CN114539325A - 一种苯并三唑类钴配合物的制备及用途 - Google Patents

一种苯并三唑类钴配合物的制备及用途 Download PDF

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CN114539325A
CN114539325A CN202210259348.7A CN202210259348A CN114539325A CN 114539325 A CN114539325 A CN 114539325A CN 202210259348 A CN202210259348 A CN 202210259348A CN 114539325 A CN114539325 A CN 114539325A
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crystal
benzotriazole
cobalt complex
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罗梅
卡西姆
阿米尔
牛峰
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Anhui Tianniu Biotechnology Co ltd
Hefei University of Technology
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Hefei University of Technology
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Abstract

一种苯并三唑类钴配合物(I)的制备，其结构式如下：
Figure DDA0003550154330000011
该苯并三唑类钴配合物(I)晶体的合成方法，所述的合成是称取Co(NO3)2·6H2O 2.90g溶解在无水甲醇溶液50ml溶液中，再加入配体三唑类化合物0.7200g,回流反应24小时后，热过滤反应溶液,并加入少量DMF溶剂溶解，数天后有晶体析出；将晶体用石油醚和正己烷冲洗3次，真空干燥30min，得目标产物,数天后有晶体析出；将晶体用石油醚和正己烷冲洗3次，真空干燥30min，得目标产物；该苯并三唑类钴配合物(I)晶体的用途，其作为催化剂在色酮‑3‑甲醛的鲁卡特反应中显示了较好的催化效果，其转化率为58％。

Description

一种苯并三唑类钴配合物的制备及用途
一、技术领域
本发明涉及一种新化合物及其制备方法，特别涉及一种钴化合物及其制备方法，确切地说是一种钴配合物的制备及合成方法。
二、背景技术
钴配合物是重要的催化剂和医药化工产品.其合成方法及用途见参考文献【1-3】
1.Kalalbandi VKA,Seetharamappa J.Synthesis,Characterization,CrystalStudies of (E)-3-(3-(4-Fluorophenyl)-1-isopropyl-1H-indol-2-yl)Acrylaldehyde.Cryst Struct Theory Appl.2013；02(04):148-154.doi:10.4236/csta.2013.24020
2.Shivankar VS,Vaidya RB,Dharwadkar SR,Thakkar N V.Synthesis,Characterization,and Biological Activity of Mixed Ligand Co(II)Complexes of8-Hydroxyquinoline and Some Amino Acids.Synth React Inorg Met Chem.2003；33(9):1597-1622.doi:10.1081/SIM-120025443
3.SalamaMM,Ahmed SG,Hassan SS.Synthesis,Characterizations,Biological,andMolecular Docking Studies ofSome AminoAcid SchiffBases with Their Cobalt(II)Complexes.Adv Biol Chem.2017；07(05):182-194.doi:10.4236/abc.2017.75013
三、发明内容
本发明旨在提供含钴的配合物，所要解决的技术问题是一步合成得到目标产物。
本发明所称的钴配合物是由制备的由以下化学式所示的配合物：
Figure BDA0003550154310000011
化学名称：含两分子氮，氮二甲基甲酰胺结晶的苯并三唑类钴配合物,简称配合物(I)。
该配合物在二苯甲酮亚胺的腈硅化反应和色酮-3-甲醛的鲁卡特反应中显示了一定的催化性能，其转化率分别达99％,99％。
本合成方法包括合成和分离,其合成方法是称取Co(NO3)2·6H2O(2.90g,0.0100mmol)溶解在无水甲醇溶液50ml溶液中，再加入配体三唑类化合物(0.7200g,0.0020mmol)回流反应24小时后，热过滤反应溶液，滤液自然挥发，数天后有晶体析出；将晶体用石油醚和dandan冲洗3次，真空干燥30min，得目标产物。其合成反应如下：
Figure BDA0003550154310000021
本合成方法一步得到目标产物，工艺简单，操作方便。
该反应的反应机理可推测为两分子的配体三唑类化合物，在无水甲醇分子的作用下与六水合硝酸钴作用，一步形成目标配合物晶体。
四、附图说明
图1是含氮，氮二甲基甲酰胺结晶的苯并三唑类钴配合物的单晶X-衍射图。
五、具体实施方式
1.钴配合物的制备：
称取Co(NO3)2·6H2O(2.90g,0.0100mmol)溶解在无水甲醇溶液50ml溶液中，再加入配体三唑类化合物(0.7200g,0.0020mmol)回流反应24小时后，热过滤反应溶液，滤液自然挥发，并加入少量DMF溶剂溶解，数天后有晶体析出；将晶体用石油醚和正己烷冲洗3次，真空干燥30min，得目标产物,产率：85％；m.p 115-120℃，IR(KBr；ν,cm–1):3397,2955,1651,1559,1478,1437,1387,1360,1248,1202,1003,1048,937,845,834,805,752,708,670,638,587.The yield was 87％,m.p.115–120℃.1H NMR(600MHz,cdcl3)δ8.02–7.99(s,1H),3.54–3.51(s,2H),3.49–3.46(s,3H),3.44–3.41(s,4H),3.36–3.33(s,2H),2.99–2.96(s,2H),2.94–2.91(s,4H),2.90–2.87(s,5H),2.85–2.82(s,5H),2.82–2.79(s,5H),2.75–2.72(s,3H),2.63–2.60(s,1H),1.31–1.28(s,1H).元素分析：[C4H16Cl2CuN4O8]，理论值：anal.calcd.,％:C,12.56；H,4.18；N,14.63；测试值：Found,％:C,12.98；H,4.332；N,15.05；
化合物的晶体数据：
Figure BDA0003550154310000031
晶体典型的键长数据：
Figure BDA0003550154310000032
Figure BDA0003550154310000041
Figure BDA0003550154310000051
晶体典型的键角数据
Figure BDA0003550154310000052
Figure BDA0003550154310000061
Figure BDA0003550154310000071
2.鲁卡特反应应用
Figure BDA0003550154310000072
称取0.2mmol晶体合物，置于25mL小烧瓶中，加入5mL氯苯，再向溶液中加入0.0841g色酮-3-甲醛和0.2571g的甲酸铵，回流搅拌24h，进行1HNMR检测。催化转化率:58％；1H NMR(600MHz,298K,CDCl3 and DMSO)δ10.6(s,1H,OH),9.32(s,1H),9.0(s,2H),7.48-7.49(m,2H),6.96-6.99(m,2H)。

