CN109320503B - 苯并咪唑炔胺类化合物的无金属一锅合成方法 - Google Patents

苯并咪唑炔胺类化合物的无金属一锅合成方法 Download PDF

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CN109320503B
CN109320503B CN201811501911.7A CN201811501911A CN109320503B CN 109320503 B CN109320503 B CN 109320503B CN 201811501911 A CN201811501911 A CN 201811501911A CN 109320503 B CN109320503 B CN 109320503B
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赵子剑
罗正红
朱桥
周博博
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Abstract

本发明涉及一种苯并咪唑炔胺类化合物的无金属一锅合成方法，包括如下步骤：在保护气体的氛围下，1‑R1甲酰甲基‑2‑R2基苯并咪唑类化合物、吡啶盐和有机碱在有机溶剂中进行反应，所述苯并咪唑炔胺类化合物具有通式2所示结构，所述1‑R1甲酰甲基‑2‑R2基苯并咪唑类化合物具有通式1所示结构，
Figure DDA0001898394590000011
其中，R1和R2分别独立地选自：H、烷基、取代的烷基、芳基、取代的芳基、杂芳基、取代的杂芳基；所述有机碱为分子中不含金属的胺类化合物。该方法不需要用到金属催化剂，反应条件温和，并且反应的产率高。

Description

苯并咪唑炔胺类化合物的无金属一锅合成方法
技术领域
本发明涉及化学合成技术领域，特别是涉及一种苯并咪唑炔胺类化合物的无金属一锅合成方法。
背景技术
苯并咪唑炔胺类化合物含有炔烃和苯并咪唑的基本结构，兼有这两类化合物的基本性质，是一类在有机合成、生物化学中非常重要的有机合成中间体。并且这类化合物兼具生物特性和光电导特性。
文献报道的有关苯并咪唑炔胺衍生物的合成方法主要是消除法，炔基异构化，炔基碘鎓盐偶联，金属催化等。这些方法都有一定的局限性：原料难以获取，金属盐对环境污染性较大或者步骤繁琐。因而，开发一种简洁、方便、具有广泛应用价值的苯并咪唑炔胺类化合物的新的合成法有着非常重要的理论和实际意义。
发明内容
基于此，本发明提供了一种新的苯并咪唑炔胺类化合物的合成方法，该方法不需要用到金属催化剂，反应条件温和，并且反应的产率高。
具体技术方案如下：
一种苯并咪唑炔胺类化合物的合成方法，包括如下步骤：
在保护气体的氛围下，1-R1甲酰甲基-2-R2基苯并咪唑类化合物、吡啶盐和有机碱在有机溶剂中进行反应，
所述苯并咪唑炔胺类化合物具有通式2所示结构，所述1-R1甲酰甲基-2-R2基苯并咪唑类化合物具有通式1所示结构，
Figure BDA0001898394570000011
其中，R1和R2分别独立地选自：H、烷基、取代的烷基、芳基、取代的芳基、杂芳基、取代的杂芳基；
所述有机碱为分子中不含金属的胺类化合物。
在其中一些实施例中，R1和R2分别独立地选自：C1-10烷基、取代的C1-10烷基、C6-10芳基、取代的C6-10芳基、C1-9杂芳基、取代的C1-9杂芳基。
在其中一些实施例中，R1和R2分别独立地选自：C6-10芳基、R4取代的C6-10芳基、C1-9杂芳基、R4取代的C1-9杂芳基；R4选自：卤素、C1-4烷基、C1-4烷氧基、苯基、硝基。
在其中一些实施例中，R1选自：苯基、卤素取代的苯基、甲基取代的苯基、甲氧基取代的苯基、3、4-二亚甲氧基苯基、联苯基、萘基、甲氧基取代的萘基、呋喃基、噻吩基、C1-4烷基；R2选自：H、C1-4烷基、呋喃基、苯基、卤素取代的苯基、甲基取代的苯基、甲氧基取代的苯基、3、4-二亚甲氧基苯基、硝基取代的苯基。
在其中一些实施例中，所述吡啶盐选自2-氯-1-甲基碘化吡啶、1，2-二甲基碘化吡啶中的至少一种。
在其中一些实施例中，所述有机碱为三乙胺。
在其中一些实施例中，所述有机溶剂选自二氯甲烷、二氯乙烷中的至少一种。
在其中一些实施例中，所述1-R1甲酰甲基-2-R2基苯并咪唑类化合物、所述吡啶盐和所述有机碱的摩尔比为：1:0.8-1.2:0.8-1.2。
在其中一些实施例中，所述反应的温度为10-40℃。
在其中一些实施例中，所述反应的时间为2-4小时。
在其中一些实施例中，所述保护气体为氮气。
本发明的新的苯并咪唑炔胺类化合物的合成方法与过去已经报道的方法相比，具有以下优点和有益效果：
(1)实用性好，反应条件温和，为室温反应，易于实现含有各种不同取代基组合的苯并咪唑炔胺类化合物的制备；(2)反应收率高(利用本发明的方法以不小于90％的收率制备得到了一系列苯并咪唑炔胺类化合物)，并且反应操作简便，为一锅法反应，不需要对中间体进行分离，且目标化合物易分离和提纯；(3)原料廉价易得，不需要使用各种昂贵的芳炔试剂和金属催化剂。
附图说明
图1为化合物2a的1HNMR图谱；
