CN109456180B - 一种无金属催化的β,β-二氯内脂化合物的合成方法 - Google Patents

一种无金属催化的β,β-二氯内脂化合物的合成方法 Download PDF

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CN109456180B
CN109456180B CN201811406201.6A CN201811406201A CN109456180B CN 109456180 B CN109456180 B CN 109456180B CN 201811406201 A CN201811406201 A CN 201811406201A CN 109456180 B CN109456180 B CN 109456180B
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冯秀娟
张西涛
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Abstract

本发明涉及医药化工中间体的制备方法，具体涉及一种无金属催化的β,β‑二氯内脂化合物的合成方法。β,β‑二氯内脂是许多药物和生物活性分子的重要组成部分，在有机合成及药物化学等领域有着重要的应用，具有广阔的市场前景。本项目涉及一种无金属催化的β,β‑二氯内脂化合物的合成方法，该方法以羧酸和端炔为原料，在自由基引发剂的存在下，在温和的条件下合成β,β‑二氯内脂化合物。该发明专利的方法具有步骤简单、原料易得、反应条件温和等优点。本发明具有较大的使用价值和社会经济效益。

Description

一种无金属催化的β,β-二氯内脂化合物的合成方法
技术领域
本发明涉及医药化工中间体的制备方法，涉及一种β,β-二氯内脂化合物的合成方法。
背景技术
炔烃是有机合成中最常见和可用的官能团之一，因此烷烃的多官能团化是产生一系列不同取代基的有效途径。过渡金属催化的羧酸对炔烃的加成是一种最直接的方法来构建多取代的烯脂[Chem.Commun.2003,39,706；J.Org.Chem.2016,81,476]。但是这些反应都需要贵重金属，例如：钌、钯、银等作为催化剂来活化炔烃，才能实现羧酸对炔烃的加成。然而贵重金属是有毒的，而且很难清除产品中残留的金属，这限制此类反应的药物中的应用。所以开发一种无金属的催化的通过羧酸对炔烃的来制备β,β-二氯内脂化合物是非常令人渴望的。
最近，通过对端烃的自由基加成来制备复杂分子已引起人们的注意。一些高度复杂或多环分子结构已经通过分子间对炔烃的自由基加成实现了[Chem.Eur.J.2015,21,14328；J.Am.Chem.Soc.2018,140,5701]。但是由于羧酸自由基易于发生脱羧反应，至今还没有人报道羧酸对端炔的自由基加成反应。
发明内容
本发明的目的是通过羧酸对端炔的自由基加成合成β,β-二氯内脂化合物的新方法。该方法条件温和，没有金属参与，经济又环保。
本发明的技术方案：
一种无金属催化的β,β-二氯内脂化合物的合成方法，以廉价易得的羧酸和端炔为原料，在自由基引发剂的存在下，构建一系列含C-Cl和C-O键的β,β-二氯内脂化合物，反应式如下：
Figure BDA0001877419590000011
式中：R1和R2选烷烃、烯烃、芳基、萘环、杂环中的一种；R1与R2相同或者不同。
在上述合成方法的反应中，所述的自由基引发剂为次氯酸叔丁酯其加入量为羧酸的100～500mol％。
在上述合成方法的反应中，所述的有机溶剂为CH2Cl2、CH2Br2、CHCl3、CCl4、THF、CHCl3、CCl4、CH3CN、acetone、1,4-dioxane、toluene、benzene、DMF、DMSO、DMA、EtOH中的一种或两种以上混合，羧酸在有机溶剂中的摩尔浓度为0.1mmol/mL～2mmol/mL。
在上述合成方法的反应中，反应温度为25～60℃，反应时间为1～30h。
本发明的有益效果是：β,β-二氯内脂化合物是许多药物和生物活性分子的重要组成部分，在有机合成及药物化学等领域有着重要的应用，具有广阔的市场前景。该方法具有步骤简单、条件温和、原料易得等优点。本发明具有较大的使用价值和社会经济效益。
附图说明
图1为化合物3a的1H-NMR谱图。
图2为化合物3a的13C-NMR谱图。
图3为化合物3b的1H-NMR谱图。
图4为化合物3b的13C-NMR谱图。
图5为化合物3c的1H-NMR谱图。
图6为化合物3c的13C-NMR谱图。
图7为化合物3d的1H-NMR谱图。
图8为化合物3d的13C-NMR谱图。
图9为化合物3e的1H-NMR谱图。
图10为化合物3e的13C-NMR谱图。
图11为化合物3f的1H-NMR谱图。
图12为化合物3f的13C-NMR谱图。
图13为化合物3g的1H-NMR谱图。
图14为化合物3g的13C-NMR谱图。
图15为化合物3h的1H-NMR谱图。
图16为化合物3h的13C-NMR谱图。
具体实施方式
下面结合实施例子进一步说明本发明以及本发明方法进行的方式。这些实施例子仅是为了进一步阐述本发明而非本发明的保护范围仅限于此。
实施例1：1-(tert-butoxy)-2,2-dichloro-2-phenylethyl benzoate(3a)的合成
Figure BDA0001877419590000031
称取苯甲酸(36.6mg,0.3mmol)、苯乙炔(99μL,0.9mmol)，次氯酸叔丁酯(136μL,1.2mmol)到25mL的Schlenk反应瓶中，然后加入CCl4(0.5mL)置于30℃油浴中反应2h。反应结束后，减压除去溶剂，使用石油醚/乙酸乙酯作为洗脱剂，硅胶柱分离，产物的收率为90％。