Claims (4)

1.一种苯并三唑类钴配合物(I)的制备，其结构式如下：
Figure FDA0003550154300000011
2.由权利要求1所述的苯并三唑类钴配合物(I)晶体，在293(2)K温度下，牛津X-射线单晶衍射仪上，用经石墨单色器单色化的MoKα射线
Figure FDA0003550154300000012
以ω-θ扫描方式收集衍射数据，其特征在于：该晶体属斜方晶系，空间群，P121/c1；晶胞参数
Figure FDA0003550154300000013
alpha＝90°；
Figure FDA0003550154300000014
beta＝105.7200(10)°。
Figure FDA0003550154300000015
gamma＝90°。
3.由权利要求1所述的该苯并三唑类钴配合物(I)晶体的合成方法，所述的合成是包括合成和分离,其合成方法是称取Co(NO3)2·6H2O 2.90g溶解在无水甲醇溶液50ml溶液中，再加入配体三唑类化合物0.7200g,回流反应24小时后，热过滤反应溶液,并加入少量DMF溶剂溶解，数天后有晶体析出；将晶体用石油醚和正己烷冲洗3次，真空干燥30min，得目标产物,数天后有晶体析出；将晶体用石油醚和正己烷冲洗3次，真空干燥30min，得目标产物。
4.由权利要求1所述的该苯并三唑类钴配合物(I)晶体的用途，其作为催化剂在色酮-3-甲醛的鲁卡特反应中显示了较好的催化效果，其转化率为58％。
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Citations (6)

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US20030232717A1 (en) * 2002-04-12 2003-12-18 Symyx Technologies, Inc. Ethylene-styrene copolymers and phenol-triazole type complexes, catalysts, and processes for polymerizing
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WO2006000544A2 (en) * 2004-06-28 2006-01-05 Ciba Specialty Chemicals Holding Inc. Electroluminescent metal complexes with triazoles and benzotriazoles
US20090095642A1 (en) * 2001-05-11 2009-04-16 Abbott Diabetes Care Inc. Transition metal complexes with pyridyl-imidazole ligands
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Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB796738A (en) * 1954-09-28 1958-06-18 Bayer Ag Monoazo dyestuffs of the benztriazole series and metal complexes thereof
US20090095642A1 (en) * 2001-05-11 2009-04-16 Abbott Diabetes Care Inc. Transition metal complexes with pyridyl-imidazole ligands
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Title
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