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Na2SO4 and concentrated, and used for the next synthetic step. MHz, CDCl3) d: 144.11 (C), 143.71 (C), 143.35 (C), 141.85 (C),
A mixture of the previous methanesulfonate 4 and various 141.03 (CH), 140.93 (CH), 139.11 (C), 133.64 (C), 127.05 (CH),
substituted imidazole, benzimidazole or triazole (6 mmol) and 126.87 (CH), 125.08 (CH), 124.84 (CH), 122.99 (CH), 122.63
K2CO3 (3 mmol) was stirred in toluene (20 mL) at reux for 24– (CH), 122.44 (CH), 120.22 (CH), 120.00 (CH), 110.82 (CH),
48 h (monitored by TLC). Aer cooling to room temperature, the 55.57 (CH), 36.87 (CH2), 21.80 (CH3). Anal. calcd for C22H18N2:
solvent was concentrated, and the residue was diluted with C, 85.13; H, 5.85; N, 9.03. Found: C, 85.03; H, 5.89; N, 8.86.
EtOAc (20 mL). The organic layer was washed with water (20 mL) HRMS (ESI-TOF) m/z calcd for C22H19N2 [M + H]+ 311.1548,
and brine (20 mL), dried over anhydrous Na2SO4 and concen- found 311.1551.
trated. The residue was puried by column chromatography
(ꢀ)-1-(1-(9H-Fluoren-3-yl)ethyl)-2-methyl-1H-benzo[d]imidazole
(silica gel, petroleum ether 60–90 ꢁC: EtOAc ¼ 1 : 1) to afford 5– (9). Yield 53%. White solid, mp 166–168 ꢁC. IR nmax (cmꢃ1):
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10 in 53–78% yield as white powder. See ESI† le for charac- 3048, 2991, 2880, 1609, 1520, 1391, 1283, 1145, 1007, 737. H
terization data.
NMR (300 MHz, CDCl3) d: 7.71–7.76 (3H, m), 7.52 (1H, d, J ¼ 7.2
(ꢀ)-1-(1-(9H-Fluoren-3-yl)ethyl)-1H-imidazole (5). Yield 62%. Hz), 7.25–7.39 (3H, m), 7.16–7.22 (2H, m), 7.07 (2H, d, J ¼ 3.6
White solid, mp 188–190 C. IR nmax (cmꢃ1): 2971, 1605, 1498, Hz), 5.80–5.87 (1H, m), 3.83 (2H, s), 2.64 (3H, s), 2.01 (3H, d, J ¼
ꢁ
1397, 1225, 1085, 740. H NMR (300 MHz, CDCl3) d: 7.70–7.75 7.2 Hz). 13C NMR (75 MHz, CDCl3) d: 151.50 (C), 143.97 (C),
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(2H, m), 7.62 (1H, s), 7.51 (1H, d, J ¼ 7.2 Hz), 7.31–7.38 (3H, m), 143.39 (C), 141.71 (C), 141.57 (C), 140.92 (C), 137.67 (C), 133.67
7.16 (1H, d, J ¼ 7.8 Hz), 7.09 (1H, s), 6.95 (1H, s), 5.34–5.41 (1H, (C), 127.07 (CH), 126.89 (CH), 125.11 (CH), 124.95 (CH), 123.07
m), 3.83 (2H, s), 1.87 (3H, d, J ¼ 6.9 Hz). 13C NMR (75 MHz, (CH), 122.24 (CH), 122.14 (CH), 120.07 (CH), 118.79 (CH),
CDCl3) d: 143.97 (C), 143.34 (C), 141.75 (C), 140.94 (C), 140.03 111.25 (CH), 53.74 (CH), 36.92 (CH2), 18.84 (CH3), 14.45 (CH3).
