1860
T. Malinauskas et al. / Tetrahedron 67 (2011) 1852e1861
CDCl3) 148.0, 147.4, 140.7, 139.9, 129.5, 128.0, 121.0, 120.1, 118.3, 94.1,
57.2, 37.1, 30.9, 28.9, 24.1, 23.4, 14.3,10.9; MS (APCIþ, 20 V), m/z: 435
([MþH]þ).
118.5, 108.84, 108.80, 95.6, 78.47, 78.44, 73.89, 73.76, 68.6, 67.7, 56.3,
54.3, 45.77, 45.67; MS (APCIþ, 20 V), m/z: 1103 ([MþH]þ).
4.4.6. 5-Bis[3-ethoxy-7-(carbazol-9-yl)-6-(carbazol-9-methyl)-5-
oxa-1-heptylamino]-2-phenyl-1,2,3-benzotriazole (6). Compound 5
(4.8 g, 4.35 mmol), Na2SO4 (0.31 g, 2.18 mmol), and powdered 85%
KOH (0.86 g; 13.1 mmol) were refluxed in 40 mL of iodoethane for
24 h. After termination of the reaction (TLC: acetone/n-hexane, 7:18
v/v), mixture was cooled to room temperature and filtered off. The
organic part was extracted with ethyl acetate distilled water. The
organic layer was dried over anhydrous Na2SO4, filtered, and sol-
vents were removed. The residue was purified by column chro-
matography using acetone/n-hexane (1:4 v/v) as the eluent to
obtain 6 (3.73 g, 74%) as a yellow-green powder; [found: C, 78.79; H,
6.15; N, 9.71. C76H70N8O4 requires C, 78.73; H, 6.09; N, 9.66%]; Rf
(acetone/n-hexane, 7:18, v/v) 0.45; nmax (KBr) 3048, 2969, 2867,
4.4.3. Tetrakis{5-bis[(2-ethylhexyl)]amino-2-phenyl-1,2,3-benzo-
2
0
triazole-N,C }(
m-dichloro)diiridium (3). Iridium trichloride hydrate
(0.4 g, 1.33 mmol) and 5-bis[(2-ethylhexyl)amino]-2-phenyl-
1,2,3-benzotriazole (2) (1.7 g, 4.01 mmol) were dissolved in the
mixture of 2-ethoxyethanol (10 mL) and water (5 mL). The mix-
ture was refluxed under argon atmosphere for 24 h, and cooled
down to the room temperature (TLC: acetone/n-hexane, 1:4 v/v).
Obtained solution was extracted with chloroform and distilled
water several times. The organic layer was dried over anhydrous
MgSO4, filtered, and solvents were evaporated. The residue was
purified by column chromatography using n-hexane and acetone/
n-hexane (3:22 v/v) as eluent to obtain 3 (0.95 g, 32%) as an or-
ange solid.
1120 cmꢁ1
; dH (300 MHz, CDCl3) 8.38e8.30 (m, 2H), 8.01 (d,
J¼7.5 Hz, 8H), 7.71e7.60 (m, 1H), 7.59e7.49 (m, 2H), 7.45e7.04 (m,
25H), 6.85e6.75 (m, 1H), 6.69e6.63 (m, 1H), 4.59e4.45 (m, 4H),
4.43e4.20 (m, 6H), 3.07e2.70 (m, 14H), 0.73 (t, J¼7.0 Hz, 6H); dC
(75 MHz, CDCl3) 147.2,147.0,140.7,140.47,140.41,140.0,129.5,128.1,
126.03, 125.99, 123.11, 123.07, 120.56, 120.48, 120.1, 119.50, 119.46,
118.4, 108.9, 93.8, 77.9, 76.15, 76.06, 72.1, 65.69, 65.65, 53.6, 52.9,
46.1, 45.8, 15.6; MS (APCIþ, 20 V), m/z: 1159 ([MþH]þ).
