CN109928898B - Green preparation method of azoxy compound by taking MOFs derived magnetic nanoparticles as recyclable catalyst - Google Patents
Green preparation method of azoxy compound by taking MOFs derived magnetic nanoparticles as recyclable catalyst Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 28
- -1 azoxy compound Chemical class 0.000 title claims abstract description 26
- 239000012621 metal-organic framework Substances 0.000 title claims abstract description 17
- 239000002122 magnetic nanoparticle Substances 0.000 title claims abstract description 12
- 238000002360 preparation method Methods 0.000 title claims description 8
- 238000006243 chemical reaction Methods 0.000 claims abstract description 17
- 238000000034 method Methods 0.000 claims abstract description 17
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 12
- 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 abstract description 9
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000011943 nanocatalyst Substances 0.000 claims abstract description 6
- 239000002994 raw material Substances 0.000 claims abstract description 5
- 230000009471 action Effects 0.000 claims abstract description 3
- 238000006479 redox reaction Methods 0.000 claims abstract description 3
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 claims description 15
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 12
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims description 9
- 239000000463 material Substances 0.000 claims description 8
- CZGCEKJOLUNIFY-UHFFFAOYSA-N 4-Chloronitrobenzene Chemical compound [O-][N+](=O)C1=CC=C(Cl)C=C1 CZGCEKJOLUNIFY-UHFFFAOYSA-N 0.000 claims description 5
- 125000005337 azoxy group Chemical group [N+]([O-])(=N*)* 0.000 claims description 5
- 238000003763 carbonization Methods 0.000 claims description 5
- PLAZTCDQAHEYBI-UHFFFAOYSA-N 2-nitrotoluene Chemical compound CC1=CC=CC=C1[N+]([O-])=O PLAZTCDQAHEYBI-UHFFFAOYSA-N 0.000 claims description 3
- 229910021536 Zeolite Inorganic materials 0.000 claims description 3
- 238000010000 carbonizing Methods 0.000 claims description 3
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 3
- 239000010457 zeolite Substances 0.000 claims description 3
- FWIROFMBWVMWLB-UHFFFAOYSA-N 1-bromo-3-nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC(Br)=C1 FWIROFMBWVMWLB-UHFFFAOYSA-N 0.000 claims description 2
- ZDFBKZUDCQQKAC-UHFFFAOYSA-N 1-bromo-4-nitrobenzene Chemical compound [O-][N+](=O)C1=CC=C(Br)C=C1 ZDFBKZUDCQQKAC-UHFFFAOYSA-N 0.000 claims description 2
- BFCFYVKQTRLZHA-UHFFFAOYSA-N 1-chloro-2-nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1Cl BFCFYVKQTRLZHA-UHFFFAOYSA-N 0.000 claims description 2
- KMAQZIILEGKYQZ-UHFFFAOYSA-N 1-chloro-3-nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC(Cl)=C1 KMAQZIILEGKYQZ-UHFFFAOYSA-N 0.000 claims description 2
- QZYHIOPPLUPUJF-UHFFFAOYSA-N 3-nitrotoluene Chemical compound CC1=CC=CC([N+]([O-])=O)=C1 QZYHIOPPLUPUJF-UHFFFAOYSA-N 0.000 claims description 2
- NKJIFDNZPGLLSH-UHFFFAOYSA-N 4-nitrobenzonitrile Chemical compound [O-][N+](=O)C1=CC=C(C#N)C=C1 NKJIFDNZPGLLSH-UHFFFAOYSA-N 0.000 claims description 2
- BTJIUGUIPKRLHP-UHFFFAOYSA-N 4-nitrophenol Chemical compound OC1=CC=C([N+]([O-])=O)C=C1 BTJIUGUIPKRLHP-UHFFFAOYSA-N 0.000 claims description 2
- CODVACFVSVNQPY-UHFFFAOYSA-N [Co].[C] Chemical group [Co].[C] CODVACFVSVNQPY-UHFFFAOYSA-N 0.000 claims description 2
- 239000002114 nanocomposite Substances 0.000 claims description 2
- 238000000746 purification Methods 0.000 claims description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 abstract description 10
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical group OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- 239000000047 product Substances 0.000 description 6
- 229910017052 cobalt Inorganic materials 0.000 description 5
- 239000010941 cobalt Substances 0.000 description 5
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 229910001429 cobalt ion Inorganic materials 0.000 description 3
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical compound [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 238000003917 TEM image Methods 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- GAUZCKBSTZFWCT-UHFFFAOYSA-N azoxybenzene Chemical compound C=1C=CC=CC=1[N+]([O-])=NC1=CC=CC=C1 GAUZCKBSTZFWCT-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000004440 column chromatography Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 239000003480 eluent Substances 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000007800 oxidant agent Substances 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000004809 thin layer chromatography Methods 0.000 description 2
- YUCNDEWLRLACNP-UHFFFAOYSA-N (4,4-dichlorocyclohexa-1,5-dien-1-yl)-oxido-phenyliminoazanium Chemical compound C=1CC(Cl)(Cl)C=CC=1[N+]([O-])=NC1=CC=CC=C1 YUCNDEWLRLACNP-UHFFFAOYSA-N 0.000 description 1
