CN110041340B - 6-芳基-苯并呋喃并咔唑类化合物及制备和应用 - Google Patents

6-芳基-苯并呋喃并咔唑类化合物及制备和应用 Download PDF

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CN110041340B
CN110041340B CN201910451860.XA CN201910451860A CN110041340B CN 110041340 B CN110041340 B CN 110041340B CN 201910451860 A CN201910451860 A CN 201910451860A CN 110041340 B CN110041340 B CN 110041340B
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陈文腾
罗峰
应智敏
刘双容
柯迪
邵加安
俞永平
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Zhejiang University ZJU
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Abstract

本发明公开了一种6‑芳基‑苯并呋喃并咔唑类化合物，以2‑羟基苯基硝基烯烃为起始原料，利用邻位羟基的诱导作用，主要在室温、酸性条件下，取代的(E)‑2‑(2‑硝基乙烯基)苯酚与芳基乙酰基硫叶立德、取代吲哚一锅法反应合成。本发明提供的制备方法具有反应条件温和，操作简单，无需金属催化剂，原料易得，底物适用范围广，能同时引入多个取代基等优点。为高效合成6‑芳基‑苯并呋喃并咔唑类化合物提供了一种简单易行的方法。本发明制备的6‑芳基‑苯并呋喃并咔唑类化合物具有一定的光学特性，可作为潜在的荧光分子。其结构式为：

Description

6-芳基-苯并呋喃并咔唑类化合物及制备和应用
技术领域
本发明属化合物的合成方法，主要涉及6-芳基-苯并呋喃并咔唑类化合物及其制备和应用。
背景技术
多组分反应是近年来化学及相关领域研究中应用广泛的合成技术，也是实现多样导向性合成的主要途径之一。硫叶立德因其易于制备、反应可控等优点，已经成为多种碳/杂环化合物合成的重要试剂。硫叶立德作为一种常见带有离去基团的特殊亲核试剂，为串联反应的设计提供了很好的方向。硝基烯烃式杂环合成中重要的合成中间体，其结构上的硝基具有强吸电子效应，使得与硝基共轭的双键电子云发生极化，易于受到亲核或亲电试剂的进攻，而用于构建含C-O、C-N键的杂环类化合物。
如式II,W.-J.Xiao报道了一种以硫叶立德和硝基烯烃为原料，以硫脲和N,N-二甲基吡啶为催化剂的串联环化反应，合成了噁唑啉-2-酮类衍生物。(Journal of AmericanChemistry Society,2008,130,6946-6948)
Figure GDA0002489311020000011
如式III,W.-J.Xiao报道了一种以硫叶立德和硝基烯烃为原料,[4+1]/[3+2]串联环化反应，合成了多元杂环衍生物。(Angew.Chem.Int.Ed.2009,48,9542-9545)
Figure GDA0002489311020000012
已报道的硫叶立德和硝基烯烃的环化反应都是硝基基团参与环的构建，且通过构建复杂的反应底物来实现多官能团反应。
发明内容
本发明的目的是提供一种6-芳基-苯并呋喃并咔唑类化合物，结构式I为：
Figure GDA0002489311020000021
其中：
R1为氢、甲氧基、萘基、甲氧碳基、卤素，所述卤素选用氟、氯、溴；
R2为氢、甲基、苄基；
R3为氢、甲氧基、苄氧基、甲基、溴；
R4为氢、萘基、甲基、硝基、甲氧基、氰基、羟基、三氟甲基、苯基、卤素，所述卤素选用氯、溴。
本发明作为一种新的6-芳基-苯并呋喃并咔唑类化合物，其结构选自如下任意一种：
7-甲基-6-苯基-7H-苯并呋喃并[2,3-b]咔唑(实施例1)
7-甲基-6-(对甲苯基)-7H-苯并呋喃并[2,3-b]咔唑(实施例2)
6-(3-溴苯基)-7-甲基-7H-苯并呋喃并[2,3-b]咔唑(实施例3)
6-(4-溴苯基)-7-甲基-7H-苯并呋喃并[2,3-b]咔唑(实施例4)
6-(2-溴苯基)-7-甲基-7H-苯并呋喃并[2,3-b]咔唑(实施例5)
6-(4-氯苯基)-7-甲基-7H-苯并呋喃并[2,3-b]咔唑(实施例6)
7-甲基-6-(4-硝基苯基)-7H-苯并呋喃并[2,3-b]咔唑(实施例7)
7-甲基-6-(萘-2-基)-7H-苯并呋喃并[2,3-b]咔唑(实施例8)
6-(3-甲氧基苯基)-7-甲基-7H-苯并呋喃并[2,3-b]咔唑(实施例9)
4-(7-甲基-7H-苯并呋喃并[2,3-b]咔唑-6-基)苄腈(实施例10)
