CN108659048A - 含氮配位钌卡宾催化剂及制备方法及应用 - Google Patents

含氮配位钌卡宾催化剂及制备方法及应用 Download PDF

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CN108659048A
CN108659048A CN201710198119.8A CN201710198119A CN108659048A CN 108659048 A CN108659048 A CN 108659048A CN 201710198119 A CN201710198119 A CN 201710198119A CN 108659048 A CN108659048 A CN 108659048A
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王建辉
段玉莲
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Tianjin University
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Abstract

本发明公开了含氮配位钌卡宾催化剂及制备方法及应用，含氮配位钌卡宾催化剂，其特征是用式(I)所示：本发明的含氮配位钌卡宾催化剂在催化闭环和交叉复分解反应中具有高引发速率和高催化活性。

Description

含氮配位钌卡宾催化剂及制备方法及应用
技术领域
本发明属过渡金属有机催化剂领域，涉及一种含氮配位钌卡宾催化剂及制备方法及应用。
背景技术
在过去的几十年里，烯烃复分解反应已被广泛应用于有机合成中碳碳双键的形成，如聚合物、药物和天然产物的合成1。Grubbs组报道了两个最具代表性的催化剂，见图3，一个是含有两个三环己基膦(PCy3)配体的催化剂1(Grubbs一代)，另外一个是含有N-杂环卡宾配体的催化剂2(Grubbs二代)2。在Grubbs催化剂的基础上，Hoveyda 3开发了两种以酚氧螯合钌卡宾的催化剂3和4，见图3，称为Grubbs-Hoveyda型催化剂。相较与催化剂1和2来说，由于催化剂3和4是通过酚氧螯合钌金属中心形成了更稳定的五元环框架，使得催化剂3和4更加稳定，通常用于催化剂回收研究.42004年，Grela报道了一个配合物[(H2IMes)(Cl)2Ru]C(H)[p-NO2(C6H3)OCH(CH3)2]4a5，见图3。其基本结构框架与配合物4相似，区别在于它在苄亚卡宾对位上连有一个吸电子基(-NO2)。硝基的引入明显地降低了氧原子的供电子性能，改变了苯环上的电子云密度，可以通过加速配体解离过程来提高这些配合物的引发速率。这一成功的设计提醒我们，吸电子基团的引入可以显著提高氧螯合钌催化剂的催化活性。
近年来，人们还合成了许多含有其氮原子螯合的钌烯烃复分解催化剂，如Grubbs等人6合成了以亚胺氮配位的钌卡宾催化剂5和6，见图4，在此体系中碳氮双键的位置极大地影响了催化剂的引发速率。在此基础上，再引入另外一个配位原子(O,S)，使其形成“3-点螯合(3-point chelate)”的配位形式的配合物7，见图4。这种配位形式的催化剂可以提高催化剂本身的热力学稳定性，但同时也降低了催化剂的引发速率。
现有技术的不足之处：由于配位原子氮与金属钌中心的配位能力较强，从而导致含氮配体很难从钌中心解离下来，进而降低了催化剂的引发速率。为了提高进一步这类含氮配体的配合物的催化活性，人们在催化反应中通常用质子酸和Lewis酸作为助催化剂，或者通过提高反应温度等方法提高催化效率。
目前亟需合成一种在室温或低温条件下具有高引发速率和高催化活性的含氮配位烯烃复分解催化剂。
发明内容
本发明的目的是克服现有技术存在的含氮配位烯烃复分解催化剂配体难以解离，催化活性低的不足，提供一种含氮配位钌卡宾催化剂。
本发明的第二个目的是提供一种含氮配位钌卡宾催化剂的制备方法。
本发明的第三个目的是提供一种含氮配位钌卡宾催化剂的应用。
本发明的技术方案概述如下：
含氮配位钌卡宾催化剂，是用式(I)所示：
其中：
R1＝-H、-OCH3、-F、-CF3或-COOCH2CH3。
含氮配位钌卡宾催化剂的制备方法，包括如下步骤：
氮气保护下，将Grubbs II催化剂(III)，氯化亚铜和化合物(II)溶于二氯甲烷中，在搅拌下，加热回流，降温至室温，旋干，过色谱硅胶柱，向所述色谱硅胶柱内加入体积比为1:1的石油醚和二氯甲烷的混合液洗脱杂质，再加入二氯甲烷洗脱得到含氮配位钌卡宾催化剂(I)；