图2为化合物2b的1HNMR图谱；
图3为化合物2c的1HNMR图谱；
图4为化合物2d的1HNMR图谱；
图5为化合物2e的1HNMR图谱；
图6为化合物2f的1HNMR图谱；
图7为化合物2g的1HNMR图谱；
图8为化合物2h的1HNMR图谱；
图9为化合物2i的1HNMR图谱；
图10为化合物2j的1HNMR图谱；
图11为化合物2k的1HNMR图谱；
图12为化合物2l的1HNMR图谱；
图13为化合物2m的1HNMR图谱；
图14为化合物2n的1HNMR图谱；
图15为化合物2o的1HNMR图谱；
图16为化合物2p的1HNMR图谱；
图17为化合物2q的1HNMR图谱；
图18为化合物2r的1HNMR图谱；
图19为化合物2s的1HNMR图谱；
图20为化合物2t的1HNMR图谱；
图21为化合物2u的1HNMR图谱；
图22为化合物2v的1HNMR图谱；
图23为化合物2w的1HNMR图谱。
具体实施方式
以下结合具体的实施例对本发明做进一步详细的说明。
以下实施例的苯并咪唑炔胺类化合物的制备方法如下：
Figure BDA0001898394570000031
1)在氮气保护下，1-R1甲酰甲基-2-R2基苯并咪唑类化合物(化合物1，1.0mmol)，Mukaiyama试剂(1，2-二甲基碘化吡啶(DMPI))(1.0mmol)、三乙胺(1.0mmol)加入5.0mL二氯甲烷中，搅拌反应3小时。
2)用饱和氯化铵溶液猝灭反应，将混合液注入水中，用乙酸乙酯萃取，有机相用饱和食盐水洗涤，无水硫酸钠干燥，过滤后减压蒸除溶剂；残余物通过硅胶柱层析分离，淋洗液为[石油醚：乙酸乙酯＝5:1]，得苯并咪唑炔胺类化合物(化合物2)。
实施例1
2-(2-呋喃基)-1-(2-苯乙炔基)-1H-苯并咪唑，2-(2-Furanyl)-1-(2-phenylethynyl)--1H-benzimidazole(2a):白色固体,m.p.:100-101℃.产率:92％(127mg).
Figure BDA0001898394570000041
1H-NMR(400MHz,d6-DMSO)(ppm):8.08(s,1H),7.76(d,J＝7.4Hz,1H),7.70(s,3H),7.55(s,1H),7.47(s,3H),7.44–7.34(m,2H),6.80(s,1H).13C-NMR(100MHz,d6-DMSO)(ppm):146.1,143.8,142.8,141.5,135.2,131.4,129.2,128.9,124.8,124.7,120.7,120.0,113.8,112.5,110.9,76.8,75.4.IR(neat)(cm-1):3056,2260,1621,1516,1456,1436,1417,1315,1259,1229,1177,1139,1017,741,689.MS(EI)m/z(％):77.1(5),89.1(1.5),102.1(3),128.1(8),142.1(4),255.1(100),284.1(M+,85).HRMS(EI):calcd.for[C19H12ON2]+:284.0942,Found 284.0944.
实施例2
2-(2-呋喃基)-1-(2-对甲苯基乙炔基)-1H-苯并咪唑，2-(2-Furanyl)-1-(2-(4-methylphenyl)ethynyl)-1H-benzimid-azole(2b):白色固体,m.p.:128-129℃.产率:90％(125mg).
Figure BDA0001898394570000042
1H-NMR(400MHz,CDCl3)(ppm):7.85(dd,J＝5.9,3.1Hz,1H),7.71(s,1H),7.65(dd,J＝6.0,3.1Hz,1H),7.56(dd,J＝8.6,5.9Hz,3H),7.44–7.37(m,2H),7.29(s,3H),2.45(s,3H).13C-NMR(100MHz,CDCl3)(ppm):145.1,144.8,143.9,142.2,139.6,136.0,132.0,129.6,124.7,124.6,120.6,118.5,113.3,112.1,111.0,77.4,76.1,21.7.IR(neat)(cm-1):3056,2930,2836,2258,1620,1517,1460,1458,1440,1390,1313,1260,1116,1017,741.MS(EI)m/z(％):77.1(6),91.1(4),102.1(10),115.1(15),140.1(9),207.1(8),255.2(43),269.2(80),298.2(M+,100).HRMS(EI):calcd.for[C20H14ON2]+:298.1106,Found 298.1109.
实施例3
2-(2-呋喃基)-1-(2-邻甲苯基乙炔基)-1H-苯并咪唑，2-(2-Furanyl)-1-(2-(2-methylphenyl)ethynyl)-1H-benzimid-azole(2c):白色固体,m.p.:116-118℃.产率:91％(128mg).