1H NMR(400MHz,CDCl3):δ8.09–8.07(m,2H),7.85–7.83(m,2H),7.57(dd,J＝7.6,7.6Hz,1H),7.46–7.42(m,2H),7.40–7.35(m,3H),6.62(s,1H),1.10(s,9H).13C NMR(100MHz,CDCl3):δ165.4,133.6,130.1,129.5,129.4,128.5,127.8,94.8,92.2,78.0,27.8.IR(KBr):ν3062,2980,1727,1601,1492,1370,1267,1144,1086,1025,974,748,710,658cm-1.HRMS(ESI)calcd for[C19H20Cl2NaO3,M+Na]+:389.0687,found:389.0678.
实施例2：1-(tert-butoxy)-2,2-dichloro-2-phenylethyl 4-methyl-benzoate(3b)的合成
Figure BDA0001877419590000041
称取对甲基苯甲酸(40.8mg,0.3mmol)、苯乙炔(66μL,0.6mmol)，次氯酸叔丁酯(102μL,0.9mmol)到25mL的Schlenk反应瓶中，然后加入CCl4(0.5mL)置于30℃油浴中反应12h。反应结束后，减压除去溶剂，使用石油醚/乙酸乙酯作为洗脱剂，硅胶柱分离，产物的收率为62％。
1H NMR(400MHz,CDCl3):δ7.88–7.86(m,2H),7.75–7.73(m,2H),7.28–7.25(m,3H),7.15–7.13(m,2H),6.51(s,1H),2.30(s,3H),1.10(s,9H).13C NMR(100MHz,CDCl3):δ165.4,144.4,138.4,130.2,129.3,129.3，128.5,127.7,126.8,94.6,92.3,77.9,27.8,21.8.IR(KBr):ν3061,2980,1724,1612,1493,1370,1268,1118,1081,974,820,750,696cm-1.HRMS(ESI)calcd for[C20H22Cl2NaO3,M+Na]+:403.0844,found:403.0834.
实施例3：1-(tert-butoxy)-2,2-dichloro-2-phenylethyl 2-nitrobenzoate(3c)的合成
Figure BDA0001877419590000042
称取邻硝基苯甲酸(50.1mg,0.3mmol)、苯乙炔(99μL,0.9mmol)，次氯酸叔丁酯(136μL,1.2mmol)到25mL的Schlenk反应瓶中，然后加入CCl4(0.5mL)置于60℃油浴中反应8h。反应结束后，减压除去溶剂，使用石油醚/乙酸乙酯作为洗脱剂，硅胶柱分离，产物的收率为53％。
1H NMR(400MHz,CDCl3):δ7.88–7.85(m,1H),7.84–7.81(m,3H),7.68–7.64(m,2H),7.42–7.38(m,3H),6.59(s,1H),1.11(s,9H).13C NMR(100MHz,CDCl3):δ163.4,149.0,138.1,132.5,132.5,128.4,127.9,126.2,124.0,95.8,92.1,78.8,27.7.IR(KBr):ν3064,2980,1739,1607,1540,1485,1371,1354,1262,1153,1064,959,748,731,695cm-1.HRMS(ESI)calcd for[C19H19Cl2NNaO5,M+Na]+:434.0538,found:434.0533.
实施例4：1-(tert-butoxy)-2,2-dichloro-2-phenylethyl 1-naphthoate(3d)的合成
Figure BDA0001877419590000051
称取邻硝基苯甲酸(51.6mg,0.3mmol)、苯乙炔(33μL,0.3mmol)，次氯酸叔丁酯(68μL,0.6mmol)到25mL的Schlenk反应瓶中，然后加入CCl4(1mL)置于25℃油浴中反应6h。反应结束后，减压除去溶剂，使用石油醚/乙酸乙酯作为洗脱剂，硅胶柱分离，产物的收率为63％。
1H NMR(400MHz,CDCl3):δ8.97(dd,J＝8.8,0.8Hz,1H),8.36(dd,J＝7.2,1.2Hz,1H),8.06(d,J＝8.4Hz,1H),7.93–7.89(m,3H),7.67–7.63(m,1H),7.58–7.52(m,2H),7.45–7.40(m,3H),6.80(s,1H),1.19(s,9H).13C NMR(100MHz,CDCl3):δ166.0,138.5,134.1,133.9,131.6,131.1,129.4,128.5,128.0,127.9,126.4,126.1,125.7,124.7,94.7,92.4,78.0,27.9.IR(KBr):ν3059,2979,1720,1594,1490,1369,1241,1150,1077,973,781,756,696cm-1.HRMS(ESI)calcd for[C23H22Cl2NaO3,M+Na]+:423.0297,found:423.0281.
实施例5：1-(tert-butoxy)-2,2-dichloro-2-phenylethyl cinnamate(3e)的合成