反应式如下：
其中：
R1＝-H、-OCH3、-F、-CF3或-COOCH2CH3；
所述Grubbs II催化剂的结构见式(III)：
优选地，所述Grubbs II催化剂，氯化亚铜和化合物(II)的摩尔比为1:1:1.5。
上述含氮配位钌卡宾催化剂在催化闭环和交叉复分解中的应用。
本发明的优点：
本发明的含氮配位钌卡宾催化剂在催化闭环和交叉复分解反应中具有高引发速率和高催化活性。
附图说明
图1为催化剂Ia-f的稳定性实验。
图2为催化剂Ia-f的动力学曲线。
图3为商用Grubbs型催化剂和Hoveyda-Grubbs型催化剂。
图4为已报道过的氮螯合钌卡宾催化剂。
具体实施方式
下面结合具体实施例对本发明作进一步的说明。
化合物II的结构为：
当R1＝-H、-OCH3、-F、-CF3或-COOCH2CH3时，依次用II-b、II-c、II-d、II-e、II-f表示。
实施例1
化合物II-b的制备：
将化合物IV-b(2.66g,20mmol)和化合物3,3,3-三氟丙酮酸乙酯V(4.0g,24mmol)溶于20mL甲苯中，在搅拌下，加热回流3小时，降温至室温，旋干，过色谱硅胶柱，向所述色谱硅胶柱内加入体积比为1:1的石油醚和二氯甲烷的混合液洗脱直接得到所需产品，旋干，得到黄色油状物质。化合物II-b.产率:85％.1H NMR(400MHz,CDCl3):δ7.29(d,J＝6.3Hz,1H),7.26–7.18(m,2H),6.69(t,J＝8.5Hz,1H),6.01–5.80(m,1H),5.12–5.04(m,2H),4.19(q,J＝7.1Hz,2H),3.39(d,J＝6.5Hz,2H),1.09(t,J＝7.1Hz,3H)ppm；13C NMR(100MHz,CDCl3):δ159.2,145.2,135.8,131.5,129.9,127.2,126.7,117.0,116.2,62.6,35.9,13.5ppm.
其中：
R1＝-H、-OCH3、-F、-CF3或-COOCH2CH3。
实施例2
化合物II-c的制备：
将化合物IV-c(3.26g,20mmol)和化合物3,3,3-三氟丙酮酸乙酯V(4.0g,24mmol)溶于20mL甲苯中，在搅拌下，加热回流3小时，降温至室温，旋干，过色谱硅胶柱，向所述色谱硅胶柱内加入体积比为1:1的石油醚和二氯甲烷的混合液洗脱直接得到所需产品，旋干，得到黄色油状物质。化合物II-c.产率:88％.1H NMR(400MHz,CDCl3):δ6.83(d,J＝8.5Hz,1H),6.72(t,J＝5.1Hz,2H),5.97–5.81(m,1H),5.11–5.00(m,2H),4.24(q,J＝7.1Hz,2H),3.82(s,3H),3.42(d,J＝6.6Hz,2H),1.17(t,J＝7.1Hz,3H)ppm.13C NMR(100MHz,CDCl3):δ160.0,159.4,137.9,135.8,135.3,118.7,116.2,115.4,111.7,62.5,55.4,36.1,13.6ppm.
实施例3
化合物II-d的制备：
将化合物IV-d(3.0g,20mmol)和化合物3,3,3-三氟丙酮酸乙酯V(4.0g,24mmol)溶于20mL甲苯中，在搅拌下，加热回流3小时，降温至室温，旋干，过色谱硅胶柱，向所述色谱硅胶柱内加入体积比为1:1的石油醚和二氯甲烷的混合液洗脱直接得到所需产品，旋干，得到黄色油状物质。化合物II-d.产率:82％.1H NMR(400MHz,CDCl3):δ7.01(dt,J＝16.0,8.0Hz,1H),6.89(tt,J＝14.7,7.4Hz,1H),6.70(dd,J＝8.6,5.0Hz,1H),5.89(m,J＝16.8,10.1,6.6Hz,1H),5.10(dd,J＝20.0,4.8Hz,2H),4.23(q,J＝7.1Hz,2H),3.38(d,J＝6.6Hz,2H),1.30(s,3H),1.14(t,J＝7.1Hz,3H)ppm.13C NMR(100MHz,CDCl3):δ163.0,160.5,159.2,141.0,135.0–134.4,119.5,118.5,117.0–116.5,113.5,113.3,62.7,35.7,13.6ppm.
