CN112410807B - 一种电催化下四取代磺化烯醚的制备方法 - Google Patents
一种电催化下四取代磺化烯醚的制备方法 Download PDFInfo
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Abstract
本发明公开了属于有机合成技术领域的一种电催化下四取代磺化烯醚的制备方法。所述方法为:向反应器中,加入摩尔比为1:3:1的取代炔烃、芳基磺酰肼以及四乙基六氟磷酸铵,加入体积为4.5mL的醇类物质,加入硝基甲烷作为溶剂,通过电催化策略促进反应进行。待反应完毕后,使用旋转蒸发仪浓缩得到粗产物,再经过硅胶柱层析分离得到目标产物。本发明提供的四取代磺化烯醚化合物的合成方法科学合理,合成途径绿色环保,无金属催化剂的使用;反应温度为室温,反应条件温和;反应在弱电流下即可发生;合成方法简单,反应快速;目标化合物收率高,产品易于纯化。其反应方程式如下:
Description
技术领域
本发明属于有机合成技术领域,具体涉及一种电催化下四取代磺化烯醚的制备方法。
背景技术
四取代烯烃广泛存在于生物活性化合物、药物和先进材料中,并可作为合成有价值分子的关键中间体。((a)J.Am.Chem.Soc.,1997,119,3427;(b)Eur.J.Cancer,1999,35,1628;(c)Angew.Chem.Int.Ed.,2006,45,2838;(d)Eur.J.Org.Chem.,2007,4981;(e)Acc.Chem.Res.,2008,41,1474;(f)Top.Curr.Chem.,2012,327,1;(g)Chem.Rev.,2014,114,12174.)
四取代磺化烯醚具有生物活性以及药用价值。因此,发展一种快速高效地合成四取代磺化烯醚的新方法具有重要的实用意义。然而,由于双键的空间位阻,有效的区域选择性和立体选择性合成这些化合物仍然是一个挑战。
东北师范大学李艳课题组报道了合成硒基砜类化合物的方法:在铜催化下炔烃、芳基磺酰肼以及二苯基二硒醚的三组分反应合成硒基砜类化合物。(J.Org.Chem.2017,82,2269-2275)反应式见式Ⅰ:
上述方法具有使用金属催化剂以及有毒溶剂、反应时间长等明显的缺陷。
发明内容
为了克服上述合成四取代磺化烯醚现有技术的缺陷,本发明提供了一种在电催化促进下制备四取代磺化烯醚的方法。
电催化合成反应具有很多显著的优势:可以避免使用难以处理或有毒的金属催化剂,电子作为环保绿色的反应物,反应产物易分离且纯度高,对环境零污染;在电催化反应中,可通过改变电流或电极电压来调节反应速率以避免副反应的发生,从而提高目标产品的选择性以及收率。
一种电催化下四取代磺化烯醚的制备方法,所述四取代磺化烯醚具有式Ⅱ所示的结构:
R1取代基团选自氢、甲基、甲氧基、氯;R2取代基团选自正丁基、正戊基、正己基、甲基;R3取代基团选自氟、氯、溴、甲基;R4取代基团选自甲基、乙基、异丙基、环戊基。其特征在于,向反应器中,加入摩尔比为1:3:1的取代炔烃、芳基磺酰肼以及四乙基六氟磷酸铵,加入体积为4.5mL的醇类物质,加入硝基甲烷作为溶剂,通过电催化策略促进反应进行。待反应完毕后,使用旋转蒸发仪浓缩得到粗产物,再经过硅胶柱层析分离得到目标产物。其化学过程见反应式Ⅲ:
所述的取代炔烃、芳基磺酰肼以及四乙基六氟磷酸铵的摩尔比值为1:3:1,所述醇类物质的用量为4.5mL,所述溶剂为硝基甲烷,通过电催化策略促进反应进行,所用电流为5mA,反应温度室温,反应时间为8h。
本发明的有益效果为:本发明提供的四取代磺化烯醚化合物的合成方法科学合理,提供了一种合成四取代磺化烯醚化合物的新途径,通过本方法得到了具有多种取代基的四取代磺化烯醚化合物,其特点为:无金属催化剂的使用,反应温度为室温,合成途径绿色环保;反应在弱电流下即可发生;合成方法简单,反应快速;目标化合物收率高,产品易于纯化。