4-(7-甲基-7H-苯并呋喃并[2,3-b]咔唑-6-基)苯酚(实施例11)
7-苄基-6-苯基-7H-苯并呋喃并[2,3-b]咔唑(实施例12)
2-氯-6-苯基-7H-苯并呋喃并[2,3-b]咔唑(实施例13)
2-氯-7-甲基-6-苯基-7H-苯并呋喃并[2,3-b]咔唑(实施例14)
2-甲氧基-7-甲基-6-苯基-7H-苯并呋喃并[2,3-b]咔唑(实施例15)
10-甲氧基-7-甲基-6-苯基-7H-苯并呋喃并[2,3-b]咔唑(实施例16)
9,12-二甲基-8-苯基-9H-萘并[1',2':4,5]呋喃并[2,3-b]咔唑(实施例17)
7-甲基-6-(4-(三氟甲基)苯基)-7H-苯并呋喃并[2,3-b]咔唑(实施例18)
10-溴-7-甲基-6-苯基-7H-苯并呋喃并[2,3-b]咔唑(实施例19)
10-溴-2-氯-7-甲基-6-苯基-7H-苯并呋喃并[2,3-b]咔唑(实施例20)
3-甲氧基-7-甲基-6-苯基-7H-苯并呋喃并[2,3-b]咔唑(实施例21)。
本发明还同时提供了上述6-芳基-苯并呋喃并咔唑类化合物的制备方法，通过以下步骤实现：
将(E)-2-(2-硝基乙烯基)苯酚类化合物、芳乙酰基硫叶立德类化合物溶解在1，2-二氯乙烷中，于25℃反应，反应时间为0.5至2个小时后加入吲哚类化合物和三氟醋酸，反应时间为24小时，其中(E)-2-(2-硝基乙烯基)苯酚类化合物、芳乙酰基硫叶立德类化合物和吲哚类化合物的摩尔比为1:1:1；
所述的(E)-2-(2-硝基乙烯基)苯酚类化合物的结构式为：
Figure GDA0002489311020000031
其中R1为氢、甲氧基、萘基、甲氧碳基、卤素，所述卤素选用氟、氯、溴；
所述的吲哚类化合物的结构式为：
Figure GDA0002489311020000032
其中R2为氢、甲基、苄基；
R3为氢、甲氧基、苄氧基、甲基、溴。
所述的芳乙酰基硫叶立德类化合物的结构式为：
Figure GDA0002489311020000033
其中R4为氢、萘基、甲基、硝基、甲氧基、氰基、羟基、三氟甲基、苯基、卤素，所述卤素选用氯、溴。
本发明的再一个目的是提供所述的式I化合物在制备有荧光性质的荧光团中的应用。
本发明提供的合成方法，是以硝基烯烃、芳基乙酰基硫叶立德和吲哚为起始原料，通过多组分反应提供一种6-芳基-苯并呋喃并咔唑类化合物及其制备方法，反应条件温和，反应收率高，无需金属催化剂，所用的反应原料易得，为高效合成6-芳基-苯并呋喃并咔唑类化合物提供了一种简单易行的方法。本发明提出用2-羟基苯基硝基烯烃为起始原料，利用邻位羟基的诱导作用，与硝基烯烃和吲哚多组分一锅法反应，通过Michael加成/环内亲核进攻/[4+2]环合形成6-芳基-苯并呋喃并咔唑类化合物，反应条件温和，原子经济性高，可以多组分一锅法形成多元杂环化合物。此外，本发明的所述的6-芳基-苯并呋喃并咔唑类化合物未见文献报道，其所述的合成方法也未见文献报道。本发明制备的6-芳基-苯并呋喃并咔唑类化合物具有一定的光学特性，可作为潜在的荧光分子。
本发明所提供的6-芳基-苯并呋喃并咔唑类化合物合成方法具有以下特点：(1)本发明无需借助金属催化剂；(2)反应原料简便易得，多种底物结构均可耐受该反应条件，适用范围广。
附图说明
图1是实施例8的吸收和发射光谱。
图2是实施例11的吸收和发射光谱。
图3是实施例18的吸收和发射光谱。
具体实施方式
本发明将通过实施例作进一步的说明。
实施例1 7-甲基-6-苯基-7H-苯并呋喃并[2,3-b]咔唑
Figure GDA0002489311020000041
将(E)-2-(2-硝基乙烯基)苯酚(0.45mmol,75mg),苯乙酰基硫叶立德(0.45mmol,82mg),加入1mL的1,2-二氯乙烷中，加料完毕后，室温反应0.5h，点板观察，反应形成中间体时加入N-甲基吲哚(0.45mmol，56μL),三氟醋酸(0.45mmol，33μL)反应24h，反应结束，旋干体系过层析柱得到产物，黄色固体。
Yellow solid,m.p.184.2-185.0℃,1H NMR(500MHz,CDCl3)δ8.06(d,J＝7.4Hz,1H),7.86(s,1H),7.78-7.73(m,2H),7.64(t,J＝7.4Hz,2H),7.60-7.57(m,1H),7.52(d,J＝8.2Hz,1H),7.45-7.38(m,4H),7.34(t,J＝7.1Hz,1H),6.96(dd,J＝11.2,4.6Hz,1H),3.96(s,3H).13C NMR(125MHz,CDCl3)δ157.2,148.9,142.4,138.6,135.1,130.3,128.8,128.3,127.0,125.9,125.0,123.0,122.6,122.4,122.3,120.9,120.5,120.0,118.3,111.9,108.2,97.9,77.3,77.1,76.8,29.4.HRMS(ESI):m/z calcd for(C25H17NO+K)+:386.0942；found:386.0943。
