阅读说明：本技术 一种共轭二芳香配体及其制备方法 (Conjugated bi-aromatic ligand and preparation method thereof ) 是由 张冬冬 于 2020-05-19 设计创作，主要内容包括：本发明提供了一种共轭二芳香配体及其制备方法,通式如式(Ⅰ)所示<Image he="76" wi="51" file="286297DEST_PATH_IMAGE002.GIF" imgContent="drawing" imgFormat="GIF" orientation="portrait" inline="no"></Image>,其中Ar基团为苯环、单取代或多取代的苯环、吡啶环、单取代的吡啶环,苯环或吡啶环上的取代基为CH<Sub>3</Sub>、卤素、OH、NO<Sub>2</Sub>或CF<Sub>3</Sub>。Ar为吡啶环时,制备方法如下：(1)4-醛基吡啶在冰乙酸中与三氯化钛的盐酸水溶液反应得到邻二醇的中间体化合物1；(2)化合物1在浓硫酸与发烟硝酸的混酸中反应得到邻二硝酸酯化合物2；(3)化合物2在无水乙醇中反应得到共轭二吡啶配体化合物3。本发明原料成本低廉,合成步骤少、操作简单、提取纯化方便、收率高。该化合物引入了两个柔性乙基基团,增加了溶解性,更有利于和金属配位,其在金属有机配合物方面有着巨大的应用前景。(The invention provides a conjugated biaromatic ligand and a preparation method thereof, wherein the general formula is shown as formula (I) Wherein Ar group is benzene ring, mono-substituted or poly-substituted benzene ring, pyridine ring or mono-substituted pyridine ring, and the substituent on the benzene ring or the pyridine ring is CH 3 Halogen, OH, NO 2 Or CF 3 . When Ar is pyridine ring, the preparation method is as follows: (1) 4-aldehyde pyridine reacts with hydrochloric acid aqueous solution of titanium trichloride in glacial acetic acid to obtain an intermediate compound 1 of vicinal diol; (2) reacting the compound 1 in a mixed acid of concentrated sulfuric acid and fuming nitric acid to obtain a ortho-dinitrate compound 2; (3) and reacting the compound 2 in absolute ethyl alcohol to obtain a conjugated bipyridine ligand compound 3. The method has the advantages of low cost of raw materials, few synthesis steps, simple operation, convenient extraction and purification and high yield. The compound introduces two flexible ethyl groups, increases the solubility, is more favorable for coordination with metal, and can be used in metal organic fieldHas great application prospect in the aspect of the complex.)

1. The conjugated diaryl ligand is characterized by having a general formula shown in a formula (I), wherein an Ar group is a benzene ring, a mono-substituted or multi-substituted benzene ring, a pyridine ring or a mono-substituted pyridine ring, and a substituent on the benzene ring or the pyridine ring is CH₃Halogen, OH, NO₂Or CF₃，

（Ⅰ）。

2. The conjugated biaromatic ligand of claim 1 wherein said Ar group is a benzene ring, a mono-or poly-substituted benzene ring, or a pyridine ring.

3. The method of claim 2, wherein when the Ar group is a pyridine ring, the method comprises the steps of:

step 1): 4-aldehyde pyridine reacts with hydrochloric acid aqueous solution of titanium trichloride in glacial acetic acid to obtain an intermediate of vicinal diol such as a compound 1;

step 2): reacting the compound 1 in a mixed acid of concentrated sulfuric acid and fuming nitric acid to obtain ortho-dinitrate such as a compound 2;

step 3): reacting the compound 2 in absolute ethyl alcohol to obtain a conjugated bipyridine ligand such as a compound 3;

the synthetic route is as follows:

。

4. the method of claim 3, wherein the step (1) is performed under a nitrogen atmosphere.

5. The method of claim 3, wherein the volume ratio of concentrated sulfuric acid to fuming nitric acid in step (2) is 3: 4.

6. The method of claim 3, wherein the reaction temperature in the step (2) is 40 ℃ and the reaction time is overnight.

7. The method for preparing a conjugated bis-aromatic ligand according to claim 3, wherein in the step (3), the product of the reaction of the compound 2 in the absolute ethanol is purified by passing through a 200-300 mesh silica gel column to obtain the compound 3.