Figure BDA0001898394570000051
1H-NMR(400MHz,CDCl3)(ppm):7.75(dd,J＝5.9,3.0Hz,1H),7.61(s,1H),7.53(m,3H),7.35–7.28(m,2H),7.25(dd,J＝6.4,1.2Hz,2H),7.20–7.15(m,1H),6.54(dd,J＝3.5,1.7Hz,1H),2.52(s,3H).13C-NMR(100MHz,CDCl3)(ppm):145.1,144.6,143.9,142.2,140.4,136.0,132.3,130.0,129.2,126.1,124.72,124.70,121.5,120.6,113.4,112.1,110.9,80.9,74.8,21.1.IR(neat)(cm-1):3056,2923,2853,2251,1622,1517,1473,1457,1436,1398,1314,1259,1110,1016,741.MS(EI)m/z(％):77.1(9),91.1(2),102.1(7),115.1(8),140.1(6),207.1(5),255.2(39),269.2(89),283.1(23),298.2(M+,100).HRMS(EI):calcd.for[C20H14ON2]+:298.1106,Found298.1101.
实施例4
2-(2-呋喃基)-1-(2-对甲氧基苯基乙炔基)-1H-苯并咪唑，2-(2-Furanyl)-1-(2-(4--methoxyphenyl)ethynyl)-1H-benzimi-dazole(2d):淡黄色固体,m.p.:156-158℃.产率:92％(129mg).
Figure BDA0001898394570000052
1H-NMR(400MHz,CDCl3)(ppm):7.82(dd,J＝5.0,3.9Hz,1H),7.68(s,1H),7.64–7.60(m,1H),7.59–7.55(m,2H),7.54(d,J＝3.5Hz,1H),7.40–7.34(m,2H),6.95(d,J＝8.8Hz,2H),6.60(dd,J＝3.5,1.7Hz,1H),3.87(s,3H).13C-NMR(100MHz,CDCl3)(ppm):160.5,145.0,144.8,143.9,142.7,142.1,136.0,133.8,124.61,124.57,120.5,114.5,113.4,113.3,112.1,111.0,76.1,75.9,55.6.IR(neat)(cm-1):2935,2836,2259,1605,1515,1456,1436,1418,1291,1250,1174,1027,830,741.MS(EI)m/z(％):76.1(9),89.1(2),102.1(7),242.1(39),255.1(14),271.1(8),285.1(6),299.1(5),314.1(M+,100).HRMS(EI):calcd.for[C20H14O2N2]+:314.1055,Found314.1050.
实施例5
2-(2-呋喃基)-1-[2-(2,5-二甲氧基苯基)乙炔基]-1H-苯并咪唑，2-(2-Furanyl)-1-(2-(2,5--dimethoxyphenyl)ethynyl)-1H-ben-zimidazole(2e):淡黄色固体,m.p.:135-136℃.产率:91％(140mg).
Figure BDA0001898394570000061
1H-NMR(400MHz,CDCl3)(ppm):7.87(d,J＝3.6Hz,1H),7.82(dd,J＝7.2,1.4Hz,1H),7.70–7.68(m,1H),7.66(dd,J＝7.5,1.6Hz,1H),7.40–7.35(m,2H),7.09(d,J＝2.8Hz,1H),6.94–6.88(m,2H),6.62(dd,J＝3.6,1.7Hz,1H),3.92(s,3H),3.82(s,3H).13C-NMR(100MHz,CDCl3)(ppm):154.7,153.6,145.1,144.7,143.8,142.2,135.9,124.7,124.6,120.5,118.1,116.0,113.6,112.1,112.0,111.6,111.1,80.9,73.0,56.4,56.1.IR(neat)(cm-1):1745,1542,1516,1502,1488,1457,1434,1275,1224,1121,759,744,592.MS(EI)m/z(％):75(3.5),102(5),161(3),195(2.5),242(6),286(11),301(12),315(11),329(61),344(M+,100).HRMS(EI):calcd.for[C21H16O3N2]+:344.1161,Found 344.1155.
实施例6
2-(2-呋喃基)-1-(2-(3,4-亚甲二氧苯基)乙炔基)-1H-苯并咪唑，2-(2-Furanyl)-1-(2--(3,4-methylenedioxyphenyl)ethynyl)-1H-benzoimidazole(2f):类白色固体,m.p.:146–148℃.产率:96％(143mg).
Figure BDA0001898394570000062
1H-NMR(400MHz,CDCl3)(ppm):7.81(dd,J＝5.7,3.2Hz,1H),7.68(d,J＝1.2Hz,1H),7.63–7.58(m,1H),7.51(d,J＝3.5Hz,1H),7.41–7.35(m,2H),7.16(dd,J＝8.0,1.6Hz,1H),7.06(d,J＝1.5Hz,1H),6.86(d,J＝8.0Hz,1H),6.61(dd,J＝3.5,1.8Hz,1H),6.04(s,2H).13C-NMR(100MHz,CDCl3)(ppm):148.9,147.9,145.1,144.8,143.8,142.1,135.9,127.1,124.7,124.6,120.6,114.6,113.3,112.1,112.0,111.0,108.9,101.7,77.4,75.9；IR(neat)(cm-1):2898,2257,1516,1505,1458,1448,1434,1405,1241,1121,1036,741,592；MS(EI)m/z(％):75.1(6),102.1(4),146.1(10),164.1(9),190.1(12),293.1(100),328.1(M+,57)；HRMS(EI):calcd.for[C20H12O3N2]+:328.0848,found 328.0862.
