CN113105476B - 一种制备四环螺环吲哚啉类化合物的方法 - Google Patents
一种制备四环螺环吲哚啉类化合物的方法 Download PDFInfo
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D495/00—Heterocyclic compounds containing in the condensed system at least one hetero ring having sulfur atoms as the only ring hetero atoms
- C07D495/12—Heterocyclic compounds containing in the condensed system at least one hetero ring having sulfur atoms as the only ring hetero atoms in which the condensed system contains three hetero rings
- C07D495/20—Spiro-condensed systems
Abstract
本发明公开了一种制备四环螺环吲哚啉类化合物的方法,包括以下步骤:将[SO2]和吲哚炔酰胺、添加剂和光催化剂加入有机溶剂中,光照下反应得到四环螺环吲哚啉类化合物(结构式如下);其中,[SO2]和吲哚炔酰胺的摩尔比为10:1~1:10;[SO2]和添加剂的摩尔比为100:1~1:10;[SO2]和光催化剂的摩尔比为500:1~10:1;[SO2]为DABCO·SO2,焦亚硫酸钠,连二亚硫酸钠或亚硫酸氢钠。本发明的制备方法,使用廉价的无机盐作为磺酰基化试剂,不需要过渡金属催化,不需要严格的无水条件和低温高温操作,不需要使用危险的过氧化物,不需要昂贵的光催化剂,操作简单,成本低廉。
Description
技术领域
本发明属于吲哚啉类化合物合成领域,具体涉及一种制备四环螺环吲哚啉类化合物的方法。
背景技术
吲哚环作为氮杂环类的一个典型代表,广泛地存在于天然产物中,尤其是一些生物碱类化合物,因其固有的生物活性一直吸引着有机合成界的注意。其中,多环吲哚啉骨架,更是作为复杂天然产物的基本骨架结构而尤其引人注意,如(-)-perophoramidine,(-)-aspidospermidine,(-)-kopsinine和malagashanine,都具有多环吲哚啉部分。这类三维结构分子由于多个环的存在,具有很强的张力,其合成一直以来都存在着巨大的挑战。至今,许多化学家致力于通过去芳构化策略来合成这些优势分子。
一般而言,在去芳构化策略中,需要过渡金属的参与,反应条件相对较为苛刻,合成成本高;或者,涉及到氧化剂的使用,反应安全性降低。因而,使用廉价的催化剂,温和简单的反应条件,得到结构新颖的去芳构化产物,不失为一种好方法。
在已报道的文献中(Organic Letters 2019 21(8),2602-2605),作者提供了一种使用甲基保护的吲哚-炔底物合成了一系列四环螺环吲哚啉类化合物。然而,该反应必须对吲哚进行保护,同时需要过量的氧化剂参与反应,这对底物范围以及反应收率产生了较大的限制。
发明内容
为了克服现有技术的上述缺点与不足,本发明的目的在于提供一种制备四环螺环吲哚啉类化合物的方法,不需要昂贵的过渡金属催化剂,不需要使用过氧化物,且具有操作简便成本低廉等优势。
本发明的目的通过以下技术方案实现:
一种制备四环螺环吲哚啉类化合物的方法,包括以下步骤:
将[SO2]、吲哚炔酰胺、添加剂和光催化剂加入有机溶剂中,光照下反应得到四环螺环吲哚啉类化合物;
R1为氢、给电子基或吸电子基;
R3为给电子基、不饱和烃基;
[SO2]为DABCO·SO2,焦亚硫酸钠,连二亚硫酸钠或亚硫酸氢钠。
优选的,所述[SO2]和吲哚炔酰胺的摩尔比为10:1~1:10。
优选的,[SO2]和添加剂的摩尔比为100:1~1:10。
优选的,[SO2]和光催化剂的摩尔比为500:1~10:1。
优选的,反应体系还包含水,所述[SO2]和水的摩尔比为1:5000~100:1。