实施例2 7-甲基-6-(对甲苯基)-7H-苯并呋喃并[2,3-b]咔唑
Figure GDA0002489311020000051
合成步骤同实施例1，只是将苯乙酰硫叶立德换成对甲基苯乙酰硫叶立德，得到黄色固体。
Yellow solid,m.p.195.2-196.0℃,1H NMR(500MHz,CDCl3)δ8.08(d,J＝7.6Hz,1H),7.85(s,1H),7.68(d,J＝7.8Hz,2H),7.55(d,J＝8.2Hz,1H),7.51-7.40(m,6H),7.36(t,J＝7.4Hz,1H),7.01(t,J＝7.4Hz,1H),3.96(s,3H),2.58(s,3H).13C NMR(125MHz,CDCl3)δ157.3,149.1,142.4,138.7,138.1,132.1,130.2,129.7,127.1,125.9,125.1,123.1,122.7,122.5,122.3,121.0,120.6,120.2,118.4,112.0,108.3,97.8,77.4,77.5,76.9,29.6,21.7.HRMS(ESI):m/z calcd for(C26H19NO+K)+:400.1098；found:400.1096。
实施例3 6-(3-溴苯基)-7-甲基-7H-苯并呋喃并[2,3-b]咔唑
Figure GDA0002489311020000052
合成步骤同实施例1，只是将苯乙酰硫叶立德换成间溴苯乙酰硫叶立德，得到黄色固体。
Yellow solid，m.p.189.2-190.1℃,1H NMR(500MHz,CDCl3)δ8.05(dd,J＝7.6,0.6Hz,1H),7.92(t,J＝1.7Hz,1H),7.86(s,1H),7.73-7.67(m,2H),7.54-7.47(m,2H),7.45-7.38(m,4H),7.37-7.32(m,1H),7.03-6.98(m,1H),3.95(s,3H).13C NMR(125MHz,CDCl3)δ157.3,148.8,142.5,138.7,137.4,133.4,131.4,130.4,129.2,127.3,126.2,125.0,123.3,122.9,122.5,122.4,122.4,120.8,120.7,118.7,118.4,112.0,108.5,98.5,77.4,77.2,76.9,29.6.HRMS(ESI):m/z calcd for(C25H16BrNO+K)+:464.0047；found:464.0046。
实施例4 6-(4-溴苯基)-7-甲基-7H-苯并呋喃并[2,3-b]咔唑
Figure GDA0002489311020000053
合成步骤同实施例1，只是将苯乙酰硫叶立德换成对溴苯乙酰硫叶立德，得到红色固体。
Red solid，m.p.234.8-235.6℃，1H NMR(500MHz,CDCl3)δ8.04(d,J＝7.6Hz,1H),7.82(s,1H),7.74(dd,J＝8.5,1.9Hz,2H),7.66-7.58(m,2H),7.50(d,J＝8.1Hz,1H),7.43(dd,J＝14.6,7.2Hz,3H),7.38(d,J＝7.9Hz,1H),7.34(t,J＝7.1Hz,1H),7.03-6.96(m,1H),3.92(s,3H).13C NMR(125MHz,CDCl3)δ157.2,148.7,142.4,138.7,134.1,132.2,132.1,132.1,127.3,126.2,124.9,123.2,122.5,122.3,120.7,120.6,118.7,118.5,111.9,108.5,98.3,77.4,77.2,76.9,29.5.HRMS(ESI):m/z calcd for(C25H16BrNO+Na)+:448.0307；found:448.0309。
实施例5 6-(2-溴苯基)-7-甲基-7H-苯并呋喃并[2,3-b]咔唑
Figure GDA0002489311020000061
合成步骤同实施例1，只是将苯乙酰硫叶立德换成邻溴苯乙酰硫叶立德，得到白色固体。
