CN110117240A - 二硫胺类化合物及其合成方法和应用 - Google Patents

二硫胺类化合物及其合成方法和应用 Download PDF

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CN110117240A
CN110117240A CN201810122287.3A CN201810122287A CN110117240A CN 110117240 A CN110117240 A CN 110117240A CN 201810122287 A CN201810122287 A CN 201810122287A CN 110117240 A CN110117240 A CN 110117240A
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姜雪峰
薛佳晖
肖霄
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East China Normal University
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Abstract

本发明公开了一种如式(3)所示的二硫胺类化合物的合成方法，以式(1)过硫化试剂R1SSOMe与式(2)有机胺为反应原料，在催化剂作用下，反应得到所述二硫胺类化合物。本发明反应条件温和，原料廉价易得，反应操作简单，产率较高，反应中无需金属催化剂，无需加入额外的氧化或还原剂，对环境友好；反应底物容易制备。本发明制备的式(3)所示的二硫胺类化合物可以是磺胺类药物，具有潜在药物价值。本发明具有广泛应用前景和实用价值。

Description

二硫胺类化合物及其合成方法和应用
技术领域
本发明属于有机化合物工艺应用技术领域，具体涉及二硫胺类化合物及其合成方法和应用。
背景技术
氨基化合物广泛存于药物、天然产物中，具有重要的应用价值，而对氨基的直接二硫化还未见报道。现有技术中，过硫胺化合物的合成方法主要是通过一种硫醇或者苯硫酚类化合物与另一种氯代硫胺类化合物反应制备，而氯代硫胺一般需要使用一种伯胺与二氯化硫制备。此类方法，所使用的有机硫醇或苯硫酚类化合物易被氧化，并且氧化过程中选择性差，对金属催化剂有毒化作用；二氯化硫是一种剧毒，恶臭，具有强腐蚀性，难保存的液体；原料味道过重，且对环境及人体均有不同程度的伤害；使此类方法的应用受到了制约。
因此，寻找一种具有通用性的，无需金属参与的，种高效、环境友好、条件温和和经济适用的过硫化方法便显得尤其重要。
发明内容
本发明克服了传统合成二硫胺化合物的诸多缺点，使用无味、稳定、易制备的过硫化试剂R1SSOMe，该反应具有反应性强、无需金属催化等特点。鉴于此，本发明设计了通过使用路易斯酸催化剂，通过一种有机胺类化合物与过硫化试剂R1SSOMe的亲核反应来制备二硫胺类化合物的反应方法。
本发明提出的一种二硫胺类化合物，其结构如式(3)所示：
其中，R1选自直链烷基、苯乙基、丁酸酯基、苄基及其衍生物、取代苄基、1,4-二甲基苯基、1,1’-联苯-4,4’-二甲基、糖、含糖衍生物、氨基酸、氨基酸衍生物等；
R2选自C1-C5烷基、芳基、C1-C5烯基、C1-C5炔基、取代芳基、磺胺类药物、8-喹啉基、来那度胺、氨基酸衍生物等；
R3选自C1-C5烷基、H等；
优选地，R1选自癸基、对氰基苄基、吡喃糖衍生物、呋喃糖衍生物、氨基酸衍生物等；
R2选自乙基、丙烯、乙炔、苯基、甲基取代苯基、甲氧基取代苯基、叔丁基取代苯基、溴取代苯基、氯取代苯基、磺胺类药物、8-喹啉基、来那度胺、氨基酸衍生物；
R3选自甲基、乙基、H。
进一步地，本发明式(3)所示的二硫胺类化合物包括：
本发明还提出了一种二硫胺类化合物的合成方法，以式(1)所示的过硫化试剂R1SSOMe和式(2)所示的有机胺类化合物为反应原料，在催化剂作用下，在有机溶剂中，反应得到如式(3)所示的二硫胺类化合物。所述反应过程如反应式(a)所示；
其中，R1选自直链烷基、苯乙基、丁酸酯基、苄基及其衍生物、取代苄基、1,4-二甲基苯基、1,1’-联苯-4,4’-二甲基、糖、含糖衍生物、氨基酸、氨基酸衍生物等；
R2选自C1-C5烷基、芳基、C1-C5烯基、C1-C5炔基、取代芳基、磺胺类药物、8-喹啉基、来那度胺、氨基酸衍生物等；
R3选自C1-C5烷基、H等；
优选地，R1选自癸基、对氰基苄基、吡喃糖衍生物、呋喃糖衍生物、氨基酸衍生物等；
R2选自乙基、丙烯、乙炔、苯基、甲基取代苯基、甲氧基取代苯基、叔丁基取代苯基、溴取代苯基、氯取代苯基、磺胺类药物、8-喹啉基、来那度胺、氨基酸衍生物；
R3选自甲基、乙基、H。
本发明还提出了一种二硫胺类化合物的合成方法，在路易斯酸催化剂条件下，以式(1)所示的过硫化试剂R1SSOMe与式(2)所示的有机胺类化合物为反应原料，在催化剂作用下，在有机溶剂中，反应得到如式(3)所示二硫胺类化合物。
本发明中，所述反应原料式(2)所示的有机胺类化合物与式(1)所示的过硫化试剂R1SSOMe的摩尔比例为1.0：1.5-1.5：1.0。优选地，两者用量的摩尔比例为1.1：1.0或者1.0：1.5。
