CN108047198B - 一种钌催化芳酮与二苯乙炔反应制备多芳取代萘衍生物的方法 - Google Patents

一种钌催化芳酮与二苯乙炔反应制备多芳取代萘衍生物的方法 Download PDF

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CN108047198B
CN108047198B CN201711358067.2A CN201711358067A CN108047198B CN 108047198 B CN108047198 B CN 108047198B CN 201711358067 A CN201711358067 A CN 201711358067A CN 108047198 B CN108047198 B CN 108047198B
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张殊佳
高杰
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Abstract

本分案申请涉及一种钌催化芳酮与二苯乙炔反应制备多芳取代萘衍生物的方法。本发明使用较廉价的钌作为催化剂，将芳香酮β‑H活化合成六元环即生成多芳取代萘衍生物；反应过程中无需添加剂及氧化剂，仅使用简单的碱，在温和反应条件下进行。本发明提供的合成方法简单易行、科学合理、绿色环保、经济实用，适合规模化生产。

Description

一种钌催化芳酮与二苯乙炔反应制备多芳取代萘衍生物的 方法
本申请为申请号为2017113298008、申请日为2017年12月13日、发明名称为“一种钌催化芳香酮与二苯乙炔环化反应制备多芳取代萘衍生物的方法及应用”的分案申请。
技术领域
本发明涉及医药技术及光电材料领域，主要涉及多芳取代萘衍生物的制备方法及应用。
背景技术
多芳取代萘衍生物由于其独特的电化学，光化学性能以及它们在n共轭的功能材料上的应用，使其在有机荧光材料、半导体材料等方面的应用越来越广泛，并且多芳取代萘衍生物在药物合成方面也有重要应用。现有技术中已采用的制备方法相比以前的环金属化、芳基卤、芳基酸等比较苛刻的条件有了很大的突破。目前，多采用在温和条件下通过过渡金属催化芳香苯环的C-H键(甚至双C-H键)活化与炔烃发生环化反应制备多芳取代的萘衍生物。但该方法存在缺陷，这些反应需要一定量的配体或者当量的金属盐做氧化剂才能完成催化循环，不仅提高了生产成本，而且金属盐多为对环境污染的重金属(铜、银等)盐类。基于此，本领域需要更加环保、绿色、经济的方法来合成多芳取代萘衍生物。
发明内容
为弥补现有技术的不足，本发明提供了一种无需添加剂及氧化剂在温和条件下以较廉价的钌([RuCl2(p-cymene)]2)作为催化剂合成了多芳取代萘的衍生物的方法。
本发明采用如下技术方案：多芳取代萘的衍生物，具有如通式Ⅰ所示的结构：
Figure BDA0001511409970000011
其中，R1为
Figure BDA0001511409970000012
-H或-F中的一种，R2为
Figure BDA0001511409970000013
-CH2CH3、-CH3、
Figure BDA0001511409970000014
或-CH3中的一种。
优选的，所述多芳取代萘的衍生物为：
Figure BDA0001511409970000015
Figure BDA0001511409970000021
本发明另一个目的是请求保护上述多芳取代萘的衍生物的制备方法，即：将二苯乙炔与芳香酮作为原料，加入[RuCl2(p-cymene)]2、碱和非极性有机溶剂，在氮气环境下加热至80-100℃反应12-24h，经柱层析分离得到多芳取代萘的衍生物；所述的二苯乙炔与芳香酮摩尔比为1:2，[RuCl2(p-cymene)]2占二苯乙炔的15mol％，碱与芳香酮的摩尔比为1:1。
优选的，所述的芳香酮为：
Figure BDA0001511409970000022
其中R1为
Figure BDA0001511409970000023
-H或-F中的一种，R2为