实施例4
化合物II-e的制备：
将化合物IV-e(4.0g,20mmol)和化合物3,3,3-三氟丙酮酸乙酯V(4.0g,24mmol)溶于20mL甲苯中，在搅拌下，加热回流4小时，降温至室温，旋干，过色谱硅胶柱，向所述色谱硅胶柱内加入体积比为1:1的石油醚和二氯甲烷的混合液洗脱直接得到所需产品，旋干，得到黄色油状物质。化合物II-e.产率:87％.1H NMR(400MHz,CDCl3):δ7.53(d,J＝14.6Hz,1H),7.49(d,J＝8.2Hz,1H),6.78(d,J＝8.2Hz,1H),5.96–5.80(m,1H),5.21–5.04(m,2H),4.20(q,J＝7.1Hz,2H),3.37(d,J＝6.6Hz,2H),1.09(t,J＝7.1Hz,3H)ppm.13C NMR(100MHz,CDCl3):δ158.1,148.1,134.5,131.4,126.7,123.9,117.3,117.0,63.0,35.6,26.9,13.4ppm.
实施例5
化合物II-f的制备：
将化合物IV-f(4.1g,20mmol)和化合物3,3,3-三氟丙酮酸乙酯V(4.0g,24mmol)溶于20mL甲苯中，在搅拌下，加热回流4小时，降温至室温，旋干，过色谱硅胶柱，向所述色谱硅胶柱内加入体积比为1:1的石油醚和二氯甲烷的混合液洗脱直接得到所需产品，旋干，得到黄色油状物质。化合物II-f.产率:90％.1H NMR(400MHz,CDCl3):δ7.91(dd,J＝23.2,15.0Hz,2H),6.72(d,J＝8.2Hz,1H),5.89(m,J＝16.9,10.5,6.6Hz,1H),5.08(dd,J＝13.0,5.5Hz,2H),4.43–4.36(m,2H),4.18(dd,J＝14.2,7.1Hz,2H),3.36(d,J＝6.6Hz,2H),1.42(t,J＝7.1Hz,4H),1.09(dd,J＝9.6,4.6Hz,3H)ppm.13C NMR(100MHz,CDCl3):δ165.9,158.2,149.1,135.0,131.2,130.6,128.9,128.4,119.3,118.4,116.8,63.0,61.0,35.8,14.3,13.5ppm.
含氮配位钌卡宾催化剂，用式(I)所示：
实施例6
含氮配位钌卡宾催化剂(I-a)，用-H替代结构式(I)中的-CF3，R1＝-H时为(I-a)的的制备；
氮气保护下，将Grubbs II催化剂(1.96g，2.3mmol)，氯化亚铜(0.23g，2.3mmol)和化合物(II-a)(988mg，3.45mmol)溶于25mL二氯甲烷中，在搅拌下，加热回流30min，降温至室温，旋干，过色谱硅胶柱，向所述色谱硅胶柱内加入体积比为1:1的石油醚和二氯甲烷的混合液洗脱杂质，再加入二氯甲烷洗脱得到含氮配位钌卡宾催化剂(I)，旋干，得到蓝色固体(1.63g,2.39mmol，Yield:79％)；
化合物(II-a)结构式：
Grubbs II催化剂的结构见式(III)：
经检测，1H NMR(400MHz,CDCl3)δ17.56(s,1H),8.19(s,1H),7.24(t,J＝3.8Hz,2H),7.10–7.04(m,1H),7.02(s,4H),6.96(d,J＝8.1Hz,1H),4.61(d,J＝6.2Hz,2H),4.04(q,J＝7.0Hz,2H),3.98(s,4H),2.43(d,J＝53.1Hz,18H),1.28(d,J＝6.9Hz,3H).13C NMR(100MHz,CDCl3):δ334.7,216.3,166.6,149.2,145.6,137.9,137.6,131.6,131.4,129.3,127.9,127.0,118.2,64.1,60.7,53.4,51.3,22.3,21.1,19.0,17.8,14.1ppm.