本发明中，所述催化剂为B(C6F5)3。
本发明中，所所述催化剂的用量为式(1)所示的过硫化试剂R1SSOMe的1-10mol％；优选地，所述催化剂的用量为原料式(1)所示的过硫化试剂R1SSOMe的1-2.5mol％；进一步优选地，所述催化剂的用量为原料式(1)所示的过硫化试剂R1SSOMe的2.5mol％。
本发明中，所述有机溶剂是甲苯或者N,N-二甲基甲酰胺中的一种或2种。
本发明中，所述反应是在10-25℃进行的；优选地，反应的温度为20℃、25℃。
本发明中，所述反应的时间为24-48小时；优选地，为24小时。
本发明还提出了一种过硫化试剂，其结构如式(1)所示，
其中，R1选自直链烷基、苯乙基、丁酸酯基、苄基及其衍生物、取代苄基、1,4-二甲基苯基、1,1’-联苯-4,4’-二甲基、糖、含糖衍生物、氨基酸、氨基酸衍生物等；
优选地，R1选自癸基、对氰基苄基、糖、含糖衍生物、氨基酸衍生物等。
本发明中，使用R1SSOMe为过硫化试剂，在路易斯酸催化剂催化下，对胺类化合物进行过硫化反应，是一种新颖，高效的过硫化反应，是合成二硫胺类化合物的有效途径。
在一个具体实例中，本发明合成反应是在反应瓶A中，加入有机胺(2)(X mmol)，R1SSOMe(1)(Y mmol)，B(C6F5)3,(Z mmol)，有机溶剂(P mL)，反应体系在25℃，N2氛围下搅拌24小时；反应完毕后，直接加硅胶旋干，经柱层析分离得到目标产物。
本发明还提出了按照本发明上述合成方法制备得到的如式(3)所示二硫胺类化合物。
本发明合成方法制备得到的如式(3)所示的二硫胺化合物的最优条件如下所示，其中反应式(a)的收率为86％。
其中，R1选自直链烷基、苯乙基、丁酸酯基、苄基及其衍生物、取代苄基、1,4-二甲基苯基、1,1’-联苯-4,4’-二甲基、糖、含糖衍生物、氨基酸、氨基酸衍生物等；
R2选自C1-C5烷基、芳基、C1-C5烯基、C1-C5炔基、取代芳基、磺胺类药物、8-喹啉基、来那度胺、氨基酸衍生物等；
R3选自C1-C5烷基、H等；
优选地，R1选自癸基、对氰基苄基、吡喃糖衍生物、呋喃糖衍生物、氨基酸衍生物等；
R2选自乙基、丙烯、乙炔、苯基、甲氧基取代苯基、叔丁基取代苯基、溴取代苯基、氯取代苯基、磺胺类药物、8-喹啉基、来那度胺、氨基酸衍生物；
R3选自甲基、乙基、H。
本发明具有以下优点：反应高效，收率高，其中，实施例3、5、16、22、24产率都在90％以上；过硫化试剂制备简单、稳定、并且无刺激性气味；反应中条件较为温和；d)反应中不使用金属催化剂，经济实用，对环境友好；反应溶剂为无毒有机溶剂，绿色无毒；如实施例1所示，反应放大后反应效率高，具有实用价值；本发明以商业可得的有机胺化合物及制备简便的R1SSOMe为反应原料，在路易斯酸催化剂的作用下，反应得到取代的二硫胺类化合物；反应操作简单，反应条件较为温和，适合大规模工业化生产。
具体实施方式
结合以下具体实施例，对本发明作进一步的详细说明，本发明的保护内容不局限于以下实施例。在不背离发明构思的精神和范围下，本领域技术人员能够想到的变化和优点都被包括在本发明中，并且以所附的权利要求书为保护范围。实施本发明的过程、条件、试剂、实验方法等，除以下专门提及的内容之外，均为本领域的普遍知识和公知常识，本发明没有特别限制内容。以下实施例所给出的数据包括具体操作和反应条件及产物。产物纯度通过核磁鉴定。
本发明二硫胺类化合物的合成反应，包括以下步骤：
如反应式(a)，本发明合成反应是在反应瓶中加入有机胺(2)，过硫化试剂R1SSOMe(1)，催化剂B(C6F5)3，有机溶剂，反应体系在25℃，N2氛围下搅拌24小时；反应完毕后，直接加硅胶旋干，经柱层析分离得到目标产物。
如表1所示的不对称二硫胺类化合物，均为通过本发明方法合成得到的产物，尚未见有公开文献揭示这些化合物。
表1本发明的新的不对称二硫胺类化合物
实施例1
化合物3a的合成：
空气氛围下，向反应管中依次加入1a(42.3mg,0.2mmol),苯胺(22.3mg,0.24mmol),B(C6F5)3(2.6mg,0.005mmol),甲苯(0.5mL)，反应体系在常温下搅拌24小时，反应完毕后，二氯甲烷稀释，去除溶剂，柱层析得白色固体化合物3a(46.9mg,86％).1H NMR(400MHz,CDCl3)δ7.60(d,J＝8.1Hz,2H),7.39(d,J＝8.1Hz,2H),7.25(t,J＝7.8Hz,2H),7.05–6.81(m,3H),4.72(s,1H),4.08(s,2H)；13C NMR(100MHz,CDCl3)δ144.96,143.66,132.34,129.80,129.21,121.93,118.58,116.88,111.11,42.89.IR(film)3314,2975,2227,1595,1491,1397,1285,1225,1073,890,841,744,686.HRMS(EI)Calcd forC14H12N2S2272.0442,Found 272.0447.
