硅纳米片负载钯催化剂的制备及其催化Suzuki反应研究
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摘要
通过硅化钙在酸性条件下水解制得二维硅纳米片载体材料,经3-氨丙基三乙氧基硅烷化学改性后与钯配位,再经还原得到了一种新型的硅纳米片负载钯催化剂,采用透射电镜和电感耦合等离子体质谱(ICP-MS)等手段对其进行了表征.并将该催化剂成功应用于Suzuki反应,结果表明,硅纳米片负载钯催化剂在较低的钯催化量和空气氛围下即可有效地催化多种溴代芳烃和芳基硼酸的Suzuki偶联反应.此外,该催化剂经8次循环使用后,催化活性无明显下降.
Silicon nanosheets were served as supports for palladium nanoparticles which were modified with 3-aminopropyltriethoxysilane,followed by treatment with palladium chloride,and then the reduction with N2 H4·H2 O in ethanol. After vacuum drying,the functionalized nanosheets supported palladium catalysts( Pd/AS-SNS) were obtained. The products were confirmed by transmission electron microscopy( TEM) and inductively coupled plasma mass spectrometry( ICP-MS). The catalytic properties of the materials( Pd/AS-SNS) were tested for the Suzuki reactions and exhibited very high activity,recoverability and stability with a wide range of bromotoluene and phenylboronic acid with electron donating and electron-withdrawing groups or without. The recovered catalyst could maintain its original activity even in the eighth cycle under optimized conditions.
Silicon nanosheets were served as supports for palladium nanoparticles which were modified with 3-aminopropyltriethoxysilane,followed by treatment with palladium chloride,and then the reduction with N2 H4·H2 O in ethanol. After vacuum drying,the functionalized nanosheets supported palladium catalysts( Pd/AS-SNS) were obtained. The products were confirmed by transmission electron microscopy( TEM) and inductively coupled plasma mass spectrometry( ICP-MS). The catalytic properties of the materials( Pd/AS-SNS) were tested for the Suzuki reactions and exhibited very high activity,recoverability and stability with a wide range of bromotoluene and phenylboronic acid with electron donating and electron-withdrawing groups or without. The recovered catalyst could maintain its original activity even in the eighth cycle under optimized conditions.
引文
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[13]Tan J J,Chen Y G,Li H M,et al.Suzuki-miyaura crosscoupling reactions of unprotected haloimidazoles[J].J Org Chem,2014,79(18):8871-8876.
[14]Xin Y,Wen G A,Zeng W J,et.al.Hyperbranched oxadiazole-containing polyfluorenes:toward stable blue light PLEDs[J].Macromolecules,2005,38(16):6755-6758.
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[16]Zhang Fei-bao(张飞豹),Zhang Cai-hua(张蔡华),Deng Yuan(邓元),et al.Palladium Supported on SBA-15 as a new recyclable catalyst for the mizoroki-heck reaction(SBA-15负载Pd催化剂的制备及其在Heck反应中的应用研究)[J].Acta Chim Sin(China)(化学学报),2010,68(5):443-448.
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[18]Du Q W,Zhang W,Ma H,et al.Immobilized palladium on surface-modified Fe3O4/Si O2nanoparticles:as a magnetically separable and stable recyclable high-performance catalyst for Suzuki and Heck cross-coupling reactions[J].Tetrahedron,2012,68(6):3577-3584.
[19]Yuan Ding-zhong(袁定重),Chen Bi-bo(陈碧波).Synthesis and characterization of graphene oxide supported schiff base palladium catalyst and its catalytic performance to suzuki reaction(氧化石墨烯负载席夫碱钯催化剂的合成,表征及对Suzuki反应催化性能的研究)[J].Chin J Org Chem(China)(有机化学),2014,34(8):1630-1638.
[20]Changgu L,Xiao D W,Jeffrey W K,et al.Measurement of the elastic properties and intrinsic strength of monolayer graphene[J].Science,2008,321(5887):385-387.
[21]Tetsuya M,Kengo N,Masuhiro M.Formation of singleand double-layer silicon in slit pores[J].Phys Rev B,2008,77(8):081401(1-4).
[22]Cahangirow S,Topsakal M.Universal detector efficiency of a mesoscopic capacitor[J].Phys Rev Lett,2009,102(23):236801(1-4).