White solid，m.p.224.5-225.8℃，1H NMR(500MHz,CDCl3)δ8.06(d,J＝7.5Hz,1H),7.92(d,J＝1.6Hz,1H),7.87(s,1H),7.74-7.67(m,2H),7.55-7.48(m,2H),7.48-7.39(m,4H),7.35(t,J＝7.4Hz,1H),7.01(dd,J＝10.8,4.0Hz,1H),3.96(s,3H).13C NMR(125MHz,CDCl3)δ157.2,148.7,142.4,138.5,137.2,133.3,131.3,130.3,129.1,127.2,126.1,124.8,123.1,122.8,122.4,122.2,120.6,120.6,118.5,118.3,111.9,108.4,98.4,29.4.HRMS(ESI):m/z calcd for(C25H16BrNO+K)+:464.0047；found:464.0039。
实施例6 6-(4-氯苯基)-7-甲基-7H-苯并呋喃并[2,3-b]咔唑
Figure GDA0002489311020000062
合成步骤同实施例1，只是将苯乙酰硫叶立德换成对氯苯乙酰硫叶立德，得到红色固体。
Red solid，m.p.216.3-216.9℃，1H NMR(500MHz,CDCl3)δ8.04(dd,J＝7.6,0.7Hz,1H),7.83(s,1H),7.72-7.64(m,2H),7.62-7.57(m,2H),7.51(d,J＝8.1Hz,1H),7.46-7.37(m,4H),7.34(td,J＝7.5,0.9Hz,1H),7.03-6.97(m,1H),3.93(s,3H).13C NMR(125MHz,CDCl3)δ157.2,148.8,142.4,138.6,134.3,133.6,131.9,129.2,127.2,126.2,125.0,123.1,122.5,122.4,122.3,120.7,118.7,118.5,111.9,108.5,98.3,77.4,77.2,76.9,29.5.HRMS(ESI):m/z calcd for(C25H16ClNO+K)+:420.0552；found:420.0559。
实施例7 7-甲基-6-(4-硝基苯基)-7H-苯并呋喃并[2,3-b]咔唑
Figure GDA0002489311020000071
合成步骤同实施例1，只是将苯乙酰硫叶立德换成对硝基苯乙酰硫叶立德，得到浅黄色固体。
Yellow solid，m.p.>250℃，1H NMR(500MHz,CDCl3)δ8.47(d,J＝8.8Hz,2H),8.07(d,J＝7.6Hz,1H),7.94(d,J＝8.7Hz,2H),7.91(s,1H),7.53-7.42(m,4H),7.41-7.32(m,2H),7.01(s,1H),3.97(s,3H).13C NMR(125MHz,CDCl3)δ157.2,148.5,147.8,142.5,142.3,138.7,131.6,127.5,126.5,124.7,124.1,123.3,122.7,122.0,121.9,120.8,120.1,118.7,117.4,111.9,108.8,99.3,77.4,77.2,76.9,29.6.HRMS(ESI):m/z calcd for(C25H16N2O3+K)+:431.0793；found:431.0798。
实施例8 7-甲基-6-(萘-2-基)-7H-苯并呋喃并[2,3-b]咔唑
Figure GDA0002489311020000072
合成步骤同实施例1，只是将苯乙酰硫叶立德换成2-萘乙酰硫叶立德，得到黄色固体。
Yellow solid，m.p.130.6-131.2℃，1H NMR(500MHz,CDCl3)δ8.27(s,1H),8.08(dd,J＝17.0,8.0Hz,2H),8.01(d,J＝7.8Hz,1H),7.94(d,J＝7.9Hz,1H),7.86(d,J＝9.9Hz,2H),7.58(dd,J＝8.3,6.7Hz,2H),7.49(d,J＝8.1Hz,1H),7.41(dd,J＝13.0,5.4Hz,4H),7.35(d,J＝7.5Hz,1H),6.89(s,1H),3.95(s,3H).13C NMR(125MHz,CDCl3)δ157.3,149.1,142.5,138.8,133.8,133.3,132.7,129.5,128.6,128.5,128.1,127.1,126.5,126.4,126.0,125.1,123.2,122.6,122.5,122.4,121.6,121.0,120.6,120.2,120.0,118.8,118.5,112.0,108.3,98.1,77.4,77.2,76.9,29.5.HRMS(ESI):m/z calcd for(C29H19NO+K)+:436.1098；found:436.1093。吸收和发射光谱见图1。
实施例9 6-(3-甲氧基苯基)-7-甲基-7H-苯并呋喃并[2,3-b]咔唑
Figure GDA0002489311020000081
合成步骤同实施例1，只是将苯乙酰硫叶立德换成间甲氧基苯乙酰硫叶立德，得到红色固体。