实施例2
化合物3a的合成：
空气氛围下，向反应管中依次加入1a(42.3mg,0.2mmol),苯胺(22.3mg,0.24mmol),B(C6F5)3(1.0mg,0.002mmol),甲苯(0.5mL)，反应体系在常温下搅拌24小时，反应完毕后，二氯甲烷稀释，去除溶剂，柱层析得白色固体化合物3a(36.5mg,67％).
实施例3
化合物3a的合成：
空气氛围下，向反应管中依次加入1a(42.3mg,0.2mmol),苯胺(22.3mg,0.24mmol),B(C6F5)3(1.0mg,0.002mmol),甲苯(0.5mL)，反应体系在10℃下搅拌24小时，反应完毕后，二氯甲烷稀释，去除溶剂，柱层析得白色固体化合物3a(28.3mg,52％).
实施例4
化合物3b的合成：
空气氛围下，向反应管中依次加入1a(42.3mg,0.2mmol),N-甲基苯胺(23.6mg,0.22mmol),B(C6F5)3(2.6mg,0.005mmol),甲苯(0.5mL)，反应体系在常温下搅拌24小时，反应完毕后，二氯甲烷稀释，去除溶剂，柱层析得白色固体化合物3b(35.3mg,60％).1H NMR(400MHz,DMSO)δ7.76(d,J＝8.3Hz,1H),7.42(d,J＝8.3Hz,1H),7.36–7.25(m,1H),7.26–7.17(m,1H),7.09–6.83(m,0H),4.11(s,1H),3.15(s,2H)；13C NMR(100MHz,DMSO)δ149.15,143.99,132.37,129.93,128.89,121.71,118.72,118.41,109.89,43.88,42.25.IR(film)2990,2956,2227,1933,1595,1489,1413,1253,1082,1062,849,747,683.HRMS(EI)Calcdfor C15H14N2S2286.0596,Found 286.0598.
实施例5
化合物3c的合成：
空气氛围下，向反应管中依次加入1a(42.3mg,0.2mmol),对甲基苯胺(23.6mg,0.22mmol),B(C6F5)3(2.6mg,0.005mmol),甲苯(0.5mL)，反应体系在常温下搅拌24小时，反应完毕后，二氯甲烷稀释，去除溶剂，柱层析得白色固体化合物3c(53.3mg,93％).1H NMR(400MHz,DMSO)δ7.90(s,1H),7.79(d,J＝8.1Hz,2H),7.53(d,J＝8.1Hz,3H),7.05(d,J＝8.2Hz,2H),6.96(d,J＝8.3Hz,2H),4.17(s,2H),2.36(s,3H)；13C NMR(100MHz,DMSO)δ144.13,143.34,132.28,130.01,129.50,118.79,116.49,109.75,40.63,20.16.IR(film)3311,2922,2228,1603,1504,1458,1283,1224,896,841,809,740,646.HRMS(EI)Calcd forC15H14N2S2286.0596,Found 286.0593.
实施例6
化合物3d的合成：
空气氛围下，向反应管中依次加入1a(42.3mg,0.2mmol),对甲氧基苯胺(27.1mg,0.22mmol),B(C6F5)3(2.6mg,0.005mmol),甲苯(0.5mL)，反应体系在常温下搅拌24小时，反应完毕后，二氯甲烷稀释，去除溶剂，柱层析得白色固体化合物3d(49.9mg,82％).1H NMR(400MHz,DMSO)δ7.79(d,J＝8.2Hz,2H),7.75(s,1H),7.53(d,J＝8.2Hz,2H),7.00(d,J＝8.9Hz,2H),6.85(d,J＝8.9Hz,2H),4.15(s,2H),3.70(s,3H).；13C NMR(100MHz,DMSO)δ154.02,144.17,139.11,132.27,130.00,118.80,117.93,114.47,109.74,55.20,40.56.IR(film)3314,2949,2834,2228,1605,1504,1463,1280,1222,1029,900,824,753,655.HRMS(EI)Calcd for C15H14ON2S2302.0548,Found 302.0554.
实施例7
化合物3e的合成：
空气氛围下，向反应管中依次加入1a(42.3mg,0.2mmol),对叔丁基苯胺(32.9mg,0.22mmol),B(C6F5)3(2.6mg,0.005mmol),甲苯(0.5mL)，反应体系在常温下搅拌24小时，反应完毕后，二氯甲烷稀释，去除溶剂，柱层析得白色固体化合物3e(60.9mg,92％).1H NMR(400MHz,DMSO)δ7.94(s,1H),7.78(d,J＝8.2Hz,2H),7.54(d,J＝8.3Hz,2H),7.26(d,J＝8.7Hz,2H),7.00(d,J＝8.6Hz,2H),4.17(s,2H),1.23(s,9H)；13C NMR(100MHz,DMSO)δ144.11,143.20,143.01,132.25,130.03,125.71,118.78,116.07,109.76,40.57,33.73,31.27.IR(film)3332,2956,2852,2227,1607,1510,1464,1362,1282,1233,1285,998,826,733,653.HRMS(EI)Calcd for C18H20N2S2328.1070,Found 328.1068.
实施例8
化合物3f的合成：
空气氛围下，向反应管中依次加入1a(42.3mg,0.2mmol),对氯苯胺(28.1mg,0.22mmol),B(C6F5)3(2.6mg,0.005mmol),甲苯(0.5mL)，反应体系在常温下搅拌24小时，反应完毕后，二氯甲烷稀释，去除溶剂，柱层析得白色固体化合物3f(54mg,87％).1H NMR(400MHz,DMSO)δ8.20(s,1H),7.76(s,2H),7.53(s,2H),7.25(s,2H),7.05(s,2H),4.18(s,2H)；13CNMR(100MHz,DMSO)δ144.92,143.91,132.31,130.07,128.90,124.30,118.80,117.83,109.87,40.68.IR(film)3305,2962,2852,2230,1597,1486,1262,1225,1093,894,814,737.HRMS(EI)Calcd for C14H11ClN2S2306.0051,Found 306.0052.