优选的,所述反应的温度为0~50℃,反应的时间为1~60小时。
优选的,所述有机溶剂为苯、甲苯、均三甲苯、氯苯、氟苯、二氯甲烷、二氯乙烷、乙腈、乙酸乙酯、乙酸叔丁酯、四氢呋喃、乙醚、1,4-二氧六环中的至少一种。
优选的,所述有机溶剂的体积与吲哚炔酰胺的摩尔量的比为1~10:1ml/mmol。
优选的,所述添加剂为氯化锂、氯化铵、氯化钠、氢氧化锂、溴化锂、高氯酸锂中的至少一种。
优选的,所述光催化剂为Eosin Y、Rosen Bengal、Ru(bpy)3·6H2O、Methyleneblue、Fluorescein、4CzIPN、9-Mesityl-10-methylacridinium perchlorate、RhodamineB、Rhodamine 6G中的至少一种。
优选的,所述四环螺环吲哚啉类化合物具有以下结构:
与现有技术相比,本发明具有以下优点和有益效果:
(1)本发明不需要过渡金属催化,使用廉价的无机盐作为磺酰基化试剂;
(2)本发明不需要严格的无水条件和低温高温操作,不需要使用危险的过氧化物,操作简单,成本低廉;
(3)本发明不需要昂贵的光催化剂。
具体实施方式
下面结合实施例,对本发明作进一步地详细说明,但本发明的实施方式和保护范围不限于此。
实施例1
一种四环螺环吲哚啉类化合物,制备方法如下:
向100mL单口烧瓶中加入20~40mL二氯乙烷,再加入10mmol的NaHSO3和10mmol的15mmol的氯化锂和0.2mmol的Rhodamine 6G,室温光照下反应24小时,减压脱除溶剂得粗产品,然后用快速柱层析分离得产物72.6mg(91%)。产物的结构表征物理常数:1H NMR(500MHz,Chloroform-d)δ8.05–7.99(m,2H),7.48–7.39(m,3H),7.15(m,1H),6.62(d,J=8.0Hz,1H),6.55(d,J=9.0Hz,1H),5.52(s,1H),5.02(s,1H),3.91(d,J=10.0Hz,1H),3.74(d,J=10.0Hz,1H),3.47(m,1H),3.37(m,1H),1.66–1.59(m,2H),0.96(t,J=7.5Hz,3H).13C NMR(126MHz,Chloroform-d)δ158.9(d,J=249.1Hz),157.9,149.7(d,J=7.9Hz),144.5,136.8,132.0(d,J=8.8Hz),131.2,129.9,128.5,125.2,115.4(d,J=20.4Hz),108.1(d,J=20.7Hz),106.5(d,J=3.1Hz),84.9,57.7,53.5(d,J=2.1Hz),45.5,20.5,11.4.19F NMR(471MHz,Chloroform-d)δ-115.70.
实施例2
一种四环螺环吲哚啉类化合物,制备方法如下:
向100mL单口烧瓶中加入20~40mL二氯乙烷,再加入10mmol的NaHSO3和10mmol的15mmol的氯化锂和0.2mmol的Rhodamine 6G,室温光照下反应24小时,减压脱除溶剂得粗产品,然后用快速柱层析分离得产物55.1mg(70%)。产物的结构表征物理常数:1H NMR(500MHz,Chloroform-d)δ8.00(m,2H),7.42(m,3H),7.02–6.92(m,2H),6.72(d,J=8.0Hz,1H),5.29(s,1H),5.00(s,1H),3.85(d,J=9.5Hz,1H),3.65(d,J=9.5Hz,1H),3.51(dt,J=14.5,7.5Hz,1H),3.41(dt,J=14.0,7.5Hz,1H),2.23(s,3H),1.64(m,2H),0.98(t,J=7.5Hz,3H).13C NMR(126MHz,Chloroform-d)δ162.7,144.6,143.5,137.5,131.0,130.8,129.8,129.7,128.5,125.3,122.1,110.6,84.1,58.2,54.4,45.6,20.9,20.7,11.5.
