CN114950527B - Catalyst for synthesizing azobenzene compound - Google Patents
Catalyst for synthesizing azobenzene compound Download PDFInfo
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- CN114950527B CN114950527B CN202210606861.9A CN202210606861A CN114950527B CN 114950527 B CN114950527 B CN 114950527B CN 202210606861 A CN202210606861 A CN 202210606861A CN 114950527 B CN114950527 B CN 114950527B
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- 239000003054 catalyst Substances 0.000 title claims abstract description 35
- -1 azobenzene compound Chemical class 0.000 title abstract description 13
- 230000002194 synthesizing effect Effects 0.000 title abstract description 7
- 238000006243 chemical reaction Methods 0.000 claims abstract description 23
- 239000002243 precursor Substances 0.000 claims abstract description 12
- DMLAVOWQYNRWNQ-UHFFFAOYSA-N azobenzene Chemical class C1=CC=CC=C1N=NC1=CC=CC=C1 DMLAVOWQYNRWNQ-UHFFFAOYSA-N 0.000 claims abstract description 10
- 238000002360 preparation method Methods 0.000 claims abstract description 10
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 10
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000004202 carbamide Substances 0.000 claims abstract description 9
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 8
- YJVFFLUZDVXJQI-UHFFFAOYSA-L palladium(ii) acetate Chemical compound [Pd+2].CC([O-])=O.CC([O-])=O YJVFFLUZDVXJQI-UHFFFAOYSA-L 0.000 claims abstract description 8
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910021529 ammonia Inorganic materials 0.000 claims abstract description 4
- 239000012298 atmosphere Substances 0.000 claims abstract description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 14
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 12
- 230000015572 biosynthetic process Effects 0.000 claims description 8
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims description 7
- 239000003513 alkali Substances 0.000 claims description 7
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims description 7
- 150000005181 nitrobenzenes Chemical class 0.000 claims description 7
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 6
- 230000035484 reaction time Effects 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 5
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 4
- 229910002669 PdNi Inorganic materials 0.000 claims description 4
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 2
- 239000012295 chemical reaction liquid Substances 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- 239000011261 inert gas Substances 0.000 claims description 2
- 230000003197 catalytic effect Effects 0.000 abstract description 5
- 239000000758 substrate Substances 0.000 abstract description 5
- 231100000331 toxic Toxicity 0.000 abstract description 5
- 230000002588 toxic effect Effects 0.000 abstract description 5
- 239000006227 byproduct Substances 0.000 abstract description 4
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Substances [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 abstract description 3
- 238000005265 energy consumption Methods 0.000 abstract description 2
- 238000009776 industrial production Methods 0.000 abstract description 2
- WNVWWDKUMKBZQV-UHFFFAOYSA-N bis(4-methylphenyl)diazene Chemical compound C1=CC(C)=CC=C1N=NC1=CC=C(C)C=C1 WNVWWDKUMKBZQV-UHFFFAOYSA-N 0.000 description 7
- 238000000034 method Methods 0.000 description 6
- 239000000047 product Substances 0.000 description 4
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 3
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 3
- ZPTVNYMJQHSSEA-UHFFFAOYSA-N 4-nitrotoluene Chemical compound CC1=CC=C([N+]([O-])=O)C=C1 ZPTVNYMJQHSSEA-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical group [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- GAUZCKBSTZFWCT-UHFFFAOYSA-N azoxybenzene Chemical class C=1C=CC=CC=1[N+]([O-])=NC1=CC=CC=C1 GAUZCKBSTZFWCT-UHFFFAOYSA-N 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 239000012530 fluid Substances 0.000 description 2
- AOPCKOPZYFFEDA-UHFFFAOYSA-N nickel(2+);dinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O AOPCKOPZYFFEDA-UHFFFAOYSA-N 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 239000006228 supernatant Substances 0.000 description 2
- 238000001308 synthesis method Methods 0.000 description 2
- 229910021642 ultra pure water Inorganic materials 0.000 description 2
- 239000012498 ultrapure water Substances 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- IOVCWXUNBOPUCH-UHFFFAOYSA-M Nitrite anion Chemical compound [O-]N=O IOVCWXUNBOPUCH-UHFFFAOYSA-M 0.000 description 1
- 238000003917 TEM image Methods 0.000 description 1
- 239000005456 alcohol based solvent Substances 0.000 description 1
