CN107814760B - Preparation method and application of metal organic cage-shaped compound for preparing aniline by catalytic reduction of nitrobenzene - Google Patents
Preparation method and application of metal organic cage-shaped compound for preparing aniline by catalytic reduction of nitrobenzene Download PDFInfo
- Publication number
- CN107814760B CN107814760B CN201710937122.7A CN201710937122A CN107814760B CN 107814760 B CN107814760 B CN 107814760B CN 201710937122 A CN201710937122 A CN 201710937122A CN 107814760 B CN107814760 B CN 107814760B
- Authority
- CN
- China
- Prior art keywords
- hours
- stirring
- cobalt
- reaction
- tpo
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 title claims abstract description 60
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 title claims abstract description 38
- 150000001875 compounds Chemical class 0.000 title claims abstract description 27
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 20
- 239000002184 metal Substances 0.000 title claims abstract description 20
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 238000010531 catalytic reduction reaction Methods 0.000 title claims abstract description 11
- 238000006243 chemical reaction Methods 0.000 claims abstract description 45
- 239000003446 ligand Substances 0.000 claims abstract description 21
- -1 transition metal salt Chemical class 0.000 claims abstract description 11
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 9
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims abstract description 6
- BSUSEPIPTZNHMN-UHFFFAOYSA-L cobalt(2+);diperchlorate Chemical compound [Co+2].[O-]Cl(=O)(=O)=O.[O-]Cl(=O)(=O)=O BSUSEPIPTZNHMN-UHFFFAOYSA-L 0.000 claims abstract description 6
- RDLMYNHWUFIVQE-UHFFFAOYSA-L cobalt(2+);trifluoromethanesulfonate Chemical compound [Co+2].[O-]S(=O)(=O)C(F)(F)F.[O-]S(=O)(=O)C(F)(F)F RDLMYNHWUFIVQE-UHFFFAOYSA-L 0.000 claims abstract description 6
- 150000003624 transition metals Chemical class 0.000 claims abstract description 5
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 66
- 239000000243 solution Substances 0.000 claims description 41
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 36
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 30
- 238000003756 stirring Methods 0.000 claims description 29
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 24
- 239000012065 filter cake Substances 0.000 claims description 24
- 239000007787 solid Substances 0.000 claims description 24
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 20
- 239000000843 powder Substances 0.000 claims description 19
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 18
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 18
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 18
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 16
- 238000000967 suction filtration Methods 0.000 claims description 16
- 239000001257 hydrogen Substances 0.000 claims description 14
- 229910052739 hydrogen Inorganic materials 0.000 claims description 14
- 238000010992 reflux Methods 0.000 claims description 13
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 12
- DOSDTCPDBPRFHQ-UHFFFAOYSA-N dimethyl 5-hydroxybenzene-1,3-dicarboxylate Chemical compound COC(=O)C1=CC(O)=CC(C(=O)OC)=C1 DOSDTCPDBPRFHQ-UHFFFAOYSA-N 0.000 claims description 10
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 10
- 238000002156 mixing Methods 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 6
- CSDSSGBPEUDDEE-UHFFFAOYSA-N 2-formylpyridine Chemical compound O=CC1=CC=CC=N1 CSDSSGBPEUDDEE-UHFFFAOYSA-N 0.000 claims description 6
- 229960000583 acetic acid Drugs 0.000 claims description 6
- 239000000706 filtrate Substances 0.000 claims description 6
- 238000001914 filtration Methods 0.000 claims description 6
- 239000012362 glacial acetic acid Substances 0.000 claims description 6
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims description 6
- 239000005457 ice water Substances 0.000 claims description 6
- 239000012046 mixed solvent Substances 0.000 claims description 6
- 239000002244 precipitate Substances 0.000 claims description 6
- 238000000926 separation method Methods 0.000 claims description 5
- IJOYGTWYIUJJRU-UHFFFAOYSA-N 5-fluorobenzene-1,3-dicarbonitrile Chemical compound FC1=CC(C#N)=CC(C#N)=C1 IJOYGTWYIUJJRU-UHFFFAOYSA-N 0.000 claims description 4
- 239000011259 mixed solution Substances 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 3
- 150000001868 cobalt Chemical class 0.000 claims description 2
- 230000001376 precipitating effect Effects 0.000 claims description 2
- 238000001291 vacuum drying Methods 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 13
- 230000009467 reduction Effects 0.000 abstract description 10
- 238000006722 reduction reaction Methods 0.000 abstract description 10
- 239000003054 catalyst Substances 0.000 abstract description 5
- 239000002994 raw material Substances 0.000 abstract description 5
- 238000005286 illumination Methods 0.000 abstract description 4