Figure BDA0001511409970000024
-CH3、-CH2CH3、-CH3、
Figure BDA0001511409970000025
或-CF3中的一种。
优选的，芳香酮为
Figure BDA0001511409970000026
Figure BDA0001511409970000027
中的一种。
进一步的，所述非极性有机溶剂为苯、甲苯、二氯乙烷、氯仿、苯乙烯、环乙烷或己烷中任一种。优选甲苯。
进一步的，所述的碱为KOAc、Na2CO3、Cs2CO3、K2CO3、Li2CO3、NaOAc、LiOAc中的一种或一种以上。优选KOAc和Na2CO3。
作为本发明优选的实施方案，该多芳取代萘衍生物的制备方法为：将芳香酮和二苯乙炔置于封管中，加入[RuCl2(p-cymene)]2和甲苯，同时加入干燥的碳酸钠和醋酸钾在氮气环境下加热至100℃反应24小时，经柱层析分离得到多芳取代萘的衍生物。
本发明第三个目的是请求保护上述多芳取代萘的衍生物在药物制备及光电材料领域上的应用。
比如用于新型酪氨酸蛋白激酶抑制剂
Figure BDA0001511409970000031
或蓝光材料
Figure BDA0001511409970000032
的制备。
与现有技术相比，本发明的有益效果是：
本发明使用较廉价的钌([RuCl2(p-cymene)]2)作为催化剂，将芳香酮β-H活化合成六元环即生成多芳取代萘衍生物；反应过程中无需添加剂及氧化剂，仅使用简单的碱，在温和反应条件下进行。本发明提供的合成方法简单易行、科学合理、绿色环保、经济实用，适合规模化生产。
具体实施方式
下面通过具体实施例详述本发明，但不限制本发明的保护范围。如无特殊说明，本发明所采用的实验方法均为常规方法，所用实验器材、材料、试剂等均可从化学公司购买。
实施例1
Figure BDA0001511409970000033
向带有磁子的25mL封管中加入二苯乙炔(18mg，0.1mmol)，相应的芳香酮(0.2mmol)，催化剂[RuCl2(p-cymene)]2(9mg，15％mol)，0.5mL甲苯，之后加入干燥的碳酸钠(21mg，0.2mmol)和醋酸钾(19mg，0.2mmol)，抽换氮气三次，100℃下反应24小时，然后经柱色谱分离(洗脱剂为：石油醚)从而得到目标化合物。表征如下。
4,5-二苯基-6-(噻吩-2-亚甲基)苯并[b]噻吩：产率：40％。1H NMR(CDCl3,400MHz)δ7.81(s,1H),7.33(d,J＝5.2Hz,1H),7.10-7.18(m,9H),7.00-7.02(m,3H),6.87(dd,J1＝3.6Hz；J2＝5.2Hz,1H),6.59-6.60(m,1H),4.07(s,2H).13C NMR(CDCl3,100MHz)δ144.1,139.7,139.4,135.7,130.8,130.4,127.5,126.7,126.5,126.4,125.9,124.2,123.8,122.1,34.5.HRMS(EI-TOF)calcd for C25H18S2(M+):382.0850,found:382.0847.
实施例2
Figure BDA0001511409970000041
向带有磁子的25mL封管中加入二苯乙炔(18mg，0.1mmol)，相应的芳香酮(0.2mmol)，催化剂[RuCl2(p-cymene)]2(9mg，15％mol)，0.5mL甲苯，之后加入干燥的碳酸钠(21mg，0.2mmol)和醋酸钾(19mg，0.2mmol)，抽换氮气三次，100℃下反应24小时，然后经柱色谱分离(洗脱剂为：石油醚)从而得到目标化合物。表征如下。
3-甲基-1,2,7-三苯基萘：产率：65％。熔点：163-165℃。1H NMR(CDCl3,400MHz)δ7.91(d,J＝8.4Hz,1H),7.79(s,1H),7.69-7.73(m,2H),7.52(d,J＝7.2Hz,2H),7.37(t,J＝8.0Hz,2H),7.29(d,J＝7.2Hz,1H),7.10-7.23(m,8H),7.02-7.05(m,2H),2.26(s,3H).13CNMR(CDCl3,100MHz)δ141.5,140.6,140.4,139.2,139.0,137.9,134.7,132.1,131.5,131.1,130.1,128.8,127.7,127.6,127.5,127.4,127.2,127.1,126.4,126.2,125.5,124.9,22.0.HRMS(EI-TOF)calcd for C29H22(M+):370.1722,found:370.1723.
