New Journal of Chemistry
Page 6 of 7
removed to give the product as a colorless liquid (yield: 69%). 1H
55 Notes and references
NMR (CDCl3, 400 MHz) δ (ppm): 4.68 (s, 4H, CH2). 13CꢀNMR
(CDCl3, 100 MHz) δ (ppm): 163.48, 32.53. ESI–MS: (m/z) 167.1
[M+H]+, calcd. for C4H4Cl2N2O = 165.97.
College of Chemistry and Chemical Engineering, Key Laboratory of
Nonferrous Metals Chemistry and Resources Utilization of Gansu
Province Lanzhou University Lanzhou, 730000, PR China.
Fax: 86-931-8912582; Tel: 86-931-8912585;
5
Synthesis of L
60 E-mail address: liuxiang@lzu.edu.cn.
† Electronic Supplementary Information (ESI) available: 1H NMR, 13C
NMR, MS spectrum, and IR spectra. See DOI: 10.1039/b000000x/
Anhydrous potassium carbonate (2.07 g, 15mmol) was added to a
solution of 2ꢀ(2ꢀHydroxyphenyl)benzothiazole (1.14 g, 5 mmol)
in acetone (30 mL), and the mixture was held at reflux. An hour
later, an acetone solution containing 2 (1.67 g, 2.5 mmol) was
1
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65
70
10 added dropwise to the mixture. The reaction mixture was held at
reflux for another 5 h. The reaction mixture was then poured into
ice water (50 mL) and filtered. The white solid was obtained at a
84% yield. 1H NMR (DMSOꢀd6, 400 MHz): δ (ppm): 8.42 (dd, J
= 7.8, 1.3 Hz, 2H, ArꢀH), 8.02 (d, J = 8.1 Hz, 2H, ArꢀH), 7.84 (d,
15 J = 7.9 Hz, 2H, ArꢀH), 7.51 (ddd, J = 21.0, 11.2, 4.6 Hz, 6H, Arꢀ
H), 7.32 (t, J = 7.4 Hz, 2H, ArꢀH), 7.27 – 7.15 (m, 2H, ArꢀH),
5.83 (s, 4H, OCH2). 13CꢀNMR (DMSOꢀd6, 100 MHz) δ (ppm):
163.28, 161.67, 154.87, 151.42, 135.29, 132.21, 129.00, 126.20,
124.91, 122.46, 122.34, 121.72, 121.54, 113.87, 60.26. ESI–
20 MS(m/z): 549.3 [M+H]+, calcd. for C30H20N4O3S2 = 548.
2
75
3
80
Synthesis of compound 3
Diethylene glycol (190 mL, 2 mol) was slowly added to 294 mL
(4.1 mol) of thionyl chloride in 0.5 h, and then the mixture was
react at 110 ℃ until the gas was not formed. Meanwhile, the
25 resulting gas was guided to basic solution. Then the mixture was
cooled and distilled at reduced pressure. A colorless liquid 3 was
obtained at a 84% yield. 1H NMR (400 MHz, CDCl3) δ 3.77 (t, J
= 5.8 Hz, 4H, OCH2), 3.63 (t, J = 5.8 Hz, 4H, CH2Cl). 13C NMR
(100 MHz, CDCl3) δ (ppm): 71.23, 42.56.
85
4
5
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90
30 Synthesis of compound 4
2ꢀ(2ꢀHydroxyphenyl)benzothiazole (1.14 g, 5 mmol) was added
to 50% NaOH aqueous solution (10 ml H2O ), and the mixture
was held at 80 ℃ for 0.5 h. Then Compound 3 (0.72 g, 5 mmol)
and PEG1000 (1 g) was added to the mixture. After the mixture
35 refluxed for 7 h, a 50% solution of KOH (10 ml H2O) was added
to the mixture for another 13 h at 90℃, and then the mixture was
heated to 120 ℃ for 3 h. The reaction mixture was poured into
water (50 mL) and was extracted with ethyl acetate three times (3
×20 mL). The organic layer was dried with sodium sulfate, then
40 it was purified on silica gel eluting with ethyl acetate / petroleum
95
100
105
110
115
120
6
7
1
ether (1/3), yield 54.3%. H NMR (400 MHz, CDCl3) δ 8.54 (dd,
J = 7.9, 1.6 Hz, 2H, ArꢀH), 8.09 (d, J = 8.2 Hz, 2H, ArꢀH), 7.81
(d, J = 7.9 Hz, 2H, ArꢀH), 7.55 – 7.45 (m, 2H, ArꢀH), 7.45 – 7.38
(m, 2H, ArꢀH), 7.37 – 7.29 (m, 2H, ArꢀH), 7.13 (t, J = 7.6 Hz, 2H,
45 ArꢀH), 7.06 (d, J = 8.3 Hz, 2H, ArꢀH), 4.43 (t, J = 5.0 Hz, 4H,
CH2OCH2), 4.23 (t, J = 5.0 Hz, 4H, ArꢀOCH2). 13C NMR (100
MHz, CDCl3) δ (ppm): 162.99, 156.37, 152.07, 136.04, 131.72,
129.68, 125.86, 124.58, 122.76, 122.56, 121.45, 121.14, 112.68,
69.80, 68.60. ESI–MS(m/z): 525.2 [M+H]+, calcd. for
50 C30H24N2O3S2 = 524.12.
8
9
Acknowledagements
(a) V. Bénéteau, T. Besson, J. Guillard, S. Léonce, B. Pfeiffer, Eur. J.
Med. Chem., 1999, 34, 1053; (b) A. Benazzouz, T. Boraud, P.
Dubédat, A. Boireau, J.M. Stutzmann, C. Gross, Eur. J. Pharmacol.,
1995, 284, 299.
We acknowledge Key Laboratory of Nonferrous Metals
Chemistry and Resources Utilization of Gansu Province for
financial support.
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