Technical Field

The invention belongs to the technical field of organic synthesis, and particularly relates to a conjugated bi-aromatic ligand and a preparation method thereof.

Background

With the continuous development of scientific technology and the continuous progress of society, the metal organic complex is widely concerned by more and more researchers as a novel multifunctional material. The multifunctional material is formed by self-assembly of metal ions or metal clusters and organic ligands through coordination, and relates to multiple disciplines such as organic chemistry, inorganic chemistry, coordination chemistry, physical chemistry, crystallography, material chemistry, supermolecular chemistry, biochemistry, topology and the like. Compared with other materials, the metal organic complex has the characteristics of small density, high specific surface area, mild preparation conditions and the like. More interestingly, by designing organic ligands with different structures, sizes and functions, the metal-organic complexes can be conveniently structurally modified. Generally, the metal organic complex material has a microporous structure (less than 2 nm), and has wide application in aspects of gas capture and storage, catalysis, fluorescence detection, separation and the like.

The conjugated skeleton of the molecule plays an important role in the optical performance of the material, and the molecule with a good conjugated skeleton can effectively improve the conjugated performance of the system, so that the optical nonlinear polarizability of the material is increased.

The conjugated biaromatic ligand molecule synthesized by the method is favorable for electron mobility due to the superstrong pi electron conjugation effect existing in the double bond of olefin and pyridine rings on two sides of the conjugated biaromatic ligand molecule, and has great application in the aspect of metal organic complexes.

Disclosure of Invention

In order to solve the problems of the prior art, the invention aims to provide an aromatic derivative mononitrate and a preparation method thereof.

In order to achieve the purpose, the invention provides the following technical scheme:

a conjugated biaromatic ligand has a general formula shown in formula (I), wherein Ar group is a benzene ring, a mono-substituted or multi-substituted benzene ring, a pyridine ring or a mono-substituted pyridine ring, and a substituent on the benzene ring or the pyridine ring is CH₃Halogen, OH, NO₂Or CF₃，

（Ⅰ）

Preferably, the Ar group is a pyridine ring.

Further, when the Ar group is a pyridine ring, the preparation method of the conjugated biaromatic ligand comprises the following steps:

step 1): 4-aldehyde pyridine reacts with hydrochloric acid aqueous solution of titanium trichloride in glacial acetic acid to obtain an intermediate of vicinal diol such as a compound 1;

step 2): reacting the compound 1 in a mixed acid of concentrated sulfuric acid and fuming nitric acid to obtain ortho-dinitrate such as a compound 2;

step 3): reacting the compound 2 in absolute ethyl alcohol to obtain a conjugated bipyridine ligand such as a compound 3;

the synthetic route is as follows:

。

further, the step (1) is carried out in a nitrogen environment.

Further, the volume ratio of the concentrated sulfuric acid to the fuming nitric acid in the step (2) is 3: 4.

Further, the reaction temperature of the step (2) is 40 ℃, and the reaction time is overnight.

Further, in the step (3), a product obtained by reacting the compound 2 in absolute ethyl alcohol is purified by passing through a 200-300-mesh silica gel column to obtain the compound 3.

Has the advantages that: the invention provides a conjugated biaromatic ligand and a preparation method thereof, the cost of raw materials adopted in the preparation of the conjugated biaromatic ligand is low, the steps of the synthetic process are few, the operation is simple, the extraction and purification are convenient, the yield of the final conjugated biaromatic ligand is higher, and the yield of each step is more than 75%. In addition, two flexible ethyl groups are introduced into the conjugated biaromatic ligand, so that the solubility is increased, and the coordination with metal is facilitated. The invention also provides a new method for preparing the new compound conjugated bi-aromatic ligand, and the obtained product has great application prospect in the aspect of metal organic complexes.

Drawings

FIG. 1 is a NMR spectrum of Compound 1.

FIG. 2 is a NMR spectrum of Compound 2.

Detailed Description

The present invention is further described below with reference to specific examples, which are only exemplary and do not limit the scope of the present invention in any way. It will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the spirit and scope of the invention, and that such changes and modifications may be made without departing from the spirit and scope of the invention.