Figure BDA0001877419590000052
称取肉桂酸(44.5mg,0.3mmol)、苯乙炔(102μL,0.9mmol)，次氯酸叔丁酯(68μL,0.6mmol)到25mL的Schlenk反应瓶中，然后加入CCl4(1mL)置于60℃油浴中反应1h。反应结束后，减压除去溶剂，使用石油醚/乙酸乙酯作为洗脱剂，硅胶柱分离，产物的收率为70％。
1H NMR(400MHz,CDCl3):δ7.84–7.82(m,2H),7.74(d,J＝16Hz,1H),7.53–7.52(m,2H),7.39–7.37(m,6H),6.49(s,1H),6.44(d,J＝16Hz),1.10(s,9H).13C NMR(100MHz,CDCl3):δ165.6,146.5,138.4,134.1,130.7,129.4,129.0,128.5,128.3,127.7,117.3,94.2,92.2,77.9,27.8.IR(KBr):ν3059,2980,1717,1635,1490,1448,1369,1247,1113,1057,977,766,695cm-1.HRMS(ESI)calcd for[C21H22Cl2NaO3,M+Na]+:415.0844,found:415.0845.
实施例6：1-(tert-butoxy)-2,2-dichloro-2-phenylethyl pivalate的合成
Figure BDA0001877419590000061
称取新戊酸(30.6mg,0.3mmol)、苯乙炔(102μL,0.9mmol)，次氯酸叔丁酯(102μL,0.9mmol)到25mL的Schlenk反应瓶中，然后加入CCl4(1mL)置于60℃油浴中反应1h。反应结束后，减压除去溶剂，使用石油醚/乙酸乙酯作为洗脱剂，硅胶柱分离，产物的收率为76％。
1H NMR(400MHz,CDCl3):δ7.68–7.66(m,2H),7.26–7.24(m,3H),6.28(d,J＝1.2Hz1H),1.10(s,9H).13C NMR(100MHz,CDCl3):δ177.1,138.5,129.2,128.4,127.7,93.8,92.2,77.5,38.9,27.8,26.8.IR(KBr):ν3061,2980,1739,1480,1369,1276,1167,1106,982,822,747,696cm-1.HRMS(ESI)calcd for[C17H24Cl2NaO3,M+Na]+:369.1000,found:369.0933.
实施例7：1-(tert-butoxy)-2,2-dichloro-2-phenylethyl picolinate(3g)的合成
Figure BDA0001877419590000071
称取吡啶-2-甲酸(50.4mg,0.3mmol)、苯乙炔(102μL,0.9mmol)，次氯酸叔丁酯(68μL,0.6mmol)到25mL的Schlenk反应瓶中，然后加入CCl4(1mL)置于30℃油浴中反应1h。反应结束后，减压除去溶剂，使用石油醚/乙酸乙酯作为洗脱剂，硅胶柱分离，产物的收率为76％。
1H NMR(400MHz,CDCl3):δ8.80(d,J＝8.4Hz,1H),8.13(dd,J＝8,0.8Hz,1H),7.86–7.82(m,3H),7.50–7.47(m,1H),7.40–7.36(m,3H),6.66(s,1H),1.10(s,9H).13C NMR(100MHz,CDCl3):δ163.6,150.4,147.4,138.1,137.0,129.4,128.5,127.8,127.2,125.6,95.5,92.0,78.3,27.7.IR(KBr):ν3060,2982,1744,1588,1453,1368,1241,1147,1106,963,747,693cm-1.HRMS(ESI)calcd for[C18H19Cl2NNaO3,M+Na]+:390.0640,found:390.0654.
实施例8：1-(tert-butoxy)-2,2-dichloro-2-(p-tolyl)ethyl benzoate(3h)的合成
Figure BDA0001877419590000072
称取苯甲酸(36.6mg,0.3mmol)、对甲基苯乙炔(102μL,0.9mmol)，次氯酸叔丁酯(134μL,1.2mmol)到25mL的Schlenk反应瓶中，然后加入CCl4(1mL)置于50℃油浴中反应12h。反应结束后，减压除去溶剂，使用石油醚/乙酸乙酯作为洗脱剂，硅胶柱分离，产物的收率为53％。
1H NMR(400MHz,CDCl3):δ8.09–8.07(m,2H),7.72–7.70(m,2H),7.60–7.56(m,1H),7.47–7.43(m,2H),7.19–7.17(m,2H),6.60(s,1H),2.37(s,3H),1.11(s,9H).13C NMR(100MHz,CDCl3):δ165.5,139.4,135.4,133.5,130.1,129.6,128.5,128.4,128.4,94.8,92.3,77.9,27.8,21.1.IR(KBr):ν3055,2978,1726,1598,1504,1451,1370,1266,1143,1086,1025,971,796,747,710 cm-1.HRMS(ESI)calcd for[C20H22Cl2NaO3,M+Na]+:403.0844,found:403.0839.