实施例9
化合物3g的合成：
空气氛围下，向反应管中依次加入1a(42.3mg,0.2mmol),对溴苯胺(37.9mg,0.22mmol),B(C6F5)3(2.6mg,0.005mmol),甲苯(0.5mL)，反应体系在常温下搅拌24小时，反应完毕后，二氯甲烷稀释，去除溶剂，柱层析得白色固体化合物3g(50mg,71％).1H NMR(400MHz,DMSO)δ8.20(s,1H),7.79(d,J＝8.1Hz,2H),7.54(d,J＝8.1Hz,2H),7.40(d,J＝8.7Hz,2H),7.01(d,J＝8.8Hz,2H),4.20(s,2H)；13C NMR(100MHz,DMSO)δ145.34,143.88,132.31,131.75,130.05,118.77,118.29,111.99,109.85,40.70.IR(film)3300,2960,2850,2231,1587,1482,1226,1072,894,814.HRMS(EI)Calcd for C14H11BrN2S2349.9547,Found 349.9556.
实施例10
化合物3h的合成：
空气氛围下，向反应管中依次加入1a(42.3mg,0.2mmol),8-氨基喹啉(32.9mg,0.22mmol),B(C6F5)3(2.6mg,0.005mmol),甲苯(0.5mL)，反应体系在常温下搅拌24小时，反应完毕后，二氯甲烷稀释，去除溶剂，柱层析得白色固体化合物3h(38.9mg,70％).1H NMR(400MHz,DMSO)δ1H NMR(400MHz,DMSO)δ9.35(dd,J＝4.2,1.7Hz,1H),8.90(s,1H),8.85(dd,J＝8.3,1.6Hz,1H),8.29(d,J＝8.3Hz,2H),8.16(d,J＝8.3Hz,2H),8.10(dd,J＝8.3,4.2Hz,1H),8.08-8.04(m,1H),7.99(dd,J＝7.6,1.3Hz,1H),7.95(dd,J＝8.0,1.3Hz,1H),4.79(s,2H)；13C NMR(100MHz,DMSO)δ113C NMR(101MHz,DMSO)δ148.22,144.77,141.71,139.14,136.28,132.32,130.17,128.26,127.14,122.07,118.95,118.83,111.30,109.77,40.48.IR(film)3318,3045,2221,1610,1464,1407,1372,1308,1083,908,840,820,745,628.HRMS(EI)Calcd for C17H13N3S2323.0551,Found 323.0560.
实施例11
化合物3i的合成：
空气氛围下，向反应管中依次加入1a(42.3mg,0.2mmol),烯丙胺(12.6mg,0.22mmol),B(C6F5)3(2.6mg,0.005mmol),甲苯(0.5mL)，反应体系在常温下搅拌24小时，反应完毕后，二氯甲烷稀释，去除溶剂，柱层析得白色固体化合物3i(32.1mg,67％).1H NMR(400MHz,DMSO)δ7.82(d,J＝7.8Hz,2H),7.54(d,J＝7.7Hz,2H),5.87-5.75(m,1H),5.20(d,J＝17.2Hz,1H),5.13-5.11(m,2H),4.15(s,2H),3.43(s,2H)；13C NMR(100MHz,DMSO)δ144.51,135.55,132.28,130.13,118.84,116.74,109.65,52.36,40.60.IR(film)3292,2928,2228,1919,1604,1501,1417,1200,1053,991,929,839,680.HRMS(EI)Calcd forC11H12N2S2236.0442,Found236.0446.
实施例12
化合物3j的合成：
空气氛围下，向反应管中依次加入1a(42.3mg,0.2mmol),炔丙胺(12.2mg,0.22mmol),B(C6F5)3(2.6mg,0.005mmol),甲苯(0.5mL)，反应体系在常温下搅拌24小时，反应完毕后，二氯甲烷稀释，去除溶剂，柱层析得白色固体化合物3j(26.4mg,56％).1H NMR(400MHz,DMSO)δ1H NMR(400MHz,CDCl3)δ7.80(s,2H),7.55(s,2H),5.36(s,1H),4.16(s,2H),3.60(s,2H),3.25(s,1H)；13C NMR(100MHz,DMSO)δ144.30,132.31,130.16,118.85,109.72,81.16,74.94,40.65,38.56.IR(film)3293,2925,2361,2225,1603,1503,1418,1320,1048,838,658.HRMS(EI)Calcd for C11H10N2S2234.0285,Found 234.0282.
实施例13
化合物3k的合成：
空气氛围下，向反应管中依次加入1a(42.3mg,0.2mmol),二乙胺(17.6mg,0.22mmol),B(C6F5)3(2.6mg,0.005mmol),甲苯(0.5mL)，反应体系在常温下搅拌24小时，反应完毕后，二氯甲烷稀释，去除溶剂，柱层析得白色固体化合物3k(34.7mg,69％).1H NMR(400MHz,CDCl3)δ7.61(d,J＝8.3Hz,2H),7.42(d,J＝8.4Hz,2H),4.09(s,2H),2.82(q,J＝7.1Hz,4H),1.15(t,J＝7.1Hz,6H)；13C NMR(100MHz,CDCl3)δ144.26,132.35,129.54,118.72,110.97,51.30,44.39,13.33.IR(film)2977,2935,2847,2229,1606,1504,1465,1379,1178,1060,1024,904,844,841,614.HRMS(EI)Calcd for C12H16N2S2252.0755,Found252.0760.