[23]Takeda K,Shiraishi K.Electronic structure of siliconoxygen high polymers[J].Sol Sta Commun,1993,85(4):301-305.
[24]Hideyuki N,Takuya M,Masashi H,et al.Soft synthesis of singl-crystal silicon monolayer sheets[J].Angew Chem,2006,45(38):6303-6306.
[25]Yusuke S,Hirotaka O,Takuya M,et al.Synthesis and optical properties of monolayer organosilicon nanosheets[J].J Am Chem Soc,2010,132(17):5946-5947.
[26]a.Basu B,Paul S.An improved preparation of mesoporous silica-supported Pd as sustainable catalysts for phosphine-free Suzuki-Miyaura and Heck coupling reactions[J].Appl Org Chem,2013,27(10):588-594.b.Wang Qing-yun(王清云),Tong Yong-chun(佟永纯),Xu Xin-jian(徐新建),et al.The influence of the stone-wales defect in graphene on the platinum catalyzed dissociation of oxygen(石墨烯中的stone-wales缺陷对铂原子催化解离氧分子的影响)[J].J Mol Catal(China)(分子催化),2016,30(1):80-87.c.Yang Qin(杨琴),Zhou Juan(周娟),Yin Meng-yun(尹梦云),et al.Lysine-graphene oxideasa heterogeneous ligand applied in Cu I-catalyzed C—N coupling reaction(赖氨酸修饰氧化石墨烯固体配体在C—N偶联中的应用研究)[J].J Mol Catal(China)(分子催化),2016,30(2):99-104.d.Ni Jun(倪军),Lup Xiao-fang(罗小芳),Zhan Yong(詹勇),et al.Application and progress of the novel activated carbon in the field of catalysis(新型碳材料在催化领域中的应用及进展)[J].J Mol Catal(China)(分子催化),2016,30(3):282-296.
[27]a.Adam F,Appaturi J N,Iqbal A.The utilization of rice husk silica as a catalyst:Review and recent progress[J].Catal Today,2012,190(1):2-14.b.Pang Shao-feng(庞少峰),Yuan Hang-kong(袁航空),Wu Ya-juan(吴亚娟),et al.Co@N-graphene/C catalyzed oxidative amination of toluene derivatives(Co@N-石墨烯/C催化甲苯衍生物氧化胺化研究)[J].J Mol Catal(China)(分子催化),2017,31(2):105-120.c.Lu Gong-xuan(吕功煊),Tian Bin(田彬).Formation of deuterium and helium during photocatalytic hydrogen generation from water catalyzed by Pt-graphene sensitized with Br-dye under visible light irradiation9溴染料敏化担载Pt石墨烯催化可见光制氢、氘和氦)[J].J Mol Catal(China)(分子催化),2017,31(2):101-104.d.Lu Gong-xuan(吕功煊),Zhang Wen-yan(张文妍).Photocatalytic hydrogen evolution and induced transmutation of potassium to calcium via low-energy nuclear reaction(LENR)driven by visible light(可见光驱动的光催化产氢同时诱导低能核反应嬗变钾为钙)[J].J Mol Catal(China)(分子催化),2017,31(5):401-410.
[28]Hideyuki N,Masahiko I,Hiroshi N.Preparation and structure of novel siloxene nanosheets[J].Chem Commun,2005,23(0):2945-2947.
[29]Hideyuki N,Mitsuru N,Koji N,et al.Preparation of alkyl-modified silicon nanosheets by hydrosilylation of layered polysilane(Si6H6)[J].J Am Chem Soc,2012,134(12):5452-5455.
[30]Zhang F B,Lv S F,Jiang J X,et al.Preparation of siloxene nanosheet-supported palladium as sustainable catalyst for Mizoroki-Heck reaction[J].Appl Org Chem,2014,28(11):826-830.
[2]Shen X,Jones G O,Watson D A,et al.Enantioselective synthesis of axially chiral biaryls by the Pd-catalyzed suzukimiyaura reaction:Substrate scope and quantum mechanical investigations[J].J Am Chem Soc,2010,132(32):11278-11287.
[3]Guo M P(郭孟萍),Zhou Li(周丽),He R(何仁).Study on suzuki reaction for the synthesis of fluorinated liquid crystals catalyzed by P,N coordinated palladium complexes.(P,N配位的环钯配合物催化Suzuki偶联合成含氟液晶化合物的研究)[J].J Mol Catal(China)(分子催化),2006,20(3):203-206.