实施例3
Figure BDA0001511409970000042
向带有磁子的25mL封管中加入二苯乙炔(18mg，0.1mmol)，相应的芳香酮(0.2mmol)，催化剂[RuCl2(p-cymene)]2(9mg，15％mol)，0.5mL甲苯，之后加入干燥的碳酸钠(21mg，0.2mmol)和醋酸钾(19mg，0.2mmol)，抽换氮气三次，100℃下反应24小时，然后经柱色谱分离(洗脱剂为：石油醚)从而得到目标化合物。表征如下。
3-乙基-1,2-二苯基萘：产率：25％。熔点：124-125℃。1H NMR(CDCl3,400MHz)δ7.79-7.81(m,1H),7.72(s,1H),7.37-7.40(m,2H),7.22-7.26(m,1H),7.01-7.14(m,8H),6.96-6.98(m,2H),2.51(dd,J1＝7.6Hz；J2＝14.8Hz,2H),1.08(t,J＝7.6Hz,3H).13C NMR(CDCl3,100MHz)δ140.4,140.3,139.6,139.5,138.8,133.0,131.2,131.0,130.4,127.4,127.4,126.8,126.3,126.1,125.8,125.7,125.3,27.4,15.1.HRMS(EI-TOF)calcd forC24H20(M+):308.1565,found:308.1567.
实施例4
Figure BDA0001511409970000051
向带有磁子的25mL封管中加入二苯乙炔(18mg，0.1mmol)，相应的芳香酮(0.2mmol)，催化剂[RuCl2(p-cymene)]2(9mg，15％mol)，0.5mL甲苯，之后加入干燥的碳酸钠(21mg，0.2mmol)和醋酸钾(19mg，0.2mmol)，抽换氮气三次，100℃下反应24小时，然后经柱色谱分离(洗脱剂为：石油醚)从而得到目标化合物。表征如下。
7-氟-3-甲基-1,2-二苯基萘：产率：30％。熔点：139-140℃。1H NMR(CDCl3,400MHz)δ7.81(dd,J1＝6.0Hz；J2＝8.8Hz,1H),7.75(s,1H),7.06-7.23(m,10H),7.01-7.03(m,2H),2.24(s,3H).13C NMR(CDCl3,100MHz)δ161.6,159.2,140.8,140.3,138.9,138.2(d,JC-F＝5.6Hz),133.7(d,JC-F＝2.3Hz),132.3,132.2,130.9,129.9(d,JC-F＝5.6Hz),129.4(d,JC-F＝8.6Hz),127.6(d,JC-F＝4.9Hz),127.3,126.6,126.3,116.2,115.9,110.3,110.1,21.8.HRMS(EI-TOF)calcd for C23H17F(M+):312.1314,found:312.1312.
实施例5
Figure BDA0001511409970000052
向带有磁子的25mL封管中加入二苯乙炔(18mg，0.1mmol)，相应的芳香酮(0.2mmol)，催化剂[RuCl2(p-cymene)]2(9mg，15％mol)，0.5mL甲苯，之后加入干燥的碳酸钠(21mg，0.2mmol)和醋酸钾(19mg，0.2mmol)，抽换氮气三次，100℃下反应24小时，然后经柱色谱分离(洗脱剂为：石油醚)从而得到目标化合物。表征如下。