实施例7
2-(2-呋喃基)-1-(2-对氟苯基乙炔基)-1H-苯并咪唑，2-(2-Furanyl)-1-(2-(4-fluorophenyl)-ethynyl)-1H-benzimidazole(2g):淡黄色固体,m.p.:97–98℃.产率:95％(133mg).
Figure BDA0001898394570000071
1H-NMR(400MHz,CDCl3)(ppm):7.82(dd,J＝5.1,3.8Hz,1H),7.68(d,J＝1.2Hz,1H),7.65–7.58(m,3H),7.50(d,J＝3.4Hz,1H),7.42–7.35(m,2H),7.13(t,J＝8.7Hz,2H),6.61(dd,J＝3.5,1.8Hz,1H).13C-NMR(100MHz,CDCl3)(ppm):164.4,161.9,145.1,144.7,143.8,142.1,135.8,134.1,134.0,124.8,124.7,120.6,117.62,117.58,116.3,116.1,113.3,112.1,110.9,77.5,77.2,77.0,76.8,74.9.IR(neat)(cm-1):3057,2260,1748,1715,1621,1600,1541,1515,1456,1435,1417,1339,1229,835,741.MS(EI)m/z(％):102(3.5),107(5),208(3),273(2.5),302(M+,100).HRMS(EI):calcd.for[C19H11ON2F]+:302.0855,found 302.0850.
实施例8
2-(2-呋喃基)-1-(2-对氯苯基乙炔基)-1H-苯并咪唑，2-(2-Furanyl)-1-(2-(4-chlorophenyl)-ethynyl)-1H-benzimid-azole(2h):类白色固体,m.p.:98-100℃.产率:96％(139mg).
Figure BDA0001898394570000072
1H-NMR(400MHz,CDCl3)(ppm):7.82(dd,J＝4.9,4.1Hz,1H),7.68(d,J＝1.1Hz,1H),7.63–7.58(m,1H),7.54(d,J＝8.5Hz,2H),7.49(d,J＝3.5Hz,1H),7.39(dd,J＝10.5,6.1Hz,4H),6.61(dd,J＝3.5,1.8Hz,1H).13C-NMR(100MHz,CDCl3)(ppm):145.2,144.6,143.7,142.2,135.7,135.4,133.1,129.2,124.8,124.7,120.6,120.1,113.3,112.1,110.9,78.1,74.8.IR(neat)(cm-1):3054,2260,1521,1591,1516,1455,1437,1417,1315,1258,1138,1092,1015,824,741.MS(EI)m/z(％):75.1(3.5),87.1(5),102.1(3),136.1(2.5),255.1(88),283.1(61),289.1(51),318.1(M+,100).HRMS(EI):calcd.for[C19H11ON2Cl]+:318.0560,found 318.0554.
实施例9
2-(2-呋喃基)-1-(2-对溴苯基乙炔基)-1H-苯并咪唑，2-(2-Furanyl)-1-(2-(4-bromophenyl)ethynyl)-1H-benzimid-azole(2i):淡黄色固体,m.p.:111-112℃.产率:92％(149mg).
Figure BDA0001898394570000073
1H-NMR(400MHz,CDCl3)(ppm):7.82(dd,J＝5.2,3.9Hz,7H),7.68(d,J＝1.6Hz,7H),7.64–7.52(m,22H),7.48(t,J＝5.7Hz,21H),7.43–7.29(m,15H),7.26(s,2H),6.62(dd,J＝3.3,1.5Hz,7H).13C-NMR(100MHz,CDCl3)(ppm):145.2,144.6,143.7,142.2,135.7,133.3,132.1,124.9,124.8,123.6,120.6,120.5,113.4,112.1,110.9,78.3,74.9.IR(neat)ν(cm-1):3054,2259,1621,1586,1516,1455,1437,1416,1315,1258,1138,1066,1009,820,756,741.MS(EI)m/z(％):76.1(5),88.2(7),127.6(25),255.2(100),283.1(48),335.1(23),362.1(M+,66).HRMS(EI):calcd.for[C19H11ON2Br]+:362.0050,found362.0049.
实施例10
2-(2-呋喃基)-1-(2-对碘苯基乙炔基)-1H-苯并咪唑，2-(2-Furanyl)-1-(2-(4-iodo--phenyl)ethynyl)-1H-benzimidazole(2j):类白色固体,m.p.:121–122℃.产率:90％(162mg).
