CN112725824A - 一种含亚胺二氢噻吩类化合物的制备方法 - Google Patents
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Abstract
本发明公开了属于有机合成技术领域的一种含亚胺二氢噻吩类化合物的制备方法。所述方法为：向反应器中加入硫代酰胺、DABCO、电解质、溶剂，在通电的作用下反应，反应完毕后，用硅胶柱层析分离得到纯的目标产物。本发明所提供的二氢噻吩类化合物的制备方法具有科学合理、条件温和、操作简单、反应时间短等特点。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，具体涉及一种含亚胺二氢噻吩类化合物的制备方法。
背景技术
二氢噻吩类化合物作为杂环化合物中重要的一类结构具有广泛的生理活性，在医药和农药等领域有着重要的应用价值，因此，发展一种绿色、高效合成含亚胺二氢噻吩类化合物的新方法具有重要意义。
含亚胺二氢噻吩类化合物的制备方法有：
1)以邻炔基异硫氰酸酯、异腈为原料
Li课题组以邻炔基异硫氰酸酯、异腈为原料，镍催化一步制备了含亚胺二氢噻吩类类化合物(Adv.Synth.Catal.2017,359,1373–1378)。
2)以苯甲酸、2-氨基乙酸为原料
Kostyuk课题组以1-甲基-2-硝基甲基吡咯烷与异硫氰酸酯为原料，加入NaH，70-80℃得到含亚胺二氢噻吩类类化合物(Tetrahedron Letters 2014,55,5639–5642)。
利用上述方法合成含亚胺二氢噻吩类化合物，具有明显的缺点和不足：1)需要加热；2)操作繁琐；3)金属催化，价格昂贵。
发明内容
为了克服上述现有技术的不足，本发明提供了一种含亚胺二氢噻吩类化合物的制备方法。
一种含亚胺二氢噻吩类化合物的制备方法，所述含亚胺二氢噻吩类化合物的结构式如下：
其中R1选自苯基、取代苯基，取代基为氟、氯、溴、甲氧基、甲基、乙基；R2选自苯基。其特征在于，向反应器中加入摩尔比为1：1：0.2的硫代酰胺、DABCO和四丁基四氟硼酸铵，加入乙腈作为溶剂，在电的作用下，室温下搅拌反应，反应方程式如下：
本发明的有益效果为：本发明提供的含亚胺二氢噻吩类化合物的合成方法科学合理，建立了一种合成多种取代基的含亚胺二氢噻吩类化合物的新方法；该方法具有原料易得、操作简单、反应条件温和、反应时间短等特点。
附图说明
图1为实施例1制备的化合物2a的NMR图谱；
图2为实施例9制备的化合物2i的NMR图谱；
图3为实施例10制备的化合物2j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
含亚胺二氢噻吩化合物2a的制备
向10mL两口瓶中加入3-氧代-N,3-二苯基丙硫胺1a(0.1mmol,25.5mg)，DABCO(0.1mmol,11.2mg),nBu4NBF4(0.02mmol,6.6mg)和乙腈(5mL)。两片石墨毡(1.5cm×1cm×0.5cm)分别作为阳极和阴极。将反应混合物在2V的恒定电压下室温搅拌2小时。反应完成后，用旋转蒸发仪除去溶剂。通过硅胶快速色谱法，使用石油醚和乙酸乙酯作为洗脱液，得到产物2a，产率52％。
谱图解析数据2a:
1H NMR(CDCl3,500MHz):δ7.96–7.93(m,4H),7.59(t,J＝7.4Hz,2H),7.47(t,J＝7.8Hz,4H),7.32(t,J＝7.8Hz,4H),7.17(t,J＝7.4Hz,2H),6.97(d,J＝7.5Hz,4H).13C NMR(CDCl3,126MHz):δ190.81,149.97,149.93,135.81,134.48,129.91,129.18,128.66,126.57,120.28.HRMS(ESI-TOF,[M+H]+):calcd for C30H21N2O2S,473.1324,found473.1319.
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2b:
1H NMR(CDCl3,500MHz):δ7.85(d,J＝8.2Hz,4H),7.32(t,J＝7.8Hz,4H),7.28–7.25(m,4H),7.16(t,J＝7.4Hz,2H),6.97(d,J＝7.6Hz,4H),2.41(s,6H).13C NMR(CDCl3,126MHz):δ190.32,160.55,150.07,149.67,145.70,133.37,130.11,129.39,129.12,126.42,120.24,21.90.HRMS(ESI-TOF,[M+H]+):calcd for C32H25N2O2S,501.1637,found501.1636.
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2c:
1H NMR(CDCl3,500MHz):δ7.93(d,J＝8.8Hz,4H),7.33(t,J＝7.7Hz,4H),7.17(t,J＝7.3Hz,2H),6.96(dd,J＝23.9,8.2Hz,8H),3.86(s,6H).13C NMR(CDCl3,126MHz):δ189.14,164.75,160.71,150.11,149.35,132.53,129.14,128.92,126.41,120.26,114.03,55.57.HRMS(ESI-TOF,[M+H]+):calcd for C32H25N2O4S,533.1535,found 533.1539.
