H), 6.83 (d, J= 8.8 Hz, 2H), 3.80 (s, 1H); 13C NMR (CDCl3
16、, 50 MHz) = 160.03, 138.15, 135.43, 114.70, 55.29; 77Se NMR (CDCl3, 76.28 MHz) = 394.2; IR (KBr), (cm-1): 2908, 1581, 1288, 817. 1,2-bis(3-methoxyphenyl)diselenide (2i):7 Yield: 84%; 1H NMR (CDCl3, 200 MHz): = 7.27 7.11 (m, 3H), 6.81 6.73 (m, 1H), 3.74 (s,3H); 13C NMR (CDCl3, 50 MHz) = 159.74, 131.7
17、4, 129.81, 123.38, 116.45, 113.71, 55.19; 77Se NMR (CDCl3, 76.28 MHz) = 333.2; IR (KBr), (cm-1): 2939, 1573, 1284, 848. S6 1,2-bis(2-methoxyphenyl)diselenide (2j):7 Yield: 84%; 1H NMR (CDCl3, 200 MHz): = 7.56 7.51 (m, 1H), 7.24 7.19 (m, 1H), 6.89 6.78 (m, 2H), 3.88 (s, 3H); 13C NMR (CDCl3, 50 MHz) =
18、 156.70, 130.40, 128.07, 121.79, 110.04, 97.48, 55.84; 77Se NMR (CDCl3, 76.28 MHz) = 338.6; IR (KBr), (cm-1): 2931, 1573, 1288, 748. 1,2-bis(2,4-dimethoxyphenyl)diselenide (2k):12 Yield: 50%; 1H NMR (CDCl3, 200 MHz): = 7.52 7.48 (m, 1H), 7.45 7.39 (m, 2H), 3.81 (s, 3H), 3.77 (s,3H); 13C NMR (CDCl3,
19、50 MHz) = 161.16, 158.48, 133.71, 110.00, 105.58, 98.50, 55.80, 55.41; 77Se NMR (CDCl3, 76.28 MHz) = 413.3; IR (KBr), (cm-1): 2931, 1589, 1211, 833. 2,2-diselenidediyldianiline (2l):8 Yield: 93%; 1H NMR (CDCl3, 200 MHz): = 7.62 (dd, J1= 7.8 Hz, J2= 1.4 Hz, 1H), 7.16 7.07 (m,1H), 6.72 (dd, J1= 7.8 Hz
20、, J2= 1.4 Hz, 1H), 6.50 6.41 (m, 1H), 4.05 (s, 2H); 13C NMR (CDCl3, 50 MHz) = 146.62, 138.84, 129.22, 119.86, 114.64, 84.11; 77Se NMR (CDCl3, 76.28 MHz) = 405.3; IR (KBr), (cm-1): 3441, 1612, 1311, 848. 1,2-di(pyridin-3-yl)diselenide (2m):9 Yield: 82%; 1H NMR (CDCl3, 200 MHz): = 8.79 8.75 (m, 1H), 8
21、.53 8.50 (m, 1H), 7.93 7.87 (m, 1H), 7.26 7.19 (m, 1H); 13C NMR (CDCl3, 50 MHz) = 152.37, 149.37, 149.19, 140.08, 124.23; 77Se NMR (CDCl3, 76.28 MHz) = 473.9; IR (KBr), (cm-1): 3441, 1558, 1002, 702. S7 4,4-diselenidediyldibenzaldehyde (2n): yellow solid, melting point.72-74 oC Yield: 72%; 1H NMR (C
22、DCl3, 200 MHz): = 9.88 (s, 1H), 7.39 (d, J= 8.4 Hz, 2H), 7.14 (d, J= 8.4 Hz, 2H); 13C NMR (CDCl3, 50 MHz) = 191.19, 136.01, 131.65, 126.79, 123.79; 77Se NMR (CDCl3, 76.28 MHz) = 481.3; IR (KBr), (cm-1): 3422, 1635, 1157, 833. HRMS (ESI-FT-ICR) m/z: 369.9011 M+ +; calcd. for C7H6OSe2 fragment. 265.87
23、40. 1,2-diheptyldiselenide (2o):13 Yield: 96%; 1H NMR (CDCl3, 200 MHz): = 2.90 (t, J= 7.2 Hz, 2H), 1.72 (qui, J= 7.2 Hz, 2H), 1.41 1.28 (m, 8H), 0.91 0.85 (m, 3H); 13C NMR (CDCl3, 50 MHz) = 31.68, 30.93, 30.16, 29.44, 28.76, 22.56, 14.02; 77Se NMR (CDCl3, 76.28 MHz) = 509.6; IR (KBr), (cm-1): 2924,