- PEXGTUZWTLMFID-UHFFFAOYSA-N 2-phenyldiazenylphenol Chemical compound OC1=CC=CC=C1N=NC1=CC=CC=C1 PEXGTUZWTLMFID-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N N-phenyl amine Natural products NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 1
- 238000006531 Wallach Azoxybenzene rearrangement reaction Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- QGUAJWGNOXCYJF-UHFFFAOYSA-N cobalt dinitrate hexahydrate Chemical compound O.O.O.O.O.O.[Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O QGUAJWGNOXCYJF-UHFFFAOYSA-N 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000011258 core-shell material Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
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- 238000002149 energy-dispersive X-ray emission spectroscopy Methods 0.000 description 1
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- 239000008103 glucose Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000005389 magnetism Effects 0.000 description 1
- UKVIEHSSVKSQBA-UHFFFAOYSA-N methane;palladium Chemical compound C.[Pd] UKVIEHSSVKSQBA-UHFFFAOYSA-N 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 150000005181 nitrobenzenes Chemical class 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 238000005691 oxidative coupling reaction Methods 0.000 description 1
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- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
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- 238000001878 scanning electron micrograph Methods 0.000 description 1
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- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Images
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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
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The invention discloses a method for preparing azoxybenzene compound by taking MOFs derived magnetic nanoparticles as a recyclable catalyst in an environment-friendly way, which is characterized in that an aromatic nitro compound and a reducing agent are subjected to oxidation-reduction reaction under the action of a Co-containing magnetic nano catalyst to obtain an azoxybenzene compound, Co @ C-N is used as a catalyst, an aromatic hydrocarbon nitro compound is used as a raw material, hydrazine hydrate is used as a reducing agent to synthesize the azoxybenzene compound in an alcohol solution, and the catalyst participating in the reaction can be recycled in a magnetic way, so that the production cost is reduced, the method is environment-friendly, the reaction condition is simple, and the yield is high.
Description
Technical Field
The invention relates to the field of azo oxide compounds, in particular to a green preparation method of an azo oxide compound by taking MOFs derived magnetic nanoparticles as a recyclable catalyst.
Background
In recent years, azo oxide compounds have attracted more and more attention due to their specific structures, and are widely used in dyes, pigments, reducing agents, analytical reagents, chemical stabilizers, polymerization inhibitors, organic synthesis intermediates, and the like, for example, azoxybenzene is a precursor of Wallach rearrangement reaction, which provides a simple method for preparing hydroxyazobenzene.
At present, the traditional method for synthesizing azoxy compounds is to use zinc, glucose and NaBH under alkaline condition4When the reducing agent is used for reducing the nitrobenzene compound, the method can generate a large amount of alkali waste liquid, damage can be caused to the environment, and simultaneously, harsh reaction conditions are required, so that the process cost is high, and the requirements of environment-friendly and green synthesis are not met; the other common synthesis method of the azoxy compound is to perform oxidative coupling on the aniline compound by using an oxidant, however, most of the oxidants cause damage to the environment and are not favorable for sustainable development.
Nowadays, environmental-friendly green chemistry is getting more and more attention, and various heavy-environment pollution processes (including palladium-carbon hydrogenation reduction process for replacing the original iron powder and zinc powder process) are continuously eliminated globally and domestically due to environmental protection requirements. Therefore, how to design the use of an environmentally-friendly and non-toxic metal catalyst in green chemistry becomes a key point, Metal Organic Frameworks (MOFs) materials are widely concerned and researched due to the characteristics of ordered and regular structures, high specific surface areas, structural adjustability and the like, and have more attractive application prospects as rapidly-developed emerging porous materials compared with traditional porous materials, however, as the MOFs have relatively poor stability, the practical application and development of the MOFs are greatly limited.
