Fumitoshi Shibahara et al.
with CH2Cl2 (3 mL), and to this was added aqueous ammonia. The or-
ganic layer was extracted with CH2Cl2 (3ꢁ10 mL), washed with saturated
brine (5 mL), dried over Na2SO4, filtered, and concentrated in vacuo.
The residue was purified by flash column chromatography on silica gel to
4H; Ar), 8.10 ppm (d, J=8.1 Hz, 2H; Ar); 13C NMR (CDCl3): d=55.3
(MeO), 113.3, 114.3, 117.6, 118.9, 120.5, 121.7, 122.0, 129.6, 136.4, 139.8,
160.2 ppm (Ar); 77Se NMR (CDCl3): d=412.4 ppm (C-SeSe-C); MS
(FAB): m/z: 607 [M+H+]+; HRMS (FAB): m/z: calcd for
C28H23N4O2Se2: 607.0151 [M+H+]+; found: 607.0178.
give a mixture of bisimidazoACTHUNTGRNENUG[1,5-a]pyridylselenide (8) and bisimidazoACHTUNTGREN[NUGN 1,5-
a]pyridyldiselenide (9). The ratio (selenide/diselenide) was estimated by
1H NMR spectroscopic analysis. Further isolation was performed by
preparative gel permeation chromatography to give analytically pure sel-
enide and diselenide, respectively.
Bis(3-(2-thienyl)imidazoACTHNURTGNEU[GN 1,5-a]pyridin-1-yl)selenide (8e)
M.p. 200–2028C; Rf =0.48 (hexane/AcOEt 1:1); 1H NMR (CDCl3): d=
6.44 (dd, J=7.4, 6.3 Hz, 2H; Ar), 6.82 (dd, J=9.0, 6.3 Hz, 2H; Ar), 7.14
(dd, J=5.0, 3.7 Hz, 2H; Ar), 7.39 (d, J=5.0 Hz, 2H; Ar), 7.47 (d, J=
3.7 Hz, 2H; Ar), 7.98 (d, J=9.0 Hz, 2H; Ar), 8.24 ppm (d, J=7.4 Hz,
2H; Ar); 13C NMR (CDCl3): d=114.2, 118.6, 119.2, 120.1, 121.8, 125.3,
125.7, 126.2, 127.6, 131.9, 134.8 ppm (Ar); 77Se NMR (CDCl3): d=
144.1 ppm (C-Se-C); IR (KBr): n˜ =2925, 2360, 2341, 1628, 1499, 1403,
1362, 1004, 911, 849, 739, 691 cmÀ1; MS (FAB): m/z: 479 [M+H+]+;
HRMS (FAB): m/z: calcd for C22H15N4S2Se: 478.9903 [M+H+]+; found:
478.9922.
Bis(3-phenylimidazoACHTUNGTRENNUNG[1,5-a]pyridin-1-yl)selenide (8a)
M.p. 168–1708C; Rf =0.63 (hexane/AcOEt 1:1); 1H NMR (CDCl3): d=
6.53 (dd, J=7.3, 6.3 Hz, 2H; Ar), 6.78 (dd, J=9.3, 6.3 Hz, 2H; Ar), 7.39
(t, J=7.3 Hz, 2H; Ar), 7.47 (t, J=7.3 Hz, 4H; Ar), 7.74 (d, J=7.3 Hz,
4H; Ar), 7.98 (d, J=9.3 Hz, 2H; Ar), 8.15 ppm (d, J=7.3 Hz, 2H; Ar);
13C NMR (CDCl3): d=113.6, 118.3, 120.0, 120.1, 121.5, 128.2, 128.8,
128.9, 129.8, 134.6, 138.5 ppm (Ar); 77Se NMR (CDCl3): d=139.9 ppm;
IR (KBr): n˜ =3055, 2993, 2852, 1633, 1599, 1506, 1456, 1364, 1355, 1264,
1011, 776, 741, 702, 692 cmÀ1; MS (FAB): m/z: 467 [M+H+]+; HRMS
(FAB): m/z calcd for C26H19N4Se: 467.0775 [M+H+]+; found: 467.0765.