- 230000003321 amplification Effects 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000012954 diazonium Substances 0.000 description 1
- 150000001989 diazonium salts Chemical class 0.000 description 1
- 238000006193 diazotization reaction Methods 0.000 description 1
- 239000011363 dried mixture Substances 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 238000012377 drug delivery Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000002778 food additive Substances 0.000 description 1
- 235000013373 food additive Nutrition 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000000024 high-resolution transmission electron micrograph Methods 0.000 description 1
- 238000002173 high-resolution transmission electron microscopy Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 238000003760 magnetic stirring Methods 0.000 description 1
- 238000001819 mass spectrum Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- NLRKCXQQSUWLCH-UHFFFAOYSA-N nitrosobenzene Chemical compound O=NC1=CC=CC=C1 NLRKCXQQSUWLCH-UHFFFAOYSA-N 0.000 description 1
- 238000003199 nucleic acid amplification method Methods 0.000 description 1
- 238000005580 one pot reaction Methods 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Classifications
-
- 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
-
- 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
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a catalyst for synthesizing azobenzene compounds, and relates 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 synthesizing the azobenzene compound from the nitrobenzene compound, has good applicability to catalytic substrates and high yield, does not generate toxic and harmful byproducts in the reaction process, has mild reaction conditions and low energy consumption, and can be suitable for industrial production of the azobenzene compound.
Description
Technical field:
the invention relates to the technical field of organic synthesis catalysts, in particular to a catalyst for synthesizing azobenzene compounds.
The background technology is as follows:
aromatic azo derivatives having conjugated nitrogen-nitrogen double bonds possess unique photochemical and photophysical properties, showing advantages in organic dyes, food additives, colorants, drugs and drug delivery media.
Traditionally, the general procedure for the preparation of aromatic azo compounds is: (1) The diazonium salt or nitrosobenzene intermediate is prepared first, and the compound is very unstable, dangerous in reaction process and easy to explode. (2) The nitrite (NaNO) is used in a large amount 2 ) Or toxic oxidizing agents to treat the substrate. Such a method is prone to the generation of harmful by-products, and has disadvantages of low isolation yield and complicated synthesis steps. Therefore, the research of a novel synthetic method of asymmetric azobenzene and azoxybenzene compounds and derivatives thereof with high efficiency, green and high atom economy has very important value.
The application range of the synthesis method disclosed in the patent CN 201910800189.5 and the patent CN 202111607378.4 is smaller; patent CN 201410499441.0 discloses a preparation method of asymmetric aromatic azo, which uses aromatic hydrazine and halogenated aromatic hydrocarbon as raw materials to obtain an asymmetric aromatic azo compound, although the method avoids diazotization step and reduces reaction danger, the aromatic hydrazine compound is easy to decompose and emits toxic nitrogen oxide smoke when heated, and the method has the defects of low atomic utilization rate, incapability of selectively regulating and controlling synthesis of azobenzene and azoxybenzene, and the like.
The invention comprises the following steps:
the invention aims to solve the technical problem of providing 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, no toxic or 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 urea is 110-130 ℃ and the reaction time is 5-8h.
The reaction temperature of the precursor and palladium acetate is 370 ℃ and the reaction time is 2h.
It is a further object of the present invention to provide a catalyst prepared according to the aforementioned preparation method.
The structural formula of the catalyst is PdNi&Ni 3 N。
It is a further object of the present invention to provide the use of the aforementioned catalyst in the synthesis of azobenzene compounds.
The fourth object of the invention is to provide a synthesis method of azobenzene compound, wherein nitrobenzene compound, the catalyst, alkali and hydrazine hydrate are added into solvent to react under the protection of inert gas, after the reaction, the reaction liquid is contacted with air, the product is collected, and dried to obtain azobenzene compound.
