CN113620838B - 一种烯基腈的合成方法 - Google Patents

一种烯基腈的合成方法 Download PDF

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CN113620838B
CN113620838B CN202011403756.2A CN202011403756A CN113620838B CN 113620838 B CN113620838 B CN 113620838B CN 202011403756 A CN202011403756 A CN 202011403756A CN 113620838 B CN113620838 B CN 113620838B
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郑学丽
蒋燕鑫
陈华
付海燕
袁茂林
李瑞祥
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Chengdu Xinhuayuan Science And Technology Co ltd
Sichuan University
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Abstract

本发明公开了一种烯基腈的合成方法，包括以下步骤：首先将铑催化剂和膦配体按比例称量放入釜中，再加入溶剂将其两者溶解，随后加入腈类化合物，烯烃或炔烃，碱，并在反应釜中充入CO和H2，后加热反应，反应通过氢甲酰化反应和Knoevenagel反应机制得到烯基腈类化合物。其中腈类底物范围广泛，苯乙腈中芳基的对位和间位的取代基为吸电子基团或供电子基团都能取得不错的效果，且将芳基换成杂环也能够实现。该方法的反应条件温和，操作简单，原料容易得到，底物来源广泛，可转化为多种其他有用的分子，具有很强的实用性。

Description

一种烯基腈的合成方法
技术领域
本发明属于有机合成技术领域，具体涉及一种烯基腈的合成方法。
背景技术
烯基腈至少具有一个碳碳双键和一个氰基，这两个位点具有选择性反应的潜力。氰基可以通过继续反应转变成酸、醛、醇和胺等化合物，碳碳双键也可以通过加成反应等添加各种基团。烯基腈存在于许多天然产物中，尤为突出的腈类化合物和药学上重要的化合物。因此合成这类化合物的方法受到广泛的关注。其中人们采用了醛和腈反应，醇和腈获得烯基腈的方法成为研究的热门。然而在已报道的方法中，存在着反应原料不易得，Z/E选择性不好，反应条件不够温和等缺点。因此，一种操作简单、条件温和、具有底物普适性且便于工业应用的方法急于被开发。
发明内容
针对上述现有技术，本发明提供一种烯基腈的合成方法，以拓宽烯基腈的合成路径。
为了达到上述目的，本发明所采用的技术方案是：提供一种烯基腈的合成方法，其特征在于，包括以下步骤：
先将底物、铑前体、膦配体、碱和溶剂投入反应容器中，然后通入CO和H2，于40～120℃下反应1～12h，得烯基腈；底物包括腈类化合物和烯烃或炔烃。反应方程式如下。
Figure BDA0002817929640000011
烯烃为直链烯烃、环状烯烃或带芳香环的烯烃；炔烃为邻位、间位或对位被取代基取代的苯乙炔；腈类化合物为邻位、间位和/或对位被取代基取代的苯乙腈或在β位带有不饱和键的直链腈。
在上述技术方案的基础上，本发明还可以做如下改进。
进一步，底物中腈类化合物与烯烃的摩尔比为1:1～3；铑前体相对于底物的用量为0.1～4.0mmol％，膦配体相对于底物的用量为0.3～10.0mmol％，碱相对于底物的用量为0.5～5.0mmol％。
进一步，的铑前体为Rh(acac)(CO)2、[RhCl(CH2＝CH2)2]2、Rh(cod)2BF4h和Rh(acac)(CH2＝CH2)2中的任意一种。
进一步，膦配体为式(L1)～式(L10)所示化合物中的任意一种；
Figure BDA0002817929640000021
进一步，碱为KOH、NaOH、DBU、PivOK和DIPA中的至少一种。
进一步，溶剂为甲苯、正己烷、正戊烷、十三烷和四氢呋喃中的至少一种。