Figure BDA0001898394570000081
1H-NMR(400MHz,CDCl3)(ppm):7.82(dd,J＝5.0,3.9Hz,1H),7.77(d,J＝8.4Hz,2H),7.69(d,J＝1.2Hz,1H),7.60(dd,J＝5.8,3.2Hz,1H),7.49(d,J＝3.3Hz,1H),7.42–7.36(m,2H),7.34(d,J＝8.4Hz,2H),6.62(dd,J＝3.5,1.8Hz,1H).13C-NMR(100MHz,CDCl3)(ppm):145.2,144.6,143.7,142.2,138.0,135.7,133.3,124.9,124.8,121.1,120.7,113.4,112.1,110.9,95.2,78.5,75.1.IR(neat)ν(cm-1):3054,2258,1747,1715,1621,1584,1516,1455,1436,1417,1406,1315,1258,1138,1005,817,741；MS(EI)m/z(％):77(3.5),88(5),102(3),127(11),255(57),318(4),381(12),283(2.5),410(M+,100)；HRMS(EI):calcd.for[C19H11ON2I]+:409.9916,found409.9911.
实施例11
2-(2-呋喃基)-1-[2-(2-萘基)乙炔基]-1H-苯并咪唑，2-(2-Furanyl)-1-(2-(2-naphthyl)-ethynyl)-1H-benzimidazole(2k):淡黄色固体,m.p.:118–120℃.产率:90％(134mg).
Figure BDA0001898394570000082
1H-NMR(400MHz,CDCl3)(ppm):8.14(s,1H),7.90–7.83(m,4H),7.70–7.63(m,3H),7.60(d,J＝3.5Hz,1H),7.55(dd,J＝6.2,3.2Hz,2H),7.43–7.37(m,2H),6.63(dd,J＝3.5,1.7Hz,1H).13C-NMR(100MHz,CDCl3)(ppm):145.1,144.7,143.8,142.2,135.9,133.2,133.1,132.0,128.6,128.2,128.0,127.9,127.3,127.0,124.8,124.7,120.6,118.8,113.4,112.1,111.0,77.5,76.4.IR(neat)ν(cm-1):3057,2377,1868,1748,1733,1697,1683,1670,1653,1647,1635,1558,1541,1521,1507,1489,1473,1457,1339,742,687.MS(EI)m/z(％):77.1(7),127.1(5.5),139.1(7.5),152.1(13),255.1(12),305(100),318.1(11),334.1(M+,84).HRMS(EI):calcd.for[C23H14ON2]+:334.1106,found 334.1101.
实施例12
2-(2-呋喃基)-1-[2-(6-甲氧基-2-萘基)乙炔基]-1H-苯并咪唑，2-(2-Furanyl)-1-(2-(6-methoxy-2-naphthyl)ethynyl)-1H-benzimidazole(2l):淡黄色固体,m.p.:140–141℃.产率:92％(149mg).
Figure BDA0001898394570000091
1H-NMR(400MHz,CDCl3)(ppm):8.07(s,1H),7.84(dd,J＝5.9,2.9Hz,1H),7.77(dd,J＝8.7,3.0Hz,2H),7.70(d,J＝1.1Hz,1H),7.67(dd,J＝6.1,2.9Hz,1H),7.64–7.58(m,2H),7.43–7.35(m,2H),7.21(dd,J＝8.9,2.5Hz,1H),7.15(d,J＝2.3Hz,1H),6.62(dd,J＝3.5,1.7Hz,1H),3.95(s,3H).13C-NMR(100MHz,CDCl3)(ppm):158.8,145.1,144.7,143.8,142.2,135.9,134.7,132.0,129.5,129.0,128.6,127.3,124.7,124.6,120.6,119.9,116.2,113.3,112.1,111.0,106.0,77.4,76.5,55.5.IR(neat)ν(cm-1):3056,2937,2248,1629,1602,1515,1489,1456,1436,1391,1314,1266,1256,1222,1202,1118,1029,1018,925,885,852,757,741.MS(EI)m/z(％):76.1(6),126.1(7),182.1(11),267.1(4),292.1(47),305.1(13),321.1(37),335.1(33),349.1(18),364.1(M+,100).HRMS(EI):calcd.for[C24H16O2N2]+:364.1212,found 364.1206.
实施例13
2-(2-呋喃基)-1-(2-噻吩基乙炔基)-1H-苯并咪唑，2-(2-Furanyl)-1-(2-thiophenylethynyl)-1H-benzimidazole(2m):类白色固体,m.p.:123–124℃.产率:91％(122mg).
Figure BDA0001898394570000092
1H-NMR(400MHz,CDCl3)(ppm):7.82(dd,J＝6.1,3.0Hz,1H),7.67(d,J＝1.5Hz,1H),7.60(dd,J＝6.2,3.0Hz,1H),7.49(d,J＝3.5Hz,1H),7.45–7.41(m,2H),7.41–7.34(m,2H),7.11–7.07(m,1H),6.60(dd,J＝3.4,1.6Hz,1H).13C-NMR(100MHz,CDCl3)(ppm):145.2,144.8,143.6,142.1,135.8,133.9,129.1,127.5,124.8,124.8,121.3,120.6,113.5,112.1,111.0,80.5,69.6.IR(neat)ν(cm-1):3103,2248,1621,1516,1458,1444,1399,1386,1314,1312,1255,1229,1174,1124,1106,1016,927,852,758,741,705,591.MS(EI)m/z(％):76(11),196(5),207(4),236(6),261(97),290(M+,100).HRMS(EI):calcd.for[C17H10ON2S]+:290.0514,found 290.0508.