实施例3
一种四环螺环吲哚啉类化合物,制备方法如下:
向100mL单口烧瓶中加入20~40mL二氯乙烷,再加入10mmol的NaHSO3和10mmol的15mmol的氯化锂和0.2mmol的Rhodamine 6G,室温光照下反应24小时,减压脱除溶剂得粗产品,然后用快速柱层析分离得产物66.4mg(80%)。产物的结构表征物理常数:1H NMR(500MHz,Chloroform-d)δ8.03–7.97(m,2H),7.50–7.41(m,3H),7.16(m,1H),7.12(d,J=2.0Hz,1H),6.74(d,J=8.5Hz,1H),5.43(s,1H),5.02(s,1H),3.86(d,J=9.5Hz,1H),3.66(d,J=9.5Hz,1H),3.58–3.37(m,2H),1.64(m,3H),0.99(t,J=7.5Hz,3H).13C NMR(126MHz,Chloroform-d)δ162.3,145.4,144.2,136.7,131.2,131.1,130.3,129.7,128.6,125.9,125.1,122.0,111.6,83.9,58.0,54.2,45.6,20.7,11.4.
实施例4
一种四环螺环吲哚啉类化合物,制备方法如下:
向100mL单口烧瓶中加入20~40mL二氯乙烷,再加入10mmol的NaHSO3和10mmol的15mmol的氯化锂和0.2mmol的Rhodamine 6G,室温光照下反应24小时,减压脱除溶剂得粗产品,然后用快速柱层析分离得产物32.5mg(40%)。产物的结构表征物理常数:1H NMR(500MHz,DMSO-d6)δ8.78(s,1H),7.85(d,J=7.5Hz,2H),7.60(d,J=8.5Hz,1H),7.50(m,3H),7.40(s,1H),6.91(d,J=8.5Hz,1H),5.66(s,1H),4.10(d,J=9.5Hz,1H),3.60(d,J=10.0Hz,1H),3.40(m,2H),1.57(m,2H),0.89(t,J=7.5Hz,3H).13CNMR(126MHz,DMSO-d6)δ162.1,152.0,143.8,138.4,135.4,131.2,131.2,129.7,128.9,125.9,125.8,120.0,110.2,100.7,84.2,57.5,53.7,45.3,20.4,11.8.IR(KBr):3362,2924,2218,1689,1482,1303,1125,744.HRMS(ESI)m/z calculated for C22H19N3NaO3S[M+Na]+:428.1039;found:428.1045.
实施例5
一种四环螺环吲哚啉类化合物,制备方法如下:
向100mL单口烧瓶中加入20~40mL二氯乙烷,再加入10mmol的NaHSO3和10mmol的15mmol的氯化锂和0.2mmol的Rhodamine 6G,室温光照下反应24小时,减压脱除溶剂得粗产品,然后用快速柱层析分离得产物67.2mg(70%)。产物的结构表征物理常数:1H NMR(400MHz,CDCl3)δ7.27(t,J=8.0Hz,1H),6.84(d,J=8.4Hz,1H),6.79(d,J=8.0Hz,1H),6.73(s,1H),6.56(d,J=3.4Hz,1H),5.87(d,J=3.4Hz,1H),3.76(s,3H),3.40(s,3H),1.00(s,9H);13C NMR(100MHz,CDCl3)δ166.58,160.50,159.63,146.01,145.88,130.04,119.45,117.83,113.06,112.98,103.89,55.46,38.53,32.74,28.58.
实施例6
一种四环螺环吲哚啉类化合物,制备方法如下:
向100mL单口烧瓶中加入20~40mL二氯乙烷,再加入10mmol的NaHSO3和10mmol的15mmol的氯化锂和0.2mmol的Rhodamine 6G,室温光照下反应24小时,减压脱除溶剂得粗产品,然后用快速柱层析分离得产物72.2mg(71%)。产物的结构表征物理常数:1H NMR(500MHz,Chloroform-d)δ8.03–7.94(m,2H),7.49–7.39(m,3H),7.38–7.26(m,5H),6.85(d,J=1.5Hz,1H),6.82–6.74(m,2H),4.94(s,1H),4.74(d,J=14.5Hz,1H),4.43(d,J=14.5Hz,1H),3.67(d,J=9.5Hz,1H),3.46(d,J=9.5Hz,1H).13CNMR(126MHz,Chloroform-d)δ162.2,148.0,144.5,136.8,134.8,131.3,129.7,129.1,128.8,128.7,128.5,128.5,125.1,123.9,123.7,122.8,113.7,83.8,57.5,53.7,47.9.
