CN109665984B - 一种2-取代吲哚类化合物的合成方法 - Google Patents
一种2-取代吲哚类化合物的合成方法 Download PDFInfo
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Abstract
本发明公开了一种2‑取代吲哚类化合物的合成方法,属于有机合成领域。本发明用式1所示的2‑氟甲苯类化合物和式2所示的腈类化合物在强碱和铯盐添加剂存在的条件下,与有机溶剂混合,反应合成式3所示的2‑取代吲哚类化合物。本发明合成方法简单、经济、适用性更加广泛,适于规模化生产,对合成吲哚类化合物有着很重要的影响。
Description
技术领域
本发明属于有机合成领域,特别涉及一种2-取代吲哚类化合物的合成方法。
背景技术
吲哚类化合物是重要的有机原料和化工产品,具有各种各样的生理活性。作为医药、农药、染料、香料及其他精细化工产品的中间体,吲哚类化合物和其衍生物得到广泛应用,因此其合成一直是全球化学领域的重要内容之一。当前已经发展了很多方法来合成吲哚类化合物,如苯肼法、苯胺法、邻氨基乙苯法、邻氯甲苯法等,但这些方法均有各自的缺点,如需要两步反应导致收率低,合成需要催化剂不易得到,需要过渡金属催化,或者所用辅助原料复杂等。由于以上原因导致吲哚类化合物的合成收率不高,不易实现规模化制备,且污染环境。
本发明中目标产物类似化合物合成已有报道(A.B.Smith,III,M.Visnick,J.N.Haseltine,P.A.Sprengeler,Tetrahedron 1986,42,2957-2969),具体路线如下:
该方法以2-甲基苯胺作为原料,经过两步反应得到2-取代吲哚化合物。此反应需要两步,且第二步反应温度需要-78℃,条件苛刻,较为局限,不易规模化制备,并且产率只有62%。
发明内容
本发明的目的在于提供一种解决以上问题,合成方法简单、经济适用性更加广泛或适于规模化生产的2-取代吲哚类化合物的合成方法。
实现上述目的的技术方案如下:
一种2-取代吲哚类化合物的合成方法,式1所示的2-氟甲苯类化合物和式2所示的腈类化合物、强碱和铯盐添加剂,有机溶剂混合,反应合成式3所示的2-取代吲哚类化合物。
其中R1选自氢、卤素基、甲氧基、甲基或苯基,R2选自氢、苯基或取代苯基,R3选自苯基、取代苯基、吡啶、萘、叔丁基,其中苯基的取代基选自甲基,叔丁基,甲氧基,三氟甲基,卤素基。本发明方法为一锅法生成吲哚类化合物,减少了反应步骤,从而可提高产物收率;本合成方法所用原料简单经济,不用使用过渡金属催化剂,更加经济与绿色环保;本发明中的R1、R2、R3可以为多种选择,适用性更广。
优选的,R1选自氢,苯基或单取代或多取代卤素基,优选的,R1选自氢,单取代或多取代卤素基;R2选自氢或苯基,R3选自苯基、对叔丁基苯基或2-萘基。
更加优选的,R1选自6-氯,3,6-二氟,3,4,5,6,-四氟。
优选的,R1为氢,R2为苯基,R3为苯基。
优选的,反应在惰性气体保护下进行。
优选的,式2所示的腈类化合物、式1所示的2-氟甲苯类化合物、强碱、铯盐添加剂的摩尔比为:4:1~12:2~12:4~8,反应温度为90℃~130℃。
优选的,反应温度为100℃~120℃。
优选的,反应温度为110℃。
优选的,强碱为二(三甲基硅基)氨基锂,二(三甲基硅基)氨基钾或二(三甲基硅基)氨基铯的一种或多种。
优选的,有机溶剂为环戊基甲基醚,二甲醚,四氢呋喃,1,4-二氧六环或异丙醚。
优选的,铯盐添加剂为氟化铯、三氟乙酸铯或碳酸铯或二(三甲基硅基)氨基铯。
优选的,铯盐添加剂为氟化铯。
优选的,惰性气体为氩气或氮气。
优选的,采用本发明方法,可以合成如下结构的2-取代吲哚类化合物:
在强碱和铯盐添加剂的存在下,2-氟甲苯的甲基去质子化,得到苄基金属中间体,然后苄基金属中间体进攻腈得到金属亚胺中间体。生成的金属亚胺中间体经过分子内SNAr(亲核芳得取代反应)环化和异构化,得到吲哚。
采用本发明的技术方案至少可以达到如下有益效果之一:
本发明提供一种新的取代吲哚的合成方法,该方法未用到过渡金属催化剂,因此更加经济,更适于工业普及;
本发明采用一锅法合成方法,由于反应步骤少,减少了原料的损失,提高了产物的产率;
本发明所需操作步骤较为简便,无需极端的升温或降温,更易于操作和控制;
本发明中的R1、R2、R3可以为多种选择,因此本发明方法适用性更加广泛,可以合成多种2-取代吲哚类化合物,对合成吲哚类化合物有着很重要的影响。
附图说明
图1~38分别为实施例1~38产物的核磁共振谱图
其中每一实施例产物的谱图中,A图为对应实施例产物的氢谱图,B图为对应实施例产物的碳谱图,C图为对应实施例产物的氟谱图。
具体实施方式
为了便于本领域技术人员理解,下面结合实施例对本发明的构思做进一步的说明。以下实施例的具体说明并非对本发明的限制,只是为了方便本领域技术人员理解本技术方案。说明书中所涉及的各种原料,均购自市场,二(三甲基硅基)氨基锂(Aldrich,97%),二(三甲基硅基)氨基钾(Aldrich,95%),氟化铯(Aldrich,99%),其他药品等购自Sigma-Aldrich,Acros,Alfa Aesar,TCI China,Adamas-beta或者J&K.,核磁共振谱仪型号为布鲁克400兆。
实施例1
在手套箱中将二(三甲基硅基)氨基锂(66.8mg,0.4mmol)与氟化铯(30.4mg,0.2mmol)加入微波管中,加入0.4mL环戊基甲基醚,然后用微量注射器分别加入2-氟甲苯(66μL,0.60mmol)和苯甲腈(20μL,0.20mmol),加盖从手套箱取出,在110℃下回流12小时,冷却至室温,启盖并加三滴水淬灭反应,减压去除溶剂,粗产品柱层析分离(石油醚:乙酸乙酯=20:1),即可得2-苯基吲哚(34.7mg,90%yield)。产物的比移值Rf=0.34(石油醚:乙酸乙酯=20:1),产物的氢谱和碳谱核磁共振谱图分别为图1A和图1B,谱图数据为:1H NMR(400MHz,CDCl3)δ:8.34(brs,1H),7.69–7.65(m,3H),7.48–7.40(m,3H),7.36–7.32(m,1H),7.26–7.20(m,1H),7.17–7.13(m,1H),6.85(d,J=2.1Hz,1H)ppm.13C{1H}NMR(101MHz,CDCl3)δ:138.0,136.9,132.5,129.4,129.2,127.8,125.3,122.5,120.8,120.4,111.0,100.1ppm.