附图说明
图1为实施例1制备的化合物4aaa的NMR图谱;
图2为实施例2制备的化合物4baa的NMR图谱;
图3为实施例3制备的化合物4caa的NMR图谱。
具体实施方式
下面结合附图和具体的实施例对本发明进一步详细的说明:
下述实施例中所述试验方法,如无特殊说明,均为常规方法;所述试剂和材料,如无特殊说明,均可从商业途径获得。
实施例1
四取代磺化烯醚4aaa的制备
向10mL无隔膜电解槽加入1-苯基1-丙炔1a(0.2mmol,23.2mg)、对甲苯磺酰肼2a(0.6mmol,111.7mg)、四乙基六氟磷酸铵(0.2mmol,55.0mg),阴、阳电极均采用石墨毡电极(1cm x 1cm x 0.5cm)。后向体系充换氮气,加入4.5mL乙醇3a、0.5mL硝基甲烷。于室温、5mA恒定电流下进行电解,反应8h。反应完毕后,使用旋转蒸发仪除去溶剂得到粗产物,粗产物经柱层析分离(200-300目硅胶,石油醚/乙酸乙酯=10/1),使用旋转蒸发仪除去溶剂,得到目标产物四取代磺化烯醚4aaa,其收率为78%。
谱图解析数据4aaa:
1H NMR(500MHz,CDCl3):δ7.40(d,J=7.9Hz,3H),7.38–7.28(m,2H),7.23–7.17(m,2H),7.14(d,J=8.0Hz,2H),3.48(q,J=7.0,7.0,7.1Hz,2H),2.37(s,3H),2.10(s,3H),1.14(t,J=7.0,7.0Hz,3H).13C NMR(126MHz,CDCl3):δ=162.78,142.99,139.29,132.27,129.78,129.49,129.16,127.78,127.31,118.75,77.31,77.06,76.80,65.11,21.49,15.19,12.78.
实施例2
用1b代替实例1中的1a,其他条件同实例1,实验结果见表1。
谱图解析数据4baa:
1H NMR(500MHz,CDCl3):δ7.42(d,J=8.4Hz,2H),7.18–7.13(m,4H),7.10(d,J=8.1Hz,2H),3.49(q,J=7.0,7.0,7.1Hz,2H),2.39(s,3H),2.38(s,3H),2.07(s,3H),1.13(t,J=7.0,7.0Hz,3H).13C NMR(126MHz,CDCl3):δ=163.02,142.92,139.53,139.35,129.67,129.30,129.09,128.49,127.34,118.41,77.28,77.03,76.78,64.97,21.49,15.19,12.81.
实施例3
用1c代替实例1中的1a,其他条件同实例1,实验结果见表1。
谱图解析数据4caa:
1H NMR(400MHz,CDCl3):δ7.41(d,J=8.3Hz,2H),7.37(ddd,J=1.8,7.4,8.3Hz,1H),7.20(dd,J=1.8,7.5Hz,1H),7.12(d,J=8.0Hz,2H),6.98(td,J=1.0,7.4,7.4Hz,1H),6.76(d,J=8.3Hz,1H),3.65(s,3H),3.61–3.42(m,2H),2.36(s,3H),2.11(s,3H),1.15(t,J=7.1,7.1Hz,3H).13C NMR(101MHz,CDCl3):δ=160.61,156.76,142.56,139.45,132.33,131.33,128.85,127.30,120.91,120.00,117.31,110.14,77.40,77.08,76.76,64.27,55.10,21.47,15.14,12.47.