实施例7
一种四环螺环吲哚啉类化合物,制备方法如下:
向100mL单口烧瓶中加入20~40mL二氯乙烷,再加入10mmol的NaHSO3和10mmol的15mmol的氯化锂和0.2mmol的Rhodamine 6G,室温光照下反应24小时,减压脱除溶剂得粗产品,然后用快速柱层析分离得产物75.8mg(96%)。产物的结构表征物理常数:1H NMR(500MHz,Chloroform-d)δ8.03–7.95(m,2H),7.48–7.36(m,3H),7.02(m,2H),6.78(t,J=7.5Hz,1H),5.02(s,1H),3.87(d,J=9.5Hz,1H),3.68(d,J=9.5Hz,1H),3.57–3.50(m,1H),3.38(m,1H),2.25(s,3H),1.65(m,2H),0.98(t,J=7.5Hz,3H).13CNMR(126MHz,Chloroform-d)δ162.6,145.6,143.6,137.5,131.1,131.0,129.7,129.1,128.5,125.3,121.5,120.5,119.0,83.5,58.3,54.9,45.6,20.7,16.6,11.5.
实施例8
一种四环螺环吲哚啉类化合物,制备方法如下:
向100mL单口烧瓶中加入20~40mL二氯乙烷,再加入10mmol的NaHSO3和10mmol的15mmol的氯化锂和0.2mmol的Rhodamine 6G,室温光照下反应24小时,减压脱除溶剂得粗产品,然后用快速柱层析分离得产物79.9mg(97%)。产物的结构表征物理常数:1H NMR(500MHz,Chloroform-d)δ7.79(m,1H),7.72(m,1H),7.25–7.12(m,3H),6.85–6.78(m,2H),5.51(s,1H),5.03(s,1H),3.84(d,J=9.5Hz,1H),3.64(d,J=9.5,1H),3.52(m,1H),3.36(m,1H),2.28(d,J=2.0Hz,3H),1.63(m,2H),0.97(t,J=7.5Hz,3H).13C NMR(126MHz,Chloroform-d)δ160.8(d,J=245.8Hz),159.9,146.8,142.7(d,J=2.6Hz),137.6,131.5(d,J=5.4Hz),130.3,129.5,128.5(d,J=17.1Hz),125.4(d,J=3.4Hz),124.4(d,J=8.8Hz),121.6,121.1,116.2(d,J=25.2Hz),110.7,83.8,58.3,54.4,45.6,20.7,14.7(d,J=3.5Hz),11.5.19F NMR(471MHz,Chloroform-d)δ-115.87.
实施例9
一种四环螺环吲哚啉类化合物,制备方法如下:
向100mL单口烧瓶中加入20~40mL二氯乙烷,再加入10mmol的NaHSO3和10mmol的15mmol的氯化锂和0.2mmol的Rhodamine 6G,室温光照下反应24小时,减压脱除溶剂得粗产品,然后用快速柱层析分离得产物70.0mg(78%)。产物的结构表征物理常数:1H NMR(500MHz,Chloroform-d)δ8.11(d,J=8.5Hz,2H),7.68(d,J=8.5Hz,2H),7.23(m,1H),7.19–7.13(m,1H),6.90–6.81(m,2H),5.40(s,1H),5.05(s,1H),3.89(d,J=9.5Hz,1H),3.71(d,J=9.5Hz,1H),3.54(m,1H),3.39(m,1H),1.69–1.62(m,2H),0.99(t,J=7.5Hz,3H).13C NMR(126MHz,Chloroform-d)δ162.2,146.7,142.4,139.5,132.7,132.4,130.5,130.1,129.2,128.8,125.4(q,J=3.8Hz),121.6,121.4,110.8,84.0,58.4,54.6,45.7,20.7,11.5.19F NMR(471MHz,Chloroform-d)δ-63.11.IR(KBr):2965,1692,1473,1318,1129,748.
