CN113881956A - 一种异硫氰酸苄酯类化合物的制备方法 - Google Patents
一种异硫氰酸苄酯类化合物的制备方法 Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 10
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- YDNLNVZZTACNJX-UHFFFAOYSA-N isocyanatomethylbenzene Chemical class O=C=NCC1=CC=CC=C1 YDNLNVZZTACNJX-UHFFFAOYSA-N 0.000 claims abstract description 8
- 238000000034 method Methods 0.000 claims abstract description 6
- XLTUPERVRFLGLJ-UHFFFAOYSA-N isothiocyanato(trimethyl)silane Chemical compound C[Si](C)(C)N=C=S XLTUPERVRFLGLJ-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000002904 solvent Substances 0.000 claims abstract description 5
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- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 claims description 4
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- 230000002194 synthesizing effect Effects 0.000 description 3
- FANCTJAFZSYTIS-IQUVVAJASA-N (1r,3s,5z)-5-[(2e)-2-[(1r,3as,7ar)-7a-methyl-1-[(2r)-4-(phenylsulfonimidoyl)butan-2-yl]-2,3,3a,5,6,7-hexahydro-1h-inden-4-ylidene]ethylidene]-4-methylidenecyclohexane-1,3-diol Chemical compound C([C@@H](C)[C@@H]1[C@]2(CCCC(/[C@@H]2CC1)=C\C=C\1C([C@@H](O)C[C@H](O)C/1)=C)C)CS(=N)(=O)C1=CC=CC=C1 FANCTJAFZSYTIS-IQUVVAJASA-N 0.000 description 2
- URFPRAHGGBYNPW-UHFFFAOYSA-N 1-bromo-4-ethylbenzene Chemical compound CCC1=CC=C(Br)C=C1 URFPRAHGGBYNPW-UHFFFAOYSA-N 0.000 description 2
- HDNRAPAFJLXKBV-UHFFFAOYSA-N 1-ethyl-4-methoxybenzene Chemical compound CCC1=CC=C(OC)C=C1 HDNRAPAFJLXKBV-UHFFFAOYSA-N 0.000 description 2
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- 150000001412 amines Chemical class 0.000 description 2
- MDKCFLQDBWCQCV-UHFFFAOYSA-N benzyl isothiocyanate Chemical compound S=C=NCC1=CC=CC=C1 MDKCFLQDBWCQCV-UHFFFAOYSA-N 0.000 description 2
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- QLVGHFBUSGYCCG-UHFFFAOYSA-N 2-amino-n-(1-cyano-2-phenylethyl)acetamide Chemical compound NCC(=O)NC(C#N)CC1=CC=CC=C1 QLVGHFBUSGYCCG-UHFFFAOYSA-N 0.000 description 1
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Abstract
本发明公开了属于有机合成技术领域的一种异硫氰酸苄酯类化合物的制备方法。所述方法为：向反应器中加入苄基苯、异硫氰酸三甲基硅酯、电解质、溶剂，在恒电流作用下反应，反应完毕后，用硅胶柱层析分离得到纯的目标产物。本发明所提供的异硫氰酸苄酯类化合物的制备方法具有科学合理、条件温和、操作简单等特点。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，具体涉及一种异硫氰酸苄酯类化合物的制备方法。
