阅读说明：本技术 一种乙二胺高氯酸铜配合物的制备及用途 (Preparation and application of ethylenediamine copper perchlorate complex ) 是由 罗梅 卡西姆 阿米尔 于 2021-11-08 设计创作，主要内容包括：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％。(An ethylenediamine copper perchlorate complex (I) has a structural formula as follows: the synthesis method of the ethylenediamine copper perchlorate complex (I) comprises the steps of weighing 0.710g of ethylenediamine, putting the ethylenediamine into a 100mL round-bottom flask, adding 40mL of absolute ethyl alcohol, and stirring to dissolve the ethylenediamine copper perchlorate complex; 2.964g of copper perchlorate hexahydrate is added into the solution, and heating reflux is carried out for 48 hours; after the reaction is finished, heat is appliedFiltering the reaction solution, naturally volatilizing the filtrate, and separating out crystals after several days; and washing the crystal with petroleum ether and n-hexane for 3 times, and vacuum drying for 30min to obtain the target crystal compound I. The application of the ethylenediamine copper perchlorate complex (I) as a catalyst shows better catalytic effect in nitrile silicification reaction of benzophenone imine and Lukat reaction of chromone-3-formaldehyde, and the conversion rate of the ethylenediamine copper perchlorate complex is more than 99%.)

1. An ethylenediamine copper perchlorate complex (I) has a structural formula as follows:

2. the crystal of ethylenediamine copper perchlorate complex according to claim 1, which is monochromatized by MoK alpha rays with a graphite monochromator on an Oxford X-ray single crystal diffractometer at a temperature of 293(2) KCollecting diffraction data in an omega-theta scan, characterized by: the crystal belongs to a triclinic system, P-1, unit cell parameters:alpha＝75..313(4)°.；beta＝79.154(5)°；gamma＝77.952(4)°。

3. the method for synthesizing ethylenediamine copper perchlorate complex (I) according to claim 1, which comprises the steps of synthesizing and isolating, wherein 0.710g of ethylenediamine is weighed and placed in a 100mL round-bottom flask, 40mL of absolute ethanol is added, and then stirring is carried out to dissolve the ethylenediamine copper perchlorate complex (I); 2.964g of copper perchlorate hexahydrate is added into the solution, and heating reflux is carried out for 48 hours; after the reaction is finished, filtering the reaction solution by heat, naturally volatilizing the filtrate, and separating out crystals after several days; and washing the crystal with petroleum ether and n-hexane for 3 times, and vacuum drying for 30min to obtain the target crystal compound I.

4. The use of the ethylenediamine copper perchlorate complex (I) as defined in claim 1 as a catalyst shows better catalytic effect in nitrile silicification of benzophenone imine and in the lucart reaction of chromone-3-formaldehyde, with conversion rates of more than 99%.

One, the technical field

The invention relates to a new compound and a preparation method thereof, in particular to a copper compound and a preparation method thereof, and specifically relates to a preparation method and a synthesis method of a complex.

Second, background Art

The copper complex is an important catalyst and a pharmaceutical chemical product, and has a good catalytic effect when used as a catalyst in reactions such as enantioselective addition reaction of diethyl zinc and benzaldehyde. [ 1-5 ]

Reference documents:

1.Asymmetric hydrogenation catalyzed by bis(dimethylglyoximato)cobalt(II)-achiral base complex and chiral amino alcohol conjugated systems.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)complexes with 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-chelating aminoalcohols 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)complexes with amino alcohol ligands Okamoto,Martha S.No Corporate Source data available|(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。

third, the invention

The invention aims to provide a complex, and aims to solve the technical problem of obtaining a target product by one-step synthesis.

The copper complex is prepared from ethylenediamine and copper perchlorate hexahydrate and is shown by the following chemical formula:

chemical name: the complex of bis (ethylenediamine) and copper perchlorate is called complex (I) for short.

The complex shows certain catalytic performance in Henry reaction of benzaldehyde, nitrile silicification reaction of benzophenone imine and Lukat reaction of chromone-3-formaldehyde, and the conversion rates of the complex respectively reach 99%, 99% and 99%.

The synthesis method comprises synthesis and separation, and comprises the steps of weighing 0.710g of ethylenediamine, putting the ethylenediamine into a 100mL round-bottom flask, adding 40mL of absolute ethyl alcohol, and stirring to dissolve the ethylenediamine; 2.964g of copper perchlorate hexahydrate is added into the solution, and heating reflux is carried out for 48 hours; after the reaction is finished, filtering the reaction solution by heat, naturally volatilizing the filtrate, and separating out blue crystals after several days; and washing the crystal with petroleum ether and n-hexane for 3 times, and vacuum drying for 30min to obtain the target product.

The synthesis reaction is as follows:

the synthesis method can obtain the target product in one step, and has simple process and convenient operation.

The reaction mechanism of the reaction is presumed to be the action of two molecules of ethylenediamine and the hexahydrated copper perchlorate to form the bisethylenediamine copper perchlorate complex in one step.

Description of the drawings

FIG. 1 is a single crystal X-ray diffraction pattern of copper bisethylenediamine perchlorate complex.

Fifth, detailed description of the invention

1. Preparation of copper complex:

weighing 0.710g of ethylenediamine, putting the ethylenediamine into a 100mL round-bottom flask, adding 40mL of absolute ethyl alcohol, and stirring to dissolve the ethylenediamine; 2.964g of copper perchlorate hexahydrate is added into the solution, and heating reflux is carried out for 48 hours; after the reaction is finished, filtering the reaction solution by heat, naturally volatilizing the filtrate, and separating out crystals after several days; washing the crystal with petroleum ether and n-hexane for 3 times, and vacuum drying for 30min to obtain a target product with yield: 80%, melting point: 280 ℃ and 282 ℃ and IR (KBr; v, cm)^–1) 3337,3281,2988,1590,1467,1321,1280,1108,1066,1021,919,884,701,620; elemental analysis: [ C ]₄H₁₆Cl₂CuN₄O₈]The theoretical value is as follows: calcd.,%: C, 12.56; h, 4.18; n, 14.63; test values are: found,%: C, 12.98; h, 4.332; n, 15.05;

crystal data for compound:

typical bond length data for crystals:

typical bond angle data for crystals

2. Application of silicon cyanation reaction

The silicon cyanation reaction is also a commonly used organic synthesis reaction, and is an important method for synthesizing chiral nitrile alcohol. Also has wide application in the aspect of organic medical intermediates.

Reaction equation for the experiment:

weighing 0.1mmol of complex, placing in a 25mL small flask, adding 2mL of anhydrous methanol, adding 0.1mL of benzophenone imine and 0.3mL of trimethylsilonitrile into the solution, stirring at normal temperature for 24h, and carrying out¹And (4) HNMR detection. Catalytic conversion rate:>99％；¹H NMR(600MHz,CDCl₃,27℃)δ7.23–7.59(m,10H),4.10(s,2H)。

3. lucate (Leuckart) reaction application

0.2mmol of complex is weighed, placed in a 25mL flask, 5mL of chlorobenzene is added, 0.0841g of chromone-3-formaldehyde and 0.2571g of ammonium formate are added to the solution, and the mixture is refluxed and stirred for 24 hours¹And (4) HNMR detection. Catalytic conversion rate>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)。