Red solid，m.p.170.4-171.5℃，1H NMR(500MHz,CDCl3)δ8.06-8.02(m,1H),7.83(s,1H),7.57-7.50(m,2H),7.46(d,J＝7.9Hz,1H),7.44-7.39(m,2H),7.39-7.28(m,4H),7.13(dd,J＝8.3,2.6Hz,1H),6.98(t,J＝7.4Hz,1H),3.92(s,3H),3.86(s,3H).13C NMR(125MHz,CDCl3)δ160.0,157.3,148.8,142.4,138.6,136.5,130.0,127.1,126.0,125.0,123.1,122.7,122.6,122.6,122.4,120.9,120.6,119.9,118.5,115.5,114.4,112.0,108.3,98.0,77.4,77.2,76.9,55.5,29.5.HRMS(ESI):m/z calcd for(C26H19NO2+K)+:416.1047；found:416.1042。
实施例10 4-(7-甲基-7H-苯并呋喃并[2,3-b]咔唑-6-基)苄腈
Figure GDA0002489311020000082
合成步骤同实施例1，只是将苯乙酰硫叶立德换成对氰基苯乙酰硫叶立德，得到黄色固体。
Yellow solid，m.p.192.3-193.0℃，1H NMR(500MHz,CDCl3)δ8.08-8.04(m,1H),7.92-7.85(m,5H),7.53-7.41(m,4H),7.37(ddd,J＝8.0,3.8,2.8Hz,2H),7.01(s,1H),3.96(s,3H).13C NMR(125MHz,CDCl3)δ157.2,148.5,142.5,140.3,138.6,132.6,131.4,127.5,126.4,124.8,123.3,122.7,122.0,122.0,120.8,120.2,119.2,118.7,117.8,112.1,111.9,108.7,99.1,77.4,77.2,76.9,29.6.HRMS(ESI):m/z calcd for(C26H16N2O+Na)+:395.1155；found:395.1153。
实施例11 4-(7-甲基-7H-苯并呋喃并[2,3-b]咔唑-6-基)苯酚
Figure GDA0002489311020000083
合成步骤同实施例1，只是将苯乙酰硫叶立德换成对羟基苯乙酰硫叶立德，得到黄色固体。
Yellow solid，m.p.201.6-202.8℃，1H NMR(500MHz,CDCl3)δ8.05(d,J＝7.5Hz,1H),7.83(s,1H),7.63(d,J＝8.5Hz,2H),7.51(dd,J＝14.1,8.0Hz,2H),7.45–7.37(m,3H),7.34(t,J＝7.4Hz,1H),7.09(d,J＝8.5Hz,2H),6.99(t,J＝7.4Hz,1H),3.95(s,3H).13C NMR(125MHz,CDCl3)δ157.3,155.7,149.1,142.4,138.7,131.8,127.5,127.1,125.9,125.1,123.1,122.7,122.5,122.4,121.1,120.6,119.8,118.4,115.9,112.0,108.3,97.7,77.4,77.2,76.9,29.5.HRMS(ESI):m/z calcd for(C25H17NO2+H)+:364.1332；found:364.1335。吸收和发射光谱见图2。
实施例12 7-苄基-6-苯基-7H-苯并呋喃并[2,3-b]咔唑
Figure GDA0002489311020000091
合成步骤同实施例1，只是将N-甲基吲哚换成N-苄基吲哚，得到黄色固体。
Yellow solid，m.p.200.4-201.2℃，1H NMR(500MHz,CDCl3)δ7.99(d,J＝7.5Hz,1H),7.83(s,1H),7.79(d,J＝7.2Hz,2H),7.66(t,J＝7.3Hz,2H),7.62-7.57(m,1H),7.50(d,J＝8.1Hz,1H),7.45-7.36(m,4H),7.30(dd,J＝16.3,8.6Hz,4H),7.23(d,J＝7.4Hz,2H),6.98(t,J＝6.0Hz,1H),5.66(s,2H).13C NMR(125MHz,CDCl3)δ157.3,149.1,142.1,138.3,137.2,135.2,130.4,129.0,128.9,128.4,127.7,127.2,126.5,126.2,124.9,123.3,122.9,122.6,122.3,121.2,120.7,120.3,118.8,112.0,108.7,98.4,77.4,77.2,76.9,46.9.HRMS(ESI):m/z calcd for(C31H21NO+K)+:462.1255；found:462.1253。