- 239000000126 substance Substances 0.000 abstract description 4
- 238000003889 chemical engineering Methods 0.000 abstract description 2
- 239000012847 fine chemical Substances 0.000 abstract description 2
- 238000005160 1H NMR spectroscopy Methods 0.000 description 12
- IAZDPXIOMUYVGZ-WFGJKAKNSA-N DMSO-d6 Substances [2H]C([2H])([2H])S(=O)C([2H])([2H])[2H] IAZDPXIOMUYVGZ-WFGJKAKNSA-N 0.000 description 12
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 8
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 8
- 238000002330 electrospray ionisation mass spectrometry Methods 0.000 description 8
- 238000004519 manufacturing process Methods 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 6
- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 description 4
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 238000000921 elemental analysis Methods 0.000 description 4
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 4
- LAQPNDIUHRHNCV-UHFFFAOYSA-N isophthalonitrile Chemical compound N#CC1=CC=CC(C#N)=C1 LAQPNDIUHRHNCV-UHFFFAOYSA-N 0.000 description 4
- 239000011541 reaction mixture Substances 0.000 description 4
- 239000011734 sodium Substances 0.000 description 4
- 229910052724 xenon Inorganic materials 0.000 description 4
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 3
- 239000011668 ascorbic acid Substances 0.000 description 3
- 229960005070 ascorbic acid Drugs 0.000 description 3
- 235000010323 ascorbic acid Nutrition 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 150000002431 hydrogen Chemical class 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 230000003712 anti-aging effect Effects 0.000 description 2
- 239000012300 argon atmosphere Substances 0.000 description 2
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 239000000543 intermediate Substances 0.000 description 2
- 150000002736 metal compounds Chemical class 0.000 description 2
- 239000012860 organic pigment Substances 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- KLLLJCACIRKBDT-UHFFFAOYSA-N 2-phenyl-1H-indole Chemical compound N1C2=CC=CC=C2C=C1C1=CC=CC=C1 KLLLJCACIRKBDT-UHFFFAOYSA-N 0.000 description 1
- 239000002890 Aclonifen Substances 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- GXDVEXJTVGRLNW-UHFFFAOYSA-N [Cr].[Cu] Chemical compound [Cr].[Cu] GXDVEXJTVGRLNW-UHFFFAOYSA-N 0.000 description 1
- DDBMQDADIHOWIC-UHFFFAOYSA-N aclonifen Chemical compound C1=C([N+]([O-])=O)C(N)=C(Cl)C(OC=2C=CC=CC=2)=C1 DDBMQDADIHOWIC-UHFFFAOYSA-N 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- 239000005441 aurora Substances 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000004440 column chromatography Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- MCPLVIGCWWTHFH-UHFFFAOYSA-M disodium;4-[4-[[4-(4-sulfoanilino)phenyl]-[4-(4-sulfonatophenyl)azaniumylidenecyclohexa-2,5-dien-1-ylidene]methyl]anilino]benzenesulfonate Chemical compound [Na+].[Na+].C1=CC(S(=O)(=O)O)=CC=C1NC1=CC=C(C(=C2C=CC(C=C2)=[NH+]C=2C=CC(=CC=2)S([O-])(=O)=O)C=2C=CC(NC=3C=CC(=CC=3)S([O-])(=O)=O)=CC=2)C=C1 MCPLVIGCWWTHFH-UHFFFAOYSA-M 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 239000010408 film Substances 0.000 description 1
- 239000000417 fungicide Substances 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 239000002917 insecticide Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000001819 mass spectrum Methods 0.000 description 1
- 230000001699 photocatalysis Effects 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- MFOUDYKPLGXPGO-UHFFFAOYSA-N propachlor Chemical compound ClCC(=O)N(C(C)C)C1=CC=CC=C1 MFOUDYKPLGXPGO-UHFFFAOYSA-N 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 235000013599 spices Nutrition 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- ANRHNWWPFJCPAZ-UHFFFAOYSA-M thionine Chemical compound [Cl-].C1=CC(N)=CC2=[S+]C3=CC(N)=CC=C3N=C21 ANRHNWWPFJCPAZ-UHFFFAOYSA-M 0.000 description 1
- 239000002966 varnish Substances 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/24—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with substituted hydrocarbon radicals attached to ring carbon atoms
- C07D213/36—Radicals substituted by singly-bound nitrogen atoms
- C07D213/42—Radicals substituted by singly-bound nitrogen atoms having hetero atoms attached to the substituent nitrogen atom
-
- 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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/22—Organic complexes
- B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
- B01J31/2208—Oxygen, e.g. acetylacetonates
- B01J31/2217—At least one oxygen and one nitrogen atom present as complexing atoms in an at least bidentate or bridging ligand
-
- B01J35/39—
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
- C07C209/30—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds
- C07C209/32—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds by reduction of nitro groups
