CN115594624A - 一种n-端烯基氮杂芳烃的制备方法 - Google Patents

一种n-端烯基氮杂芳烃的制备方法 Download PDF

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CN115594624A
CN115594624A CN202110781319.2A CN202110781319A CN115594624A CN 115594624 A CN115594624 A CN 115594624A CN 202110781319 A CN202110781319 A CN 202110781319A CN 115594624 A CN115594624 A CN 115594624A
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郭灿城
聂志文
郭欣
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Abstract

本发明公开了一种N‑端烯基氮杂芳烃的制备方法，该方法是在大气气氛和二甲亚砜溶剂中，芳醛与氮杂芳烃在碱的作用下进行一锅反应，即得N‑端烯基氮杂芳烃化合物。该方法得到的N‑端烯基氮杂芳烃化合物的芳烯基来源于原料醛，但比原来的醛原料增加了一个双键碳原子。反应过程中，原料芳醛的碳氧双键转变为碳碳双键，芳醛羰基碳上的氢原子被氮杂芳烃分子中的氮原子取代。该方法原料来源广泛易得，绿色环保，价格低廉，操作简单，有利于工业化生产。

Description

一种N-端烯基氮杂芳烃的制备方法
技术领域
本发明涉及一种N-端烯基氮杂芳烃的制备方法，特别涉及一种以芳醛和氮杂芳烃在二甲亚砜中一锅反应合成N-端烯基氮杂芳烃的方法，属于有机合成领域。
背景技术
N-端烯基氮杂芳烃是一类具有氮杂芳烃氮原子上连接有端烯基的特殊结构化合物，N-端烯基氮杂芳烃分子中同时具有氮杂芳烃和烯胺结构，它们是难得的重要的有机合成中间体和高分子合成原料，同时，N-端烯基氮杂芳烃也存在生物体中并表现出优异的生理活性。N-端烯基氮杂芳烃中N-端烯双键的存在使得这类化合物的合成比较困难。目前合成N-端烯基氮杂芳烃主要有下面三种方法：
一种方法是端基炔烃与氮杂芳烃的反应：
Figure RE-GDA0003189684940000011
这种方法需要金和铜的催化，产物为N-非端烯基氮杂芳烃和N-端烯基氮杂芳烃的混合物，其中N-端烯基氮杂芳烃的比例很小。
第二种方法是端基卤代烯烃与氮杂芳烃反应：
Figure RE-GDA0003189684940000012
这种方法需要贵金属Pd的催化，原料需要用到卤代烯烃。卤代烯烃，除了卤代乙烯以外，大都需要用到特殊的制备方法，原料来源困难。
合成N-端烯基氮杂芳烃的第三种方法是在贵金属Pd的催化下，使用甲基芳基酮对甲苯磺酰肼作为原料与氮杂芳烃反应：
Figure RE-GDA0003189684940000021
该反应的原料甲基芳基酮对甲苯磺酰肼来源困难，不稳定，并且反应收率一般小于40％。
上述方法使用的原料端基炔烃或者端基卤代烯烃或者甲基芳基酮对甲苯磺酰肼都都不是常见的基本化学原料，催化剂都需要使用贵金属，并且反应需要用特殊的工艺条件，不适合工业生产应用。所得产物中N-端烯基的碳原子数与其原料的碳原子数相同。
发明内容
针对现有N-端烯基氮杂芳烃合成方法存在的使用原料难得到、使用昂贵金属催化剂以及反应条件苛刻的缺陷，本发明的目的是在于提供一种由芳醛和氮杂芳烃为原料，亚砜为溶剂和反应试剂在温和反应条件下一锅反应高产率合成比原来芳醛多一个双键碳原子的N-端烯基氮杂芳烃的方法，该方法原料来源广泛易得，绿色环保，价格低廉，操作简单，有利于工业化生产。