进一步，所通入的CO和H2的体积比为1:1，并且所通入的气体量以反应容器中压力达到0.2～4MPa为准。
本发明中的反应为两步反应，依次为氢甲酰化反应和Knoevenagel反应，CO和H2主要是在第一步中起作用将烯烃变成多一个碳的醛，在让醛和苯乙腈类化合物进行反应得到烯基腈。
本发明的有益效果是：通过铑催化，膦配体和碱的协同作用，在CO和H2下，一锅反应得到烯基腈类化合物，该方法存在Z/E选择性高，底物范围广泛，活性高等特点，且反应条件温和，操作简单，原料容易得到，产物可转化为多种其他有用的分子，具有很强的实用性。
附图说明
图1为本发明合成反应的反应通式；
图2为本发明合成反应的反应原理。
具体实施方式
为使本发明实施例的目的、技术方案和优点更加清楚，下面将对本发明实施例中的技术方案进行清楚、完整地描述。实施例中未注明具体条件者，按照常规条件或制造商建议的条件进行。所用试剂或仪器未注明生产厂商者，均为可以通过市售购买获得的常规产品。
本发明实施例中化合物的熔点通过XRC-I型显微熔点仪测得，温度计未校正；核磁共振波谱由Bruker DPX-400MHz核磁共振仪(溶剂：CDCl3，内标TMS)测得；高分辨质谱采用Water Micromass GCT质谱仪(ESI源)；薄层色谱采用[HFGF254硅胶板]。
下面结合实施例对本发明的具体实施方式做详细的说明。
实施例1
本实施例中提供了氢甲酰化和Knoevenagel反应串联制备如式I-a所示的化合物的方法。
Figure BDA0002817929640000031
其制备步骤如下：在空气中，向高压反应釜中加入铑前体氯双(乙烯)铑(I)二聚物[RhCl(CH2＝CH2)2]2(1.8mmol％)，如式(L2)所示的膦配体(3.6mmol％)，间甲基苯乙腈(1mmol)，1-己烯(1mmol)，KOH(1mmol％)和溶剂甲苯(3mL)，充入CO和H2，共计4MPa。
Figure BDA0002817929640000032
在80℃下搅拌反应4h。反应完成后冷却至室温。经分离，得无色透明液体，产率为83％。对产物I-b进行结构表征，结果如下：1H NMR(400MHz,CDCl3)δ7.27–7.17(m,3H),7.08(d,J＝7.4Hz,1H),6.74(t,J＝7.8Hz,1H),2.50(m,J＝15.0,7.6Hz,2H),2.30(s,3H),1.51–1.45(m,2H),1.37–1.29(m,2H),1.28–1.21(m,4H),0.83(m,J＝9.1,4.8Hz,3H).13C NMR(101MHz,CDCl3)δ146.0,137.7,132.2,128.6,127.8,125.3,121.7,115.8,114.9,31.2,30.6,27.7,21.52(s),20.4,13.0.HRMS(ESI)m/z:calc for[C16H21NNa]+:250.1566；Found:250.1562.
实施例2
本实施例中提供了氢甲酰化和Knoevenagel反应串联制备如式I-b所示的化合物的方法。
Figure BDA0002817929640000041
其制备步骤如下：在空气中，向高压反应釜中加入铑前体二(1,5-环辛二烯)四氟硼酸铑(I)Rh(cod)2BF4(1.8mmol％)，如式(L6)所示的膦配体(3.6mmol％)，苯乙腈(1mmol)，苯乙炔(1mmol)，KOH(1mmol％)和溶剂甲苯(3mL)，充入CO和H2，共计0.4MPa。
Figure BDA0002817929640000042
在80℃下搅拌反应4h。反应完成后冷却至室温。经分离，得白色固体，产率为35％。对产物I-b进行结构表征，结果如下：1H NMR(400MHz,CDCl3)δ7.58(dd,J＝7.5,1.7Hz,2H),7.47(dd,J＝8.3,6.7Hz,2H),7.40(dt,J＝7.9,5.0Hz,1H),7.29–7.23(m,6H),6.78(d,J＝15.6Hz,1H),6.02(dd,J＝15.6,10.0Hz,1H),4.64(d,J＝10.0Hz,1H).HRMS(ESI)m/z:calcfor[C17H14N]+:232.1121；Found:232.1121.
