CN113582915B - 一种4-取代吡啶类化合物的合成方法 - Google Patents

一种4-取代吡啶类化合物的合成方法 Download PDF

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CN113582915B
CN113582915B CN202110840580.5A CN202110840580A CN113582915B CN 113582915 B CN113582915 B CN 113582915B CN 202110840580 A CN202110840580 A CN 202110840580A CN 113582915 B CN113582915 B CN 113582915B
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cyanopyridine
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马春华
吉钰
祝亮
张淑婷
汪瑾
姜玉钦
何兴
李伟
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Henan Normal University
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Abstract

本发明公开了一种4‑取代吡啶类化合物的合成方法，属于取代吡啶类化合物的合成技术领域。本发明的技术方案要点为：将苯乙烯类化合物、氰基吡啶类化合物和2,2‑二乙氧基羧酸类化合物置于溶剂中，在蓝光照射、氮气环境的条件下进行反应，反应结束后向反应液中加水淬灭反应，再用乙酸乙酯萃取反应液，合并有机相之后用无水硫酸钠干燥，经柱层析得到目标产物4‑取代吡啶类化合物。本发明首次提供了一种4‑取代吡啶类化合物的合成方法，不需要使用传统的过渡金属光敏剂和外加氧化剂，光源为可见光，是一种绿色可持续的能源。

Description

一种4-取代吡啶类化合物的合成方法
技术领域
本发明属于取代吡啶类化合物的合成技术领域，具体涉及一种4-取代吡啶类化合物的合成方法。
背景技术
吡啶作为一种具有独特物理化学性质的杂环类化合物，在天然产物、药物和催化反应配体中广泛存在。它作为优势骨架出现在90种上市药物的结构中(J.Med.Chem.,2014,57,10257-10274；J.Med.Chem.,2021,64,2339-2381)。因此，吡啶的引入是有机化学研究的重要方向。另一方面，醛基是醇、羧酸和烯烃等重要官能团的关键合成前体，因此它在药物的有机合成和结构修饰中发挥着重要作用。缩醛作为醛基的前体，能够通过在盐酸水溶液中简单搅拌的操作快速转化为醛基。近些年，乙醛酸缩醛被用作醛基等价物被用于苯乙烯和迈克尔加成受体的缩醛化反应，进而合成醛基(J.Am.Chem.Soc.,2017,139,9799；Chem.Commun.,2017,53,11642)。但是，目前尚无在商业可用的烯烃原料中同时引入吡啶基团和缩醛基团(醛基)的方法被报道。
发明内容
本发明解决的技术问题是提供了一种4-取代吡啶类化合物的合成方法，以有效解决目前对烯烃同时进行缩醛化-吡啶化修饰研究较少的问题。
本发明为解决上述技术问题采用如下技术方案：
一种4-取代吡啶类化合物的合成方法，其特征在于具体步骤为：在催化剂和碱的作用下，将苯乙烯类化合物、氰基吡啶类化合物和2,2-二乙氧基羧酸类化合物置于溶剂中，在蓝光照射、氮气环境的条件下进行反应，反应结束后向反应液中加水淬灭反应，再用乙酸乙酯萃取反应液，合并有机相之后用无水硫酸钠干燥，经柱层析得到目标产物烯烃缩醛-吡啶类化合物，其中催化剂为2,4,5,6-四(9-咔唑基)-间苯二腈，碱为碳酸铯，氰基吡啶类化合物的结构式如式A所示，苯乙烯类化合物的结构式如式B所示，2,2-二乙氧基羧酸类化合物的结构式如式C所示，目标产物烯烃缩醛-吡啶类化合物的结构式如式 D所示；
R1为H、C1-5烷基、C1-5烷氧基、苯基、取代苯基或卤素；R2为H、C1-5烷基、C1-5烷氧基、三氟甲基、酰胺类取代基、杂环类取代基或卤素；R3为H、C1-5烷基或苯乙基。
进一步限定，所述烯烃缩醛-吡啶类化合物的具体结构式为：
一种4-取代吡啶类化合物的合成方法，其特征在于具体步骤为：在催化剂和碱的作用下，将苯乙烯类化合物、氰基吡啶类化合物和2,2-二乙氧基羧酸类化合物置于溶剂中，在蓝光照射、氮气环境的条件下进行反应，反应结束后向反应液中加水淬灭反应，再用乙酸乙酯萃取反应液，合并有机相之后用无水硫酸钠干燥，经柱层析得到目标产物烯烃缩醛-吡啶类化合物其中催化剂为2,4,5,6-四(9- 咔唑基)-间苯二腈，碱为碳酸铯，苯乙烯类化合物为1,2-二苯基乙烯或α-甲基苯乙烯，氰基吡啶类化合物为4-氰基吡啶，2,2-二乙氧基羧酸类化合物为2,2-二乙氧基乙酸。
一种4-取代吡啶类化合物的合成方法，其特征在于具体步骤为：在催化剂和碱的作用下，将苯乙烯类化合物、氰基吡啶类化合物和2,2-二乙氧基羧酸类化合物置于溶剂中，在蓝光照射、氮气环境的条件下进行反应，再加入盐酸溶液进行反应，反应结束后向反应液中加NaHCO3水溶液淬灭反应，再用乙酸乙酯萃取反应液，合并有机相之后用无水硫酸钠干燥，经柱层析得到目标产物烯烃醛基(酮基)-吡啶类化合物，其中催化剂为 2,4,5,6-四(9-咔唑基)-间苯二腈，碱为碳酸铯，苯乙烯类化合物为苯乙烯、4-甲氧基苯乙烯或4-氯苯乙烯，氰基吡啶类化合物为4-氰基吡啶，2,2-二乙氧基羧酸类化合物为2,2- 二乙氧基乙酸或2,2-二乙氧基丙酸，目标产物烯烃醛基(酮基)-吡啶类化合物的具体结构式为：
进一步限定，所述氰基吡啶类化合物、苯乙烯类化合物、2,2-二乙氧基羧酸类化合物、催化剂与碱的投料摩尔比为1:1-3:1-3:0.01-0.05:1-3。
进一步限定，所述溶剂为无水二甲基亚砜。
进一步限定，蓝光的光源为蓝色LED灯，其波长为450-455nm，功率为5-10W。
进一步限定，反应过程的反应温度为20-30℃，反应时间为12-24h。
本发明与现有技术相比具有以下优点：本发明提供了一种4-取代吡啶类化合物的合成方法，相比于现有技术而言，该方法不需要使用过渡金属催化剂和外加氧化剂，不需要高温加热相对苛刻的反应条件，该方法所涉及的操作简便安全、反应条件温和，而且该方法使用的光源为可见光，绿色无公害，所使用的催化剂和反应介质均对环境较为友好。同时，本方法合成目标产物的收率相对较高。
具体实施方式
以下通过实施例对本发明技术方案进行具体的描述。有必要在此指出的是，以下实施例只用于对本发明作进一步的说明，不能理解为对本发明保护范围的限制。该领域的专业技术人员根据上述本发明的内容做出的一些非本质性的改进和调整仍属于本发明的保护范围。另外，如果没有其它说明，所用原料都是市售的。
实施例1
向装有磁子的10mL反应管中依次加入4-氰基吡啶(0.2mmol)，碳酸铯(0.4mmol)，催化剂2,4,5,6-四(9-咔唑基)-间苯二腈(0.006mmol)；对反应管抽真空，用氮气置换三次，随后加入苯乙烯(0.5mmol)，2,2-二乙氧基乙酸(0.5mmol)和溶剂无水二甲基亚砜(2mL)，反应管在波长为455nm的蓝光LED灯照射及25℃的反应温度下搅拌24h。反应结束后，加入水淬灭反应，用乙酸乙酯萃取反应液，合并有机相之后用无水硫酸钠干燥，柱层析得到目标产物，目标产物为淡黄色油状物。以4-氰基吡啶摩尔量为100％计，目标产物的产率为86％。目标产物的结构式如下：
对上述淡黄色油状物进行核磁波谱及质谱分析，数据如下：1H NMR(600MHz,CDCl3)δ8.49(d,J＝5.5Hz,2H),7.31–7.29(m,2H),7.23–7.21(m,3H),7.18(d,J＝5.9Hz,2H),4.26(t,J＝5.9Hz,1H),4.10(t,J＝7.9Hz,1H),3.64–3.56(m,2H),3.44–3.37(m,2H),2.35(dd,J＝7.9,5.9Hz,2H),1.19–1.16(m,6H)。13C NMR(150MHz,CDCl3)δ153.8, 149.9,142.6,128.9,128.0,127.0,123.4,101.0,61.6,61.3,46.6,38.7,15.49,15.47。HRMSCalcd for C18H24NO2[M+H]+:m/z 286.1802,Found:286.1803。
实施例2
向装有磁子的10mL反应管中依次加入3-甲基-4-氰基吡啶(0.2mmol)，碳酸铯(0.4mmol)，催化剂2,4,5,6-四(9-咔唑基)-间苯二腈(0.006mmol)；对反应管抽真空，用氮气置换三次，随后加入苯乙烯(0.5mmol)，2,2-二乙氧基乙酸(0.5mmol)和溶剂无水二甲基亚砜(2mL)，反应管在波长为455nm的蓝光LED灯照射及25℃的反应温度下搅拌24 h。反应结束后，加入水淬灭反应，用乙酸乙酯萃取反应液，合并有机相之后用无水硫酸钠干燥，柱层析得到目标产物，目标产物为无色油状物。以3-甲基-4-氰基吡啶摩尔量为100％计，目标产物的产率为90％。目标产物的结构式如下：
对上述无色油状物进行核磁波谱及质谱分析，数据如下：1H NMR(600MHz,CDCl3) δ8.42(d,J＝5.1Hz,1H),8.33(s,1H),7.29–7.26(m,2H),7.24(d,J＝5.2Hz,1H),7.20–7.18(m,3H),4.31–4.28(m,2H),3.64–3.57(m,2H),3.47–3.35(m,2H),2.34–2.30(m, 2H),2.26(s,3H),1.22–1.14(m,6H)。13C NMR(150MHz,CDCl3)δ151.3,151.2,147.9, 142.2,132.0,128.8,128.2,126.8,121.5,100.9,61.4,61.3,42.3,39.1,16.7,15.5,15.4。HRMS Calcdfor C19H26NO2[M+H]+:m/z 300.1958,Found:300.1958。