- C07C209/36—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds by reduction of nitro groups by reduction of nitro groups bound to carbon atoms of six-membered aromatic rings in presence of hydrogen-containing gases and a catalyst
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic System
- C07F15/06—Cobalt compounds
- C07F15/065—Cobalt compounds without a metal-carbon linkage
-
- 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
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/02—Compositional aspects of complexes used, e.g. polynuclearity
- B01J2531/0238—Complexes comprising multidentate ligands, i.e. more than 2 ionic or coordinative bonds from the central metal to the ligand, the latter having at least two donor atoms, e.g. N, O, S, P
- B01J2531/0241—Rigid ligands, e.g. extended sp2-carbon frameworks or geminal di- or trisubstitution
- B01J2531/0244—Pincer-type complexes, i.e. consisting of a tridentate skeleton bound to a metal, e.g. by one to three metal-carbon sigma-bonds
-
- 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
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/80—Complexes comprising metals of Group VIII as the central metal
- B01J2531/84—Metals of the iron group
- B01J2531/845—Cobalt
Abstract
The invention relates to the technical field of fine chemical engineering, in particular to a preparation method and application of a metal organic cage-shaped compound for preparing aniline by catalytic reduction of nitrobenzene, wherein the preparation method is Co in transition metal salt2+The metal organic cage-shaped compound is prepared by taking L as a ligand through a reaction by taking the L as a node, and the synthetic route is as follows2++ L → Co-L, the ligand L is selected from H4TPO, wherein the transition metal salt is selected from one of cobalt perchlorate, cobalt nitrate, cobalt tetrafluoroborate or cobalt trifluoromethanesulfonate; the metal organic cage-shaped compound prepared by the method has the advantages of low raw material price, high yield, stable chemical property of the obtained compound and easy application in practical application, and the cycle number of reduction of nitrobenzene as a catalyst under the condition of illumination can reach 200000.
Description
Technical Field
The invention relates to a preparation method and application of a metal organic cage-shaped compound for preparing aniline by catalytic reduction of nitrobenzene, belonging to the technical field of fine chemical engineering.
Background
Aniline is one of the most important intermediates in chemical industrial production, and can be used for manufacturing acid ink blue G, acid medium BS, acid bright yellow and the like in the dye industry; in the aspect of organic pigments, the organic pigments are used for manufacturing aurora red, scarlet powder, phenol cyanine red and the like; in the agrochemical industry for the production of many insecticides, fungicides such as DDV, aclonifen, propachlor and the like; aniline is an important raw material of a rubber auxiliary agent and is used for manufacturing an anti-aging agent A, an anti-aging agent D and the like; can also be used as raw material of sulfa drugs, and is also an intermediate for producing spices, plastics, varnish, films and the like; and can be used as a stabilizer in explosives, an explosion-proof agent in gasoline and a solvent; other compounds may also be used for the production of hydroquinone, 2-phenylindole, and the like. Research shows that there are two methods for preparing aniline by reducing nitrobenzene in industry: iron powder nitrobenzene reduction and catalytic hydrogenation nitrobenzene reduction. The iron powder nitrobenzene reduction method is mostly produced by a batch method. Aniline waste water, partial iron powder and hydrochloric acid are put into a reduction pot, heated by direct steam, added with nitrobenzene and iron powder in batches after a period of time, and reacted until the reflux condensate has no nitrobenzene. The method has low reaction efficiency, serious pollution and high energy consumption, and is basically stopped at present. Catalytic hydrogenation of nitrobenzene is divided into gas phase and liquid phase, but gas phase is mostly used in industrial production. Typically, the fixed bed process of Sumitomo in Japan is to feed fresh hydrogen and recycle hydrogen together to a preheater where a certain pressure is maintained for preheating. The preheated hydrogen and nitrobenzene are fed into evaporator, and fed into reactor after regulating mixing ratio, the fixed bed reactor is tubular, and the copper-chromium catalyst is placed in the tube. The reaction takes hydrogen as hydrogen source, the pressure of the hydrogen is 0.4Mpa in the reaction process, and the reaction temperature is 270 ℃. The reaction method uses high-temperature hydrogen, has certain potential safety hazard in the process, has higher reaction temperature and needs to consume a large amount of energy. It is used as a traditional process, and fossil energy is consumed and utilized at will.