变换实施例1中的原料、强碱、溶剂的比例,设计如下38组实验实施例,其中第1组实验即为实施例1,对应的产物的核磁共振谱图为图1。其余2-38各组产物的核磁共振谱图的序号对应相应的实施例的序号。
表中列出了1-38各实施例中R1、R2、R3以及对应的产物的结构式,最后一列列出了各实施例的产物的产率,并标示出了各实施例的具体实施条件,各实施例实施条件的具体含义如表格下方所示。
[a]腈类化合物(0.2mmol),二氟甲苯类化合物(0.6mmol),二(三甲基硅基)氨基锂(0.4mmol),氟化铯(0.2mmol),环戊基甲基醚(0.4mL)
[b]二(三甲基硅基)氨基锂(0.2mmol)与二(三甲基硅基)氨基钾(0.2mmol),其他跟条件[a]相同
[c]环戊基甲基醚(0.2mL),其他跟条件[a]相同
[d]腈类化合物(0.8mmol),二氟甲苯类化合物(0.2mmol),二甲醚(0.4mL),其他跟条件[a]相同
[e]二甲醚(0.2mL),其他跟条件[a]相同
[f]二(三甲基硅基)氨基锂(0.2mmol)与二(三甲基硅基)氨基钾(0.2mmol),氟化铯(0.3mmol),二甲醚(0.5mL),其他跟条件[a]相同
[g]环戊基甲基醚(0.2mL),其他跟条件[d]相同
[h]二(三甲基硅基)氨基钾(0.6mmol),氟化铯(0.3mmol),异丙醚(0.4mL),其他跟条件[a]相同
[i]1,4-二氧六环(0.2mL),其他跟条件[a]相同
[j]二(三甲基硅基)氨基锂(0.6mmol),氟化铯(0.4mmol),四氢呋喃(0.1mL),其他跟条件[a]相同
[k]二甲醚(0.4mL),其他跟条件[a]相同
[l]二甲醚(0.1mL),其他跟条件[a]相同
[m]四氢呋喃(0.2mL),其他跟条件[a]相同
以下为2-38各个实施例产物的1H和13C的核磁共振谱图(NMR)图谱数据结果以及部分产物的熔点Mp、红外光谱(IR)、高分辨质谱(HRMS)数据结果。
实施例2
用2,6-二氟甲苯(68μL,0.60mmol)代替实施例1中的2-氟甲苯,其余操作与实施例1相同,最终以81%的收率(34.1mg)得到4-氟-2-苯基-1H-吲哚,产物的比移值Rf=0.17(石油醚:乙酸乙酯=20:1),产物的氢谱和碳谱核磁共振谱图分别如图2A和图2B所示,谱图数据为:1H NMR(400MHz,CDCl3)δ:8.42(brs,1H),7.68–7.65(m,2H),7.49–7.44(m,2H),7.38–7.34(m,1H),7.20–7.18(m,1H),7.14–7.09(m,1H),6.91(dd,J=2.3,0.9Hz,1H),6.84–6.79(m,1H)ppm.13C{1H}NMR(101MHz,CDCl3)δ:156.5(d,J1 C-F=247.9Hz),139.4(d,J4 C-F=11.2Hz),138.0,132.0,129.3,128.2,125.4,122.9(d,J5 C-F=7.7Hz),118.6(d,J2 C-F=22.5Hz),107.1(d,J6 C-F=3.6Hz),105.2(d,J3 C-F=19.0Hz),96.0ppm。
实施例3
用2-氟-6-氯甲苯(68μL,0.60mmol)代替实施例1中的2-氟甲苯,其余操作与实施例1相同,最终以87%的收率(39.5mg)得到4-氯-2-苯基-1H-吲哚,产物的比移值Rf=0.34(石油醚:乙酸乙酯=20:1),产物的氢谱和碳谱核磁共振谱图分别如图3A和图3B所示,谱图数据为:1H NMR(400MHz,CDCl3)δ:8.38(brs,1H),7.65–7.61(m,2H),7.45–7.41(m,2H),7.35–7.31(m,1H),7.26–7.22(m,1H),7.13–7.06(m,2H),6.91–6.90(m,1H)ppm.13C{1H}NMR(101MHz,CDCl3)δ:138.6,137.5,131.8,129.2,128.3,128.2,126.0,125.4,123.0,120.1,109.6,98.6ppm。
实施例4
实施例4所得产物的比移值Rf=0.29(石油醚:乙酸乙酯=20:1),产物的氢谱和碳谱核磁共振谱图分别为图4A和4B,谱图数据为:,1H NMR(400MHz,CDCl3)δ:8.48(brs,1H),7.69–7.67(m,2H),7.48–7.45(m,2H),7.38–7.29(m,3H),7.07–7.03(m,1H),6.89–6.88(m,1H)ppm.13C{1H}NMR(101MHz,CDCl3)δ:138.6,137.0,131.8,130.1,129.2,128.3,125.4,123.3,114.7,110.2,100.3ppm。
实施例5
