CN114950527A - Catalyst for synthesis of azobenzene compounds - Google Patents
Catalyst for synthesis of azobenzene compounds Download PDFInfo
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- CN114950527A CN114950527A CN202210606861.9A CN202210606861A CN114950527A CN 114950527 A CN114950527 A CN 114950527A CN 202210606861 A CN202210606861 A CN 202210606861A CN 114950527 A CN114950527 A CN 114950527A
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- 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C245/00—Compounds containing chains of at least two nitrogen atoms with at least one nitrogen-to-nitrogen multiple bond
- C07C245/02—Azo compounds, i.e. compounds having the free valencies of —N=N— groups attached to different atoms, e.g. diazohydroxides
- C07C245/06—Azo compounds, i.e. compounds having the free valencies of —N=N— groups attached to different atoms, e.g. diazohydroxides with nitrogen atoms of azo groups bound to carbon atoms of six-membered aromatic rings
- C07C245/08—Azo compounds, i.e. compounds having the free valencies of —N=N— groups attached to different atoms, e.g. diazohydroxides with nitrogen atoms of azo groups bound to carbon atoms of six-membered aromatic rings with the two nitrogen atoms of azo groups bound to carbon atoms of six-membered aromatic rings, e.g. azobenzene
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
Abstract
The invention discloses a catalyst for synthesizing azobenzene compounds, relating to the technical field of organic synthesis catalysts, wherein the preparation method of the catalyst comprises the steps of firstly reacting nickel nitrate with urea to prepare a precursor, and then reacting the precursor with palladium acetate in an ammonia atmosphere to prepare the catalyst; the novel catalyst prepared by the invention has high catalytic activity and low preparation cost, can be repeatedly applied to synthesis of azobenzene compounds from nitrobenzene compounds, has good applicability to catalytic substrates, high yield, no toxic and harmful byproducts generated in the reaction process, mild reaction conditions and low energy consumption, and can be suitable for industrial production of azobenzene compounds.
Description
The technical field is as follows:
the invention relates to the technical field of organic synthesis catalysts, in particular to a catalyst for synthesizing azobenzene compounds.
Background art:
aromatic azo derivatives having conjugated nitrogen-nitrogen double bonds have unique photochemical and photophysical properties that show advantages in organic dyes, food additives, colorants, drugs and drug delivery vehicles.
Traditionally, industrially, aromatic productionThe general procedure for azo compounds is: (1) the diazonium salts or nitrosobenzene intermediates are prepared first, and these compounds are very unstable, dangerous in reaction process and prone to explosion. (2) Reuse of large amounts of nitrite (NaNO) 2 ) Or toxic oxidizing agents to treat the substrate. Such a method easily produces harmful by-products, and has disadvantages of low isolation yield and complicated synthesis steps. Therefore, the research on the new synthesis method of the asymmetric azobenzene and azoxybenzene compounds and the derivatives thereof with high efficiency, green and high atom economy has very important value.
The synthetic methods disclosed in patent CN 201910800189.5 and patent CN 202111607378.4 have a small application range; patent CN 201410499441.0 discloses a method for preparing asymmetric aromatic azo, which uses aromatic hydrazine and halogenated aromatic hydrocarbon as raw materials to obtain asymmetric aromatic azo compound, although the method avoids diazotization step and reduces reaction danger, aromatic hydrazine compound is easily decomposed by heating and releases toxic nitrogen oxide smoke, and the method has the defects of low atom utilization rate, incapability of selectively regulating azobenzene and azoxybenzene synthesis, etc.
The invention content is as follows:
the technical problem to be solved by the invention is to provide a catalyst for synthesizing azobenzene compounds, which can efficiently and stably synthesize the azobenzene compounds in one step, has good applicability to substrates, mild reaction conditions and no generation of toxic and harmful byproducts, and simplifies the synthesis process of the azobenzene compounds; meanwhile, the catalyst material is simple in synthesis operation, low in preparation cost and good in reaction repeatability.
The invention aims to provide a preparation method of a catalyst, which comprises the steps of firstly reacting nickel nitrate with urea to prepare a precursor, and then reacting the precursor with palladium acetate in an ammonia atmosphere to prepare the catalyst.