实施例13 2-氯-6-苯基-7H-苯并呋喃并[2,3-b]咔唑
Figure GDA0002489311020000092
合成步骤同实施例1，只是将(E)-2-(2-硝基乙烯基)苯酚换成(E)-4-氯-2-(2-硝基乙烯基)苯酚，将N-甲基吲哚换成吲哚，得到黄色固体。
Yellow solid，m.p.219.6-220.4℃，1H NMR(500MHz,CDCl3)δ8.25(s,1H),7.99(d,J＝2.0Hz,1H),7.88(s,1H),7.75(d,J＝6.9Hz,2H),7.65(t,J＝7.3Hz,2H),7.60(d,J＝7.3Hz,1H),7.47-7.42(m,2H),7.41-7.36(m,3H),6.98(t,J＝7.2Hz,1H).13C NMR(126MHz,CDCl3)δ155.7,149.8,141.4,137.1,134.9,130.4,128.9,128.5,128.5,128.3,127.9,127.1,126.5,123.3,122.7,122.4,120.5,120.4,119.2,113.0,110.6,100.2,77.4,77.2,76.9.HRMS(ESI):m/z calcd for(C24H14ClNO+H)+:368.0837；found:368.0838。
实施例14 2-氯-7-甲基-6-苯基-7H-苯并呋喃并[2,3-b]咔唑
Figure GDA0002489311020000101
合成步骤同实施例1，只是将(E)-2-(2-硝基乙烯基)苯酚换成(E)-4-氯-2-(2-硝基乙烯基)苯酚，得到棕色固体。
Brown solid，m.p.220.8-222.5℃，1H NMR(500MHz,CDCl3)δ8.03(d,J＝2.0Hz,1H),7.82(s,1H),7.76-7.71(m,2H),7.65(dd,J＝11.4,4.3Hz,2H),7.61-7.57(m,1H),7.47-7.34(m,5H),7.00-6.94(m,1H),3.97(s,3H).13C NMR(125MHz,CDCl3)δ155.6,155.4,149.5,142.6,138.6,134.9,130.3,128.9,128.5,127.8,127.0,126.6,126.3,122.6,122.1,121.6,120.4,120.4,118.6,113.0,108.4,98.1,77.4,77.2,76.9,29.6.HRMS(ESI):m/z calcd for(C25H16ClNO+K)+:420.0552；found:420.0558。
实施例15 2-甲氧基-7-甲基-6-苯基-7H-苯并呋喃并[2,3-b]咔唑
Figure GDA0002489311020000102
合成步骤同实施例1，只是将(E)-2-(2-硝基乙烯基)苯酚换成(E)-4-甲氧基-2-(2-硝基乙烯基)苯酚，得到黄色固体。
Yellow solid，m.p.206.2-207.6℃，1H NMR(500MHz,CDCl3)δ7.85(s,1H),7.77(dd,J＝8.1,1.3Hz,2H),7.67(dd,J＝7.7,0.9Hz,1H),7.64-7.59(m,2H),7.58-7.53(m,1H),7.45-7.37(m,3H),7.28(d,J＝7.9Hz,1H),6.96(ddd,J＝9.4,7.1,1.1Hz,2H),4.00(s,3H),3.97(s,3H).13C NMR(125MHz,CDCl3)δ148.9,146.3,145.7,142.5,138.7,135.1,130.5,128.8,128.2,126.6,126.0,123.3,123.0,122.7,122.5,121.1,120.5,118.4,112.8,109.8,108.3,97.9,77.4,77.2,76.9,56.3,29.5.HRMS(ESI):m/z calcd for(C26H19NO2+H)+:378.1489；found:378.1488。
实施例16 10-甲氧基-7-甲基-6-苯基-7H-苯并呋喃并[2,3-b]咔唑
Figure GDA0002489311020000111
合成步骤同实施例1，只是将N-甲基吲哚换成N-甲基-5-甲氧基吲哚，得到黄色固体。