实施例5所得产物的比移值Rf=0.29(石油醚:乙酸乙酯=20:1),熔点Mp 136–138℃,产物的氢谱和碳谱核磁共振谱图分别为图5A和5B,谱图数据为:1H NMR(400MHz,CDCl3)δ:8.47(brs,1H),7.67–7.64(m,2H),7.55(d,J=7.5Hz,1H),7.48–7.44(m,2H),7.38–7.33(m,2H),6.93(t,J=7.8Hz,1H),6.78–6.77(m,1H)ppm.13C{1H}NMR(101MHz,CDCl3)δ:138.3,135.6,133.8,131.7,129.8,129.2,128.3,125.3,123.7,111.0,103.5,87.3ppm.IR(neat):3432,3062,1602,1566,1486,1451,1179,904,753,685,492cm-1.HRMS:calcd for C14H11IN[M+H]+319.9936,found 319.9939。
实施例6
实施例6所得产物的比移值Rf=0.41(石油醚:乙酸乙酯=20:1),产物的氢谱和碳谱核磁共振谱图分别为图6A和6B,谱图数据为:1H NMR(400MHz,CDCl3)δ:8.35(brs,1H),7.70–7.67(m,2H),7.47–7.43(m,2H),7.35–7.31(m,1H),7.27–7.25(m,1H),7.12(t,J=7.5Hz,1H),6.95–6.93(m,1H),6.87–6.86(m,1H),2.60(s,3H)ppm.13C{1H}NMR(101MHz,CDCl3)δ:137.4,136.6,132.6,130.4,129.3,129.2,127.7,125.2,122.6,120.5,108.6,98.7,18.9ppm.
实施例7
实施例7所得产物的比移值Rf=0.37(石油醚:乙酸乙酯=20:1),产物的氢谱和碳谱核磁共振谱图分别为图7A和7B,谱图数据为:1H NMR(400MHz,CDCl3)δ:8.37(brs,1H),7.66–7.64(m,2H),7.46–7.42(m,2H),7.34–7.30(m,1H),7.17–7.13(m,1H),7.05–6.98(m,2H),6.59–6.57(m,1H),4.00(s,3H)ppm.13C{1H}NMR(101MHz,CDCl3)δ:153.4,138.2,136.6,132.5,129.1,127.6,125.1,123.3,120.1,104.5,100.1,97.3,55.5ppm。
实施例8
实施例8所得产物的比移值Rf=0.29(石油醚:乙酸乙酯=20:1),熔点Mp:80–82℃,产物的氢谱和碳谱核磁共振谱图分别为图8A和8B,谱图数据为:1H NMR(400MHz,CDCl3)δ:8.41(brs,1H),7.66–7.64(m,2H),7.44(t,J=7.6Hz,2H),7.35–7,31(m,1H),7.16(t,J=7.8Hz,1H),7.03–6.99(m,2H),6.60(d,J=7.5Hz,1H),3.07(s,6H)ppm.13C{1H}NMR(101MHz,CDCl3)δ:146.6,138.3,136.0,132.5,129.1,127.5,125.1,123.2,122.0,106.2,104.6,99.5,43.5ppm.IR(neat):3449,3081,1602,1578,1540,1507,1441,1359,1340,1224,755,493cm-1.HRMS:calcd for C16H17N2[M+H]+237.1397,found 237.1394.
实施例9
实施例9所得产物的比移值Rf=0.48(石油醚:乙酸乙酯=10:1),产物的氢谱和碳谱核磁共振谱图分别为图9A和9B,谱图数据为:1H NMR(400MHz,CDCl3)δ:8.30(brs,1H),7.64–7.62(m,2H),7.46–7.42(m,2H),7.35–7.24(m,3H),6.95–6.90(m,1H),6.78–6.77(m,1H)ppm.13C{1H}NMR(101MHz,CDCl3)δ:158.3(d,J1 C-F=235.6Hz),139.8,133.4,132.2,129.7(d,J3 C-F=10.4Hz),129.2,128.2,125.3,111.6(d,J3 C-F=9.8Hz),110.8(d,J2 C-F=26.5Hz),105.5(d,J2 C-F=23.6Hz),100.2(d,J4 C-F=4.6Hz)ppm.
实施例10
实施例10所得产物的比移值Rf=0.30(石油醚:乙酸乙酯=20:1),产物的氢谱和碳谱核磁共振谱图分别为图10A和10B,谱图数据为:1H NMR(400MHz,CDCl3)δ:8.37(brs,1H),7.66–7.63(m,2H),7.59(d,J=2.0Hz,1H),7.48–7.44(m,2H),7.37–7.30(m,2H),7.16–7.13(m,1H),6.77–6.76(m,1H)ppm.13C{1H}NMR(101MHz,CDCl3)δ:139.4,135.2,132.0,130.5,129.2,128.3,126.0,125.4,122.7,120.1,112.0,99.7ppm.