实施例3
向装有磁子的10mL反应管中依次加入3-甲氧基-4-氰基吡啶(0.2mmol)，碳酸铯(0.4mmol)，催化剂2,4,5,6-四(9-咔唑基)-间苯二腈(0.006mmol)；对反应管抽真空，用氮气置换三次，随后加入苯乙烯(0.5mmol)，2,2-二乙氧基乙酸(0.5mmol)和溶剂无水二甲基亚砜(2mL)，反应管在波长为455nm的蓝光LED灯照射及25℃的反应温度下搅拌24h。反应结束后，加入水淬灭反应，用乙酸乙酯萃取反应液，合并有机相之后用无水硫酸钠干燥，柱层析得到目标产物，目标产物为无色油状物。以3-甲氧基-4-氰基吡啶摩尔量为100％计，目标产物的产率为80％。目标产物的结构式如下：
对上述无色油状物进行核磁波谱及质谱分析，数据如下：1H NMR(600MHz,CDCl3) δ8.20–8.18(m,2H),7.28–7.26(m,1H),7.26–7.24(m,3H),7.19–7.16(m,2H),4.51(t,J＝8.0Hz,1H),4.29(t,J＝6.0Hz,1H),3.86(s,3H),3.64–3.56(m,2H),3.45–3.36(m,2H),2.37–2.28(m,2H),1.19–1.13(m,6H)。13C NMR(150MHz,CDCl3)δ153.4,143.0,142.6,141.4,133.7,128.5,128.2,126.6,122.3,101.2,61.6,61.1,56.2,39.4,38.0,15.5,15.4。HRMS Calcd for C19H26NO3[M+H]+:m/z 316.1907,Found:316.1907。
实施例4
向装有磁子的10mL反应管中依次加入2-甲基-4-氰基吡啶(0.2mmol)，碳酸铯(0.4mmol)，催化剂2,4,5,6-四(9-咔唑基)-间苯二腈(0.006mmol)；对反应管抽真空，用氮气置换三次，随后加入苯乙烯(0.5mmol)，2,2-二乙氧基乙酸(0.5mmol)和溶剂无水二甲基亚砜(2mL)，反应管在波长为455nm的蓝光LED灯照射及25℃的反应温度下搅拌24 h。反应结束后，加入水淬灭反应，用乙酸乙酯萃取反应液，合并有机相之后用无水硫酸钠干燥，柱层析得到目标产物，目标产物为无色油状物。以2-甲基-4-氰基吡啶摩尔量为100％计，目标产物的产率为92％。目标产物的结构式如下：
对上述无色油状物进行核磁波谱及质谱分析，数据如下：1H NMR(600MHz,CDCl3) δ8.36(d,J＝5.2Hz,1H),7.31–7.28(m,2H),7.23–7.20(m,3H),7.03(s,1H),6.98(d,J＝5.2Hz,1H),4.25(t,J＝5.9Hz,1H),4.05(t,J＝7.9Hz,1H),3.63–3.56(m,2H),3.44–3.38(m,2H),2.50(s,3H),2.33(dd,J＝7.9,5.9Hz,2H),1.19–1.16(m,6H)。13C NMR(150MHz,CDCl3)δ158.6,153.8,149.3,142.9,128.9,128.0,126.9,122.8,120.4,101.0,61.5,61.2,46.5,38.7,24.6,15.48,15.47。HRMS Calcd for C19H26NO2[M+H]+:m/z 300.1958,Found:300.1958。
实施例5
向装有磁子的10mL反应管中依次加入2,6-二甲基-4-氰基吡啶(0.2mmol)，碳酸铯(0.4mmol)，催化剂2,4,5,6-四(9-咔唑基)-间苯二腈(0.006mmol)；对反应管抽真空，用氮气置换三次，随后加入苯乙烯(0.5mmol)，2,2-二乙氧基乙酸(0.5mmol)和溶剂无水二甲基亚砜(2mL)，反应管在波长为455nm的蓝光LED灯照射及25℃的反应温度下搅拌24h。反应结束后，加入水淬灭反应，用乙酸乙酯萃取反应液，合并有机相之后用无水硫酸钠干燥，柱层析得到目标产物，目标产物为无色油状物。以2,6-二甲基-4-氰基吡啶摩尔量为100％计，目标产物的产率为94％。目标产物的结构式如下：
对上述无色油状物进行核磁波谱及质谱分析，数据如下：1H NMR(600MHz,CDCl3) δ7.30–7.28(m,2H),7.23–7.19(m,3H),6.84(s,2H),4.25(t,J＝5.9Hz,1H),4.00(t,J＝7.9Hz,1H),3.63–3.56(m,2H),3.43–3.38(m,2H),2.46(s,6H),2.33–2.30(m,2H),1.19–1.15 (m,6H)。13C NMR(150MHz,CDCl3)δ157.9,154.0,143.0,128.8,128.0,126.8,119.8,101.0,61.4,61.2,46.4,38.7,24.6,15.5。HRMS Calcd for C20H28NO2[M+H]+:m/z314.2115,Found:314.2117。
实施例6
向装有磁子的10mL反应管中依次加入3-氯-4-氰基吡啶(0.2mmol)，碳酸铯(0.4mmol)，催化剂2,4,5,6-四(9-咔唑基)-间苯二腈(0.006mmol)；对反应管抽真空，用氮气置换三次，随后加入苯乙烯(0.5mmol)，2,2-二乙氧基乙酸(0.5mmol)和溶剂无水二甲基亚砜(2mL)，反应管在波长为455nm的蓝光LED灯照射及25℃的反应温度下搅拌24 h。反应结束后，加入水淬灭反应，用乙酸乙酯萃取反应液，合并有机相之后用无水硫酸钠干燥，柱层析得到目标产物，目标产物为无色油状物。以3-氯-4-氰基吡啶摩尔量为100％计，目标产物的产率为52％。目标产物的结构式如下：
对上述无色油状物进行核磁波谱及质谱分析，数据如下：1H NMR(600MHz,CDCl3) δ8.52(s,1H),8.42(d,J＝5.1Hz,1H),7.31–7.28(m,3H),7.26(d,J＝1.5Hz,1H),7.25(s,1H),7.23–7.20(m,1H),4.63(t,J＝7.8Hz,1H),4.31(t,J＝5.9Hz,1H),3.65–3.58(m,2H),3.45–3.38(m,2H),2.35(dd,J＝7.8,5.9Hz,2H),1.19–1.15(m,6H)。13C NMR(150MHz,CDCl3)δ150.6,149.9,148.0,141.3,132.3,128.9,128.3,127.1,123.2,100.9,61.7,61.4,42.6,38.6,15.5,15.4。HRMS Calcd for C18H23ClNO2[M+H]+:m/z 320.1412,Found:320.1416。
实施例7
向装有磁子的10mL反应管中依次加入2-氯-4-氰基吡啶(0.2mmol)，碳酸铯(0.4mmol)，催化剂2,4,5,6-四(9-咔唑基)-间苯二腈(0.006mmol)；对反应管抽真空，用氮气置换三次，随后加入苯乙烯(0.5mmol)，2,2-二乙氧基乙酸(0.5mmol)和溶剂无水二甲基亚砜(2mL)，反应管在波长为455nm的蓝光LED灯照射及25℃的反应温度下搅拌24 h。反应结束后，加入水淬灭反应，用乙酸乙酯萃取反应液，合并有机相之后用无水硫酸钠干燥，柱层析得到目标产物，目标产物为无色油状物。以2-氯-4-氰基吡啶摩尔量为100％计，目标产物的产率为42％。目标产物的结构式如下：
对上述无色油状物进行核磁波谱及质谱分析，数据如下：1H NMR(600MHz,CDCl3) δ8.26(d,J＝5.1Hz,1H),7.33–7.31(m,2H),7.24(t,J＝7.4Hz,1H),7.21–7.20(m,3H),7.09(dd,J＝5.2,1.2Hz,1H),4.25(t,J＝5.9Hz,1H),4.09(t,J＝7.9Hz,1H),3.64–3.56(m,2H),3.44–3.37(m,2H),2.34–2.32(m,2H),1.19–1.16(m,6H)。13C NMR(150MHz,CDCl3) δ157.1,152.0,149.8,141.9,129.1,128.0,127.3,123.7,122.2,100.8,61.8,61.3,46.4,38.6,15.48,15.45。HRMS Calcd for C18H23ClNO2[M+H]+:m/z 320.1412,Found:320.1413。
实施例8
向装有磁子的10mL反应管中依次加入2-苯基异烟腈(0.2mmol)，碳酸铯(0.4mmol)，催化剂2,4,5,6-四(9-咔唑基)-间苯二腈(0.006mmol)；对反应管抽真空，用氮气置换三次，随后加入苯乙烯(0.5mmol)，2,2-二乙氧基乙酸(0.5mmol)和溶剂无水二甲基亚砜(2mL)，反应管在波长为455nm的蓝光LED灯照射及25℃的反应温度下搅拌24 h。反应结束后，加入水淬灭反应，用乙酸乙酯萃取反应液，合并有机相之后用无水硫酸钠干燥，柱层析得到目标产物，目标产物为无色油状物。以2-苯基异烟腈摩尔量为 100％计，目标产物的产率为83％。目标产物的结构式如下：
对上述无色油状物进行核磁波谱及质谱分析，数据如下：1H NMR(600MHz,CDCl3) δ8.58(d,J＝5.1Hz,1H),7.95–7.94(m,2H),7.61(s,1H),7.47–7.45(m,2H),7.41–7.39(m,1H),7.33–7.31(m,2H),7.29–7.27(m,2H),7.24–7.21(m,1H),7.13(dd,J＝5.1,1.5Hz,1H),4.31(t,J＝5.9Hz,1H),4.18(t,J＝7.9Hz,1H),3.66–3.59(m,2H),3.46–3.40(m,2H),2.43–2.41(m,2H),1.21–1.28(m,6H)。13C NMR(150MHz,CDCl3)δ157.9,154.3,149.9,142.7,139.6,129.0,128.9,128.8,128.0,127.1,127.0,121.8,120.3,101.0,61.6,61.3,46.8,38.8,15.50,15.48。HRMS Calcd for C24H28NO2[M+H]+:m/z 362.2115,Found:362.2117。