为了实现上述技术目的，本发明提供了一种N-端烯基氮杂芳烃的合成方法，该方法是在大气气氛下，芳香醛和氮杂芳烃为原料，在碱存在下，在DMF溶液体系中进行一锅反应，即得N-端烯基氮杂芳烃化合物。产物结构中，原料芳醛的碳氧双键转变为碳碳双键，芳醛羰基碳上的氢原子被氮杂芳烃分子中的氮原子取代，得到的N-端烯基氮杂芳烃化合物的芳烯基比原来的醛原料增加了一个双键碳原子。
所述芳醛具有式1结构：
Figure RE-GDA0003189684940000022
所述氮杂芳烃具有式2结构：
Figure RE-GDA0003189684940000023
Figure RE-GDA0003189684940000031
所述N-端烯基氮杂芳烃具有式3结构：
Figure RE-GDA0003189684940000032
其中，
式1中Ar为苯基、萘、噻吩、喹啉或者它们的取代衍生物，芳环上的取代基可以为氢、甲基、乙基、丙基、丁基、异丁基、异丙基、苄基、环己甲基、甲氧基、亚甲二氧基的一个或者多个，取代基可以位于芳环中的不同位置；
式2中的氮杂芳烃可以是吲哚、氮杂吲哚、咪唑、吡唑、吡咯或它们的取代衍生物，取代基可以是氟、氯、溴、甲基、甲氧基的一个或多个，氮杂吲哚中的氮原子可以位于吲哚环的不同位置。
芳香醛中的芳基Ar与羰基形成p-π共轭，明显增加羰基碳原子的反应活性，比较常见的Ar是苯基、萘或取代苯基或者取代萘。取代苯基或者取代萘的芳环上可以包含1～3个取代基，最好是包含一个取代基。取代的的位置不限，可以为邻位、间位或对位。芳环上取代基的种类选择对目标产物的合成影响并不很大，具有较大的选择范围，如可以选自烷基(如C1～C5的短链烷基，具体来说，如甲基、乙基、丙基、异丙基、异丁基等等)、卤素取代基(如氟、氯、溴或碘)、氰基、硝基、氨基、烷氧基(如C1～C5的短链烷氧基)或烷氧酰基(如甲氧甲酰基、乙氧酰基)。Ar选自芳杂环基时，Ar可以选自含氧、氮、硫中至少一种的芳杂环，如常见的噻吩、呋喃、吡咯、吡啶、喹啉。
最优选的芳香醛包括：苯甲醛、2-甲基苯甲醛、3-甲基苯甲醛、4-甲基苯甲醛、3-氟苯甲醛、4-氟苯甲醛、4-氯苯甲醛、4-溴苯甲醛、4-腈基苯甲醛、4-硝基苯甲醛、4-甲氧基苯甲醛、4-乙酰基苯甲醛、4-乙氧基苯甲醛、3-三氟甲基苯甲醛，1-呋喃甲醛、1-萘甲醛、2-萘甲醛、6-喹啉甲醛、3-噻吩甲醛。
优选的方案，所述碱包含至少一种无机碱或者有机碱，例如，氢氧化钠、氢氧化钾、碳酸钾、叔丁醇钠、叔丁醇钾，优选氢氧化钾。
优选的方案，醛与氮杂芳烃的摩尔比例为1:2。
本发明的含氧气氛可以为空气，也可以是纯氧气氛。
优选的方案，所述反应的条件为：在空气或氧气气氛下，于70～100℃温度下，反应10～50min。较优选的方案，所述反应的条件为：在空气气氛下，于80℃温度下，反应30min。
本发明的N-端烯基氮杂芳烃合成过程中，二甲亚砜同时作为溶剂和反应底物，可以大量过量。
优选的方案，反应结束后采用柱层析法分离提纯产物；所述柱层析采用的洗脱液为石油醚和乙酸乙酯的混合溶剂，其中石油醚和乙酸乙酯之间的体积比为(20～40):1。
本发明提出的合成N-端烯基氮杂芳烃的方法，反应方程式如下：
Figure RE-GDA0003189684940000041
该方法得到的N-端烯基氮杂芳烃化合物的芳烯基来源于原料醛，但比原来的醛原料增加了一个双键碳原子。该反应的反应原理可以通过苯甲醛与吲哚得到产物N-(1-苯乙烯基)吲哚的过程予以说明：在碱性环境下，苯甲醛与DMSO 发生Aldol反应生成中间体1-甲基亚硫酰基-2-苯乙烯A，接着，空气将亚硫酰中间体A氧化成硫酰中间体B，然后，吲哚作为亲核试剂与中间体B发生亲核加成生成中间体C，最后，在碱作用下，中间体C发生甲基硫酰基离去生成比原来醛化合物原料增加了一个碳原子的N-(1-苯乙烯基)吲哚。DMSO对该反应能形成N-端烯基氮杂芳烃起到了至关重要的作用：一是提供一个亲核碳原子将醛的碳氧双键转化成碳碳双键；二是向双键碳原子提供一个甲基亚硫酰基，甲基亚硫酰基使碳碳双键的亲电性反转而表现出亲核性双键性质，同时也是一个很好的离去基团。上述过程中的中间体A、B、C都能在反应体系中检测到，并且，分别以中间体A、B、C作为起始原料都能得到产物N-(1-苯乙烯基)吲哚。