实施例3
本实施例中提供了氢甲酰化和Knoevenagel反应串联制备如式I-c所示的化合物的方法。
Figure BDA0002817929640000043
其制备步骤如下：在空气中，向高压反应釜中加入铑前体乙酰丙酮酰双(亚乙基)化铑Rh(acac)(CH2＝CH2)2(1.8mmol％)，如式(L4)所示的膦配体(3.2mmol％)，对甲氧基苯乙腈(1mmol)，1-己烯(1mmol)，KOH(1mmol％)和溶剂正己烷(3mL)，充入CO和H2，共计2MPa。
Figure BDA0002817929640000051
在80℃下搅拌反应4h。反应完成后冷却至室温。经分离，得无色透明液体，产率为83％。对产物I-c进行结构表征，结果如下：1H NMR(400MHz,CDCl3)δ7.72–7.34(m,1H),7.03–6.82(m,1H),6.69(t,J＝7.8Hz,1H),3.82(s,2H),2.55(dd,J＝15.0,7.6Hz,1H),1.62–1.46(m,1H),1.35(dtd,J＝14.2,7.3,3.2Hz,3H),0.90(dd,J＝9.1,4.6Hz,2H).13C NMR(101MHz,CDCl3)δ159.1,144.0,125.9,124.9,115.8,114.2,113.3,76.4,76.0,75.7,54.4,31.1,30.6,27.8,27.7,21.5,13.0.HRMS(ESI)m/z:calc for[C16H21NNaO]+:266.1515；Found:266.1514.
实施例4
本实施例中提供了氢甲酰化和Knoevenagel反应串联制备如式I-d所示的化合物的方法。
Figure BDA0002817929640000052
其制备步骤如下：在空气中，向高压反应釜中加入铑前体氯双(乙烯)铑(I)二聚物[RhCl(CH2＝CH2)2]2(1.6mmol％)，如式(L5)所示的膦配体(3.6mmol％)，3,4-亚甲二氧基苯乙腈(1mmol)，1-己烯(2mmol)，KOH(1.5mmol％)和溶剂四氢呋喃(3mL)，充入CO:H2，共计2MPa。
Figure BDA0002817929640000053
在80℃下搅拌反应4h。反应完成后冷却至室温。经分离，得无色透明液体，产率为72％。对产物I-d进行结构表征，结果如下：1H NMR(400MHz,CDCl3)δ6.91(dd,J＝8.1,1.9Hz,1H),6.85(d,J＝1.9Hz,1H),6.67(d,J＝8.1Hz,1H),6.55(t,J＝7.8Hz,1H),5.85(s,2H),2.42(dd,J＝15.0,7.6Hz,2H),1.55–1.34(m,2H),1.31–1.16(m,6H),0.79(t,J＝6.9Hz,3H).13C NMR(101MHz,CDCl3)δ147.3,147.2,144.4,126.5,119.0,115.6,114.3,107.4,104.5,100.5,31.1,30.5,27.8,27.7,21.5,13.0.HRMS(ESI)m/z:calc for[C16H19NNaO2]+:280.1308；Found:280.1308.
实施例5
本实施例中提供了氢甲酰化和Knoevenagel反应串联制备如式I-e所示的化合物的方法。
Figure BDA0002817929640000061
其制备步骤如下：在空气中，向高压反应釜中加入铑前体Rh(acac)(CO)2(1.8mmol％)，如式(L6)所示的膦配体膦配体(3.6mmol％)，对氟苯乙腈(1mmol)，1-己烯(1.5mmol)，NaOH(1mmol％)和溶剂四氢呋喃(3mL)，充入CO和H2，共计2MPa。
Figure BDA0002817929640000062
在80℃下搅拌反应4h。反应完成后冷却至室温。经分离，得无色透明液体，产率为82％。对产物I-e进行结构表征，结果如下：1H NMR(400MHz,CDCl3)δ7.39(m,J＝8.8,5.1Hz,2H),6.96(t,J＝8.6Hz,2H),6.66(t,J＝7.8Hz,1H),2.46(q,J＝7.5Hz,2H),1.52–1.39(m,2H),1.36–1.17(m,6H),0.80(t,J＝6.7Hz,3H).13C NMR(101MHz,CDCl3)δ163.2,160.7,146.1(d,J＝1.8Hz),128.5(d,J＝3.5Hz),126.4,126.4(s),117.0–112.2(m),31.2,30.5,27.8,27.6,21.5,13.0.HRMS(ESI)m/z:calc for[C15H17FN]-:230.1351；Found:230.1350.
