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Yan H, et al. Sci China Chem February (2014) Vol.57 No.2
saturated aqueous NaCl (3 × 30 mL), dried over NaSO4 and
concentrated in vacuo. The crude product was purified by
chromatography (eluting with PE: DCM, v/v = 5:1) to give
41.60, 40.02, 27.34, 19.74, 18.89; IR (KBr): 619 (w), 725
(m), 752 (s), 1002 (w), 1023 (w), 1046 (w), 1130 (m), 1215
(m), 1327 (m), 1382 (w), 1454 (s), 1484 (m), 1596 (w),
1626 (w), 2809 (m), 2926 (m), 3050 (w), 3431 cm1 (w);
HRMS (ES+) calcd. for C27H38N7 [M+H]+: 460.3189, found
460.3199.
1
5b as a colorless oil (0.239 g, 95%). H NMR (400 MHz,
CDCl3) 8.10 (d, J = 7.8, 2H), 7.48 (m, 2H), 7.44 (d, J =
8.0, 2H), 7.25 (d, J = 8.2, 2H), 4.42 (t, J = 6.5, 2H), 3.30 (t,
J = 6.3, 2H), 2.14 (m, 2H); 13C NMR (101 MHz, CDCl3)
140.28, 125.84, 122.92, 120.44, 119.10, 108.44, 48.62,
39.66, 28.18; MS (ES+): m/z = 253.2 [M+H] +.
1-[3-(9H-carbazol-9-yl)propyl]-1,5,9-triazacylododecane (3)
To a solution of 5b (1.44 g, 5 mmol) in toluene (15 mL)
was added 9 (0.91 g, 5 mmol). The reaction was refluxed
for 48 h. After being cooled down to room temperature, the
resulting precipitates were filtered and taken into aqueous
HCl solution (1 M, 20 mL). The mixture was refluxed for 6
h and allowed to cool to room temperature, after which time
it was washed with CHCl3 (3 × 20 mL) followed by the ad-
dition of concentrated aqueous NaOH solution, adjusting
the pH to about 13. Then the mixture was extracted with
CHCl3 (3 × 20 mL) and the combined organic phase was
dried over Na2SO4, filtered and concentrated to give 3 as a
N-{2-[4-(1,5,9-triazacylododec-1-ylmethyl)-1,2,3-triazol-1-
yl]ethyl}carbazol (2a)
To a solution of 7 (54 mg, 0.13 mmol) in H2O/DMF (1/2, 3
mL) were added 6a (31 mg, 0.13 mmol), CuSO4 (3 mg, 0.02
mmol), and sodium ascorbate (8 mg, 0.04 mmol). The reac-
tion was stirred at room temperature for 8 h. Then the mix-
ture was poured into water and filtered. The solid was
washed with water and dried in vacuo, after which the solid
was added into HCl solution (Prepared by slowly adding 0.5
mL of acetyl chloride into 8 mL of methanol and then stir-
ring for 5 min at 0 °C) and stirred for 1 h. Then the solvents
were removed in vacuo and the resulting solid was dried to
give 2a as its hydrochloric salt (63 mg, 78%). 1H NMR (400
MHz, D2O) 7.92 (d, J = 7.7, 2H), 7.26 (t, J = 7.4, 2H),
7.10 (m, 4H), 4.78 (t, J = 5.1, 2H), 4.61 (t, J = 5.1, 2H),
3.46 (s, 2H), 3.05 (t, J = 5.5, 4H), 2.92 (t, J = 5.7, 4H), 2.06
(m, 6H), 1.62 (t, J = 5.5, 4H); 13C NMR (101 MHz, D2O)
139.45, 138.57, 126.46, 126.11, 122.12, 120.25, 119.53,
108.54, 48.98, 48.46, 44.57, 43.65, 42.12, 41.98, 19.51,
19.44; IR (KBr): 725 (m), 751 (s), 852 (w), 1046 (w),
1071 (w), 1123 (m), 1226 (m), 1287 (m), 1326 (m), 1351
(m), 1458 (s), 1485 (m), 1597 (w), 1626 (w), 2812 (m),
2928 (m), 3050 (w), 3432 cm1 (w); HRMS (ES+) calcd. for
C26H36N7 [M+H]+: 446.3032, found 446.3016.