Figure RE-GDA0003189684940000051
实验发现，如果用酮代替醛，则无法得到相应结构的产物。
相对于现有的合成方法和技术，本发明具有以下优点和效果：
1)本发明首次实现了醛的碳氧双键结构向N-端烯基氮杂芳烃结构的直接转化，产物为比醛化合物原料增加了一个碳原子的N-端烯基氮杂芳烃；
2)本发明采用简单且常见的醛、氮杂芳烃、DMSO作为原料，原料来源广，成本低，满足工业生产要求；
3)本发明的反应过程在较低温度下进行反应，反应时间短，产物收率高，适合工业生产；
4)本发明的反应过程中没有使用毒性的原料、溶剂和添加剂、反应条件温和，溶剂同时是反应物，符合绿色环保要求；
5)本发明的合成过程通过一锅法反应，反应步骤少，操作简单。
实施例
以下结合具体实施例对本发明作进一步地具体详尽的描述，但本发明的实施方式不限于此，对于未特别注明的工艺参数，可参照常规技术进行。
除另有说明外，所有反应均在Schlenk试管中进行。
所有反应原料溶剂从商业来源获得，并且不经进一步纯化而使用。
产品分离采用硅胶色谱柱，硅胶(粒度300目～400目)。
1H NMR(400MHz)和13C NMR(100MHz)检测采用Bruker ADVANCE III光谱仪，以CDCl3为溶剂，以TMS为内标，化学位移以百万分率(ppm)计，以四甲基硅烷的0.0ppm为参考位移。使用以下缩写(或其组合)来解释多重性： s＝单峰，d＝双峰，t＝三重峰，q＝四重峰，m＝多重峰，br＝宽峰。偶合常数J的单位为赫兹(Hz)。化学位移以ppm表示，参考氘代氯仿在77.0ppm三重态的中心线或参考氘代DMSO在39.52ppm七重态的中心线。
1、条件优化实验:
以苯甲醛与吲哚在DMF中的反应为例，对碱化合物、反应温度、时间等条件的影响因素进行了探讨，以寻求最佳的反应条件。
反应路线如下：
Figure RE-GDA0003189684940000061
Figure RE-GDA0003189684940000062
反应条件:苯甲醛(0.5mmol),吲哚(1mmol),base(2mmol),and DMSO(2.5mL).a使用1,4-二氯作内标的GC产率。
1)碱化合物的选择
实验表明，反应必须在强碱性条件下反应。没有碱或者弱碱性，反应几乎不能反应，如表1中项目2和3；强碱性无机碱或者有机碱存在下，反应都能发生，但KOH的效果明显优于其它碱，如表1中项目1和4-5。
2)反应温度的选择
反应温度是影响化学反应过程的一个重要因素，本发明考察70～90℃温度范围内，在不同温度下该反应的产率，如表1中项目5和8-9。在70～90℃温度范围内，随着温度升高，相应目标产物产率也升高，但是温度达到80℃以上时，反应产率不再增加，因此，80℃为该反应的最适温度。
3)反应时间的选择
反应时间对反应产率的影响见表1中项目5-9。反应时间在30分钟时反应产率最高，并且，随着反应时间增加，反应产率不再增加。
2、实施过程：
称取0.5mmol醛化合物，1.0mmol氮杂芳烃，2equiv.KOH于25mL带有搅拌子的封管中，并加入2mL DMSO。把反应封管放进80℃的油浴锅中加热，持续反应30min取出反应封管，停止反应，将反应液冷却至室温之后，向反应液中加入6mL饱和的NaCl水溶液和10mL左右的乙酸乙酯(EtOAc)，通过振荡，静置数分钟之后，取出上层有机相，下层的液体按上述步骤重复萃取 3次。用无水硫酸钠将有机相中的水分除去，得到的混合物放进旋转蒸发仪蒸干后装入填充硅胶的柱层析进行分离提纯，得到产物，计算产率。
3、实施效果：
Figure RE-GDA0003189684940000071
Figure RE-GDA0003189684940000072
3、部分产物的氢谱和碳谱：
N-(1-苯乙烯基)吲哚(1-(1-phenylvinyl)-1H-indole)(1).