Claims (2)

1.一种无金属催化的β,β-二氯内脂化合物的合成方法，其特征在于，以羧酸和端炔为原料，在自由基引发剂的存在下，构建一系列含C-Cl和C-O键的β,β-二氯内脂化合物，反应式如下：
Figure FDA0002929303810000011
式中：R1和R2选自烷烃、烯烃、芳基、杂环中的一种；R1与R2相同或不同；
所述的自由基引发剂为次氯酸叔丁酯，其加入量为羧酸的100～500mol％；
反应温度为25～60℃，反应时间为1～30h。
2.根据权利要求1所述的合成方法，其特征在于，所述的有机溶剂为CH2Cl2、CH2Br2、CHCl3、THF、CHCl3、CCl4、CH3CN、丙酮、1,4-二氧六环、甲苯、苯、N,N-二甲基甲酰胺、二甲基亚砜、N,N-二甲基乙酰胺、乙醇中的一种或两种以上混合，羧酸在有机溶剂中的摩尔浓度为0.1mmol/mL～2mmol/mL。
CN201811406201.6A 2018-11-23 2018-11-23 一种无金属催化的β,β-二氯内脂化合物的合成方法 Active CN109456180B (zh)

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Metal-Free, n‑Bu4NI-Catalyzed Regioselective Difunctionalization of Unactivated Alkenes;Qicai Xue,et al.;《ACS Catal.》;20130520(第3期);1365-1368 *
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