24、1705, 1111, 833. 1,2-diphenylditelluride (3a):3 Yield: 86%; 1H NMR (CDCl3, 200 MHz): = 7.81 7.76 (m, 2H), 7.24 7.12 (m, 3H); 13C NMR (CDCl3, 50 MHz) = 137.59, 129.25, 128.05, 107.90; IR (KBr), (cm-1): 3016, 1566, 1465, 732. 1,2-dio-tolylditelluride (3b):4 Yield: 88%; 1H NMR (CDCl3, 200 MHz): = 7.46
25、(d, J= 7.6 Hz, 1H), 7.22 7.10 (m, 2H), 6.97 6.89 (m, 1H), 2.45 (s, 3H); 13C NMR (CDCl3, 50 MHz) = 142.50, 138.14, 129.35, 128.33, 126.81, 118.45, 26.85; IR (KBr), (cm-1): 3040, 1897, 1442, 794. 1,2-di(pyridin-3-yl)ditelluride (3c):10 Yield: 72%; 1H NMR (CDCl3, 200 MHz): = 8.92 8.91 (m, 1H), 8.49 8.4
26、6 (m, 1H), 8.08 8.02 (m, 1H), 7.21 7.12 (m, 1H); 13C NMR (CDCl3, 50 MHz) = 152.34, 149.35, 149.18, 140.08, 124.27; IR (KBr), (cm-1): 3461, 1530, 1012, 702. S8 1,2-bis(4-chlorophenyl)ditelluride (3d):4 Yield: 90%; 1H NMR (CDCl3, 200 MHz): = 7.66 (d, J= 8.4 Hz, 2H), 7.13 (d, J= 8.4 Hz, 2H); 13C NMR (C
27、DCl3, 50 MHz) = 139.26, 139.11, 129.81, 129.42. IR (KBr); (cm-1): 3070, 1465, 1002, 717. 2,2-ditelluridediyldiphenol (3e):2 Yield: 86%; 1H NMR (CDCl3, 200 MHz): = 7.43 7.37 (m, 1H), 7.25 7.17 (m, 1H), 6.99 6.96 (m, 1H), 6.85 6.79 (m, 1H), 1.68 (br, 1H);13C NMR (CDCl3, 50 MHz) = 155.70, 138.08, 128.5
28、6, 120.30, 114.49, 83.44; IR (KBr), (cm-1): 3430, 1460, 1000, 842. 2,2- ditelluridediyldianiline (3f):8 Yield: 90%; 1H NMR (CDCl3, 200 MHz): = 7.68 7.62 (m, 1H), 7.14 7.05 (m,1H), 6.73 6.66 (m, 1H), 6.52 6.44 (m, 1H), 4.16 (s, 2H); 13C NMR (CDCl3, 50 MHz) = 150.41, 142.92, 131.35, 118.77, 113.42, 94
29、.69; IR (KBr), (cm-1): 3440, 1632, 1372, 870. 1,2-bis(4-methoxyphenyl)ditelluride (3g):2 Yield: 84%; 1Hz NMR (CDCl3, 200 MHz): = 7.66 (d, J= 8.8 Hz, 2H), 6.72 (d, J= 8.8 Hz, 2H), 3.76 (s, 1H); 13C NMR (CDCl3, 50 MHz) = 160.08, 138.11, 135.40, 114.72, 55.23; IR (KBr), (cm-1): 3052, 1461, 1280, 800. 1
30、,2-diheptylditelluride (3h):14 Yield: 84%; 1H NMR (CDCl3, 200 MHz): = 2.62 (t, J= 7.4 Hz, 2H), 1.75 1.68 (m, 2H), 1.35 1.28 (m, 8H), 0.91 0.85 (m, 3H); 13C NMR (CDCl3, 50 MHz) = 33.62, 32.00, 31.73, 28.64, 28.54, 22.61, 14.07; IR (KBr), (cm-1): 2930, 1745, 1100, 810. S9 Copies of 1H NMR and 13C NMR
31、1H NMR (200 MHz, CDCl3) spectrum of 1, 2-diphenyldiselenide (2a). 13C NMR (50 MHz, CDCl3) spectrum of 1,2-diphenyldiselenide (2a). S10 1H NMR (200 MHz, CDCl3) spectrum of 1,2-dip-tolyldiselenide(2b). 13C NMR (50 MHz, CDCl3) spectrum of 1,2-dip-tolyldiselenide(2b). S11 1H NMR (200 MHz, CDCl3) spectru
32、m of 1,2-dio-tolyldiselenide(2c). 13C NMR (50 MHz, CDCl3) spectrum of 1,2-dio-tolyldiselenide(2c). S12 1H NMR (200 MHz, CDCl3) spectrum of 1,2-bis(4-chlorophenyl)diselenide(2d). 13C NMR (50 MHz, CDCl3) spectrum of 1,2-bis(4-chlorophenyl)diselenide(2d). S13 1H NMR (200 MHz, CDCl3) spectrum of 1,2-bis
