CN112047902A - 非对称二硫醚类化合物的制备方法 - Google Patents
非对称二硫醚类化合物的制备方法 Download PDFInfo
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Abstract
本发明涉及一种非对称二硫醚类化合物的合成方法。本发明以方便易得的硫醇及对称的二硫醚化合物为原料,在钯盐或铜盐的催化作用下,高效地合成非对称的二硫醚类化合物。该方法具有原料易得、催化体系简单、操作方便、官能团兼容性好、产率高等优点。该方法尤其适合在复杂底物中选择性地引入二硫键,将在药物和食品等行业中得到广泛的应用。
Description
技术领域
本发明涉及非对称二硫醚类化合物的制备方法。
背景技术
二硫醚类化合物由于含有两个共价键连接的硫原子的二硫化物骨架,其具有独特的药理和理化性质,是生命科学、医药科学和食品科学中的重要分子结构。二硫键广泛存在于许多生物活性的天然产物和药物分子中,参见Chinese Chemical Letters 2018,29,1079;Angew.Chem.Int.Ed.2018,57,12290。在各种生化氧化还原过程中发挥着多方面的作用;蛋白质的二级和三级结构也通过二硫键桥形成和稳定,参见Nat Commun,2018,9,2191;Angew.Chem.Int.Ed.2015,54,9218;Tetrahedron Lett.1990,31,2389。因此,二硫醚化合物具有重要的科学意义和应用价值。文献报道的含有二硫键的生物分子有:
文献中曾报道的非对称二硫化合物的合成方法主要有以下几种:
非对称的二硫化合物可以通过不同的两种硫醇来合成,但是不可避免会生成对称的二硫醚类化合物,造成分离困难。见参考文献:(a)Org.Chem.Front.,2019,6,2220.(b)Green Chem.2019,21,1432.(c)Org.Chem.Front.2015,2,677.Tetrahedron 2011,67,8895。
2006年,Roy报道了通过含有易离去基团的硫化合物(如硫氯化合物,LG=Cl)和硫醇来合成不对称的二硫醚化合物,但是这类原料不稳定,原料需要当场制备使用,反应操作较为复杂。见参考文献:J.Org.Chem.2006,71,8268;J.Org.Chem.1991,56,6697。
2013年,Parkin等人报道了通过从氧化的硫代亚砜出发来合成非对称二硫化物,但原料硫代亚砜需要选择性的氧化其中一个硫原子为亚砜,存在过氧化和两个硫原子均被氧化的情况,因此合成过程较复杂。见参考文献:J.Agric.Food Chem.2013,61,3030。
2018年,雷爱文教授课题组报道了通过电化学氧化S-H来合成非对称二硫化物,该种合成方法,虽然绿色环保,但是由于该方法是通过芳香硫醇与烷基硫醇氧化电位的差异来实现S-S键的非对称合成。因而底物的受限,只能合成芳香-烷基二硫醚。见参考文献:Angew.Chem.Int.Ed.2018,57,8115。
2016年,姜雪峰老师课题组在过硫结构的外端成功装上新型“面具”RSSOAc,从而反转了电性。运用“面具”的电子、立体以及偶极性质,依据动力学与热力学的交互调控”来合成了非对称二硫醚类化合物。见参考文献:Angew.Chem.Int.Ed.,2016,55,14121。2018年,再次反转电性,由亲核过硫试剂获得亲电过硫试剂(RSSOMe),实现更多分子的过硫化的安装,见参考文献:Nat.Commun.,2018,9,2191。
综上所述,非对称二硫醚类化合物的合成方法大多数反应存在步骤较长、操作繁琐、副产物多、官能团兼容性差,底物受限等缺点,严重制约了非对称二硫醚类化合物的应用研究。因此,开发一种操作简便,路线短,底物范围广的合成方法是非常有必要的。高效的非对称二硫醚类化合物的合成方法将有力地促进非对称二硫醚的研究。