实施例14
化合物3l的合成：
空气氛围下，向反应管中依次加入1a(42.3mg,0.2mmol),磺胺(41.4mg,0.22mmol),B(C6F5)3(2.6mg,0.005mmol),甲苯(0.5mL)，反应体系在常温下搅拌24小时，反应完毕后，二氯甲烷稀释，去除溶剂，柱层析得白色固体化合物3k(61mg,86％).1H NMR(400MHz,CDCl3)δ8.55(s,1H),7.82(d,J＝8.1Hz,2H),7.71(d,J＝8.7Hz,2H),7.57(d,J＝8.2Hz,2H),7.32–7.03(m,4H),4.23(s,2H)；13C NMR(100MHz,DMSO)δ149.05,143.77,135.80,132.38,130.12,127.28,118.78,115.70,109.91,40.75.IR(film)3292,2918,2232,1593,1496,1334,1246,1152,1093,890,824,771,649.HRMS(EI)Calcd forC14H13N3O2S3351.0170,Found 351.0168.
实施例15
化合物3m的合成：
空气氛围下，向反应管中依次加入1b(42.3mg,0.3mmol),乙酰磺胺(42.9mg,0.2mmol),B(C6F5)3(2.6mg,0.005mmol),N,N-二甲基甲酰胺(0.5mL)，反应体系在常温下搅拌24小时，反应完毕后，二氯甲烷稀释，去除溶剂，柱层析得白色固体化合物3m(67mg,80％).1H NMR(400MHz,DMSO-d6)δ11.84(brs,1H),8.64(s,1H),7.76(d,J＝8.7Hz,2H),7.17(d,J＝8.7Hz,2H),2.91(t,J＝7.3Hz,2H),1.89(s,3H),1.72–1.58(m,2H),1.33–1.19(m,14H),0.85(t,J＝6.5Hz,3H).13C NMR(100MHz,DMSO-d6)δ168.4,151.2,129.8,129.3,115.2,38.1,31.2,29.1,28.9,28.6,28.5,27.8,23.1,22.0,13.9.IR(film)3329,3240,2966,2921,1698,1590,1490,1449,1254,1152,1080,1048,831,681,627.HRMS(ESI)Calcdfor C18H30N2O3S3(M+Na+)441.1311,Found441.1303.
实施例16
化合物3n的合成：
空气氛围下，向反应管中依次加入1b(42.3mg,0.3mmol),磺胺吡啶(49.8mg,0.2mmol),B(C6F5)3(2.6mg,0.005mmol),N,N-二甲基甲酰胺(0.5mL)，反应体系在常温下搅拌24小时，反应完毕后，二氯甲烷稀释，去除溶剂，柱层析得白色固体化合物3n(78mg,86％).1H NMR(400MHz,DMSO-d6)δ11.48(brs,1H),8.48(s,1H),8.3(m,1H),7.75(d,J＝8.8Hz,2H),7.67(m,1H),7.14–7.05(m,3H),6.87(m,1H),2.87(t,J＝7.3Hz,2H),1.67–1.56(m,2H),1.31–1.19(m,14H),0.85(t,J＝6.8Hz,3H).13C NMR(100MHz,DMSO-d6)δ152.1,149.6,144.3,138.9,131.7,127.9,115.8,114.8,112.4,37.5,30.7,28.5,28.3,28.1,28.0,27.3,21.5,13.4.IR(film)3315,2978,2905,1591,1453,1386,1251,1073,890,767,683.HRMS(ESI)Calcd for C21H31N3O2S3(M+H+)454.1651,Found 454.1642.
实施例17
化合物3o的合成：
空气氛围下，向反应管中依次加入1b(42.3mg,0.3mmol),磺胺嘧啶(50.1mg,0.2mmol),B(C6F5)3(2.6mg,0.005mmol),N,N-二甲基甲酰胺(0.5mL)，反应体系在常温下搅拌24小时，反应完毕后，二氯甲烷稀释，去除溶剂，柱层析得白色固体化合物3o(54.5mg,60％).1H NMR(400MHz,DMSO-d6)δ11.52(brs,1H),8.65–8.38(m,3H),7.84(d,J＝8.7Hz,2H),7.13(d,J＝8.8Hz,2H),7.03(t,J＝4.8Hz,1H),2.88(t,J＝7.2Hz,2H),1.72–1.56(m,2H),1.3–1.15(m,14H),0.85(t,J＝6.7Hz,3H).13C NMR(100MHz,DMSO-d6)δ158.3,157.0,150.6,130.9,129.4,115.7,115.1,38.0,31.3,29.1,28.9,28.6,28.5,27.8,22.1,13.9.IR(film)3303,2979,2904,1583,1406,1356,1249,1153,1052,892,801,673.HRMS(ESI)Calcdfor C20H30N4O2S3(M+Na+)477.1423,Found477.1420.
