一种off-on型检测tbt荧光探针及其制备方法与应用_2

文档序号:9822156阅读:来源:国知局
, TMS): δ (ppm) 8.00 - 7.89 (m, IH), 7.53-7.40 (m, 2H), 7.17 - 7.05 (m, IH), 6.55 - 6.37 (m, 4H), 6.29 (d, J=8.4 Hz, 2H), 3.61 (s, 2H), 3.34 (dd, J=13.8 Hz, 6.8, 8H), 1.37 - 1.01 (m, 12H). "C NMR (CDCI3, 100 MHz, TMS): δ (卵m) 166.1, 153.8, 151.5, 148.8, 132.5, 129.9, 128.1, 123.8, 122.9, 107.9, 104.4, 97.9, 65.9, 44.4, 12.6. MS(ESI) calcd. for C2祖32N4O2 [M + 扣+ : 457.2604,found: 457.2598. b、探针2a-2c的合成:在100 mL Ξ口瓶中加入罗丹明B酷阱(0.461 g,1 mmol)、胡椒 醒(O.lSOg,1.2 mmol)或胡椒醒衍生物及30 mL无水乙醇,加热回流24小时,反应液冷却 至室溫,有大量白色固体产生,抽滤,无水乙醇洗数次,干燥。粗产物柱层析分离,洗脱剂为 乙酸乙醋:石油酸=1:1。相关结构使用核磁共振与飞行质谱进行表征。
[0021 ]:白色固体0.46g,产率:78.P/0。
[002引 1h NMR (CDC13, 400 MHz, TMS): δ (ppm) 8.71 (s, IH), 7.97 (d, J=6.7 Hz, IH), 7.47 (t, J=5.6 Hz, 2H), 7.20 (s, IH), 7.12 (d, J=6.9 Hz, IH), 6.89 (d, J =8.0 Hz, IH), 6.69 (d, J=8.0 Hz, IH), 6.51 (d, J=8.8 Hz, 2H), 6.43 (d, J=1.8 Hz, 2H), 6.31-6.20 (m, 2H), 5.92 (s, 2H), 3.32 (q, J=6.9 Hz, 8H), 1.16 (t, J= 7.0 Hz, 12H). 1化 NMR (CDCI3, 100 MHz, TMS) δ (卵m) 164.6, 153.0, 151.4, 148.9, 148.7, 147.6, 147.3, 133.0, 129.7, 127.9, 123.6, 123.0, 107.6, 105.9, 105.7, 100.9, 97.6, 76.5, 65.8, 44.1, 12.4. MS(ESI) calcd. for C36H36N4O4 [M + 扣+: 589.2815, found: 589.2799. 2b:白色固体0.49g,产率:73.30/0. 1h 醒R (CDCI3, 400 MHz, TMS): δ (卵m) 8.67 (s, IH), 8.00 (d, J=6.9 Hz, IH), 7.58 - 7.38 (m, 3H), 7.10 (d, J=7.1 Hz, IH), 6.83 (s, IH), 6.52 (d, J= 8.8 Hz, 2H), 6.42 (s, 2H), 6.25 (d, J=8.6 Hz, 2H), 5.92 (s, 2H), 3.42 - 3.19 (m, 8H), 1.15 (t, J=6.9 Hz, 12H). 13c NMR (CDCI3,100 MHz, TMS): δ (卵m) 165.1,152.9,152.2,149.5,148.8, 147.4, 144.8, 133.5, 128.2, 127.9, 123.7, 123.4, 116.8, 112.2, 108.1, 106.6, 105.2, 101.8, 98.0, 65.7, 44.3, 12.6. MS(ESI) calcd. for C36出巧rN404 [M + Na] + : 691.1719,found: 668.1703. 2c:黄色固体0.45g,产率:71.0〇/〇. 1h 醒R (CDCI3, 400 MHz, TMS): δ (卵m) 8.87 (s, IH), 8.01 (d, J=7.2 Hz, IH), 7.61 - 7.42 (m, 3H), 7.35 (s, IH), 7.11 (d, J=7.3 Hz, IH), 6.58 - 6.37 (m, 4H), 6.25 (d, J=7.7 Hz, 2H), 6.06 (s, 2H), 3.32 (d, J=6.8 Hz, 8H), 1.15 (t, J=6.8 Hz, 12H). 1化 NMR (CDCI3, 100 MHz, TMS): δ (卵m) 165.4, 152.9, 152.3, 151.5, 148.9, 148.5, 143.1, 140.6, 133.8, 128.2, 127.7, 127.4, 123.9, 123.7, 108.0, 106.4, 104.9, 102.9, 98.2, 65.8, 44.3, 12.5. MS(ESI) calcd. for C36H36化〇6 [M + 扣+ : 6:34.2666,found: 6:34.2658. 实施例2:探针3a-3c的合成:
