CN115448809B - 一种三嗪卡宾钯催化合成二芳基化合物的方法 - Google Patents

一种三嗪卡宾钯催化合成二芳基化合物的方法 Download PDF

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CN115448809B
CN115448809B CN202211270100.7A CN202211270100A CN115448809B CN 115448809 B CN115448809 B CN 115448809B CN 202211270100 A CN202211270100 A CN 202211270100A CN 115448809 B CN115448809 B CN 115448809B
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高子伟
裴姗姗
姚彦秀
张伟强
孙华明
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Shaanxi Normal University
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Abstract

本发明公开了一种三嗪卡宾钯催化合成二芳基化合物的方法，以溴苯类化合物和苯硼酸类化合物作为原料，三嗪卡宾钯为催化剂，在无机碱，高效、高产率地制备二芳基化合物。本发明所用催化剂用量少和催化活性高、对空气稳定，操作简单，原子经济性高，为二芳基化合物的制备开辟了低成本的且绿色高效的途径，具有广阔的应用前景。

Description

一种三嗪卡宾钯催化合成二芳基化合物的方法
技术领域
本发明属于二芳基化合物合成技术领域，具体涉及一种三嗪卡宾钯高效催化合成二芳基化合物的方法。
背景技术
二芳基单元是重要的药物分子、材料分子和天然产物结构的组成部分。合成双芳基化合物离不开过渡金属钯的催化，钯能够在短时间内高效地构建二芳基化合物。在过去的四十年来，通过膦配体调控的钯催化的Suzuki-Miyaura交叉偶联反应已经取得了长足的发展，然而催化剂用量较多，使反应成本增加，而且膦配体对空气敏感，对环境不友好，因此限制了其广泛应用。
近年来，N杂环卡宾(NHC)作为过渡金属的有效配体在均相催化中得到了广泛关注。卡宾配体由于其较强的供电子能力，能够很好地稳定零价钯而不使钯团聚失活，使其在钯催化偶联反应中表现出良好的促进能力，因为减少贵金属钯的催化用量和使用绿色溶剂一直是科学家致力和研究的目标，这样不仅可以降低成本，同时也更有利于环境友好性，由于膦配体在催化过程中会表现出一定的毒性和容易被氧化等问题，与膦配体相比，N杂环卡宾配体由于取代基数量多，结构多样，稳定性好，越来越受到科学家的关注。之后，有很多课题组先后报道了许多氮杂卡宾配合物(Pompeo M,Farmer J.L,Froese R.D,Organ M.G,Room-temperature amination of deactivated aniline and aryl halide partnerswith carbonate base using a Pd-PEPPSI-IPentCl-o-picoline catalyst[J].Angew.Chem.Int.Ed.,2014,53(12):3223-3226；Atwater B,Chandrasoma N,Mitchell D,Rodriguez M.J,Pompeo M,Froese R.D,Organ M.G,The selective cross-coupling ofsecondary alkyl zinc reagents to five-membered-ring heterocycles using Pd-PEPPSI-IHept(Cl)[J].Angew.Chem.Int.Ed.,2015,54(33):9502-9506；Khadra A,MayerS,Mitchell D,Rodriguez M.J,Organ M.G,A general protocol for the broad-spectrum cross-coupling of nonactivated sterically hindered 1°and 2°amines[J].Organometallics,2017,36(18):3573-3577；Khadra A,Mayer S,Organ M.G,Pd-PEPPSI-IPent(Cl):A useful catalyst for the coupling of 2-aminopyridinederivatives[J].Chemistry,2017,23(13):3206-3212；Sinha N,Champagne P.A,Rodriguez M.J,Lu Y,Kopach M.E,Mitchell D,Organ M.G,One-pot sequential kumada–tamao–corriu couplings of(hetero)aryl polyhalides in the presence ofgrignard-sensitive functional groups using Pd-PEPPSI-IPentCl[J].Chem.Eur.J.,2019,25(26):6508-6512.)，这些配合物主要结构为卡宾-膦钯配合物、卡宾-烯丙基钯配合物、卡宾-氮钯双齿配合物和卡宾-氧钯环骨架配合物，研究发现，该类配合物可以有效的促进芳基卤代物的胺化反应以及C-C键偶联反应。
发明内容
本发明的目的是克服现有二芳基类化合物合成方法存在的缺点，提供一种条件温和、操作简单、反应产物单一、底物适用性好、绿色高效的合成二芳基化合物的方法。
针对上述目的，本发明所采用的技术方案是：将式I所示的溴苯类化合物和式II所示的苯硼酸类化合物、三嗪卡宾钯、无机碱加入溶剂中，在55～60℃下反应10～14小时，分离纯化产物，得到式Ш所示的二芳基化合物。