实施例18
化合物3p的合成：
空气氛围下，向反应管中依次加入1b(42.3mg,0.3mmol),磺胺甲基嘧啶(52.9mg,0.2mmol),B(C6F5)3(2.6mg,0.005mmol),N,N-二甲基甲酰胺(0.5mL)，反应体系在常温下搅拌24小时，反应完毕后，二氯甲烷稀释，去除溶剂，柱层析得白色固体化合物3p(84.4mg,90％).1HNMR(400MHz,CDCl3)δ8.54(d,J＝5.2Hz,1H),8.00(d,J＝8.7Hz,2H),7.09(d,J＝8.8Hz,2H),6.78(d,J＝5.2Hz,1H),5.64(s,1H),2.87(t,J＝7.3Hz,2H),2.42(s,3H),1.75–1.59(m,2H),1.38–1.21(m,14H),0.87(t,J＝6.8Hz,3H).13C NMR(100MHz,CDCl3)δ169.5,157.3,156.5,150.2,131.2,130.6,115.1,115.1,39.4,31.8,29.7,29.5,29.4,29.2,29.1,28.4,24.0,22.6,14.1.IR(film)3314,2981,2903,1593,1404,1250,1070,892,745.HRMS(ESI)Calcd for C21H32N4O2S3(M+Na+)491.1580,Found 491.1577.
实施例19
化合物3q的合成：
空气氛围下，向反应管中依次加入1b(42.3mg,0.3mmol),磺胺二甲基嘧啶(56.7mg,0.2mmol),B(C6F5)3(2.6mg,0.005mmol),N,N-二甲基甲酰胺(0.5mL)，反应体系在常温下搅拌24小时，反应完毕后，二氯甲烷稀释，去除溶剂，柱层析得白色固体化合物3q(78.1mg,81％).1HNMR(400MHz,DMSO-d6)δ11.38(brs,1H),8.49(s,1H),7.86(d,J＝8.8Hz,2H),7.12(d,J＝8.8Hz,2H),6.74(s,1H),2.88(t,J＝7.3Hz,2H),2.24(s,6H),1.66-1.59(m,2H),1.30–1.16(m,14H),0.85(t,J＝6.8Hz,3H).13C NMR(100MHz,DMSO-d6)δ167.3,156.3,150.3,131.2,129.8,114.7,113.7,38.1,31.2,29.0,28.8,28.6,28.4,27.7,22.9,22.0,13.9.IR(film)3316,2977,2903,1593,1489,1384,1249,1151,1075,872,832,676.HRMS(ESI)Calcd for C22H34N4O2S3(M+H+)483.1917,Found483.1913.
实施例20
化合物3r的合成：
空气氛围下，向反应管中依次加入1b(42.3mg,0.3mmol),磺胺噻唑(51.1mg,0.2mmol),B(C6F5)3(2.6mg,0.005mmol),N,N-二甲基甲酰胺(0.5mL)，反应体系在常温下搅拌24小时，反应完毕后，二氯甲烷稀释，去除溶剂，柱层析得白色固体化合物3r(59.8mg,65％).1H NMR(400MHz,DMSO-d6)δ12.57(brs,1H),8.43(s,1H),7.66(d,J＝8.7Hz,2H),7.21(d,J＝4.6Hz,1H),7.14(d,J＝8.7Hz,2H),6.78(d,J＝4.6Hz,1H),2.88(t,J＝7.3Hz,2H),1.68-1.61(m,2H),1.31-1.17(m,14H),0.85(t,J＝6.7Hz,3H).13C NMR(100MHz,DMSO-d6)δ168.4,149.7,133.5,127.4,124.2,115.3,38.0,31.2,29.1,28.9,28.6,28.5,27.8,22.0,13.9.IR(film)3319,2953,2923,2853,1573,1536,1490,1289,1138,1186,930,856,750,683,637.HRMS(ESI)Calcd forC19H29N3O2S4(M+Na+)482.1035,Found 482.1034.
实施例21
化合物3s的合成：
空气氛围下，向反应管中依次加入1b(42.3mg,0.3mmol),磺胺甲恶唑(50.7mg,0.2mmol),B(C6F5)3(2.6mg,0.005mmol),N,N-二甲基甲酰胺(0.5mL)，反应体系在常温下搅拌24小时，反应完毕后，二氯甲烷稀释，去除溶剂，柱层析得白色固体化合物3s(78.7mg,86％).1HNMR(400MHz,DMSO-d6)δ11.17(s,1H),8.60(s,1H),7.70(d,J＝8.8Hz,2H),7.15(d,J＝8.8Hz,2H),6.11(s,1H),2.89(t,J＝7.3Hz,2H),2.29(s,3H),1.73–1.58(m,2H),1.32-1.15(m,14H),0.85(t,J＝6.7Hz,3H).13C NMR(100MHz,DMSO-d6)δ167.0,157.6,150.9,130.1,128.4,115.5,95.3,38.0,31.2,29.0,28.8,28.6,28.5,27.8,22.0,13.9,11.9(8),11.9(5).IR(film)3339,3284,2978,2918,1590,1463,1376,1256,1155,1054,887,823,682.HRMS(ESI)Calcd forC19H29N3O2S4(M+Na+)480.1420,Found 480.1416.
实施例22
化合物3t的合成：
空气氛围下，向反应管中依次加入1b(42.3mg,0.3mmol),来那度胺(51.9mg,0.2mmol),B(C6F5)3(2.6mg,0.005mmol),N,N-二甲基甲酰胺(0.5mL)，反应体系在常温下搅拌24小时，反应完毕后，二氯甲烷稀释，去除溶剂，柱层析得白色固体化合物3t(57.5mg,62％).1H NMR(400MHz,CDCl3)δ11.02(s,1H),8.01(s,1H),7.44-7.42(m,2H),7.27(d,J＝6.0Hz,1H),5.13(dd,J＝12.7,4.1Hz,1H),4.33(q,J＝17.3Hz,2H),2.96-2.88(m,3H),2.64-2.59(m,1H),2.38-2.29(m,1H),2.05-2.04(m,1H),1.62-1.60(m,2H),1.35-1.20(m,14H),0.84(t,J＝6.4Hz,3H).13C NMR(100MHz,CDCl3)δ172.8,171.0,167.9,141.5,132.9,129.8,129.0,118.6,115.3,51.6,46.2,37.8,31.3,31.2,29.2,28.9,28.6,28.5,27.8,22.7,22.1,13.9.IR(film)3287,2982,2920,1703,1669,1600,1406,1237,1050,865,748,658.HRMS(EI)Calcd for C23H33N3O3S2463.1963,Found 463.1959.