Yellow solid，m.p.144.9-145.6℃，1H NMR(500MHz,CDCl3)δ8.06(d,J＝7.6Hz,1H),7.83(s,1H),7.79-7.71(m,2H),7.64(t,J＝7.5Hz,2H),7.57(t,J＝7.4Hz,1H),7.51(d,J＝8.1Hz,1H),7.45-7.40(m,1H),7.35(dd,J＝10.9,4.0Hz,1H),7.29(d,J＝8.8Hz,1H),7.07(dd,J＝8.8,2.5Hz,1H),6.87(d,J＝2.5Hz,1H),3.94(s,3H),3.60(s,3H).13C NMR(125MHz,CDCl3)δ157.4,152.9,148.6,139.3,137.6,135.2,130.6,128.8,128.4,127.1,125.1,123.2,122.9,122.3,120.7,120.6,119.9,115.2,111.9,108.9,105.5,98.0,77.4,77.2,76.9,55.8,29.6.HRMS(ESI):m/z calcd for(C26H19NO2+Na)+:400.1308；found:400.1302。
实施例17 9,12-二甲基-8-苯基-9H-萘并[1',2':4,5]呋喃并[2,3-b]咔唑
Figure GDA0002489311020000112
合成步骤同实施例1，只是将(E)-2-(2-硝基乙烯基)苯酚换成(E)-1-(2-硝基乙烯基)萘-2-醇，将N-甲基吲哚换成N-甲基-5-甲基吲哚，得到黄色固体。
Yellow solid，m.p.239.6-240.5℃，1H NMR(500MHz,CDCl3)δ8.80(d,J＝8.2Hz,1H),8.24(s,1H),8.05(d,J＝8.1Hz,1H),7.90(d,J＝8.9Hz,1H),7.83-7.77(m,3H),7.73(d,J＝8.9Hz,1H),7.70-7.53(m,5H),7.33(d,J＝8.2Hz,1H),7.22(s,1H),4.05(s,3H),2.33(s,3H).13C NMR(125MHz,CDCl3)δ155.6,148.7,140.9,139.4,135.4,130.6,130.5,129.5,129.4,128.8,128.4,127.6,127.3,127.1,124.2,123.7,123.4,122.7,122.5,120.3,119.9,117.9,113.2,108.0,99.0,29.6,21.6.HRMS(ESI):m/z calcd for(C30H21NO+Na)+:434.1515；found:434.1511。
实施例18 7-甲基-6-(4-(三氟甲基)苯基)-7H-苯并呋喃并[2,3-b]咔唑
Figure GDA0002489311020000121
合成步骤同实施例1，只是将苯乙酮硫叶立德换成对三氟甲基苯乙酮硫叶立德，得到黄色固体。
Yellow solid，m.p.204.5-205.8℃，1H NMR(500MHz,CDCl3)δ8.08(d,J＝7.1Hz,1H),7.91(d,J＝7.0Hz,5H),7.52(d,J＝8.1Hz,1H),7.48-7.42(m,3H),7.40-7.34(m,2H),7.03-6.96(m,1H),4.00(s,3H).13C NMR(125MHz,CDCl3)δ157.3,148.8,142.6,139.1,138.7,131.0,130.6,130.3,127.4,126.3,125.8,125.8,125.8,125.6,124.9,123.5,123.3,122.6,122.3,122.2,120.7,120.6,118.7,118.4,111.9,108.6,98.7,77.4,77.2,76.9,29.5.HRMS(ESI):m/z calcd for(C26H16F3NO+Na)+:438.1076；found:438.1084。吸收和发射光谱见图3。
实施例19 10-溴-7-甲基-6-苯基-7H-苯并呋喃并[2,3-b]咔唑
Figure GDA0002489311020000122
合成步骤同实施例1，只是将N-甲基吲哚换成N-甲基-5-溴吲哚，得到棕色固体。
Brown solid，m.p.230.1-231.0℃，1H NMR(500MHz,CDCl3)δ8.06(d,J＝7.6Hz,1H),7.85(s,1H),7.76-7.69(m,2H),7.65(t,J＝7.3Hz,2H),7.61(d,J＝7.2Hz,1H),7.54-7.48(m,3H),7.44(t,J＝7.7Hz,1H),7.35(t,J＝7.4Hz,1H),7.27(s,1H),3.94(s,3H).13CNMR(125MHz,CDCl3)δ157.5,149.0,141.1,139.0,134.6,130.3,129.0,128.7,128.6,127.5,125.0,123.9,122.5,120.7,120.4,119.9,112.1,111.2,109.7,98.2,77.4,77.2,76.9,29.6.HRMS(ESI):m/z calcd for(C25H16BrNO+H)+:426.0488；found:426.0491。
实施例20 10-溴-2-氯-7-甲基-6-苯基-7H-苯并呋喃并[2,3-b]咔唑