背景技术
异硫氰酸苄酯类化合物广泛存在于天然产物和药物分子中，也是合成硫脲或杂环衍生物的重要合成中间体。经研究表明，此类化合物具有多种生物活性，如杀菌(Molecules2018,23,624)、抗癌(Cancer Res.2015,75,5130)等。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、高效合成异硫氰酸苄酯类化合物的新方法具有重要意义。
异硫氰酸苄酯类化合物的制备方法有：
1)以胺、二硫化碳为原料
Dolman课题组以胺和二硫化碳为原料，经两步反应制备了异硫氰酸苄酯类化合物(J.Org.Chem.2007,72,10)。
2)以醇、硫氰酸钠为原料
Tyndall课题组以醇和硫氰酸钠为原料，加入草酸，在60摄氏度条件下制备得到异硫氰酸苄酯类化合物(Eur.J.Med.Chem.2015,93,26)。
利用上述方法合成异硫氰酸苄酯类化合物，具有明显的缺点和不足：1)步骤繁琐；2)使用有毒试剂；3)反应条件剧烈。
发明内容
为了克服上述现有技术的不足，本发明提供了一种异硫氰酸苄酯类化合物的制备方法。
一种异硫氰酸苄酯类化合物的制备方法，所述异硫氰酸苄酯类化合物具有式Ⅰ所示的结构：
式Ⅰ中，其中R1取代基为氟、氯、溴、甲氧基、乙基、叔丁基、异丙基、环己基、苄氧基、氯甲基。其特征在于，向反应器中加入摩尔比为1：2的取代乙苯与异硫氰酸三甲基硅酯，加入四丁基六氟膦酸铵或四丁基高氯酸铵作为电解质，加入体积比3：1的二氯乙烷与六氟异丙醇作为溶剂，在恒电流的作用下室温反应，反应方程式如式II：
本发明的有益效果为：本发明提供的异硫氰酸苄酯类化合物的合成方法科学合理，建立了一种合成异硫氰酸苄酯类化合物的新方法；该方法具有原料易得、操作简单、反应条件温和等特点。
附图说明
图1为实施例1制备的化合物3a的NMR图谱；
图2为实施例7制备的化合物3d的NMR图谱；
图3为实施例9制备的化合物3i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
异硫氰酸苄酯化合物3a的制备
向10mL三口瓶中加入4-乙基苯甲醚1a(0.3mmol,41mg)，异硫氰酸三甲基硅酯2(0.6mmol,79mg)，四丁基六氟膦酸铵(0.6mmol,232mg)和二氯乙烷与六氟异丙醇(3:1,6mL)。石墨毡(1cm x 1.5cm x 1cm)做阳极，镍片(1cm x 1cm x 0.1mm)做阴极。将反应混合物在7mA的恒定电流下室温搅拌6小时。反应完成后，用旋转蒸发仪除去溶剂。通过硅胶柱层析法，使用石油醚和乙酸乙酯(20:1)作为洗脱液，得到产物3a，产率72％。
谱图解析数据3a:
1H NMR(500MHz,CDCl3)δ7.25(d,J＝8.5Hz,2H),6.90(d,J＝8.7Hz,2H),4.87(q,J＝6.8Hz,1H),3.81(s,3H),1.65(d,J＝6.8Hz,3H).
13C NMR(125MHz,CDCl3)δ159.6,132.4,132.1,126.9,114.3,56.7,55.5,25.0.
实施例2
向10mL三口瓶中加入对溴乙苯1b(0.3mmol,56mg)，异硫氰酸三甲基硅酯2(0.6mmol,79mg)，四丁基高氯酸铵(0.6mmol,205mg)和二氯乙烷与六氟异丙醇(3:1,6mL)。石墨毡(1cm x 1.5cm x 1cm)做阳极，镍片(1cm x 1cm x 0.1mm)做阴极。将反应混合物在7mA的恒定电流下室温搅拌6小时。反应完成后，用旋转蒸发仪除去溶剂。通过硅胶柱层析法，使用石油醚和乙酸乙酯(40:1)作为洗脱液，得到产物3b，产率62％。
谱图解析数据3b:
1H NMR(500MHz,CDCl3)δ7.51(d,J＝8.5Hz,2H),7.20(d,J＝8.5Hz,2H),4.88(q,J＝6.8Hz,1H),1.65(d,J＝6.8Hz,3H).
13C NMR(125MHz,CDCl3)δ139.3,133.5,132.2,127.3,122.2,56.6,25.0.
实施例3
用1c代替实例2中的1b，其他条件同实例2，实验结果见表1。
谱图解析数据3c:
1H NMR(500MHz,CDCl3)δ7.35(d,J＝8.4Hz,2H),7.26(d,J＝8.5Hz,2H),4.90(q,J＝6.8Hz,1H),1.65(d,J＝6.8Hz,3H).
13C NMR(125MHz,CDCl3)δ138.8,134.2,133.4,129.2,127.0,56.6,25.1.
实施例4
用1d代替实例2中的1b，其他条件同实例2，实验结果见表1。
谱图解析数据3d:
1H NMR(500MHz,CDCl3)δ7.40(d,J＝7.9Hz,2H),7.25(d,J＝7.9Hz,2H),4.89(q,J＝6.8Hz,1H),1.66(d,J＝6.8Hz,3H),1.32(s,9H).
13C NMR(125MHz,CDCl3)δ151.4,137.3,132.0,125.9,125.3,56.9,34.7,31.4,25.0.