1
brown oil (1.80 g, 95%). H NMR (400 MHz, CDCl3)
8.10 (d, J = 7.7, 2H), 7.46 (m, 4H), 7.22 (d, J = 6.7, 2H),
4.34 (t, J = 7.4, 2H), 2.72 (ddd, J = 27.3, 11.5, 5.3, 8H),
2.50 (t, J = 5.7, 6H), 2.04 (m, 2H), 1.62 (m, 6H); 13C NMR
(101 MHz, CDCl3) 140.41, 125.68, 122.97, 120.38,
118.86, 108.64, 52.89, 50.36, 49.33, 47.08, 41.61, 26.20,
25.63; IR (KBr): 728 (w), 756 (m), 1069 (w), 1154 (w),
1215 (w), 1327 (m), 1383 (w), 1454 (s), 1484 (m), 1594 (m),
1626 (w), 2747 (m), 2951 (m), 3421 cm1 (m); HRMS (ES+)
calcd. for C24H35N4 (M+H)+: 379.2862, found 379.2867.
Diethyl 2-[3-(9H-carbazol-9-yl)]propylmalonate (8a)
Metal sodium (0.23 g, 10 mmol) was cut into small pieces
and added into absolute ethanol (30 mL) under argon. Once
the reaction was complete, diethyl malonate (1.59 g, 10
mmol) was added, after which time a solution of compound
5b (2.30 g, 8.0 mmol) in absolute ethanol (20 mL) was
added dropwise. The reaction mixture was stirred at room
temperature for 8 h. Then the solvent was removed in vacuo.
The resulting oil was dissolved in water (50 mL) and ex-
tracted with ethyl acetate (3 × 50 mL). The combined or-
ganic phase was dried over Na2SO4, filtered and concen-
trated in vacuo. The residual was purified by chromatog-
raphy (eluting with ethyl acetate/petroleum ether, v/v = 1:10)
N-{3-[4-(1,5,9-triazacylododec-1-ylmethyl)-1,2,3-triazol-1-
yl]propyl}carbazol (2b)
To a solution of 7 (64 mg, 0.16 mmol) in H2O/DMF (1/2, 3
mL) were added 6b (40 mg, 0.16 mmol), CuSO4 (3 mg,
0.02 mmol), and sodium ascorbate (8 mg, 0.04 mmol). The
reaction was stirred at room temperature for 8 h. Then the
mixture was poured into water and filtered. The solid was
washed with water and dried in vacuo, after which the solid
was added into HCl solution (Prepared by slowly adding 0.5
mL of acetyl chloride into 8 mL of methanol and then stir-
ring for 5 min at 0 °C) and stirred for 1 h. Then the solvents
were removed in vacuo and the resulting solid was dried to
1
to give 8a as a white solid (2.55 g, 87%). H NMR (400
MHz, CDCl3) 8.09 (d, J = 7.7 Hz, 2H), 7.49–7.42 (m, 2H),
7.39 (d, J = 8.2 Hz, 2H), 7.24–7.18 (m, 2H), 4.32 (t, J = 7.0
Hz, 2H), 4.14 (dtt, J = 10.8, 7.0, 3.7 Hz, 4H), 3.31 (t, J = 7.2
Hz, 1H), 2.05–1.86 (m, 4H), 1.20 (t, J = 7.1 Hz, 6H); 13C
NMR (101 MHz, CDCl3) 169.07, 140.23, 125.70, 122.87,
120.37, 118.90, 108.51, 61.47, 51.58, 42.53, 26.60, 26.33,
13.99; IR (KBr): 610 (w), 724 (m), 760 (m), 867 (w), 939
(w), 1020 (m), 1053 (m), 1092 (m), 1149 (m), 1185 (m),
1254 (m), 1296 (m), 1326 (m), 1371 (m), 1452 (m), 1467
(m), 1479 (m), 1587 (w), 1620 (w), 1721 (s), 1739 (s), 2976
1
give 2b as its hydrochloric salt (98 mg, 81%). H NMR
(400 MHz, D2O) 7.61 (d, J = 7.3, 2H), 7.15 (t, J = 7.5,
2H), 7.03 (d, J = 7.7, 2H), 6.91 (t, J = 7.2, 2H), 6.83 (s, 1H),
3.8514.02 (br, 4H), 3.45 (s, 2H), 3.202.90 (br, 8H),
2.402.70 (br, 4H), 1.90–2.20 (br, 4H), 1.701.85 (br, 4H);
13C NMR (101 MHz, D2O) 139.61, 137.11, 125.99,
125.19, 122.00, 119.97, 119.13, 109.02, 48.68, 46.53, 42.91,