实施例11
实施例11所得产物的比移值Rf=0.20(石油醚:乙酸乙酯=20:1),产物的氢谱和碳谱核磁共振谱图分别为图11A和11B,谱图数据为:1H NMR(400MHz,CDCl3)δ:8.24(brs,1H),7.63–7.60(m,2H),7.43–7.39(m,2H),7.32–7.23(m,2H),7.09–7.08(m,1H),6.86–6.84(m,1H),6.75–6.74(m,1H),3.85(s,3H)ppm.13C{1H}NMR(101MHz,CDCl3)δ:154.6,138.7,132.5,132.1,129.8,129.1,127.8,125.2,112.7,111.8,102.4,99.9,56.0ppm.
实施例12
实施例12所得产物的比移值Rf=0.19(石油醚:乙酸乙酯=20:1),熔点Mp:195-197℃,产物的氢谱和碳谱核磁共振谱图分别为图12A和12B,谱图数据为:1H NMR(400MHz,CDCl3)δ:8.39(brs,1H),7.85(s,1H),7.71–7.65(m,4H),7.48–7.43(m,6H),7.37–7.30(m,2H),6.89–6.88(m,1H)ppm.13C{1H}NMR(101MHz,CDCl3)δ:142.6,138.7,136.5,134.0,132.4,129.9,129.2,128.8,128.0,127.5,126.5,125.3,122.4,119.3,111.2,100.4ppm.IR(neat):3444,1633,1546,1504,1460,1448,884,755,690,501cm-1.HRMS:calcd for C20H16N[M+H]+270.1283,found 270.1280.
实施例13
实施例13所得产物的比移值Rf=0.36(石油醚:乙酸乙酯=20:1),产物的氢谱和碳谱核磁共振谱图分别为图13A和13B,谱图数据为:1H NMR(400MHz,CDCl3)δ:8.36(brs,1H),7.65–7.62(m,2H),7.55–7.52(m,1H),7.47–7.42(m,2H),7.36–7.31(m,1H),7.10–7.07(m,1H),6.93–6.87(m,1H),6.80–6.79(m,1H)ppm.13C{1H}NMR(101MHz,CDCl3)δ:160.2(d,J1 C-F=239.0Hz),138.5(d,J6 C-F=3.8Hz),136.8(d,J4 C-F=12.6Hz),132.2,129.2,127.9,125.9,125.1,121.5(d,J5 C-F=10.1Hz),109.1(d,J3 C-F=24.6Hz),100.0,97.4(d,J2 C-F=26.3Hz)ppm.
实施例14
实施例14所得产物的比移值Rf=0.35(石油醚:乙酸乙酯=20:1),熔点Mp 205.6–206.8℃,产物的氢谱和碳谱核磁共振谱图分别为图14A和14B,谱图数据为:1H NMR(400MHz,DMSO-d6)δ:11.65(brs,1H),7.90–7.88(m,2H),7.70–7.60(m,4H),7.50–7.44(m,4H),7.35–7.31(m,3H),6.95–6.94(m,1H)ppm.13C{1H}NMR(101MHz,DMSO-d6)δ:141.6,138.5,137.8,134.0,132.1,129.0,128.9,128.2,127.5,126.7,126.6,125.0,120.5,118.9,109.2,98.7ppm.IR(neat):3432,2908,2839,2058,1636,1488,1441,825,760,741,689cm-1.HRMS:calcd for C20H16N[M+H]+270.1283,found 270.1279.
实施例15
实施例15所得产物的比移值Rf=0.60(石油醚:乙酸乙酯=20:1),熔点Mp 116–119℃,产物的氢谱和碳谱核磁共振谱图分别为图15A和15B,谱图数据为:1H NMR(400MHz,CDCl3)δ:8.51(brs,1H),7.70–7.67(m,2H),7.49–7.45(m,2H),7.41–7.34(m,2H),7.07–7.02(m,1H),6.95–6.90(m,1H),6.87–6.85(m,1H)ppm.13C{1H}NMR(101MHz,CDCl3)δ:149.5(d,J1 C-F=244.1Hz),138.9,132.9(d,J5 C-F=5.2Hz),132.0,129.2,128.2,125.4,125.2(d,J3 C-F=13.0Hz),120.6(d,J4 C-F=6.2Hz),116.5(d,J6 C-F=3.5Hz),107.3(d,J2 C-F=16.1Hz),100.6(d,J7 C-F=2.5Hz)ppm.IR(neat):3438,3055,1604,1549,1506,1452,1248,1034,775,725,497cm-1.HRMS:calcd for C14H11FN[M+H]+212.0876,found 212.0879.
实施例16
实施例16所得产物的比移值Rf=0.62(石油醚:乙酸乙酯=20:1),产物的氢谱和碳谱核磁共振谱图分别为图16A和16B,谱图数据为:1H NMR(400MHz,CDCl3)δ:8.50(brs,1H),7.72–7.69(m,2H),7.54–7.45(m,3H),7.39–7.35(m,1H),7.21–7.19(m,1H),7.08–7.04(m,1H),6.87–6.85(m,1H)ppm.13C{1H}NMR(101MHz,CDCl3)δ:138.8,134.2,131.9,130.7,129.2,128.3,125.5,121.7,121.2,119.4,116.5,100.9ppm.
实施例17
实施例17所得产物的比移值Rf=0.56(石油醚:乙酸乙酯=20:1),产物的氢谱和碳谱核磁共振谱图分别为图17A和17B,谱图数据为:1H NMR(400MHz,CDCl3)δ:8.22(brs,1H),7.72–7.70(m,2H),7.52–7.45(m,3H),7.37–7.33(m,1H),7.09–7.01(m,2H),6.86(d,J=2.1Hz,1H),2.57(s,3H)ppm.13C{1H}NMR(101MHz,CDCl3)δ:137.8,136.5,132.7,129.1,128.9,127.8,125.3,123.1,120.6,120.2,118.5,100.7,16.9ppm.