实施例9
向装有磁子的10mL反应管中依次加入2-(邻甲苯基)异烟腈(0.2mmol)，碳酸铯(0.4mmol)，催化剂2,4,5,6-四(9-咔唑基)-间苯二腈(0.006mmol)；对反应管抽真空，用氮气置换三次，随后加入苯乙烯(0.5mmol)，2,2-二乙氧基乙酸(0.5mmol)和溶剂无水二甲基亚砜(2mL)，反应管在波长为455nm的蓝光LED灯照射及25℃的反应温度下搅拌24h。反应结束后，加入水淬灭反应，用乙酸乙酯萃取反应液，合并有机相之后用无水硫酸钠干燥，柱层析得到目标产物，目标产物为无色油状物。以2-(邻甲苯基)异烟腈摩尔量为100％计，目标产物的产率为87％。目标产物的结构式如下：
对上述无色油状物进行核磁波谱及质谱分析，数据如下：1H NMR(600MHz,CDCl3) δ8.56–8.55(m,1H),7.36–7.35(m,1H),7.32–7.30(m,2H),7.28–7.27(m,2H),7.26–7.25(m,4H),7.23–7.20(m,1H),7.13(dd,J＝5.2,1.6Hz,1H),4.30(t,J＝5.8Hz,1H),4.14(t,J ＝7.8Hz,1H),3.65–3.57(m,2H),3.45–3.38(m,2H),2.42–2.36(m,2H),2.29(s,3H),1.17(q,J＝7.2Hz,6H)。13C NMR(150MHz,CDCl3)δ160.2,153.7,149.4,142.8,140.6,135.8, 130.8,129.7,128.9,128.4,128.0,127.0,126.0,123.7,121.3,101.0,61.6,61.3,46.7,38.8,20.4,15.49,15.47。HRMS Calcd for C25H30NO2[M+H]+:m/z 376.2271,Found:376.2275。
实施例10
向装有磁子的10mL反应管中依次加入2-(3-(三氟甲基)苯基)异烟腈(0.2mmol)，碳酸铯(0.4mmol)，催化剂2,4,5,6-四(9-咔唑基)-间苯二腈(0.006mmol)；对反应管抽真空，用氮气置换三次，随后加入苯乙烯(0.5mmol)，2,2-二乙氧基乙酸(0.5mmol)和溶剂无水二甲基亚砜(2mL)，反应管在波长为455nm的蓝光LED灯照射及25℃的反应温度下搅拌24h。反应结束后，加入水淬灭反应，用乙酸乙酯萃取反应液，合并有机相之后用无水硫酸钠干燥，柱层析得到目标产物，目标产物为无色油状物。以2-(3-(三氟甲基)苯基)异烟腈摩尔量为100％计，目标产物的产率为50％。目标产物的结构式如下：
对上述无色油状物进行核磁波谱及质谱分析，数据如下：1H NMR(600MHz,CDCl3) δ8.60(d,J＝5.1Hz,1H),8.24(s,1H),8.12(d,J＝7.8Hz,1H),7.66–7.63(m,2H),7.57(t,J＝7.8Hz,1H),7.34–7.32(m,2H),7.29–7.27(m,2H),7.25–7.22(m,1H),7.18(dd,J＝5.1,1.4Hz,1H),4.31(t,J＝5.9Hz,1H),4.20(t,J＝7.9Hz,1H),3.66–3.59(m,2H),3.47–3.40(m,2H),2.42(dd,J＝7.9,5.9Hz,2H),1.21–1.18(m,6H)。13C NMR(150MHz,CDCl3)δ 156.3,154.8,150.2,142.5,140.4,131.3(q,J＝33.0Hz),130.3,129.3,129.0,128.0,127.1,125.6(q,J＝4.5Hz),124.3(q,J＝270.0Hz),124.0(q,J＝3.0Hz),122.4,120.3,101.0,61.7, 61.4,46.8,38.8,15.50,15.48。19F NMR(376MHz,CDCl3)δ-62.55。HRMS Calcd forC25H27F3NO2[M+H]+:m/z 430.1988,Found:430.1982。
实施例11
向装有磁子的10mL反应管中依次加入4-氰基吡啶(0.2mmol)，碳酸铯(0.4mmol)，催化剂2,4,5,6-四(9-咔唑基)-间苯二腈(0.006mmol)；对反应管抽真空，用氮气置换三次，随后加入4-甲基苯乙烯(0.5mmol)，2,2-二乙氧基乙酸(0.5mmol)和溶剂无水二甲基亚砜(2mL)，反应管在波长为455nm的蓝光LED灯照射及25℃的反应温度下搅拌24h。反应结束后，加入水淬灭反应，用乙酸乙酯萃取反应液，合并有机相之后用无水硫酸钠干燥，柱层析得到目标产物，目标产物为无色油状物。以4-氰基吡啶摩尔量为100％计，目标产物的产率为77％。目标产物的结构式如下：
对上述无色油状物进行核磁波谱及质谱分析，数据如下：1H NMR(600MHz,CDCl3) δ8.47(dd,J＝4.8,1.2Hz,2H),7.16(dd,J＝4.8,1.2Hz,2H),7.11(s,4H),4.25(t,J＝5.9Hz,1H),4.05(t,J＝7.9Hz,1H),3.63–3.56(m,2H),3.44–3.37(m,2H),2.34–2.31(m,5H),1.19–1.16(m,6H)。13C NMR(150MHz,CDCl3)δ153.9,150.0,139.7,136.6,129.6,127.9,123.3,101.0,61.7,61.3,46.1,38.8,21.1,15.50,15.48。HRMS Calcd for C19H26NO2[M+ H]+:m/z 300.1958,Found:300.1957。
实施例12
向装有磁子的10mL反应管中依次加入4-氰基吡啶(0.2mmol)，碳酸铯(0.4mmol)，催化剂2,4,5,6-四(9-咔唑基)-间苯二腈(0.006mmol)；对反应管抽真空，用氮气置换三次，随后加入4-叔丁基苯乙烯(0.5mmol)，2,2-二乙氧基乙酸(0.5mmol)和溶剂无水二甲基亚砜(2mL)，反应管在波长为455nm的蓝光LED灯照射及25℃的反应温度下搅拌24h。反应结束后，加入水淬灭反应，用乙酸乙酯萃取反应液，合并有机相之后用无水硫酸钠干燥，柱层析得到目标产物，目标产物为无色油状物。以4-氰基吡啶摩尔量为100％计，目标产物的产率为89％。目标产物的结构式如下：
对上述无色油状物进行核磁波谱及质谱分析，数据如下：1H NMR(600MHz,CDCl3) δ8.48(d,J＝5.4Hz,2H),7.30(d,J＝8.4Hz,2H),7.18(d,J＝6.0Hz,2H),7.14(d,J＝8.3Hz,2H),4.27(t,J＝5.9Hz,1H),4.05(t,J＝7.9Hz,1H),3.63–3.56(m,2H),3.43–3.48(m, 2H),2.34(t,J＝7.3Hz,2H),1.32–1.29(m,9H),1.19–1.15(m,6H)。13C NMR(150MHz, CDCl3)δ153.8,149.9,149.8,139.6,127.6,125.8,123.4,101.0,61.5,61.1,46.1,38.8,34.5,31.6,31.5,15.5。HRMS Calcd for C22H32NO2[M+H]+:m/z 342.2428,Found:342.2430。
实施例13
向装有磁子的10mL反应管中依次加入4-氰基吡啶(0.2mmol)，碳酸铯(0.4mmol)，催化剂2,4,5,6-四(9-咔唑基)-间苯二腈(0.006mmol)；对反应管抽真空，用氮气置换三次，随后加入4-甲氧基苯乙烯(0.5mmol)，2,2-二乙氧基乙酸(0.5mmol)和溶剂无水二甲基亚砜(2mL),反应管在波长为455nm的蓝光LED灯照射及25℃的反应温度下搅拌24h。反应结束后，加入水淬灭反应，用乙酸乙酯萃取反应液，合并有机相之后用无水硫酸钠干燥，柱层析得到目标产物，目标产物为无色油状物。以4-氰基吡啶摩尔量为100％计，目标产物的产率为82％。目标产物的结构式如下：
对上述无色油状物进行核磁波谱及质谱分析，数据如下：1H NMR(600MHz,CDCl3) δ8.48(d,J＝5.5Hz,2H),7.16–7.12(m,4H),6.84(d,J＝8.7Hz,2H),4.25(t,J＝5.9Hz,1H),4.04(t,J＝7.9Hz,1H),3.78(s,3H),3.64–3.56(m,2H),3.44–3.37(m,2H),2.33–2.30 (m,2H),1.19–1.16(m,6H)。13C NMR(150MHz,CDCl3)δ158.5,154.0,150.0,134.7,129.0,123.2,114.3,101.0,61.6,61.3,55.4,45.7,38.9,15.50,15.48。HRMS Calcd for C19H26NO3[M+H]+:m/z 316.1907,Found:316.1909。
实施例14
向装有磁子的10mL反应管中依次加入4-氰基吡啶(0.2mmol)，碳酸铯(0.4mmol)，催化剂2,4,5,6-四(9-咔唑基)-间苯二腈(0.006mmol)；对反应管抽真空，用氮气置换三次，随后加入3-甲基苯乙烯(0.5mmol)，2,2-二乙氧基乙酸(0.5mmol)和溶剂无水二甲基亚砜(2mL)，反应管在波长为455nm的蓝光LED灯照射及25℃的反应温度下搅拌24h。反应结束后，加入水淬灭反应，用乙酸乙酯萃取反应液，合并有机相之后用无水硫酸钠干燥，柱层析得到目标产物，目标产物为无色油状物。以4-氰基吡啶摩尔量为100％计，目标产物的产率为66％。目标产物的结构式如下：