Bis(3-(2-pyridyl)imidazoACTHNURTGNEU[GN 1,5-a]pyridin-1-yl)selenide (8 f)
M.p. 188–1898C; Rf =0.55 (hexane/AcOEt 1:1); 1H NMR (CDCl3): d=
6.74 (dd, J=7.3, 6.3 Hz, 2H; Ar), 6.94 (dd, J=9.3, 6.3 Hz, 2H; Ar), 7.18
(dd, J=7.0, 4.6 Hz, 2H; Ar), 7.76 (dd, J=8.3, 7.0 Hz, 2H; Ar), 7.97 (d,
J=9.3 Hz, 2H; Ar), 8.42 (d, J=8.3 Hz, 2H; Ar), 8.59 (d, J=4.6 Hz, 2H;
Ar), 9.91 ppm (d, J=7.3 Hz, 2H; Ar); 13C NMR (CDCl3): d=114.4,
119.1, 121.8, 122.0, 122.4, 122.4, 126.2, 135.7, 136.5, 136.6, 148.0,
148.1 ppm (Ar); 77Se NMR (CDCl3): d=144.2 ppm (C-Se-C); IR (KBr):
n˜ =3106, 2360, 1587, 1496, 1420, 1358, 1018, 784, 751, 685 cmÀ1; MS
(FAB): m/z: 469 [M+H+]+; HRMS (FAB): m/z: calcd for C22H17N6Se:
469.0680 [M+H+]+; found: 469.0665.
Bis(3-phenylimidazoACHTUNGTRENNUNG[1,5-a]pyridin-1-yl)diselenide (9a)
Rf =0.63 (hexane:AcOEt 1:1). 1H NMR (CDCl3): d=6.53 (dd, J=7.0,
5.8 Hz, 2H; Ar), 6.58 (dd, J=8.8, 5.8 Hz, 2H; Ar), 7.09 (d, J=8.8 Hz,
2H; Ar), 7.48 (t, J=7.5 Hz, 2H; Ar), 7.54 (dd, J=7.5, 6.8 Hz, 4H; Ar),
7.82 (d, J=6.8 Hz, 4H; Ar), 8.19 ppm (d, J=7.0 Hz, 2H; Ar); 13C NMR
(CDCl3): d=113.7, 119.1, 119.9, 120.1, 121.0, 121.5, 121.9, 128.2, 128.8,
128.95, 129.00 ppm (Ar); 77Se NMR (CDCl3): d=412.3 ppm; MS (FAB):
m/z: 546 [M+H+]+; HRMS (FAB): m/z calcd for C26H19N4Se2: 546.9940
[M+H+]+; found: 546.9916.
Reaction of diphenyl diselenide (10) and 3-(4-
Bis(3-(4-trifluoromethylphenyl)imidazoACTHUNTGRNEUNG[1,5-a]pyridin-1-yl)selenide (8b)
methoxyphenyl)imidazoACHTUGNTREN[NUNG 1,5-a]pyridine (1d)
M.p. 221–2228C; Rf =0.33 (hexane/AcOEt 3:1); 1H NMR (CDCl3): d=
6.67 (dd, J=7.3, 6.3 Hz, 2H; Ar), 6.90 (dd, J=9.3, 6.3 Hz, 2H; Ar), 7.75
(d, J=8.3 Hz, 4H; Ar), 7.91 (d, J=8.3 Hz, 4H; Ar), 8.03 (d, J=9.3 Hz,
2H; Ar), 8.22 ppm (d, J=7.3 Hz, 2H; Ar); 13C NMR (CDCl3): d=114.4,
119.0, 120.0, 120.7, 121.3 (Ar), 124.0 (q, J=272.9 Hz, F3C), 125.9 (q, J=
3.3 Hz, F3C-C=C), 128.0 (Ar), 130.4 (q, J=33.1 Hz, F3C-C), 133.3, 135.2,
137.1 ppm (Ar); 19F NMR (CDCl3): d=À62.6 ppm (CF3); 77Se NMR
(CDCl3): d=142.7 ppm; IR (KBr): n˜ =2926, 1616, 1325, 1168, 1111, 1066,
1012, 845, 739 cmÀ1; MS (FAB): m/z: 603 [M+H+]+; HRMS (FAB): m/
z: calcd for C28H17F6N4Se: 603.0523 [M+H+]+; found: 603.0503.