实施例23
化合物3u的合成：
空气氛围下，向反应管中依次加入1a(42.3mg,0.2mmol),L-缬氨酸甲酯(25.8mg,0.22mmol),B(C6F5)3(2.6mg,0.005mmol),甲苯(0.5mL)，反应体系在常温下搅拌24小时，反应完毕后，二氯甲烷稀释，去除溶剂，柱层析得无色液体化合物3u(27.9mg,45％).1H NMR(400MHz,CDCl3)δ7.61(d,J＝8.1Hz,2H),7.43(d,J＝8.1Hz,2H),4.01(s,2H),3.73(s,3H),3.42(d,J＝8.2Hz,1H),3.27(dd,J＝8.2,5.9Hz,1H),1.89(dq,J＝13.3,6.7Hz,1H),0.89(d,J＝6.8Hz,3H),0.86(d,J＝6.8Hz,3H).13C NMR(100MHz,CDCl3)δ174.4,143.2,132.3,129.9,118.6,111.1,70.6,52.1,42.2,31.9,18.8,18.1.IR(film)3317,2940,2229,1732,1606,1505,1437,1301,1201,1140,994,845,743,648.HRMS(EI)Calcd forC14H18N2O2S2310.0810,Found 310.0815.
实施例24
化合物3v的合成：
在空气氛围下，向反应管中依次加入1c(85.3mg,0.2mmol),苯胺(20.5mg,0.22mmol),B(C6F5)3(2.6mg,0.005mmol),甲苯(0.5mL)，反应体系在常温下搅拌24小时，反应完毕后，二氯甲烷稀释，去除溶剂，柱层析得白色固体化合物3v(92.5mg,95％).1H NMR(400MHz,CDCl3)δ7.23(t,J＝7.9Hz,2H),7.03(d,J＝7.7Hz,2H),6.92(t,J＝7.3Hz,1H),5.67(s,1H),5.42(t,J＝9.5Hz,1H),5.24(t,J＝9.4Hz,1H),5.13(t,J＝9.7Hz,1H),4.68(d,J＝9.7Hz,1H),4.26–4.14(m,2H),3.79–3.66(m,1H),2.09(s,3H),2.03(s,3H),2.00(s,3H),1.95(s,3H).13CNMR(100MHz,CDCl3)δ170.6,170.0,169.3,169.2,145.2,129.0,121.7,116.8,85.5,76.2,73.7,69.5,68.0,61.7,20.7,20.6,20.5,20.4.IR(film)3338,2995,1744,1597,1375,1222,1045,912,760,690,630.HRMS(EI)Calcd for C20H25NO9S2487.0971,Found 487.0978.
实施例25
化合物3w的合成：
在空气氛围下，向反应管中依次加入1d(84.9mg,0.2mmol),苯胺(20.5mg,0.22mmol),B(C6F5)3(2.6mg,0.005mmol),甲苯(0.5mL)，反应体系在常温下搅拌24小时，反应完毕后，二氯甲烷稀释，去除溶剂，柱层析得无色液体化合物3w(74.7mg,77％).1H NMR(400MHz,CDCl3)δ7.25(t,J＝7.9Hz,2H),7.06(d,J＝7.7Hz,2H),6.93(t,J＝7.3Hz,1H),5.87(d,J＝3.7Hz,1H),5.47(s,1H),5.29(s,1H),4.47(d,J＝3.7Hz,1H),4.20(t,J＝2.8Hz,2H),4.13–4.05(m,1H),4.05–3.97(m,1H),2.88(t,J＝7.0Hz,2H),2.44(t,J＝7.1Hz,2H),2.03(p,J＝7.2Hz,2H),1.52(s,3H),1.40(s,3H),1.31(s,6H).13C NMR(100MHz,CDCl3)δ171.6,145.4,129.1,121.5,116.6,112.2,109.3,105.0,83.3,79.8,76.1,72.4,67.3,37.9,32.3,26.8,26.6,26.1,25.2,24.7.IR(film)3334,2981,2903,1742,1598,1490,1378,1222,1070,889,752,693.HRMS(EI)Calcd forC22H31NO7S2485.1542,Found485.1540.