对上述无色油状物进行核磁波谱及质谱分析，数据如下：1H NMR(600MHz,CDCl3) δ8.49(d,J＝4.3Hz,2H),7.20–7.17(m,3H),7.03–7.02(m,3H),4.26(t,J＝5.9Hz,1H), 4.05(t,J＝7.9Hz,1H),3.63–3.57(m,2H),3.44–3.38(m,2H),2.35–2.31(m,5H),1.19–1.16 (m,6H)。13C NMR(150MHz,CDCl3)δ153.7,145.0,142.6,138.5,128.79,128.75,127.8, 125.0,123.3,101.0,61.6,61.2,46.5,38.7,21.6,15.49,15.46。HRMS Calcd for C19H26NO2[M+H]+:m/z 300.1958,Found:300.1958。
实施例15
向装有磁子的10mL反应管中依次加入4-氰基吡啶(0.2mmol)，碳酸铯(0.4mmol)，催化剂2,4,5,6-四(9-咔唑基)-间苯二腈(0.006mmol)；对反应管抽真空，用氮气置换三次，随后加入2-甲基苯乙烯(0.5mmol)，2,2-二乙氧基乙酸(0.5mmol)和溶剂无水二甲基亚砜(2mL)，反应管在波长为455nm的蓝光LED灯照射及25℃的反应温度下搅拌24h。反应结束后，加入水淬灭反应，用乙酸乙酯萃取反应液，合并有机相之后用无水硫酸钠干燥，柱层析得到目标产物，目标产物为无色油状物。以4-氰基吡啶摩尔量为100％计，目标产物的产率为62％。目标产物的结构式如下：
对上述无色油状物进行核磁波谱及质谱分析，数据如下：1H NMR(600MHz,CDCl3) δ8.47(d,J＝5.8Hz,2H),7.28(d,J＝7.6Hz,1H),7.23–7.20(m,1H),7.15–7.12(m,4H),4.34(t,J＝7.8Hz,1H),4.29(t,J＝5.9Hz,1H),3.64–3.57(m,2H),3.47–3.42(m,1H), 3.39–3.34(m,1H),2.33(dd,J＝7.8,5.9Hz,2H),2.28(s,3H),1.21–1.14(m,6H)。13C NMR(150MHz,CDCl3)δ153.5,149.9,140.4,136.5,131.0,126.91,126.89,126.5,123.6,100.9,61.7,61.1,42.0,39.1,19.9,15.5,15.4。HRMS Calcd for C19H26NO2[M+H]+:m/z 300.1958,Found:300.1959。
实施例16
向装有磁子的10mL反应管中依次加入4-氰基吡啶(0.2mmol)，碳酸铯(0.4mmol)，催化剂2,4,5,6-四(9-咔唑基)-间苯二腈(0.006mmol)；对反应管抽真空，用氮气置换三次，随后加入4-氟苯乙烯(0.5mmol)，2,2-二乙氧基乙酸(0.5mmol)和溶剂无水二甲基亚砜(2mL)，反应管在波长为455nm的蓝光LED灯照射及25℃的反应温度下搅拌24h。反应结束后，加入水淬灭反应，用乙酸乙酯萃取反应液，合并有机相之后用无水硫酸钠干燥，柱层析得到目标产物，目标产物为无色油状物。以4-氰基吡啶摩尔量为100％计，目标产物的产率为73％。目标产物的结构式如下：
对上述无色油状物进行核磁波谱及质谱分析，数据如下：1H NMR(600MHz,CDCl3) δ8.50(d,J＝5.0Hz,2H),7.18(dd,J＝8.5,5.3Hz,2H),7.14(d,J＝5.8Hz,2H),6.99(t,J＝8.6Hz,2H),4.24(t,J＝5.9Hz,1H),4.09(t,J＝7.9Hz,1H),3.63–3.56(m,2H),3.43–3.37(m,2H),2.36–2.27(m,2H),1.19–1.16(m,6H)。13C NMR(150MHz,CDCl3)δ161.8(d,J＝244.5Hz),153.4,150.1,138.4(d,J＝3.0Hz),129.5(d,J＝9.0Hz),123.2,115.8(d,J＝21.0Hz),100.8,61.6,61.4,45.8,38.8,15.48,15.46。19F NMR(376MHz,CDCl3)δ-115.86。HRMS Calcd for C18H23FNO2[M+H]+:m/z 304.1707,Found:304.1709。
实施例17
向装有磁子的10mL反应管中依次加入4-氰基吡啶(0.2mmol)，碳酸铯(0.4mmol)，催化剂2,4,5,6-四(9-咔唑基)-间苯二腈(0.006mmol)；对反应管抽真空，用氮气置换三次，随后加入4-氯苯乙烯(0.5mmol)，2,2-二乙氧基乙酸(0.5mmol)和溶剂无水二甲基亚砜(2mL)，反应管在波长为455nm的蓝光LED灯照射及25℃的反应温度下搅拌24h。反应结束后，加入水淬灭反应，用乙酸乙酯萃取反应液，合并有机相之后用无水硫酸钠干燥，柱层析得到目标产物，目标产物为无色油状物。以4-氰基吡啶摩尔量为100％计，目标产物的产率为68％。目标产物的结构式如下：
对上述无色油状物进行核磁波谱及质谱分析，数据如下：1H NMR(600MHz,CDCl3) δ8.50(d,J＝4.9Hz,2H),7.28–7.27(m,2H),7.16–7.13(m,4H),4.23(t,J＝5.9Hz,1H), 4.08(t,J＝7.9Hz,1H),3.63–3.56(m,2H),3.43–3.37(m,2H),2.36–2.27(m,2H),1.19–1.16 (m,6H)。13C NMR(150MHz,CDCl3)δ153.1,150.1,141.2,132.6,129.4,129.1,123.2, 100.8,61.6,61.5,45.9,38.7,15.48,15.47。HRMS Calcd for C18H23ClNO2[M+H]+:m/z 320.1412,Found:320.1414。
实施例18
向装有磁子的10mL反应管中依次加入4-氰基吡啶(0.2mmol)，碳酸铯(0.4mmol)，催化剂2,4,5,6-四(9-咔唑基)-间苯二腈(0.006mmol)；对反应管抽真空，用氮气置换三次，随后加入4-溴苯乙烯(0.5mmol)，2,2-二乙氧基乙酸(0.5mmol)和溶剂无水二甲基亚砜(2mL)，反应管在波长为455nm的蓝光LED灯照射及25℃的反应温度下搅拌24h。反应结束后，加入水淬灭反应，用乙酸乙酯萃取反应液，合并有机相之后用无水硫酸钠干燥，柱层析得到目标产物，目标产物为无色油状物。以4-氰基吡啶摩尔量为100％计，目标产物的产率为74％。目标产物的结构式如下：
对上述无色油状物进行核磁波谱及质谱分析，数据如下：1H NMR(600MHz,CDCl3) δ8.49–8.48(m,2H),7.43–7.41(m,2H),7.13–7.12(m,2H),7.10–7.08(m,2H),4.23(t,J＝5.9Hz,1H),4.06(t,J＝7.9Hz,1H),3.62–3.56(m,2H),3.43–3.36(m,2H),2.35–2.26(m,2H),1.18–1.15(m,6H)。13C NMR(150MHz,CDCl3)δ152.9,150.1,141.7,132.0,129.7,123.2,120.9,100.8,61.6,61.5,45.9,38.6,15.5。HRMS Calcd for C18H23BrNO2[M+H]+: m/z 364.0907,Found:364.0908。
实施例19
向装有磁子的10mL反应管中依次加入4-氰基吡啶(0.2mmol)，碳酸铯(0.4mmol)，催化剂2,4,5,6-四(9-咔唑基)-间苯二腈(0.006mmol)；对反应管抽真空，用氮气置换三次，随后加入3-氟苯乙烯(0.5mmol)，2,2-二乙氧基乙酸(0.5mmol)和溶剂无水二甲基亚砜(2mL)，反应管在波长为455nm的蓝光LED灯照射及25℃的反应温度下搅拌24h。反应结束后，加入水淬灭反应，用乙酸乙酯萃取反应液，合并有机相之后用无水硫酸钠干燥，柱层析得到目标产物，目标产物为无色油状物。以4-氰基吡啶摩尔量为100％计，目标产物的产率为68％。目标产物的结构式如下：
对上述无色油状物进行核磁波谱及质谱分析，数据如下：1H NMR(600MHz,CDCl3) δ8.51(d,J＝5.2Hz,2H),7.28–7.25(m,1H),7.15(d,J＝5.8Hz,2H),7.01(d,J＝7.8Hz, 1H),6.93–6.90(m,2H),4.25(t,J＝5.9Hz,1H),4.10(t,J＝7.9Hz,1H),3.63–3.57(m,2H),3.44–3.38(m,2H),2.34–2.31(m,2H),1.19–1.16(m,6H)。13C NMR(150MHz,CDCl3)δ 163.1(d,J＝244.5Hz),152.8,150.2,145.3(d,J＝6.0Hz),130.4(d,J＝7.5Hz),123.7(d,J ＝1.5Hz),123.2,115.0(d,J＝22.5Hz),114.0(d,J＝21.0Hz),100.8,61.6,61.4,46.3,38.6,15.46,15.45。19F NMR(376MHz,CDCl3)δ-112.48。HRMS Calcd for C18H23FNO2[M+H]+: m/z304.1707,Found:304.1707。
实施例20
向装有磁子的10mL反应管中依次加入4-氰基吡啶(0.2mmol)，碳酸铯(0.4mmol)，催化剂2,4,5,6-四(9-咔唑基)-间苯二腈(0.006mmol)；对反应管抽真空，用氮气置换三次，随后加入3-氯苯乙烯(0.5mmol)，2,2-二乙氧基乙酸(0.5mmol)和溶剂无水二甲基亚砜(2mL)，反应管在波长为455nm的蓝光LED灯照射及25℃的反应温度下搅拌24h。反应结束后，加入水淬灭反应，用乙酸乙酯萃取反应液，合并有机相之后用无水硫酸钠干燥，柱层析得到目标产物，目标产物为无色油状物。以4-氰基吡啶摩尔量为100％计，目标产物的产率为89％。目标产物的结构式如下：