a、罗丹明6G酷阱的合成:在500血Ξ口瓶中加入罗丹明6G (25 g,60.2 mmol)与200 mL无水乙醇,滴加过量的50 mL水合阱。反应液剧烈揽拌回流24小时,深澄黄色悬浊液逐渐 变得澄清。反应完毕后,降溫,倒入500 mL水中,立刻产生大量淡黄色的沉淀。静置抽滤,固 体用少量水洗、无水乙醇洗至无色。粗产物用乙醇重结晶,干燥。
[0023] 罗丹明6G酷阱:色固体19.46 g。产率:76.4〇/〇。
[0024] 1h 匪R (CDCl3,400 MHz, TMS): δ (邮m) 7.96 (dd, J=5.9 Hz, 2.7,IH), 7.52 - 7.41 (m, 2H), 7.15 - 7.02 (m, IH), 6.40 (s, 2H), 6.26 (s, 2H), 3.58 (s, 2H), 3.22 (q, J=7.1 Hz, 4H), 1.92 (s, 6H), 1.33 (t, J=7.1 Hz, 6H). "C NMR (CDCI3, 100 MHz, TMS): δ (卵m) 166.2, 152.2, 151.7, 147.5, 132.6, 129.8, 128.1, 127.7, 123.8, 123.0, 117.9, 104.8, 96.8, 66.0, 38.3, 16.7, 14.7. MS(ESI) calcd. for C2曲?8Ν4Ο2 [M + 扣+ : 429.2291,found: 429.2294. b、探针3a-3c的合成:在100血Ξ口瓶中加入罗丹明6G酷阱(0.428 g,1 mmol)、胡 椒醒(O.lSOg,1.2 mmol)或胡椒醒衍生物及30 mL无水乙醇,加热回流24小时,反应液冷 却至室溫,有大量白色固体产生,抽滤,无水乙醇洗数次,干燥。粗产物柱层析分离,洗脱剂 为乙酸乙醋:石油酸=1:1。相关结构使用核磁共振与飞行质谱进行表征。
[002引:白色固体0.39g,产率:69.60/0. 1h NMR (CDC13, 400 MHz, TMS): δ (卵m) 8.47 (S, 1H), 8.00 (dd, J=6.0 Hz, 2.6, IH), 7.51 - 7.43 (m, 2H), 7.18 (s, IH), 7.05 (dd, J=5.8 Hz, 2.7, IH), 6.87- 6.79 (m, IH), 6.66 (d, J=8.0 Hz, IH), 6.39 (s, 2H), 6.32 (s, 2H), 5.90 (s, 2H), 3.20 (q, J=7.1 Hz, 4H), 1.87 (s, 6H), 1.31 (t, J=7.1 Hz, 6H). "C NMR (CDCI3, 100 MHz, TMS): δ (卵m) 164.9, 152.1, 151.3, 149.0, 147.9, 147.4, 146.6, 133.3, 129.9, 129.0, 128.2, 127.7, 123.7, 123.3, 117.9, 107.7, 106.3, 105.9, 101.2, 96.7, 38.4, 16.7, 14.7. MS(ESI) calcd. for C3祖33N4O4 [M + 扣+ : 561.2502,found: 561.2482. 3b:白色固体0.31g,产率:48.30/0. 1h NMR (CDCI3, 400 MHz, TMS): δ (ppm) 8.59 (s, IH), 8.13 - 7.95 (m, IH), 7.47 (dd, J=7.5 Hz, 3.8, 3H), 7.11 - 6.98 (m, IH), 6.82 (s, IH), 6.40 (s, 2H), 6.33 (s, 2H), 5.92 (s, 2H), 3.49 (s, 2H), 3.21 (dd, J=14.0 Hz, 6.9 Hz, 4H), 1.88 (s, 6H), 1.31 (t, J=7.1 Hz, 6H). "C NMR (CDCI3, 100 MHz, TMS): δ (卵m) 165.2, 152.5, 151.2, 149.5, 147.4, 144.5, 133.6, 128.1, 127.6, 123.5, 118.0, 116.9, 112.2, 106.4, 105.6, 101.9, 96.9, 65.7, 38.4, 16.7, 14.7 ppm. MS化SI) calcd. for C34H32BrN404 [M + H] + : 641.1586,found: 641.1586. 3c:黄色固体
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