实施例10
一种四环螺环吲哚啉类化合物,制备方法如下:
向100mL单口烧瓶中加入20~40mL二氯乙烷,再加入10mmol的NaHSO3和10mmol的15mmol的氯化锂和0.2mmol的Rhodamine 6G,室温光照下反应24小时,减压脱除溶剂得粗产品,然后用快速柱层析分离得产物67.1mg(78%)。产物的结构表征物理常数:1H NMR(500MHz,Chloroform-d)δ8.56(d,J=2.0Hz,1H),8.07(m,1H),7.86(m,2H),7.80(d,J=8.0Hz,1H),7.53–7.43(m,2H),7.18–7.12(m,2H),6.82(t,J=7.5Hz,1H),6.76(d,J=8.0Hz,1H),5.06(s,1H),3.74(dd,J=9.5,3.0Hz,1H),3.55–3.49(m,1H),3.49–3.43(m,1H),3.27(m,1H),1.61–1.50(m,2H),0.91(t,J=7.5Hz,3H).13C NMR(126MHz,Chloroform-d)δ162.7,146.9,143.8,137.7,134.3,132.8,130.2,130.0,129.7,129.1,128.2,127.7,127.7,126.5,126.5,122.9,121.6,121.0,110.7,84.0,58.2,54.5,45.5,20.7,11.5.
实施例11
一种四环螺环吲哚啉类化合物,制备方法如下:
向100mL单口烧瓶中加入20~40mL二氯乙烷,再加入10mmol的NaHSO3和10mmol的15mmol的氯化锂和0.2mmol的Rhodamine 6G,室温光照下反应24小时,减压脱除溶剂得粗产品,然后用快速柱层析分离得产物65.6mg(85%)。产物的结构表征物理常数1H NMR(400MHz,DMSO-d6)δ8.07–7.84(m,3H),7.25–6.98(m,3H),6.83–6.66(m,2H),5.51(s,1H),4.09(d,J=9.6Hz,1H),3.54(d,J=9.6Hz,1H),3.45(m,1H),3.32(m,1H),1.57(m,2H),0.89(t,J=7.2Hz,3H).13C NMR(101MHz,DMSO-d6)δ162.9,148.2,137.9,134.7,132.7,132.1,130.6,130.0,128.0,126.7,121.6,119.7,110.0,84.9,58.1,54.4,45.1,20.6,11.8.
实施例12
一种四环螺环吲哚啉类化合物,制备方法如下:
向100mL单口烧瓶中加入20~40mL二氯乙烷,再加入10mmol的NaHSO3和10mmol的15mmol的氯化锂和0.2mmol的Rhodamine 6G,室温光照下反应24小时,减压脱除溶剂得粗产品,然后用快速柱层析分离得产物67.1mg(87%)。产物的结构表征物理常数1H NMR(400MHz,Chloroform-d)δ8.62(m,1H),8.06(dd,J=5.2,1.2Hz,1H),7.37(m,1H),7.25–7.12(m,2H),6.84(m,2H),5.44(s,1H),5.02(s,1H),3.86(d,J=9.6Hz,1H),3.67(d,J=9.2Hz,1H),3.56(m,1H),3.41(m,1H),1.66(m,2H),1.01(t,J=7.2Hz,3H).13C NMR(101MHz,Chloroform-d)δ163.1,146.7,138.8,134.0,130.6,130.2,129.8,128.2,125.8,125.7,121.7,121.2,110.7,83.4,58.4,54.6,45.6,20.8,11.5.