实施例7
采用实施例6方法制备含氮配位钌卡宾催化剂(I-b)，(R1＝-H)；原料之一化合物为相应的(II-b)，得到的固体为绿色；
1H NMR(400MHz,CDCl3)δ17.30(t,J＝6.1Hz,1H),7.20–7.08(m,2H),7.02–6.90(m,5H),6.44(d,J＝7.4Hz,1H),4.27–3.59(m,8H),2.42(d,J＝56.5Hz,18H),1.31(t,J＝6.9Hz,3H).13C NMR(100MHz,CDCl3):δ337.2,212.3,165.8,149.0,137.9,137.0,131.0,129.4,126.0,124.0,120.9,65.4,61.7,53.7,51.4,27.2,26.0,21.1,20.1–19.4,19.1,14.0ppm.
实施例8
采用实施例6方法制备含氮配位钌卡宾催化剂(I-c)，(R1＝-OCH3)；原料之一化合物为相应的(II-c)，得到的固体为绿色；
1HNMR(400MHz,CDCl3)δ17.32(t,J＝6.4Hz,1H),7.02(s,4H),6.73(s,1H),6.47(s,2H),4.16–3.92(m,6H),3.75(s,3H),2.99–2.23(m,18H),1.34(t,J＝7.1Hz,3H).13C NMR(100MHz,CDCl3):δ335.6,213.0,165.8,161.9,143.9,143.5,143.2,137.6,129.3,126.7,122.6,119.9,117.1,116.3,111.0,65.2,61.8,55.7,53.8,51.5–49.4,25.9,21.1,19.0,14.0ppm.
实施例9
采用实施例6方法制备含氮配位钌卡宾催化剂(I-d)，(R1＝-F)；原料之一化合物为相应的(II-d)，得到的固体为绿色；
1H NMR(400MHz,CDCl3)δ17.36(t,J＝6.5Hz,1H),7.04(s,4H),6.95(dd,J＝8.3,2.0Hz,1H),6.73–6.63(m,1H),6.47(dd,J＝8.1,4.9Hz,1H),4.18–3.88(m,6H),3.11–2.07(m,18H),1.36(t,J＝7.1Hz,3H).13C NMR(100MHz,CDCl3):δ336.4,212.2,165.7,164.7,162.2,146.0,145.7,145.2,138.1,137.4,129.4,126.7,122.5,119.7,117.7,117.5,116.9,113.2,113.0,65.4,61.5,53.5,31.9,29.7,29.3,26.9,22.7,21.1,19.1–18.9,14.0ppm.
实施例10
采用实施例6方法制备含氮配位钌卡宾催化剂(I-e)，(R1＝-CF3)；原料之一化合物为相应的(II-e)，得到的固体为绿色；
1H NMR(400MHz,CDCl3)δ17.42(t,J＝6.5Hz,1H),7.44(d,J＝12.1Hz,1H),7.24(d,J＝5.5Hz,1H),7.08–6.94(m,4H),6.52(d,J＝8.2Hz,1H),4.03(d,J＝42.9Hz,6H),2.93–2.26(m,19H),1.33(d,J＝7.1Hz,3H).13C NMR(100MHz,CDCl3):δ339.2,211.2,165.7,150.6,136.8,132.0,131.7,129.4,127.8,124.6,124.3,123.1,121.0,65.6,61.4,31.9,29.5,27.8,26.8,22.6,20.1,17.5,14.0,13.5ppm.
实施例11
采用实施例6方法制备含氮配位钌卡宾催化剂(I-f)，(R1＝-COOCH2CH3)；原料之一化合物为相应的(II-f)，得到的固体为绿色；
1H NMR(400MHz,CDCl3)δ17.43(t,J＝6.5Hz,1H),7.95–7.83(m,1H),7.67(d,J＝8.1Hz,1H),6.99(d,J＝24.7Hz,4H),6.49(d,J＝8.2Hz,1H),5.13(s,1H),4.23–3.85(m,8H),2.98–2.31(m,18H),1.36(dd,J＝14.8,7.3Hz,6H).13C NMR(100MHz,CDCl3):δ338.7–337.7,211.4,171.0,165.8,165.1,151.7,146.6,146.2,137.8–137.6,132.0,130.1–128.5,128.5–128.2,127.3,123.7,120.7,119.8,65.5,61.5,61.3,60.3,53.6,21.0,20.4,19.2,18.9,14.2,13.9ppm.