The solvent is one of alcohol solvents such as methanol, ethanol, isopropanol, ethylene glycol and the like. As a preferred embodiment, the solvent is ethanol.
The alkali is one of proton alkali such as potassium hydroxide, sodium hydroxide, ammonia water and the like. As a preferred embodiment, the base is potassium hydroxide.
The dosage of the alkali is 5-7 times of the molar quantity of the nitrobenzene compounds.
The dosage of the catalyst is 3-5wt% of the mass of nitrobenzene compounds.
The reaction temperature is 60+/-5 ℃ and the reaction time is 6-9h.
The dosage of the hydrazine hydrate is 0.2-0.5mL of hydrazine hydrate used for each 1mmol of nitrobenzene compounds.
The beneficial effects of the invention are as follows: the novel catalyst prepared by the invention has high catalytic activity and low preparation cost, can be repeatedly applied to synthesizing the azobenzene compound from the nitrobenzene compound, has good applicability to catalytic substrates and high yield, does not generate toxic and harmful byproducts in the reaction process, has mild reaction conditions and low energy consumption, and can be suitable for industrial production of the azobenzene compound.
Description of the drawings:
FIG. 1 is an XRD pattern of a catalyst prepared in accordance with the present invention;
FIG. 2 is a structural representation of the catalyst prepared according to the present invention: (a) a TEM image; (b) HRTEM images; (c-f) HRTEM amplification;
FIG. 3 is a hydrogen spectrum of the synthetic product 4,4' -dimethyl azobenzene of the present invention;
FIG. 4 is a carbon spectrum of the synthetic product 4,4' -dimethyl azobenzene of the present invention;
FIG. 5 is a mass spectrum of the synthesized product 4,4' -dimethyl azobenzene of the present invention;
FIG. 6 shows the recycling performance of the catalyst prepared according to the present invention.
The specific embodiment is as follows:
the invention is further described below with reference to specific embodiments and illustrations in order to make the technical means, the creation features, the achievement of the purpose and the effect of the implementation of the invention easy to understand.
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 into a baking oven at 120 ℃ for reaction for 6 hours, pouring out supernatant fluid in the reaction kettle after the reaction is finished, collecting turbid matters at the bottom into a centrifuge tube, adding a proper amount of ultrapure water, shaking uniformly, centrifuging for 1min at the rotating speed of 9000r/min, pouring out supernatant fluid, collecting turbid matters at the bottom, repeating the centrifugation four times (three times of ultrapure water and one time of ethanol), and finally drying in a vacuum baking oven at 60 ℃ for 24 hours to obtain a precursor.
(2) 200mg of precursor and 10mg of palladium acetate are weighed, uniformly mixed and dried; taking 50mg of the dried mixture, heating to 370 ℃ in an ammonia atmosphere, reacting for 2 hours, and collecting the catalyst after the reaction is finished.
As shown in FIG. 1, the diffraction peak position of the XRD pattern is consistent with the standard card number 100280, which proves that the substance is Ni as the main substrate 3 N, two more peaks are located between the standard card number (461043) diffraction peak position of palladium and the corresponding standard card number (040850) diffraction peak position of nickel, and are the diffraction peaks of PdNi alloy.
As shown in FIG. 2, the XRD pattern was confirmed by the images obtained by a transmission electron microscope and a high-resolution transmission electron microscope, and the majority of the images had a lattice spacing of 0.203nm, which was equal to Ni 3 The (111) crystal face of N is consistent, the lattice spacing of other positions is 0.188nm, and the lattice spacing is consistent with the (200) crystal face of PdNi alloy.