实施例18
实施例18所得产物的比移值Rf=0.63(石油醚:乙酸乙酯=20:1),产物的氢谱、碳谱和氟谱的核磁共振谱图分别为图18A、18B和18C,谱图数据为:1H NMR(400MHz,CDCl3)δ:8.60(brs,1H),7.69–7.66(m,2H),7.50–7.45(m,2H),7.40–7.36(m,1H),6.90(dd,J=2.4,3.2Hz,1H),6.83–6.77(m,1H),6.71–6.65(m,1H)ppm.13C{1H}NMR(101MHz,CDCl3)δ:152.2(dd,J4 C-F=1.8Hz,J1 C-F=243.7Hz),145.7(dd,J4 C-F=2.8Hz,J1 C-F=239.8Hz),138.9,131.4,129.3,128.6,126.7(dd,J2 C-F=15.5Hz,J3 C-F=11.6Hz),125.5,121.2(dd,J2 C-F=25.2Hz,J3 C-F=5.4Hz),106.9(dd,J2 C-F=19.3Hz,J3 C-F=8.5Hz),104.6(dd,J2 C-F=22.3Hz,J3 C-F=7.1Hz),96.8ppm.19F NMR(376MHz,CDCl3)δ:-127.7(d,J=22.4Hz),-140.6(d,J=22.4Hz)ppm.IR(neat):3457,3082,3037,1958,1635,1606,1548,1519,1488,1453,793,782,728cm-1.HRMS:calcd for C14H10NF2[M+H]+230.0781,found 230.0784.
实施例19
实施例19所得产物的比移值Rf=0.62(石油醚:乙酸乙酯=20:1),熔点Mp 125–127℃,产物的氢谱、碳谱和氟谱的核磁共振谱图分别为图19A、19B和19C,谱图数据为1HNMR(400MHz,CDCl3)δ:8.46(brs,1H),7.63–7.60(m,2H),7.46–7.41(m,2H),7.36–7.32(m,1H),7.26–7.22(m,1H),6.96–6.89(m,1H),6.76(dd,J=2.2,3.3Hz,1H)ppm.13C{1H}NMR(101MHz,CDCl3)δ:146.4(dd,J1 C-F=239.3Hz,J2 C-F=9.4Hz),139.5(dd,J4=3.8Hz,J5=1.5Hz),137.5(dd,J1 C-F=246.3Hz,J2 C-F=16.5Hz),131.7,129.3,128.8(dd,J3 C-F=8.7Hz,J4 C-F=5.0Hz),128.3,125.9(dd,J3 C-F=9.4Hz,J4 C-F=4.2Hz),125.3,115.7(dd,J2 C-F=8.1Hz,J3 C-F=4.2Hz),110.3(dd,J2 C-F=20.5Hz,J3 C-F=0.8Hz),100.4ppm.19F NMR(376MHz,CDCl3)δ:-148.1(d,J=20.1Hz),-160.7(d,J=20.4Hz)ppm.IR(neat):3477,2905,2837,2046,1635,1521,1491,1450,811,760,727,686cm-1.HRMS:calcd for C14H10NF2[M+H]+230.0781,found 230.0779.
实施例20
实施例20所得产物的比移值Rf=0.60(石油醚:乙酸乙酯=20:1),熔点Mp 125–127℃,产物的氢谱、碳谱和氟谱的核磁共振谱图分别为图20A、20B和20C,谱图数据为:1HNMR(400MHz,CDCl3)δ:8.60(brs,1H),7.67–7.64(m,2H),7.51–7.46(m,2H),7.42–7.38(m,1H),6.26(dd,J=2.4,2.8Hz,1H)ppm.13C{1H}NMR(101MHz,CDCl3)δ:140.2,139.6(m),136.9(m),135.5(m),134.2(m),130.8,129.4,128.9,125.5,121.3(m),115.4(dd,J2 C-F=20.2Hz,J3 C-F=4.0Hz),96.6ppm.19F NMR(376MHz,CDCl3)δ:-149.9(d,J=3.2Hz),-161.5,-165.3,-168.8(d,J=42.9Hz)ppm.
实施例21
实施例21所得产物的比移值Rf=0.39(石油醚:乙酸乙酯=20:1),产物的氢谱和碳谱核磁共振谱图分别为图21A和21B,谱图数据为:1H NMR(400MHz,CDCl3)δ:8.11(brs,1H),7.70(d,J=8.0Hz,1H),7.37–7.26(m,7H),7.24–7.13(m,5H),7.08–7.04(m,1H)ppm.13C{1H}NMR(101MHz,CDCl3)δ:136.0,135.2,134.2,132.8,130.3,128.9,128.8,128.7,128.3,127.8,126.4,122.8,120.6,119.8,115.1,111.0ppm.
实施例22
实施例22所得产物的比移值Rf=0.38(石油醚:乙酸乙酯=20:1),产物的氢谱和碳谱核磁共振谱图分别为图22A和22B,谱图数据为:1H NMR(400MHz,CDCl3)δ:8.32(brs,1H),7.45(d,J=8.1Hz,1H),7.35–7.21(m,11H),7.12–7.08(m,1H),2.03(s,3H)ppm.13C{1H}NMR(101MHz,CDCl3)δ:137.9,135.9,134.6,133.9,133.0,131.7,130.4,129.7,128.9,127.6,127.3,126.9,126.0,122.7,120.3,120.1,114.9,110.9,20.3ppm.