式中，R1代表C1～C4烷基、C1～C4烷氧基、硝基、乙酰基、醛基、三氟甲基、萘基、二苯胺基中任意一种，具体如甲基、甲氧基、硝基、醛基、三氟甲基、萘基、二苯胺基等；R2代表代表H、C1～C4烷氧基等。
上述三嗪卡宾钯的结构式如下所示：
上述三嗪卡宾钯的制备方法为：将式A化合物与二氯化钯、碳酸氢钾按摩尔比为1.1:1:2加入吡啶中，在45℃下反应14～15h，反应结束后，用乙腈洗涤，得到三嗪卡宾钯，反应方程式如下：
上述二芳基化合物的合成方法中，所述溴苯类化合物与苯硼酸类化合物的摩尔比为1:1～1.5；所述三嗪卡宾钯的加入量为溴苯类化合物摩尔量的0.1％～0.2％；所述无机碱为碳酸铯或碳酸钾，无机碱的加入量为溴苯类化合物摩尔量的1～1.5倍；所述溶剂为乙醇或甲醇。
本发明的有益效果如下：
本发明以苯硼酸类化合物、溴苯类化合物作为原料，碳酸铯或碳酸钾为碱、三嗪卡宾为催化剂，可高效、高产率合成二芳基化合物。本发明所用催化剂用量少、对空气稳定，操作简单，原子经济性高，实现了ppm级钯催化的溴苯类化合物活化的Suzuki-Miyaura反应合成二芳基化合物，为二芳基化合物的合成开辟了新的低成本且绿色高效的途径，具有广阔的应用前景。
具体实施方式
下面结合实施例对本发明进一步详细说明，但本发明所要保护的范围不仅限于这些实施例。
下面实施例中所用的三嗪卡宾钯的结构式如下：
其制备方法为：将2-氯-4-甲氧基-6-(4-甲氧基苯基)-1,3,5-三嗪与N-乙基咪唑按摩尔比为1:1.5加入丙酮中，在35℃下反应10h，得到1-乙基-3-(4-甲氧基-6-(4-甲氧基苯基)-1,3,5-三嗪)-1H-咪唑-3-氯化鎓(式A化合物)；将式A化合物与二氯化钯、碳酸氢钾按摩尔比为1.1:1:2加入吡啶中，在45℃下反应14.5h，反应结束后，用乙腈洗涤，得到三嗪卡宾钯。所得产物用Bruker Avance型超导傅立叶数字化核磁共振谱仪进行表征，表征数据为：1H NMR(400MHz,CDCl3)δ9.07(d,J＝5.0Hz,2H),8.76(d,J＝8.8Hz,2H),8.14(d,J＝2.0Hz,1H),7.82–7.74(m,1H),7.32(d,J＝6.9Hz,2H),7.10(d,J＝2.0Hz,1H),6.73(d,J＝8.8Hz,2H),4.92(q,J＝7.3Hz,2H),4.24(s,3H),3.80(s,3H),1.72(t,J＝7.3Hz,3H)；13CNMR(101MHz,CDCl3)δ174.65,172.02,164.08,163.50,156.20,151.73,138.05,131.99,127.30,124.47,121.71,121.13,113.89,56.09,55.52,47.80,15.72。
实施例1
合成结构式如下的4-甲氧基-1,1'-联苯
向20mL反应瓶中加入0.1870g(1mmol)对甲氧基溴苯、0.1829g(1.5mmol)苯硼酸、0.0011g(0.002mmol)三嗪卡宾钯、0.4887g(1.5mmol)碳酸铯、6mL乙醇，在55℃下搅拌反应14小时，反应完后自然降至室温，旋转蒸发除去乙醇，用硅胶柱分离(洗脱剂是二氯甲烷与石油醚的体积比为1:1的混合液)，得到4-甲氧基-1,1'-联苯，其产率为98％。
所得产物用Bruker Avance型超导傅立叶数字化核磁共振谱仪进行表征，表征数据为：1H NMR(400MHz,CDCl3)δ7.59–7.52(m,4H),7.46–7.40(m,2H),7.35–7.29(m,1H),7.03–6.97(m,2H),3.86(s,3H)；13C NMR(101MHz,CDCl3)δ159.29,140.98,133.93,128.86，128.30,126.88,126.80,114.35,55.48。
实施例2
合成结构式如下的4-硝基-1,1'-联苯
向20mL反应瓶中加入0.2020g(1mmol)对硝基溴苯、0.1829g(1.5mmol)苯硼酸、0.0011g(0.002mmol)三嗪卡宾钯、0.4887g(1.5mmol)碳酸铯、6mL乙醇，在55℃下搅拌反应14小时，反应完后自然降至室温，旋转蒸发除去乙醇，用硅胶柱分离(洗脱剂是二氯甲烷与石油醚的体积比为1:1的混合液)，得到4-硝基-1,1'-联苯，其产率为95％。
所得产物用Bruker Avance型超导傅立叶数字化核磁共振谱仪进行表征，表征数据为：1H NMR(400MHz,CDCl3)δ8.29(d,J＝8.9Hz,2H),7.73(d,J＝8.9Hz,2H),7.63(d,J＝6.9Hz,2H),7.48(dt,J＝21.3,7.1Hz,3H)；13C NMR(101MHz,CDCl3)δ147.68,147.15,138.82,129.24,129.02,127.86,127.46,124.17。
实施例3
合成结构式如下的4-乙酰联苯
向20mL反应瓶中加入0.1990g(1mmol)4-溴苯乙酮、0.1829g(1.5mmol)苯硼酸、0.0011g(0.002mmol)三嗪卡宾钯、0.4887g(1.5mmol)碳酸铯、6mL乙醇，在55℃下搅拌反应14小时，反应完后自然降至室温，旋转蒸发除去乙醇，用硅胶柱分离(洗脱剂是二氯甲烷与石油醚的体积比为1:1的混合液)，得到4-乙酰联苯，其产率为88％。
所得产物用Bruker Avance型超导傅立叶数字化核磁共振谱仪进行表征，表征数据为：1H NMR(400MHz,CDCl3)δ8.03(d,J＝8.5Hz,2H),7.65(dd,J＝20.5,7.8Hz,4H),7.44(dt,J＝26.9,7.2Hz,3H),2.63(s,3H)；13C NMR(101MHz,CDCl3)δ197.71,145.74,139.84,135.87,128.99,128.94,128.27,127.28,127.21,26.66。
实施例4
合成结构式如下的4-三氟甲基-1,1'-联苯