A
mixture of 3-(4-methoxyphenyl)imidazoACTHNUTRGNEU[GN 1,5-a]pyridine (1d, 0.11 g,
0.50 mmol), diphenyldiselenide (10, 0.16 g, 0.50 mmol), CuBr (14 mg,
0.10 mmol, 20 mol%), and DMSO (1 mL) was stirred at 1208C for 20 h.
The resulting solution was diluted with CH2Cl2 (3 mL) and then aqueous
ammonia was added. The organic layer was extracted with CH2Cl2 (3ꢁ
10 mL), washed with saturated brine (5 mL), dried over Na2SO4, filtered,
and concentrated in vacuo. The residue was purified by flash column
chromatography on silica gel (hexane/AcOEt 4:1) to give phenyl-[3-(4-
methoxyphenyl)imidazoACHTUNGRTNE[NUG 1,5-a]pyrid-1-yl]selenide (11) as a light green
solid (0.18 g, 0.46 mmol, 93%). M.p. 88–898C; Rf =0.70 (hexane/AcOEt
1:1); 1H NMR (CDCl3): d=3.89 (s, 3H; OMe), 6.65 (dd, J=7.2, 6.3 Hz,
1H; Ar), 6.84 (dd, J=9.4, 6.3 Hz, 1H; Ar), 7.06 (d, J=8.5 Hz, 2H; Ar),
7.17 (m, 3H; Ar), 7.37 (d, J=8.1 Hz, 2H; Ar), 763 (d, J=9.4 Hz, 1H;
Ar), 7.77 (d, J=8.5 Hz, 2H; Ar), 8.25 ppm (d, J=7.2 Hz, 1H; Ar);
13C NMR (CDCl3): d=55.4 (OMe), 113.6, 114.4, 115.9, 119.1, 120.6,
121.9, 126.1, 129.0, 129.7, 129.8 (two carbon atoms were overlapped),
133.3, 135.4, 139.7 ppm (Ar); 77Se NMR (CDCl3): d=258.8 ppm; IR
(KBr): n˜ =1608, 1577, 1524, 1476, 1458, 1254, 1183, 1024, 1012, 835, 740,
691 cmÀ1; MS (FAB): m/z: 381 [M+H+]+; HRMS (FAB): m/z: calcd for
C20H17N2OSe: 381.0506 [M+H+]+; found: 381.0511.
Bis(3-(4-trifluoromethylphenyl)imidazoACHTGNUTREN[NUNG 1,5-a]pyridin-1-yl)diselenide (9b;
not isolated)
Rf =0.33 (hexane/AcOEt 3:1); 1H NMR (CDCl3): d=6.67 (t, J=6.8 Hz,
2H; Ar), 6.71 (dd, J=9.3, 6.8 Hz, 2H; Ar), 7.29 (d, J=9.3 Hz, 2H; Ar),
7.77 (d, J=8.3 Hz, 4H; Ar), 7.95 (d, J=8.3 Hz, 4H; Ar), 8.25 ppm (d,
J=6.8 Hz, 2H; Ar); MS (FAB): m/z: 683 [M+H+]+; HRMS (FAB): m/
z: calcd for C28H17F6N4Se2: 682.9688 [M+H+]+; found: 682.9686.