Figure RE-GDA0003189684940000081
黄色固体。1H NMR(400MHz,CDCl3)δ7.73–7.65(m,1H),7.46–7.31(m, 5H),7.21(d,J＝3.2Hz,1H),7.18–7.10(m,3H),6.65(d,J＝3.2Hz,1H),5.61(s, 1H),5.40(s,1H).13C NMR(101MHz,CDCl3)δ144.95,137.00,136.40,129.26, 129.10,128.65,128.54,126.90,121.96,120.90,120.16,111.85,108.06,103.06.
N-(1-邻甲苯乙烯基)吲哚(1-(1-(o-tolyl)vinyl)-1H-indole)(2).
Figure RE-GDA0003189684940000082
黄色固体。1H NMR(400MHz,CDCl3)δ7.64–7.57(m,1H),7.44–7.42(m, 1H),7.33–7.24(m,3H),7.14-7.10(m,3H),7.01(s,1H),6.54(s,1H),5.49(s,1H), 5.18(s,1H),1.83(s,3H).13C NMR(101MHz,CDCl3)δ145.27,137.45,136.93, 135.62,130.63,130.01,129.65,129.05,127.47,126.03,122.22,120.99,120.35, 111.71,106.62,103.59,19.19.HRMS(ESI):calcd for C17H15N:233.1204,found: 233.1206.
N-(1-对甲氧苯乙烯基)吲哚(1-(1-(4-methoxyphenyl)vinyl)-1H-indole)(3)
Figure RE-GDA0003189684940000083
黄色固体。1H NMR(400MHz,CDCl3)δ7.62(d,J＝7.2Hz,1H),7.25–7.03 (m,6H),6.79(d,J＝8.0Hz,2H),6.57(s,1H),5.42(s,1H),5.21(s,1H),3.73(s,3H). 13C NMR(101MHz,CDCl3)δ160.32,144.52,136.39,129.46,129.25,128.66, 128.22,121.87,120.84,120.08,113.87,111.93,106.24,102.88,55.19.
N-(1-(3,4-亚甲二氧苯)乙烯基)吲哚(1-(1-(benzo[d][1,3]dioxol-5-yl)vinyl)-1H- indole)(4)
Figure RE-GDA0003189684940000091
黄色固体。1H NMR(400MHz,CDCl3)δ7.74–7.61(m,1H),7.23–7.07(m, 4H),6.88–6.73(m,3H),6.62(d,J＝3.2Hz,1H),5.99(s,2H),5.48(s,1H),5.27(s, 1H).13C NMR(101MHz,CDCl3)δ148.45,147.97,144.56,136.39,131.31,129.25, 128.67,121.97,121.10,120.90,120.16,111.89,108.25,107.29,106.91,103.04, 101.36.HRMS(EI):calcd for C17H13NO2:263.0946,found:263.0942.
N-(1-对氟苯乙烯基)吲哚(1-(1-(4-fluorophenyl)vinyl)-1H-indole)(5)
Figure RE-GDA0003189684940000092
白色固体。1H NMR(400MHz,CDCl3)δ7.65(d,J＝5.3Hz,1H),7.33–7.28 (m,1H),7.18–6.97(m,7H),6.63(s,1H),5.61(s,1H),5.41(s,1H).13C NMR(101 MHz,CDCl3)δ162.94(d,J＝246.5Hz),143.91,136.33,130.13(d,J＝8.2Hz), 129.27,128.50,122.61(d,J＝2.8Hz),122.15,120.68(d,J＝67.9Hz),116.08(d,J＝ 21.3Hz),113.89(d,J＝22.7Hz),111.68,109.23,103.42.
N-(1-间氯苯乙烯基)吲哚(1-(1-(3-chlorophenyl)vinyl)-1H-indole)(6)
Figure RE-GDA0003189684940000093
淡绿色固体。1H NMR(400MHz,CDCl3)δ7.68(d,J＝5.6Hz,1H),7.38(d,J ＝5.2Hz,2H),7.30(d,J＝10.2Hz,1H),7.17(d,J＝8.8Hz,5H),6.66(s,1H),5.63(s, 1H),5.44(s,1H).13C NMR(101MHz,CDCl3)δ143.76,138.94,136.30,134.68, 129.85,129.28,129.23,128.45,126.96,125.15,122.19,121.03,120.37,111.68, 109.24,103.49.HRMS(EI):calcd for C16H12ClN:253.0658,found:253.0657.