实施例4
用1d代替实例1中的1a,其他条件同实例1,实验结果见表1。
谱图解析数据4daa:
1H NMR(500MHz,CDCl3):δ7.44–7.39(m,2H),7.37–7.30(m,2H),7.20–7.13(m,4H),3.48(q,J=6.9,7.0,7.0Hz,2H),2.38(s,3H),2.08(s,3H),1.15(t,J=7.0,7.0Hz,3H).13CNMR(101MHz,CDCl3):δ=161.30,143.32,138.98,135.75,131.16,130.74,129.27,128.16,127.32,119.70,77.37,77.05,76.74,65.27,21.53,15.18,12.84.
实施例5
用1e代替实例1中的1a,其他条件同实例1,实验结果见表1。
谱图解析数据4eaa:
1H NMR(500MHz,CDCl3):δ7.36(t,J=7.4,7.4Hz,1H),7.28(td,J=3.7,8.7,9.3Hz,4H),7.12(d,J=7.0Hz,2H),7.07(d,J=7.9Hz,2H),3.45(q,J=7.0,7.0,7.0Hz,2H),2.61–2.55(m,2H),2.35(s,3H),1.65–1.57(m,2H),1.40(h,J=7.2,7.2,7.2,7.3,7.3Hz,2H),1.14(t,J=7.0,7.0Hz,3H),0.95(t,J=7.4,7.4Hz,3H).13C NMR(126MHz,CDCl3):δ=163.42,142.62,139.95,132.18,129.99,129.33,128.92,127.71,127.25,124.42,77.28,77.02,76.77,65.05,31.57,26.97,22.68,21.43,15.14,13.88.
实施例6
用1f代替实例1中的1a,其他条件同实例1,实验结果见表1。
谱图解析数据4faa:
1H NMR(500MHz,CDCl3):δ7.36(t,J=7.3,7.3Hz,1H),7.33–7.24(m,4H),7.15–7.05(m,4H),3.44(q,J=7.0,7.0,7.0Hz,2H),2.60–2.53(m,2H),2.35(s,3H),1.60(t,J=7.9,7.9Hz,2H),1.44–1.28(m,4H),1.13(t,J=7.0,7.0Hz,3H),0.94–0.88(m,3H).13C NMR(126MHz,CDCl3):δ=163.41,142.64,139.90,132.17,129.98,129.34,128.94,127.72,127.25,124.35,77.29,77.04,76.78,65.06,31.80,29.00,27.22,22.37,21.45,15.16,14.05.
实施例7
用1g代替实例1中的1a,其他条件同实例1,实验结果见表1。
谱图解析数据4gaa:
1H NMR(500MHz,CDCl3):δ7.36(t,J=7.3,7.3Hz,1H),7.33–7.24(m,4H),7.15–7.05(m,4H),3.44(q,J=7.0,7.0,7.0Hz,2H),2.60–2.53(m,2H),2.35(s,3H),1.60(t,J=7.9,7.9Hz,2H),1.44–1.28(m,4H),1.13(t,J=7.0,7.0Hz,3H),0.94–0.88(m,3H).13C NMR(126MHz,CDCl3):δ=163.41,142.64,139.90,132.17,129.98,129.34,128.94,127.72,127.25,124.35,77.29,77.04,76.78,65.06,31.80,29.00,27.22,22.37,21.45,15.16,14.05.
实施例8
用2b代替实例1中的2a,其他条件同实例1,实验结果见表1。
谱图解析数据4aba:
1H NMR(500MHz,CDCl3):δ7.50–7.46(m,2H),7.43–7.38(m,1H),7.34(t,J=7.4,7.4Hz,2H),7.20–7.14(m,2H),7.00(t,J=8.6,8.6Hz,2H),3.49(q,J=7.0,7.0,7.0Hz,2H),2.13(s,3H),1.15(t,J=7.0,7.0Hz,3H).13C NMR(126MHz,CDCl3):δ=165.86,163.84,163.36,138.37,138.35,132.00,129.94,129.87,129.80,129.66,127.90,118.66,115.75,115.57,77.31,77.06,76.81,65.29,15.17,12.68.
