6
14 J. Chin. Chem. Soc., Vol. 57, No. 4A, 2010
Xi et al.
1
61.3; 161.8. ESI-MS: 529 (33), 513(100), 491 (35,
2.50 (t, 8H); 2.57 (s, 16H); 4.01-4.04 (t, 8H); 6.07 (s, 4H);
13
+
M+1] ), 103(3).
[
6.69 (s, 4H); 6.79-6.81 (d, 4H); 7.43-7.45 (d, 4H).
C
1
,4-(7-(3-bromopropoxy)-4-methyl-coumarin) piper-
azine (1b)
Yield: 84.0%. White solid. mp 166.7-167.7 °C. H
NMR (CDCl ) d: 1.99-2.04 (m, 4H); 2.40 (s, 6H);
.53-2.56 (t, 4H); 2.54 (s, 8H); 4.07-4.10 (t, 4H); 6.14 (s,
NMR (CDCl ) d: 18.6; 27.0; 51.9; 53.4; 66.7; 101.2; 111.8;
3
112.6; 113.4; 125.5; 152.6; 155.2; 161.3; 162.2. ESI-MS:
+
1059 (7), 1037 (26, [M+1] ), 784 (5), 658 (4), 625 (13),
1
3
595 (20), 530 (79), 473 (9), 407 (8), 395 (11), 338 (16).
1,4,7,10-(7-(4-bromobutoxy)-4-methyl-coumarin)
cyclen (2c)
2
2
1
3
H); 6.82 (s, 2H); 6.85-6.87 (d, 2H); 7.48-7.50 (d, 2H). C
) d: 18.6; 26.5; 53.3; 54.9; 66.9; 101.5; 111.9;
12.7; 113.5; 125.5; 152.5; 155.3; 161.3; 162.1. ESI-MS:
1
Yield: 98.8%. White solid. mp 174.4-174.6 °C. H
NMR (CDCl
3
1
5
3
NMR (CDCl ) d: 1.60-1.68 (m, 8H); 1.82-1.88 (m, 8H);
+
41 (100), 519 (60, [M+1] ), 437(7), 353 (6), 330 (3), 258
2.36 (s, 12H); 2.43-2.46 (t, 8H); 2.62 (s, 16H); 3.97-3.99 (t,
8H); 6.08 (s, 4H); 6.70 (s, 4H); 6.79-6.81 (d, 4H); 7.43-
(
6).
,4-(7-(4-bromobutoxy)-4-methyl-coumarin) piper-
azine (1c)
Yield: 80.0%. White solid. mp 168.0-168.5 °C. H
NMR (CDCl ) d: 1.66-1.72 (m, 4H); 1.82-1.87 (m, 4H);
.40 (s, 6H); 2.41-2.43 (t, 4H); 2.45-2.54 (t, 8H); 4.03-4.05
t, 4H); 6.13 (s, 2H); 6.81 (s, 2H); 6.83-6.86 (d, 2H);
1
3
1
3
7.45 (d, 4H). C NMR (CDCl ) d: 18.6; 24.0; 27.2; 52.9;
55.6; 68.6; 101.3; 111.8; 112.6; 113.4; 125.5; 152.6; 155.2;
+
161.2; 162.2. ESI-MS: 1093 (4, [M+1] ), 814 (7), 701(18),
1
3
558 (100), 547 (11), 475(10), 362 (3), 304 (7).
2
(
ACKNOWLEDGMENTS
1
.48-7.49 (d, 2H). C NMR (CDCl
3
7
5
1
3
) d: 18.7; 23.4; 27.0;
This research was carried out with the financial sup-
port from the National Natural Science Foundation of
China (Grant Nos. 20872051) and Jiangsu Province post-
graduate science and technology innovation fund.
3.3; 58.2; 68.3; 101.3; 111.9; 112.7; 113.5; 125.5; 152.6;
55.3; 161.4; 162.1. ESI-MS: 585 (41), 570 (70), 547 (100,
+
M+1] ), 424 (8), 367 (13), 297 (18), 243 (18), 211(54),
[
1
89 (6), 127 (20).
General Procedure and Spectral data for the Com-
pounds 2a–2c
Received November 24, 2009.
To a solution of cyclen (0.05 g, 0.3 mmol), a, b or c
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3
CN was added K
2
CO
3
(0.16 g, 1.0
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/
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3
material (ca. 19 h), the remaining solids were filtered off
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2
CH
,4,7,10-(7-(2-bromoethoxy)-4-methyl-coumarin)
cyclen (2a)
Yield: 91.3%. White solid. mp 212.5-212.7 °C. H
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H); 4.01-4.02 (t, 8H); 6.04 (s, 4H); 6.60 (s, 4H); 6.75-6.77
3
CN.
1
1
5. Padilla, T. M. E.; Lloris, J. M.; Martnez, M. R. Eur. J. Inorg.
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6
7
8
9
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8
1
d, 4H); 7.38-7.40 (d, 4H). C NMR (CDCl
3
(
3
) d: 21.2; 53.3;
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Trans. 2. 2001, 929.
5
1
4
1
4.4; 66.9; 101.2; 111.8; 112.6; 113.4; 125.5; 152.6; 155.2;
+
61.3; 162.2. ESI-MS: 981 (3, [M+1] ), 663 (17), 502 (96),
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1
0. Cullis, P. M.; Merson, D. L.; Weaver, R. J. Am. Chem. Soc.
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550.
,4,7,10-(7-(3-bromopropoxy)-4-methyl-coumarin)
1
cyclen (2b)
Yield: 88.3%. White solid. mp 192.5-193.5 °C. H
NMR (CDCl ) d: 1.87-1.90 (m, 8H); 2.36 (s, 12H); 2.48-
1
4
3