实施例23
实施例23所得产物的比移值Rf=0.38(石油醚:乙酸乙酯=20:1),产物的氢谱和碳谱核磁共振谱图分别为图23A和23B,谱图数据为:1H NMR(400MHz,CDCl3)δ:8.26(brs,1H),7.62–7.60(m,1H),7.54–7.52(m,2H),7.37–7.35(m,1H),7.24–7.09(m,4H),6.77–6.76(m,1H),2.38(s,3H)ppm.13C{1H}NMR(101MHz,CDCl3)δ:138.2,137.8,136.8,129.8,129.7,129.4,125.2,122.2,120.6,120.3,110.9,99.5,21.4ppm.。
实施例24
实施例24所得产物的比移值Rf=0.44(石油醚:乙酸乙酯=20:1),产物的氢谱和碳谱核磁共振谱图分别为图24A和24B,谱图数据为:1H NMR(400MHz,CDCl3)δ:8.32(brs,1H),7.66–7.60(m,3H),7.50–7.47(m,2H),7.42–7.40(m,1H),7.23–7.13(m,2H),6.83–6.82(m,1H),1.39(s,9H)ppm.13C{1H}NMR(101MHz,CDCl3)δ:151.0,138.1,136.8,129.7,129.5,126.1,125.0,122.2,120.7,120.3,111.0,99.6,34.8,31.4ppm.
实施例25
实施例25所得产物的比移值Rf=0.3(石油醚:乙酸乙酯=20:1),产物的氢谱和碳谱核磁共振谱图分别为图25A和25B,谱图数据为:1H NMR(400MHz,DMSO-d6)δ:11.41(brs,1H),7.80–7.78(m,2H),7.49(d,J=7.8Hz,1H),7.39–7.37(m,1H),7.08–6.96(m,4H),6.75–6.74(m,1H),3.80(s,3H)ppm.13C{1H}NMR(101MHz,DMSO-d6)δ:158.8,137.8,137.0,128.9,126.4,125.0,121.1,119.7,119.3,114.4,111.1,97.4,55.2ppm.
实施例26
实施例26所得产物的比移值Rf=0.56(石油醚:乙酸乙酯=20:1),产物的氢谱和碳谱核磁共振谱图分别为图26A和26B,谱图数据为:1H NMR(400MHz,DMSO-d6)δ:11.76(brs,1H),8.06(d,J=8.1Hz,2H),7.80(d,J=8.2Hz,2H),7.57(d,J=7.9Hz,1H),7.44(d,J=8.2Hz,1H),7.17–7.13(m,1H),7.07–7.01(m,2H)ppm.13C{1H}NMR(101MHz,DMSO-d6)δ:137.6,136.1,135.9,128.5,127.3(q,J2 C-F=31.9Hz),125.9(q,J3 C-F=4.0Hz),125.4,124.4(q,J1 C-F=272.8Hz),122.5,120.6,119.8,111.6,100.8ppm.
实施例27
实施例27所得产物的比移值Rf=0.46(石油醚:乙酸乙酯=20:1),产物的氢谱和碳谱核磁共振谱图分别为图27A和27B,谱图数据为:1H NMR(400MHz,CDCl3)δ:8.25(brs,1H),7.65–7.59(m,3H),7.41–7.39(m,1H),7.24–7.20(m,1H),7.17–7.12(m,3H),6.77(d,J=2.1Hz,1H)ppm.13C{1H}NMR(101MHz,CDCl3)δ:162.5(d,J1 C-F=248.6Hz),137.1,136.9,129.4,128.8(d,J4 C-F=3.3Hz),127.0(d,J3 C-F=8.1Hz),122.5,120.8,120.5,116.2(d,J2 C-F=21.8Hz),111.0,100.0(d,J5 C-F=1.3Hz)ppm.
实施例28
实施例28所得产物的比移值Rf=0.30(石油醚:乙酸乙酯=20:1),熔点Mp 298–300℃,产物的氢谱和碳谱核磁共振谱图分别为图28A和28B,谱图数据为:1H NMR(400MHz,DMSO-d6)δ:11.61(brs,1H),7.98–7.95(m,2H),7.80–7.73(m,4H),7.56–7.47(m,3H),7.44–7.36(m,2H),7.13–7.09(m,1H),7.03–6.96(m,2H)ppm.13C{1H}NMR(101MHz,DMSO-d6)δ:139.6,138.9,137.2,131.3,129.0,128.7,127.6,127.1,126.5,125.5,121.7,120.1,119.5,111.3,98.9ppm.One resonance was not observed due to overlappingresonances.IR(neat):3447,2922,2851,1667,1600,1448,1420,1345,837,795,764,746cm-1.HRMS:calcd for C20H16N[M+H]+270.1283,found 270.1288.
实施例29
实施例29所得产物的比移值Rf=0.27(石油醚:乙酸乙酯=20:1),产物的氢谱和碳谱核磁共振谱图分别为图29A和29B,谱图数据为:1H NMR(400MHz,CDCl3)δ:8.30(brs,1H),7.63–7.61(m,1H),7.36–7.30(m,2H),7.22–7.16(m,3H),7.13–7.09(m,1H),6.87–6.84(m,1H),6.81–6.80(m,1H),3.84(s,3H)ppm.13C{1H}NMR(101MHz,CDCl3)δ:160.2,137.9,136.9,133.9,130.2,129.3,122.5,120.8,120.4,117.8,113.2,111.10,111.06,100.3,55.5ppm.
实施例30
实施例30所得产物的比移值Rf=0.27(石油醚:乙酸乙酯=20:1),产物的氢谱和碳谱核磁共振谱图分别为图30A和30B,谱图数据为:1H NMR(400MHz,CDCl3)δ:8.36(brs,1H),7.67–7.64(m,1H),7.41–7.38(m,1H),7.24–7.20(m,1H),7.17–7.13(m,1H),6.84–6.82(m,3H),6.48–6.46(m,1H),3.87(s,6H)ppm.13C{1H}NMR(101MHz,CDCl3)δ:161.3,137.9,136.8,134.4,129.2,122.6,120.8,120.4,111.1,103.7,100.5,99.7,55.6ppm.