发明内容
本发明的目的在于提供一种非对称二硫醚类化合物的制备方法。
为达到上述目的,本发明方法采用的机理如下:
其中R1,R2=烷基,苯基,芳香杂环,氨基酸类衍生物等。
催化剂为:PdCl2,Pd(OAc)2,CuCl2,CuSO4,CuCl,CuI,CuBr2,Cu(OAc)2等钯盐或铜盐。
溶剂为DMF,DMSO,DMA,NMP,THF,EtOH,dioxane等。
反应温度为:25~120℃。
根据上述反应机理,本发明采用如下技术方案:
一种非对称二硫醚类化合物的合成方法,该化合物的结构式为:
其特征在于该方法的具体步骤为:在惰性气氛保护下,将硫醇或硫酚和二硫醚按照1:(1.0~5.0)的摩尔比溶于溶剂中,再加入催化量的金属催化剂,反应温度为25~120℃,反应时间为1~24小时;除去蒸馏溶剂后所得粗产物,再进行分离提纯得到非对称二硫醚类化合物。所述的硫醇或硫酚的结构式为:R1-SH;所述的二硫醚的结构式为:
上述的催化剂为:PdCl2、Pd(OAc)2、CuCl2、CuSO4、CuCl、CuI、CuBr2或Cu(OAc)2等金属盐。
上述的溶剂为:N,N’-二甲基甲酰胺,二甲基亚砜、N,N’-二甲基乙酰胺、N-甲基吡咯烷酮、四氢呋喃、乙醇,或1,4-二氧六环等常见溶剂。
本反应具有高度的官能团兼容性,对水和空气不敏感,底物中的游离的胺基,羟基和羧酸等官能团均不参与反应,具有高度的官能团选择性,尤其适合合成具有复杂结构的二硫醚类化合物。所得非对称二硫醚类化合物的结构构特征如下:
其中R1,R2=烷基,苯基,芳香杂环,氨基酸类衍生物等。
本发明以方便易得的硫醇及对称的二硫醚化合物为原料,在钯盐或铜盐的催化作用下,高效地合成非对称的二硫醚类化合物。该方法具有原料易得、催化体系简单、操作方便、官能团兼容性好、产率高等优点。该方法尤其适合在复杂底物中选择性地引入二硫键,将在药物和食品等行业中得到广泛的应用。
具体实施方式
实施例一:2-(丁基二硫醚基)苯并[d]噻唑
一种制备上述非对称二硫醚化合物的方法,其特征在于具体步骤如下:氮气保护下,在25mLSchlenk管中加入83.7mg2-巯基苯并噻唑和178.4mg二丁基二硫醚以及4.5mg的二氯化钯,在通氮气的情况下加入2.0mLDMSO,加热至80℃,反应2h。冷却后倒入5mL水中,用30mL二氯甲烷萃取产物,饱和食盐水洗,无水硫酸钠干燥,用旋转蒸发仪去掉溶剂,得到粗产物。粗产物用柱层析(PE:EA=100:1)纯化,得到109.5mg黄色油状液体产物,产率86%。所得产物的表征数据如下:IR(KBr,cm-1):3426,2960,2916,1461,1454,1432,1002,752,719;1H NMR(500MHz,CDCl3):δ7.87–7.85(m,1H),7.81–7.79(m,1H),7.44–7.41(m,1H),7.34–7.30(m,1H),2.97–2.94(m,2H),1.77–1.71(m,2H),1.48–1.41(m,2H),0.92(t,J=7.4Hz,3H);13C NMR(125MHz,CDCl3):δ173.84,155.73,136.39,126.78,125.07,122.67,121.69,39.87,31.58,22.19,14.18;LRMS(EI)calcd forC11H13NS3[M]+255.0。
实施例二:2-(甲基二硫醚基)-吡啶
