甲基磺酸镉的结构及催化性能研究
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摘要
以甲基磺酸和碳酸镉为原料,采用普通溶液法制备甲基磺酸镉(Ⅱ),其产物为白色结晶固体。采用红外、核磁、热重、扫描电镜和X射线单晶衍射多种方法对化合物进行表征。结果表明:甲基磺酸镉含有两个结晶水,热稳定性好,属于三斜晶系,■空间群;晶胞参数a=0.4785(5)nm,b=0.6101(5)nm,c=0.8232(5)nm,α=87.137(5)°,β=84.461(5)°,γ=85.614(5)°,V=0.2383(3)nm~3,Z=1。以N1-甲基3,4-二氢嘧啶酮的合成为探针反应,考察了甲基磺酸镉对Biginelli反应的催化性能。在无溶剂、绿色条件下,产品收率达90.1%,重复使用三次后。产品收率仍可以达到80.3%。最后,对甲基磺酸镉连续催化后,催化活性略有下降的原因进行了分析。
Cadmium(Ⅱ)methanesulfonate was prepared from methanesulfonic acid and cadmium carbonate using the common solution method,and the product is white crystalline solid.It was characterized by IR,NMR,TG,SEM and X-ray single crystal diffraction techniques.The results show cadmium methanesulfonate contains two crystal water molecules and has good thermal stability.It is triclinic,belonged to the ■space group with a=0.4785(5)nm,b=0.6101(5)nm,c=0.8232(5)nm,α=87.137(5)°,β=84.461(5)°,γ=85.614(5)°,V=0.2383(3)nm~3,Z=1.The catalytic activity of cadmium methanesulfonate was investigated by using the synthesis of N1-methyl 3,4-dihydropyrimidinone as a probe reaction.The yield of the product reaches 90.1%under solvent-free and green conditions.The yield of the product was as high as 80.3%even if the catalyst was reused after three cycles.At last,the reasons for the slight decrease in catalytic activity after continuous catalysis of cadmium methanesulfonate were analyzed.
Cadmium(Ⅱ)methanesulfonate was prepared from methanesulfonic acid and cadmium carbonate using the common solution method,and the product is white crystalline solid.It was characterized by IR,NMR,TG,SEM and X-ray single crystal diffraction techniques.The results show cadmium methanesulfonate contains two crystal water molecules and has good thermal stability.It is triclinic,belonged to the ■space group with a=0.4785(5)nm,b=0.6101(5)nm,c=0.8232(5)nm,α=87.137(5)°,β=84.461(5)°,γ=85.614(5)°,V=0.2383(3)nm~3,Z=1.The catalytic activity of cadmium methanesulfonate was investigated by using the synthesis of N1-methyl 3,4-dihydropyrimidinone as a probe reaction.The yield of the product reaches 90.1%under solvent-free and green conditions.The yield of the product was as high as 80.3%even if the catalyst was reused after three cycles.At last,the reasons for the slight decrease in catalytic activity after continuous catalysis of cadmium methanesulfonate were analyzed.
引文
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[3]Liu Y C,Romero J R.Electrocatalytic oxidation of beta-dicarbonyl compounds using ceric methanesulphonate as mediator[J].Quím Nova,1998,21(2):144-145.
[4]Low C T J,Walsh F C.The stability of an acidic tin methanesulfonate electrolyte in the presence of a hydroquinone antioxidant[J].Electrochim Acta,2008,53(16):5280-5286.
[5]林燕,江小勇,魏喆良.甲基磺酸盐体系下铜粉浸镀锡工艺的研究[J].表面技术,2014,43(2):89-94.
[6]Aricó E M,Zinner L B,Apostolidis C,et al.Structures of the anhydrous Yb(III)and the hydrated Ce(III),Sm(III)and Tb(III)methanesulfonates[J].J Alloys Compd,1997,249(1-2):111-115.
[7]Aricó E M,Zinner L B,Kanellakopulos B,et al.Structure and properties of hydrated La(III),Nd(III)and Er(III)methanesulfonates[J].J Alloys Compd,2001,323-324(1):39-44.
[8]Moura M D F V D,Matos J D R,Farias R F D.Thermal degradation study of gadolinium and lutetium methanesulfonates[J].Thermochim Acta,2004,414(2):159-166.
[9]Ramírez A,Gómez M L,Guerrero A,et al.Thermal decomposition of Co(II),Cu(II)and Zn(II)methanesulfonates[J].Thermochim Acta,1988,124(2):9-16.
[10]Wang M,Song Z G,Jiang H,et al.Thermal decomposition of metal methanesulfonates in air[J].J Therm Anal Calorim,2009,98(3):801-806.
[11]Ren Y X,Zhou S H,Wang Z X,et al.A series of cadmium(II)complexes with 2-substituted terephthalate building block and N-donor co-ligands:structural diversity and fluorescence properties[J].J Mol Struct,2017,1147:292-299.
[12]彭振山,刘建湘,申晓明,等.两个镉配合物的超分子作用力和催化酯化反应的研究[J].湘潭大学自然科学学报,2009,31(1):77-81.
[13]Mi L W,Hou H W,Song Z Y,et al.Polymeric zinc ferrocenyl zulfonate as a molecular aspirator for the removal of toxic metal ions[J].Chem Eur J,2008,14(6):1814-1821.
[14]Fernando I R,Jianrattanasawat S,Daskalakis N,et al.Mapping the supramolecular chemistry of pyrazole-4-sulfonate:layered inorganic–organic networks with Zn2+,Cd2+,Ag+,Na+ and NH4+,and their use in copper anticorrosion protective films[J].Cryst EngComm,2012,14(3):908-919.
[15]Salehi H,Guo Q X.Efficient magnesium bromide catalyzed one-pot synthesis of substituted 1,2,3,4-tetrahydropyrimidin-2-ones under solvent-free conditions[J].Chin J Chem,2005,23(1):91-97.
[16]Paraskar A S,Dewkar G K,Sudalai A.Cu(OTf)2:a reusable catalyst for high-yield synthesis of 3,4-dihydropyrimidin-2(1H)-ones[J].Tetrahedron Lett,2003,44(16):3305-3308.
[17]Aridoss G,Jeong Y T.A convenient one-pot Biginelli reaction catalyzed by Y(OAc)3:an improved protocol for the synthesis of 3,4-dihydropyrimidin-2(1H)-ones and their sulfur analogues[J].Bull Korean Chem Soc,2010,31(4):863-868.