CN108484372B - 一种由芳基肼和溴代芳烃制备联芳烃的方法 - Google Patents

一种由芳基肼和溴代芳烃制备联芳烃的方法 Download PDF

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CN108484372B
CN108484372B CN201810298656.4A CN201810298656A CN108484372B CN 108484372 B CN108484372 B CN 108484372B CN 201810298656 A CN201810298656 A CN 201810298656A CN 108484372 B CN108484372 B CN 108484372B
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赵保丽
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Abstract

本发明公开了一种由芳基肼和溴代芳烃制备联芳烃的方法，包括：在二价钯催化剂和配体的作用下，芳基肼和溴代芳烃在有机溶剂中发生脱氮偶联反应，反应结束后经过后处理得到所述的联芳烃。该制备方法使用廉价易得的溴代芳烃作为芳基来源，无论对芳基肼还是溴代芳烃，该反应均显示出良好的官能团耐受性，反应通过碱促进钯催化过程进行。

Description

一种由芳基肼和溴代芳烃制备联芳烃的方法
技术领域
本发明属于有机合成领域，具体涉及一种由芳基肼和溴代芳烃制备联芳烃的方法。
背景技术
联芳烃化合物是很多天然产物和药物的主要构架，同时其衍生物在化工领域中占有重要地位，是一类关键中间体，并且广泛地应用于有机导体、染料、半导体、药物和液晶材料领域。联芳烃衍生物也可以用作不对称合成的配体和助剂。((a)F.Bellina,A.Carpitaand R.Rossi,Synthesis,2004, 2419；(b)S.Lightowler and M.Hird,Chem.,Mater.,2005,17,5538.)而在多种多样的联芳烃合成方法中，使用钯催化的交叉偶联的反应策略来构筑联芳烃结构在有机合成领域有举足轻重的作用。((a)Metal-Catalyzed Cross-Coupling Reactions,ed.F.Diederich and A.Meijere,Wiley-VCH, Weinheim,Germany,2004；(b)J.Corbet and G.Mignani,Chem.Rev.,2006, 106,2651；(c)E.Negishi,Bull.Chem.Soc.Jpn.,2007,80,233.)
由于碳-氮键的解离能很高，碳-氮键很稳定，所以碳-氮键的断裂在有机化学中吸引了很多关注。在过去的几十年中，C(sp2)-N键的活化用来为药物、天然产物和农药的基本结构提高联芳衍生物的反应得到快速发展。 (Transition-metal catalysed C–N bondactivation Quanjun Wang,Yijin Su, Lixin Li and Hanmin Huang，Chem.Soc.Rev.2016,45,1257.)
最近，过渡金属催化的通过C-N键的断裂实现的偶联反应引起了有机化学家的广泛关注，报道了芳基重氮盐、三唑和氮杂环参与的偶联反应。然而这些方法普遍存在着反应条件苛刻、底物范围狭窄和底物稳定性差的缺点。可以在温和条件下显示良好的化学选择性和区域选择性的环境友好的卤代芳烃替代物的发展就显得尤为重要。
芳基肼是一类重要的有机化合物，可以用来合成有机磷农药三唑磷的中间体1-苯基氨基脲和哒嗪硫磷的中间体3,6-二羟基苯基哒嗪，同时也是新型杀菌剂咪唑菌酮(fenamidone)和噁唑菌酮(famoxadone)的中间体。另外，芳基肼化合物作为一种有机合成原料，在医药、染料以及有机导电材料中很广阔的应用，因此收到了有机化学家的广泛关注。芳基肼价廉易得，稳定性好并兼具高反应活性，离去基团以氮气分子形式离去，环境友好无污染，已经应用于各种通过C-N键断裂实现的钯催化偶联反应中。 (Zhu,M.-K.；Zhao,J.-F.；Loh,T.-P.Org.Lett.2011,13,6308.)
发明内容
本发明提供了一种由芳基肼和溴代芳烃制备联芳烃的方法，该方法使用的原料价廉易得，同时，反应条件温和，反应收率高。
一种由芳基肼和溴代芳烃制备联芳烃的方法，包括：在二价钯催化剂和配体的作用下，芳基肼和溴代芳烃在有机溶剂中发生脱氮偶联反应，反应结束后经过后处理得到所述的联芳烃；
所述的芳基肼的结构如式(II)所示：
Figure BDA0001619266920000021
所述的溴代芳烃的结构如式(III)所示：
Figure BDA0001619266920000022
所述的联芳烃的结构如式(I)所示：
Figure BDA0001619266920000023
式(I)～(III)中，R和R1独立地选自H、甲基、甲氧基、F、-CN、乙酰基、羟基、氨基、甲酰基、Cl、-CF3、-NO2中的一个或者多个。
作为优选，所述的R和R1独立地选自H、C1～C5烷基、C1～C5烷氧基、卤素、-CN、C1～C5烷酰基、羟基、氨基、-CF3、-NO2中的一个或者多个。
作为优选，所述的二价钯催化剂选自Pd(OAc)2、PdCl2、Pd(TFA)2、 Pd(OTs)2、Pd(dba)2、Pd(PPh3)4、Pd(PPh3)3Cl2或Pd(dppf)Cl2。
作为优选，所述的配体选自TFP、P(p-tol)3、P(m-tol)3、P(o-tol)3、Dppp、 Dppe、Dppm、Dppb、Dppf、Dmpe、BINAP、PPh3或P(OPh)3。
作为优选，所述的有机溶剂为NMP、DMSO、DMF、DMA、toluene、xylene、CH3CN、THF或DME。
作为优选，所述的脱氮偶联反应的温度为50～70℃，反应时间为2～10 小时。
作为优选，所述的联芳烃为以下化合物中的一种：
Figure BDA0001619266920000031