实施例13
一种四环螺环吲哚啉类化合物,制备方法如下:
向100mL单口烧瓶中加入20~40mL二氯乙烷,再加入10mmol的NaHSO3和10mmol的15mmol的氯化锂和0.2mmol的Rhodamine 6G,室温光照下反应24小时,减压脱除溶剂得粗产品,然后用快速柱层析分离得产物65.4mg(75%)。产物的结构表征物理常数1H NMR(400MHz,DMSO-d6)δ8.33(s,1H),8.03(m,3H),7.44(m,2H),7.15(m,1H),7.05(d,J=7.6Hz,1H),6.85–6.68(m,2H),5.57(s,1H),4.14(d,J=9.6Hz,1H),3.58(d,J=9.6Hz,1H),3.47(m,1H),3.38(m,1H),1.59(m,2H),0.92(t,J=7.2Hz,3H).13C NMR(101MHz,DMSO-d6)δ162.7,148.2,141.5,138.6,138.2,137.6,130.4,130.1,128.8,127.1,127.0,125.5,125.4,122.8,121.6,119.8,110.0,85.1,58.1,54.7,45.2,20.6,11.8.
实施例14
一种四环螺环吲哚啉类化合物,制备方法如下:
向100mL单口烧瓶中加入20~40mL二氯乙烷,再加入10mmol的NaHSO3和10mmol的15mmol的氯化锂和0.2mmol的Rhodamine 6G,室温光照下反应24小时,减压脱除溶剂得粗产品,然后用快速柱层析分离得产物31.8mg(50%)。产物的结构表征物理常数1H NMR(500MHz,Chloroform-d)δ7.18(m,1H),7.11–7.07(m,1H),6.81(m,2H),5.47(s,1H),4.92(s,1H),3.76(d,J=9.5Hz,1H),3.63(d,J=9.5Hz,1H),3.54(m,1H),3.34(m,1H),2.37(s,3H),1.63(m,2H),0.99(t,J=7.5Hz,3H).13C NMR(126MHz,Chloroform-d)δ163.2,146.8,141.8,138.4,130.1,129.2,121.5,121.0,110.6,84.4,58.6,54.1,45.2,20.7,11.5,7.6.
实施例15
一种四环螺环吲哚啉类化合物,制备方法如下:
向100mL单口烧瓶中加入20~40mL二氯乙烷,再加入10mmol的NaHSO3和10mmol的15mmol的氯化锂和0.2mmol的Rhodamine 6G,室温光照下反应24小时,减压脱除溶剂得粗产品,然后用快速柱层析分离得产物45.3mg(63%)。产物的结构表征物理常数1H NMR(500MHz,Chloroform-d)δ7.18(m,1H),7.06(d,J=7.5Hz,1H),6.84–6.78(m,2H),5.32(s,1H),4.79(s,1H),3.78(d,J=9.5Hz,1H),3.59(d,J=9.5Hz,1H),3.51(m,6.4Hz,1H),3.46–3.37(m,1H),1.65(m,2H),1.52(s,9H),0.98(t,J=7.5Hz,3H).13C NMR(126MHz,Chloroform-d)δ162.8,154.3,146.7,138.3,130.4,130.1,121.4,121.1,110.6,83.3,57.8,54.1,45.5,35.1,29.4,20.7,11.4.
实施例16
一种四环螺环吲哚啉类化合物,制备方法如下:
向100mL单口烧瓶中加入20~40mL二氯乙烷,再加入10mmol的NaHSO3和10mmol的15mmol的氯化锂和0.2mmol的Rhodamine 6G,室温光照下反应24小时,减压脱除溶剂得粗产品,然后用快速柱层析分离得产物33.8mg(47%)。产物的结构表征物理常数:1H NMR(500MHz,Chloroform-d)δ7.17(m,1H),7.09(d,J=7.5Hz,1H),6.81(m,2H),5.61–5.50(m,1H),4.92(m,1H),3.74(dd,J=9.5,2.5Hz,1H),3.63–3.58(m,1H),3.53(m,1H),3.38–3.28(m,1H),3.04(m,1H),2.72(m,1H),1.65(m,4H),1.35(m,2H),0.98(t,J=7.5Hz,3H),0.88(t,J=7.5,3H).13C NMR(126MHz,Chloroform-d)δ163.3,146.9,146.8,146.0,138.6,130.1,129.4,121.4,121.0,120.9,110.5,110.5,84.7,84.7,58.6,53.9,45.2,30.3,23.1,22.4,20.7,13.6,11.4.
