(2H) 1, 4-benzothiazine compounds as well as preparation method and application thereof
A benzothiazine and compound technology, which is applied in the field of chemical drug preparation, can solve the problems of few reports on the antitumor activity of 1,4-benzothiazine compounds, and achieves great promotion and application potential, low price and simple process. Effect
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Embodiment 1
[0020] Synthesis of compound 1
[0021]
[0022] 10g (74.1mmol, 1.0eq.) of benzothiazole and 11.8mL (93.33mmol, 1.3eq.) of dimethyl acetylene dicarboxylate were refluxed in a solution of methanol (50mL): water (10mL) = 5:1 and reacted overnight , methanol and water were evaporated to dryness, and through solid silica gel column chromatography, the column condition volume ratio of petroleum ether: ethyl acetate=3:1 was the eluent, and the eluted fraction was concentrated to obtain 17.3g of yellow solid target (compound 1), Yield: 79%.
[0023] 1 H NMR (500MHz, CDCl 3 )δ: 8.96(s,1H),7.12-7.06(m,3H),7.04-7.01(m,1H),3.76(s,3H),3.59(s,3H),3.57(s,1H),3.55 (s,1H).; 13 C NMR (125MHz, CDCl 3 )δ: 169.08, 168.50, 158.36, 137.30, 126.71, 125.93, 125.34, 122.28, 110.21, 73.03, 53.73, 51.90, 39.76; MS-ESI m / z: 296.05 [M+H] + .
Embodiment 2
[0024] Embodiment 2: the synthesis of compound 2
[0025]
[0026] The benzothiazole was replaced with 6-bromobenzothiazole, and the synthesis method was the same as that in Example 1 to obtain compound 2 with a yield of 68%.
[0027] 1 H NMR (500MHz, CDCl 3 )δ: 8.71(s, 1H), 7.33(d, J=2.0Hz, 1H), 7.29(dd, J=9.0, 2.0Hz, 1H), 7.07(d, J=8.5Hz, 1H), 6.15( d,J=3.5Hz,1H),4.50(d,J=3.0Hz,1H),3.74(s,3H),3.72(s,3H).; 13 C NMR (125MHz, CDCl 3 )δ: 168.85, 167.13, 161.19, 132.19, 129.50, 129.29, 123.85, 121.40, 118.79, 53.45, 53.44, 50.13, 41.61; MS-ESI m / z: 395.95 [M+Na] + .
Embodiment 3
[0028] Embodiment 3: the synthesis of compound 3
[0029]
[0030] 10g (33.89mmol) compound 1 of Example 1 was dissolved in methanol:hydrochloric acid=3:1 (volume ratio) in 40ml solution and refluxed for four hours, evaporated to dryness of methanol and water, through solid silica gel column chromatography, the column condition volume Petroleum ether: ethyl acetate = 4:1 was the eluent, and the eluted fraction was concentrated to obtain 5.9 g of the target (compound 3) as a yellow solid, with a yield of 65%.
[0031] 1 H NMR (500MHz, CDCl 3 )δ: 7.00 (dd, J = 7.5, 1Hz, 1H), 6.96 (t, J = 7.5Hz, 1H), 6.68 (t, J = 7.5Hz, 1H), 6.62 (d, J = 8Hz, 1H) ,4.71(d,J=4.5Hz,1H),4.26(d,J=4.5Hz,1H),3.76(s,3H),3.59(s,3H).; 13 C NMR (125MHz, CDCl 3 )δ: 170.70, 169.63, 139.55, 127.43, 126.51, 119.03, 115.93, 113.30, 55.63, 53.19, 53.07, 41.47; MS-ESI m / z: 268.06[M+H] + .
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