一种制备上述非对称二硫醚化合物的方法,其特征在于具体步骤如下:氮气保护下,在25mL Schlenk管中加入55.6mg 2-巯基吡啶和94.2mg二甲基二硫醚以及4.5mg的二氯化钯,在通氮气的情况下加入2.0mL DMSO,加热至80℃,反应2h。冷却后倒入5mL水中,用30mL二氯甲烷萃取产物,饱和食盐水洗,无水硫酸钠干燥,用旋转蒸发仪去掉溶剂,得到粗产物;粗产物用柱层析(PE:EA=50:1)纯化,得到65.9mg黄色油状液体产物,产率84%。所得产物的表征数据如下:IR(KBr,cm-1):3425,3046,2982,2916,1569,1416,1118,814,760;1HNMR(500MHz,CDCl3):δ8.47–8.45(m,1H),7.68–7.61(m,2H),7.08–7.05(m,1H),2.49(s,3H).13C NMR(125MHz,CDCl3):δ160.00,149.86,137.12,120.66,119.54,23.06;LRMS(EI)calcd forC6H7NS2[M]+157.0。
实施例三:2-(甲基二硫醚基)-嘧啶
一种制备上述非对称二硫醚化合物的方法,其特征在于具体步骤如下:氮气保护下,在25mL Schlenk管中加入56mg 2-巯基嘧啶和94.2mg二甲基二硫醚以及4.5mg的二氯化钯,在通氮气的情况下加入2.0mL DMSO,加热至80℃,反应2h。冷却后倒入5mL水中,用30mL二氯甲烷萃取产物,饱和食盐水洗,无水硫酸钠干燥,用旋转蒸发仪去掉溶剂,得到粗产物;粗产物用柱层析(PE:EA=50:1)纯化,得到56.7mg浅黄色油状液体产物,产率72%。所得产物的表征数据如下:IR(KBr,cm-1):3452,2916,2842,1553,1369,1186,767,627;1H NMR(500MHz,CDCl3):δ8.62(d,J=5.45Hz,2H),7.09(t,J=5.6Hz,1H),2.55(s,3H).13C NMR(125MHz,CDCl3):δ171.65,157.98,117.90,22.83;LRMS(EI)calcd forC5H6N2S2[M]+158.0。
实施例四:2-(甲基二硫醚基)-噻吩
一种制备上述非对称二硫醚化合物的方法,其特征在于具体步骤如下:氮气保护下,在25mL Schlenk管中加入58.1mg 2-巯基噻吩和94.2mg二甲基二硫醚以及4.5mg的二氯化钯,在通氮气的情况下加入2.0mL DMSO,加热至80℃,反应2h。冷却后倒入5mL水中,用30mL二氯甲烷萃取产物,饱和食盐水洗,无水硫酸钠干燥,用旋转蒸发仪去掉溶剂,得到粗产物;粗产物用柱层析(PE:EA=100:1)纯化,得到38.6mg浅黄色油状液体产物,产率47%。所得产物的表征数据如下:IR(KBr,cm-1):3419,2909,1487,1215,840,705;1H NMR(500MHz,CDCl3):δ7.75(dd,J=5.3,1.2Hz,1H),7.58(dd,J=3.6,1.1Hz,1H),7.34(dd,J=5.35,3.6,1H)7.2Hz),2.87(s,3H).13C NMR(125MHz,CDCl3):δ136.58,134.22,131.02,127.79,23.30.LRMS(EI)calcd forC5H6S3[M]+162.0。
实施例五:2-(对氯苯二硫醚基)苯并[d]噻唑
一种制备上述非对称二硫醚化合物的方法,其特征在于具体步骤如下:氮气保护下,在25mL Schlenk管中加入83.7mg 2-巯基苯并噻唑和287.2mg二-4-氯苯基二硫醚以及4.5mg的二氯化钯,在通氮气的情况下加入2.0mL DMSO,加热至80℃,反应2h。冷却后倒入5mL水中,用30mL二氯甲烷萃取产物,饱和食盐水洗,无水硫酸钠干燥,用旋转蒸发仪去掉溶剂,得到粗产物;粗产物用柱层析(PE:EA=500:1)纯化,得到109.7mg浅黄色产物,熔点:58-59℃,产率71%。