实施例31
实施例31所得产物的比移值Rf=0.51(石油醚:乙酸乙酯=20:1),产物的氢谱和碳谱核磁共振谱图分别为图31A和31B,谱图数据为:1H NMR(400MHz,CDCl3)δ:8.28(brs,1H),7.63(d,J=7.8Hz,1H),7.42–7.31(m,4H),7.24–7.19(m,1H),7.15–7.11(m,1H),7.03–6.98(m,1H),6.83(d,J=2.2Hz,1H)ppm.13C{1H}NMR(101MHz,CDCl3)δ:163.4(d,J1 C-F=247.0Hz),137.0,136.7(d,J7 C-F=2.9Hz),134.7(d,J5 C-F=8.2Hz),130.8(d,J4 C-F=8.5Hz),129.2,123.0,121.0,120.8(d,J6 C-F=2.9Hz),120.6,114.6(d,J3 C-F=21.4Hz),112.2(d,J2 C-F=23.0Hz),111.1,101.0ppm.
实施例32
实施例32所得产物的比移值Rf=0.41(石油醚:乙酸乙酯=20:1),产物的氢谱和碳谱核磁共振谱图分别为图32A和32B,谱图数据为:1H NMR(400MHz,CDCl3)δ:8.41(brs,1H),8.00–7.99(m,1H),7.87–7.76(m,4H),7.66–7.64(m,1H),7.51–7.44(m,2H),7.41–7.38(m,1H),7.23–7.12(m,2H),6.93–6.92(m,1H)ppm.13C{1H}NMR(101MHz,CDCl3)δ:138.0,137.1,133.7,133.0,129.8,129.5,128.9,128.1,127.9,126.8,126.3,123.9,123.1,122.7,120.9,120.5,111.1,100.8ppm.
实施例33
实施例33所得产物的比移值Rf=0.16(石油醚:乙酸乙酯=20:1),熔点Mp 206–208℃,产物的氢谱和碳谱核磁共振谱图分别为图33A和33B,谱图数据为:1H NMR(400MHz,CDCl3)δ:8.36(brs,1H),7.92–7.91(m,1H),7.65–7.56(m,2H),7.42–7.37(m,2H),7.20–7.10(m,3H),6.80(dd,J=1.0,2.1Hz,1H),6.55(dd,J=0.9,3.2Hz,1H),3.82(s,3H)ppm.13C{1H}NMR(101MHz,CDCl3)δ:139.8,136.8,136.6,130.0,129.8,129.0,124.2,121.7,120.4,120.1,120.0,117.6,110.8,110.0,101.5,98.7,33.1ppm.IR(neat):3407,3100,2942,2217,1560,1449,1340,1266,1243,1147,1080,892,801,731cm-1.HRMS:calcd for C17H15N2[M+H]+247.1235,found 247.1238.
实施例34
实施例34所得产物的比移值Rf=0.11(石油醚:乙酸乙酯=5:1),产物的氢谱和碳谱核磁共振谱图分别为图34A和34B,谱图数据为:1H NMR(400MHz,CDCl3)δ:8.95(brs,1H),8.66–8.65(m,2H),7.68–7.66(m,1H),7.57–7.55(m,2H),7.44–7.42(m,1H),7.28–7.24(m,1H),7.18–7.14(m,1H),7.06–7.05(m,1H)ppm.13C{1H}NMR(101MHz,CDCl3)δ:150.5,139.7,137.6,134.7,128.9,123.9,121.5,120.9,119.3,111.4,103.0ppm.
实施例35
实施例35所得产物的比移值Rf=0.27(石油醚:乙酸乙酯=20:1),产物的氢谱和碳谱核磁共振谱图分别为图35A和35B,谱图数据为:1H NMR(400MHz,CDCl3)δ:8.98(dd,J=0.8,2.3Hz,1H),8.83(brs,1H),8.56(dd,J=4.8,1.6Hz,1H),7.97–7.94(m,1H),7.65(d,J=8.0Hz,1H),7.44–7.41(m,1H),7.39–7.36(m,1H),7.25–7.21(m,1H),7.17–7.13(m,1H),6.91–6.90(m,1H)ppm.13C{1H}NMR(101MHz,CDCl3)δ:148.6,146.5,137.4,134.6,132.6,129.1,128.7,124.0,123.2,121.0,120.7,111.3,101.4ppm.
实施例36
实施例36所得产物的比移值Rf=0.66(石油醚:乙酸乙酯=20:1),产物的氢谱和碳谱核磁共振谱图分别为图36A和36B,谱图数据为:1H NMR(400MHz,CDCl3)δ:7.96(brs,1H),7.61–7.58(m,1H),7.36–7.34(m,1H),7.19–7.10(m,2H),6.31–6.30(m,1H),1.43(s,9H)ppm.13C{1H}NMR(101MHz,CDCl3)δ:148.9,135.9,128.6,121.2,120.1,119.7,110.5,97.1,31.9,30.4ppm.
实施例37
实施例37所得产物的比移值Rf=0.28(石油醚:乙酸乙酯=10:1),产物的氢谱和碳谱核磁共振谱图分别为图37A和37B,谱图数据为:1H NMR(400MHz,CDCl3)δ:9.90(brs,1H),8.60–8.58(m,1H),7.55–7.39(m,8H),7.36–7.34(m,1H),7.27–7.23(m,1H),7.11–7.07(m,2H)ppm.13C{1H}NMR(101MHz,CDCl3)δ:150.6,149.3,136.3,135.5,135.4,132.1,130.7,129.8,129.0,127.2,123.7,122.0,121.7,120.22,120.19,117.1,111.3ppm.IR(neat):3433,3205,3057,1591,1564,1495,1450,1329,1250,742,702cm-1.HRMS:calcd forC19H15N2[M+H]+271.1235,found 271.1232.