The mass ratio of the nickel nitrate to the urea is 1 (1-1.5).
The mass ratio of the precursor to the palladium acetate is 100 (4-10).
The reaction temperature of the nickel nitrate and the urea is 110-130 ℃, and the reaction time is 5-8 h.
The temperature of the reaction between the precursor and palladium acetate is 370 ℃, and the time is 2 h.
Another object of the present invention is to provide a catalyst prepared by the above-mentioned preparation method.
The structural formula of the catalyst is PdNi&Ni 3 N。
The invention also aims to provide the application of the catalyst in the synthesis of azobenzene compounds.
The invention also provides a synthesis method of the azobenzene compound, which comprises the steps of adding the nitrobenzene compound, the catalyst, alkali and hydrazine hydrate into a solvent, reacting under the protection of inert gas, contacting reaction liquid with air after the reaction is finished, collecting a product, and drying to obtain the azobenzene compound.
The solvent is one of alcohol solvents such as methanol, ethanol, isopropanol, ethylene glycol, etc. As a preferred embodiment, the solvent is ethanol.
The alkali is one of proton alkali such as potassium hydroxide, sodium hydroxide, ammonia water, etc. As a preferred embodiment, the base is potassium hydroxide.
The dosage of the alkali is 5 to 7 times of the molar weight of the nitrobenzene compounds.
The dosage of the catalyst is 3-5 wt% of the mass of the nitrobenzene compound.
The reaction temperature is 60 +/-5 ℃ and the reaction time is 6-9 h.
The dosage of the hydrazine hydrate is 0.2-0.5mL of hydrazine hydrate per 1mmol of nitrobenzene compounds.
The invention has the beneficial effects that: the novel catalyst prepared by the invention has high catalytic activity and low preparation cost, can be repeatedly applied to synthesis of azobenzene compounds from nitrobenzene compounds, has good applicability to catalytic substrates, high yield, generates no toxic and harmful byproducts in the reaction process, has mild reaction conditions and low energy consumption, and can be suitable for industrial production of azobenzene compounds.
Description of the drawings:
FIG. 1 is an XRD pattern of a catalyst prepared according to the present invention;
FIG. 2 is a structural representation of the catalyst made according to the invention: (a) a TEM image; (b) HRTEM image; (c-f) HRTEM magnification;
FIG. 3 is a hydrogen spectrum of 4,4' -dimethylazobenzene synthesized according to the present invention;
FIG. 4 is a carbon spectrum of 4,4' -dimethyl azobenzene synthesized by the present invention;
FIG. 5 is a mass spectrum of 4,4' -dimethylazobenzene synthesized according to the present invention;
FIG. 6 shows the recycling performance of the catalyst prepared by the present invention.
The specific implementation mode is as follows:
in order to make the technical means, the original characteristics, the achieved purposes and the effects of the invention easy to understand, the invention is further explained by combining the specific embodiments and the drawings.
Example 1
Preparation of the catalyst:
(1) weighing 0.3g of nickel nitrate hexahydrate and 0.3g of urea, placing the nickel nitrate hexahydrate and the urea in a reaction kettle to react for 6 hours in a 120 ℃ oven, pouring out supernatant liquid in the reaction kettle after the reaction is finished, collecting bottom turbidity substances in a centrifuge tube, adding a proper amount of ultrapure water, shaking up, centrifuging for 1min at a rotating speed of 9000r/min, pouring out supernatant liquid, collecting bottom turbidity substances, repeatedly centrifuging for four times (three times of ultrapure water and one time of ethanol), and finally placing the mixture in a 60 ℃ vacuum oven to dry for 24 hours to obtain a precursor.
(2) Weighing 200mg of precursor and 10mg of palladium acetate, uniformly mixing and drying; taking 50mg of the dried mixture, heating to 370 ℃ in an ammonia atmosphere, reacting for 2h, and collecting the catalyst after the reaction is finished.
