CN110803998B - A kind of method for photocatalytic preparation of asymmetric azobenzene and azobenzene oxide compounds - Google Patents

A kind of method for photocatalytic preparation of asymmetric azobenzene and azobenzene oxide compounds Download PDF

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CN110803998B
CN110803998B CN201911100238.0A CN201911100238A CN110803998B CN 110803998 B CN110803998 B CN 110803998B CN 201911100238 A CN201911100238 A CN 201911100238A CN 110803998 B CN110803998 B CN 110803998B
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张东升
苏韧
乔玮
刘悟雯
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Abstract

本发明涉及一种光催化制备不对称偶氮苯和氧化偶氮苯类化合物的方法，通过光催化剂，在光照、惰性气体条件下使芳香硝基化合物与芳香氨基化合物反应得到式I所示的不对称偶氮苯类化合物和式II所示的不对称氧化偶氮苯类化合物，

Figure DDA0002269636700000011
Figure DDA0002269636700000012
可以用于代替现有成熟的有机合成工艺，条件温和、选择性高、具有普适性、适合于工业化生产。

Figure 201911100238

The invention relates to a method for preparing asymmetric azobenzene and azobenzene oxide compounds by photocatalysis. Through the photocatalyst, under the conditions of illumination and inert gas, an aromatic nitro compound and an aromatic amino compound are reacted to obtain the compound shown in formula I. Asymmetric azobenzene compounds and asymmetric azobenzene oxide compounds represented by formula II,

Figure DDA0002269636700000011
Figure DDA0002269636700000012
It can be used to replace the existing mature organic synthesis process, with mild conditions, high selectivity, universality and suitability for industrial production.

Figure 201911100238

Description

一种光催化制备不对称偶氮苯和氧化偶氮苯类化合物的方法A kind of method for photocatalytic preparation of asymmetric azobenzene and azobenzene oxide compounds

技术领域technical field

本发明属于光催化不对称合成技术领域，具体涉及一种光催化制备不对称偶氮苯和氧化偶氮苯类化合物的方法。The invention belongs to the technical field of photocatalytic asymmetric synthesis, and in particular relates to a method for preparing asymmetric azobenzene and azobenzene oxide compounds by photocatalysis.

背景技术Background technique

光催化技术是利用太阳能获得清洁能源的理想途径之一。近年来，光催化有机合成技术由于其反应条件温和、无需使用额外氧化还原剂及选择性可控等优点，为合成多种高附加值化学品提供了绿色经济的技术路线。Photocatalytic technology is one of the ideal ways to use solar energy to obtain clean energy. In recent years, photocatalytic organic synthesis technology has provided a green and economical technical route for the synthesis of a variety of high value-added chemicals due to its mild reaction conditions, no need for additional redox agents, and controllable selectivity.

偶氮苯和氧化偶氮苯是工业上重要的原材料，作为有机合成中间体，在染料合成、生物医药、电子液晶材料等行业中有着广泛的应用。传统合成不对产偶氮苯和氧化偶氮苯的重氮化过程中产生的重氮盐化合物是非常不稳定的，反应过程十分危险容易发生爆炸。中国专利(申请号：201410499441.0)公开了一种不对称芳香偶氮的制备方法。该方法以芳香肼和卤代芳烃为原料，得到不对称芳香偶氮化合物。虽然该方法避免了重氮化步骤，降低了反应危险性，但是芳香肼类化合物受热易分解并放出有毒的氧化氮烟气，并且该方法原子利用率不高、不能选择性调控偶氮苯和氧化偶氮苯合成等缺陷。Azobenzene and azobenzene oxide are important raw materials in industry. As organic synthesis intermediates, they are widely used in dye synthesis, biomedicine, electronic liquid crystal materials and other industries. The traditional synthesis does not produce the diazonium salt compound produced in the diazotization process of azobenzene and azobenzene oxide, which is very unstable, and the reaction process is very dangerous and prone to explosion. Chinese patent (application number: 201410499441.0) discloses a preparation method of asymmetric aromatic azo. The method uses aromatic hydrazine and halogenated aromatic hydrocarbons as raw materials to obtain asymmetric aromatic azo compounds. Although this method avoids the diazotization step and reduces the risk of the reaction, the aromatic hydrazine compounds are easily decomposed and emit toxic nitrogen oxide flue gas when heated, and the atom utilization rate of this method is not high, and the azobenzene and azobenzene cannot be selectively controlled by this method. Defects in the synthesis of azobenzene oxide.

因此，高效、绿色、高原子经济性不对称偶氮苯和氧化偶氮苯类化合物及其衍生物的新合成方法研究具有非常重要的价值。并且，我们用硝基苯和苯胺作为反应原料，其中硝基苯参与光催化中的还原反应，苯胺参与光催化中的氧化反应，从而实现高的原子利用率。并且，光催化合成具有无毒、安全、稳定性高、可回收等优点。所以说，发展光催化合成不对称偶氮苯和氧化偶氮苯具有十分重要的意义和应用前景。Therefore, the research on new synthetic methods of high-efficiency, green, and high atom-economic asymmetric azobenzene and azobenzene oxide compounds and their derivatives is of great value. Moreover, we use nitrobenzene and aniline as the reaction raw materials, in which nitrobenzene participates in the reduction reaction in photocatalysis, and aniline participates in the oxidation reaction in photocatalysis, so as to achieve high atom utilization. Moreover, photocatalytic synthesis has the advantages of non-toxicity, safety, high stability, and recyclability. Therefore, the development of photocatalytic synthesis of asymmetric azobenzene and azobenzene oxide has great significance and application prospects.

发明内容SUMMARY OF THE INVENTION

为克服现有技术中的缺陷，本发明旨在提供一种光催化制备不对称偶氮苯和氧化偶氮苯类化合物的方法。In order to overcome the defects in the prior art, the present invention aims to provide a method for photocatalytically preparing asymmetric azobenzene and azobenzene oxide compounds.

为达到上述目的，本发明采用的技术方案是：一种光催化制备不对称偶氮苯和氧化偶氮苯类化合物的方法，通过光催化剂，在光照、惰性气体条件下使芳香硝基化合物与芳香氨基化合物反应得到式I所示的不对称偶氮苯类化合物和式II所示的不对称氧化偶氮苯类化合物，In order to achieve the above object, the technical scheme adopted in the present invention is: a method for preparing asymmetric azobenzene and azobenzene oxide compounds by photocatalysis, by photocatalyst, under the conditions of illumination and inert gas, the aromatic nitro compound is combined with the azobenzene compound. The aromatic amino compound is reacted to obtain the asymmetric azobenzene compound shown in formula I and the asymmetric azobenzene oxide compound shown in formula II,

Figure BDA0002269636680000011
Figure BDA0002269636680000011

Figure BDA0002269636680000021
Figure BDA0002269636680000021

式I和式II中，R1和R2相互独立地为连接在苯环上的1、2、3、4或5个取代基，每个所述取代基相互独立地为氢、卤素、C1-C10烷基、C2-C10烯基、C2-C10炔基、C6-C20芳基、-OR’、-OCF3、-NHR’、-C(＝O)OR’、-NHC(＝O)R’和-C(＝O)R’中的任意一种，所述R’为H、C1-C6烷基、C2-C6烯基、C2-C6炔基、苯基和苄基中的任意一种。In formula I and formula II, R 1 and R 2 are independently 1, 2, 3, 4 or 5 substituents connected to the benzene ring, each of which is independently hydrogen, halogen, C 1 -C 10 alkyl, C 2 -C 10 alkenyl, C 2 -C 10 alkynyl, C 6 -C 20 aryl, -OR', -OCF 3 , -NHR', -C(=O)OR ', -NHC(=O)R' and -C(=O)R', wherein R' is H, C 1 -C 6 alkyl, C 2 -C 6 alkenyl, C 2 -Any one of C 6 alkynyl, phenyl and benzyl.