实施例14
2-(2-呋喃基)-1-(3,3-二甲基丁炔基)-1H-苯并咪唑，2-(2-Furanyl)-1-(3,3-dimethyl-1--butyn-1-yl)-1H-benzimidazole(2n):类白色固体,m.p.:92-94℃；产率:90％(112mg).
Figure BDA0001898394570000101
1H-NMR(400MHz,CDCl3)(ppm):7.78(dd,J＝6.3,2.7Hz,1H),7.65(d,J＝1.6Hz,1H),7.49(dd,J＝5.2,2.9Hz,2H),7.33–7.35(m,2H),6.60(dd,J＝3.5,1.7Hz,1H),1.44(s,9H).13C-NMR(100MHz,CDCl3)(ppm):144.8,144.7,144.0,142.0,136.1,124.33,124.31,120.4,112.8,111.8,110.7,84.1,68.1,31.1,28.0.IR(neat)ν(cm-1):2964,2376,1868,1772,1716,1697,1653,1647,1558,1541,1521,1516,1507,1473,1457,1436,1418,1339,744.MS(EI)m/z(％):77(11),117(53),128(3),140(8),208(29),221(22),234(10),249(51),264(M+,100).HRMS(EI):calcd.for[C17H16ON2]+:264.1263,found 264.1257.
实施例15
2-丙基-1-(苯基乙炔基)-1H-苯并咪唑,2-propyl-1-(phenylethynyl)-1H-benzimidazole(2o):无色油状物.产率:91％(119mg).
Figure BDA0001898394570000102
1H-NMR(400MHz,CDCl3)(ppm):7.74(dd,J＝6.4,2.4Hz,1H),7.62–7.53(m,3H),7.45–7.38(m,3H),7.36–7.30(m,2H),3.06(t,J＝7.5Hz,2H),2.00(dd,J＝15.0,7.5Hz,2H),1.10(t,J＝7.4Hz,3H).13C-NMR(100MHz,CDCl3)(ppm):157.0,141.8,135.5,131.8,129.7,129.0,128.7,123.9,123.8,121.8,119.8,115.7,110.7,76.5,76.0,30.0,20.9,14.0.IR(neat)ν(cm-1):3056,2962,2931,2872,2256,1683,1616,1541,1521,1507,1457,1409,1247,1202,743,690.MS(EI)m/z(％):77.0(34),89.0(30),115.0(33),132.1(100),143.0(39),171.0(55),186.1(26),218.1(28),231.1(43),245.1(55),260.1(M+,52).HRMS(EI):calcd.for[C18H16N2]+:260.1313,found260.1308.
实施例16
2-苯基-1-(苯基乙炔基)-1H-苯并咪唑，2-Phenyl-1-(phenylethynyl)-1H-benzimidazole(2p):类白色固体,m.p.:78–80℃.产率:91％(119mg).
Figure BDA0001898394570000111
1H-NMR(400MHz,d6-DMSO)(ppm):8.23(dd,J＝5.8,2.2Hz,2H),7.81(d,J＝7.6Hz,1H),7.74(d,J＝7.8Hz,1H),7.63–7.57(m,5H),7.47–7.37(m,5H).13C-NMR(100MHz,d6-DMSO)(ppm):152.1,141.6,136.1,131.3,131.0,129.2,128.92,128.88,128.5,128.3,124.8,124.6,120.8,120.1,111.2,77.5,75.3.IR(neat)ν(cm-1):3056,2258,1683,1653,1540,1521,1507,1488,1474,1457,1444,1404,1307,1275,1140,757,741,689.MS(EI)m/z(％):77.1(4),89.1(3),190.1(11),217.1(4),294.2(M+,100).HRMS(EI):calcd.for[C21H14N2]+:294.1157,found294.1152.
实施例17
2-(4-甲基苯基)-1-(2-苯基乙炔基)-1H-苯并咪唑，2-(4-Methylphenyl)-1--(2-phenylethynyl)-1H-benzimidazole(2q):类白色固体,m.p.:80–81℃.产率:90％(131mg).
Figure BDA0001898394570000112
1H-NMR(400MHz,d6-DMSO)(ppm):8.12(d,J＝8.0Hz,2H),7.78(d,J＝7.6Hz,1H),7.72(d,J＝7.7Hz,1H),7.64–7.57(m,2H),7.47–7.35(m,7H),2.37(s,3H).13C-NMR(100MHz,d6-DMSO)(ppm):152.2,141.7,141.0,136.0,131.3,129.4,129.2,128.9,128.4,125.6,124.6,124.5,120.9,119.9,111.1,77.6,75.2,21.1.IR(neat)ν(cm-1):3035,2910,2257,1716,1697,1683,1652,1647,1558,1541,1507,1489,1521,1473,1456,1397,741,689.MS(EI)m/z(％):89.1(3),91.1(2),190.1(6),293.1(35),308.2(M+,100).HRMS(EI):calcd.for[C22H16N2]+:308.1313,found308.1308.