所得产物的表征数据如下:IR(KBr,cm-1):3059,2820,1483,1248,1189,1009,756,602,506;1H NMR(500MHz,CDCl3):δ7.89(d,J=8.1Hz,1H),7.78(d,J=8.0Hz,1H),7.60-7.53(m,2H),7.47-7.41(m,1H),7.38-7.27(m,3H).13C NMR(125MHz,CDCl3)δ170.77,154.91,135.9,134.9,133.6,130.6,129.6,126.5,124.9,122.4,121.2;LRMS(EI)calcd forC13H8NClS3[M]+309.0。
实施例六:2-(对甲氧基苯基二硫醚基)苯并[d]噻唑
种制备上述非对称二硫醚化合物的方法,其特征在于具体步骤如下:氮气保护下,在25mL Schlenk管中加入83.7mg 2-巯基苯并噻唑和278.3mg二-4-甲氧基苯基二硫醚以及4.5mg的二氯化钯,在通氮气的情况下加入2.0mL DMSO,加热至80℃,反应2h。冷却后倒入5mL水中,用30mL二氯甲烷萃取产物,饱和食盐水洗,无水硫酸钠干燥,用旋转蒸发仪去掉溶剂,得到粗产物;粗产物用柱层析(PE:EA=500:1)纯化,得到131.1mg浅黄色产物,熔点:57-58℃,产率86%。所得产物的表征数据如下:IR(KBr,cm-1):3059,2831,1586,1483,1414,815,616;1H NMR(500MHz,CDCl3):7.89(d,J=8.1Hz,1H),7.81(d,J=7.3Hz,1H),7.67-7.64(m,2H),7.48-7.40(m,1H),7.39-7.31(m,1H),6.90-6.83(m,2H),3.81(s,3H).13CNMR(125MHz,CDCl3)δ172.16,160.92,155.07,135.99,133.48,126.38,125.93,124.76,122.37,121.27,115.12,55.56;LRMS(EI)calcd for C14H11NOS3[M]+305.0。
实施例七:1-(4-甲氧基苯基)-2-甲基二硫醚
一种制备上述非对称二硫醚化合物的方法,其特征在于具体步骤如下:氮气保护下,在25mL Schlenk管中加入70.1mg对甲氧基苯硫醇和94.2mg二甲基二硫醚以及4.5mg的二氯化钯,在通氮气的情况下加入2.0mL DMSO,加热至80℃,反应2h。冷却后倒入5mL水中,用30mL二氯甲烷萃取产物,饱和食盐水洗,无水硫酸钠干燥,用旋转蒸发仪去掉溶剂,得到粗产物;粗产物用柱层析(PE:EA=100:1)纯化,得到52.4mg浅黄色油状液体产物,产率56%。所得产物的表征数据如下:IR(KBr,cm-1):3621,2961,2034,1589,1487,1258,1182,1018,804;1H NMR(500MHz,CDCl3):δ7.52-7.50(m,2H),6.91-6.89(m,2H),3.83(s,3H),2.46(s,3H);13C NMR(125MHz,CDCl3)δ159.85,132.23,127.95,114.82,55.53,23.00.;HRMS(EI)calcd forC8H10OS2[M]186.0173,found 186.0168。
实施例八:1-(乙酸乙酯基)-2-甲基二硫醚