优化地，所述芳香硝基化合物的结构通式如式Ⅲ所示：Optimally, the general structural formula of the aromatic nitro compound is shown in formula III:

Figure BDA0002269636680000022
Figure BDA0002269636680000022

进一步地，所述芳香氨基化合物的结构通式如式Ⅳ所示：Further, the general structural formula of the aromatic amino compound is shown in formula IV:

Figure BDA0002269636680000023
Figure BDA0002269636680000023

具体地，它包括以下步骤：Specifically, it includes the following steps:

(a)将所述芳香硝基化合物、所述芳香氨基化合物和碱按摩尔比1：(0.1～10)：(1～10)进行混合，再加入溶剂、光催化剂进行超声分散得混合溶液；(a) mixing the aromatic nitro compound, the aromatic amino compound and the base in a molar ratio of 1:(0.1-10):(1-10), then adding a solvent and a photocatalyst for ultrasonic dispersion to obtain a mixed solution;

(b)将所述混合溶液在惰性气氛保护下，于0.001～50W/cm2光照下进行搅拌反应并控制反应温度为0-100℃；(b) under the protection of an inert atmosphere, the mixed solution is stirred and reacted under the illumination of 0.001-50W/cm 2 and the reaction temperature is controlled to be 0-100°C;

(c)将步骤(b)得到的有机相干燥、浓缩得不对称偶氮苯和氧化偶氮苯类化合物。(c) drying and concentrating the organic phase obtained in step (b) to obtain asymmetric azobenzene and azobenzene oxide compounds.

优化地，所述光催化剂是带宽范围1～4eV的半导体材料。更具体地，所述光催化剂为选自金属氧化物半导体、金属氮化合物半导体、金属硫化物半导体、金属硒化物半导体、钙钛矿半导体、铜铁矿半导体、碳基聚合物半导体和氮基聚合物半导体中的一种或多种组成的混合物。所述惰性气体为He、Ar、N2、CO2、CO或H2。步骤(a)中，所述混合溶液中芳香硝基化合物的浓度为1～100mmol/L，光催化剂的浓度为1～100mg/mL。步骤(a)中，所述碱为氢氧化钠、氢氧化钾、叔丁醇钾和叔丁醇钠、碳酸钠或碳酸氢钠Optimally, the photocatalyst is a semiconductor material with a bandwidth ranging from 1 to 4 eV. More specifically, the photocatalyst is selected from the group consisting of metal oxide semiconductors, metal nitrogen compound semiconductors, metal sulfide semiconductors, metal selenide semiconductors, perovskite semiconductors, delafossite semiconductors, carbon-based polymer semiconductors and nitrogen-based polymer semiconductors. A mixture of one or more of these semiconductors. The inert gas is He, Ar, N 2 , CO 2 , CO or H 2 . In step (a), the concentration of the aromatic nitro compound in the mixed solution is 1-100 mmol/L, and the concentration of the photocatalyst is 1-100 mg/mL. In step (a), described alkali is sodium hydroxide, potassium hydroxide, potassium tert-butoxide and sodium tert-butoxide, sodium carbonate or sodium bicarbonate

由于上述技术方案运用，本发明与现有技术相比具有下列优点：本发明光催化制备不对称偶氮苯和氧化偶氮苯类化合物的方法，通过光催化剂作用实现芳香硝基化合物与芳香氨基化合物反应得到不对称偶氮苯和氧化偶氮苯类化合物，可以用于代替现有成熟的有机合成工艺，条件温和、选择性高、具有普适性、适合于工业化生产。Due to the application of the above-mentioned technical solutions, the present invention has the following advantages compared with the prior art: the method for preparing asymmetric azobenzene and azobenzene oxide compounds by photocatalysis of the present invention realizes aromatic nitro compounds and aromatic amino groups through the action of photocatalysts. The compounds are reacted to obtain asymmetric azobenzene and azobenzene oxide compounds, which can be used to replace the existing mature organic synthesis process, with mild conditions, high selectivity, universality and suitability for industrial production.

附图说明Description of drawings

图1为实施例1中4-氯苯偶氮苯的质谱图。Fig. 1 is the mass spectrum of 4-chlorobenzeneazobenzene in Example 1.

具体实施方式Detailed ways

本发明光催化制备不对称偶氮苯和氧化偶氮苯类化合物的方法，通过光催化剂，在光照、惰性气体条件下使芳香硝基化合物与芳香氨基化合物反应得到式I所示的不对称偶氮苯类化合物和式II所示的不对称氧化偶氮苯类化合物，

Figure BDA0002269636680000031
Figure BDA0002269636680000032
式I和式II中，R1和R2相互独立地为连接在苯环上的1、2、3、4或5个取代基，每个所述取代基相互独立地为氢、卤素、C1-C10烷基、C2-C10烯基、C2-C10炔基、C6-C20芳基、-OR’、-OCF3、-NHR’、-C(＝O)OR’、-NHC(＝O)R’和-C(＝O)R’中的任意一种，所述R’为H、C1-C6烷基、C2-C6烯基、C2-C6炔基、苯基和苄基中的任意一种。通过光催化剂作用实现芳香硝基化合物与芳香氨基化合物反应得到不对称偶氮苯和氧化偶氮苯类化合物，可以用于代替现有成熟的有机合成工艺，条件温和、选择性高、具有普适性、适合于工业化生产。上述芳香硝基化合物的结构通式如式Ⅲ所示：
Figure BDA0002269636680000033
所述芳香氨基化合物的结构通式如式Ⅳ所示：
Figure BDA0002269636680000034
In the method for preparing asymmetric azobenzene and azobenzene oxide compounds by photocatalysis of the present invention, an aromatic nitro compound is reacted with an aromatic amino compound under the conditions of illumination and inert gas through a photocatalyst to obtain the asymmetric azo compound shown in formula I Azobenzene compounds and asymmetric azobenzene oxide compounds represented by formula II,
Figure BDA0002269636680000031
Figure BDA0002269636680000032
In formula I and formula II, R 1 and R 2 are independently 1, 2, 3, 4 or 5 substituents connected to the benzene ring, each of which is independently hydrogen, halogen, C 1 -C 10 alkyl, C 2 -C 10 alkenyl, C 2 -C 10 alkynyl, C 6 -C 20 aryl, -OR', -OCF 3 , -NHR', -C(=O)OR ', -NHC(=O)R' and -C(=O)R', wherein R' is H, C 1 -C 6 alkyl, C 2 -C 6 alkenyl, C 2 -Any one of C 6 alkynyl, phenyl and benzyl. Asymmetric azobenzene and azobenzene oxide compounds are obtained by the reaction of aromatic nitro compounds and aromatic amino compounds through the action of photocatalysts, which can be used to replace the existing mature organic synthesis processes, with mild conditions, high selectivity, and universal application. It is suitable for industrial production. The general structural formula of the above-mentioned aromatic nitro compound is shown in formula III:
Figure BDA0002269636680000033
The general structural formula of the aromatic amino compound is shown in formula IV:
Figure BDA0002269636680000034