Example 2
Synthesis of 4,4' -dimethyl azobenzene (1, 2-di-p-tolyldiazene):
to a 100mL round bottom flask, 20mL of ethanol, 5mmol of potassium hydroxide, 1mmol of paranitrotoluene, 5mg of the catalyst prepared in example 1, and a nitrogen system were added under magnetic stirring, 0.5mL of hydrazine hydrate was injected, the reaction was allowed to react at 60℃for 8 hours, after the completion of the reaction, the reaction solution was allowed to contact with air, filtered, extracted with dichloromethane and water, recrystallized from ethanol, and dried to give 103.9mg of a yellow solid in 99% yield. 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' -dimethyl azobenzene by one-step reaction using the catalyst prepared in example 1, and the yield reached 99%.
Example 3
The catalyst prepared in example 1 was repeatedly applied to the synthesis of 4,4' -dimethyl azobenzene from paranitrotoluene using the method of example 2, and the result is shown in fig. 6.
As can be seen from fig. 6a, the catalytic effect after catalyst circulation is still stable.
As can be seen from fig. 6b, the catalyst is structurally stable after recycling.
The foregoing has shown and described the basic principles and main features of the present invention and the advantages of the present invention. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, and that the above embodiments and descriptions are merely illustrative of the principles of the present invention, and various changes and modifications may be made without departing from the spirit and scope of the invention, which is defined in the appended claims. The scope of the invention is defined by the appended claims and equivalents thereof.
Claims (5)
1. The application of the catalyst in the synthesis of azobenzene compounds is disclosed, and the preparation method of the catalyst comprises the following steps: firstly, nickel nitrate reacts with urea to prepare a precursor, and then the precursor reacts with palladium acetate in an ammonia atmosphere to prepare a 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 urea is 110-130 ℃ and the reaction time is 5-8 h; the reaction temperature of the precursor and palladium acetate is 370 ℃ and the reaction time is 2 h;
the structural formula of the catalyst is PdNi&Ni 3 N。
2. The use according to claim 1, characterized in that: adding nitrobenzene compounds, catalysts, alkali and hydrazine hydrate into a solvent, reacting under the protection of inert gas, enabling reaction liquid to contact with air after the reaction is finished, collecting products, and drying to obtain azobenzene compounds.
3. The use according to claim 2, characterized in that: the dosage of the catalyst is 3-5wt% of the mass of nitrobenzene compounds.
4. The use according to claim 2, characterized in that: the solvent is one of methanol, ethanol, isopropanol and ethylene glycol; the alkali is one of potassium hydroxide, sodium hydroxide and ammonia water.
5. The use according to claim 2, characterized in that: the dosage of the alkali is 5-7 times of the molar quantity of the nitrobenzene compounds; the dosage of the hydrazine hydrate is 0.2-0.5. 0.5mL hydrazine hydrate used for each 1mmol of nitrobenzene compounds; the reaction temperature is 60+/-5 ℃ and the reaction time is 6-9h.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH04134056A (en) * | 1990-09-21 | 1992-05-07 | Ube Ind Ltd | Production of dinitroazobenzene |
| CN105148971A (en) * | 2015-08-26 | 2015-12-16 | 中国科学院理化技术研究所 | High-performance ultrathin nitride electrocatalyst for producing hydrogen and oxygen by electrochemically and completely decomposing water and synthesis method and application thereof |
| 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 |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP5331011B2 (en) * | 2008-02-20 | 2013-10-30 | 昭和電工株式会社 | Catalyst carrier, catalyst and method for producing the same |
| IS2972B (en) * | 2014-06-13 | 2017-07-15 | Háskóli Íslands | Process and system for electrolytic production of ammonia |
| KR101912251B1 (en) * | 2016-09-19 | 2018-10-29 | 한국과학기술연구원 | Catalyst for dehydrogenation reaction of formic acid and method for preparing the same |
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH04134056A (en) * | 1990-09-21 | 1992-05-07 | Ube Ind Ltd | Production of dinitroazobenzene |
| CN105148971A (en) * | 2015-08-26 | 2015-12-16 | 中国科学院理化技术研究所 | High-performance ultrathin nitride electrocatalyst for producing hydrogen and oxygen by electrochemically and completely decomposing water and synthesis method and application thereof |
| 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 |
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