磁性纳米钯催化沙坦联苯的合成研究
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摘要
研究了一种磁性纳米钯催化廉价的邻氯苯腈与对甲基苯硼酸Suzuki偶联合成沙坦联苯的新方法。目标产物经熔点、红外、核磁及质谱表征。考察了溶剂、温度、催化剂用量及反应时间的影响,确定了最佳的反应条件。邻氯苯腈2.0 mmol,对甲基苯硼酸2.2 mmol,碳酸钾4.0 mmol,四丁基溴化铵0.2 mmol,钯催化剂1.0 mol%,DMF 20 m L,110℃反应12 h,产率可达92%。此外,催化剂经简单磁分离即可高效回收,重复使用4次,活性无明显下降。
A novel method for the synthesis of sartanbiphenyl via the Suzuki coupling with 2-chlorobenzonitrile and 4-tolylboronic acid by the magnetic nano-palladium catalyst was reported. The target product was characterized by melt point,FTIR,1 H NMR and MS. The effects of solvent,temperature,usage of catalyst and time on the reaction were investigated and the best reaction conditions were obtained. The mixture of 2-chlorobenzonitrile( 2. 0 mmol),4-tolylboronic acid( 2. 2 mmol),K2 CO3( 4. 0 mmol),TBAB( 0. 2 mmol),MNP-Pd( 1. 0 mol%) and DMF( 20 m L) were reacted at 110 ℃ for 12 h,which afforded 92% yield. Moreover,the catalyst could be efficiently recycled by the simple magnetic separation and it could be reused4 times without a significant loss of catalytic activity.
A novel method for the synthesis of sartanbiphenyl via the Suzuki coupling with 2-chlorobenzonitrile and 4-tolylboronic acid by the magnetic nano-palladium catalyst was reported. The target product was characterized by melt point,FTIR,1 H NMR and MS. The effects of solvent,temperature,usage of catalyst and time on the reaction were investigated and the best reaction conditions were obtained. The mixture of 2-chlorobenzonitrile( 2. 0 mmol),4-tolylboronic acid( 2. 2 mmol),K2 CO3( 4. 0 mmol),TBAB( 0. 2 mmol),MNP-Pd( 1. 0 mol%) and DMF( 20 m L) were reacted at 110 ℃ for 12 h,which afforded 92% yield. Moreover,the catalyst could be efficiently recycled by the simple magnetic separation and it could be reused4 times without a significant loss of catalytic activity.
引文
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[15]Geng L F,Li Y,Qi Z L,et al.Highly efficient palladium catalysts supported on nitrogen contained polymers for Suzuki-Miyaura reaction[J].Catalysis Communications,2016,82:24-28.
[16]Fan H P,Qi Z L,Sui D J,et al.Palladium nanoparticles in cross-linked polyaniline as highly efficient catalysts for Suzuki-Miyaura reactions[J].Chinese Journal of Catalysis,2017,38:589-596.
[17]冯翠兰,刘建平,桂建舟,等.磁性纳米粒子负载钯催化剂在C-C键偶联反应中的应用[J].应用化学,2015,32(1):19-26.
[18]Zhang Q,Su H,Luo J,et al.“Click”magnetic nanoparticle supported palladium catalyst:a phosphine-free,highly efficient and magnetically recoverable catalyst for SuzukiMiyaura coupling reactions.Catalysis Science&Technology,2013,3:235-243.
[19]张强,李继航,赵鑫.磁性纳米粒子负载亚胺吡啶钯催化Suzuki反应研究[J].有机化学,2016,36:130-136.
[20]Zhang Q,Zhao X,Wei H X,et al.Silica-coated nanoFe3O4-supported iminopyridine palladium complex as an active,phosphine-free and magnetically separable catalyst for Heck reactions[J].Applied Organometallic Chemistry,2017,31:e3608.
[21]Hassankhani A,Sadeghzadeh S M,Zhiani R.C-C and C-Hcoupling reactions by Fe3O4/KCC-1/APTPOSS supported palladium-salen-bridged ionic networks as a reusable catalyst[J].RSC Advances,2018,8:8761-8769.