上述光催化制备不对称偶氮苯和氧化偶氮苯类化合物的方法具体包括以下步骤：(a)将所述芳香硝基化合物、所述芳香氨基化合物和碱按摩尔比1：(0.1～10)：(1～10)进行混合，再加入溶剂(也可以根据需要不使用溶剂)、光催化剂进行超声分散得混合溶液；(b)将所述混合溶液在惰性气氛保护下，于0.001～50W/cm2光照下进行搅拌反应并控制反应温度为0-100℃；(c)将步骤(b)得到的有机相干燥、浓缩得不对称偶氮苯和氧化偶氮苯类化合物。The above-mentioned photocatalytic method for preparing asymmetric azobenzene and azobenzene oxide compounds specifically includes the following steps: (a) molar ratio of the aromatic nitro compound, the aromatic amino compound and the base is 1:(0.1～10 ): (1-10) mix, then add solvent (you can also do not use solvent as needed), photocatalyst and ultrasonically disperse to obtain mixed solution; (b) under the protection of inert atmosphere, at 0.001-50W The stirring reaction is carried out under the illumination of /cm 2 and the reaction temperature is controlled to be 0-100° C.; (c) the organic phase obtained in step (b) is dried and concentrated to obtain asymmetric azobenzene and azobenzene oxide compounds.

上述光催化剂需要是带宽范围1～4eV的半导体材料以保证不对称合成的选择性。可以为选自金属氧化物半导体、金属氮化合物半导体、金属硫化物半导体、金属硒化物半导体、钙钛矿半导体、铜铁矿半导体、碳基聚合物半导体和氮基聚合物半导体中的一种或多种组成的混合物。即光催化剂为金属氧化物半导体、金属硫(硒)化物半导体、金属氮(氧)化合物半导体、钙钛矿半导体(perovskite，ABO3)、铜铁矿半导体(delafossite，ABO2)、碳(氮)基聚合物半导体材料或上述任意两种材料的复合；金属氧化物半导体，包括Ti、Zn、Zr、W、V、Cu、Fe、Ce、Ta、In或Nb的含氧化物；金属硫(硒)化物半导体，包括Cd、Zn、Cu、W、或Bi的含硫、硒化合物；金属氮(氧)化合物半导体，包括C、Ti、Ga、Ge或Ta的含氮、氧化合物。该光催化剂通常还负载有助催化剂，助催化剂为Pt、Au、Ag、Pd、Ir、Ru、Ni和NiO中的一种或多种。The above-mentioned photocatalysts need to be semiconductor materials with a bandwidth of 1-4 eV to ensure the selectivity of asymmetric synthesis. can be one selected from the group consisting of metal oxide semiconductors, metal nitride semiconductors, metal sulfide semiconductors, metal selenide semiconductors, perovskite semiconductors, delafossite semiconductors, carbon-based polymer semiconductors, and nitrogen-based polymer semiconductors or Mixtures of various compositions. That is, the photocatalyst is metal oxide semiconductor, metal sulfur (selenide) compound semiconductor, metal nitrogen (oxygen) compound semiconductor, perovskite semiconductor (perovskite, ABO 3 ), delafossite (delafossite, ABO 2 ), carbon (nitrogen) )-based polymer semiconductor material or a composite of any two of the above materials; metal oxide semiconductors, including oxides of Ti, Zn, Zr, W, V, Cu, Fe, Ce, Ta, In or Nb; metal sulfur ( Selenide semiconductors, including sulfur and selenium compounds of Cd, Zn, Cu, W, or Bi; metal nitrogen (oxygen) compound semiconductors, including nitrogen and oxygen compounds of C, Ti, Ga, Ge or Ta. The photocatalyst is usually also supported with a co-catalyst, and the co-catalyst is one or more of Pt, Au, Ag, Pd, Ir, Ru, Ni and NiO.

所述惰性气体为He、Ar、N2、CO2、CO或H2。步骤(a)中，所述混合溶液中芳香硝基化合物的浓度为1～100mmol/L，光催化剂的浓度为1～100mg/mL。步骤(a)中，所述碱为氢氧化钠、氢氧化钾、叔丁醇钾和叔丁醇钠、碳酸钠或碳酸氢钠。溶剂为水、甲基亚砜、乙腈、N,N-二甲基甲酰胺或1,4-二氧六环中，或者以下体积比的混合溶剂：甲基亚砜：水(v/v)＝1：(0-100)、乙腈：水(v/v)＝1：(0-100)、N,N-二甲基甲酰胺：水(v/v)＝1：(0-100)、1,4-二氧六环：水(v/v)＝1：(0-100)、或上述4种溶剂的任意两种之间的组合(比例为溶剂1：溶剂2(v/v)＝1：(1-100))、或上述4种溶剂的任意两种和水之间的组合(比例为溶剂1：溶剂2：水(v/v/v)＝1：(1-100)：(1-100))或上述4种溶剂中的3种的任意组合(比例为溶剂1：溶剂2：溶剂3(v/v/v)＝1：(1-100)：(1-100))。The inert gas is He, Ar, N 2 , CO 2 , CO or H 2 . In step (a), the concentration of the aromatic nitro compound in the mixed solution is 1-100 mmol/L, and the concentration of the photocatalyst is 1-100 mg/mL. In step (a), the alkali is sodium hydroxide, potassium hydroxide, potassium tert-butoxide and sodium tert-butoxide, sodium carbonate or sodium bicarbonate. The solvent is water, methyl sulfoxide, acetonitrile, N,N-dimethylformamide or 1,4-dioxane, or a mixed solvent of the following volume ratio: methyl sulfoxide: water (v/v) = 1: (0-100), acetonitrile: water (v/v) = 1: (0-100), N,N-dimethylformamide: water (v/v) = 1: (0-100) , 1,4-dioxane: water (v/v) = 1: (0-100), or a combination of any two of the above four solvents (the ratio is solvent 1: solvent 2 (v/v) )=1: (1-100)), or a combination between any two of the above four solvents and water (the ratio is solvent 1: solvent 2: water (v/v/v)=1: (1-100 ): (1-100)) or any combination of 3 of the above 4 solvents (the ratio is solvent 1: solvent 2: solvent 3 (v/v/v) = 1: (1-100): (1- 100)).

下面将结合实例对本发明进行进一步说明。The present invention will be further described below with reference to examples.