Figure GDA0002489311020000123
合成步骤同实施例1，只是将(E)-2-(2-硝基乙烯基)苯酚换成(E)-4-氯-2-(2-硝基乙烯基)苯酚，将N-甲基吲哚换成N-甲基-5-溴吲哚,得到黄色固体。
Yellow solid，m.p.>250℃，1H NMR(500MHz,CDCl3)δ7.99(d,J＝2.0Hz,1H),7.76(s,1H),7.70(dd,J＝8.0,1.4Hz,2H),7.67-7.60(m,3H),7.52-7.47(m,2H),7.41(d,J＝8.7Hz,1H),7.36(dd,J＝8.7,2.1Hz,1H),7.26(d,J＝2.5Hz,1H),3.90(s,3H).13C NMR(125MHz,CDCl3)δ155.7,149.6,141.2,139.0,134.3,130.2,129.1,128.9,128.9,128.0,127.4,126.3,125.1,124.2,122.9,120.7,120.5,113.0,111.3,109.8,98.3,77.4,77.2,76.9,29.7.HRMS(ESI):m/z calcd for(C25H15BrClNO+H)+:460.0098；found:460.0100。
实施例21 3-甲氧基-7-甲基-6-苯基-7H-苯并呋喃并[2,3-b]咔唑
Figure GDA0002489311020000131
合成步骤同实施例1，只是将(E)-2-(2-硝基乙烯基)苯酚换成(E)-5-甲氧基-2-(2-硝基乙烯基)苯酚,得到黄色固体。
Yellow solid，m.p.185.2-186.0℃，1H NMR(500MHz,CDCl3)δ7.91(d,J＝8.5Hz,1H),7.77-7.73(m,3H),7.66-7.61(m,2H),7.60-7.55(m,1H),7.43-7.37(m,3H),7.06(d,J＝2.2Hz,1H),6.95(ddd,J＝8.4,5.3,2.0Hz,2H),3.95(s,3H),3.87(s,3H).13C NMR(125MHz,CDCl3)δ160.0,158.7,149.1,142.2,138.8,135.3,130.4,128.9,128.3,125.6,123.4,122.8,122.2,121.0,120.0,119.6,118.3,118.1,110.8,108.3,97.2,96.8,77.4,77.2,76.9,55.8,29.5.HRMS(ESI):m/z calcd for(C26H19NO2+H)+:378.1489；found:378.1485。
实施例22化合物荧光性质测定
探针的吸收波长、激发波长与发射波长检测方法具体如下：
称取约1mg的化合物粉末，以DMSO为溶剂，分别配成1mM的初始溶液，然后用无水乙醇稀释得到10μM的探针溶液，随后进行光学性质的检测，即用TU-1901紫外可见分光光度计获取紫外吸收光谱，然后用Jascoo FP-6500型荧光光谱仪获取荧光发射光谱，得到探针的最大激发波长与发射波长。
表1.化合物的荧光性质
Figure GDA0002489311020000132
Figure GDA0002489311020000141
结果见表1，实施例8、实施例11和实施例18具有较大的斯托克斯位移，这些较好的荧光性质，提示可以作为潜在的荧光团在分子成像中应用。

Claims (2)

1.一种6-芳基-苯并呋喃并咔唑类化合物的制备方法，其特征在于，通过以下步骤实现：
将（E）-2-（2-硝基乙烯基）苯酚类化合物、芳乙酰基硫叶立德类化合物溶解在1，2-二氯乙烷中，于25℃反应，反应时间为0.5至2个小时后加入吲哚类化合物和三氟醋酸，反应时间为24小时，（E）-2-（2-硝基乙烯基）苯酚类化合物、芳乙酰基硫叶立德类化合物和吲哚类化合物的摩尔比为1:1:1；
所述的（E）-2-（2-硝基乙烯基）苯酚类化合物的结构式为：
Figure DEST_PATH_IMAGE002
其中R1为氢、甲氧基、萘基、甲氧碳基、卤素，
所述的吲哚类化合物的结构式为：
Figure DEST_PATH_IMAGE004
其中R2为氢、甲基、苄基；
R3为氢、甲氧基、苄氧基、甲基、溴；
所述的芳乙酰基硫叶立德类化合物的结构式为：
Figure DEST_PATH_IMAGE006
其中R4为氢、萘基、甲基、硝基、甲氧基、氰基、羟基、三氟甲基、苯基、卤素；
所述6-芳基-苯并呋喃并咔唑类化合物的结构式为：
Figure DEST_PATH_IMAGE008
。
2.根据权利要求1所述的一种6-芳基-苯并呋喃并咔唑类化合物的制备方法，其特征在于，R1、R4所述卤素选用氟、氯、溴。
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