[2]张翘楚,郭梦萍.2-氰基-4’-甲基联苯合成方法综述[J].中国医药工业杂志,2007,38(11):819-821.
[3]李有桂,吴祥瑞,何伟.2-氰基-4’-甲基联苯的合成研究[J].化学研究与应用,2010,22(7):948-952.
[4]Carini D J,Duneia J V,Aldrieh P E,et al.Nonpeptide angiotensin II receptor antagonists:the discovery of a series of N-(biphenylylmethyl)imidazole as spotent,orally active antihypertensives[J].Journal of Medicinal Chemistry,1991,34(8):2525-2547.
[5]张卫军,吴运东,刘西洋,等.Mn Cl2催化交叉偶联合成沙坦联苯的工艺改进[J].合成化学,2009,17(3):388-389.
[6]鲁金樑.沙坦联苯的合成工艺研究[J].江西化学,2009,27(2):259-262.
[7]陈安成,范玉华,毕彩丰,等.沙坦联苯的合成工艺[J].广东化工,2012,39(12):52-53.
[8]郭孟萍,亓亮,张翘楚,等.Hiyama反应催化合成沙坦联苯[J].中国药房,2015,26(1):24-26.
[9]Herrmann W A,Brossmer C,fele K,et al.Palladacycles as structurally defined catalysts for the Heck olefination of chloro-and bromoarenes[J].Angewandte Chemie International Edition,1995,34(17):1844-1847.
[10]亓亮,闻永举,吕美云,等.沙坦联苯的合成研究[J].化学研究与应用,2015,27(1):107-109.
[11]Rao X F,Liu C,Zhang Y X,et al.Pd/C-catalyzed ligandfree and aerobic Suzuki reaction in water[J].Chinese Journal of Catalysis,2014,35(3):357-361.
[12]Pandarus V,Desplantier-Giscard D,Gingras G,et al.Greening the valsartan synthesis:scale-up of key Suzuki?Miyaura coupling over Silia Cat DPP-Pd[J].Organic Process Research&Development,2013,17:1492-1497.
[13]Santra S,Hota P K,Bhattacharyya R,et al.Palladium nanoparticles on graphite oxide:a recyclable catalyst for the synthesis of biaryl cores[J].ACS Catalysis,2013,3:2776-2789.
[14]浙江大学.2-氰基-4’-甲基联苯的制备方法:中国,201510776200.0[P].2016-03-30.
[15]Geng L F,Li Y,Qi Z L,et al.Highly efficient palladium catalysts supported on nitrogen contained polymers for Suzuki-Miyaura reaction[J].Catalysis Communications,2016,82:24-28.
[16]Fan H P,Qi Z L,Sui D J,et al.Palladium nanoparticles in cross-linked polyaniline as highly efficient catalysts for Suzuki-Miyaura reactions[J].Chinese Journal of Catalysis,2017,38:589-596.
[17]冯翠兰,刘建平,桂建舟,等.磁性纳米粒子负载钯催化剂在C-C键偶联反应中的应用[J].应用化学,2015,32(1):19-26.
[18]Zhang Q,Su H,Luo J,et al.“Click”magnetic nanoparticle supported palladium catalyst:a phosphine-free,highly efficient and magnetically recoverable catalyst for SuzukiMiyaura coupling reactions.Catalysis Science&Technology,2013,3:235-243.
[19]张强,李继航,赵鑫.磁性纳米粒子负载亚胺吡啶钯催化Suzuki反应研究[J].有机化学,2016,36:130-136.
[20]Zhang Q,Zhao X,Wei H X,et al.Silica-coated nanoFe3O4-supported iminopyridine palladium complex as an active,phosphine-free and magnetically separable catalyst for Heck reactions[J].Applied Organometallic Chemistry,2017,31:e3608.
[21]Hassankhani A,Sadeghzadeh S M,Zhiani R.C-C and C-Hcoupling reactions by Fe3O4/KCC-1/APTPOSS supported palladium-salen-bridged ionic networks as a reusable catalyst[J].RSC Advances,2018,8:8761-8769.