N-(1-对溴苯乙烯基)吲哚(1-(1-(4-bromophenyl)vinyl)-1H-indole)(7)
Figure RE-GDA0003189684940000101
黄色油状液体。1H NMR(400MHz,CDCl3)δ7.67–7.65(m,1H),7.47(d,J＝ 8.4Hz,2H),7.21–7.04(m,6H),6.63(d,J＝3.2Hz,1H),5.58(s,1H),5.39(s,1H). 13C NMR(101MHz,CDCl3)δ144.07,136.26,135.95,131.80,129.30,128.51, 128.49,123.33,122.14,121.02,120.34,111.76,108.61,103.41.
N-(1-对三氟甲基苯乙烯基)吲哚(1-(1-(3-(trifluoromethyl)phenyl)vinyl)-1H- indole)(8)
Figure RE-GDA0003189684940000102
淡绿色油状液体。1H NMR(400MHz,CDCl3)δ7.79–7.65(m,3H),7.64– 7.56(m,2H),7.54–7.44(m,3H),7.33(t,J＝7.4Hz,1H),7.23(t,J＝7.4Hz,1H), 6.76–6.65(m,2H).HRMS(EI):calcd for C17H12F3N:253.0658,found:253.0657.
N-(1-(2-萘乙烯基))吲哚(1-(1-(naphthalen-2-yl)vinyl)-1H-indole)(9)
Figure RE-GDA0003189684940000103
黄色固体。1H NMR(400MHz,CDCl3)δ7.84–7.75(m,4H),7.67(d,J＝8.0 Hz,1H),7.51–7.41(m,3H),7.22(d,J＝2.8Hz,1H),7.20–7.04(m,3H),6.65(s, 1H),5.70(s,1H),5.45(s,1H).13C NMR(101MHz,CDCl3)δ144.99,136.49, 134.43,133.62,133.13,129.29,128.76,128.43,128.33,127.64,126.67,126.48, 126.37,124.47,122.05,120.93,120.22,111.91,108.63,103.17.
N-(1-(2-噻吩乙烯基))吲哚(1-(1-(thiophen-2-yl)vinyl)-1H-indole)(10)
Figure RE-GDA0003189684940000104
黄色油状液体。1H NMR(400MHz,CDCl3)δ7.65(d,J＝8.0Hz,1H),7.29(d, J＝4.0Hz,2H),7.24(s,1H),7.18–7.10(m,2H),6.96(t,J＝3.6Hz,1H),6.89(s, 1H),6.61(d,J＝2.0Hz,1H),5.64(s,1H),5.27(s,1H).13C NMR(101MHz,CDCl3) δ140.60,138.86,136.46,129.07,128.42,127.52,126.65,126.30,122.05,120.94, 120.29,111.58,107.96,103.09.HRMS(EI):calcd for C14H11NS:225.0612,found: 225.0615.
N-(1-苯乙烯基)-2-甲基吲哚(2-methyl-1-(1-phenylvinyl)-1H-indole)(11)
Figure RE-GDA0003189684940000111
黄色固体。1H NMR(400MHz,CDCl3)δ7.60(d,J＝7.4Hz,1H),7.36–7.31 (m,3H),7.08–7.20(m,5H),6.42(s,1H),6.08(s,1H),5.45(s,1H),2.25(s,3H).13C NMR(101MHz,CDCl3)δ142.88,138.01,137.09,137.01,128.88,128.67,128.28, 125.65,121.00,119.92,119.49,113.62,110.48,101.26,13.05.
N-(1-苯乙烯基)-3-甲基吲哚(3-methyl-1-(1-phenylvinyl)-1H-indole)(12)
Figure RE-GDA0003189684940000112
黄色固体。1H NMR(400MHz,CDCl3)δ7.64(d,J＝7.2Hz,1H),7.50–7.32 (m,5H),7.22–7.13(m,3H),7.00(s,1H),5.53(s,1H),5.36(s,1H),2.40(s,3H).13C NMR(101MHz,CDCl3)δ144.98,137.32,136.65,129.81,129.01,128.49,127.10, 126.18,121.93,119.59,118.95,112.21,111.83,106.95,9.57.
N-(1-苯乙烯基)-5-甲氧基吲哚(5-methoxy-1-(1-phenylvinyl)-1H-indole)(13)
Figure RE-GDA0003189684940000113
黄色固体。1H NMR(400MHz,CDCl3)δ7.44–7.31(m,5H),7.16(d,J＝17.8 Hz,2H),7.03(d,J＝8.8Hz,1H),6.79(d,J＝8.8Hz,1H),6.57(s,1H),5.54(s,1H), 5.36(s,1H),3.87(s,3H).13C NMR(101MHz,CDCl3)δ154.36,145.08,137.05, 131.59,129.79,129.17,129.12,128.53,127.01,112.66,112.02,107.37,102.75, 102.59,55.75.