实施例26
化合物3x的合成：
在空气氛围下，向反应管中依次加入1e(134.2mg,0.2mmol),苯胺(20.5mg,0.22mmol),B(C6F5)3(2.6mg,0.005mmol),甲苯(0.5mL)，反应体系在常温下搅拌24小时，反应完毕后，二氯甲烷稀释，去除溶剂，柱层析得无色液体化合物3x(134.4mg,92％).1H NMR(400MHz,CDCl3)δ8.07(d,J＝7.8Hz,2H),8.03(d,J＝7.8Hz,2H),7.91(d,J＝7.9Hz,2H),7.62–7.43(m,5H),7.39(t,J＝7.7Hz,2H),7.34(t,J＝7.7Hz,2H),7.23(t,J＝7.8Hz,2H),7.05(d,J＝8.3Hz,2H),6.92(t,J＝7.3Hz,1H),5.98–5.82(m,2H),5.71-5.67(m,2H),5.26(d,J＝3.5Hz,1H),4.63–4.49(m,2H),4.44-5.38(m,1H),3.50(s,3H),2.84(t,J＝7.6Hz,2H),2.55(t,J＝7.0Hz,2H),2.01(p,J＝7.1Hz,2H).13C NMR(100MHz,CDCl3)δ172.0,166.0,165.9(7),165.4,145.4,133.3,133.2,129.8,129.6,129.4,129.3,129.1,128.4,128.3(5),121.3,116.7,97.6,68.8,68.5,68.4,66.4,62.1,55.6,37.8,32.3,25.0.IR(film)3340,2970,2904,1721,1597,1403,1261,1072,891,753,709.HRMS(ESI)Calcd forC38H37NO10S2(M+Na+)754.1751,Found 754.1732.
实施例27
化合物3y的合成：
在空气氛围下，向反应管中依次加入1f(59.5mg,0.2mmol),辅氨酸甲酯(20.5mg,0.22mmol),B(C6F5)3(2.6mg,0.005mmol),甲苯(0.5mL)，反应体系在常温下搅拌24小时，反应完毕后，二氯甲烷稀释，去除溶剂，柱层析得无色液体化合物3y(64.6mg,82％).1HNMR(400MHz,CDCl3)δ5.35(d,J＝7.5Hz,1H),4.57(s,1H),3.87–3.59(m,7H),3.34(s,2H),3.27(d,J＝4.6Hz,1H),3.06(q,J＝7.9Hz,1H),2.25–2.04(m,1H),1.90-1.85(m,3H),1.41(s,9H).13CNMR(100MHz,CDCl3)δ172.8,170.9,154.9,80.1,65.8,55.7,53.6,52.5,52.1,43.1,30.5,28.2,24.5.IR(film)3380,2980,2905,1743,1714,1403,1252,1164,1074,1048,869,754.HRMS(EI)Calcd for C15H26N2O6S2394.1232,Found 394.1234.
本发明的保护内容不局限于以上实施例。在不背离发明构思的精神和范围下，本领域技术人员能够想到的变化和优点都被包括在本发明中，并且以所附的权利要求书为保护范围。

Claims (10)

1.一种二硫胺类化合物，其特征在于，其结构如式(3)所示：
其中，R1选自直链烷基、苯乙基、丁酸酯基、苄基及其衍生物、取代苄基、1,4-二甲基苯基、1,1’-联苯-4,4’-二甲基、糖、含糖衍生物、氨基酸、氨基酸衍生物；
R2选自C1-C5烷基、芳基、C1-C5烯基、C1-C5炔基、取代芳基、磺胺类药物、8-喹啉基、来那度胺、氨基酸衍生物；
R3选自C1-C5烷基、H。
2.如权利要求1所述的二硫胺类化合物，其特征在于，所述R1选自癸基、对氰基苄基、吡喃糖衍生物、呋喃糖衍生物、氨基酸衍生物；R2选自乙基、丙烯、乙炔、苯基、甲基取代苯基、甲氧基取代苯基、叔丁基取代苯基、溴取代苯基、氯取代苯基、磺胺类药物、8-喹啉基、来那度胺、氨基酸衍生物；R3选自甲基、乙基、H。
3.如权利要求1-2之任一项所述的二硫胺类化合物，其特征在于，所述二硫胺类化合物为：
4.一种二硫胺类化合物的合成方法，其特征在于，以式(1)所示的过硫化试剂R1SSOMe和式(2)所示的有机胺类化合物为反应原料，在催化剂作用下，在有机溶剂中，反应得到如式(3)所示的二硫胺类化合物，所述反应过程如反应式(a)所示：
其中，R1选自直链烷基、苯乙基、丁酸酯基、苄基及其衍生物、取代苄基、1,4-二甲基苯基、1,1’-联苯-4,4’-二甲基、糖、含糖衍生物、氨基酸、氨基酸衍生物；
R2选自C1-C5烷基、芳基、C1-C5烯基、C1-C5炔基、取代芳基、磺胺类药物、8-喹啉基、来那度胺、氨基酸衍生物；
R3选自C1-C5烷基、H。
5.如权利要求4所述的合成方法，其特征在于，所述催化剂为B(C6F5)3；所述催化剂的用量为式(1)所示过硫化试剂R1SSOMe的1-10mol％。
6.如权利要求4所述的合成方法，其特征在于，所述有机溶剂选自甲苯，N,N-二甲基甲酰胺中的一种或2种。
7.如权利要求4所述的合成方法，其特征在于，所述反应在10-25℃下进行；所述反应的时间为24-48小时。
8.如权利要求4所述的合成方法，其特征在于，所述反应原料式(2)所示的有机胺类化合物与式(1)所示的过硫化试剂R1SSOMe的摩尔比例为1.0：1.5-1.5：1.0。
9.如权利要求4所述的合成方法，其特征在于，所述反应原料式(2)所示的有机胺类化合物与式(1)所示的过硫化试剂R1SSOMe的摩尔比例为1.1：1.0或者1.0：1.5。
10.一种过硫化试剂，其特征在于，其结构如式(1)所示，
其中，R1选自直链烷基、苯乙基、丁酸酯基、苄基及其衍生物、取代苄基、1,4-二甲基苯基、1,1’-联苯-4,4’-二甲基、糖、含糖衍生物、氨基酸、氨基酸衍生物。
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