向20mL反应瓶中加入0.2250g(1mmol)对三氟甲基溴苯、0.2039g(1.5mmol)苯硼酸、0.0011g(0.002mmol)三嗪卡宾钯、0.4887g(1.5mmol)碳酸铯、6mL乙醇，在55℃下搅拌反应14小时，反应完后自然降至室温，旋转蒸发除去乙醇，用硅胶柱分离(洗脱剂是二氯甲烷与石油醚的体积比为1:1的混合液)，得到4-三氟甲基-1,1'-联苯，其产率为64％。
合成产物用Bruker Avance型超导傅立叶数字化核磁共振谱仪进行表征，表征数据为：1H NMR(400MHz,CDCl3)δ7.71(s,4H),7.61(d,J＝7.0Hz,2H),7.46(dt,J＝27.5,7.2Hz,3H)；13C NMR(101MHz,CDCl3)δ144.90(s),139.93(s),129.67(s),129.34(s),129.13(s),128.33(s),127.50(d,J＝14.1Hz),125.85(q,J＝3.8Hz)。
实施例5
合成结构式如下的4-醛基-1,1'-联苯
向20mL反应瓶中加入0.1850g(1mmol)对溴苯甲醛、0.2039g(1.5mmol)苯硼酸、0.0011g(0.002mmol)三嗪卡宾钯、0.4887g(1.5mmol)碳酸铯、6mL乙醇，在55℃下搅拌反应14小时，反应完后自然降至室温，旋转蒸发除去乙醇，用硅胶柱分离(洗脱剂是二氯甲烷与石油醚的体积比为1:1的混合液)，得到4-醛基-1,1'-联苯，其产率为92％。
所得产物用Bruker Avance型超导傅立叶数字化核磁共振谱仪进行表征，表征数据为：1H NMR(400MHz,CDCl3)δ10.05(s,1H),7.95(d,J＝8.2Hz,2H),7.75(d,J＝8.2Hz,2H),7.64(d,J＝7.0Hz,2H),7.45(dt,J＝14.6,6.5Hz,3H)；13C NMR(101MHz,CDCl3)δ191.94,147.19,139.73,135.26,130.31,129.07,128.54,127.71,127.41。
实施例6
合成结构式如下的2-醛基-1,1'-联苯
向20mL反应瓶中加入0.1850g(1mmol)2-溴苯甲醛、0.2039g(1.5mmol)苯硼酸、0.0011g(0.002mmol)三嗪卡宾钯、0.4887g(1.5mmol)碳酸铯、6mL乙醇，在55℃下搅拌反应14小时，反应完后自然降至室温，旋转蒸发除去乙醇，用硅胶柱分离(洗脱剂是二氯甲烷与石油醚的体积比为1:1的混合液)，得到2-醛基-1,1'-联苯，其产率为59％。
所得产物用Bruker Avance型超导傅立叶数字化核磁共振谱仪进行表征，表征数据为：1H NMR(400MHz,CDCl3)δ10.00(s,1H),8.04(d,J＝6.7Hz,1H),7.64(t,J＝7.5Hz,1H),7.58-7.35(m,7H)；13C NMR(101MHz,CDCl3)δ192.43,146.00,137.80,133.77,133.60,130.83,130.15,128.48,128.17,127.82,127.61。
实施例7
合成结构式如下的4-甲基-1,1'-联苯
向20mL反应瓶中加入0.1710g(1mmol)4-甲基溴苯、0.2039g(1.5mmol)苯硼酸、0.0011g(0.002mmol)三嗪卡宾钯、0.4887g(1.5mmol)碳酸铯、6mL乙醇，在55℃下搅拌反应14小时，反应完后自然降至室温，旋转蒸发除去乙醇，用硅胶柱分离(洗脱剂是二氯甲烷与石油醚的体积比为1:1的混合液)，得到4-甲基-1,1'-联苯，其产率为63％。
所得产物用Bruker Avance型超导傅立叶数字化核磁共振谱仪进行表征，表征数据为：1H NMR(400MHz,CDCl3)δ7.63(d,J＝7.1Hz,2H),7.58-7.42(m,4H),7.41-7.25(m,3H),2.44(s,3H)；13C NMR(101MHz,CDCl3)δ141.30,138.50,137.14,129.62,128.85,127.13,127.11,21.23。
实施例8
合成结构式如下的4-(二苯氨基)联苯
向20mL反应瓶中加入0.3250g(1mmol)4-溴三苯胺、0.2039g(1.5mmol)苯硼酸、0.0011g(0.002mmol)三嗪卡宾钯、0.4887g(1.5mmol)碳酸铯、6mL乙醇，在55℃下搅拌反应14小时，反应完后自然降至室温，旋转蒸发除去乙醇，用硅胶柱分离(洗脱剂是二氯甲烷与石油醚的体积比为1:1的混合液)，得到4-(二苯氨基)联苯，其产率为64％。
所得产物用Bruker Avance型超导傅立叶数字化核磁共振谱仪进行表征，表征数据为：1H NMR(400MHz,CDCl3)δ7.60(d,J＝7.1Hz,3H),7.54–7.40(m,6H),7.38–7.25(m,8H),7.21–7.14(m,9H),7.06(t,J＝7.3Hz,3H)；13C NMR(101MHz,CDCl3)δ147.83,147.32,140.79,135.28,129.41,128.87,127.91,126.94,126.79,124.55,124.05,123.05。
实施例9
合成结构式如下的1-苯基萘
向20mL反应瓶中加入0.2070g(1mmol)1-溴萘、0.2039g(1.5mmol)苯硼酸、0.0011g(0.002mmol)三嗪卡宾钯、0.4887g(1.5mmol)碳酸铯、6mL乙醇，在55℃下搅拌反应14小时，反应完后自然降至室温，旋转蒸发除去乙醇，用硅胶柱分离(洗脱剂是二氯甲烷与石油醚的体积比为1:1的混合液)，得到1-苯基萘，其产率为31％。
所得产物用Bruker Avance型超导傅立叶数字化核磁共振谱仪进行表征，表征数据为：1H NMR(400MHz,CDCl3)δ7.91(dd,J＝18.8,8.7Hz,3H),7.60–7.41(m,9H)；13C NMR(101MHz,CDCl3)δ140.91,140.41,133.94,131.77,130.22,128.39,127.77,127.37,127.06,126.17,126.15,125.90,125.51。