同现有技术相比，本发明的有益效果体现在：
(1)本发明使用廉价易得的溴代芳烃作为芳基来源，无论对芳基肼还是溴代芳烃，该反应均显示出良好的官能团耐受性，反应通过碱促进钯催化过程进行。
(2)本发明通过采用特殊的催化剂和配体，有效地降低了反应温度，提高了反应收率。
具体实施方式
实施例1
在反应瓶中，加入苯肼(1mmol)、溴代苯(1.1mmol)，Pd(OAc)2(0.02 mmol)、配体ligand(0.03mmol)、K2CO3(2.0mmol)和2mL溶剂NMP，搅拌，然后加热至60℃进行反应，反应在空气氛围下进行，反应3小时后， TLC监测反应完全，降至室温，滤除固体，加入1mL水后用2mL乙醚萃取三次，合并萃取液旋干溶剂后，以石油醚和乙酸乙酯的混合溶剂作为洗脱剂进行柱分离即得产品。反应条件和反应结果见表1，反应式如下：
Figure BDA0001619266920000041
表1
Figure BDA0001619266920000042
实施例2
在反应瓶中，加入苯肼(1mmol)、溴代苯(1.1mmol)，催化剂(0.02 mmol)、配体TFP(0.03mmol)、碱(2.0mmol)和2mL溶剂，搅拌，然后加热至60℃进行反应，反应在空气氛围下进行，反应3小时后，TLC监测反应完全，降至室温，滤除固体，加入1mL水后用2mL乙醚萃取三次，合并萃取液旋干溶剂后，以石油醚和乙酸乙酯的混合溶剂作为洗脱剂进行柱分离即得产品。反应条件和反应结果见表2，反应式如下：
Figure BDA0001619266920000051
表2
Figure BDA0001619266920000052
实施例3
在反应瓶中，加入芳基肼(1mmol)、溴代苯(1.1mmol)，Pd(OAc)2 (0.02mmol)、配体TFP(0.03mmol)、K2CO3(2.0mmol)和2mL NMP，搅拌，然后加热至60℃进行反应，反应3小时后，TLC监测反应完全，降至室温，滤除固体，加入1mL水后用2mL乙醚萃取三次，合并萃取液旋干溶剂后，以石油醚和乙酸乙酯的混合溶剂作为洗脱剂进行柱分离即得产品。反应条件和反应结果见表3，反应式如下：
Figure BDA0001619266920000053
表3
Figure BDA0001619266920000061
实施例4
在反应瓶中，加入芳基肼(1mmol)、溴代芳烃(1.1mmol)，Pd(OAc)2 (0.02mmol)、配体TFP(0.03mmol)、K2CO3(2.0mmol)和2mL NMP，搅拌，然后加热至60℃进行反应，反应3小时后，TLC监测反应完全，降至室温，滤除固体，加入1mL水后用2mL乙醚萃取三次，合并萃取液旋干溶剂后，以石油醚和乙酸乙酯的混合溶剂作为洗脱剂进行柱分离即得产品。反应条件和反应结果见表4，反应式如下：
Figure 100002_DEST_PATH_IMAGE001
表4
Figure 100002_DEST_PATH_IMAGE002
部分产物表征数据如下：
[1,1'-biphenyl]-3-amine(3h):
1H NMR(CDCl3,400MHz):δ7.28-7.21(m,3H)6.85-6.81(m,3H),6.75-6.72(m,3H),3.59(s,2H).13C NMR(CDCl3,100MHz):146.47,146.36,129.37,129.28,118.60,115.18.HRMS(EI)Calcd for C12H11N(M+)169.0891,Found 169.0885.
[1,1'-biphenyl]-3-carbaldehyde(3j):
1H NMR(CDCl3,400MHz):δ10.13(s,1H),8.01(s,1H),7.91-7.88(m,2H),7.68-7.62(m, 3H),7.53-7.50(m,2H),7.46-7.42(m,1H).13C NMR(CDCl3,100MHz):δ192.35,142.20,139.73,136.95,133.08,129.52,129.02,128.66,128.22,128.04,127.18.HRMS(EI)Calcdfor C13H10O(M+)182.0732,Found 182.0728.
2,4-dinitro-1,1'-biphenyl(3r):
1H NMR(CDCl3,400MHz):δ8.74-8.72(m,1H),8.52-8.48(m,1H),7.74-7.68(m,1H),7.54-7.49(m,3H),7.40-7.36(m,2H).13C NMR(CDCl3,100MHz):δ149.11,146.89, 142.30,135.25,133.28,129.60,129.14,127.73,126.54.119.75.HRMS(EI)Calcd for C12H8N2O4(M+)244.0484,Found 244.0479.
5-(4-methoxyphenyl)pyrimidine(4g):
1H NMR(CDCl3,400 MHz):δ9.20(s,1H),8.99(s,2H),7.57(d,J＝8.0 Hz,2H),7.06(d,J ＝8.0 Hz,2H),3.15(s,3H).13C NMR(CDCl3,100 MHz):δ160.68,156.15,154.52,128.30, 126.13,120.04,115.11,55.49.HRMS(EI)Calcd for C11H10N2O(M+)186.1793,Found 186.1787.
4'-acetyl-[1,1'-biphenyl]-4-carbonitrile(4l):
1H NMR(CDCl3,400 MHz):δ8.62(dd,J＝8.8,1.8 Hz,2H),7.71(m,6H), 2.64(s,3H).13C NMR(CDCl3,100 MHz):δ197.49,144.33,143.56,136.93, 132.75,129.13,127.93,127.47,118.65,111.93,26.73.HRMS(EI)Calcd for C15H11NO(M+)221.0841,Found221.0834.