实施例1Example 1

本实施例提供一种光催化制备不对称偶氮苯和氧化偶氮苯类化合物的方法，包括以下步骤：The present embodiment provides a photocatalytic method for preparing asymmetric azobenzene and azobenzene oxide compounds, comprising the following steps:

(a)将50mg 1wt％的铜/石墨烯光催化剂(铜/石墨烯光催化剂的合成如下：400mg氮化碳石墨烯、53.6mg二水氯化铜、2ml乙醇和50ml水均匀混合后，在模拟太阳光的LED灯照射与氮气保护下，室温搅拌2～3h，离心后，放置烘箱60℃干燥24h即可)、80μmol硝基苯、800μmol的对氯苯胺、100μmol的氢氧化钾与10mL二甲基亚砜：水(v/v)＝7:3的混合溶剂混合均匀后，超声(电功率80W)分散10min得悬浮液；(a) 50 mg of 1wt% copper/graphene photocatalyst (the copper/graphene photocatalyst was synthesized as follows: 400 mg of carbon nitride graphene, 53.6 mg of copper chloride dihydrate, 2 ml of ethanol and 50 ml of water were mixed uniformly, Under the illumination of the LED lamp simulating sunlight and under the protection of nitrogen, stir at room temperature for 2 to 3 hours, after centrifugation, place it in an oven at 60 °C for drying for 24 hours), 80 μmol of nitrobenzene, 800 μmol of p-chloroaniline, 100 μmol of potassium hydroxide and 10 mL of dichloromethane. After the mixed solvent of methyl sulfoxide:water (v/v)=7:3 is evenly mixed, ultrasonically (electric power 80W) is dispersed for 10min to obtain a suspension;

(b)将分散好的悬浮液在模拟太阳光的LED灯照射和氮气保护下，室温搅拌反应6h；(b) The dispersed suspension is irradiated by an LED lamp simulating sunlight and protected by nitrogen, and stirred for 6 hours at room temperature;

(c)将步骤(b)得到的有机相干燥、浓缩得4-氯苯氧化偶氮苯

Figure BDA0002269636680000041
通过气相色谱仪测试分析，硝基苯转化率为90％，4-氯苯氧化偶氮苯选择性为94％；室温搅拌反应12h反应可得到4-氯苯偶氮苯
Figure BDA0002269636680000042
结果通过气相色谱仪测试分析：硝基苯转化率为95％，4-氯苯偶氮苯选择性为98％。(c) drying and concentrating the organic phase obtained in step (b) to obtain 4-chlorobenzene azobenzene oxide
Figure BDA0002269636680000041
Through gas chromatography test and analysis, the conversion rate of nitrobenzene is 90%, and the selectivity of 4-chlorobenzene azobenzene oxide is 94%; 4-chlorobenzene azobenzene can be obtained by stirring reaction at room temperature for 12 h.
Figure BDA0002269636680000042
The results were analyzed by gas chromatography: the conversion rate of nitrobenzene was 95%, and the selectivity of 4-chlorobenzeneazobenzene was 98%.

实施例2Example 2

本实施例提供一种光催化制备不对称偶氮苯和氧化偶氮苯类化合物的方法，它与实施例1中的基本一致，不同的是：步骤(a)中，使用的碱为叔丁醇钾；最终步骤(c)的结果为通过气相色谱仪测试分析，硝基苯转化率为89％，4-氯苯氧化偶氮苯选择性为82％；室温搅拌反应12h反应可得到4-氯苯偶氮苯

Figure BDA0002269636680000051
硝基苯转化率为78％，4-氯苯偶氮苯选择性为85％。This embodiment provides a photocatalytic method for preparing asymmetric azobenzene and azobenzene oxide compounds, which is basically the same as that in Embodiment 1, except that: in step (a), the base used is tert-butyl Potassium alkoxide; the result of the final step (c) is that the conversion rate of nitrobenzene is 89%, and the selectivity of 4-chlorobenzene azobenzene oxide is 82% by gas chromatograph test and analysis; stirring reaction at room temperature for 12h can obtain 4- Chlorobenzene azobenzene
Figure BDA0002269636680000051
The conversion of nitrobenzene was 78%, and the selectivity of 4-chlorobenzeneazobenzene was 85%.

实施例3Example 3

本实施例提供一种光催化制备不对称偶氮苯和氧化偶氮苯类化合物的方法，它与实施例1中的基本一致，不同的是：步骤(a)中，使用的碱为碳酸氢钠；最终步骤(c)的结果为通过气相色谱仪测试分析，硝基苯转化率为79％，4-氯苯氧化偶氮苯选择性为81％；室温搅拌反应12h反应可得到4-氯苯偶氮苯

Figure BDA0002269636680000052
硝基苯转化率为85％，4-氯苯偶氮苯选择性为65％。This embodiment provides a photocatalytic method for preparing asymmetric azobenzene and azobenzene oxide compounds, which is basically the same as that in Embodiment 1, except that: in step (a), the base used is hydrogen carbonate Sodium; the result of the final step (c) is that the conversion rate of nitrobenzene is 79% and the selectivity of 4-chlorobenzene azobenzene oxide is 81% by gas chromatograph test and analysis; 4-chlorobenzene can be obtained by stirring reaction at room temperature for 12h. Benzazobenzene
Figure BDA0002269636680000052
The conversion of nitrobenzene was 85%, and the selectivity of 4-chlorobenzeneazobenzene was 65%.

实施例4Example 4

本实施例提供一种光催化制备不对称偶氮苯和氧化偶氮苯类化合物的方法，它与实施例1中的基本一致，不同的是：步骤(a)中，使用的碱为800μmol的氢氧化钾；最终步骤(c)的结果通过气相色谱仪测试分析，硝基苯转化率为80％，4-氯苯氧化偶氮苯选择性为32％；室温搅拌反应12h反应可得到4-氯苯偶氮苯

Figure BDA0002269636680000053
硝基苯转化率为84％，4-氯苯偶氮苯选择性为55％。This embodiment provides a photocatalytic method for preparing asymmetric azobenzene and azobenzene oxide compounds, which is basically the same as that in Embodiment 1, except that in step (a), the base used is 800 μmol of Potassium hydroxide; the result of the final step (c) is tested and analyzed by gas chromatography, the conversion rate of nitrobenzene is 80%, and the selectivity of 4-chlorobenzene azobenzene oxide is 32%; the reaction is stirred at room temperature for 12h to obtain 4- Chlorobenzene azobenzene
Figure BDA0002269636680000053
The conversion of nitrobenzene was 84%, and the selectivity of 4-chlorobenzeneazobenzene was 55%.

实施例5Example 5

本实施例提供一种光催化制备不对称偶氮苯和氧化偶氮苯类化合物的方法，它与实施例1中的基本一致，不同的是：步骤(a)中，使用的碱为80μmol的氢氧化钾；最终步骤(c)的结果通过气相色谱仪测试分析，硝基苯转化率为77％，4-氯苯氧化偶氮苯选择性为91％；室温搅拌反应12h反应可得到4-氯苯偶氮苯

Figure BDA0002269636680000054
硝基苯转化率为85％，4-氯苯偶氮苯选择性为76％。This embodiment provides a photocatalytic method for preparing asymmetric azobenzene and azobenzene oxide compounds, which is basically the same as that in Embodiment 1, except that in step (a), the base used is 80 μmol of Potassium hydroxide; the results of the final step (c) are tested and analyzed by gas chromatography, the conversion rate of nitrobenzene is 77%, and the selectivity of 4-chlorobenzene azobenzene oxide is 91%; the reaction is stirred at room temperature for 12h to obtain 4- Chlorobenzene azobenzene
Figure BDA0002269636680000054
The conversion of nitrobenzene was 85%, and the selectivity of 4-chlorobenzeneazobenzene was 76%.