实施例6
本实施例中提供了氢甲酰化和Knoevenagel反应串联制备如式I-f所示的化合物的方法。
Figure BDA0002817929640000063
其制备步骤如下：在空气中，向高压反应釜中加入铑前体乙酰丙酮酰双(亚乙基)化铑Rh(acac)(CH2＝CH2)2(1.8mmol％)，如式(L7)所示的膦配体(3.6mmol％)，萘乙腈(1mmol)，1-己烯(1mmol)，NaOH(1mmol％)和溶剂正十三烷(3mL)，充入CO和H2＝1:1，共计4MPa。
Figure BDA0002817929640000071
在100℃下搅拌反应2h。反应完成后冷却至室温。经分离，得无色透明液体，产率为27％。对产物I-f进行结构表征，结果如下：1H NMR(400MHz,CDCl3)δ7.91(dd,J＝7.8,1.8Hz,3H),7.65–7.45(m,3H),7.37(dd,J＝7.0,1.0Hz,1H),6.94(t,J＝7.7Hz,1H),2.03(dd,J＝14.9,7.5Hz,2H),1.38(q,J＝14.9,7.3Hz,2H),1.24–1.08(m,6H),0.81(t,J＝7.0Hz,3H).13C NMR(101MHz,CDCl3)δ152.8,133.7,130.9,129.6,129.6,128.6,127.5,127.0,126.5,125.3,124.5,119.4,113.4,31.4,29.8,28.7,28.3,22.4,14.0.HRMS(ESI)m/z:calc for[C19H22N]+:264.1747；Found:264.1743.
实施例7
本实施例中提供了氢甲酰化和Knoevenagel反应串联制备如式I-g所示的化合物的方法。
Figure BDA0002817929640000072
其制备步骤如下：在空气中，向高压反应釜中加入铑前体二(1,5-环辛二烯)四氟硼酸铑(I)Rh(cod)2BF4(1mmol％)，如式(L8)所示的膦配体(1mmol％)，对氯苯乙腈(1mmol)，1-己烯(2mmol)，KOH(1mmol)和溶剂正己烷(3mL)，充入CO和H2，共计2MPa。
Figure BDA0002817929640000073
在60℃下搅拌反应3h。反应完成后冷却至室温。经分离，得无色透明液体，产率为79％。对产物I-g进行结构表征，结果如下：1H NMR(400MHz,CDCl3)δ7.38–7.30(m,2H),7.25–7.17(m,2H),6.71(t,J＝7.8Hz,1H),2.46(dd,J＝15.0,7.6Hz,2H),1.50–1.38(m,2H),1.34–1.17(m,6H),0.79(t,J＝6.8Hz,3H).13C NMR(101MHz,CDCl3)δ146.7,133.7,130.8,128.1,125.8,115.2,113.8,31.3,30.5,27.9,27.6,21.5,13.0.HRMS(ESI)m/z:calc for[C15H17ClN]-:246.1055；Found:246.1054.
实施例8
本实施例中提供了氢甲酰化和Knoevenagel反应串联制备如式I-h所示的化合物的方法。
Figure BDA0002817929640000081
其制备步骤如下：在空气中，向高压反应釜中加入铑前体Rh(acac)(CO)2(0.5mmol％)，如式(L9)所示的膦配体(1mmol％)，间溴苯乙腈(2mmol)，1-己烯(3mmol)，KOH(1mmol％)和溶剂正戊烷(3mL)，充入CO和H2，共计2MPa。
Figure BDA0002817929640000082
在80℃下搅拌反应3h。反应完成后冷却至室温。经分离，得无色透明液体，产率为79％。对产物I-h进行结构表征，结果如下：1H NMR(400MHz,CDCl3)δ7.58(t,J＝1.8Hz,1H),7.47–7.30(m,2H),7.18(dd,J＝8.6,7.2Hz,1H),6.77(t,J＝7.8Hz,1H),2.51(dd,J＝15.0,7.6Hz,2H),1.63–1.39(m,2H),1.38–1.16(m,6H),0.82(t,J＝6.9Hz,3H).13C NMR(101MHz,CDCl3)δ148.7,135.3,131.8,130.4,128.5,124.4,123.1,116.1,114.7,32.3,31.5,28.9,28.6,22.5,14.1.HRMS(ESI)m/z:calc for[C15H17BrN]-:290.0550；Found:290.0556.