一种制备上述非对称二硫醚化合物的方法,其特征在于具体步骤如下:氮气保护下,在25mL Schlenk管中加入60.4mg巯基乙酸乙酯和94.2mg二甲基二硫醚以及4.5mg的二氯化钯,在通氮气的情况下加入2.0mL DMSO,加热至80℃,反应2h。冷却后倒入5mL水中,用30mL二氯甲烷萃取产物,饱和食盐水洗,无水硫酸钠干燥,用旋转蒸发仪去掉溶剂,得到粗产物;粗产物用柱层析(PE:EA=20:1)纯化,得到34.8mg无色液体产物,产率42%。所得产物的表征数据如下:IR(KBr,cm-1):2963,2361,1740,1454,1263,1096,1023,803;1H NMR(400MHz,CDCl3):δ4.29-4.15(q,J=7.0Hz,2H),3.46(s,2H),2.46(s,3H),1.33-1.28(t,J=7.1Hz,3H).13C NMR(100MHz,CDCl3)δ169.89,61.70,41.12,23.16,14.25.HRMS(EI)calcdforC5H10O2S2[M]+166.0122,found 166.0117。
实施例九:2-甲基二硫醚基-5-甲基-1,3,4-噻二唑
一种制备上述非对称二硫醚化合物的方法,其特征在于具体步骤如下:氮气保护下,在25mL Schlenk管中加入66.1mg 2-巯基-5-甲基-1,3,4-噻二唑和94.2mg二甲基二硫醚以及4.5mg的二氯化钯,在通氮气的情况下加入2.0mL DMSO,加热至80℃,反应2h。冷却后倒入5mL水中,用30mL二氯甲烷萃取产物,饱和食盐水洗,无水硫酸钠干燥,用旋转蒸发仪去掉溶剂,得到粗产物。粗产物用柱层析(PE:EA=10:1)纯化,得到81.2mg无色液体产物,产率91%。所得产物的表征数据如下:IR(KBr,cm-1):3625,3434,2908,2971,1428,1388,1193,1075,958,756,598;1H NMR(500MHz,CDCl3):δ2.75-2.73(s,3H),2.64-2.62(s,3H);13C NMR(125MHz,CDCl3)δ171.29,167.08,23.50,16.02;HRMS(EI)calcd for C4H6N2S3[M]+177.9693,found 177.9688。
实施例十:S-硫甲基-L-半胱氨酸甲酯
一种制备上述非对称二硫醚化合物的方法,其特征在于具体步骤如下:氮气保护下,在25mL Schlenk管中加入85.8mg L-半胱氨酸甲酯盐酸盐和235.5mg二甲基二硫醚以及4.5mg的二氯化钯,在通氮气的情况下加入2.0mL DMSO,加热至80℃,反应12h。冷却后倒入5mL水中,用30mL二氯甲烷萃取产物,饱和食盐水洗,无水硫酸钠干燥,用旋转蒸发仪去掉溶剂,得到粗产物。粗产物用柱层析(MeOH:DCM=1:50)纯化,得到70.8mg无色液体产物,产率78%。所得产物的表征数据如下:IR(KBr,cm-1):3362,2951,2359,1737,1669,1442,1216,1015;1HNMR(400MHz,CDCl3):δ3.84-3.78(dd,J=7.7,4.6,1H),3.73(s,3H),3.13-3.06(dd,J=13.7,4.6,1H),2.92-2.83(dd,J=13.7,7.7,1H),2.40(s,3H);13C NMR(100MHz,CDCl3)δ174.42,53.55,52.37,42.79,22.99;HRMS(DART)calcd for C5H11NO2S2[M]+181.0231,found182.0304。
Claims (3)
2.根据权利要求1所述的方法,其特征在于所述的催化剂为:PdCl2、Pd(OAc)2、CuCl2、CuSO4、CuCl、CuI、CuBr2或Cu(OAc)2。
3.根据权利要求1所述的方法,其特征在于所述的溶剂为:N,N’-二甲基甲酰胺,二甲基亚砜、N,N’-二甲基乙酰胺、N-甲基吡咯烷酮、四氢呋喃、乙醇或1,4-二氧六环。
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