对上述无色油状物进行核磁波谱及质谱分析，数据如下：1H NMR(600MHz,CDCl3) δ8.51(d,J＝6.0Hz,2H),7.23(t,J＝7.8Hz,1H),7.20–7.19(m,2H),7.15–7.14(m,2H),7.11–7.10(m,1H),4.24(t,J＝5.9Hz,1H),4.07(t,J＝7.9Hz,1H),3.63–3.57(m,2H), 3.43–3.37(m,2H),2.36–2.28(m,2H),1.19–1.16(m,6H)。13C NMR(150MHz,CDCl3)δ 152.6,150.2,144.8,134.7,130.1,128.2,127.2,126.2,123.2,100.7,61.6,61.4,46.2,38.5,15.5,15.4。HRMS Calcd for C18H23ClNO2[M+H]+:m/z 320.1412,Found:320.1412。
实施例21
向装有磁子的10mL反应管中依次加入4-氰基吡啶(0.2mmol)，碳酸铯(0.4mmol)，催化剂2,4,5,6-四(9-咔唑基)-间苯二腈(0.006mmol)；对反应管抽真空，用氮气置换三次，随后加入3-溴苯乙烯(0.5mmol)，2,2-二乙氧基乙酸(0.5mmol)和溶剂无水二甲基亚砜(2mL)，反应管在波长为455nm的蓝光LED灯照射及25℃的反应温度下搅拌24h。反应结束后，加入水淬灭反应，用乙酸乙酯萃取反应液，合并有机相之后用无水硫酸钠干燥，柱层析得到目标产物，目标产物为无色油状物。以4-氰基吡啶摩尔量为100％计，目标产物的产率为72％。目标产物的结构式如下：
对上述无色油状物进行核磁波谱及质谱分析，数据如下：1H NMR(600MHz,CDCl3) δ8.51(d,J＝4.5Hz,2H),7.36–7.35(m,2H),7.19–7.14(m,4H),4.24(t,J＝5.9Hz,1H),4.07(t,J＝7.9Hz,1H),3.63–3.57(m,2H),3.44–3.38(m,2H),2.36–2.28(m,2H),1.19–1.16 (m,6H)。13C NMR(150MHz,CDCl3)δ152.7,150.2,145.1,131.1,130.5,130.2,126.7, 123.3,123.0,100.7,61.6,61.4,46.2,38.6,15.47,15.45。HRMS Calcd for C18H23BrNO2[M +H]+:m/z 364.0907,Found:364.0904。
实施例22
向装有磁子的10mL反应管中依次加入4-氰基吡啶(0.2mmol)，碳酸铯(0.4mmol)，催化剂2,4,5,6-四(9-咔唑基)-间苯二腈(0.006mmol)；对反应管抽真空，用氮气置换三次，随后加入2-氟苯乙烯(0.5mmol)，2,2-二乙氧基乙酸(0.5mmol)和溶剂无水二甲基亚砜(2mL)，反应管在波长为455nm的蓝光LED灯照射及25℃的反应温度下搅拌24h。反应结束后，加入水淬灭反应，用乙酸乙酯萃取反应液，合并有机相之后用无水硫酸钠干燥，柱层析得到目标产物，目标产物为无色油状物。以4-氰基吡啶摩尔量为100％计，目标产物的产率为74％。目标产物的结构式如下：
对上述无色油状物进行核磁波谱及质谱分析，数据如下：1H NMR(600MHz,CDCl3) δ8.49–8.48(m,2H),7.29–7.26(m,1H),7.23–7.18(m,3H),7.12–7.10(m,1H),7.02–6.99(m,1H),4.41(t,J＝7.9Hz,1H),4.29(t,J＝5.9Hz,1H),3.64–3.57(m,2H),3.45–3.36(m, 2H),2.38–2.36(m,2H),1.16(q,J＝7.0Hz,6H)。13C NMR(150MHz,CDCl3)δ161.0(d,J ＝244.5Hz),152.4,150.0,129.7(d,J＝13.5Hz),128.8(d,J＝3.0Hz),128.7(d,J＝9.0Hz),124.5(d,J＝3.0Hz),123.3,116.0(d,J＝22.5Hz),101.0,61.9,61.1,39.6(d,J＝1.5Hz),37.6,15.4,15.3。19F NMR(376MHz,CDCl3)δ-116.71。HRMS Calcd for C18H23FNO2[M+H]+: m/z 304.1707,Found:304.1711。
实施例23
向装有磁子的10mL反应管中依次加入4-氰基吡啶(0.2mmol)，碳酸铯(0.4mmol)，催化剂2,4,5,6-四(9-咔唑基)-间苯二腈(0.006mmol)；对反应管抽真空，用氮气置换三次，随后加入2-氯苯乙烯(0.5mmol)，2,2＝二乙氧基乙酸(0.5mmol)和溶剂无水二甲基亚砜(2mL)，反应管在波长为455nm的蓝光LED灯照射及25℃的反应温度下搅拌24h。反应结束后，加入水淬灭反应，用乙酸乙酯萃取反应液，合并有机相之后用无水硫酸钠干燥，柱层析得到目标产物，目标产物为无色油状物。以4-氰基吡啶摩尔量为100％计，目标产物的产率为83％。目标产物的结构式如下：
对上述无色油状物进行核磁波谱及质谱分析，数据如下：1H NMR(600MHz,CDCl3) δ8.49–8.48(m,2H),7.37–7.33(m,2H),7.27–7.25(m,1H),7.19–7.16(m,3H),4.68(t,J＝7.8Hz,1H),4.30(t,J＝5.9Hz,1H),3.64–3.58(m,2H),3.47–3.36(m,2H),2.37–2.34(m,2H),1.19–1.15(m,6H)。13C NMR(150MHz,CDCl3)δ152.3,150.0,140.0,134.4,130.2,128.6,128.2,127.3,123.5,100.9,62.1,61.0,42.3,38.5,15.5,15.4。HRMS Calcd forC18H23ClNO2[M+H]+:m/z 320.1412,Found:320.1414。
实施例24
向装有磁子的10mL反应管中依次加入4-氰基吡啶(0.2mmol)，碳酸铯(0.4mmol)，催化剂2,4,5,6-四(9-咔唑基)-间苯二腈(0.006mmol)；对反应管抽真空，用氮气置换三次，随后加入2-溴苯乙烯(0.5mmol)，2,2-二乙氧基乙酸(0.5mmol)和溶剂无水二甲基亚砜(2mL)，反应管在波长为455nm的蓝光LED灯照射及25℃的反应温度下搅拌24h。反应结束后，加入水淬灭反应，用乙酸乙酯萃取反应液，合并有机相之后用无水硫酸钠干燥，柱层析得到目标产物，目标产物为无色油状物。以4-氰基吡啶摩尔量为100％计，目标产物的产率为62％。目标产物的结构式如下：
对上述无色油状物进行核磁波谱及质谱分析，数据如下：1H NMR(400MHz,CDCl3) δ8.48(d,J＝5.4Hz,2H),7.57–7.55(m,1H),7.34–7.30(m,2H),7.19(d,J＝5.9Hz,2H),7.11–7.07(m,1H),4.68(t,J＝7.8Hz,1H),4.30(t,J＝5.9Hz,1H),3.67–3.56(m,2H), 3.48–3.36(m,2H),2.36–2.33(m,2H),1.19–1.15(m,6H)。13C NMR(150MHz,CDCl3)δ152.3, 150.0,141.6,133.5,128.8,128.6,128.0,125.4,123.5,100.6,62.1,61.0,44.8,38.9,15.5,15.4。HRMS Calcd for C18H23BrNO2[M+H]+:m/z 364.0907,Found:364.0907。
实施例25
向装有磁子的10mL反应管中依次加入4-氰基吡啶(0.2mmol)，碳酸铯(0.4mmol)，催化剂2,4,5,6-四(9-咔唑基)-间苯二腈(0.006mmol)；对反应管抽真空，用氮气置换三次，随后加入N-(4-乙烯基-苯基)-乙酰胺(0.5mmol)，2,2-二乙氧基乙酸(0.5mmol)和溶剂无水二甲基亚砜(2mL)，反应管在波长为455nm的蓝光LED灯照射及25℃的反应温度下搅拌24h。反应结束后，加入水淬灭反应，用乙酸乙酯萃取反应液，合并有机相之后用无水硫酸钠干燥，柱层析得到目标产物，目标产物为无色油状物。以4-氰基吡啶摩尔量为100％计，目标产物的产率为57％。目标产物的结构式如下：
对上述无色油状物进行核磁波谱及质谱分析，数据如下：1H NMR(600MHz,CDCl3) δ8.48(s,2H),7.55(s,1H),7.45(d,J＝8.4Hz,2H),7.16–7.15(m,4H),4.24(t,J＝5.9Hz,1H),4.06(t,J＝7.9Hz,1H),3.63–3.56(m,2H),3.43–3.37(m,2H),2.33–2.30(m,2H),2.14(s,3H),1.18–1.15(m,6H)。13C NMR(150MHz,CDCl3)δ168.5,153.9,149.7,138.4,136.9,128.5,123.4,120.3,100.9,61.7,61.4,46.0,38.7,24.6,15.48,15.46。HRMS Calcd forC20H27N2O3[M+H]+:m/z 343.2016,Found:343.2015。
实施例26
向装有磁子的10mL反应管中依次加入4-氰基吡啶(0.2mmol)，碳酸铯(0.4mmol)，催化剂2,4,5,6-四(9-咔唑基)-间苯二腈(0.006mmol)；对反应管抽真空，用氮气置换三次，随后加入4-三氟甲基苯乙烯(0.5mmol)，2,2-二乙氧基乙酸(0.5mmol)和溶剂无水二甲基亚砜(2mL)，反应管在波长为455nm的蓝光LED灯照射及25℃的反应温度下搅拌24 h。反应结束后，加入水淬灭反应，用乙酸乙酯萃取反应液，合并有机相之后用无水硫酸钠干燥，柱层析得到目标产物，目标产物为无色油状物。以4-氰基吡啶摩尔量为100％计，目标产物的产率为44％。目标产物的结构式如下：