实施例12
1-(4-甲基苯磺酰基)-2,5-二氢-1H-吡咯(化合物14)的合成
在40℃条件下，将N,N-二烯丙基-4-甲基苯磺酰胺(化合物13,251mg,1mmol)[7]和6.82mg(1mol％)I-a加入1ml的二氯甲烷，搅拌，反应5h，旋干反应溶剂后提纯产品，产率为83％，经核磁确定，1H NMR(400MHz,CDCl3):δ7.72(dd,J＝8.2,1.6Hz,2H),7.32(d,J＝7.6Hz,2H),5.65(s,2H),4.11(d,J＝2.1Hz,4H),2.42(d,J＝1.8Hz,3H).13C NMR(100MHz,CDCl3):δ143.49,134.23,129.79,127.40,125.46,54.86,21.52.(产物是1-(4-甲基苯磺酰基)-2,5-二氢-1H-吡咯(化合物14)。
实验证明，分别用3.75mg(0.5mol％)I-b、3.9mg(0.5mol％)I-c、3.84mg(0.5mol％)I-d、2mg(0.25mol％)I-e和2mg(0.25mol％)I-f代替本实施例的6.82mg(1mol％)I-a，所获得的1-(4-甲基苯磺酰基)-2,5-二氢-1H-吡咯(化合物14)的反应时间及产率见表1。
同实施例12方法，采用催化剂Ia-f催化各种底物(化合物15,17,21,23,25,27和29)进行闭环复分解反应，见实施例13-20
实施例13
4-丙二酸二乙酯基环戊烯(化合物16)的合成(催化剂用量、反应时间及产率，见表1)
1H NMR(400Hz,CDCl3):δ5.59(s,2H),4.18(q,J＝7.1Hz,4H),3.00(s,4H),1.23(t,J＝7.1Hz,6H).13C NMR(100MHz,CDCl3):δ172.16,127.77,61.46,58.80,40.80,13.98.
实施例14
1-(甲苯-4-磺酰基)-2,5-二氢-3-甲基吡咯(化合物18)的合成(催化剂用量、反应时间及产率，见表1)
1H NMR(400MHz,CDCl3):δ7.72(t,J＝6.5Hz,2H),7.32(d,J＝7.9Hz,2H),5.25(d,J＝1.4Hz,1H),4.01(d,J＝40.1Hz,4H),2.42(d,J＝6.1Hz,3H),1.65(s,3H).13C NMR(100MHz,CDCl3):δ143.40,135.05,134.22,129.75,127.41,119.08,57.69,55.15,21.50,14.04.
实施例15
1-(甲苯-4-磺酰基)-2,3,6-三氢吡啶(化合物22)的合成(催化剂用量、反应时间及产率，见表1)
1H NMR(400MHz,CDCl3):δ7.69(d,J＝7.2Hz,2H),7.34(d,J＝7.9Hz,2H),5.83–5.55(m,2H),3.59(d,J＝1.9Hz,2H),3.27–3.11(m,2H),2.45(s,3H),2.28–2.14(m,2H).13CNMR(100MHz,CDCl3):δ143.52,133.39,129.64,127.69,125.07,122.77,44.79,42.66,25.28,21.52.
实施例16
1-(甲苯-4-磺酰基)-2,3,6,7-四氢-1H吖庚因(化合物24)的合成(催化剂用量、反应时间及产率，见表1)
1H NMR(400MHz,CDCl3):δ7.68(d,J＝8.1Hz,2H),7.31(d,J＝8.0Hz,2H),5.81–5.71(m,2H),3.35–3.21(m,4H),2.42(s,3H),2.32(d,J＝4.7Hz,4H).13C NMR(100MHz,CDCl3):δ159.03,136.29,128.99,128.04,127.61,125.92,124.15,121.66,71.30,31.99.