实施例17
一种四环螺环吲哚啉类化合物,制备方法如下:
向100mL单口烧瓶中加入20~40mL二氯乙烷,再加入10mmol的NaHSO3和10mmol的15mmol的氯化锂和0.2mmol的Rhodamine 6G,室温光照下反应24小时,减压脱除溶剂得粗产品,然后用快速柱层析分离得产物62.7mg(83%)。产物的结构表征物理常:1H NMR(500MHz,Chloroform-d)δ8.00(d,J=7.0Hz,2H),7.43(m,3H),7.22–7.10(m,2H),6.89–6.75(m,2H),5.77(m,1H),5.43(s,1H),5.34–5.23(m,2H),5.01(s,1H),4.20(dd,J=15.0,6.5Hz,1H),4.00(dd,J=15.0,6.5Hz,1H),3.80(d,J=9.5Hz,1H),3.64(d,J=9.5Hz,1H).13C NMR(126MHz,Chloroform-d)δ162.3,146.8,144.1,137.2,131.1,130.9,130.3,129.7,129.6,128.6,125.3,121.7,121.2,120.4,110.7,83.7,57.8,54.4,46.4.
实施例18
一种四环螺环吲哚啉类化合物,制备方法如下:
向100mL单口烧瓶中加入20~40mL二氯乙烷,再加入10mmol的NaHSO3和10mmol的15mmol的氯化锂和0.2mmol的Rhodamine 6G,室温光照下反应24小时,减压脱除溶剂得粗产品,然后用快速柱层析分离得产物60.9mg(81%)。产物的结构表征物理常数:1H NMR(500MHz,Chloroform-d)δ8.04–7.94(m,2H),7.49–7.40(m,3H),7.24–7.17(m,2H),6.85(t,J=8.0Hz,2H),5.39(s,1H),5.04(s,1H),4.44(dd,J=17.5,2.5Hz,1H),4.21(dd,J=17.5,2.5Hz,1H),3.94(d,J=9.5Hz,1H),3.85(d,J=9.5Hz,1H),2.31(t,J=2.5Hz,1H).13C NMR(126MHz,Chloroform-d)δ162.0,146.7,144.8,136.3,131.3,130.4,129.7,129.3,128.6,125.1,121.8,121.3,110.8,83.6,73.8,57.5,54.4,33.0.
实施例19
一种四环螺环吲哚啉类化合物,制备方法如下:
向100mL单口烧瓶中加入20~40mL二氯乙烷,再加入10mmol的NaHSO3和10mmol的15mmol的氯化锂和0.2mmol的Rhodamine 6G,室温光照下反应24小时,减压脱除溶剂得粗产品,然后用快速柱层析分离得产物79.8mg(83%)。产物的结构表征物理常数:1H NMR(400MHz,DMSO-d6)δ10.88(bs,1H),7.92(s,1H),7.80(m,2H),7.59(d,J=8.0Hz,1H),7.48(m,3H),7.37(d,J=8.0Hz,1H),7.22(d,J=2.4Hz,1H),7.14–7.05(m,2H),6.99(t,J=7.6Hz,1H),6.80(d,J=7.6Hz,1H),6.75(d,J=8.0Hz,1H),6.56(t,J=7.6Hz,1H),5.48(s,1H),4.11(d,J=9.6Hz,1H),3.90(m,1H),3.70–3.59(m,2H),3.04(m,2H).13C NMR(101MHz,DMSO-d6)δ162.5,148.2,143.1,139.4,136.8,131.0,130.2,129.9,129.5,128.9,127.6,126.2,123.4,121.8,121.5,119.6,118.8,118.8,111.9,111.2,109.8,84.9,57.9,54.4,43.8,23.3.