4.4.4. Iridium(III)-bis{5-bis[(2-ethylhexyl)]amino-2-phenyl-1,2,3-
2
0
benzotriazolato-N,C }acetylacetonate (4). The
m-chloride-bridged
dimer
3 (0.91 g, 0.415 mmol), 2,4-pentanedione (0.125 g,
1.25 mmol) and sodium carbonate (0.44 g, 4.15 mmol) were
refluxed in 8 mL of degassed 2-ethoxyethanol under argon atmo-
sphere for 1 h. After termination of the reaction (TLC: acetone/n-
hexane, 3:97 v/v) obtained solution was extracted with chloroform
and distilled water several times. The organic layer was dried over
anhydrous MgSO4, filtered, and solvents were evaporated. The
residue was purified by column chromatography using n-hexane
and acetone/n-hexane (1:99 v/v) as eluent to obtain 4 (0.4 g, 42%) as
a brown solid; [found: C, 63.29; H, 7.68; N, 9.60. C61H89IrN8O2 re-
quires C, 63.24; H, 7.74; N, 9.67%]; Rf (acetone/n-hexane, 3:97 v/v)
4.4.7. Tetrakis{5-bis[3-hydroxy-7-(carbazol-9-yl)-6-(carbazol-9-
2
0
methyl)-5-oxa-1-heptylamino]-2-phenyl-1,2,3-benzotriazole-N,C }
(m-dichloro)diiridium (7a). Iridium trichloride hydrate (0.2 g,
0.67 mmol) and 5 (1.85 g, 1.67 mmol) were dissolved in the mixture
of 2-ethoxyethanol (10 mL) and water (5 mL) and refluxed under
argon atmosphere for 24 h (TLC: acetone/n-hexane, 2:3 v/v). A
yellow precipitate was filtered and washed with water and ethanol
0.53; nmax (KBr) 3050, 2927, 2871, 1698 cmꢁ1
; dH (300 MHz, CDCl3)
7.82e7.71 (m, 3H, 6-H of 1-subst Ph, 7-HHt of one tetrazole frag-
ment), 7.50 (dd, J¼9.5 Hz, J¼3.8 Hz, 1H, 7-HHt of other tetrazole
fragment), 7.20 (d, J¼9.5 Hz, 1H, 6-HHt of one tetrazole fragment),
7.14e7.06 (m, 1H, 6-HHt of other tetrazole fragment), 6.97e6.84 (m,
3H, 5-H of 1-subst Ph, 4-HHt of one tetrazole fragment), 6.78e6.73
(m,1H, 4-HHt of other tetrazole fragment), 6.70e6.59 (m, 2H, 4-H of
1-subst Ph), 6.34e6.22 (m, 1H, 3-H of 1-subst Ph, of one ligand
fragment), 6.19e6.08 (m, 1H, 3-H of 1-subst Ph, of other ligand
fragment), 5.25 (s, 1H, CCHC), 3.50e3.11 (m, 8H, NCH2), 1.95e1.70
(m, 10H, CH, CCH3), 1.45e1.10 (m, 32H, CH2), 0.97e0.76 (m, 24H,
CH3); dC (75 MHz, CDCl3) 186.0, 185.5, 150.53, 150.48, 146.65,
146.62, 143.3, 143.1, 135.2, 135.0, 134.7, 134.6, 127.6, 127.2, 122.4,
122.1,120.6,119.2,115.2,114.9,101.5, 95.0, 57.2, 55.4, 37.3, 37.0, 30.8,
30.6, 30.5, 29.0, 28.9, 28.8, 28.4, 24.14, 24.10, 24.04, 23.45, 23.32,
23.26, 14.32, 14.26, 14.22, 11.01, 10.97, 10.95, 10.85, 10.83, 10.79; MS
(APCIþ, 20 V), m/z: 1158 ([MþH]þ).
several times and dried. The m-chloride-bridged dimer was purified
by column chromatography using acetone/n-hexane (7:18 and 1:1
v/v) as the eluent to obtain 7a (1.3 g, 40%) as a yellow powder.
4.4.8. Tetrakis{5-bis[3-ethoxy-7-(carbazol-9-yl)-6-(carbazol-9-
2
0
methyl)-5-oxa-1-heptylamino]-2-phenyl-1,2,3-benzotriazole-N,C }
(m-dichloro)diiridium (7b). Compound 7b was synthesized by the
same procedure as 7a, except that 0.253 g (0.849 mmol) of iridium
trichloride hydrate and 2.46 g (2.12 mmol) of 6 were taken, and
dissolved in the mixture of 2-ethoxyethanol (25 mL) and water
(5 mL). Purification by column chromatography afforded 7b (1.7 g,
39%) as a yellow powder.