As shown in FIG. 1, the peak position of the XRD pattern diffraction is consistent with the standard card number of 100280, which proves that the substance is mainly based on Ni 3 N, the peak at two positions which are added is between the diffraction peak position of the standard card number (461043) of palladium and the diffraction peak position of the corresponding standard card number (040850) of nickel, and is the diffraction peak of PdNi alloy.
As shown in fig. 2, by transmission electron microscopeAnd the image obtained by the high-resolution transmission electron microscope verifies the conclusion of the XRD spectrum, the lattice spacing of most images is 0.203nm, and the most images are Ni 3 The (111) crystal plane of N is consistent, and the lattice spacing at other positions is 0.188nm, which is consistent with the (200) crystal plane of PdNi alloy.
Example 2
Synthesis of 4,4' -dimethylazobenzene (1, 2-di-p-tolyldiazene):
under magnetic stirring, 20mL of ethanol, 5mmol of potassium hydroxide, 1mmol of p-nitrotoluene, 5mg of the catalyst prepared in example 1 and a nitrogen system are added into a 100mL round-bottom flask, 0.5mL of hydrazine hydrate is injected, the reaction is carried out at 60 ℃ for 8h, after the reaction is finished, the reaction liquid is contacted with air, the filtration is carried out, dichloromethane and water are used for extraction, ethanol is recrystallized, and the drying is carried out, so that 103.9mg of yellow solid is obtained, and the yield is 99%. 1 H NMR(400MHz,CDCl 3 )δ7.80(d,J＝7.9Hz,4H),7.29(d,J＝8.0Hz,4H),2.42(s,6H). 13 C NMR(100MHz,CDCl 3 )δ150.90,141.26,129.78,122.80,21.59.MS:Calcd for C 14 H 15 N 2 [M+H] + ,211.1157；found:211.1221.
As shown in fig. 3 to 5, example 2 successfully synthesized 4,4' -dimethylazobenzene in one reaction step using the catalyst prepared in example 1, and the yield reached 99%.
Example 3
The catalyst prepared in example 1 was repeatedly used for the synthesis of 4,4' -dimethylazobenzene from p-nitrotoluene using the method of example 2, and the results are shown in fig. 6.
As can be seen from fig. 6a, the catalytic effect after catalyst cycling is still stable.
As can be seen from fig. 6b, the structure after catalyst cycling is stable.
The foregoing shows and describes the general principles and broad features of the present invention and advantages thereof. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, which are described in the specification and illustrated only to illustrate the principle of the present invention, but that various changes and modifications may be made therein without departing from the spirit and scope of the present invention, which fall within the scope of the invention as claimed. The scope of the invention is defined by the appended claims and equivalents thereof.
Claims (10)
1. A method for preparing a catalyst, which is characterized by comprising the following steps: firstly, nickel nitrate and urea are reacted to prepare a precursor, and then the precursor and palladium acetate are reacted in an ammonia atmosphere to prepare the catalyst.
2. The method of claim 1, wherein: the mass ratio of the nickel nitrate to the urea is 1 (1-1.5); the mass ratio of the precursor to the palladium acetate is 100 (4-10).
3. The method of claim 1, wherein: the reaction temperature of the nickel nitrate and the urea is 110-130 ℃, and the reaction time is 5-8 h; the temperature of the reaction between the precursor and palladium acetate is 370 ℃, and the time is 2 h.
4. The catalyst prepared by the preparation method according to any one of claims 1 to 3.
5. The catalyst of claim 4, wherein: the structural formula of the catalyst is PdNi&Ni 3 N。
6. Use of the catalyst of claim 5 in the synthesis of azobenzene compounds.
7. Use according to claim 6, characterized in that: adding a nitrobenzene compound, a catalyst, alkali and hydrazine hydrate into a solvent, reacting under the protection of inert gas, contacting reaction liquid with air after the reaction is finished, collecting a product, and drying to obtain the azobenzene compound.
8. Use according to claim 7, characterized in that: the dosage of the catalyst is 3-5 wt% of the mass of the nitrobenzene compound.
9. Use according to claim 7, characterized in that: the solvent is one of methanol, ethanol, isopropanol and glycol; the alkali is one of potassium hydroxide, sodium hydroxide and ammonia water.