实施例5
用1e代替实例2中的1b，其他条件同实例2，实验结果见表1。
谱图解析数据3e:
1H NMR(500MHz,CDCl3)δ7.33–7.24(m,2H),7.07(t,J＝8.6Hz,2H),4.91(q,J＝6.8Hz,1H),1.66(d,J＝6.8Hz,3H).
13C NMR(125MHz,CDCl3)δ162.5(d,J＝247.0Hz),136.1,133.1,127.3(d,J＝8.3Hz),115.9(d,J＝21.8Hz),56.6,25.1.
实施例6
用1f代替实例2中的1b，其他条件同实例2，实验结果见表1。
谱图解析数据3f:
1H NMR(500MHz,CDCl3)δ7.25–7.20(m,4H),4.88(q,J＝6.8Hz,1H),2.57–2.44(m,1H),1.89–1.81(m,4H),1.80–1.72(m,1H),1.67(d,J＝6.8Hz,3H),1.45–1.34(m,4H),1.32–1.20(m,1H).
13C NMR(125MHz,CDCl3)δ148.4,137.6,132.1,127.5,125.5,57.0,44.4,34.5,27.0,26.3,25.0.
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3g:
1H NMR(500MHz,CDCl3)δ7.45–7.38(m,4H),7.36–7.32(m,1H),7.25(d,J＝8.7Hz,2H),6.98(d,J＝8.7Hz,2H),5.08(s,2H),4.87(q,J＝6.7Hz,1H),1.65(d,J＝6.7Hz,3H).
13C NMR(125MHz,CDCl3)δ158.8,136.9,132.7,132.1,128.8,128.2,127.6,126.9,115.3,70.2,56.7,25.0.
实施例8
用1h代替实例2中的1b，其他条件同实例2，实验结果见表1。
谱图解析数据3h:
1H NMR(500MHz,CDCl3)δ7.41(d,J＝8.3Hz,2H),7.32(d,J＝8.2Hz,2H),4.93(q,J＝6.8Hz,1H),4.59(s,2H),1.67(d,J＝6.8Hz,3H).
13C NMR(125MHz,CDCl3)δ140.6,137.7,133.1,129.3,126.0,56.9,45.7,25.0.实施例9
用1i代替实例2中的1b，其他条件同实例2，实验结果见表1。
谱图解析数据3i:
1H NMR(500MHz,CDCl3)δ7.24(s,4H),4.89(q,J＝6.8Hz,1H),2.96–2.87(m,1H),1.67(d,J＝6.8Hz,3H),1.25(d,J＝6.9Hz,6H).
13C NMR(125MHz,CDCl3)δ149.2,137.7,132.0,127.1,125.6,57.0,34.0,25.0,24.1.
实施例10
用1j代替实例2中的1b，其他条件同实例2，实验结果见表1。
谱图解析数据3j:
1H NMR(500MHz,CDCl3)δ7.22–7.15(m,4H),4.84(q,J＝6.8Hz,1H),2.62(q,J＝7.6Hz,2H),1.62(d,J＝6.8Hz,3H),1.20(t,J＝7.6Hz,3H).
13C NMR(126MHz,CDCl3)δ144.5,137.6,132.2,128.5,125.5,57.0,28.6,25.0,15.6.
表1
Claims (2)
1.一种异硫氰酸苄酯类化合物的制备方法，所述异硫氰酸苄酯类化合物具有式Ⅰ所示的结构：
式Ⅰ中，其中R1取代基为氟、氯、溴、甲氧基、乙基、叔丁基、异丙基、环己基、苄氧基、氯甲基。其特征在于，向反应器中加入摩尔比为1：2的取代乙苯与异硫氰酸三甲基硅酯，加入四丁基六氟膦酸铵或四丁基高氯酸铵作为电解质，加入体积比3：1的二氯乙烷与六氟异丙醇作为溶剂，在恒电流的作用下室温反应，反应方程式如式II：
2.按照权利要求1所述的制备方法，其特征在于：电极为石墨毡作为阳极和镍片作为阴极，反应时间为6h，电流强度为恒流7mA。
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| CN114214651B (zh) * | 2022-01-12 | 2024-02-20 | 青岛科技大学 | 一种电催化下α-羰基-α’-硫氰基亚砜叶立德的合成方法 |
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