Hz, 2H), 8.28–8.22 (m, 3H), 8.11 (d, J = 8.40 Hz, 2H),
129.81, 129.77, 129.35, 127.3, 124.3, 123.8, 120.1, 67.6, 64.0,
25
7
7
.87–7.81 (m, 6H), 7.74–7.69 (m, 3H), 7.47 (d, J = 7.5 Hz, 4H),
.08 (d, J = 7.2 Hz, 4H), 7.00 (s, 2H), 6.61 (s, 2H), 5.73–5.62
61.93, 61.59, 50.5, 35.8, 25.6, 24.6, 23.6, 20.8, 11.3 ppm. [α]D
= −95.49 (c 1.0, DMSO). IR (KBr) ν 3154.97, 2954.41,
1938.11, 1666.20, 1591.95, 1507.10, 1458.89, 1404.89,
1388.50, 1120.44, 1093.44, 1056.80, 855.28, 780.06, 758.85.
mp: 227–229 °C. Anal. Calcd for C H N O Br : C, 64.49; H,
(m, 2H), 5.29 (d, J = 11.7 Hz, 2H), 5.17 (s, 1H), 5.11–5.05
(m, 3H), 4.94 (d, J = 10.2 Hz, 2H), 4.33 (s, 2H), 3.96–3.90
(m, 2H), 3.74 (d, J = 10.2 Hz, 2H), 2.66 (s, 2H), 2.26 (s, 5H),
46
56
4
2
2
2
.11–2.05 (m, 3H), 1.99 (s, 2H), 1.75 (s, 2H), 1.33–1.26
6.59; N, 6.54. Found: C, 64.55; H, 6.51; N, 6.38.
13
(m, 2H), 1.13 (d, J = 12.3 Hz, 4H), 0.94 (d, J = 6.6 Hz, 2H).
C
6
NMR (d -DMSO, 75 MHz) δ 150.2, 147.6, 145.37, 145.04,
Synthesis of 12CH
1
1
5
39.69, 139.25, 138.10, 138.07, 135.1, 129.89, 129.43, 128.6,
28.19, 127.3, 125.5, 124.3, 123.5, 120.1, 116.3, 67.9, 64.3,
9.2, 50.6, 46.2, 36.8, 25.9, 24.3, 20.8, 18.9 ppm. [α]
The procedure described for 12AH was followed using
−)-10,11-dihydrocinchonidine (3.0 g, 10.2 mmol) and α,α′-
dibromo m-xylene (1.32 g, 5 mmol), which gave 12CH (4.2 g,
2
5
=
D
(
−
127.43 (c 1.0, DMSO). IR (KBr) ν 3247.54, 2512.79, 1920.75,
640.16, 1590.99, 1570.74, 1509.03, 1460.81, 1208.18,
118.51, 1032.69, 1009.55, 814.78, 777.17, 755.96, 683.64,
65.04. mp: 213–215 °C. Anal. Calcd for C H N O S : C,
1
1
6
9
8% yield). H NMR (d -DMSO, 400 MHz) δ 9.00 (d, J = 4.4
Hz, 1H), 8.38 (d, J = 8.0 Hz, 1H), 8.10 (d, J = 7.2 Hz, 1H),
.95–7. 76 (m, 5H), 6.77 (s, 1H), 6.61 (s, 1H), 5.33 (d, J = 11.2
Hz, 1H), 5.13 (d, J = 11.2 Hz, 1H), 4.33 (s, 1H), 3.99 (s, 1H),
.53–3.31 (m, 2H), 2.10–1.75 (m, 6H), 1.30–1.13 (m, 3H), 0.66
1
5
6
6
0 66 4 8 2
7
9.61; H, 6.43; N, 5.41. Found: C, 69.55; H, 6.38; N, 5.35.
3
(
13
6
d, J = 7.2 Hz, 3H). C NMR (d -DMSO, 125 MHz) δ 149.9,
Synthesis of 12AH
1
1
2
47.3, 145.0, 138.7, 134.8, 129.54, 129.16, 128.3, 127.1, 124.1,
23.6, 120.0, 67.3, 63.9, 61.91, 61.01, 50.2, 35.6, 30.5, 24.5,
A mixture of (−)-10,11-dihydrocinchonidine (3.0 g, 10.2 mmol)
with 9,10-bis-(chloromethyl)anthracene (1.38 g, 5 mmol) in a
mixture of 30 mL (ethanol : DMF : CHCl /5 : 6:2) was stirred at
1
mixture was cooled at room temperature. After cooling the reac-
tion mixture to room temperature the reaction mixture was
diluted with methanol (25 mL) and then added dropwise to ether
25
3.9, 20.6, 11.0 ppm. [α] = −132.18 (c 1.0, DMSO). IR (KBr)
D
ν 3434.60, 3200.29, 2958.27, 2875.34, 2113.60, 1933.29,
3
1
1
664.27, 1590.02, 1509.03, 1458.89, 1387.53, 1116.58,
062.59, 803.21, 778.14, 754.99. mp: 224–226 °C. Anal. Calcd
00 °C for 6 h. After completion of reaction, the reaction
for C H N O Br : C, 64.49; H, 6.59; N, 6.54. Found: C,
46 56
4
2
2
6
4.32; H, 6.55; N, 6.42.