实施例20
一种四环螺环吲哚啉类化合物,制备方法如下:
向100mL单口烧瓶中加入20~40mL二氯乙烷,再加入10mmol的NaHSO3,10mmol的15mmol的氯化锂和0.2mmol的Rhodamine 6G,室温光照下反应24小时,减压脱除溶剂得粗产品,然后用快速柱层析分离得产物70.0mg(92%)。产物的结构表征物理常数:1H NMR(400MHz,Chloroform-d)δ8.06–7.99(m,2H),7.45(m,3H),7.26–7.15(m,2H),6.90–6.81(m,2H),5.50(s,1H),5.05(s,1H),3.87(dd,J=9.6,2.0Hz,1H),3.67(dd,J=9.6,2.0Hz,1H),3.55(m,1H),3.38(m,1H),1.64(m,2H),1.00(td,J=7.6,2.0Hz,3H).13C NMR(101MHz,Chloroform-d)δ162.6,146.8,143.7,137.4,131.0,130.3,129.7,129.6,128.5,125.3,121.6,121.2,110.7,83.8,58.3,54.4,45.6,20.7,11.5.
除上述实施例外,本发明的有机溶剂还可为苯、甲苯、均三甲苯、氯苯、氟苯、二氯甲烷、乙腈、乙酸乙酯、乙酸叔丁酯、四氢呋喃、乙醚、1,4-二氧六环中的至少一种。
所述添加剂还可为氯化锂、氯化铵、氯化钠、氢氧化锂、溴化锂、高氯酸锂中的至少一种。
所述光催化剂还可为Eosin Y、Rosen Bengal、Ru(bpy)3·6H2O、Methylene blue、Fluorescein、4CzIPN、9-Mesityl-10-methylacridinium perchlorate、Rhodamine B、Rhodamine 6G中的至少一种。
上述实施例为本发明较佳的实施方式,但本发明的实施方式并不受所述实施例的限制,其他的任何未背离本发明的精神实质与原理下所作的改变、修饰、替代、组合、简化,均应为等效的置换方式,都包含在本发明的保护范围之内。
Claims (5)
1.一种制备四环螺环吲哚啉类化合物的方法,其特征在于,包括以下步骤:
将[SO2]、吲哚炔酰胺、添加剂和光催化剂加入有机溶剂中,光照下反应得到四环螺环吲哚啉类化合物;
R1为氢、给电子基或吸电子基;
[SO2]为DABCO·SO2,焦亚硫酸钠,连二亚硫酸钠或亚硫酸氢钠;
所述[SO2]和吲哚炔酰胺的摩尔比为10:1~1:10;[SO2]和添加剂的摩尔比为100:1~1:10;[SO2]和光催化剂的摩尔比为500:1~10:1;
所述添加剂为氯化锂、氢氧化锂、溴化锂、高氯酸锂中的至少一种;
所述光催化剂为曙红Y、孟加拉红、三联吡啶氯化钌六水合物、亚甲基蓝、荧光素、2,4,5,6-四(9-咔唑基)-间苯二腈、9-均三甲苯基-10-甲基吖啶高氯酸盐、罗丹明B和罗丹明6G中的至少一种。
2.根据权利要求1所述的制备四环螺环吲哚啉类化合物的方法,其特征在于,反应体系还包含水,所述[SO2]和水的摩尔比为1:5000~100:1。
3.根据权利要求1所述的制备四环螺环吲哚啉类化合物的方法,其特征在于,所述反应的温度为0~50℃,反应的时间为1~60小时。
4.根据权利要求1所述的制备四环螺环吲哚啉类化合物的方法,其特征在于,所述有机溶剂为苯、甲苯、均三甲苯、氯苯、氟苯、二氯甲烷、二氯乙烷、乙腈、乙酸乙酯、乙酸叔丁酯、四氢呋喃、乙醚、1,4-二氧六环中的至少一种;所述有机溶剂的体积与吲哚炔酰胺的摩尔量的比为1~10:1ml/mmol。
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