实施例6Example 6

本实施例提供一种光催化制备不对称偶氮苯和氧化偶氮苯类化合物的方法，它与实施例1中的基本一致，不同的是：步骤(a)中，使用的碱为8μmol的对氯苯胺；最终步骤(c)的结果通过气相色谱仪测试分析，硝基苯转化率为79％，4-氯苯氧化偶氮苯选择性为88％；室温搅拌反应12h反应可得到4-氯苯偶氮苯

Figure BDA0002269636680000061
硝基苯转化率为84％，4-氯苯偶氮苯选择性为79％。This embodiment provides a photocatalytic method for preparing asymmetric azobenzene and azobenzene oxide compounds, which is basically the same as that in Embodiment 1, except that in step (a), the base used is 8 μmol of p-Chloroaniline; the result of the final step (c) is tested and analyzed by gas chromatograph, the conversion rate of nitrobenzene is 79%, and the selectivity of 4-chlorobenzene azobenzene oxide is 88%; stirring reaction at room temperature for 12h can obtain 4- Chlorobenzene azobenzene
Figure BDA0002269636680000061
The conversion of nitrobenzene was 84%, and the selectivity of 4-chlorobenzeneazobenzene was 79%.

实施例7Example 7

本实施例提供一种光催化制备不对称偶氮苯和氧化偶氮苯类化合物的方法，它与实施例1中的基本一致，不同的是：步骤(a)中，使用的碱为100μmol的对氯苯胺；最终步骤(c)的结果为通过气相色谱仪测试分析，硝基苯转化率为88％，4-氯苯氧化偶氮苯选择性为84％；室温搅拌反应12h反应可得到4-氯苯偶氮苯

Figure BDA0002269636680000062
硝基苯转化率为90％，4-氯苯偶氮苯选择性为89％。This embodiment provides a photocatalytic method for preparing asymmetric azobenzene and azobenzene oxide compounds, which is basically the same as that in Embodiment 1, except that in step (a), the base used is 100 μmol of p-Chloroaniline; the result of the final step (c) is that the nitrobenzene conversion rate is 88%, and the 4-chlorobenzene azobenzene selectivity is 84% by gas chromatograph testing and analysis; stirring at room temperature for 12h can obtain 4 - Chlorobenzene azobenzene
Figure BDA0002269636680000062
The conversion of nitrobenzene was 90%, and the selectivity of 4-chlorobenzeneazobenzene was 89%.

实施例8Example 8

本实施例提供一种光催化制备不对称偶氮苯和氧化偶氮苯类化合物的方法，它与实施例1中的基本一致，不同的是：步骤(a)中，使用的溶剂为甲基亚砜、乙腈和N,N-二甲基甲酰胺按体积比1：1：1组成的混合物；最终步骤(c)的结果为通过气相色谱仪测试分析，硝基苯转化率为88％，4-氯苯氧化偶氮苯选择性为56％；室温搅拌反应12h反应可得到4-氯苯偶氮苯

Figure BDA0002269636680000063
硝基苯转化率为90％，4-氯苯偶氮苯选择性为76％。This embodiment provides a photocatalytic method for preparing asymmetric azobenzene and azobenzene oxide compounds, which is basically the same as that in Embodiment 1, except that in step (a), the solvent used is methyl A mixture of sulfoxide, acetonitrile and N,N-dimethylformamide in a volume ratio of 1:1:1; the result of the final step (c) is that the conversion rate of nitrobenzene is 88% through gas chromatograph testing and analysis, The selectivity of 4-chlorobenzene azobenzene oxide is 56%; 4-chlorobenzene azobenzene can be obtained by stirring reaction at room temperature for 12h
Figure BDA0002269636680000063
The conversion of nitrobenzene was 90%, and the selectivity of 4-chlorobenzeneazobenzene was 76%.

实施例9Example 9

本实施例提供一种光催化制备不对称偶氮苯和氧化偶氮苯类化合物的方法，它与实施例1中的基本一致，不同的是：步骤(a)中，使用的溶剂为1,4-二氧六环；最终步骤(c)的结果为通过气相色谱仪测试分析，硝基苯转化率为89％，4-氯苯氧化偶氮苯选择性为89％；室温搅拌反应12h反应可得到4-氯苯偶氮苯

Figure BDA0002269636680000064
硝基苯转化率为95％，4-氯苯偶氮苯选择性为86％。This embodiment provides a photocatalytic method for preparing asymmetric azobenzene and azobenzene oxide compounds, which is basically the same as that in Embodiment 1, except that in step (a), the solvent used is 1, 4-dioxane; the result of the final step (c) is that the conversion rate of nitrobenzene is 89% and the selectivity of 4-chlorobenzene azobenzene is 89% by gas chromatograph test and analysis; the reaction is stirred at room temperature for 12h. 4-Chlorobenzeneazobenzene can be obtained
Figure BDA0002269636680000064
The conversion of nitrobenzene was 95%, and the selectivity of 4-chlorobenzeneazobenzene was 86%.

实施例10Example 10

本实施例提供一种光催化制备不对称偶氮苯和氧化偶氮苯类化合物的方法，它与实施例1中的基本一致，不同的是：步骤(a)中，使用的光催化剂为Pt/GaN(400mg氮化镓、97.3mg氯铂酸六水合物、2ml乙醇、50ml水均匀混合后，在模拟太阳光的LED灯照射与氮气保护下，室温搅拌2-3h，离心后，放置烘箱60℃干燥24h即可)；最终步骤(c)的结果为通过气相色谱仪测试分析，硝基苯转化率为80％，4-氯苯氧化偶氮苯选择性为81％；室温搅拌反应12h反应可得到4-氯苯偶氮苯

Figure BDA0002269636680000071
硝基苯转化率为85％，4-氯苯偶氮苯选择性为78％。This embodiment provides a photocatalytic method for preparing asymmetric azobenzene and azobenzene oxide compounds, which is basically the same as that in Embodiment 1, except that in step (a), the photocatalyst used is Pt /GaN (400mg of gallium nitride, 97.3mg of chloroplatinic acid hexahydrate, 2ml of ethanol, and 50ml of water were mixed uniformly, under the illumination of an LED lamp simulating sunlight and nitrogen protection, stirred at room temperature for 2-3h, centrifuged, and placed in an oven Dry at 60°C for 24h); the result of the final step (c) is that the conversion rate of nitrobenzene is 80% and the selectivity of 4-chlorobenzene azobenzene oxide is 81% by gas chromatograph test and analysis; the reaction is stirred at room temperature for 12h The reaction can obtain 4-chlorobenzeneazobenzene
Figure BDA0002269636680000071
The conversion of nitrobenzene was 85%, and the selectivity of 4-chlorobenzeneazobenzene was 78%.