对上述无色油状物进行核磁波谱及质谱分析，数据如下：1H NMR(600MHz,CDCl3) δ8.52–8.51(m,2H),7.56(d,J＝8.2Hz,2H),7.34(d,J＝8.2Hz,2H),7.15(d,J＝6.1Hz,2H),4.24(t,J＝5.9Hz,1H),4.17(t,J＝7.9Hz,1H),3.64–3.57(m,2H),3.43–3.38(m,2H),2.41–2.32(m,2H),1.19–1.16(m,6H)。13C NMR(150MHz,CDCl3)δ152.4,150.3,146.8, 129.4(d,J＝33.0Hz),128.4,125.9(q,J＝4.5Hz),123.2,100.7,61.6,61.5,46.4,38.6,15.5。19FNMR(376MHz,CDCl3)δ-62.51。HRMS Calcd for C19H23F3NO2[M+H]+:m/z 354.1675,Found:354.1677。
实施例27
向装有磁子的10mL反应管中依次加入4-氰基吡啶(0.2mmol)，碳酸铯(0.4mmol)，催化剂2,4,5,6-四(9-咔唑基)-间苯二腈(0.006mmol)；对反应管抽真空，用氮气置换三次，随后加入2-乙烯基噻吩(0.5mmol)，2,2-二乙氧基乙酸(0.5mmol)和溶剂无水二甲基亚砜(2mL)，反应管在波长为455nm的蓝光LED灯照射及25℃的反应温度下搅拌24h。反应结束后，加入水淬灭反应，用乙酸乙酯萃取反应液，合并有机相之后用无水硫酸钠干燥，柱层析得到目标产物，目标产物为无色油状物。以4-氰基吡啶摩尔量为100％计，目标产物的产率为65％。目标产物的结构式如下：
对上述无色油状物进行核磁波谱及质谱分析，数据如下：1H NMR(600MHz,CDCl3) δ8.52(d,J＝5.7Hz,2H),7.21–7.18(m,3H),6.94–6.93(m,1H),6.87(d,J＝3.5Hz,1H),4.34(t,J＝7.9Hz,1H),4.29(t,J＝5.9Hz,1H),3.64–3.59(m,2H),3.45–3.39(m,2H), 2.44–2.39(m,1H),2.33–2.29(m,1H),1.21–1.16(m,6H)。13C NMR(150MHz,CDCl3)δ 153.0,150.2,146.4,127.0,124.6,124.4,123.1,100.8,61.9,61.4,42.2,40.5,15.50,15.46。HRMSCalcd for C16H22NO2S[M+H]+:m/z 292.1366,Found:292.1366。
实施例28
向装有磁子的10mL反应管中依次加入4-氰基吡啶(0.2mmol)，碳酸铯(0.4mmol)，催化剂2,4,5,6-四(9-咔唑基)-间苯二腈(0.006mmol)；对反应管抽真空，用氮气置换三次，随后加入1,2-二苯基乙烯(0.5mmol)，2,2-二乙氧基乙酸(0.5mmol)和溶剂无水二甲基亚砜(2mL)，反应管在波长为455nm的蓝光LED灯照射及25℃的反应温度下搅拌24h。反应结束后，加入水淬灭反应，用乙酸乙酯萃取反应液，合并有机相之后用无水硫酸钠干燥，柱层析得到目标产物，目标产物为无色油状物。以4-氰基吡啶摩尔量为100％计，目标产物的产率为50％。目标产物的结构式如下：
对上述无色油状物进行核磁波谱及质谱分析，数据如下：1H NMR(600MHz,CDCl3) δ8.53(d,J＝5.0Hz,2H),7.35(d,J＝5.3Hz,2H),7.23(d,J＝7.5Hz,2H),7.14–7.12(m, 4H),7.10–7.05(m,3H),6.99(t,J＝7.2Hz,1H),4.55(d,J＝11.6Hz,1H),4.28(d,J＝3.5Hz,1H),3.76(dd,J＝11.5,3.5Hz,1H),3.63–3.58(m,1H),3.49–3.39(m,2H),3.12–3.07 (m,1H),1.12–1.05(m,6H)。13C NMR(150MHz,CDCl3)δ153.3,150.1,141.5,137.9,130.4, 128.6,128.4,127.7,126.6,126.5,123.7,104.2,64.0,63.9,53.2,53.1,15.4,15.2。HRMS Calcdfor C24H28NO2[M+H]+:m/z 362.2115,Found:362.2115。
实施例29
向装有磁子的10mL反应管中依次加入4-氰基吡啶(0.2mmol)，碳酸铯(0.4mmol)，催化剂2,4,5,6-四(9-咔唑基)-间苯二腈(0.006mmol)；对反应管抽真空，用氮气置换三次，随后加入α-甲基苯乙烯(0.5mmol)，2,2-二乙氧基乙酸(0.5mmol)和溶剂无水二甲基亚砜(2mL)，反应管在波长为455nm的蓝光LED灯照射及25℃的反应温度下搅拌24h。反应结束后，加入水淬灭反应，用乙酸乙酯萃取反应液，合并有机相之后用无水硫酸钠干燥，柱层析得到目标产物，目标产物为无色油状物。以4-氰基吡啶摩尔量为100％计，目标产物的产率为66％。目标产物的结构式如下：
对上述无色油状物进行核磁波谱及质谱分析，数据如下：1H NMR(400MHz,CDCl3) δ8.47(d,J＝5.8Hz,2H),7.30–7.26(m,2H),7.21(d,J＝7.1Hz,1H),7.16(d,J＝7.5Hz,2H),7.10(d,J＝5.9Hz,2H),4.14(t,J＝4.8Hz,1H),3.54–3.43(m,2H),3.31–3.22(m,2H), 2.46(d,J＝4.8Hz,2H),1.70(s,3H),1.10–1.06(m,6H)。13C NMR(150MHz,CDCl3)δ 158.9,149.8,147.6,128.4,127.4,126.5,122.7,101.3,61.4,61.1,45.1,44.8,27.7,15.33,15.31。HRMSCalcd for C19H26NO2[M+H]+:m/z 300.1958,Found:300.1958。
实施例30
向装有磁子的10mL反应管中依次加入4-氰基吡啶(0.2mmol)，碳酸铯(0.4mmol)，催化剂2,4,5,6-四(9-咔唑基)-间苯二腈(0.006mmol)；对反应管抽真空，用氮气置换三次，随后加入苯乙烯(0.5mmol)，2,2-二乙氧基丙酸(0.5mmol)和溶剂无水二甲基亚砜(2mL)，反应管在波长为455nm的蓝光LED灯照射及25℃的反应温度下搅拌24h。反应结束后，加入水淬灭反应，用乙酸乙酯萃取反应液，合并有机相之后用无水硫酸钠干燥，柱层析得到目标产物，目标产物为无色油状物。以4-氰基吡啶摩尔量为100％计，目标产物的产率为82％。目标产物的结构式如下：
对上述无色油状物进行核磁波谱及质谱分析，数据如下：1H NMR(400MHz,CDCl3) δ8.47(d,J＝5.8Hz,2H),7.30–7.26(m,2H),7.21(d,J＝7.1Hz,1H),7.16(d,J＝7.5Hz, 2H),7.10(d,J＝5.9Hz,2H),4.14(t,J＝4.8Hz,1H),3.54–3.43(m,2H),3.31–3.22(m,2H),2.46(d,J＝4.8Hz,2H),1.70(s,3H),1.10–1.06(m,6H)。13C NMR(150MHz,CDCl3)δ 158.9,149.8,147.6,128.4,127.4,126.5,122.7,101.3,61.4,61.1,45.1,44.8,27.7,15.33,15.31。HRMSCalcd for C19H26NO2[M+H]+:m/z 300.1958,Found:300.1958。
实施例31
向装有磁子的10mL反应管中依次加入4-氰基吡啶(0.2mmol)，碳酸铯(0.4mmol)，催化剂2,4,5,6-四(9-咔唑基)-间苯二腈(0.006mmol)；对反应管抽真空，用氮气置换三次，随后加入苯乙烯(0.5mmol)，2,2-二乙氧基-4-苯基丁酸(0.5mmol)和溶剂无水二甲基亚砜(2mL)，反应管在波长为455nm的蓝光LED灯照射及25℃的反应温度下搅拌24h。反应结束后，加入水淬灭反应，用乙酸乙酯萃取反应液，合并有机相之后用无水硫酸钠干燥，柱层析得到目标产物，目标产物为无色油状物。以4-氰基吡啶摩尔量为100％计，目标产物的产率为52％。目标产物的结构式如下：
对上述无色油状物进行核磁波谱及质谱分析，数据如下：1H NMR(400MHz,CDCl3) δ8.48(d,J＝5.2Hz,2H),7.36–7.27(m,6H),7.22(t,J＝7.0Hz,1H),7.16–7.07(m,3H), 6.67(d,J＝7.1Hz,2H),4.03(t,J＝5.8Hz,1H),3.49–3.27(m,4H),2.61–2.51(m,2H),2.31–2.19(m,2H),1.77–1.72(m,2H),1.15–1.11(m,6H)。13C NMR(100MHz,CDCl3)δ 155.1,150.1,144.5,141.6,129.1,128.4,128.1,128.0,127.0,125.7,123.2,102.9,55.54,55.49,46.7,38.7,36.0,30.3,15.3。HRMS Calcd for C26H32NO2[M+H]+:m/z 390.2428, Found:390.2424。
实施例32
向装有磁子的10mL反应管中依次加入4-氰基吡啶(0.2mmol)，碳酸铯(0.4mmol)，催化剂2,4,5,6-四(9-咔唑基)-间苯二腈(0.006mmol)；对反应管抽真空，用氮气置换三次，随后加入取代苯乙烯(0.5mmol)，2,2-二乙氧基乙酸(0.5mmol)和溶剂无水二甲基亚砜(2mL)，反应管在波长为455nm的蓝光LED灯照射及25℃的反应温度下搅拌24h。反应结束后，加入水淬灭反应，用乙酸乙酯萃取反应液，合并有机相之后用无水硫酸钠干燥，柱层析得到目标产物，目标产物为无色油状物。以4-氰基吡啶摩尔量为100％计，目标产物的产率为87％。目标产物的结构式如下：