Disclosure of Invention
In order to solve the problems, the invention provides a green preparation method of an azoxy compound by taking MOFs derived magnetic nanoparticles as a recyclable catalyst, which has the advantages of high yield, recyclable catalyst, no pollution and low reaction cost.
The technical scheme of the invention is to provide a method for preparing azoxy compound by taking MOFs derived magnetic nanoparticles as a recyclable catalyst in an environment-friendly way, wherein aromatic nitro compound and reducing agent are subjected to oxidation-reduction reaction under the action of Co-containing magnetic nanoparticles to obtain azoxybenzene compound.
Preferably, the aromatic nitro compound is one or more of nitrobenzene, p-chloronitrobenzene, m-chloronitrobenzene, o-chloronitrobenzene, p-bromonitrobenzene, m-bromonitrobenzene, o-nitrotoluene, m-nitrotoluene, p-nitrobenzonitrile and p-nitrophenol.
Preferably, the reducing agent is hydrazine hydrate.
Preferably, the Co-containing magnetic nano catalyst is a cobalt-carbon nano composite material Co @ C-N obtained by carbonizing a zeolite imidazole framework material (ZIF-67) serving as a raw material.
Preferably, the method further comprises the following purification steps: and dissolving the product after the reaction by using ethyl acetate, and recovering the Co-containing magnetic nano catalyst by using a magnet.
Preferably, the molar ratio of the aromatic nitro compound to the reducing agent is 1: 1-10.
Preferably, the mass ratio of the aromatic nitro compound to Co @ C-N is 100: 0.1-5.
Preferably, the carbonization temperature is 500-800 ℃, and the carbonization time is 2-5 h.
In the simple aspect of preparing the MOFs material by coordination of cobalt ions and 2-methylimidazole molecules, cobalt metal can be highly distributed among the 2-methylimidazole molecules. When MOFs are carbonized into a Co @ C-N material at high temperature, 2-methylimidazole is directly carbonized into two elements of C and N, and cobalt ions are reduced into a cobalt simple substance. Because cobalt ions are separated by C and N, a cobalt simple substance cannot be agglomerated after carbonization, and a core-shell type catalyst Co @ C-N with Co nanoparticles as a core and N-doped graphitized carbon as a shell can be formed. In the Co/C-N catalyst, C-N disperses Co active nanoclusters on the catalyst surface and provides an ideal chemical interface between the catalyst and the reaction medium, inhibiting aggregation of the active nanoclusters. Meanwhile, the C-N structure can adsorb a nitrobenzene substrate through p-p stacking interaction, improve the contact of reactants and the surface of a catalyst and promote electrons to migrate from the C-N to the Co active nanocluster. These factors result in high concentrations of nitroaromatics accumulating on the surface of the active Co/C-N catalyst and being efficiently reduced to the corresponding azoxy compounds. In addition, the electronic structure of the Co simple substance enables Co @ C-N to show stronger magnetism, so that the catalyst can be recycled by using a magnet, and the resource utilization is improved.
The invention prefers hydrazine hydrate as a reducing agent, mainly because the reaction product of hydrazine hydrate only contains water and hydrogen, which has no pollution to the environment and accords with the green reaction direction. In addition, hydrazine hydrate is less reducing than borohydride, and does not directly reduce nitrobenzene compounds to amino compounds.
The method has the beneficial effects that the Co @ C-N is used as the catalyst, the aromatic hydrocarbon nitro compound is used as the raw material, the hydrazine hydrate is used as the reducing agent to synthesize the azoxybenzene compound in the alcohol solution, the catalyst participating in the reaction can be magnetically recycled, the production cost is reduced, the method is green and environment-friendly, the reaction condition is simple, and the yield is high.
Drawings
FIG. 1 is an SEM photograph of ZIF-67 in example 1;
FIG. 2 is an SEM photograph of Co @ C-N in example 1;
FIG. 3 is a TEM image of Co @ C-N in example 1;
FIG. 4 is an EDS analysis chart of Co @ C-N in example 1.
Detailed Description
In order to make the present invention more comprehensible, the technical solutions of the present invention are further described below with reference to specific embodiments, but the present invention is not limited thereto.
The raw materials used in the invention are all common commercial products and AR pure unless specified otherwise.