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2d:
1H NMR(CDCl3,500MHz):δ7.87(d,J＝7.8Hz,4H),7.30(dt,J＝14.4,8.0Hz,8H),7.15(t,J＝7.4Hz,2H),6.97(d,J＝7.6Hz,4H),2.69(q,J＝7.6Hz,4H),1.24(t,J＝7.6Hz,6H).13C NMR(CDCl3,126MHz):δ190.40,160.60,151.76,150.10,149.76,133.58,130.23,129.15,128.23,120.26,29.14,14.96.HRMS(ESI-TOF,[M+H]+):calcd for C34H29N2O2S,529.1950,found 529.1955.
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2e:
1H NMR(CDCl3,500MHz):δ7.87–7.82(m,4H),7.34–7.31(m,4H),7.27–7.24(m,4H),7.17(t,J＝7.4Hz,2H),6.97(d,J＝7.4Hz,4H),2.51(s,6H).13C NMR(CDCl3,126MHz):δ189.60,160.46,149.99,149.58,148.34,132.04,130.28,129.17,126.53,124.82,120.29,14.62.HRMS(ESI-TOF,[M+H]+):calcd for C32H25N2O2S3,565.1078,found565.1070.
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2f:
1H NMR(CDCl3,500MHz):δ7.74(d,J＝7.8Hz,2H),7.64(dt,J＝9.0,2.0Hz,2H),7.48(td,J＝8.0,5.4Hz,2H),7.37–7.31(m,6H),7.19(t,J＝7.4Hz,2H),6.97(d,J＝7.5Hz,4H).13C NMR(CDCl3,126MHz):δ189.68,163.72,161.74,159.82,149.85(d,J＝54.0Hz),149.63,137.79(d,J＝6.5Hz),130.43(d,J＝7.6Hz),129.27,126.85,125.98,125.96,121.62(d,J＝21.6Hz),116.07(d,J＝22.7Hz).120.32.19F NMR(CDCl3,376MHz):δ-111.39ppm.HRMS(ESI-TOF,[M+H]+):calcd for C30H19F2N2O2S,509.1135,found 509.1129.
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2g:
1H NMR(CDCl3,500MHz):δ7.94(d,J＝7.2Hz,4H),7.58(t,J＝7.4Hz,2H),7.46(t,J＝7.8Hz,4H),7.13(d,J＝8.2Hz,4H),6.90(d,J＝8.2Hz,4H),2.32(s,6H).13C NMR(CDCl3,126MHz):δ191.05,159.52,149.74,147.36,136.65,135.89,134.37,129.91,129.74,128.61,120.60,21.08.HRMS(ESI-TOF,[M+Na]+):calcd for C32H24N2O2SNa,523.1456,found 523.1454.
实施例8
用1h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2h:
1H NMR(CDCl3,500MHz):δ7.93–7.89(m,4H),7.60(t,J＝7.4Hz,2H),7.47(t,J＝8.1Hz,8H),6.87–6.84(m,4H).13C NMR(CDCl3,126MHz):δ190.41,160.55,149.92,148.66,135.61,134.65,132.38,129.87,128.73,122.05,120.28.HRMS(ESI-TOF,[M+Na]+):calcdfor C30H18Br2N2O2SNa,650.9353,found 650.9352.
实施例9
用1i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2i:
1H NMR(CDCl3,500MHz):δ7.91–7.86(m,4H),7.47–7.43(m,4H),7.14(d,J＝8.2Hz,4H),6.90(d,J＝8.3Hz,4H),2.32(s,6H).13C NMR(CDCl3,126MHz):δ189.93,159.05,149.72,147.06,141.10,137.00,134.25,131.23,129.83,129.09,120.69,21.11.HRMS(ESI-TOF,[M+H]+):calcd for C32H23Cl2N2O2S,569.0857,found 569.0864.
实施例10
用1j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2j:
1H NMR(CDCl3,500MHz):δ7.80(d,J＝3.6Hz,2H),7.76(d,J＝4.7Hz,2H),7.34(t,J＝7.7Hz,4H),7.19–7.14(m,4H),7.02(d,J＝7.6Hz,4H).13C NMR(CDCl3,126MHz):δ181.87,160.05,149.93,148.35,142.75,136.69,136.66,129.21,128.57,126.64,120.31.HRMS(ESI-TOF,[M+Na]+):calcd for C26H16N2O2S3Na,507.0272,found 507.0272。
表1
Claims (2)
1.一种含亚胺二氢噻吩类化合物的制备方法，所述含亚胺二氢噻吩类类化合物具有式Ⅰ所示的结构：
式Ⅰ中，其中R1选自苯基、取代苯基，取代基为氟、氯、溴、三氟甲基、甲氧基、甲基、乙基；R2选自苯基。其特征在于，向反应器中加入摩尔比为1：1：0.2的硫代酰胺、DABCO和四丁基四氟硼酸铵，加入乙腈作为溶剂，在电的作用下，室温下搅拌反应，反应方程式如下：
2.按照权利要求1所述的制备方法，其特征在于：电极为石墨毡，溶剂为乙腈，反应时间为2h，电流强度为恒压2V。
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