Claims (4)

1.一种三嗪卡宾钯催化合成二芳基化合物的方法，其特征在于：将式I所示的溴苯类化合物和式II所示的苯硼酸类化合物、三嗪卡宾钯、无机碱加入溶剂中，在55～60℃下反应10～14小时，分离纯化产物，得到式Ш所示的二芳基化合物；
式中，R1代表C1～C4烷基、C1～C4烷氧基、硝基、乙酰基、醛基、三氟甲基、萘基、二苯胺基中任意一种；R2代表H、C1～C4烷氧基中任意一种；
上述三嗪卡宾钯的结构式如下所示：
上述的无机碱为碳酸铯，溶剂为乙醇。
2.根据权利要求1所述的三嗪卡宾钯催化合成二芳基化合物的方法，其特征在于：所述溴苯类化合物与苯硼酸类化合物的摩尔比为1:1～1.5。
3.根据权利要求1所述的三嗪卡宾钯催化合成二芳基化合物的方法，其特征在于：所述三嗪卡宾钯的加入量为溴苯类化合物摩尔量的0.1%～0.2%。
4.根据权利要求1所述的三嗪卡宾钯催化合成二芳基化合物的方法，其特征在于：所述无机碱的加入量为溴苯类化合物摩尔量的1～1.5倍。
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