实施例38
实施例38所得产物的比移值Rf=0.23(石油醚:乙酸乙酯=5:1),熔点Mp 200–202℃,产物的氢谱和碳谱核磁共振谱图分别为图38A和38B,谱图数据为:1H NMR(400MHz,CDCl3)δ:8.75–8.74(m,1H),8.68(brs,1H),8.53–8.51(m,1H),7.69–7.66(m,2H),7.48–7.38(m,5H),7.34–7.16(m,4H)ppm.13C{1H}NMR(101MHz,CDCl3)δ:148.8,148.6,136.4,135.7,134.5,130.6,130.2,129.1,129.0,128.7,126.8,123.6,123.5,120.9,120.1,116.8,111.2ppm.IR(neat):3140,3056,1598,1547,1508,1457,1251,1044,774,702cm- 1.HRMS:calcd for C19H15N2[M+H]+271.1235,found 271.1232.
其他实施例如下所示:
实施例39
将实施例7中的式1的量更换为3mmol,式2的量更换为1mmol,CPME的量更换为1ml,二(三甲基硅基)氨基锂2mmol,氟化铯1mmol,其余的条件与实施例7相同,得到产物,收率为99%。
实施例40
将实施例7中的式1的量更换为3mmol,式2的量更换为1mmol,CPME的量更换为2ml,二(三甲基硅基)氨基锂2mmol,氟化铯1mmol,其余的条件与实施例7相同,得到产物,收率为87%。
实施例41
将实施例7中的式1的量更换为15mmol,式2的量更换为5mmol,CPME的量更换为5ml,二(三甲基硅基)氨基锂10mmol,氟化铯5mmol,其余的条件与实施例7相同,得到产物,收率为81%。
实施例42
将实施例3中的式1的量更换为15mmol,式2的量更换为5mmol,CPME的量更换为10ml,其余的条件与实施例3相同,得到产物,收率为81%。
实施例43
将实施例3中的式1的量更换为75mmol,式2的量更换为25mmol,CPME的量更换为50ml,其余的条件与实施例3相同,得到产物,收率为76%。
实施例44
将实施例10中的式1的量更换为5mmol,式2的量更换为20mmol,CPME的量更换为5ml,其余的条件与实施例10相同,得到产物,收率为80%。
实施例45
将实施例10中的式1的量更换为25mmol,式2的量更换为100mmol,CPME的量更换为25ml,其余的条件与实施例10相同,得到产物,收率为78%。
实施例46
将实施例11中的式1的量更换为15mmol,式2的量更换为5mmol,CPME的量更换为10ml,其余的条件与实施例11相同,得到产物,收率为55%。
实施例47
采用2-氟甲苯(0.15mmol),苯甲腈(0.1mmol),强碱二(三甲基硅基)氨基锂(0.1mmol),溶剂为环戊基甲基醚(1mL),三氟乙酸铯(0.1mmol),其他条件与实施例1相同,产物收率为2%。
实施例48
将实施例47中铯盐添加剂改为氟化铯(0.1mmol),其他条件不变,产物收率为46%。
实施例49
将实施例47中铯盐添加剂改为碳酸铯(0.1mmol),其他条件不变,产物收率为35%。
实施例50
在手套箱中将二(三甲基硅基)氨基铯也即CsHMDS(0.20mmol)加入微波管中,加入0.1mL环戊基甲基醚,然后用微量注射器分别加入2-氟甲苯(0.30mmol)和苯甲腈(0.10mmol),加盖从手套箱取出,在110℃下回流12小时,冷却至室温,启盖并加三滴水淬灭反应,减压去除溶剂,粗产品柱层析分离(石油醚:乙酸乙酯=20:1),即可得2-苯基吲哚,产率为88%。
实施例51
在手套箱中将二(三甲基硅基)氨基锂也即LiHMDS(0.20mmol)加入微波管中,加入0.1mL环戊基甲基醚,然后用微量注射器分别加入2-氟甲苯(0.30mmol)和苯甲腈(0.30mmol),加盖从手套箱取出,在90℃下回流12小时,冷却至室温,启盖并加三滴水淬灭反应,减压去除溶剂,粗产品柱层析分离(石油醚:乙酸乙酯=20:1),即可得2-苯基吲哚,产率为49%。
实施例52
将实施例51中的反应温度改为100℃,其他条件和原料不变,得到的产物产率为70%。
实施例53
将实施例51中的反应温度改为120℃,其他条件和原料不变,得到的产物产率为74%。
实施例54
将实施例51中的反应温度改为130℃,其他条件和原料不变,得到的产物产率为68%。
Claims (10)
2.根据权利要求1所述的合成方法,其特征在于,R1选自氢、苯基或单取代或多取代卤素基,R2选自氢或苯基,R3选自苯基,对叔丁基苯基或2-萘基。
3.根据权利要求1所述的合成方法,其特征在于,R1为氢,R2为苯基,R3为苯基。
4.根据权利要求1所述的合成方法,其特征在于,反应在惰性气体保护下进行。
5.根据权利要求4所述的合成方法,其特征在于,所述的惰性气体为氩气或氮气。
6.根据权利要求1所述的合成方法,其特征在于,反应中式2所示的腈类化合物、式1所示的2-氟甲苯类化合物、强碱和铯盐添加剂的摩尔比为:4:1~12:2~12:4~8,反应温度为90℃~130℃。
7.根据权利要求6所述的合成方法,其特征在于,所述反应温度为100℃~120℃。
8.根据权利要求7所述的合成方法,其特征在于,所述反应温度是110℃。
9.根据权利要求1所述的合成方法,其特征在于,所述的有机溶剂为环戊基甲基醚,二甲醚,四氢呋喃,1,4-二氧六环或异丙醚。
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