实施例9
本实施例中提供了氢甲酰化和Knoevenagel反应串联制备如式I-i所示的化合物的方法。
Figure BDA0002817929640000083
其制备步骤如下：在空气中，向高压反应釜中加入铑前体氯双(乙烯)铑(I)二聚物[RhCl(CH2＝CH2)2]2(1.8mmol％)，如式(L10)所示的膦配体(2mmol％)，对三氟甲基苯乙腈(1mmol)，1-己烯(2mmol)，KOH(1.5mmol％)和溶剂四氢呋喃(3mL)，充入CO和H2，共计2MPa。
Figure BDA0002817929640000091
在120℃下搅拌反应2h。反应完成后冷却至室温。经分离，得无色透明液体，产率为74％。对产物I-i进行结构表征，结果如下：1H NMR(400MHz,CDCl3)δ7.52(s,4H),6.85(t,J＝7.7Hz,1H),2.50(dd,J＝14.8,7.4Hz,2H),1.46(dd,J＝14.5,7.3Hz,2H),1.36–1.08(m,6H),0.79(s,3H).13C NMR(101MHz,CDCl3)δ148.7,135.7,129.8(q,J＝32.9Hz),125.2–124.8(m),122.8(q,J＝272.1Hz),115.0,113.9,31.4,30.5,27.9,27.5,21.5,13.0.HRMS(ESI)m/z:calc for[C16H17F3N]-:280.1319；Found:280.1310.
实施例10
本实施例中提供了氢甲酰化和Knoevenagel反应串联制备如式I-j所示的化合物的方法。
Figure BDA0002817929640000092
其制备步骤如下：在空气中，向高压反应釜中加入铑前体二(1,5-环辛二烯)四氟硼酸铑(I)Rh(cod)2BF4(0.5mmol％)，如式(L6)所示的膦配体(0.5mmol％)，4-联苯乙腈(1mmol)，1-己烯(1mmo)，KOH(1mmol％)和溶剂正戊烷(3mL)，充入CO和H2，共计4MPa。
Figure BDA0002817929640000093
在100℃下搅拌反应4h。反应完成后冷却至室温。经分离，得白色固体，熔点:61.8-62.9。产率为79％。对产物I-j进行结构表征，结果如下：1H NMR(400MHz,CDCl3)δ7.62(dt,J＝10.9,4.9Hz,6H),7.46(t,J＝7.5Hz,2H),7.41–7.29(m,1H),6.88(t,J＝7.8Hz,1H),2.61(dd,J＝15.0,7.6Hz,2H),1.57(dd,J＝15.6,6.9Hz,2H),1.49–1.26(m,6H),0.91(t,J＝7.0Hz,3H).13C NMR(101MHz,CDCl3)δ146.0,140.7,139.1,131.2,127.9,126.7,126.6,126.0,125.0,115.6,114.5,31.3,30.6,27.9,27.7,21.5,13.0.HRMS(ESI)m/z:calc for[C21H23NNa]+:312.1723；Found:312.1721.
实施例11
本实施例中提供了氢甲酰化和Knoevenagel反应串联制备如式I-k所示的化合物的方法。
Figure BDA0002817929640000101
其制备步骤如下：在空气中，向高压反应釜中加入铑前体氯双(乙烯)铑(I)二聚物[RhCl(CH2＝CH2)2]2(1mmol％)，如式(L7)所示的膦配体(2mmol％)，2-氰基噻吩(1mmol)，1-己烯(1.5mmol)，KOH(1.5mmol％)和溶剂十三烷(3mL)，充入CO和H2，共计2MPa。
Figure BDA0002817929640000102
在100℃下搅拌反应4h。反应完成后冷却至室温。经分离，得无色透明液体，产率为70％。对产物I-k进行结构表征，结果如下：1H NMR(400MHz,CDCl3)δ7.23(dd,J＝13.7,8.2Hz,2H),7.01(dd,J＝4.9,3.8Hz,1H),6.65(t,J＝7.9Hz,1H),2.53(dd,J＝15.1,7.6Hz,2H),1.53(dd,J＝15.0,7.4Hz,2H),1.35(m,J＝13.8,7.1,2.7Hz,6H),0.90(t,J＝6.8Hz,3H).13C NMR(101MHz,CDCl3)δ144.2,136.7,126.7,125.2,124.5,114.5,109.4,30.9,30.5,27.8,27.6,21.5,13.0.HRMS(ESI)m/z:calc for[C13H16NS]-:218.1009；Found:218.1015.