Bis(3-(4-methoxyphenyl)imidazoACTHNUTRGENUGN[1,5-a]pyridin-1-yl)selenide (8d)
M.p. 206–2088C; Rf =0.50 (hexane/AcOEt 1:1); 1H NMR (CDCl3): d=
3.84 (s, 6H; OMe), 6.50 (t, J=6.8 Hz, 2H; Ar), 6.75 (dd, J=8.8, 6.8 Hz,
2H; Ar), 6.99 (d, J=8.6 Hz, 4H; Ar), 7.65 (d, J=8.6 Hz, 4H; Ar), 7.94
(d, J=9.3 Hz, 2H; Ar), 8.08 ppm (d, J=6.8 Hz, 2H; Ar); 13C NMR
(CDCl3): d=55.4 (MeO), 113.4, 114.3, 117.8, 119.8, 119.9, 121.4, 122.2,
129.6, 134.3, 138.5, 160.0 ppm (Ar); 77Se NMR (CDCl3): d=135.9 ppm
(C-Se-C); IR (KBr): n˜ =2936, 2835, 2358, 1608, 1523, 1457, 1432, 1353,
1252, 1187, 1173, 1010, 838, 742 cmÀ1; MS (FAB): m/z: 527 [M+H+]+;
HRMS (FAB): m/z: calcd for C28H23N4O2Se: 527.0986 [M+H+]+; found:
527.0969.
Reaction of diphenyl diselenide (10) and 1-methylindole (3)
A mixture of 1-methylindole (3, 38 mL, 0.30 mmol), diphenyldiselenide
(10, 94 mg, 0.30 mmol), CuBr (9 mg, 0.06 mmol, 20 mol%), and DMSO
(0.6 mL) was stirred at 1208C for 20 h. The resulting solution was diluted
with CH2Cl2 (2 mL) and then aqueous ammonia was added. The organic
layer was extracted with CH2Cl2 (3ꢁ7 mL), washed with saturated brine
(3 mL), dried over Na2SO4, filtered, and concentrated in vacuo. The resi-
due was purified by flash column chromatography on silica gel (hexane/
AcOEt 6:1) to give phenyl(1-methylindol-3-yl)selenide (12) as a light
orange solid (33 mg, 0.12 mmol, 38%). M.p .59–618C; Rf =0.85 (hexane/
AcOEt 1:1); 1H NMR (CDCl3): d=3.83 (s, 3H; Me), 7.11 (m, 3H; Ar),
7.17 (dd, J=7.8, 6.8 Hz, 1H; Ar), 7.23 (d, J=7.3 Hz, 2H; Ar), 7.29 (dd,
J=8.3, 6.8 Hz, 1H; Ar), 7.32 (s, 1H; Ar), 7.37 (d, J=8.3 Hz, 1H; Ar),
7.63 ppm (d, J=7.8 Hz, 1H; Ar); 13C NMR (CDCl3): d=33.1 (NMe),
95.9, 109.5, 120.39, 120.44, 122.4, 125.5, 128.5, 128.9, 130.7, 134.2, 135.6,
Bis(3-(4-methoxyphenyl)imidazoACHTUNGTRNE[NUNG 1,5-a]pyridin-1-yl)diselenide (9d; not
isolated)
Rf =0.50 (hexane/AcOEt 1:1); 1H NMR (CDCl3): d=3.90 (s, 6H; OMe),
6.49 (dd, J=8.1, 6.5 Hz, 2H; Ar), 6.52 (dd, J=8.8, 6.5 Hz, 2H; Ar), 7.05
(d, J=8.8 Hz, 4H; Ar), 7.70 (d, J=8.8 Hz, 2H; Ar), 7.73 (d, J=8.8 Hz,
Chem. Asian J. 2014, 9, 237 – 244
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