Example 1
a. ZIF-67 Synthesis: dissolving 0.6g of cobalt nitrate hexahydrate and 7.31g of 2-methylimidazole in 4ml of deionized water and 26 ml of deionized water respectively, slowly adding the second part of solution into the first solution, enabling the color to quickly change into purple, stirring for 3 hours at room temperature under the stirring condition, after the reaction is finished, centrifuging at 8000 rpm to collect a blue solid, centrifuging for 4 minutes, washing with ethanol for 3 times, and after the collected crystals are dried for 5 hours in vacuum, wherein the yield reaches 61%. The ZIF-67 structure is shown in FIG. 1 as a polyhedral particle with a diameter of approximately 400 nm.
b. Preparation of Co @ C-N catalyst: and under the condition of nitrogen atmosphere, placing 0.8g of ZIF-67 in a muffle furnace, carbonizing at 800 ℃, keeping the temperature for 2h at the heating speed of 10 ℃/min respectively, and naturally cooling to room temperature to obtain the Co @ C-N catalyst. The structure of Co @ C-N is approximately 100nm particles (as shown in the SEM image of FIG. 2), wherein the particle size of the elemental cobalt particles is approximately 25nm, and the cobalt nanoparticles are not significantly agglomerated (as shown in the TEM image of FIG. 3). Co @ C-N was further analyzed for composition by EDS testing, as shown in FIG. 4, and EDS results indicate that Co @ C-N contains a large amount of Co, C and a small amount of N.
c. Catalytic experiment: nitrobenzene (0.5g, 10 mmol) and Co/C-N (0.006-0.024g) were mixed in a round bottom bottle, 5-25ml ethanol was added, and stirred to 50 deg.C until the nitrobenzene was completely dissolved. Then 0.2-1.5g of 80% hydrazine hydrate is added to the above mixture. The reaction temperature was maintained at 50 ℃ and characterized by thin layer chromatography. After the reaction is completed, 5-25ml of ethyl acetate is added, and Co/C-N is separated by magnet adsorption. The filtrate was concentrated under reduced pressure and purified by column chromatography (eluent petroleum ether, 60-90 ℃) to give azoxybenzene in 78% yield.
Example 2
Example 2 is essentially the same as example 1 except that the deionized water in step (a) is replaced with methanol or ethanol and the ethanol in step (c) is replaced with methanol. The target product was also successfully synthesized.
Example 3
Example 4 is essentially the same as example 1 except that nitrobenzene in step (c) is replaced with methylnitrobenzene. The target product is also successfully synthesized.
Example 4
Example 4 is essentially the same as example 1 except that nitrobenzene in step (c) is replaced with p-chloronitrobenzene. The target product is also successfully synthesized.
Example 4
P-chloronitrobenzene (62.8g, 1mol) and Co/C-N (0.1g) were mixed in a round bottom flask, 500ml methanol was added and stirred to 50 ℃ until the p-chloronitrobenzene was completely dissolved. Then 100g of 80% hydrazine hydrate was added to the above mixture. The reaction temperature was maintained at 50 ℃ and the reaction was monitored by thin layer chromatography. After the reaction was completed, 300ml of ethyl acetate was added, and the Co/C-N catalyst was separated by magnet adsorption. The filtrate was concentrated under reduced pressure and purified by column chromatography (eluent petroleum ether, 60-90 ℃) to give 4, 4-dichloroazoxybenzene in 82% yield.
Example 5
Example 5 is essentially the same as example 4 except that no Co/C-N catalyst was added to the reaction system. The results showed that the desired product was not obtained.
The above description is only a preferred embodiment of the present invention, and all equivalent changes and modifications made in accordance with the claims of the present invention should be covered by the present invention.
Claims (5)
1. A method for preparing azoxy compound with MOFs derived magnetic nano particles as a recyclable catalyst in a green way is characterized in that aromatic nitro compound and a reducing agent are subjected to oxidation-reduction reaction under the action of a Co-containing magnetic nano catalyst to obtain azoxybenzene compound; the Co-containing magnetic nano catalyst is a cobalt-carbon nano composite material Co @ C-N obtained by carbonizing a zeolite imidazole framework structure material serving as a raw material; wherein the aromatic nitro compound is one or more of nitrobenzene, p-chloronitrobenzene, m-chloronitrobenzene, o-chloronitrobenzene, p-bromonitrobenzene, m-bromonitrobenzene, o-nitrotoluene, m-nitrotoluene, p-nitrobenzonitrile and p-nitrophenol; the reducing agent is hydrazine hydrate; the zeolite imidazole framework material is ZIF-67.