Disclosure of Invention
In order to overcome the defects in the prior art, the invention aims to provide a preparation method and application of a metal organic cage-shaped compound for preparing aniline by catalytic reduction of nitrobenzene. The metal organic cage-shaped compound prepared by the method comprises a quinone hydroquinone electric pair with hydrogen transfer capacity, water is used for replacing hydrogen as a hydrogen source, ether sunlight is used as an energy source, and nitrobenzene hydrogenation is realized under the conditions of normal temperature and normal pressure, so that a metal organic supermolecule catalyst is prepared by using transition metal, and nitrobenzene is subjected to normal-temperature photocatalytic reduction under the irradiation of visible light to prepare aniline.
In order to achieve the above purpose and solve the problems existing in the prior art, the invention adopts the technical scheme that: a process for preparing the organic cage-shaped metal compound used to prepare phenylamine by catalytic reduction of nitrobenzene uses Co in transition metal salt2+As a node, L is used as a ligand to prepare the metal organic cage compound by the synthetic route ofThe following:
Co2++L→Co-L；
the ligand L is selected from H4TPO；
The transition metal salt is selected from one of cobalt perchlorate, cobalt nitrate, cobalt tetrafluoroborate or cobalt trifluoromethanesulfonate;
the ligand H4TPO has the following molecular structural formula (A),
in the formula: r1 is hydrogen, R2 is hydrogen;
the preparation method of the metal organic cage-shaped compound for preparing aniline by catalytic reduction of nitrobenzene comprises the following steps:
step one, mixing dimethyl 5-hydroxyisophthalate and potassium carbonate according to a ratio of 1: adding 0.8-1.0 mol ratio of the potassium carbonate to 20-50 ml of N, N-dimethylformamide, stirring for 10-25 minutes at 75-85 ℃, adding 3, 5-dicyano fluorobenzene, stirring for 30-40 hours, adding the cooled reaction solution to 100-200 ml of ice water, performing suction filtration, adding the obtained solid to 50-80 ml of sodium hydroxide solution, stirring for 10-15 hours at the reaction temperature of 100-110 ℃, adjusting the pH value to 2-5 by using a hydrochloric acid solution, performing suction filtration, adding the precipitate to 40-80 ml of a methanol solution of sulfuric acid, stirring for 10-15 hours at the reaction temperature of 70-80 ℃, adjusting the pH value to 7-9, extracting by using dichloromethane, performing column separation to obtain a white solid, wherein the mol ratio of the potassium carbonate to the 3, 5-dicyano fluorobenzene is 1: 0.8-1.0, wherein the molar ratio of the dimethyl 5-hydroxyisophthalate to the sodium hydroxide is 1: 5-8, and the molar ratio of the dimethyl 5-hydroxyisophthalate to the methanol of the sulfuric acid is 1: 5-8;
secondly, mixing the white solid obtained in the first step with 10-60 ml of hydrazine hydrate, refluxing and stirring at 80-100 ℃ for 10-15 hours, performing suction filtration after the reaction is finished, washing the obtained filter cake with ethanol, and drying the washed filter cake in vacuum to obtain white powder;
the third step is to get the second stepAdding the obtained white powder and 2-pyridylaldehyde into 40-160 ml of ethanol according to a molar ratio of 1: 4-5, mixing, adding 5-6 drops of glacial acetic acid, refluxing the mixed solution at 80-100 ℃ for 10-15 hours, performing suction filtration after reaction is stopped, washing the obtained filter cake with methanol, and drying the washed filter cake in vacuum to obtain yellow powder, namely a ligand H4TPO；
Step four, ligand H obtained in the step three4Adding TPO and metal cobalt salt into a mixed solvent of methanol and acetonitrile according to a molar ratio of 1: 2-4, stirring for 4-6 hours at room temperature, stirring and filtering, standing filtrate at room temperature for 2 weeks, and precipitating an orange solid in the solution to obtain a target compound Co-TPO, wherein the volume ratio of methanol to acetonitrile is 1: 8 to 10.
The method and the application of the prepared metal organic cage-shaped compound in preparing aniline by catalytic reduction of nitrobenzene.