4.4.9. Iridium(III)-bis{5-bis[3-hydroxy-7-(carbazol-9-yl)-6-(carbazol-
9-methyl)-5-oxa-1-heptylamino]-2-phenyl-1,2,3-benzotriazolato-
2
0
N,C }acetylacetonate (8a). Compound 8a was synthesized by the
same procedure as 4 described above, except that m-chloride-bridged
4.4.5. 5-Bis[3-hydroxy-7-(carbazol-9-yl)-6-(carbazol-9-methyl)-5-
oxa-1-heptylamino]-2-phenyl-1,2,3-benzotriazole (5). 5-Amino-2-ph
enyl-1,2,3-benzotriazole (1) (3 g, 0.014 mol) and 1,3-bis(carbazol-9-
yl)-2-propanol glycidyl ether (19.2 g, 0.043 mol) were heated in the
melt at 160 ꢀC for 24 h. After termination of the reaction (TLC: ac-
etone/n-hexane, 7:18 v/v), benzotriazole derivative 5 was purified
by column chromatography, using acetone/n-hexane (1:4 v/v) as
eluent. Recrystallization of the residue from toluene afforded 5
(9.8 g, 62%) as a yellow-green powder, mp: 126e127 ꢀC (toluene);
[found: C, 78.42; H, 5.69; N, 10.06. C72H62N8O4 requires C, 78.38; H,
5.66; N, 10.16%]; Rf (acetone/n-hexane, 7:18, v/v) 0.31; nmax (KBr)
dimer 7a (1.3 g, 0.267 mmol), 2,4-pentanedione (0.08 g, 0.802 mmol),
and Na2CO3 (0.28 g, 2.67 mmol) were taken, and dissolved in
degassed 2-ethoxyethanol (10 mL) (TLC: acetone/n-hexane, 7:18 v/v).
The residue was purified by column chromatography using acetone/
n-hexane (1:4 and 7:18 v/v) as eluent to obtain 8a (0.79 g, 59%) as an
orange powder; [found: C, 71.79; H, 5.14; N, 8.93. C149H129IrN16O10
requires C, 71.70; H, 5.21; N, 8.98%]; Rf (acetone/n-hexane, 7:18, v/v)
0.15; nmax (KBr) 3400, 3047, 2926, 1698, 1121 cmꢁ1
; dH (300 MHz,
CDCl3) 8.21e7.87 (m, 16H), 7.84e6.03 (m, 62H), 5.03 (s, 1H),
4.72e4.06 (m, 20H), 3.21e2.51 (m, 24H), 1.43 (s, 6H); dC (75 MHz,
CDCl3) 186.3, 185.9, 150.1, 146.8, 143.2, 140.53, 140.44, 135.2, 134.9,
127.4, 126.24, 126.08, 123.16, 123.14, 122.4, 120.7, 120.4, 119.71, 119.69,
119.2, 115.2, 114.8, 108.83, 108.78, 101.2, 94.9, 78.71, 78.61, 73.86,
73.68, 69.7, 56.4, 54.0, 45.79, 45.70, 31.2, 28.4.
3542, 3048, 2927, 2870, 1121 cmꢁ1
; dH (300 MHz, CDCl3) 8.37e8.28
(m, 2H), 8.09e7.92 (m, 8H), 7.65e7.47 (m, 3H), 7.45e7.07 (m, 25H),
6.61e6.33 (m, 2H), 4.59e4.40 (m, 4H), 4.38e4.20 (m, 6H), 4.43e4.32
(m, 1H), 3.22e3.09 (m, 1H), 2.84e2.66 (m, 4H), 2.45e2.15 (m, 4H),
1.86 (d, J¼1.9 Hz, 2H); dC (75 MHz, CDCl3) 147.5, 146.9,140.65, 140.51,
140.40, 140.13, 129.6, 128.3, 126.2, 123.1, 120.9, 120.7, 120.1, 119.7,
4.4.10. Iridium(III)-bis{5-bis[3-ethoxy-7-(carbazol-9-yl)-6-(carbazol-
9-methyl)-5-oxa-1-heptylamino]-2-phenyl-1,2,3-benzotriazolato-