实施例18
2-(4-甲氧基苯基)-1-(2-苯基乙炔基)-1H-苯并咪唑，2-(4-Methoxyphenyl)-1--(phenylethynyl)-1H-benzimidazole(2r):类白色固体,m.p.:100–101℃.产率:91％(141mg).
Figure BDA0001898394570000113
1H-NMR(400MHz,d6-DMSO)(ppm):8.23(d,J＝7.8Hz,2H),7.75(dd,J＝16.9,7.6Hz,2H),7.67–7.60(m,2H),7.46(s,3H),7.40(dd,J＝15.4,7.8Hz,2H),7.17(d,J＝7.8Hz,2H),3.85(s,3H).13C-NMR(100MHz,d6-DMSO)(ppm):161.4,152.0,141.7,136.0,131.3,130.1,129.1,128.9,124.5,124.3,120.9,120.6,119.7,114.3,111.0,77.7,75.2,55.5.IR(neat)ν(cm-1):2931,2829,2256,1716,1683,1653,1647,1558,1541,1521,1507,1473,1456,1418,1398,1254,1175,756,742.MS(EI)m/z(％):77(6),89(3),140(13),164(10),224(2),281(59),293(17),309(36),324(M+,100).HRMS(EI):calcd.for[C22H16ON2]+:324.1263,found324.1257.
实施例19
2-(3,4-亚甲二氧基苯基)-1-(2-苯基乙炔基)-1H-苯并咪唑，2-(3,4-Methylenedi--oxyphenyl)-1-(phenylethynyl)-1H-benzimidazole(2s):类白色固体,m.p.:117–118℃.产率:92％(139mg).
Figure BDA0001898394570000121
1H-NMR(400MHz,d6-DMSO)(ppm):7.84(d,J＝7.6Hz,1H),7.76(d,J＝7.5Hz,1H),7.72(d,J＝7.3Hz,2H),7.62(s,2H),7.46(d,J＝2.0Hz,3H),7.43–7.35(m,2H),7.16(d,J＝8.1Hz,1H),6.15(s,2H).13C-NMR(100MHz,d6-DMSO)(ppm):151.8,149.6,147.7,141.5,136.0,131.3,129.2,128.9,124.52,124.48,123.3,122.0,120.8,119.8,111.1,108.6,108.3,101.9,77.6,75.4.IR(neat)ν(cm-1):3056,2898,2256,1540,1521,1506,1498,1473,1457,1404,1308,1271,1256,1235,1039,989,741.MS(EI)m/z(％):77(7),89(3),105(5),140(18),163(6),279(63),292(2),308(31),338(M+,100).HRMS(EI):calcd.for[C22H14O2N2]+:338.1055,found338.1050.
实施例20
2-(4-氯苯基)-1-(2-苯基乙炔基)-1H-苯并咪唑，2-(4-Chlorophenyl)-1-(2-phen--ylethynyl)-1H-benzimidazole(2t):类白色固体,m.p.:106–107℃.产率:92％(135mg).
Figure BDA0001898394570000122
1H-NMR(400MHz,d6-DMSO)(ppm):8.26(d,J＝7.4Hz,2H),7.80(dd,J＝14.9,7.8Hz,2H),7.71(d,J＝7.5Hz,2H),7.64(d,J＝2.2Hz,2H),7.51–7.39(m,5H).13C-NMR(100MHz,d6-DMSO)(ppm):151.0,141.5,136.1,135.9,131.3,130.3,129.3,129.1,128.9,127.2,125.0,124.7,120.7,120.2,111.3,77.3,75.6.IR(neat)ν(cm-1):2962,2919,2849,2258,1653,1647,1535,1558,1521,1507,1473,1456,1417,1410,1260,1092,1015,800,731,687.MS(EI)m/z(％):75.1(5),89.1(3),102.1(4),190.1(12),293.1(100),328.1(M+,58).HRMS(EI):calcd.for[C21H13N2Cl]+:328.0767,found328.0762.
实施例21
2-(4-硝基苯基)-1-(2-苯基乙炔基)-1H-苯并咪唑，2-(4-Nitrophenyl)-1--(phenylethynyl)-1H-benzimidazole(2u):无色油状物.产率:90％(132mg).
Figure BDA0001898394570000131
1H-NMR(400MHz,CDCl3)(ppm):8.54(d,J＝8.9Hz,2H),8.40(d,J＝8.8Hz,2H),7.88(d,J＝7.4Hz,1H),7.71(d,J＝7.9Hz,1H),7.56(dd,J＝6.6,3.0Hz,2H),7.51–7.38(m,5H).13C-NMR(100MHz,CDCl3)(ppm):150.2,148.9,142.2,137.0,135.0,131.8,129.6,129.5,128.9,125.6,125.1,124.0,121.1,121.0,111.5,77.4,76.6.IR(neat)ν(cm-1):2919,2838,2376,1716,1697,1683,1652,1647,1558,1540,1521,1507,1456,855,733.MS(EI)m/z(％):77.1(4),89.1(2),118.1(1),190.1(14),215.1(2),292.2(100),309.2(30),322.2(7),339.2(M+,78).HRMS(EI):calcd.for[C21H13O2N3]+:339.1008,found339.1002.