The invention has the beneficial effects that: a process for preparing the organic cage-shaped metal compound used to prepare phenylamine by catalytic reduction of nitrobenzene uses Co in transition metal salt2+The metal organic cage-shaped compound is prepared by taking L as a ligand through a reaction by taking the L as a node, and the synthetic route is as follows2++ L → Co-L, the ligand L is selected from H4TPO, wherein the transition metal salt is selected from one of cobalt perchlorate, cobalt nitrate, cobalt tetrafluoroborate or cobalt trifluoromethanesulfonate; compared with the prior art, the metal organic cage-shaped compound prepared by the method has the advantages of low raw material price, high yield, stable chemical property of the obtained compound and easy application in practical application, and the cycle number of reduction of nitrobenzene as a catalyst under the condition of illumination can reach 200000.
Drawings
FIG. 1 is a high resolution mass spectrum of a Co-TPO solution.
FIG. 2 is a graph showing the change of the TON value of the reaction for preparing aniline by reducing nitrobenzene under the illumination condition of Co-TPO.
Detailed Description
The present invention will be further described with reference to the following examples.
EXAMPLE 1 preparation of Co-TPO Compound Using cobalt perchlorate
In the first step, dimethyl 5-hydroxyisophthalate (3.55g,25mmol) and potassium carbonate (3.00g,22mmol) were added to 25 ml of N, N-dimethylformamide, and stirred at 80 ℃ for 15 minutes, and 3, 5-dicyanobenzene (2.68g,18mmol) was added and stirred for 36 hours. Cooling the reaction solution, adding the cooled reaction solution into 150 ml of ice water, carrying out suction filtration, adding the obtained solid into 150mmol of 60 ml of sodium hydroxide solution, stirring the reaction solution at 100 ℃ for 12 hours, adjusting the pH value to 4 by using a hydrochloric acid solution, carrying out suction filtration, adding the precipitate into 150mmol of 60 ml of sulfuric acid-containing methanol solution, stirring the reaction solution at 80 ℃ for 12 hours, adjusting the pH value to 8, extracting by using dichloromethane, and carrying out column separation to obtain 2.51g of white solid with the yield of 70%.1H-NMR(400MHz,CDCl3) 8.49(t,2H),7.85(d,4H),3.94(s,12H). in the second step, the white solid obtained in the first step (2.01g, 10mmol) was mixed with 20 ml of hydrazine hydrate and stirred at 95 ℃ under reflux for 12 hours. After the reaction was completed, the obtained filter cake was suction-filtered and washed with ethanol, and the washed filter cake was vacuum-dried to give a white powder (1.98g, yield 98%).1H-NMR(400MHz,DMSO-d6Ppm)9.85(s,4H),8.10(t,2H),7.58(d,4H),4.56(s,8H). The third step is to add the white powder (1.95g, 5mmol) obtained in the second step and 2-pyridinecarboxaldehyde (2.33g, 22mmol) to 100 ml of ethanol and mix them, add 5 drops of glacial acetic acid, and stir the mixture at 95 ℃ under reflux for 12 hours. After the reaction, the reaction mixture was filtered by suction and the obtained filter cake was washed with methanol, and the washed filter cake was dried in vacuo to give a yellow powder (3.43g, yield 91%), i.e., ligand H4TPO。1H-NMR(400MHz,DMSO-d6,ppm)12.28(s,4H6),8.64(d,4H1),8.51(s,4H5),8.11(s,4H8),8.01(d,4H4),7.91(t,6H2,7),7.44(t,4H3).Elemental analysis calcd for C40H30N12O5·2H2O:H 4.31,C 60.45,N 21.15％.Found:H4.69,C 60.01,N 20.27％.ESI-MS calcd for C40H30N12O5758.25,found 759.25[M+H]+,781.24[M+Na]+The fourth step, cobalt perchlorate (73.2mg,0.2mmol), ligand H4TPO (37.8mg,0.05mmol) was dissolved in a mixed solvent of 1 ml of methanol and 9 ml of acetonitrile, stirred at room temperature for 4 hours, and after stirring and filtering, the filtrate was left to stand at room temperature for 2 weeks, and an orange solid was precipitated from the solution to obtain the objective compound Co-TPO24.9mg in 42% yield. Anal calc6C120H84N36O39Cl6·4CH3CN·3CH3OH·3H2O:H,3.25；C,44.51；N,15.85％.Found:H,3.89；C,43.98；N,15.16％.ESI-MS:m/z:524.45[H2Co6(HTPO)3]5+,655.32[HCo6(HTPO)3]4+and873.41[Co6(HTPO)3]3+As shown in fig. 1.