10. Use according to claim 7, characterized in that: the dosage of the alkali is 5 to 7 times of the molar weight of the nitrobenzene compounds; the dosage of the hydrazine hydrate is 0.2-0.5mL of hydrazine hydrate per 1mmol of nitrobenzene compounds; the reaction temperature is 60 +/-5 ℃ and the reaction time is 6-9 h.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116393127A (en) * | 2023-03-03 | 2023-07-07 | 安徽大学 | Defect copper-based catalyst for synthesizing azobenzene compound and preparation method thereof |
Citations (8)
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| JPH04134056A (en) * | 1990-09-21 | 1992-05-07 | Ube Ind Ltd | Production of dinitroazobenzene |
| US20100331172A1 (en) * | 2008-02-20 | 2010-12-30 | Showa Denko K.K. | Catalyst carrier, catalyst and process for producing the same |
| CN105148971A (en) * | 2015-08-26 | 2015-12-16 | 中国科学院理化技术研究所 | High-performance ultrathin nitride electro-catalyst with functions of producing hydrogen and oxygen by means of electrochemically totally decomposing water, method for synthesizing high-performance ultrathin nitride electro-catalyst and application thereof |
| US20170122173A1 (en) * | 2014-06-13 | 2017-05-04 | Haskoli Islands | Electrolytic production of ammonia |
| US20180078925A1 (en) * | 2016-09-19 | 2018-03-22 | Korea Institute Of Science And Technology | Catalyst for dehydrogenation reaction of formic acid and method for preparing the same |
| CN108893756A (en) * | 2018-07-12 | 2018-11-27 | 湖北大学 | A kind of Ni3The synthetic method and its application of N NSs/NF nanosphere |
| CN112871197A (en) * | 2021-01-26 | 2021-06-01 | 沈阳化工大学 | Preparation method of metal nitride and sulfide composite material for electrode or cocatalyst |
| CN113908870A (en) * | 2020-06-23 | 2022-01-11 | 湖南师范大学 | Controllable preparation of bifunctional non-noble metal nitride catalyst and application of bifunctional non-noble metal nitride catalyst in high-current urea electrolysis hydrogen production |
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Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH04134056A (en) * | 1990-09-21 | 1992-05-07 | Ube Ind Ltd | Production of dinitroazobenzene |
| US20100331172A1 (en) * | 2008-02-20 | 2010-12-30 | Showa Denko K.K. | Catalyst carrier, catalyst and process for producing the same |
| US20170122173A1 (en) * | 2014-06-13 | 2017-05-04 | Haskoli Islands | Electrolytic production of ammonia |
| CN105148971A (en) * | 2015-08-26 | 2015-12-16 | 中国科学院理化技术研究所 | High-performance ultrathin nitride electro-catalyst with functions of producing hydrogen and oxygen by means of electrochemically totally decomposing water, method for synthesizing high-performance ultrathin nitride electro-catalyst and application thereof |
| US20180078925A1 (en) * | 2016-09-19 | 2018-03-22 | Korea Institute Of Science And Technology | Catalyst for dehydrogenation reaction of formic acid and method for preparing the same |
| CN108893756A (en) * | 2018-07-12 | 2018-11-27 | 湖北大学 | A kind of Ni3The synthetic method and its application of N NSs/NF nanosphere |
| CN113908870A (en) * | 2020-06-23 | 2022-01-11 | 湖南师范大学 | Controllable preparation of bifunctional non-noble metal nitride catalyst and application of bifunctional non-noble metal nitride catalyst in high-current urea electrolysis hydrogen production |
| CN112871197A (en) * | 2021-01-26 | 2021-06-01 | 沈阳化工大学 | Preparation method of metal nitride and sulfide composite material for electrode or cocatalyst |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116393127A (en) * | 2023-03-03 | 2023-07-07 | 安徽大学 | Defect copper-based catalyst for synthesizing azobenzene compound and preparation method thereof |
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Inventor after: Wu Jingbo Inventor after: Yu Zhipeng Inventor after: Xu Kun Inventor after: Gao Yanan Inventor before: Xu Kun Inventor before: Wu Jingbo Inventor before: Yu Zhipeng Inventor before: Gao Yanan |
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