3-异丁基-1,2-二苯基萘：产率：35％。熔点：107-108℃。1H NMR(CDCl3,400MHz)δ7.85-7.87(m,1H),7.73(s,1H),7.43-7.47(m,2H),7.29-7.33(m,1H),7.07-7.21(m,8H),7.01-7.03(m,2H),2.48(d,J＝7.2Hz,2H),1.66-1.73(m,1H),0.76-0.78(d,J＝6.4Hz,6H).13C NMR(CDCl3,100MHz)δ140.3,140.0,139.6,138.9,137.9,132.7,131.3,131.1,130.7,127.7,127.4,127.4,127.2,126.8,126.3,126.1,125.6,125.3,43.5,29.8,29.1,22.6.HRMS(EI-TOF)calcd for C26H24(M+):336.1878,found:336.1882.
实施例6
Figure BDA0001511409970000061
向带有磁子的25mL封管中加入二苯乙炔(18mg，0.1mmol)，相应的芳香酮(0.2mmol)，催化剂[RuCl2(p-cymene)]2(9mg，15％mol)，0.5mL甲苯，之后加入干燥的碳酸钠(21mg，0.2mmol)和醋酸钾(19mg，0.2mmol)，抽换氮气三次，100℃下反应24小时，然后经柱色谱分离(洗脱剂为：石油醚)从而得到目标化合物。表征如下。
1,2-二苯基-3-(三氟甲基)萘：产率：45％。熔点：118-119℃。1H NMR(CDCl3,400MHz)δ8.34(s,1H),8.02(d,J＝8.0Hz,1H),7.57-7.60(m,1H),7.94-7.50(m,2H),7.18-7.24(m,3H),7.13-7.16(m,3H),7.05-7.11(m,4H).13C NMR(CDCl3,100MHz)δ141.6,138.1,137.7,135.9,134.0,131.4,130.8(d,JC-F＝5.8Hz),129.4,128.9,128.4,128.3,128.2,127.6,127.1,126.9,126.9,126.8,126.2,126.2.HRMS(EI-TOF)calcd for C23H15F3(M+):348.1126,found:348.1124.
对比例：
向带有磁子的25mL封管中加入二苯乙炔0.1mmol，芳香酮
Figure BDA0001511409970000062
(0.2mmol)，催化剂[RuCl2(p-cymene)]20.01mol，之后加入0.5mL有机溶剂和与芳香酮等摩尔的干燥的碱，抽换氮气三次，100℃下反应24小时，然后经柱色谱分离(洗脱剂为：石油醚)从而得到目标化合物
Figure BDA0001511409970000063
计算产率，结果如表1所示。
表1
Figure BDA0001511409970000064
Figure BDA0001511409970000071
*催化剂为0.015mmol时的产率
由表1数据和对实施例1-6产率对比可知，当有机溶剂选择甲苯，碱为碳酸钠和醋酸钾时，催化剂用量为15mol％时，产率最高。故而，在实验过程中均采用此最佳反应条件进行。
以上所述，仅为本发明创造较佳的具体实施方式，但本发明创造的保护范围并不局限于此，任何熟悉本技术领域的技术人员在本发明创造披露的技术范围内，根据本发明创造的技术方案及其发明构思加以等同替换或改变，都应涵盖在本发明创造的保护范围之内。

Claims (1)

1.一种钌催化芳酮与二苯乙炔反应制备3-乙基-1,2-二苯基萘的方法，其特征在于，将二苯乙炔与芳香酮
Figure FDA0002436516420000011
作为原料，向带有磁子的25mL封管中加入二苯乙炔0.1mmol，芳香酮
Figure FDA0002436516420000012
0.2mmol，催化剂[RuCl2(p-cymene)]2，[RuCl2(p-cymene)]2占二苯乙炔的15mol％，0.5mL甲苯，之后加入干燥的碳酸钠0.2mmol和醋酸钾0.2mmol，抽换氮气三次，100℃下反应24小时，然后经柱色谱分离，洗脱剂为石油醚；得到多芳取代萘的衍生物3-乙基-1,2-二苯基萘。
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