实施例11Example 11

本实施例提供一种光催化制备不对称偶氮苯和氧化偶氮苯类化合物的方法，它与实施例1中的基本一致，不同的是：步骤(a)中，使用的光催化剂为Au/ZnS(400mg硫化锌、40.0mg四氯金酸三水合物、2ml乙醇、50ml水均匀混合后，在模拟太阳光的LED灯照射与氮气保护下，室温搅拌2-3h，离心后，放置烘箱60℃干燥24h即可)；最终步骤(c)的结果为通过气相色谱仪测试分析，硝基苯转化率为50％，4-氯苯氧化偶氮苯选择性为77％；室温搅拌反应12h反应可得到4-氯苯偶氮苯

Figure BDA0002269636680000072
硝基苯转化率为64％，4-氯苯偶氮苯选择性为78％。This embodiment provides a photocatalytic method for preparing asymmetric azobenzene and azobenzene oxide compounds, which is basically the same as that in Embodiment 1, except that in step (a), the photocatalyst used is Au /ZnS (400mg zinc sulfide, 40.0mg tetrachloroauric acid trihydrate, 2ml ethanol, 50ml water after uniform mixing, under the LED lamp simulating sunlight and nitrogen protection, stirring at room temperature for 2-3h, after centrifugation, placed in an oven Dry at 60°C for 24h); the result of the final step (c) is that the conversion rate of nitrobenzene is 50% and the selectivity of 4-chlorobenzene azobenzene oxide is 77% by gas chromatograph test and analysis; the reaction is stirred at room temperature for 12h The reaction can obtain 4-chlorobenzeneazobenzene
Figure BDA0002269636680000072
The conversion of nitrobenzene was 64%, and the selectivity to 4-chlorobenzeneazobenzene was 78%.

实施例12Example 12

本实施例提供一种光催化制备不对称偶氮苯和氧化偶氮苯类化合物的方法，它与实施例1中的基本一致，不同的是：使用的原料是80μmol对氯硝基苯、800μmol的对甲氧基苯胺，最终室温搅拌反应7h可得到4-甲氧基苯氧化偶氮4-氯苯

Figure BDA0002269636680000073
其中对氯硝基苯转化率为89％，4-甲氧基苯氧化偶氮4-氯苯选择性为91％；室温搅拌反应18h反应可得到4-甲氧基苯偶氮4-氯苯
Figure BDA0002269636680000074
其中对氯硝基苯转化率为93％，4-甲氧基苯偶氮4-氯苯选择性为94％。This embodiment provides a photocatalytic method for preparing asymmetric azobenzene and azobenzene oxide compounds. 4-methoxybenzene azo-4-chlorobenzene can be obtained by stirring reaction at room temperature for 7h.
Figure BDA0002269636680000073
Among them, the conversion rate of p-chloronitrobenzene is 89%, and the selectivity of 4-methoxybenzene azo-4-chlorobenzene is 91%; 4-methoxybenzene azo-4-chlorobenzene can be obtained by stirring reaction at room temperature for 18 h.
Figure BDA0002269636680000074
Among them, the conversion rate of p-chloronitrobenzene is 93%, and the selectivity of 4-methoxybenzeneazo-4-chlorobenzene is 94%.

实施例13Example 13

本实施例提供一种光催化制备不对称偶氮苯和氧化偶氮苯类化合物的方法，它与实施例1中的基本一致，不同的是：使用的原料是80μmol 2-甲基硝基苯、800μmol的4-三氟甲基苯胺，最终室温搅拌反应5h可得到4-三氟甲基苯氧化偶氮2-甲基苯，2-甲基硝基苯转化率为91％

Figure BDA0002269636680000081
4-三氟甲基苯氧化偶氮2-甲基苯选择性为92％；室温搅拌反应18h反应可得到4-三氟甲基苯偶氮2-甲基苯
Figure BDA0002269636680000082
其中2-甲基硝基苯转化率为93％，4-三氟甲基苯偶氮2-甲基苯选择性为95％。This embodiment provides a photocatalytic method for preparing asymmetric azobenzene and azobenzene oxide compounds, which is basically the same as that in Embodiment 1, except that the raw material used is 80 μmol of 2-methylnitrobenzene. , 800 μmol of 4-trifluoromethylaniline, the final stirring reaction at room temperature for 5h can obtain 4-trifluoromethylbenzene azo 2-methylbenzene, the conversion rate of 2-methylnitrobenzene is 91%
Figure BDA0002269636680000081
The selectivity of 4-trifluoromethylbenzene azo-2-methylbenzene is 92%; the reaction is stirred at room temperature for 18h to obtain 4-trifluoromethylbenzeneazo-2-methylbenzene
Figure BDA0002269636680000082
Among them, the conversion rate of 2-methylnitrobenzene is 93%, and the selectivity of 4-trifluoromethylbenzeneazo 2-methylbenzene is 95%.

实施例14Example 14

本实施例提供一种光催化制备不对称偶氮苯和氧化偶氮苯类化合物的方法，它与实施例1中的基本一致，不同的是：使用的原料是80μmol 3-溴硝基苯、800μmol的4-甲基苯胺，最终室温搅拌反应6h可得到4-甲基苯氧化偶氮3-溴苯

Figure BDA0002269636680000083
其中3-溴硝基苯转化率为90％，4-甲基甲基苯氧化偶氮3-溴苯选择性为93％；室温搅拌反应16h反应可得到4-甲基甲基苯偶氮3-溴苯
Figure BDA0002269636680000084
其中3-溴硝基苯转化率为95％，4-甲基苯偶氮3-溴苯选择性为96％。The present embodiment provides a method for photocatalytically preparing asymmetric azobenzene and azobenzene oxide compounds, which is basically the same as that in Embodiment 1, except that the raw materials used are 800μmol of 4-methylaniline, the final stirring reaction at room temperature for 6h can obtain 4-methylbenzene azo 3-bromobenzene
Figure BDA0002269636680000083
Among them, the conversion rate of 3-bromonitrobenzene is 90%, and the selectivity of 4-methylmethylbenzene azo 3-bromobenzene is 93%; 4-methylmethylbenzene azo 3 can be obtained by stirring at room temperature for 16 h. -Bromobenzene
Figure BDA0002269636680000084
Among them, the conversion rate of 3-bromonitrobenzene is 95%, and the selectivity of 4-methylbenzeneazo 3-bromobenzene is 96%.