对上述无色油状物进行核磁波谱及质谱分析，数据如下：1H NMR(600MHz,CDCl3) δ8.48(d,J＝5.6Hz,2H),7.21(d,J＝8.1Hz,1H),7.18(d,J＝5.8Hz,2H),7.01(d,J＝8.1Hz,1H),6.93(s,1H),4.27(t,J＝5.9Hz,1H),4.02(t,J＝7.9Hz,1H),3.63–3.57(m,2H), 3.44–3.38(m,2H),2.87–2.85(m,2H),2.52–2.47(m,1H),2.40–2.37(m,1H),2.33(dd,J＝7.6,6.2Hz,2H),2.28–2.24(m,1H),2.17–2.10(m,1H),2.07–1.98(m,2H),1.96–1.93(m, 1H),1.65–1.56(m,2H),1.52–1.40(m,4H),1.18(t,J＝7.0Hz,6H),0.90(s,3H)。13C NMR(150MHz,CDCl3)δ153.7,150.0,140.2,138.5,137.0,128.52,128.47,125.84,125.81,125.3,125.2,123.4,100.9,61.5,61.0,50.6,48.1,46.1,44.4,38.7,38.2,36.0,31.7,29.6,26.6,25.8,21.7,15.50,15.49,14.0。HRMS Calcd for C30H40NO3[M+H]+:m/z462.3003,Found: 462.3003。
实施例33
向装有磁子的10mL反应管中依次加入4-氰基吡啶(0.2mmol)，碳酸铯(0.4mmol)，催化剂2,4,5,6-四(9-咔唑基)-间苯二腈(0.006mmol)；对反应管抽真空，用氮气置换三次，随后加入3-(4,5-二苯基恶唑-2-基)-N-(4-乙烯基苯基)丙胺(0.5mmol)，2,2-二乙氧基乙酸(0.5mmol)和溶剂无水二甲基亚砜(2mL)，反应管在波长为455nm的蓝光LED 灯照射及25℃的反应温度下搅拌24h。反应结束后，加入水淬灭反应，用乙酸乙酯萃取反应液，合并有机相之后用无水硫酸钠干燥，柱层析得到目标产物，目标产物为无色油状物。以4-氰基吡啶摩尔量为100％计，目标产物的产率为55％。目标产物的结构式如下：
对上述无色油状物进行核磁波谱及质谱分析，数据如下：1H NMR(400MHz,CDCl3) δ8.65(s,1H),8.47(d,J＝5.2Hz,2H),7.64–7.61(m,2H),7.56–7.53(m,2H),7.44(d,J＝8.4Hz,2H),7.37–7.32(m,6H),7.14–7.12(m,4H),4.23(t,J＝5.9Hz,1H),4.04(t,J＝7.9Hz,1H),3.64–3.54(m,2H),3.44–3.35(m,2H),3.26(t,J＝6.6Hz,2H),2.94(t,J＝6.9Hz,2H),2.32–2.28(m,2H),1.18–1.15(m,6H)。13C NMR(150MHz,CDCl3)δ170.0,162.6, 153.6,150.0,145.8,138.3,137.0,134.9,132.3,128.80,128.76,128.5,128.4,127.9,126.6,123.2,120.1,101.0,61.7,61.4,45.9,38.7,34.2,24.2,15.49,15.46。HRMS Calcd forC36H38N3O4[M+H]+:m/z 576.2857,Found:576.2842。
实施例34
向装有磁子的10mL反应管中依次加入4-氰基吡啶(0.2mmol)，碳酸铯(0.4mmol)，催化剂2,4,5,6-四(9-咔唑基)-间苯二腈(0.006mmol)；对反应管抽真空，用氮气置换三次，随后加入2-(4-异丁基苯基)-N-(4-乙烯基苯基)丙胺(0.5mmol)，2,2-二乙氧基乙酸(0.5mmol)和溶剂无水二甲基亚砜(2mL)，反应管在波长为455nm的蓝光LED灯照射及 25℃的反应温度下搅拌24h。反应结束后，加入水淬灭反应，用乙酸乙酯萃取反应液，合并有机相之后用无水硫酸钠干燥，柱层析得到目标产物，目标产物为无色油状物。以 4-氰基吡啶摩尔量为100％计，目标产物的产率为73％。目标产物的结构式如下：
对上述无色油状物进行核磁波谱及质谱分析，数据如下：1H NMR(400MHz,CDCl3) δ8.45(d,J＝5.8Hz,2H),7.36(d,J＝8.4Hz,2H),7.23(d,J＝7.9Hz,2H),7.15–7.11(m,7H),4.22(t,J＝5.9Hz,1H),4.03(t,J＝7.9Hz,1H),3.70–3.63(m,1H),3.61–3.53(m,2H),3.43–3.34(m,2H),2.46(d,J＝7.2Hz,2H),2.31–2.27(m,2H),1.90–1.80(m,1H),1.57(d,J＝7.1Hz,3H),1.16(t,J＝7.0Hz,6H),0.90(d,J＝6.6Hz,6H)。13C NMR(150MHz,CDCl3) δ172.7,153.7,149.9,141.3,138.4,138.1,136.9,130.0,128.5,127.5,123.2,120.1,101.0,61.7,61.4,47.8,45.9,45.1,38.7,30.3,22.5,18.6,15.49,15.46。HRMS Calcd forC31H41N2O3[M+H]+:m/z 489.3112,Found:489.3118。
实施例35
向装有磁子的10mL反应管中依次加入4-氰基吡啶(0.2mmol)，碳酸铯(0.4mmol)，催化剂2,4,5,6-四(9-咔唑基)-间苯二腈(0.006mmol)；对反应管抽真空，用氮气置换三次，随后加入取代苯乙烯(0.5mmol)，2,2-二乙氧基乙酸(0.5mmol)和溶剂无水二甲基亚砜(2mL)，反应管在波长为455nm的蓝光LED灯照射及25℃的反应温度下搅拌24h。反应结束后，加入水淬灭反应，用乙酸乙酯萃取反应液，合并有机相之后用无水硫酸钠干燥，柱层析得到目标产物，目标产物为无色油状物。以4-氰基吡啶摩尔量为100％计，目标产物的产率为35％。目标产物的结构式如下：
对上述无色油状物进行核磁波谱及质谱分析，数据如下：1H NMR(600MHz,CDCl3) δ8.48(d,J＝5.9Hz,2H),7.45(d,J＝8.4Hz,2H),7.17–7.14(m,5H),5.37–5.31(m,2H),4.25(t,J＝5.9Hz,1H),4.06(t,J＝7.9Hz,1H),3.63–3.56(m,2H),3.43–3.37(m,2H), 2.34–2.30(m,4H),2.02–1.99(m,4H),1.73–1.68(m,2H),1.36–1.26(m,20H),1.19–1.16(m,6H),0.87(t,J＝6.8Hz,3H)。13C NMR(150MHz,CDCl3)δ171.5,153.6,150.1,136.9, 130.2,129.9,128.6,123.2,120.2,101.0,61.7,61.4,45.9,38.7,37.9,32.0,29.9,29.8,29.7,29.48,29.46,29.42,29.37,29.3,27.4,27.3,25.7,22.8,15.51,15.49,14.3。HRMS Calcdfor C36H57N2O3[M+H]+:m/z 565.4364,Found:565.4359。
实施例36
向装有磁子的10mL反应管中依次加入4-氰基吡啶(0.2mmol)，碳酸铯(0.4mmol)，催化剂2,4,5,6-四(9-咔唑基)-间苯二腈(0.006mmol)；对反应管抽真空，用氮气置换三次，随后加入5-乙烯基-1H-吲哚-1-羧酸叔丁酯(0.5mmol)，2,2-二乙氧基乙酸(0.5mmol)和溶剂无水二甲基亚砜(2mL)，反应管在波长为455nm的蓝光LED灯照射及25℃的反应温度下搅拌24h。反应结束后，加入水淬灭反应，用乙酸乙酯萃取反应液，合并有机相之后用无水硫酸钠干燥，柱层析得到目标产物，目标产物为无色油状物。以4-氰基吡啶摩尔量为100％计，目标产物的产率为53％。目标产物的结构式如下：
对上述无色油状物进行核磁波谱及质谱分析，数据如下：1H NMR(400MHz,CDCl3) δ8.47(d,J＝5.6Hz,2H),8.05(d,J＝8.3Hz,1H),7.58(d,J＝3.6Hz,1H),7.41(d,J＝1.5Hz,1H),7.20–7.15(m,3H),6.51(d,J＝3.7Hz,1H),4.27(t,J＝5.9Hz,1H),4.19(t,J＝7.9 Hz,1H),3.66–3.55(m,2H),3.45–3.36(m,2H),2.40(dd,J＝7.9,6.0Hz,2H),1.64(s,9H),1.18(q,J＝7.1Hz,6H)。13C NMR(100MHz,CDCl3)δ154.2,149.9,137.0,134.2,131.1, 126.6,124.4,123.3,120.1,115.5,107.3,101.1,83.9,61.7,61.3,46.3,39.0,28.3,15.5。HRMSCalcd for C25H33N2O4[M+H]+:m/z 425.2435,Found:425.2439。
实施例37
向装有磁子的10mL反应管中依次加入4-氰基吡啶(0.2mmol)，碳酸铯(0.4mmol)，催化剂2,4,5,6-四(9-咔唑基)-间苯二腈(0.006mmol)；对反应管抽真空，用氮气置换三次，随后加入苯乙烯(0.5mmol)，2,2-二乙氧基乙酸(0.5mmol)和溶剂无水二甲基亚砜(2mL)，反应管在波长为455nm的蓝光LED灯照射及25℃的反应温度下搅拌24h。然后加入 2M HCl溶液(2mL)，室温搅拌3h，反应结束后，加入NaHCO3水溶液淬灭反应，用乙酸乙酯萃取反应液，合并有机相之后用无水硫酸钠干燥，柱层析得到目标产物，目标产物为无色油状物。以4-氰基吡啶摩尔量为100％计，目标产物的产率为82％。目标产物的结构式如下：