2. The method for green preparation of azoxy compounds using MOFs-derived magnetic nanoparticles as recoverable catalyst according to claim 1, further comprising the purification steps of: and dissolving the product after the reaction by using ethyl acetate, and recovering the Co-containing magnetic nano catalyst by using a magnet.
3. The method for green preparation of azoxy compounds by using MOFs derived magnetic nanoparticles as recoverable catalysts according to claim 1, wherein the molar ratio of the aromatic nitro compounds to the reducing agent is 1: 1-10.
4. The method for preparing the azoxy compound by taking the MOFs-derived magnetic nanoparticles as the recyclable catalyst in the green color according to claim 1, wherein the mass ratio of the aromatic nitro compound to the Co @ C-N is 100: 0.1-5.
5. The method for green preparation of azoxy compounds by using MOFs derived magnetic nanoparticles as recoverable catalysts according to claim 1, wherein the carbonization temperature is 500-800 ℃ and the carbonization time is 2-5 h.
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Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
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JP2012020977A (en) * | 2010-07-16 | 2012-02-02 | Prefectural Univ Of Hiroshima | Solid-phase organic reaction method |
CN103443141A (en) * | 2011-03-18 | 2013-12-11 | Lg化学株式会社 | Polymer supported reagents and methods of reducing aromatic nitro compounds by using the same |
CN106914267A (en) * | 2017-03-31 | 2017-07-04 | 温州大学 | A kind of nitrogen co-doped mesoporous carbon of iron and its preparation method and application |
CN107353233A (en) * | 2017-07-17 | 2017-11-17 | 温州大学 | A kind of method for catalyzing and synthesizing asymmetric oxidation azobenzene compound |
-
2019
- 2019-04-09 CN CN201910278343.7A patent/CN109928898B/en active Active
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2012020977A (en) * | 2010-07-16 | 2012-02-02 | Prefectural Univ Of Hiroshima | Solid-phase organic reaction method |
CN103443141A (en) * | 2011-03-18 | 2013-12-11 | Lg化学株式会社 | Polymer supported reagents and methods of reducing aromatic nitro compounds by using the same |
CN106914267A (en) * | 2017-03-31 | 2017-07-04 | 温州大学 | A kind of nitrogen co-doped mesoporous carbon of iron and its preparation method and application |
CN107353233A (en) * | 2017-07-17 | 2017-11-17 | 温州大学 | A kind of method for catalyzing and synthesizing asymmetric oxidation azobenzene compound |
Non-Patent Citations (8)
Title |
---|
Catalytic nickel nanoparticles embedded in a mesoporous metal–organic framework;Young Kwan Park等;《Chem.Commun.》;20101231;第46卷;3086-3088 * |
Chemoselectiv hydrogenation of functionalized nitroarenes using MOF-derived co-based catalysts;Xi Wang等;《Journal of Molecular Catalysis A: Chemical》;20161231;第420卷;56-65 * |
Co-Ag alloy protected by nitrogen doped carbon as highly efficient and chemoselective catalysts for the hydrogenation of halogenated nitrobenzenes;Wei Zhang;《Journal of Colloid and Interface Science》;20181231;第522卷;217-227 * |
Jilan Long等.Bifunctional N‑Doped Co@C Catalysts for Base-Free Transfer Hydrogenations of Nitriles: Controllable Selectivity to Primary Amines vs Imines.《ACS Catal.》.2016,第7卷275-284. * |
Metal–Organic Framework Mediated Cobalt/Nitrogen-DopedCarbon Hybridsas Efficient and ChemoselectiveCatalystsfor the Hydrogenation of Nitroarenes;Xiao hui Sun等;《Chem Cat Chem》;20171231;第9卷;1854-1862 * |
Mild, selective and switchable transfer reduction of nitroarenes catalyzed by supported gold nanoparticles;Xiang Liu等;《Catal. Sci. Technol.》;20131231;第3卷;3200-3206 * |
Room temperature selective reduction of nitrobenzene to azoxybenzene over magnetically separable urchin-like Ni/Graphene nanocomposites;Madhavi N. Pahalagedara等;《Journal of Catalysis》;20161231;第336卷;41-48 * |
Ruthenium Nanoparticle-Catalyzed, Controlled and Chemoselective Hydrogenation of Nitroarenes using Ethanol as a Hydrogen Source;Ju Hyun Kim等;《Adv.Synth.Catal.》;20121231;第354卷;2412-2418 * |
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