实施例9
用2c代替实例1中的2a,其他条件同实例1,实验结果见表1。
谱图解析数据4aca:
1H NMR(400MHz,CDCl3):δ7.44–7.37(m,3H),7.39–7.31(m,2H),7.34–7.27(m,2H),7.20–7.13(m,2H),3.49(q,J=7.0,7.0,7.0Hz,2H),2.13(s,3H),1.15(t,J=7.1,7.1Hz,3H).13C NMR(126MHz,CDCl3):δ=163.64,140.80,138.72,131.93,129.78,129.71,128.76,128.68,127.91,118.35,77.30,77.04,76.79,65.34,15.18,12.67.
实施例10
用2d代替实例1中的2a,其他条件同实例1,实验结果见表1。
谱图解析数据4ada:
1H NMR(500MHz,CDCl3):δ7.47(d,J=8.5Hz,2H),7.44–7.38(m,1H),7.36–7.30(m,4H),7.18–7.13(m,2H),3.49(q,J=7.0,7.0,7.0Hz,2H),2.12(s,3H),1.15(t,J=7.0,7.0Hz,3H).13C NMR(126MHz,CDCl3):δ=163.68,141.33,131.91,131.74,129.77,129.72,128.78,127.92,127.23,118.28,77.31,77.05,76.80,65.34,15.19,12.67.
实施例11
用3b代替实例1中的3a,其他条件同实例1,实验结果见表1。
谱图解析数据4aab:
1H NMR(500MHz,CDCl3):δ7.44–7.33(m,5H),7.22–7.13(m,4H),3.28(s,3H),2.37(s,3H),2.08(s,3H).13C NMR(126MHz,CDCl3):δ=163.29,143.05,139.27,131.60,129.77,129.58,129.19,127.91,127.32,118.16,77.38,77.06,76.74,56.64,21.51,12.54.
实施例12
用3c代替实例1中的3a,其他条件同实例1,实验结果见表1。
谱图解析数据4aac:
1H NMR(500MHz,CDCl3):δ7.44–7.29(m,5H),7.27–7.22(m,2H),7.13(d,J=8.1Hz,2H),3.79(p,J=6.1,6.1,6.1,6.1Hz,1H),2.36(s,3H),2.10(s,3H),1.11(s,3H),1.10(s,3H).13C NMR(126MHz,CDCl3):δ=162.14,142.96,139.17,132.74,129.97,129.53,129.12,127.69,127.31,120.58,77.31,77.06,76.80,71.62,22.44,21.48,13.13.
实施例13
用3d代替实例1中的3a,其他条件同实例1,实验结果见表1。
谱图解析数据4aac:
1H NMR(500MHz,CDCl3):δ7.41–7.30(m,5H),7.24–7.19(m,2H),7.13(d,J=8.3Hz,2H),4.13–4.06(m,1H),2.36(s,3H),2.08(s,3H),1.77–1.64(m,5H),1.51–1.47(m,3H).13CNMR(126MHz,CDCl3):δ=162.21,142.96,139.24,132.77,130.09,129.39,129.14,127.68,127.31,120.40,81.04,77.38,77.06,76.74,32.99,23.74,21.50,12.94.
表1
Claims (1)
1.一种电催化下四取代磺化烯醚的制备方法,所述四取代磺化烯醚具有式Ⅰ所示的结构:
R1取代基团选自氢、甲基、甲氧基、氯;R2取代基团选自正丁基、正戊基、正己基、甲基;R3取代基团选自氟、氯、溴、甲基;R4取代基团选自甲基、乙基、异丙基、环戊基,其特征在于,向反应器中,加入摩尔比为1:3:1的取代炔烃0.2mmol、芳基磺酰肼0.6mmol以及电解质四乙基六氟磷酸铵0.2mmol,加入体积为4.5mL的醇类物质,加入0.5mL硝基甲烷作为溶剂,阴、阳电极均采用石墨毡电极(1cm x 1cm x 0.5cm),在N2氛围下,通过电催化策略促进反应进行,所用电流为5mA,反应温度是室温,反应时间为8h,待反应完毕后,使用旋转蒸发仪浓缩得到粗产物,再经过硅胶柱层析分离得到目标产物,其化学过程见反应式Ⅱ:
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