N-(1-苯乙烯基)-4-氟吲哚(4-fluoro-1-(1-phenylvinyl)-1H-indole)(14)
Figure RE-GDA0003189684940000121
黄色固体。1H NMR(400MHz,CDCl3)δ7.48–7.31(m,5H),7.19(s,1H), 7.06(dd,J＝13.8,7.3Hz,1H),6.95(d,J＝8.2Hz,1H),6.85(t,J＝8.9Hz,1H),6.77 (s,1H),5.67(s,1H),5.44(s,1H).13C NMR(101MHz,CDCl3)δ157.50,155.05, 144.80,138.92(d,J＝10.9Hz),136.61,129.28,128.63,126.79,122.48(d,J＝7.7 Hz),118.23(d,J＝22.5Hz),108.81,107.93(d,J＝3.6Hz),104.96(d,J＝18.8Hz), 99.00.HRMS(EI):calcd forC16H12FN:237.0954,found:237.0958.
N-(1-苯乙烯基)-5-溴吲哚(5-bromo-1-(1-phenylvinyl)-1H-indole)(15)
Figure RE-GDA0003189684940000122
黄色油状液体。1H NMR(400MHz,CDCl3)δ7.76(s,1H),7.40–7.31(m, 3H),7.25(d,J＝7.2Hz,2H),7.16(d,J＝10.0Hz,2H),6.95(d,J＝8.8Hz,1H),6.54 (s,1H),5.59(s,1H),5.34(s,1H).13C NMR(101MHz,CDCl3)δ144.69,136.56, 135.05,130.91,129.81,129.34,128.66,126.81,124.85,123.39,113.46,113.27, 108.57,102.57.
N-(1-苯乙烯基)-5-氮杂吲哚(1-(1-phenylvinyl)-1H-pyrrolo[3,2-c]pyridine)(16)
Figure RE-GDA0003189684940000123
黄色固体。1H NMR(400MHz,CDCl3)δ8.95(s,1H),8.21(d,J＝5.8Hz,1H), 7.39–7.33(m,3H),7.26–7.20(m,3H),6.98(d,J＝5.8Hz,1H),6.70(d,J＝2.8Hz, 1H),5.64(s,1H),5.38(s,1H).13C NMR(101MHz,CDCl3)δ144.08,143.98, 141.20,139.97,136.06,129.47,128.69,126.73,125.90,125.86,108.94,106.85, 102.42.HRMS(EI):calcd forC15H12N2:220.1000,found:220.0997.
N-(1-苯乙烯基)-7-氮杂吲哚(1-(1-phenylvinyl)-1H-pyrrolo[2,3-b]pyridine)(17)
Figure RE-GDA0003189684940000131
黄色固体。1H NMR(400MHz,CDCl3)δ8.34(d,J＝3.6Hz,1H),7.95(d,J＝ 7.8Hz,1H),7.40–7.27(m,5H),7.18(d,J＝3.0Hz,1H),7.11(dd,J＝7.2,5.1Hz, 1H),6.54(d,J＝3.0Hz,1H),5.77(d,J＝11.0Hz,2H).13C NMR(101MHz,CDCl3) δ148.30,143.50,142.84,137.30,128.95,128.92,128.84,128.44,126.74,121.31, 116.50,110.08,100.74.HRMS(EI):calcd for C15H12N2:220.1000,found: 220.1003.
N-(1-苯乙烯基)吡咯(1-(1-phenylvinyl)-1H-pyrrole)(18)
Figure RE-GDA0003189684940000132
黄色油状液体。1H NMR(400MHz,CDCl3)δ7.46(s,5H),6.90(s,2H),6.36 (d,J＝0.8Hz,2H),5.26(s,1H),5.17(s,1H).13C NMR(101MHz,CDCl3)δ146.34, 136.96,129.03,128.29,127.81,121.00,109.34,103.11.
N-(1-苯乙烯基)咔唑(9-(1-phenylvinyl)-9H-carbazole)(19)
Figure RE-GDA0003189684940000133
黄色油状液体。1H NMR(400MHz,CDCl3)δ8.19(d,J＝7.6Hz,2H),7.43– 7.30(m,11H),6.12(s,1H),5.65(s,1H).13C NMR(101MHz,CDCl3)δ142.70, 140.80,136.34,129.03,128.70,126.20,125.82,123.40,120.14,119.78,112.85, 110.84.
