CN105859598A - 一种多取代二硫芳基亚胺衍生物的制备方法 - Google Patents
一种多取代二硫芳基亚胺衍生物的制备方法 Download PDFInfo
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- C—CHEMISTRY; METALLURGY
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- C07C381/00—Compounds containing carbon and sulfur and having functional groups not covered by groups C07C301/00 - C07C337/00
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Abstract
本发明公开了属于有机合成技术领域的一种多取代二硫芳基亚胺的制备方法。所述方法为:向反应器中,加入二芳基高价碘盐,异硫氰酸酯和铜盐,抽换氮气三次后,加入溶剂,加热至反应完毕;体系冷却后,加入饱和碳酸氢钠溶液淬灭反应,用乙酸乙酯分三次进行萃取,合并有机相,加入硫酸镁干燥,过滤,旋转蒸发仪浓缩滤液得到粗产物,用洗脱剂柱层析分离得产品。本发明所提供的多取代二硫芳基亚胺衍生物的制备方法科学合理,产率较高,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,特别是涉及多取代二硫芳基亚胺衍生物的制备方法。
背景技术
亚胺化合物是一类重要的、多用途的有机反应中间体,广泛应用于合成药物、生物活性物质和精细化学品等。二硫代亚胺作为含硫亚胺衍生物,可以合成具有重要药学价值的噻唑、三唑、噁唑、嘧啶等杂环化合物。二硫芳基亚胺可以制备具有潜在抑菌作用的β-内酰胺类抗生素(J.Org.Chem.2007,72,415)。二甲硫代亚胺可以制备具有潜在生物活性的噻唑并嘧啶和噻唑并三嗪类杂环化合物(Tetrahedron 2009,65,2982)。硫代亚胺和炔烃反应可以制备呋喃类化合物(Org.Lett.2010,12,3744)。
鉴于二硫芳基亚胺衍生物具有广泛的用途,研究此类化合物的合成方法具有重要的意义。
二硫芳基亚胺衍生物的制备方法有:
1)以二硫代氰基亚胺钾盐为原料
Hantzsch等从二硫化碳、氢氧化钾和氨基氰反应出发制备二硫代氰基亚胺钾盐,然后将二硫代氰基亚胺钾盐与溴苯在二甲基吡啶中回流,溴化亚铜作催化剂,最终得到二苯硫基亚甲胺。(J.Org.Chem.1966,32,1566)
2)以二苯基-N-氰基二硫代氨基甲酸酯为原料
Eggleston等在氮气保护条件下,将苯硫酚和三乙胺溶于氯仿中,N-氰基二硫代氨基甲酸缓慢滴加到反应体系中,常温搅拌过夜,最后水洗得到二苯基-N-氰基二硫代氨基甲酸酯目标产物。(J.Heterocyclic Chem.,1987,24,275)。
3)以异腈为原料
Ogawa等在氩气保护条件下,向高硼硅玻璃管中加入苯基异腈和二硫化二苯,在40℃,500W钨灯辐射下搅拌13小时,最后柱色谱分离得到N-(苯基)-二硫苯基亚胺目标产物。(J.Org.Chem.2007,72,415)。
利用上述方法制备二硫芳基亚胺衍生物,具有明显的缺点:1)原料毒性大,反应条件苛刻;2)合成步骤多,原料制备复杂,产率低。
发明内容
为了克服上述现有技术的不足,本发明提供了一种多取代二硫芳基亚胺衍生物的制备方法。
一种多取代二硫芳基亚胺衍生物的制备方法,所述多取代二硫芳基亚胺衍生物具有式I所示的结构:
其中,R1选自苯基、萘基、2-吡啶基、取代苯基,取代基团为氟原子、氯原子、溴原子、甲基、甲氧基、三氟甲基;R2取代基团为氟原子、氯原子、溴原子、甲基、甲氧基、酯基、三氟甲基;其特征在于,向反应器中,加入二芳基高价碘盐,异硫氰酸酯和三氟甲磺酸铜,抽换氮气三次后,加入1,2-二氯乙烷,加热至反应完毕;体系冷却后,加入饱和碳酸氢钠溶液淬灭反应,用乙酸乙酯分三次进行萃取,合并有机相,加入硫酸镁干燥,过滤,旋转蒸发仪浓缩滤液得到粗产物,用洗脱剂柱层析分离得产品;其化学过程见反应式II:
所述二芳基高价碘盐中Xˉ为三氟甲磺酸阴离子基团;所述铜盐为三氟甲磺酸铜,三氟甲磺酸铜的用量为异硫氰酸酯物质的量的10%,异硫氰酸酯和二芳基高价碘盐的摩尔比值为1.0:1.5;所述溶剂选自二氯乙烷,反应温度为80℃,反应时间为3h。
本发明的有益效果为:本发明提供的多取代二硫芳基亚胺衍生物的合成方法科学合理,可以合成得到具有各种取代基的二硫芳基亚胺衍生物;而且还具有合成方法简单,产率较高、产品易于纯化等特点。
