ACCEPTED MANUSCRIPT
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.71 (dichloromethane/methanol 90/10); mp: 206 °C; IR (cm ): 525, 701, 737, 746, 997, 1037, 1123, 1219, 1261, 1301,
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315, 1399, 1439, 1496, 1518, 1591, 2814, 3306. HPLC: method 2, rt = 2.86 min, purity 98%. H NMR (300 MHz, DMSO-
d6) δ (ppm): 2.60 (t, J = 4.8 Hz, 4 H); 3.88 (t, J = 4.5 Hz, 4 H); 5.04 (s, 1 H); 7.05 – 7.13 (m, 1 H); 7.23 – 7.32 (m, 4 H); 7.36
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(td, J = 1.2 Hz, 7.5 Hz, 2 H); 7.43 (t, J = 7.5 Hz, 2 H); 7.66 (d, J = 7.2 Hz, 2 H); 7.87 (d, J = 7.5 Hz, 2 H); 9.24 (s, 1 H).
C
NMR (75 MHz, DMSO-d6) δ (ppm): 48.8 (2 x CH ); 49.2 (2 x CH ); 69.3 (CH); 120.6 (2 x CH); 124.7 (CH); 125.6 (2 x
2
2
CH); 126.3 (2 x CH); 127.7 (2 x CH); 128.4 (2 x CH); 128.8 (2 x CH); 141.0 (2 x CH); 141.5 (C); 143.8 (2 x C); 181.8 (C).
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MS (DCI/CH ) m/z: 386.17 [M+H ], 251.15 [M-134], 165.07 [M-220], 136.02 [M-249]. HRMS (DCI/CH ): for C H N S
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24 24
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[
M+H ]: calcd: 386.1691; found: 386.1690.
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.2.7.3. N-Butyl-4-(9H-fluoren-9-yl)piperazine-1-carboxamide (13). Reagents: 1-(9H-fluoren-9-yl)piperazine 3 (0.40 mmol,
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00 mg) and butyl isocyanate (0.48 mmol, 54 µL). The crude product was purified by flash chromatography (isocratic,
petroleum ether/ethyl acetate 70/30) to afford a white solid (72 mg, 51%). TLC R : 0.83 (dichloromethane/methanol 90/10);
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mp: 174 °C; IR (cm ): 737, 758, 848, 939, 1001, 1141, 1208, 1264, 1304, 1327, 1411, 1447, 1538, 1613, 2822, 2861, 2928,
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2
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956, 3353. HPLC: method 1, rt = 2.05 min, purity 98%. H NMR (300 MHz, CDCl ) δ (ppm): 0.93 (t, J = 7.2 Hz, 3 H); 1.26
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1.41 (m, 2 H); 1.41 – 1.54 (m, 2 H); 2.63 (t, J = 4.8 Hz, 4 H); 3.17 – 3.26 (m, 2 H); 3.34 (t, J = 4.8 Hz, 4 H); 4.45 (t, J = 5.7
Hz, 1 H); 4.88 (s, 1 H); 7.31 (td, J = 1.2 Hz, 7.5 Hz, 2 H); 7.41 (t, J = 7.5 Hz, 2 H); 7.63 (d, J = 7.2 Hz, 2 H); 7.71 (d, J = 7.5
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Hz, 2 H). C NMR (75 MHz, CDCl ) δ (ppm): 13.9 (CH ); 20.1 (CH ); 32.4 (CH ); 40.7 (CH ); 44.5 (2 x CH ); 48.8 (2 x
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CH ); 70.0 (CH); 119.8 (2 x CH); 126.0 (2 x CH); 127.1 (2 x CH); 128.2 (2 x CH); 141.0 (2 x C); 143.6 (2 x C); 158.0 (C).
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MS (DCI/CH ) m/z: 350.22 [M+H ], 251.16 [M-98], 184.15 [M-165], 165.07 [M-184], 143.12 [M-206]. HRMS (DCI/CH ):
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for C H N O [M+H ]: calcd: 350.2232; found: 350.2228.