N-(1-苯乙烯基)吡唑(1-(1-phenylvinyl)-1H-pyrazole)(20)
Figure RE-GDA0003189684940000134
无色油状液体。1H NMR(400MHz,CDCl3)δ7.72–7.66(m,1H),7.51–7.49 (m,1H),7.46–7.34(m,5H),6.36(t,J＝1.9Hz,1H),5.60(s,1H),5.20(s,1H).13C NMR(101MHz,CDCl3)δ145.77,140.84,135.83,129.62,129.21,128.43,127.99, 106.46,104.94.
N-(1-苯乙烯基)-2-氮杂吲哚(1-(1-phenylvinyl)-1H-indazole)(21)
Figure RE-GDA0003189684940000141
黄色油状液体。1H NMR(400MHz,CDCl3)δ8.18(s,1H),7.78(d,J＝8.0Hz, 1H),7.48–7.25(m,6H),7.21-7.15(m,2H),5.60(d,J＝10.2Hz,2H).13C NMR (101MHz,CDCl3)δ145.26,139.91,136.37,135.22,129.17,128.52,127.24,126.66, 124.93,121.34,121.06,111.44,108.21.
N-(1-苯乙烯基)咪唑(1-(1-phenylvinyl)-1H-imidazole)(22)
Figure RE-GDA0003189684940000142
黄色油状液体。1H NMR(400MHz,CDCl3)δ7.65(s,1H),7.47–7.30(m, 5H),7.13(s,1H),7.03(s,1H),5.31(d,J＝10.8Hz,2H).13C NMR(101MHz, CDCl3)δ143.20,137.14,135.58,129.70,129.54,128.71,127.22,119.29,106.43.
N-(1-苯乙烯基)-3-氮杂吲哚(1-(1-phenylvinyl)-1H-benzo[d]imidazole)(23)
Figure RE-GDA0003189684940000143
黄色固体。1H NMR(400MHz,CDCl3)δ8.04(s,1H),7.85(d,J＝8.0Hz,1H), 7.43–7.35(m,3H),7.31–7.26(m,3H),7.20(t,J＝7.6Hz,1H),7.07(d,J＝8.0Hz, 1H),5.69(s,1H),5.46(s,1H).13C NMR(101MHz,CDCl3)δ143.73,143.00, 142.14,135.23,133.74,129.74,128.83,126.69,123.44,122.68,120.35,111.71, 109.48.
N-(1-苯乙烯基)-1,2,3-三唑(1-(1-phenylvinyl)-1H-1,2,3-triazole)(24)
Figure RE-GDA0003189684940000151
黄色油状液体。1H NMR(400MHz,CDCl3)δ7.77(s,1H),7.61(s,1H),7.46– 7.37(m,3H),7.31(d,J＝6.8Hz,2H),5.79(s,1H),5.54(s,1H).13C NMR(101MHz, CDCl3)δ142.93,134.58,133.56,129.83,128.78,127.21,123.88,109.48.HRMS (EI):calcd for C10H9N3:171.0796,found:171.0794.
N-(1-苯乙烯基)-1,2,4-三唑(1-(1-phenylvinyl)-1H-1,2,4-triazole)(25)
Figure RE-GDA0003189684940000152
黄色油状液体。1H NMR(400MHz,CDCl3)δ8.15(s,1H),8.04(s,1H),7.46– 7.30(m,5H),5.68(s,1H),5.35(s,1H).13C NMR(101MHz,CDCl3)δ152.22, 143.14,142.72,134.28,129.79,128.74,127.57,107.58.HRMS(EI):calcd for C10H9N3:171.0796,found:171.0793.
N-(1-间甲氧苯乙烯基)吡唑(1-(1-(3-methoxyphenyl)vinyl)-1H-pyrazole)(26)
Figure RE-GDA0003189684940000153
无色油状液体。1H NMR(400MHz,CDCl3)δ7.68(s,1H),7.49(s,1H),7.30 (t,J＝7.9Hz,1H),6.98–6.91(m,3H),6.35(s,1H),5.60(s,1H),5.19(s,1H),3.79 (s,3H).13C NMR(101MHz,CDCl3)δ159.57,145.61,140.86,137.22,129.66, 129.47,120.49,114.82,113.67,106.47,105.04,55.25.HRMS(EI):calcd for C10H9N3:200.0950,found:200.0947.