实施例12
本实施例中提供了氢甲酰化和Knoevenagel反应串联制备如式I-l所示的化合物的方法。
Figure BDA0002817929640000111
其制备步骤如下：在空气中，向高压反应釜中加入铑前体乙酰丙酮酰双(亚乙基)化铑Rh(acac)(CH2＝CH2)2(1.8mmol％)，如式(L5)所示的膦配体(3.6mmol％)，3,4-二氯苯基乙腈(1mmol)，1-己烯(1mmol)，KOH(0.5mmol)和溶剂正己烷(3mL)，充入CO和H2，共计0.4MPa。
Figure BDA0002817929640000112
在80℃下搅拌反应4h。反应完成后冷却至室温。经分离，得无色透明液体，产率为64％。对产物I-l进行结构表征，结果如下：1H NMR(400MHz,CDCl3)δ7.60(d,J＝2.2Hz,1H),7.45(d,J＝8.4Hz,1H),7.39–7.30(m,1H),6.84(t,J＝7.8Hz,1H),2.58(dd,J＝15.0,7.6Hz,2H),1.67–1.48(m,2H),1.39(m,J＝11.8,8.6,5.9Hz,2H),1.35–1.28(m,4H),1.02–0.84(m,3H).13C NMR(101MHz,CDCl3)δ149.0,133.3,133.3,133.0,130.8,127.4,124.8,115.8,114.0,32.4,31.5,28.9,28.5,22.5,14.0.
实施例13
本实施例中提供了氢甲酰化和Knoevenagel反应串联制备如式I-m所示的化合物的方法。
Figure BDA0002817929640000113
其制备步骤如下：在空气中，向高压反应釜中加入铑前体Rh(acac)(CO)2(1.5mmol％)，如式(L1)所示的膦配体(2mmol％)，苯乙腈(1mmol)，1-辛烯(1mmol)，KOH(1mmo％l)和溶剂正己烷(3mL)，充入CO和H2，共计1MPa。
Figure BDA0002817929640000121
在90℃下搅拌反应4h。反应完成后冷却至室温。经分离，的无色透明液体，产率为81％。对产物I-m进行结构表征，结果如下：无色透明液体，1H NMR(400MHz,CDCl3)δ7.59–7.49(m,2H),7.44–7.31(m,3H),6.83(t,J＝7.8Hz,1H),2.59(dd,J＝15.0,7.6Hz,2H),1.65–1.50(m,2H),1.45–1.25(m,10H),0.89(t,J＝6.9Hz,3H).13C NMR(101MHz,CDCl3)δ146.2,132.3,127.9,127.8,124.6,115.6,114.8,31.2,30.8,28.3,28.2,28.2,27.7,21.6,13.1.HRMS(ESI)m/z:calc for[C17H23NNa]+:264.1723；Found:264.1724.
实施例14
本实施例中提供了氢甲酰化和Knoevenagel反应串联制备如式I-n所示的化合物的方法。
Figure BDA0002817929640000122
其制备步骤如下：在空气中，向高压反应釜中加入铑前体Rh(acac)(CO)2(1.5mmol％)，如式(L7)所示的膦配体(3.6mmol％)，苯乙腈(1mmol)，环戊烯(1mmol)，KOH(0.5mmol％)和溶剂正十三烷(3mL)，充入CO和H2，共计3MPa。
Figure BDA0002817929640000123
在90℃下搅拌反应4h。反应完成后冷却至室温。经分离，的无色透明液体，产率为67％。对产物I-n进行结构表征，结果如下：，1H NMR(400MHz,CDCl3)δ7.74–7.44(m,2H),7.47–7.28(m,3H),6.72(d,J＝10.1Hz,1H),3.41–2.97(m,1H),2.17–1.93(m,2H),1.97–1.64(m,4H),1.52–1.31(m,2H).13C NMR(101MHz,CDCl3)δ151.0,132.3,127.9,127.7,124.6,115.9,113.0,42.0,32.3,24.6.HRMS(ESI)m/z:calc for[C14H15NNa]+:220.1097；Found:220.1101.