EXAMPLE 2 preparation of Co-TPO Compound Using cobalt nitrate
In the first step, dimethyl 5-hydroxyisophthalate (4.26g,30.0mmol) and potassium carbonate (3.60g,26.4mmol) were added to 30 ml of N, N-dimethylformamide, and stirred at 80 ℃ for 14 minutes, and 3, 5-dicyanobenzene (3.22g,21.6mmol) was added and stirred for 35 hours. Cooling the reaction solution, adding the cooled reaction solution into 160 ml of ice water, carrying out suction filtration, adding the obtained solid into a 60 ml of sodium hydroxide solution containing 150mmol, stirring for 12 hours at the reaction temperature of 100 ℃, adjusting the pH value to 4 by using a hydrochloric acid solution, carrying out suction filtration, adding the precipitate into a methanol solution containing 150mmol of 60 ml of sulfuric acid, stirring for 12 hours at the reaction temperature of 80 ℃, adjusting the pH value to 8, extracting by using dichloromethane, and carrying out column separation to obtain 2.82g of a white solid;1H-NMR(400MHz,CDCl3):8.49(t,2H),7.85(d,4H),3.94(s,12H).
in the second step, the white solid obtained in the first step (2.52g, 12.5mmol) was mixed with 30 ml of hydrazine hydrate and stirred under reflux at 90 ℃ for 10 hours. After the reaction was completed, the obtained filter cake was suction-filtered and washed with ethanol, and the washed filter cake was vacuum-dried to give a white powder (2.49g, yield 98%).1H-NMR(400MHz,DMSO-d6Ppm)9.85(s,4H),8.10(t,2H),7.58(d,4H),4.56(s,8H) in the third step, the white powder obtained in the second step (2.00g, 5mmol) and 2-pyridinecarboxaldehyde (2.36g, 22mmol) were added to 100 mlMixing in ethanol, adding 5 drops of glacial acetic acid, and stirring the mixed solution at 95 ℃ under reflux for 12 hours. After the reaction, the reaction mixture was filtered with suction and the obtained filter cake was washed with methanol, and the washed filter cake was dried in vacuo to give a yellow powder (3.46g, yield 91%), i.e., ligand H4TPO。1H-NMR(400MHz,DMSO-d6,ppm)12.28(s,4H6),8.64(d,4H1),8.51(s,4H5),8.11(s,4H8),8.01(d,4H4),7.91(t,6H2,7),7.44(t,4H3).Elemental analysis calcd for C40H30N12O5·2H2O:H 4.31,C 60.45,N 21.15％.Found:H4.69,C 60.01,N 20.27％.ESI-MS calcd for C40H30N12O5758.25,found 759.25[M+H]+,781.24[M+Na]+In the fourth step, cobalt nitrate (58.1mg,0.2mmol) and ligand H are added4TPO (37.8mg,0.05mmol) was dissolved in a mixed solvent of 1 ml of methanol and 8 ml of acetonitrile, stirred at room temperature for 4 hours, and after stirring and filtering, the filtrate was left to stand at room temperature for 2 weeks, and an orange solid was precipitated from the solution to obtain the objective compound Co-TPO17.3mg, with a yield of 30%. Co6C120H78N36O15ESI-MS:m/z:524.45[H2Co6(HTPO)3]5+,655.32[HCo6(HTPO)3]4+and 873.41[Co6(HTPO)3]3+。
EXAMPLE 3 preparation of Co-TPO Compound Using cobalt tetrafluoroborate
In the first step, dimethyl 5-hydroxyisophthalate (3.20g,22.5mmol) and potassium carbonate (2.70g,20mmol) were added to 25 ml of N, N-dimethylformamide, and stirred at 80 ℃ for 17 minutes, and 3, 5-dicyanobenzene (2.68g,18mmol) was added and stirred for 36 hours. Cooling the reaction solution, adding the cooled reaction solution into 140 ml of ice water, carrying out suction filtration, adding the obtained solid into 60 ml of sodium hydroxide solution containing 150mmol, stirring the mixture for 10 hours at the reaction temperature of 100 ℃, adjusting the pH value to 4 by adopting hydrochloric acid solution, carrying out suction filtration, adding the precipitate into 60 ml of methanol solution containing 150mmol of sulfuric acid, stirring the mixture for 11 hours at the reaction temperature of 80 ℃, adjusting the pH value to 8.5,extracting with dichloromethane, and separating by column chromatography to obtain white solid 2.43 g;1H-NMR(400MHz,CDCl3):8.49(t,2H),7.85(d,4H),3.94(s,12H).