Claims (3)

1.一种由芳基肼和溴代芳烃制备联芳烃的方法，其特征在于，包括：在二价钯催化剂、配体和碱的作用下，芳基肼和溴代芳烃在有机溶剂中发生脱氮偶联反应，反应结束后经过后处 理得到所述的联芳烃；
所述的芳基肼的结构如式(II)所示：
Figure DEST_PATH_IMAGE001
所述的溴代芳烃的结构如式(III)所示：
Figure DEST_PATH_IMAGE002
所述的联芳烃的结构如式(I)所示：
Figure DEST_PATH_IMAGE003
式(I)～(III)中，R和R1独立地选自H、甲基、甲氧基、F、-CN、乙酰基、羟基、氨基、甲酰基、Cl、-CF3、-NO2中的一个或者多个 ；
所述的二价钯催化剂选自Pd(OAc)2；
所述的配体选自TFP；
所述的 有机溶剂为NMP；
所述的碱为碳酸钾。
2.根据权利要求1所述的由芳基肼和溴代芳烃制备联芳烃的方法，其特征在于，所述的脱氮偶联反应的温度为50～70℃，反应时间为2～10小时。
3.根据权利要求1所述的由芳基肼和溴代芳烃制备联芳烃的方法，其特征在于，所述的联芳烃为以下化合物中的一种：
Figure DEST_PATH_IMAGE005
。
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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103553856A (zh) * 2013-10-21 2014-02-05 同济大学 一种联苯类化合物的合成方法
CN103664431A (zh) * 2013-12-06 2014-03-26 刘雷芳 一种芳基-芳基联苯类化合物的制备方法
CN103804105A (zh) * 2014-02-17 2014-05-21 绍兴文理学院 一种联苯类化合物的合成方法
CN104610002A (zh) * 2014-05-29 2015-05-13 绍兴文理学院 一种芳香肼合成对称性联苯的方法
CN105175202A (zh) * 2015-07-14 2015-12-23 绍兴文理学院 由芳香肼制备联芳烃的方法

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103553856A (zh) * 2013-10-21 2014-02-05 同济大学 一种联苯类化合物的合成方法
CN103664431A (zh) * 2013-12-06 2014-03-26 刘雷芳 一种芳基-芳基联苯类化合物的制备方法
CN103804105A (zh) * 2014-02-17 2014-05-21 绍兴文理学院 一种联苯类化合物的合成方法
CN104610002A (zh) * 2014-05-29 2015-05-13 绍兴文理学院 一种芳香肼合成对称性联苯的方法
CN105175202A (zh) * 2015-07-14 2015-12-23 绍兴文理学院 由芳香肼制备联芳烃的方法

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
Palladium‐Catalyzed Suzuki Cross‐Coupling of Phenylhydrazine or (Phenylsulfonyl)hydrazine;Li Yahui等;《European Journal of Organic Chemistry》;20140415;第2014卷(第16期);第3309页表3 *

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