[4]Suzuki A.Cross-coupling reactions of organoboranes:An easy way to construct C-C bonds(Nobel Lecture)[J].Angew Chem Int Ed,2011,50(30):6722-6737.
[5]Sajith A M,Muralidharan A.Exploration of copper and amine-free sonogashira cross coupling reactions of 2-halo-3-alkyl imidazo[4,5-b]pyridines using tetrabutyl ammonium acetate as an activator under microwave enhanced conditions[J].Tetra Lett,2012,53(39):5206-5210.
[6]Xu Guang-qing(徐广庆),Zhao Qing(赵庆),Tang Wen-jun(汤文军).Development of efficient asymmetric suzuki-miyaura cross-coupling and applications in synthesis(发展高效的不对称Suzuki-Miyaura偶联反应及其合成应用)[J].Chin J Org Chem(China)(有机化学),2014,34(10):1919-1940.
[7]Li Q H,Ding Y,Yang X J.Nickel-catalyzed cross-coupling reaction of alkynyl bromides with Grignard reagents[J].Chin Chem Lett,2014,25(9):1296-1300.
[8]Li Q H,Ding Y,Huang N W.Synthesis and biological activities of dithiocarbamates containing 1,2,3-triazoles group[J].Chin Chem Lett,2014,25(11):1469-1472.
[9]Zhang Hong-ying(张红英),Yan Xue-ming(颜雪明).Synthesis of the functional MCM-41 supported bidentate nitrogen palladium complex and its catalytic properties in the suzuki coupling(功能化MCM-41负载双齿氮钯催化剂的制备及其在Suzuki偶联中的应用)[J].J Mol Catal(China)(分子催化),2013,27(5):400-405.
[10]Miyaura N,Suzuki A.Palladium-catalyzed cross-coupling reactions of organoboron compounds[J].Chem Rev,1995,95(7):2457-2483.
[11]Corbet J P,Mignani G.Selected patented cross-coupling reaction technologies[J].Chem Rev,2006,106(7):2651-2710.
[12]Richardson T I,Clarke C A,Yu K L,et al.Novel 3-aryl indoles as progesterone receptor antagonists for uterine fibroids[J].ACS Med Chem Lett,2011,2(2):148-153.
[13]Tan J J,Chen Y G,Li H M,et al.Suzuki-miyaura crosscoupling reactions of unprotected haloimidazoles[J].J Org Chem,2014,79(18):8871-8876.
[14]Xin Y,Wen G A,Zeng W J,et.al.Hyperbranched oxadiazole-containing polyfluorenes:toward stable blue light PLEDs[J].Macromolecules,2005,38(16):6755-6758.
[15]Schweizer S,Becht J M,Le Drian C.Highly efficient reusable polymer-supported Pd catalysts of general use for the Suzuki reaction[J].Tetrahedron,2010,66(3):765-772.
[16]Zhang Fei-bao(张飞豹),Zhang Cai-hua(张蔡华),Deng Yuan(邓元),et al.Palladium Supported on SBA-15 as a new recyclable catalyst for the mizoroki-heck reaction(SBA-15负载Pd催化剂的制备及其在Heck反应中的应用研究)[J].Acta Chim Sin(China)(化学学报),2010,68(5):443-448.
[17]Estrada G O D,Blanco A L P,da Silva J F M,et al.Pd/Nb2O5:efficient supported palladium heterogeneous catalyst in the production of key intermediates for the synthesis of‘sartans’via the Suzuki reaction[J].Tetra Lett,2012,53(9):1089-1093.
[18]Du Q W,Zhang W,Ma H,et al.Immobilized palladium on surface-modified Fe3O4/Si O2nanoparticles:as a magnetically separable and stable recyclable high-performance catalyst for Suzuki and Heck cross-coupling reactions[J].Tetrahedron,2012,68(6):3577-3584.
[19]Yuan Ding-zhong(袁定重),Chen Bi-bo(陈碧波).Synthesis and characterization of graphene oxide supported schiff base palladium catalyst and its catalytic performance to suzuki reaction(氧化石墨烯负载席夫碱钯催化剂的合成,表征及对Suzuki反应催化性能的研究)[J].Chin J Org Chem(China)(有机化学),2014,34(8):1630-1638.