in the second step, the white solid obtained in the first step (2.21g, 11mmol) was mixed with 22 ml of hydrazine hydrate and stirred under reflux at 95 ℃ for 12 hours. After the reaction was completed, the obtained filter cake was suction-filtered and washed with ethanol, and the washed filter cake was vacuum-dried to give a white powder (2.18g, yield 98%).1H-NMR(400MHz,DMSO-d6Ppm)9.85(s,4H),8.10(t,2H),7.58(d,4H),4.56(s,8H). The third step is to add the white powder (2.00g, 5mmol) obtained in the second step and 2-pyridinecarboxaldehyde (2.36g, 22mmol) to 90 ml of ethanol and mix them, after adding 5 drops of glacial acetic acid, the mixed solution is stirred under reflux at 90 ℃ for 13 hours. After the reaction, the reaction mixture was filtered by suction and the obtained filter cake was washed with methanol, and the washed filter cake was dried in vacuo to give a yellow powder (3.40g, yield 90%), i.e., ligand H4TPO。1H-NMR(400MHz,DMSO-d6,ppm)12.28(s,4H6),8.64(d,4H1),8.51(s,4H5),8.11(s,4H8),8.01(d,4H4),7.91(t,6H2,7),7.44(t,4H3).Elemental analysis calcd for C40H30N12O5·2H2O:H 4.31,C 60.45,N 21.15％.Found:H4.69,C 60.01,N 20.27％.ESI-MS calcd for C40H30N12O5758.25,found 759.25[M+H]+,781.24[M+Na]+In the fourth step, cobalt tetrafluoroborate (68.1mg,0.2mmol) and ligand H are added4TPO (37.8mg,0.05mmol) was dissolved in a mixed solvent of 1 ml of methanol and 8 ml of acetonitrile, stirred at room temperature for 6 hours, and after stirring and filtering, the filtrate was left to stand at room temperature for 2 weeks, and an orange solid was precipitated from the solution, to obtain the objective compound Co-TPO22.4mg with a yield of 38.2%. Co6C120H78N36O15ESI-MS:m/z:524.45[H2Co6(HTPO)3]5+,655.32[HCo6(HTPO)3]4+and 873.41[Co6(HTPO)3]3+。
EXAMPLE 4 preparation of Co-TPO Compound Using cobalt triflate
In the first step, dimethyl 5-hydroxyisophthalate (3.55g,25mmol) and potassium carbonate (3.00g,22mmol) were added to 25 ml of N, N-dimethylformamide, and stirred at 80 ℃ for 18 minutes, and 3, 5-dicyanobenzene (2.68g,18mmol) was added and stirred for 33 hours. Cooling the reaction solution, adding the cooled reaction solution into 130 ml of ice water, carrying out suction filtration, adding the obtained solid into a 60 ml of sodium hydroxide solution containing 150mmol, stirring for 13 hours at the reaction temperature of 100 ℃, adjusting the pH value to 4 by using a hydrochloric acid solution, carrying out suction filtration, adding the precipitate into a methanol solution containing 150mmol of 60 ml of sulfuric acid, stirring for 11 hours at the reaction temperature of 77 ℃, adjusting the pH value to 8.5, extracting by using dichloromethane, and carrying out column separation to obtain 2.53g of white solid;1H-NMR(400MHz,CDCl3) 8.49(t,2H),7.85(d,4H),3.94(s,12H). in the second step, the white solid obtained in the first step (2.02g, 10mmol) was mixed with 30 ml of hydrazine hydrate and stirred at 90 ℃ under reflux for 13 hours. After the reaction was completed, the obtained filter cake was suction-filtered and washed with ethanol, and the washed filter cake was vacuum-dried to give a white powder (1.97g, yield 97%).1H-NMR(400MHz,DMSO-d6Ppm)9.85(s,4H),8.10(t,2H),7.58(d,4H),4.56(s,8H). The third step is to add the white powder (1.80g, 4.5mmol) obtained in the second step and 2-pyridinecarboxaldehyde (2.16g, 20mmol) to 80 ml of ethanol, mix them, add 5 drops of glacial acetic acid, stir the mixture at 95 ℃ under reflux for 12 hours. After the reaction, the reaction mixture was filtered by suction and the obtained filter cake was washed with methanol, and the washed filter cake was dried in vacuo to give a yellow powder (3.11g, yield 91%), i.e., ligand H4TPO。