附图说明
图1为实施例3制备的化合物的NMR图谱;
图2为实施例6制备的化合物的NMR图谱;
图3为实施例8制备的化合物的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作进一步详细的说明:
下述实施例中所述实验方法,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。
下述实施例中所用的溶剂使用前均经过无水无氧处理或者加入活化后的分子筛进行简单处理。
实施例1:二硫芳基亚胺衍生物3a的制备
氮气保护下,向10mL史莱克管中加入异硫氰酸苯酯1a(0.30mmol,40mg)、二芳基碘鎓盐2a(0.45mmol,193mg)和三氟甲磺酸铜(0.03mmol,11mg)。加入1.5mL的二氯乙烷,在升温至80℃的油浴中反应3h。反应完毕后,冷却至室温,体系用饱和NaHCO3溶液淬灭,然后用二氯甲烷萃取3次,有机相用饱和NaCl洗涤并用无水MgSO4干燥30分钟,用旋转蒸发仪除去溶剂,残留物经柱层析分离(200-300目硅胶)(石油醚/乙酸乙酯=100/1)得到纯度大于99%的无色晶体N-(苯基)-二苯硫基亚胺3a,分离产率93%。
谱图解析数据3a:
1H NMR(CDCl3,500MHz):δ6.88(d,J=7.60Hz,2H),7.08(t,J=7.35Hz,1H),7.31(t,J=7.78Hz,2H),7.38-7.39(m,6H),7.58(s,4H).13C NMR(CDCl3,125MHz):δ120.2,124.0,128.8,128.9,129.5,135.7,149.7,160.8.HRMS(ESI-TOF,[M+H]+):Calcd for C19H16NS2,322.0724;Found,322.0719.
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3b:
1H NMR(CDCl3,500MHz):δ3.77(s,3H),6.81-6.85(m,4H),7.35(s,6H),7.54(s,4H).13C NMR(CDCl3,125MHz):δ55.4,114.1,121.5,129.0,129.7,135.1,136.4,142.8,156.5,160.2.HRMS(ESI-TOF,[M+H]+):Calcd for C20H18NOS2,352.0830;Found,352.0832.
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3c:
1H NMR(CDCl3,500MHz):δ6.74(d,J=8.45Hz,2H),7.37-7.39(m,8H),7.54(s,4H).13C NMR(CDCl3,125MHz):δ117.8,122.1,129.1,129.7,121.7,135.7,148.6,162.1.HRMS(ESI-TOF,[M+H]+):Calcd for C19H15NBrS2,399.9824;Found,399.9831.
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3d:
1H NMR(CDCl3,500MHz):δ2.30(s,3H),6.77(d,J=7.90Hz,2H),7.07(d,J=7.90Hz,2H),7.35(s,6H),7.54(s,4H).13C NMR(CDCl3,125MHz):δ20.9,120.1,128.9,128.8,129.4,133.6,134.9,136.3,147.1,160.2.HRMS(ESI-TOF,[M+H]+):Calcd for C20H18NS2,336.0881;Found,336.0892.
实施例5:
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3e:
1H NMR(CDCl3,500MHz):δ6.84(d,J=6.65Hz,2H),7.10(t,J=6.63Hz,1H),7.30(t,J=7.60Hz,3H),7.42(s,3H),7.51(d,J=8.05Hz,4H).13C NMR(CDCl3,125MHz):δ120.1,124.4,128.9,132.3,137.2,149.2,159.3.HRMS(ESI-TOF,[M+H]+):Calcd for C19H14NBr2S2,477.8942;Found,477.8934.