实施例15Example 15

本实施例提供一种光催化制备不对称偶氮苯和氧化偶氮苯类化合物的方法，它与实施例1中的基本一致，不同的是：使用的原料是80μmol 4-氟硝基苯、800μmol的4-甲基苯胺，最终室温搅拌反应6h可得到4-甲基苯氧化偶氮4-氟苯

Figure BDA0002269636680000085
其中4-氟硝基苯转化率为90％，4-甲基苯氧化偶氮4-氟苯选择性为93％；室温搅拌反应16h反应可得到4-甲基苯偶氮4-氟苯
Figure BDA0002269636680000091
其中4-氟硝基苯转化率为95％，4-甲基苯偶氮4-氟苯选择性为96％。This embodiment provides a photocatalytic method for preparing asymmetric azobenzene and azobenzene oxide compounds, which is basically the same as that in Embodiment 1, except that the raw materials used are 80 μmol of 4-fluoronitrobenzene, 800μmol of 4-methylaniline, the final stirring reaction at room temperature for 6h can obtain 4-methylbenzene azo-4-fluorobenzene
Figure BDA0002269636680000085
Among them, the conversion rate of 4-fluoronitrobenzene is 90%, and the selectivity of 4-methylbenzene azo-4-fluorobenzene is 93%; 4-methylbenzeneazo-4-fluorobenzene can be obtained by stirring reaction at room temperature for 16h.
Figure BDA0002269636680000091
The conversion rate of 4-fluoronitrobenzene was 95%, and the selectivity of 4-methylbenzeneazo-4-fluorobenzene was 96%.

实施例16Example 16

本实施例提供一种光催化制备不对称偶氮苯和氧化偶氮苯类化合物的方法，它与实施例1中的基本一致，不同的是：使用的原料是80μmol硝基苯、800μmol的4-(N,N-二甲基)苯胺，最终室温搅拌反应5h可得到4-(N,N-二甲基)苯氧化偶氮苯

Figure BDA0002269636680000092
其中硝基苯转化率为90％，4-(N,N-二甲基)苯氧化偶氮苯选择性为89％；室温搅拌反应20h反应可得到4-(N,N-二甲基)苯偶氮苯
Figure BDA0002269636680000093
其中硝基苯转化率为96％，4-(N,N-二甲基)苯偶氮苯选择性为98％。This embodiment provides a photocatalytic method for preparing asymmetric azobenzene and azobenzene oxide compounds. -(N,N-Dimethyl)aniline, the final stirring reaction at room temperature for 5h can obtain 4-(N,N-dimethyl)benzene azobenzene oxide
Figure BDA0002269636680000092
Among them, the conversion rate of nitrobenzene is 90%, and the selectivity of 4-(N,N-dimethyl)benzene azobenzene oxide is 89%; 4-(N,N-dimethyl) can be obtained by stirring reaction at room temperature for 20h. Benzazobenzene
Figure BDA0002269636680000093
The conversion rate of nitrobenzene was 96%, and the selectivity of 4-(N,N-dimethyl)benzeneazobenzene was 98%.

对比例1Comparative Example 1

本例与实施例1中的基本一致，不同的是：使用的光催化剂为ZrO2(带宽为5eV)，最终步骤(c)的结果为无法获得不对称偶氮苯与氧化偶氮苯类化合物。This example is basically the same as that in Example 1, except that the photocatalyst used is ZrO 2 (with a bandwidth of 5 eV), and the result of the final step (c) is that asymmetric azobenzene and azobenzene oxide compounds cannot be obtained .

对比例2Comparative Example 2

本例与实施例1中的基本一致，不同的是：未使用的光催化剂，无法获得不对称偶氮苯和氧化偶氮苯类化合物。This example is basically the same as that in Example 1, the difference is that the asymmetric azobenzene and azobenzene oxide compounds cannot be obtained without using the photocatalyst.

上述实例只为说明本发明的技术构思及特点，其目的在于让熟悉此项技术的人士能够了解本发明的内容并据以实施，并不能以此限制本发明的保护范围。凡根据本发明精神实质所作的等效变化或修饰，都应涵盖在本发明的保护范围之内。The above examples are only for illustrating the technical concept and characteristics of the present invention, and the purpose thereof is to enable those skilled in the art to understand the content of the present invention and implement accordingly, and cannot limit the protection scope of the present invention. All equivalent changes or modifications made according to the spirit of the present invention should be included within the protection scope of the present invention.

Claims (3)