(C), 136.08 (CH), 129.32 (CH), 127.02 (CH), 126.86 (CH), 125.08 Anal. calcd for C23H20N2: C, 85.15; H, 6.21; N, 8.63. Found: C,
(CH), 124.85 (CH), 122.68 (CH), 120.11 (CH), 120.00 (CH), 84.97; H, 6.17; N, 8.36. HRMS (ESI-TOF) m/z calcd for C23H21N2
118.03 (CH), 56.78 (CH), 36.87 (CH2), 22.21 (CH3). Anal. calcd [M + H]+ 325.1705, found 325.1705.
for C18H16N2: C, 83.04; H, 6.19; N, 10.76. Found: C, 82.74; H,
(ꢀ)-1-(1-(9H-Fluoren-3-yl)ethyl)-5,6-dimethyl-1H-benzo[d]imidazole
5.81; N, 10.65. HRMS (ESI-TOF) m/z calcd for C18H17N2 [M + H]+ (10). Yield 60%. White solid, mp 182–184 ꢁC. IR nmax (cmꢃ1):
261.1392, found 261.1395.
(ꢀ)-1-(1-(9H-Fluoren-3-yl)ethyl)-2-methyl-1H-imidazole
3007, 2969, 2933, 2876, 1617, 1480, 1392, 1224, 1030, 839, 743.
(6). 1H NMR (300 MHz, CDCl3) d: 8.00 (1H, s), 7.73 (2H, t, J ¼ 7.2 Hz),
Yield 56%. White solid, mp 134–136 C. IR nmax (cmꢃ1): 3161, 7.58 (1H, s), 7.50 (1H, d, J ¼ 7.2 Hz), 7.24–7.37 (2H, m), 7.21 (2H,
2974, 1660, 1490, 1268, 1105, 990, 737. 1H NMR (300 MHz, d, J ¼ 7.8 Hz), 6.98 (1H, s), 5.58–5.65 (1H, m), 3.80 (2H, s), 2.33
CDCl3) d: 7.70–7.76 (2H, m), 7.53 (1H, d, J ¼ 7.2 Hz), 7.26–7.39 (3H, s), 2.27 (3H, s), 2.00 (3H, d, J ¼ 7.2 Hz). 13C NMR (75 MHz,
(2H, m), 7.18 (1H, s), 7.01–7.10 (3H, m), 5.33–5.40 (1H, m), 3.84 CDCl3) d: 144.04 (C), 143.35 (C), 142.80 (C), 141.66 (C), 141.01
(2H, s), 2.31 (3H, s), 1.85 (3H, d, J ¼ 6.9 Hz). 13C NMR (75 MHz, (C), 140.30 (CH), 139.57 (C), 132.31 (C), 131.96 (C), 131.13 (C),
CDCl3) d: 143.99 (C), 143.31 (C), 141.42 (C), 140.99 (C), 126.97 (CH), 126.84 (CH), 125.06 (CH), 124.77 (CH), 122.55
140.31(C), 126.95 (CH), 126.84 (CH), 125.07 (CH), 124.55 (CH), (CH), 120.33 (CH), 120.16 (CH), 119.96 (CH), 110.77 (CH), 55.25
122.32 (C), 120.09 (CH), 119.95 (CH), 116.78 (CH), 55.27 (CH), (CH), 36.87 (CH2), 21.88 (CH3), 20.59 (CH3), 20.22 (CH3). Anal.
36.89 (CH2), 22.55 (CH3), 13.52 (CH3). Anal. calcd for C19H18N2: calcd for C24H22N2: C, 85.17; H, 6.55; N, 8.28. Found: C, 84.79;
C, 83.18; H, 6.61; N, 10.21. Found: C, 83.13; H, 6.65; N, 9.69. H, 6.39; N, 7.98. HRMS (ESI-TOF) m/z calcd for C24H23N2 [M +
HRMS (ESI-TOF) m/z calcd for C19H19N2 [M + H]+ 275.1548, H]+ 339.1861, found 339.1863.
ꢁ
found 275.1553.