实施例15
本实施例中提供了氢甲酰化和Knoevenagel反应串联制备如式I-o所示的化合物的方法。
Figure BDA0002817929640000131
其制备步骤如下：在空气中，向高压反应釜中加入铑前体Rh(acac)(CO)2(1.8mmol％)，如式(L9)所示的膦配体(3.6mmol％)，苯乙腈(1mmol)，苯乙烯(1mmol)，KOH(1mmol％)和溶剂正己烷(3mL)，充入CO和H2，共计2MPa。
Figure BDA0002817929640000132
在100℃下搅拌反应4h。反应完成后冷却至室温。经分离，得无色透明液体，产率为29％。对产物I-o进行结构表征，结果如下：1H NMR(400MHz,CDCl3)δ7.54–7.36(m,2H),7.27(m,J＝6.8,3.4,0.7Hz,7H),7.18(m,J＝8.5,3.3,2.2Hz,1H),6.77(d,J＝10.4Hz,1H),4.46–3.93(m,1H),1.47(d,J＝6.9Hz,3H).13C NMR(101MHz,CDCl3)δ149.4,141.7,131.9,128.0,127.9,127.9,126.1,126.0,124.8,115.6,113.2,41.3,19.6.HRMS(ESI)m/z:calcfor[C17H16N]+:234.1277；Found:234.1277.
实施例16
本实施例中提供了氢甲酰化和Knoevenagel反应串联制备如式I-p所示的化合物的方法。
Figure BDA0002817929640000133
其制备步骤如下：在空气中，向高压反应釜中加入铑前体二(1,5-环辛二烯)四氟硼酸铑(I)Rh(cod)2BF4(1.8mmol％)，如式(L10)所示的膦配体(3.6mmol％)，苯乙腈(1mmol)，萘丙烯(1mmol),KOH(1mmol％)和溶剂正己烷(3mL)，充入CO和H2，共计4MPa。
Figure BDA0002817929640000141
在80℃下搅拌反应4h。反应完成后冷却至室温。经分离，得白色固体，产率为55％。对产物I-p进行结构表征，结果如下：1H NMR(400MHz,CDCl3)δ8.04(d,J＝8.3Hz,1H),7.92–7.81(m,1H),7.79–7.66(m,1H),7.63–7.46(m,4H),7.45–7.33(m,5H),6.81(t,J＝7.7Hz,1H),3.35–3.03(t,2H),2.73(q,J＝15.1,7.6Hz,2H),2.23–1.84(m,2H).13C NMR(101MHz,CDCl3)δ146.5,137.5,134.0,133.2,131.7,129.0,128.9,128.9,127.0,126.2,126.0,125.6,125.6,125.6,123.6,116.6,116.4,32.6,32.2,29.7.HRMS(ESI)m/z:calc for[C22H20N]+:298.1590；Found:298.1592.
虽然结合实施例对本发明的具体实施方式进行了详细地描述，但不应理解为对本专利的保护范围的限定。在权利要求书所描述的范围内，本领域技术人员不经创造性劳动即可作出的各种修改和变形仍属本专利的保护范围。

Claims (3)

1.一种烯基腈的合成方法，其特征在于，包括以下步骤：
先将底物、铑前体、膦配体、碱和溶剂投入反应容器中，然后通入CO和H2，于40～120℃下反应1～12h，得烯基腈；所述底物由腈类化合物和烯烃或炔烃组成；
所述烯烃为直链烯烃、环状烯烃或带芳香环的烯烃；所述炔烃为邻位、间位或对位被取代基取代的苯乙炔；所述腈类化合物为邻位、间位和/或对位被取代基取代的苯乙腈或在β位带有不饱和键的直链腈；
所述的铑前体为Rh(acac)(CO)2、[RhCl(CH2＝CH2)2]2、Rh(cod)2BF4和Rh(acac)(CH2＝CH2)2中的任意一种；
所述膦配体为式(L1)～式(L10)所示化合物中的任意一种；
Figure FDA0003684716660000011
所述碱为KOH、NaOH、DBU、PivOK和DIPA的至少一种；
所述溶剂为甲苯、正己烷、正戊烷、十三烷和四氢呋喃中的至少一种。
2.根据权利要求1所述的烯基腈的合成方法，其特征在于：所述底物中腈类化合物与烯烃或炔烃的摩尔比为1:1～3。
3.根据权利要求1所述的烯基腈的合成方法，其特征在于：所通入的CO和H2的体积比为1:1，并且所通入的气体量以反应容器中压力达到0.2～4MPa为准。
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