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.2.7.4. 4-(9H-Fluoren-9-yl)-N-octylpiperazine-1-carboxamide (14). Reagents: 1-(9H-fluoren-9-yl)piperazine 3 (0.40
mmol, 100 mg) and octyl isocyanate (0.48 mmol, 85 µL). The crude product was purified by flash chromatography (isocratic,
petroleum ether/ethyl acetate 70/30) to afford a white solid (85 mg, 52%). TLC R : 0.83 (dichloromethane/methanol 90/10);
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mp: 139 °C; IR (cm ): 618, 738, 844, 1006, 1127, 1143, 1177, 1206, 1260, 1301, 1326, 1406, 1444, 1466, 1540, 1616, 2851,
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925, 3298. HPLC: method 1, rt = 3.12 min, purity 99%. H NMR (300 MHz, CDCl ) δ (ppm): 0.86 – 0.95 (m, 3 H); 1.22 –
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.38 (m, 10 H); 1.49 (quint, J = 6.6 Hz, 2 H); 2.64 (t, J = 4.8 Hz, 4 H); 3.16 – 3.25 (m, 2 H); 3.35 (t, J = 4.8 Hz, 4 H); 4.36 (s,
H); 4.89 (s, 1 H); 7.31 (td, J = 1.2 Hz, 7.2 Hz, 2 H); 7.41 (t, J = 7.2 Hz, 2 H); 7.64 (d, J = 7.5 Hz, 2 H); 7.72 (d, J = 7.5 Hz,
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H). C NMR (75 MHz, CDCl ) δ (ppm): 14.1 (CH ); 22.7 (CH ); 27.0 (CH ); 29.2 (CH ); 29.3 (CH ); 30.3 (CH ); 31.8
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(
CH ); 41.0 (CH ); 44.5 (2 x CH ); 48.7 (2 x CH ); 70.0 (CH); 119.8 (2 x CH); 126.0 (2 x CH); 127.1 (2 x CH); 128.2 (2 x
2 2 2 2
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CH); 141.0 (2 x C); 143.6 (2 x C); 157.7 (C). MS (DCI/CH ) m/z: 406.28 [M+H ], 251.16 [M-154], 240.21 [M-165], 199.18
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[
M-206], 165.07 [M-240]. HRMS (DCI/CH ): for C H N O [M+H ]: calcd: 406.2858; found: 406.2840.
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26 36
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.2.7.5. 4-(9H-Fluoren-9-yl)-N-(4-nitrophenyl)piperazine-1-carboxamide (15). Reagents: 1-(9H-fluoren-9-yl)piperazine 3
(0.40 mmol, 100 mg) and 4-nitrophenylisocyanate (0.40 mmol, 65 mg). The crude product was purified by flash
chromatography chromatography (dry-load, gradient 100% petroleum ether to 100% ethyl acetate in 15 minutes) to afford a
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white solid (82 mg, 82%). TLC R : 0.71 (dichloromethane/methanol 90/10); mp: 263 °C; IR (cm ): 620, 672, 690, 739, 807,
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42, 1001, 1110, 1237, 1299, 1328, 1424, 1497, 1541, 1599, 1611, 1639, 2827, 2913, 3341. HPLC: method 1, rt = 2.68 min,
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purity 95%. H NMR (300 MHz, DMSO-d6) δ (ppm): 2.57 (t, J = 5.1 Hz, 4 H); 3.47 (t, J = 5.1 Hz, 4 H); 5.02 (s, 1 H); 7.34
(td, J = 1.5 Hz, 7.5 Hz, 2 H); 7.43 (t, J = 7.2 Hz, 2 H); 7.65 (d, J = 7.2 Hz, 2 H); 7.67 – 7.73 (m, 2 H); 7.86 (d, J = 7.5 Hz, 2
13
H); 8.10 – 8.19 (m, 2 H); 9.18 (s, 1 H). C NMR (75 MHz, DMSO-d6) δ (ppm): 45.1 (2 x CH ); 49.0 (2 x CH ); 69.6 (CH);
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18.7 (2 x CH); 120.6 (2 x CH); 125.2 (2 x CH); 126.3 (2 x CH); 127.7 (2 x CH); 128.7 (2 x CH); 141.0 (2 x C); 141.2 (C);
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43.8 (2 x CH); 148.0 (C); 154.3 (C). MS (DCI/CH ) m/z: 415.186 [M+H ]. HRMS (DCI/CH ): for C H N O [M+H ]:
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calcd: 415.1770; found: 415.1779.
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