CN113861036B - 一种乙二胺高氯酸铜配合物的制备及用途 - Google Patents

一种乙二胺高氯酸铜配合物的制备及用途 Download PDF

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CN113861036B
CN113861036B CN202111315588.6A CN202111315588A CN113861036B CN 113861036 B CN113861036 B CN 113861036B CN 202111315588 A CN202111315588 A CN 202111315588A CN 113861036 B CN113861036 B CN 113861036B
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ethylenediamine
reaction
copper perchlorate
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CN113861036A (zh
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罗梅
卡西姆
阿米尔
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Hefei University of Technology
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
    • B01J31/1805—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing nitrogen
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C253/00—Preparation of carboxylic acid nitriles
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D239/00—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings
    • C07D239/02—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings
    • C07D239/24—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members
    • C07D239/28—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, directly attached to ring carbon atoms
    • C07D239/32—One oxygen, sulfur or nitrogen atom
    • C07D239/34—One oxygen atom
    • C07D239/36—One oxygen atom as doubly bound oxygen atom or as unsubstituted hydroxy radical
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
    • B01J2231/30—Addition reactions at carbon centres, i.e. to either C-C or C-X multiple bonds
    • B01J2231/34—Other additions, e.g. Monsanto-type carbonylations, addition to 1,2-C=X or 1,2-C-X triplebonds, additions to 1,4-C=C-C=X or 1,4-C=-C-X triple bonds with X, e.g. O, S, NH/N
    • B01J2231/341—1,2-additions, e.g. aldol or Knoevenagel condensations
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/10—Complexes comprising metals of Group I (IA or IB) as the central metal
    • B01J2531/16—Copper
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    • C07—ORGANIC CHEMISTRY
    • C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
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Abstract

一种乙二胺高氯酸铜配合物(I)，其结构式如下：该乙二胺高氯酸铜配合物(I)的合成方法，是称取0.710g乙二胺放入100mL圆底烧瓶中，加入40mL无水乙醇后，搅拌使其溶解；将2.964g六水合高氯酸铜加入上述溶液，加热回流48h；反应结束后，热过滤反应溶液，滤液自然挥发，数天后有晶体析出；将晶体用石油醚和正己烷冲洗3次，真空干燥30min，得目标晶体化合物I。该乙二胺高氯酸铜配合物(I)的用途，其作为催化剂在二苯甲酮亚胺的的腈硅化反应及色酮‑3‑甲醛的鲁卡特反应中显示了较好的催化效果，其转化率均大于99％。

Description

一种乙二胺高氯酸铜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，特别涉及一种铜化合物及其制备方法，确切地说是一种配合物的制备及合成方法。
二、背景技术
铜配合物是重要的催化剂和医药化工产品，其作为催化剂在二乙基锌与苯甲醛对映选择性加成反应等反应中有较好的催化效果。【1-5】
参考文献：
1.Asymmetric hydrogenation catalyzed by bis(dimethylglyoximato)cobalt(II)-achiral base complex and chiral amino alcohol conjugatedsystems.Oxidoreductase model with enantioselectivity，Ohgo,Yoshiaki；Natori,Yukikazu；Takeuchi,Seiji；Yoshimura,Juji,Chemistry Letters(1974),(11),1327-30.
Synthesis,structure and acid-base properties of cobalt(III)complexeswith aminoalcohols tepanenko,O.N.；Reiter,
2.L.G.Ukrainskii Khimicheskii Zhurnal(Russian Edition),(1992),58(12),1047-54.
3.Cobalt(III)mono-and trinuclear complexes with O,N-chelatingaminoalcohols apanadze,T.Sh.；Gulya,A.P.；Novotortsev,V.M.；Ellert,O.G.；Shcherbakov,V.M.；Kokunov,Yu.V.；Bushaev,Yu.A.Koordinatsionnaya Khimiya(1991),17(7),934-40.
4.Magnetic properties of cobalt complexes with amino alcohols,Evreev,V.N.；Bogdanov,A.P.13Vses.Chugaev.Soveshch.po Khimii Kompleks.Soedin.,1978(1978),137.
5.Synthesis,stereochemistry,and reactions of cobalt(III)complexeswith amino alcohol ligands Okamoto,Martha S.No Corporate Source dataavailable|(1974),146.
6.Synthesis and properties of isomeric tris(N-[2-hydroxyethyl]ethylenediamine)cobalt(III)and tris(N-[2-hydroxypropyl]ethylenediamine)cobalt(III)chlorides,arpeiskaya,E.I.；Kukushkin,Yu.N.；Trofimov,V.A.；Yakovlev,I.P.,Zhurnal Neorganicheskoi Khimii(1971),16(7),1960-4。
三、发明内容
本发明旨在提供含配合物，所要解决的技术问题是一步合成得到目标产物。
本发明所称的铜配合物是由乙二胺与六水高氯酸铜制备的由以下化学式所示的配合物：
化学名称：双乙二胺高氯酸铜配合物,简称配合物(I)。
该配合物在苯甲醛的亨利反应、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％及99％。
本合成方法包括合成和分离,其合成方法是称取0.710g乙二胺放入100mL圆底烧瓶中，加入40mL无水乙醇后，搅拌使其溶解；将2.964g六水高氯酸铜加入上述溶液，加热回流48h；反应结束后，热过滤反应溶液，滤液自然挥发，数天后有蓝色晶体析出；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。
合成反应如下：
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乙二胺与六水合高氯酸铜的作用，一步形成双乙二胺高氯酸铜配合物。
四、附图说明
图1是双乙二胺高氯酸铜配合物的单晶X-衍射图。
五、具体实施方式
1.铜配合物的制备：
称取0.710g乙二胺放入100mL圆底烧瓶中，加入40mL无水乙醇后，搅拌使其溶解；将2.964g六水合高氯酸铜加入上述溶液，加热回流48h；反应结束后，热过滤反应溶液，滤液自然挥发，数天后有晶体析出；将晶体用石油醚和正己烷冲洗3次，真空干燥30min，得目标产物，产率：80％，熔点：280-282℃，IR(KBr；ν,cm–1):3337,3281,2988,1590,1467,1321,1280,1108,1066,1021,919,884,701,620；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：
晶体典型的键长数据：
晶体典型的键角数据
2.硅腈化反应应用
硅腈化反应也是一种常用的有机合成反应，是合成手性腈醇一种重要方法。在有机医药中间体方面也有广泛的应用。
实验的反应方程式：
称取0.1mmol配合物，置于25mL小烧瓶中，加入2mL无水甲醇，再向溶液中加入0.1mL二苯甲酮亚胺和0.3mL三甲基硅腈，常温下搅拌24h，进行1HNMR检测。催化转化率:>99％；1H NMR(600MHz,CDCl3,27℃)δ7.23–7.59(m,10H),4.10(s,2H)。
3.鲁卡特(Leuckart)反应应用
称取0.2mmol配合物，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>99％；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 (1)

1.一种有如下结构式(I)所示的，而且具备如下晶胞参数的乙二胺高氯酸铜配合物(Ⅰ)的用途，其作为催化剂在二苯甲酮亚胺的的腈硅化反应及色酮-3-甲醛的鲁卡特反应中显示了较好的催化效果，其转化率均大于99％，
乙二胺高氯酸铜配合物晶体的晶胞参数如下：在293K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，以ω-θ扫描方式收集衍射数据，其特征在于：该晶体属三斜晶系，P-1，晶胞参数：/> alpha＝75.313°；/>beta＝79.154°；/>gamma＝77.952°。
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