(300 mL) with stirring. The solid precipitated was filtered,
washed with ether (200 mL). The crude solid was reprecipitated
Synthesis of disulfonate 9e
from methanol–ether to afford 3.82 g (88% yield) of product.
2
5
1
6
[
3
(
α]
= −229.53 (c 1.0, DMSO). H NMR (d -DMSO,
00 MHz) δ 9.04–8.90 (m, 4H), 8.71–8.66 (m, 2H), 8.17–8.04
m, 2H), 7.95–7.75 (m, 8H), 7.69–7.53 (m, 4H), 7.01 (brs, 1H),
D
A mixture of α,α′-dibromo p-xylene (10 mmol, 2.64 g) in
DMSO (30 mL) and Na SO (22 mmol, 2.77 g) in H O (20 mL)
2
3
2
was stirred at 100 °C for 12 hours. After completion of the reac-
tion, the reaction mixture was filtered and filtrate was collected.
The amount of solvent in the filtrate was reduced to 15 mL by
pump. The concentrated solution was added into ethanol
6
3
.58–5.41 (m, 3H), 4.69–4.38 (m, 2H), 4.00–3.41 (m, 3H),
.20–3.11 (m, 2H), 2.20–1.93 (m, 4H), 1.75 (s, 4H), 1.52–1.37
(
(
m, 5H), 1.31–1.02 (m, 8H), 0.75–0.70 (m, 3H), 0.55–0.519
m, 5H). C NMR (d -DMSO, 75 MHz) δ 150.1, 147.70,
13
6
(250 mL) with stirring. The white precipitate obtained was
1
1
2
2
7
7
47.66, 147.14, 146.0, 132.8, 129.66, 129.23, 126.9, 124.67,
24.14, 120.5, 118.8, 65.7, 59.5, 54.9, 42.6, 34.6, 25.61, 25.47,
4.3, 22.5, 17.2, 11.3 ppm. IR (KBr) ν 3170.40, 2957.30,
560.04, 1662.34, 1590.02, 1509.03, 1457.92, 1385.60, 781.03,
filtered, washed with methanol, hexane and dried under vacuum
1
to give 9e in 98% yield. H NMR (D O, 300 MHz) δ = 7.44
2
13
(
s, 2H), 4.21 (s, 2H). C NMR (D O, 75 MHz) δ 131.6, 56.6.
2
IR (KBr) ν 3468, 2978, 1629.55, 1516.74, 1425.14, 1148.40,
1057.76, 969.05, 852.38, 743.42, 633.86, 533.22. Anal. Calcd
for C H Na O S : C, 30.97; H, 2.60. Found: C, 31.05; H, 2.58.
58.85. mp: 181–183 °C. Anal. Calcd for C H N O Cl : C,
5
4
60
4
2
2
4.72; H, 6.97; N, 6.45. Found: C, 74.68; H, 6.83; N, 6.35.
8
8
2 6 2
Synthesis of 12BH
The procedure described for 12AH was followed using
Synthesis of disulfonate 9f
A mixture of trans-1,4-dibromo-2-butene (10 mmol 2.1390 g) in
(
−)-10,11-dihydrocinchonidine (3.0 g, 10.2 mmol) and α,α′-
DMF (15 mL) and Na SO (22 mmol, 2.77 g) in H O (15 mL)
were stirred at 100 °C for 11 h. After cooling the reaction
2
3
2
dibromo p-xylene (1.32 g, 5 mmol), which gave 12BH (4.12 g,
9
1
6
6% yield). H NMR (d -DMSO, 300 MHz) δ 9.00 (d, J = 4.2
mixture to room temperature, H O (30 mL) and ethanol (20 mL)
2
Hz, 1H), 8.36 (d, J = 8.4 Hz, 1H), 8.12 (d, J = 9.0 Hz, 1H), 7.95
were added successively to the reaction mixture. The excess
(
(
(
3
3
1
s, 1H), 7.89 (s, 1H), 7.84 (d, J = 5.1 Hz, 2H), 7.78–7.73
m, 1H), 6.74 (d, J = 4.5 Hz, 1H), 6.58 (d, J = 3.6 Hz, 1H), 5.28
d, J = 12 Hz, 1H), 5.10 (d, J = 12 Hz, 1H), 4.28 (s, 1H),
Na SO precipitated was filtered out and the filtrate was col-
2
3
lected, washed with CH Cl2 (3 × 20 mL) to remove the
2
unreacted trans-1,4-dibromo-2-butene. The volume of the reac-
tion mixture was reduced by rotary evaporator and dried under
vacuum to obtain the crude product. The crude product was
.98–3.93 (m, 1H), 3.71–3.63 (m, 1H), 3.52 (d, J = 9.9, 1H),
.43 (d, J = 5.1, 1H), 2.14–2.07 (m, 1H), 1.99–1.83 (m, 4H),
13
.35–1.28 (m, 1H), 1.24–1.05 (m, 2H), 0.71–0.66 (m, 3H).
C
recrystallized in ethanol–H O (6 : 4) mixture to give 9f in 96%
2
6
1
NMR (d -DMSO, 75 MHz) δ 150.15, 147.6, 145.3, 134.0,
yield as a white solid. H NMR (D O, 300 MHz) δ = 5.89–5.85
2
2876 | Org. Biomol. Chem., 2012, 10, 2870–2877
This journal is © The Royal Society of Chemistry 2012