实施例17
2,5-二氢苯并恶庚英(化合物26)的合成(催化剂用量、反应时间及产率，见表1)
1H NMR(400MHz,CDCl3):δ7.41–7.13(m,4H),6.07–5.90(m,1H),5.64–5.55(m,1H),4.72(dd,J＝4.8,2.4Hz,2H),3.64(d,J＝2.7Hz,2H).13C NMR(100MHz,CDCl3):δ159.03,136.29,128.99,128.04,127.61,125.92,124.15,121.66,71.30,31.99.
实施例18
4-甲基-2,5-二氢苯并恶庚英(化合物28)的合成(催化剂用量、反应时间及产率，见表1)
1H NMR(400MHz,CDCl3):δ7.37–7.29(m,1H),7.26–7.12(m,3H),5.40(d,J＝1.0Hz,1H),4.70(dd,J＝3.2,1.6Hz,2H),3.60(s,2H),2.01(s,3H).13C NMR(100MHz,CDCl3):δ158.86,134.97,134.07,129.19,128.04,123.67,121.26,70.40,37.39,26.30.
实施例19
2,5-二氢-1H吡咯基苯基甲酮(化合物30)的合成(催化剂用量、反应时间及产率，见表1)
1H NMR(400MHz,CDCl3):δ7.21–7.09(m,2H),7.02(d,J＝2.7Hz,3H),5.48(s,1H),5.34(d,J＝1.5Hz,1H),4.04(s,2H),3.77(s,2H).13C NMR(100MHz,CDCl3):δ169.26,136.57,129.59,128.06,126.60,125.33,55.45,53.14.
实施例20
1-(甲苯-4-磺酰基)-2,5-二氢-3，4-二甲基吡咯(化合物20)的合成
在80℃条件下，将N,N-双(2-甲基烯丙基)-4-甲基苯磺酰胺(化合物19,279mg,1mmol)[7]和31.4mg(5mol％)I-a加入1ml的1,2-二氯乙烷，搅拌，反应24h，旋干反应溶剂后提纯产品，产率为70％，经核磁确定，1HNMR(400MHz,CDCl3):δ7.73(d,J＝8.0Hz,2H),7.34(d,J＝7.8Hz,2H),3.99(s,4H),2.44(s,3H),1.56(s,6H).13C NMR(100MHz,CDCl3):δ143.29,134.30,129.72,127.49,126.21,58.83,21.52,11.12.(产物是1-(甲苯-4-磺酰基)-2,5-二氢-3，4-二甲基吡咯(化合物20)。
实验证明，用37.5mg(5mol％)I-b、39mg(5mol％)I-c、38.4mg(5mol％)I-d、40mg(5mol％)I-e和40mg(5mol％)I-f代替本实施例的31.4mg(5mol％)I-a，所获得的1-(甲苯-4-磺酰基)-2,5-二氢-3，4-二甲基吡咯(化合物20)的反应时间及产率见表1
实施例21
催化剂Ia-f在交叉复分解反应
苯甲酸肉桂酯(33)的合成
在40℃条件下，将苯甲酸烯丙酯(化合物31,162mg,1mmol)、苯乙烯(化合物32,208mg，2mmo)和6.82mg(1mol％)I-a加入1ml的二氯甲烷，搅拌，反应10h，旋干反应溶剂后提纯产品，产率为83％，经核磁确定，1H NMR(400Hz,CDCl3):δ8.12(d,J＝7.22Hz,2H),7.60(t,J＝7.38Hz,2H),7.44-7.50(q,J＝7.51Hz,2H),7.36(t,J＝7.19Hz,1H),7.29(t,J＝7.10Hz,1H),6.78(d,J＝16.0Hz,4H),6.40-6.44(m,1H),5.02(dd,J＝6.39Hz andJ＝0.97Hz,3H).