33、(2-chlorophenyl)diselenide(2e). 13C NMR (50 MHz, CDCl3) spectrum of 1,2-bis(2-chlorophenyl)diselenide(2e). S14 1H NMR (200 MHz, CDCl3) spectrum of 2,2-diselenidediyldiphenol(2f). 13C NMR (50 MHz, CDCl3) spectrum of 2,2-diselenidediyldiphenol(2f). S15 1H NMR (200 MHz, CDCl3) spectrum of 1,2-bis(4-bro
34、mophenyl)diselenide(2g). 13C NMR (50 MHz, CDCl3) spectrum of 1,2-bis(4-bromophenyl)diselenide(2g). S16 1H NMR (200 MHz, CDCl3) spectrum of 1,2-bis(4-methoxyphenyl)diselenide(2h). 13C NMR (50 MHz, CDCl3) spectrum of 1,2-bis(4-methoxyphenyl)diselenide(2h). S17 1H NMR (200 MHz, CDCl3) spectrum of 1,2-b
35、is(3-methoxyphenyl)diselenide(2i). 13C NMR (50 MHz, CDCl3) spectrum of 1,2-bis(3-methoxyphenyl)diselenide(2i). S18 1H NMR (200 MHz, CDCl3) spectrum of 1,2-bis(2-methoxyphenyl)diselenide(2j). 13C NMR (50 MHz, CDCl3) spectrum of 1,2-bis(2-methoxyphenyl)diselenide(2j). S19 1H NMR (200 MHz, CDCl3) spect
36、rum of 1,2-bis(2,4-dimethoxyphenyl)diselenide(2k). 13C NMR (50 MHz, CDCl3) spectrum of 1,2-bis(2,4-dimethoxyphenyl)diselenide(2k). S20 1H NMR (200 MHz, CDCl3) spectrum of 2,2-diselenidediyldianiline(2l). 13C NMR (50 MHz, CDCl3) spectrum of 2,2-diselenidediyldianiline(2l). S21 1H NMR (200 MHz, CDCl3)
37、 spectrum of 1,2-di(pyridin-3-yl)diselenide(2m). 13C NMR (50 MHz, CDCl3) spectrum of 1,2-di(pyridin-3-yl)diselenide(2m). S22 1H NMR (200 MHz, CDCl3) spectrum of 4,4-diselenidediyldibenzaldehyde(2n). 13C NMR (50 MHz, CDCl3) spectrum of 4,4-diselenidediyldibenzaldehyde(2n). S23 Mass spectrum of 4,4-di
38、selenidediyldibenzaldehyde(2n). S24 1H NMR (200 MHz, CDCl3) spectrum of 1,2-diheptyldiselenide(2o). 13C NMR (50 MHz, CDCl3) spectrum of 1,2-diheptyldiselenide(2o). S25 1H NMR (200 MHz, CDCl3) spectrum of 1,2-diphenylditelluride (3a). 13C NMR (50 MHz, CDCl3) spectrum of 1,2-diphenylditelluride (3a).
39、S26 1H NMR (200 MHz, CDCl3) spectrum of 1,2-dio-tolylditelluride(3b). 13C NMR (50 MHz, CDCl3) spectrum of 1,2-dio-tolylditelluride(3b). S27 1H NMR (200 MHz, CDCl3) spectrum of 1,2-bis(4-chlorophenyl)ditelluride(3c). 13C NMR (50 MHz, CDCl3) spectrum of 1,2-bis(4-chlorophenyl)ditelluride(3c). S28 1H N
40、MR (200 MHz, CDCl3) spectrum of 2,2-ditelluridediyldiphenol(3d). 13C NMR (50 MHz, CDCl3) spectrum of 2,2-ditelluridediyldiphenol(3d). S29 1H NMR (200 MHz, CDCl3) spectrum of 1,2-bis(4-methoxyphenyl)ditelluride(3e). 13C NMR (50 MHz, CDCl3) spectrum of 1,2-bis(4-methoxyphenyl)ditelluride(3e). S30 1H NMR (200 MHz, CDCl3) spectrum of 2,2- ditelluridediyldianiline(3f). 13C NMR (50 MHz, CDCl3) spectrum of 2,2- ditelluridediyldianiline(3f).