对上述无色油状物进行核磁波谱及质谱分析，数据如下：1H NMR(400MHz,CDCl3) δ9.76(s,1H),8.50–8.48(m,2H),7.34–7.30(m,2H),7.24–7.19(m,3H),7.15(d,J＝6.1Hz,2H),4.61(t,J＝7.6Hz,1H),3.20(dd,J＝7.6,1.4Hz,2H)。13C NMR(150MHz,CDCl3)δ 199.7,152.5,150.0,141.6,129.2,127.9,127.6,123.2,48.8,44.2。HRMS Calcd for C14H14NO[M+H]+:m/z 212.1070,Found:212.1065。
实施例38
向装有磁子的10mL反应管中依次加入4-氰基吡啶(0.2mmol)，碳酸铯(0.4mmol)，催化剂2,4,5,6-四(9-咔唑基)-间苯二腈(0.006mmol)；对反应管抽真空，用氮气置换三次，随后加入4-甲氧基苯乙烯(0.5mmol)，2,2-二乙氧基乙酸(0.5mmol)和溶剂无水二甲基亚砜(2mL)，反应管在波长为455nm的蓝光LED灯照射及25℃的反应温度下搅拌24h。然后加入2MHCl溶液(2mL)，室温搅拌3h，反应结束后，加入NaHCO3水溶液淬灭反应，用乙酸乙酯萃取反应液，合并有机相之后用无水硫酸钠干燥，柱层析得到目标产物，目标产物为无色油状物。以4-氰基吡啶摩尔量为100％计，目标产物的产率为75％。目标产物的结构式如下：
对上述无色油状物进行核磁波谱及质谱分析，数据如下：1H NMR(400MHz,CDCl3) δ9.75(s,1H),8.50(d,J＝4.1Hz,2H),7.14–7.11(m,4H),6.87–6.83(m,2H),4.56(t,J＝7.6Hz,1H),3.78(s,3H),3.16(dd,J＝7.6,1.4Hz,2H)。13C NMR(150MHz,CDCl3)δ200.0,158.9,152.8,150.1,133.6,128.9,123.1,114.5,55.4,49.0,43.5。HRMS Calcd forC15H16NO2[M+H]+:m/z 242.1176,Found:242.1182。
实施例39
向装有磁子的10mL反应管中依次加入4-氰基吡啶(0.2mmol)，碳酸铯(0.4mmol)，催化剂2,4,5,6-四(9-咔唑基)-间苯二腈(0.006mmol)；对反应管抽真空，用氮气置换三次，随后加入4-氯苯乙烯(0.5mmol)，2,2-二乙氧基乙酸(0.5mmol)和溶剂无水二甲基亚砜(2mL)，反应管在波长为455nm的蓝光LED灯照射及25℃的反应温度下搅拌24h。然后加入2MHCl溶液(2mL)，室温搅拌3h，反应结束后，加入NaHCO3水溶液淬灭反应，用乙酸乙酯萃取反应液，合并有机相之后用无水硫酸钠干燥，柱层析得到目标产物，目标产物为无色油状物。以4-氰基吡啶摩尔量为100％计，目标产物的产率为62％。
目标产物的结构式如下：
对上述无色油状物进行核磁波谱及质谱分析，数据如下：1H NMR(600MHz,CDCl3) δ9.75(s,1H),8.51(d,J＝5.9Hz,2H),7.30–7.28(m,2H),7.14–7.12(m,4H),4.59(t,J＝7.5Hz,1H),3.20–3.18(m,2H)。13C NMR(150MHz,CDCl3)δ199.2,151.9,150.2,140.1,133.3,129.3,129.3,123.0,48.7,43.5。HRMS Calcd for C14H13ClNO[M+H]+:m/z 246.0680,Found:246.0668。
实施例40
向装有磁子的10mL反应管中依次加入4-氰基吡啶(0.2mmol)，碳酸铯(0.4mmol)，催化剂2,4,5,6-四(9-咔唑基)-间苯二腈(0.006mmol)；对反应管抽真空，用氮气置换三次，随后加入苯乙烯(0.5mmol)，2,2-二乙氧基丙酸(0.5mmol)和溶剂无水二甲基亚砜(2mL)，反应管在波长为455nm的蓝光LED灯照射及25℃的反应温度下搅拌24h。然后加入 2M HCl溶液(2mL)，室温搅拌3h，反应结束后，加入NaHCO3水溶液淬灭反应，用乙酸乙酯萃取反应液，合并有机相之后用无水硫酸钠干燥，柱层析得到目标产物，目标产物为无色油状物。以4-氰基吡啶摩尔量为100％计，目标产物的产率为88％。目标产物的结构式如下：
对上述无色油状物进行核磁波谱及质谱分析，数据如下：1H NMR(600MHz,CDCl3) δ8.48(d,J＝5.9Hz,2H),7.30–7.28(m,2H),7.22–7.18(m,3H),7.13(d,J＝6.1Hz,2H),4.57(t,J＝7.4Hz,1H),3.18(d,J＝7.4Hz,2H),2.11(s,3H)。13C NMR(150MHz,CDCl3) δ205.9,152.8,150.1,142.2,129.0,127.9,127.1,123.1,48.8,45.2,30.7。HRMS Calcd forC15H16NO[M+H]+:m/z 226.1226,Found:226.1226。
以上显示和描述了本发明的基本原理，主要特征和优点，在不脱离本发明精神和范围的前提下，本发明还有各种变化和改进，这些变化和改进都落入要求保护的本发明的范围。

Claims (10)

1.一种4-取代吡啶类化合物的合成方法，其特征在于具体步骤为：在催化剂和碱的作用下，将苯乙烯类化合物、氰基吡啶类化合物和2,2-二乙氧基羧酸类化合物置于溶剂中，在蓝光照射、氮气环境的条件下进行反应，反应结束后向反应液中加水淬灭反应，再用乙酸乙酯萃取反应液，合并有机相之后用无水硫酸钠干燥，经柱层析得到目标产物烯烃缩醛-吡啶类化合物，其中催化剂为2,4,5,6-四(9-咔唑基)-间苯二腈，碱为碳酸铯，氰基吡啶类化合物的结构式如式A所示，苯乙烯类化合物的结构式如式B所示，2,2-二乙氧基羧酸类化合物的结构式如式C所示，目标产物烯烃缩醛-吡啶类化合物的结构式如式D所示：
R1为H、C1-5烷基、C1-5烷氧基、苯基、取代苯基或卤素；R2为H、C1-5烷基、C1-5烷氧基、三氟甲基、酰胺类取代基、杂环类取代基或卤素；R3为H、C1-5烷基或苯乙基；
所述溶剂为无水二甲基亚砜。
2.根据权利要求1所述的4-取代吡啶类化合物的合成方法，其特征在于：所述烯烃缩醛-吡啶类化合物的具体结构式为：
3.一种4-取代吡啶类化合物的合成方法，其特征在于具体步骤为：在催化剂和碱的作用下，将苯乙烯类化合物、氰基吡啶类化合物和2,2-二乙氧基羧酸类化合物置于溶剂无水二甲基亚砜中，在蓝光照射、氮气环境的条件下进行反应，反应结束后向反应液中加水淬灭反应，再用乙酸乙酯萃取反应液，合并有机相之后用无水硫酸钠干燥，经柱层析得到目标产物烯烃缩醛-吡啶类化合物其中催化剂为2,4,5,6-四(9-咔唑基)-间苯二腈，碱为碳酸铯，苯乙烯类化合物为1,2-二苯基乙烯或α-甲基苯乙烯，氰基吡啶类化合物为4-氰基吡啶，2,2-二乙氧基羧酸类化合物为2,2-二乙氧基乙酸。
4.一种4-取代吡啶类化合物的合成方法，其特征在于具体步骤为：在催化剂和碱的作用下，将苯乙烯类化合物、氰基吡啶类化合物和2,2-二乙氧基羧酸类化合物置于溶剂无水二甲基亚砜中，在蓝光照射、氮气环境的条件下进行反应，再加入盐酸溶液进行反应，反应结束后向反应液中加NaHCO3水溶液淬灭反应，再用乙酸乙酯萃取反应液，合并有机相之后用无水硫酸钠干燥，经柱层析得到目标产物烯烃醛基(酮基)-吡啶类化合物，其中催化剂为2,4,5,6-四(9-咔唑基)-间苯二腈，碱为碳酸铯，苯乙烯类化合物为苯乙烯、4-甲氧基苯乙烯或4-氯苯乙烯，氰基吡啶类化合物为4-氰基吡啶，2,2-二乙氧基羧酸类化合物为2,2-二乙氧基乙酸或2,2-二乙氧基丙酸，目标产物烯烃醛基(酮基)-吡啶类化合物的具体结构式为：
5.根据权利要求1、3或4所述的4-取代吡啶类化合物的合成方法，其特征在于：所述氰基吡啶类化合物、苯乙烯类化合物、2,2-二乙氧基羧酸类化合物、催化剂与碱的投料摩尔比为1:1-3:1-3:0.01-0.05:1-3。
6.根据权利要求1、3或4所述的4-取代吡啶类化合物的合成方法，其特征在于：蓝光的光源为蓝色LED灯，其波长为450-455nm，功率为5-10W。
7.根据权利要求1、3或4所述的4-取代吡啶类化合物的合成方法，其特征在于：反应过程的反应温度为20-30℃，反应时间为12-24h。
8.一种4-取代吡啶类化合物的合成方法，其特征在于具体步骤为：向装有磁子的10mL反应管中依次加入4-氰基吡啶0.2mmol，碳酸铯0.4mmol，催化剂2,4,5,6-四(9-咔唑基)-间苯二腈0.006mmol；对反应管抽真空，用氮气置换三次，随后加入2-乙烯基噻吩0.5mmol，2,2-二乙氧基乙酸0.5mmol和溶剂无水二甲基亚砜2mL，反应管在波长为455nm的蓝光LED灯照射及25℃的反应温度下搅拌24h，反应结束后，加入水淬灭反应，用乙酸乙酯萃取反应液，合并有机相之后用无水硫酸钠干燥，柱层析得到目标产物，目标产物为无色油状物
9.一种4-取代吡啶类化合物的合成方法，其特征在于具体步骤为：向装有磁子的10mL反应管中依次加入4-氰基吡啶0.2mmol，碳酸铯0.4mmol，催化剂2,4,5,6-四(9-咔唑基)-间苯二腈0.006mmol；对反应管抽真空，用氮气置换三次，随后加入取代苯乙烯0.5mmol，2,2-二乙氧基乙酸0.5mmol和溶剂无水二甲基亚砜2mL，反应管在波长为455nm的蓝光LED灯照射及25℃的反应温度下搅拌24h，反应结束后，加入水淬灭反应，用乙酸乙酯萃取反应液，合并有机相之后用无水硫酸钠干燥，柱层析得到目标产物
10.一种4-取代吡啶类化合物的合成方法，其特征在于具体步骤为：向装有磁子的10mL反应管中依次加入4-氰基吡啶0.2mmol，碳酸铯0.4mmol，催化剂2,4,5,6-四(9-咔唑基)-间苯二腈0.006mmol；对反应管抽真空，用氮气置换三次，随后加入5-乙烯基-1H-吲哚-1-羧酸叔丁酯0.5mmol，2,2-二乙氧基乙酸0.5mmol和溶剂无水二甲基亚砜2mL，反应管在波长为455nm的蓝光LED灯照射及25℃的反应温度下搅拌24h，反应结束后，加入水淬灭反应，用乙酸乙酯萃取反应液，合并有机相之后用无水硫酸钠干燥，柱层析得到目标产物
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