实验证明，用3.75mg(0.5mol％)I-b、3.9mg(0.5mol％)I-c、3.84mg(0.5mol％)I-d、4mg(0.5mol％)I-e和4mg(0.5mol％)I-f代替本实施例的6.82mg(1mol％)I-a，其他同本实施例，所获得的苯甲酸肉桂酯(33)的的产率见表1。
表1为催化剂Ia-f对不同底物催化活性测试实验a
表头及表中：
a所有反应都是在40℃的二氯甲烷(1M)中反应；
b此反应在80℃的1,2-二氯乙烷中反应；
c此溶液浓度为0.1M；
d产率为分离产率
实施例23
化合物Ia-f(15μmol)的稳定性实验
在23℃时，将所测试的化合物Ia-f溶于0.6mL的CDCl3中(以0.75μmol二苯甲酮作为内标)(主要体现带有不同取代基时，催化剂在溶液状态下的分解速率)测试结果经1HNMR测试得到，见图1。
实施例24
在30℃条件下，测试了催化剂Ia-f(1.0mol％)在CD2Cl2(0.1M)中对二烯丙基丙二酸二乙酯关环复分解反应(RCM)的催化活性(主要比较的是催化剂Ia-f在相同条件下，各个催化剂催化同一底物(15)所表现出来的催化活性及引发速率)见图2。
参考文献
[1](a)S.Werrel,J.C.L.Walker and T.J.Donohoe,Tetrahedron Lett.,2015,56,5261–5268.(b)T.K.Olszewski,M.Bieniek,K.Skowerski and K.Grela,Synlett.,2013,24,903–919.(c)K.C.Nicolaou,P.G.Bulger and D.Sarlah,Angew.Chem.,Int.Ed.,2005,44,4490–4527.(d)Olefin Metathesis Theory and Practice；K.Grela,Ed.；JohnWiley&Sons:Hoboken,NJ,United States,2014.(e)R.H.Grubbs,Ed.HandbookofMetathesis；Wiley-VCH:Weinheim,2003.(f)A.C.Knall and C.Slugovc,OlefinMetathesis Polymerization.In Olefin Metathesis Theory and Practice；K.Grela,Ed.；John Wiley&Sons:Hoboken,NJ,United States,2014.(g)C.Slugovc,IndustrialApplications of Olefin Metathesis Polymerizations.In Olefin Metathesis TheoryandPractice；K.Grela,Ed.；John Wiley&Sons:Hoboken,NJ,United States,2014.(h)J.Kong,C.-Y.Chen,J.Balsells-Padros,Y.Cao,R.F.Dunn,S.J.Dolman,J.Janey,H.Li andM.J.Zacuto,J.Org.Chem.,2012,77,3820–3828.(i)C.Shu,X.Zeng,M.-H.Hao,X.Wei,N.H.Yee,C.A.Busacca,Z.Han V.,Farina and C.H.Senanayake,Org.Lett.,2008,10,1303–1306.
[2](a)P.Schwab,M.B.France,R.H.Grubbs and Ziller,J.W.Angew.Chem.Int.Ed.,1995,34,2039–2041.(b)P.Schwab and R.H.Grubbs,J.Am.Chem.Soc.,1996,118,100–110.(c)M.Scholl,S.Ding,C.Woo Lee and R.H.Grubbs,Org.Lett.,1999,1,953–956.(d)A.K.Chatterjee,and R.H.Grubbs,Org.Lett.,1999,1,1751–1753.
[3]B.Garber,J.S.Kingsbury,B.L.Gray and A.H.Hoveyda,J.Am.Chem.Soc.,2000,122,8168–8179.
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Claims (4)

1.含氮配位钌卡宾催化剂，其特征是用式(I)所示：
其中：
R1＝-H、-OCH3、-F、-CF3或-COOCH2CH3。
2.权利要求1的含氮配位钌卡宾催化剂的制备方法，其特征是包括如下步骤：
氮气保护下，将Grubbs II催化剂(III)，氯化亚铜和化合物(II)溶于二氯甲烷中，在搅拌下，加热回流，降温至室温，旋干，过色谱硅胶柱，向所述色谱硅胶柱内加入体积比为1:1的石油醚和二氯甲烷的混合液洗脱杂质，再加入二氯甲烷洗脱得到含氮配位钌卡宾催化剂(I)；
反应式如下：
其中：
R1＝-H、-OCH3、-F、-CF3或-COOCH2CH3；
所述Grubbs II催化剂的结构见式(III)：
3.根据权利要求2所述的制备方法，其特征是所述Grubbs II催化剂，氯化亚铜和化合物(II)的摩尔比为1:1:1.5。
4.权利要求1的含氮配位钌卡宾催化剂在催化闭环和交叉复分解中的应用。
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