实施例6:
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3f:
1H NMR(CDCl3,500MHz):δ2.38(s,6H),6.87(d,J=7.75Hz,2H),7.07(t,J=7.38Hz,1H),7.18-7.20(m,3H),7.29(t,J=7.73Hz,3H),7.46(s,4H).13C NMR(CDCl3,125MHz):δ21.33,120.2,123.8,128.8,129.8,135.9,149.9,161.7.HRMS(ESI-TOF,[M+H]+):Calcd for C21H20NS2,350.1037;Found,350.1043.
实施例7:
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3g:
1H NMR(CDCl3,500MHz):δ3.91(s,6H),6.84(d,J=7.80Hz,2H),7.08(t,J=7.35Hz,1H),7.28(t,J=7.78Hz,2H),7.60-7.61(m,4H),8.00(d,J=8.20Hz,4H).13C NMR(CDCl3,125MHz):δ52.4,120.1,124.5,128.9,130.0,130.9,135.4,149.0,158.1,166.4.HRMS(ESI-TOF,[M+H]+):Calcd for C23H20NO4S2,438.0828;Found,430.0838.
实施例8:
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3h:
1H NMR(CDCl3,500MHz):δ6.82(d,J=7.95Hz,1H),6.97-6.99(m,1H),7.36-7.60(m,5H),8.41(d,J=4.60Hz,1H).13C NMR(CDCl3,125MHz):δ117.9,119.7,129.0,129.6,136.0,137.7,148.0,160.0,165.4.HRMS(ESI-TOF,[M+H]+):Calcd for C18H15N2S2,323.0671;Found,323.0678.
实施例9:
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3i:
1H NMR(CDCl3,500MHz):δ6.97(d,J=7.3Hz,1H),7.37-7.46(m,9H),7.56(d,J=8.3Hz,1H),7.59-7.60(m,4H),7.69(d,J=8.1Hz,1H),7.78(d,J=7.9Hz,1H).13C NMR(CDCl3,125MHz):δ114.9,123.5,124.1,125.4,125.5,126.1,126.5,127.7,129.0,129.7,134.2,136.0,145.8,161.7.HRMS(ESI-TOF,[M+H+]:Calcdfor 372.0881,Found:372.0892.
实施例10: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3j:
1H NMR(CDCl3,500MHz):δ6.79(d,J=8.50Hz,2H),7.24(d,J=8.50Hz,2H),7.37-7.38(m,6H),7.54(s,4H).13C NMR(CDCl3,125MHz):δ121.7,128.9,129.1,129.3,129.7,135.8,148.2,162.2.HRMS(ESI-TOF,[M+H]+):Calcd forC19H15NClS2,356.0329;Found,356.0336.
表一
Claims (3)
1.一种多取代二硫芳基亚胺衍生物的制备方法,所述多取代二硫芳基亚胺衍生物具有式Ⅰ所示的结构:
其中,R1选自苯基、萘基、2-吡啶基、取代苯基,取代基团为氟原子、氯原子、溴原子、甲基、甲氧基、三氟甲基;R2取代基团为氟原子、氯原子、溴原子、甲基、甲氧基、酯基、三氟甲基;其特征在于,向反应器中,加入二芳基高价碘盐,异硫氰酸酯和铜盐,抽换氮气三次后,加入溶剂,加热至反应完毕;体系冷却后,加入饱和碳酸氢钠溶液淬灭反应,用乙酸乙酯分三次进行萃取,合并有机相,加入硫酸镁干燥,过滤,旋转蒸发仪浓缩滤液得到粗产物,用洗脱剂柱层析分离得产品;其化学反应过程见式II:
。
2.根据权利要求1所述的制备方法,其特征在于,X-为三氟甲磺酸阴离子基团;所述铜盐为三氟甲磺酸铜,三氟甲磺酸铜的用量为异硫氰酸酯物质的量的10%,异硫氰酸酯和二芳基高价碘盐的摩尔比值为1.0:1.5。
3.根据权利要求1所述的制备方法,其特征在于,所述溶剂选自二氯乙烷,反应温度为80℃,反应时间为3h。
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