Synthesis of (ꢀ)-3-substituted uorene–imidazolium/
(ꢀ)-1-(1-(9H-Fluoren-3-yl)ethyl)-1H-1,2,4-triazole (7). Yield triazolium salts (11–43). A mixture of (ꢀ)-3-substituted uo-
58%. White solid, mp 108–110 C. IR nmax (cmꢃ1): 3118, 3085, rene–imidazole hybrids 5–10 (0.2 mmol) and phenacyl
ꢁ
2968, 2933, 1678, 1614, 1499, 1269, 1140, 1005, 946, 841, 734. 1H bromides or alkyl bromides (0.24 mmol) was stirred in toluene
NMR (300 MHz, CDCl3) d: 8.07 (1H, s), 7.99 (1H, s), 7.70–7.74 (5 mL) at reux at for 8–12 h. An insoluble substance was
(2H, m), 7.50 (1H, d, J ¼ 7.2 Hz), 7.40 (1H, s), 7.37 (1H, s), 7.24– formed. Aer completion of the reaction as indicated by TLC,
7.35 (2H, m), 5.55–5.61 (1H, m), 3.83 (2H, s), 1.95 (3H, d, J ¼ 6.9 the precipitate was ltered through a small pad of Celite, and
Hz). 13C NMR (75 MHz, CDCl3) d: 151.93 (CH), 144.01 (CH), washed with toluene (3 ꢂ 10 mL), then dried to afford imida-
143.39 (C), 142.11 (C), 140.91 (C), 138.38 (C), 127.10 (CH), 126.87 zolium salts 11–43 in 68–98% yields. See ESI† le for charac-
(CH), 125.37 (CH), 125.08 (CH), 123.23 (CH), 120.21 (CH), terization data of all novel compounds.
120.07 (CH), 59.87 (CH), 36.88 (CH2), 21.47 (CH3). Anal. calcd
(ꢀ)-3-(Naphthalen-2-ylmethyl)-1-(1-(9H-uoren-3-yl)ethyl)-2-methyl-
for C17H15N3: C, 78.13; H, 5.79; N, 16.08. Found: C, 78.03; H, 1H-benzo[d]imidazol-3-ium bromide (37). Yield 80%. White solid,
5.72; N, 15.80. HRMS (ESI-TOF) m/z calcd for C17H16N3 [M + H]+ mp 165–167 C. IR nmax (cmꢃ1): 3021, 1685, 1623, 1520, 1470,
ꢁ
1
262.1344, found 262.1349.
1075, 926, 823, 739. H NMR (300 MHz, CDCl3) d: 9.24 (1H, s),
(ꢀ)-1-(1-(9H-Fluoren-3-yl)ethyl)-1H-benzo[d]imidazole (8). Yield 8.21 (1H, d, J ¼ 8.1 Hz), 8.12 (1H, d, J ¼ 7.2 Hz), 7.92 (1H, d, J ¼
68%. White solid, mp 179–181 C. IR nmax (cmꢃ1): 3051, 2970, 8.4 Hz), 7.74–7.86 (4H, m), 7.53–7.65 (4H, m), 7.27–7.46 (5H, m),
ꢁ
1
1607, 1484, 1223, 744. H NMR (300 MHz, CDCl3) d: 8.15 (1H, 7.25 (1H, s), 6.95 (2H, s), 6.25–6.31 (1H, m), 3.91 (2H, s), 3.21
s), 7.83 (1H, d, J ¼ 7.8 Hz), 7.71 (2H, dd, J ¼ 15.0, 7.2 Hz), 7.48 (3H, s), 2.21 (3H, d, J ¼ 7.2 Hz). 13C NMR (75 MHz, CDCl3) d:
(1H, d, J ¼ 6.9 Hz), 7.27–7.36 (3H, m),7.14–7.23 (4H, m), 5.61– 190.66 (C), 152.64 (C), 144.58 (C), 143.55 (C), 142.72 (C), 140.49
5.68 (1H, m), 3.78 (2H, s), 2.00 (3H, d, J ¼ 6.9 Hz). 13C NMR (75 (C), 136.37 (C), 134.14 (C), 132.60 (C), 132.48 (CH), 130.59 (CH),
63942 | RSC Adv., 2015, 5, 63936–63944
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