[20]Changgu L,Xiao D W,Jeffrey W K,et al.Measurement of the elastic properties and intrinsic strength of monolayer graphene[J].Science,2008,321(5887):385-387.
[21]Tetsuya M,Kengo N,Masuhiro M.Formation of singleand double-layer silicon in slit pores[J].Phys Rev B,2008,77(8):081401(1-4).
[22]Cahangirow S,Topsakal M.Universal detector efficiency of a mesoscopic capacitor[J].Phys Rev Lett,2009,102(23):236801(1-4).
[23]Takeda K,Shiraishi K.Electronic structure of siliconoxygen high polymers[J].Sol Sta Commun,1993,85(4):301-305.
[24]Hideyuki N,Takuya M,Masashi H,et al.Soft synthesis of singl-crystal silicon monolayer sheets[J].Angew Chem,2006,45(38):6303-6306.
[25]Yusuke S,Hirotaka O,Takuya M,et al.Synthesis and optical properties of monolayer organosilicon nanosheets[J].J Am Chem Soc,2010,132(17):5946-5947.
[26]a.Basu B,Paul S.An improved preparation of mesoporous silica-supported Pd as sustainable catalysts for phosphine-free Suzuki-Miyaura and Heck coupling reactions[J].Appl Org Chem,2013,27(10):588-594.b.Wang Qing-yun(王清云),Tong Yong-chun(佟永纯),Xu Xin-jian(徐新建),et al.The influence of the stone-wales defect in graphene on the platinum catalyzed dissociation of oxygen(石墨烯中的stone-wales缺陷对铂原子催化解离氧分子的影响)[J].J Mol Catal(China)(分子催化),2016,30(1):80-87.c.Yang Qin(杨琴),Zhou Juan(周娟),Yin Meng-yun(尹梦云),et al.Lysine-graphene oxideasa heterogeneous ligand applied in Cu I-catalyzed C—N coupling reaction(赖氨酸修饰氧化石墨烯固体配体在C—N偶联中的应用研究)[J].J Mol Catal(China)(分子催化),2016,30(2):99-104.d.Ni Jun(倪军),Lup Xiao-fang(罗小芳),Zhan Yong(詹勇),et al.Application and progress of the novel activated carbon in the field of catalysis(新型碳材料在催化领域中的应用及进展)[J].J Mol Catal(China)(分子催化),2016,30(3):282-296.
[27]a.Adam F,Appaturi J N,Iqbal A.The utilization of rice husk silica as a catalyst:Review and recent progress[J].Catal Today,2012,190(1):2-14.b.Pang Shao-feng(庞少峰),Yuan Hang-kong(袁航空),Wu Ya-juan(吴亚娟),et al.Co@N-graphene/C catalyzed oxidative amination of toluene derivatives(Co@N-石墨烯/C催化甲苯衍生物氧化胺化研究)[J].J Mol Catal(China)(分子催化),2017,31(2):105-120.c.Lu Gong-xuan(吕功煊),Tian Bin(田彬).Formation of deuterium and helium during photocatalytic hydrogen generation from water catalyzed by Pt-graphene sensitized with Br-dye under visible light irradiation9溴染料敏化担载Pt石墨烯催化可见光制氢、氘和氦)[J].J Mol Catal(China)(分子催化),2017,31(2):101-104.d.Lu Gong-xuan(吕功煊),Zhang Wen-yan(张文妍).Photocatalytic hydrogen evolution and induced transmutation of potassium to calcium via low-energy nuclear reaction(LENR)driven by visible light(可见光驱动的光催化产氢同时诱导低能核反应嬗变钾为钙)[J].J Mol Catal(China)(分子催化),2017,31(5):401-410.
[28]Hideyuki N,Masahiko I,Hiroshi N.Preparation and structure of novel siloxene nanosheets[J].Chem Commun,2005,23(0):2945-2947.
[29]Hideyuki N,Mitsuru N,Koji N,et al.Preparation of alkyl-modified silicon nanosheets by hydrosilylation of layered polysilane(Si6H6)[J].J Am Chem Soc,2012,134(12):5452-5455.
[30]Zhang F B,Lv S F,Jiang J X,et al.Preparation of siloxene nanosheet-supported palladium as sustainable catalyst for Mizoroki-Heck reaction[J].Appl Org Chem,2014,28(11):826-830.