实施例22
2-(3-硝基苯基)-1-(2-苯基乙炔基)-1H-苯并咪唑，2-(3-Nitrophenyl)-1-(pheny-lethynyl)-1H-benzimidazole(2v):类白色固体,m.p.:152–153℃.产率:90％(129mg).
Figure BDA0001898394570000132
1H-NMR(400MHz,CDCl3)(ppm):9.38(d,J＝1.7Hz,1H),8.66(dd,J＝7.8,1.0Hz,1H),8.38(dd,J＝8.2,0.9Hz,1H),7.86(d,J＝7.5Hz,1H),7.77–7.68(m,2H),7.65–7.58(m,2H),7.50–7.38(m,5H).13C-NMR(100MHz,CDCl3)(ppm):149.9,148.4,142.0,134.7,131.7,130.8,130.0,129.3,128.8,125.4,125.2,125.0,123.3,121.2,120.8,111.5,77.1,76.9.IR(neat)ν(cm-1):2816,2850,2376,1716,1683,1653,1647,1558,1540,1533,1521,1507,1473,1456,736,689.MS(EI)m/z(％):76.1(5),89.1(4),105.1(26),190.1(22),215.1(3),292.2(100),305.2(34),322.2(6),339.2(M+,95).HRMS(EI):calcd.for[C21H13O2N3]:339.1008,found339.1002.
实施例23
1-(2-苯基乙炔基)-1H-苯并咪唑，1-(Phenylethynyl)-1H-benzimidazole(2w):无色油装物.产率:90％(51mg).
Figure BDA0001898394570000143
1H-NMR(400MHz,CDCl3)(ppm):8.16(s,1H),7.84(d,J＝7.7Hz,1H),7.70–7.63(m,1H),7.63–7.55(m,2H),7.47–7.35(m,5H).13C-NMR(100MHz,CDCl3)(ppm):143.7,142.1,134.7,131.9,129.1,128.7,124.9,124.2,121.5,121.0,111.1,77.4,73.7.IR(neat)ν(cm-1):3056,2956,2925,2852,2258,1614,1540,1505,1490,1476,1456,1403,1296,1283,1244,1170,1144,778,742,689,590.MS(EI)m/z(％):90.0(7),116.0(7),190.1(17),218.1(M+,100).HRMS(EI):calcd.for[C15H10N2]+:218.0844,found218.0838.
实施例1-实施例23的产物收率如下表所示：
Figure BDA0001898394570000141
Figure BDA0001898394570000142
Figure BDA0001898394570000151
以上所述实施例的各技术特征可以进行任意的组合，为使描述简洁，未对上述实施例中的各个技术特征所有可能的组合都进行描述，然而，只要这些技术特征的组合不存在矛盾，都应当认为是本说明书记载的范围。
以上所述实施例仅表达了本发明的几种实施方式，其描述较为具体和详细，但并不能因此而理解为对发明专利范围的限制。应当指出的是，对于本领域的普通技术人员来说，在不脱离本发明构思的前提下，还可以做出若干变形和改进，这些都属于本发明的保护范围。因此，本发明专利的保护范围应以所附权利要求为准。

Claims (5)

1.一种苯并咪唑炔胺类化合物的合成方法，其特征在于，包括如下步骤：
在保护气体的氛围下，1-R1甲酰甲基-2-R2基苯并咪唑类化合物、吡啶盐和有机碱在有机溶剂中进行反应，
所述苯并咪唑炔胺类化合物具有通式2所示结构，所述1-R1甲酰甲基-2-R2基苯并咪唑类化合物具有通式1所示结构，
Figure FDA0003079444810000011
其中，R1选自：苯基、卤素取代的苯基、甲基取代的苯基、甲氧基取代的苯基、3、4-二亚甲氧基苯基、萘基、甲氧基取代的萘基、呋喃基、噻吩基、C1-4烷基；R2选自：H、C1-4烷基、呋喃基、苯基、卤素取代的苯基、甲基取代的苯基、甲氧基取代的苯基、3、4-二亚甲氧基苯基、硝基取代的苯基；
所述吡啶盐选自2-氯-1-甲基碘化吡啶、1，2-二甲基碘化吡啶中的至少一种；所述有机碱为三乙胺；所述有机溶剂选自二氯甲烷、二氯乙烷中的至少一种。
2.根据权利要求1所述的苯并咪唑炔胺类化合物的合成方法，其特征在于，所述1-R1甲酰甲基-2-R2基苯并咪唑类化合物、所述吡啶盐和所述有机碱的摩尔比为：1:0.8-1.2:0.8-1.2。
3.根据权利要求1所述的苯并咪唑炔胺类化合物的合成方法，其特征在于，所述反应的温度为10-40℃。
4.根据权利要求1所述的苯并咪唑炔胺类化合物的合成方法，其特征在于，所述反应的时间为2-4小时。
5.根据权利要求1-4任一项所述的苯并咪唑炔胺类化合物的合成方法，其特征在于，所述保护气体为氮气。
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