N-(1-对甲氧苯乙烯基)吡唑(1-(1-(4-methoxyphenyl)vinyl)-1H-pyrazole(27)
Figure RE-GDA0003189684940000154
无色油状液体。1H NMR(400MHz,CDCl3)δ7.69(s,1H),7.52(s,1H),7.32 (d,J＝8.0Hz,2H),6.92(d,J＝8.0Hz,2H),6.36(s,1H),5.51(s,1H),5.13(s,1H), 3.83(s,3H).13CNMR(101MHz,CDCl3)δ160.23,145.34,140.61,129.47,129.18, 128.15,113.70,106.24,103.50,55.14.
N-(1-(3,4-亚甲二氧苯)乙烯基)吡唑(1-(1-(benzo[d][1,3]dioxol-5-yl)vinyl)-1H- pyrazole)(28)
Figure RE-GDA0003189684940000161
无色油状液体。1H NMR(400MHz,CDCl3)δ7.66(s,1H),7.51(s,1H),6.87 (d,J＝8.0Hz,1H),6.80(d,J＝7.2Hz,2H),6.34(s,1H),5.97(s,2H),5.46(s,1H), 5.10(s,1H).13CNMR(101MHz,CDCl3)δ148.42,147.65,145.38,140.79,129.83, 129.61,122.08,108.28,108.13,106.41,104.15,101.29.
N-(1-(2-噻吩乙烯基))吡唑(1-(1-(thiophen-3-yl)vinyl)-1H-pyrazole(29)
Figure RE-GDA0003189684940000162
黄色固体。1H NMR(400MHz,CDCl3)δ7.68(s,1H),7.59(s,1H),7.38(s, 1H),7.34(d,J＝2.8Hz,1H),7.16(d,J＝4.8Hz,1H),6.36(s,1H),5.51(s,1H),5.25 (s,1H).13C NMR(101MHz,CDCl3)δ140.98,140.77,136.96,129.39,126.92, 126.01,124.83,106.44,104.45.HRMS(EI):calcd for C12H10N2O2:214.0742, found:214.0746.
N-(1-(间-三氟甲基)苯乙烯基)吡咯(1-(1-(3-(trifluoromethyl)phenyl)vinyl)-1H- pyrrole)(30)
Figure RE-GDA0003189684940000163
黄色油状液体。1H NMR(400MHz,CDCl3)δ7.63(s,1H),7.54(d,J＝7.2Hz, 1H),7.51–7.42(m,2H),7.36(d,J＝14.6Hz,1H),7.01(s,2H),6.60(d,J＝14.6Hz, 1H),6.32(s,2H).HRMS(EI):calcd for C13H10F3N:237.0765,found:237.0765.

Claims (6)

1.一种N-端烯基氮杂芳烃的制备方法，其特征在于：在大气条件下，芳醛和氮杂芳烃在二甲亚砜中反应生成N-端烯基氮杂芳烃：
所述芳醛具有式1结构：
Figure FDA0003157259070000011
所述氮杂芳烃具有式2结构：
Figure FDA0003157259070000012
所述N-端烯基氮杂芳烃具有式3结构：
Figure FDA0003157259070000013
其中，
式1中Ar为苯基、萘、噻吩、喹啉或者它们的取代衍生物，芳环上的取代基可以为氢、甲基、乙基、丙基、丁基、异丁基、异丙基、苄基、环己甲基、甲氧基、亚甲二氧基的一个或者多个，取代基可以位于芳环中的不同位置；
式2中的氮杂芳烃可以是吲哚、氮杂吲哚、咪唑、吡唑、吡咯或它们的取代衍生物，取代基可以是氟、氯、溴、甲基、甲氧基的一个或多个，氮杂吲哚中的氮原子可以位于吲哚环的不同位置。
2.根据权利要求1所述的一种N-端烯基氮杂芳烃的制备方法，其特征在于：所选碱为氢氧化钠、氢氧化钾、碳酸钾、叔丁醇钠，优选氢氧化钾。
3.根据权利要求1所述的一种N-端烯基氮杂芳烃的制备方法，其特征在于：反应温度从70-100℃，优选温度为80℃。
4.根据权利要求1所述的一种N-端烯基氮杂芳烃的制备方法，其特征在于：反应时间为10-50分钟，优选时间为30分钟。
5.根据权利要求1所述的一种N-端烯基氮杂芳烃的制备方法，其特征在于：二甲亚砜既作为溶剂，又作为反应试剂。
6.根据权利要求1所述的一种N-端烯基氮杂芳烃的制备方法，其特征在于：醛与氮杂芳烃的当量比例为1:2。
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