1. A method for preparing asymmetric azobenzene and azoxybenzene compounds by photocatalysis is characterized by comprising the following steps:
(a) uniformly mixing 50mg of 1wt% copper/graphene photocatalyst, 80 mu mol of nitrobenzene, 800 mu mol of parachloroaniline and alkali with 10mL of mixed solvent, and performing ultrasonic dispersion for 10min by using electric power of 80W to obtain suspension; the copper/graphene photocatalyst is synthesized as follows: uniformly mixing 400mg of carbon nitride graphene, 53.6mg of copper chloride dihydrate, 2ml of ethanol and 50ml of water, stirring at room temperature for 2-3h under the irradiation of an LED lamp simulating sunlight and the protection of nitrogen, centrifuging, and drying in an oven at 60 ℃ for 24 h; the mixed solvent is formed by mixing dimethyl sulfoxide and water according to the volume ratio of 7: 3;
the alkali is potassium tert-butoxide or sodium bicarbonate, and the usage amount is 100 mu mol; or the like, or, alternatively,
the alkali is potassium hydroxide, and the usage amount of the alkali is 80 mu mol, 100 mu mol or 800 mu mol;
(b) stirring and reacting the dispersed suspension for 6 hours at room temperature under the irradiation of an LED lamp simulating sunlight and the protection of nitrogen;
(c) drying and concentrating the organic phase obtained in the step (b) to obtain 4-chlorobenzene azoxybenzene; stirring at room temperature for 12h to obtain 4-chlorophenylazobenzene;
or, comprising the steps of:
(a) uniformly mixing 50mg of 1wt% copper/graphene photocatalyst, 80 mu mol of nitrobenzene, 800 mu mol of parachloroaniline, 100 mu mol of potassium hydroxide and 10mL of mixed solvent, and performing ultrasonic dispersion for 10min by using electric power of 80W to obtain suspension; the copper/graphene photocatalyst is synthesized as follows: uniformly mixing 400mg of carbon nitride graphene, 53.6mg of copper chloride dihydrate, 2ml of ethanol and 50ml of water, stirring at room temperature for 2-3h under the irradiation of an LED lamp simulating sunlight and the protection of nitrogen, centrifuging, and drying in an oven at 60 ℃ for 24 h; the mixed solvent is methyl sulfoxide, acetonitrile and N, N-dimethylformamide according to the volume ratio of 1: 1: 1;
(b) stirring and reacting the dispersed suspension for 6 hours at room temperature under the irradiation of an LED lamp simulating sunlight and the protection of nitrogen;
(c) drying and concentrating the organic phase obtained in the step (b) to obtain 4-chlorobenzene azoxybenzene; stirring at room temperature for 12h to obtain 4-chlorophenylazobenzene;
or, comprising the steps of:
(a) uniformly mixing 50mg of 1wt% copper/graphene photocatalyst, 80 mu mol of nitrobenzene, 800 mu mol of parachloroaniline, 100 mu mol of potassium hydroxide and 10mL of solvent, and performing ultrasonic dispersion for 10min by using electric power of 80W to obtain a suspension; the copper/graphene photocatalyst is synthesized as follows: uniformly mixing 400mg of carbon nitride graphene, 53.6mg of copper chloride dihydrate, 2ml of ethanol and 50ml of water, stirring at room temperature for 2-3h under the irradiation of an LED lamp simulating sunlight and the protection of nitrogen, centrifuging, and drying in an oven at 60 ℃ for 24 h; the solvent is 1, 4-dioxane;
(b) stirring and reacting the dispersed suspension for 6 hours at room temperature under the irradiation of an LED lamp simulating sunlight and the protection of nitrogen;
(c) drying and concentrating the organic phase obtained in the step (b) to obtain 4-chlorobenzene azoxybenzene; stirring the mixture at room temperature for 12 hours to react to obtain the 4-chlorophenylazobenzene.
2. A method for preparing asymmetric azobenzene and azoxybenzene compounds by photocatalysis is characterized by comprising the following steps:
(a) uniformly mixing 50mg of 1wt% photocatalyst, 80 mu mol of nitrobenzene, 800 mu mol of parachloroaniline, 100 mu mol of potassium hydroxide and 10mL of mixed solvent, and performing ultrasonic dispersion for 10min by using electric power of 80W to obtain suspension; the mixed solvent is formed by mixing dimethyl sulfoxide and water according to the volume ratio of 7: 3; the photocatalyst is Pt/GaN or Au/ZnS, and the synthesis of the Pt/GaN is as follows: uniformly mixing 400mg of gallium nitride, 97.3mg of chloroplatinic acid hexahydrate, 2ml of ethanol and 50ml of water, stirring at room temperature for 2-3h under the irradiation of an LED lamp simulating sunlight and the protection of nitrogen, centrifuging, and drying in an oven at 60 ℃ for 24 h; the synthesis of Au/ZnS is as follows: uniformly mixing 400mg of zinc sulfide, 40.0mg of tetrachloroauric acid trihydrate, 2ml of ethanol and 50ml of water, stirring at room temperature for 2-3h under the irradiation of an LED lamp simulating sunlight and the protection of nitrogen, centrifuging, and drying in an oven at 60 ℃ for 24 h;
(b) stirring and reacting the dispersed suspension for 6 hours at room temperature under the irradiation of an LED lamp simulating sunlight and the protection of nitrogen;
(c) drying and concentrating the organic phase obtained in the step (b) to obtain 4-chlorobenzene azoxybenzene; stirring the mixture at room temperature for 12 hours to react to obtain the 4-chlorophenylazobenzene.
3. A method for preparing asymmetric azobenzene and azoxybenzene compounds by photocatalysis is characterized by comprising the following steps:
(a) uniformly mixing 50mg of 1wt% copper/graphene photocatalyst, 80 mu mol of p-chloronitrobenzene, 800 mu mol of p-anisidine, 100 mu mol of potassium hydroxide and 10mL of mixed solvent, and performing ultrasonic dispersion for 10min by using electric power of 80W to obtain suspension; the copper/graphene photocatalyst is synthesized as follows: uniformly mixing 400mg of carbon nitride graphene, 53.6mg of copper chloride dihydrate, 2ml of ethanol and 50ml of water, stirring at room temperature for 2-3h under the irradiation of an LED lamp simulating sunlight and the protection of nitrogen, centrifuging, and drying in an oven at 60 ℃ for 24 h; the mixed solvent is formed by mixing dimethyl sulfoxide and water according to the volume ratio of 7: 3;
(b) stirring the dispersed suspension at room temperature for reaction for 7 hours under the irradiation of an LED lamp simulating sunlight and the protection of nitrogen;
(c) drying and concentrating the organic phase obtained in the step (b) to obtain 4-methoxybenzene azoxy 4-chlorobenzene; stirring at room temperature for 18h to obtain 4-methoxybenzeneazo-4-chlorobenzene;
or, comprising the steps of:
(a) uniformly mixing 50mg of 1wt% copper/graphene photocatalyst, 80 mu mol of 3-bromonitrobenzene, 800 mu mol of 4-methylaniline, 100 mu mol of potassium hydroxide and 10mL of mixed solvent, and ultrasonically dispersing for 10min by using 80W electric power to obtain a suspension; the copper/graphene photocatalyst is synthesized as follows: uniformly mixing 400mg of carbon nitride graphene, 53.6mg of copper chloride dihydrate, 2ml of ethanol and 50ml of water, stirring at room temperature for 2-3h under the irradiation of an LED lamp simulating sunlight and the protection of nitrogen, centrifuging, and drying in an oven at 60 ℃ for 24 h; the mixed solvent is formed by mixing dimethyl sulfoxide and water according to the volume ratio of 7: 3;
(b) stirring and reacting the dispersed suspension for 6 hours at room temperature under the irradiation of an LED lamp simulating sunlight and the protection of nitrogen;
(c) drying and concentrating the organic phase obtained in the step (b) to obtain 4-methylbenzene azoxy 3-bromobenzene; stirring at room temperature for 16h to obtain 4-methylbenzene azo 3-bromobenzene;
or, comprising the steps of:
(a) uniformly mixing 50mg of 1wt% copper/graphene photocatalyst, 80 mu mol of 4-fluoronitrobenzene, 800 mu mol of 4-methylaniline, 100 mu mol of potassium hydroxide and 10mL of mixed solvent, and ultrasonically dispersing for 10min by using 80W of electric power to obtain a suspension; the copper/graphene photocatalyst is synthesized as follows: uniformly mixing 400mg of carbon nitride graphene, 53.6mg of copper chloride dihydrate, 2ml of ethanol and 50ml of water, stirring at room temperature for 2-3h under the irradiation of an LED lamp simulating sunlight and the protection of nitrogen, centrifuging, and drying in an oven at 60 ℃ for 24 h; the mixed solvent is formed by mixing dimethyl sulfoxide and water according to the volume ratio of 7: 3;
(b) stirring and reacting the dispersed suspension for 6 hours at room temperature under the irradiation of an LED lamp simulating sunlight and the protection of nitrogen;
(c) drying and concentrating the organic phase obtained in the step (b) to obtain 4-methylbenzene azoxy 4-fluorobenzene; stirring at room temperature for 16h to obtain 4-methylbenzeneazo 4-fluorobenzene;
or, comprising the steps of:
(a) uniformly mixing 50mg of 1wt% copper/graphene photocatalyst, 80 mu mol of nitrobenzene, 800 mu mol of 4- (N, N-dimethyl) aniline, 100 mu mol of potassium hydroxide and 10mL of mixed solvent, and performing ultrasonic dispersion for 10min by using electric power of 80W to obtain suspension; the copper/graphene photocatalyst is synthesized as follows: uniformly mixing 400mg of carbon nitride graphene, 53.6mg of copper chloride dihydrate, 2ml of ethanol and 50ml of water, stirring at room temperature for 2-3h under the irradiation of an LED lamp simulating sunlight and the protection of nitrogen, centrifuging, and drying in an oven at 60 ℃ for 24 h; the mixed solvent is formed by mixing dimethyl sulfoxide and water according to the volume ratio of 7: 3;
(b) stirring and reacting the dispersed suspension for 5 hours at room temperature under the irradiation of an LED lamp simulating sunlight and the protection of nitrogen;
(c) drying and concentrating the organic phase obtained in the step (b) to obtain 4- (N, N-dimethyl) benzene azoxybenzene; stirring the mixture at room temperature for 20 hours to react to obtain 4- (N, N-dimethyl) phenylazobenzene.
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