1H-NMR(400MHz,DMSO-d6,ppm)12.28(s,4H6),8.64(d,4H1),8.51(s,4H5),8.11(s,4H8),8.01(d,4H4),7.91(t,6H2,7),7.44(t,4H3).Elementalanalysis calcd for C40H30N12O5·2H2O:H 4.31,C 60.45,N 21.15％.Found:H 4.69,C60.01,N 20.27％.ESI-MS calcd for C40H30N12O5758.25,found 759.25[M+H]+,781.24[M+Na]+In the fourth step, cobalt trifluoromethanesulfonate (71.4mg,0.2mmol) and ligand H are reacted4TPO (37.8mg,0.05mmol) was dissolved in a mixed solvent of 1 ml of methanol and 10 ml of acetonitrile, stirred at room temperature for 6 hours, and after stirring and filtering, the filtrate was left to stand at room temperature for 2 weeks, and an orange solid was precipitated from the solution, to obtain the objective compound Co-TPO15.4mg with a yield of 25.5%. Co6C120H78N36O15ESI-MS:m/z:524.45[H2Co6(HTPO)3]5+,655.32[HCo6(HTPO)3]4+and 873.41[Co6(HTPO)3]3+。
EXAMPLE 5 reduction of Nitrobenzene to produce aniline Using Co-TPO
In a 20 ml photoreaction tube, 2.5 ml of acetonitrile and 2.5 ml of water were added, followed by 1.1 mg of Ru (bpy)3(PF6)212.5 microliter of 1 mmol/L acetonitrile solution of Co-TPO, 88.0 mg ascorbic acid, adjusting pH to 4.75 with hydrochloric acid and sodium hydroxide solution, adding 11 mg benzoquinone, mixing with 15 microliter nitrobenzene, placing the reactor in argon atmosphere, and illuminating for 10 hours by using a 500W xenon lamp, wherein the light intensity of the xenon lamp is 150, the wavelength is more than 400nm, 93% of nitrobenzene can be converted into aniline, and TON can reach 11500.
EXAMPLE 6 reduction of Nitrobenzene to produce aniline Using Co-TPO
In a 50 ml photoreaction tube, 10 ml of acetonitrile and 10 ml of water were added, followed by 1.1 mg of Ru (bpy)3(PF6)212.5 microliter Co-TPO solution of 1 mmol/L acetonitrile, 88.0 mg ascorbic acid, hydrochloric acid and sodium hydroxide solution to adjust pH to 4.75, then adding 13.2 mg benzoquinone, and 400 microliter nitrobenzene, placing the reactor in argon atmosphere, using 500W xenon lamp to illuminate for 12 hours, the xenon lamp light intensity is 150, the wavelength is more than 400nm, adding 88.0 mg ascorbic acid every 10 hours, the TON of 80 hours reaction can reach 200000, as shown in figure 2.
The invention has the advantages that: the metal organic cage-shaped compound prepared by the method has the advantages of low raw material price, high yield, stable chemical property of the obtained compound and easy investment in practical application. The cycle number of nitrobenzene reduction as a catalyst under the condition of illumination can reach 200000.
Claims (1)
1. A preparation method of a metal organic cage-shaped compound for preparing aniline by catalytic reduction of nitrobenzene is characterized by comprising the following steps: with Co in transition metal salts2+L is used as a node to prepare the metal organic cage compound by reaction, and the synthetic route is as follows:
Co2++L→Co-L；
the ligand L is selected from H4TPO；
The transition metal salt is selected from one of cobalt perchlorate, cobalt nitrate, cobalt tetrafluoroborate or cobalt trifluoromethanesulfonate;
the ligand H4TPO has the following molecular structural formula (A),
in the formula: r1 is hydrogen, R2 is hydrogen;
the preparation method of the metal organic cage-shaped compound for preparing aniline by catalytic reduction of nitrobenzene comprises the following steps:
step one, mixing dimethyl 5-hydroxyisophthalate and potassium carbonate according to a ratio of 1: adding 0.8-1.0 mol ratio of the potassium carbonate to 20-50 ml of N, N-dimethylformamide, stirring for 10-25 minutes at 75-85 ℃, adding 3, 5-dicyano fluorobenzene, stirring for 30-40 hours, adding the cooled reaction solution to 100-200 ml of ice water, performing suction filtration, adding the obtained solid to 50-80 ml of sodium hydroxide solution, stirring for 10-15 hours at the reaction temperature of 100-110 ℃, adjusting the pH value to 2-5 by using a hydrochloric acid solution, performing suction filtration, adding the precipitate to 40-80 ml of a methanol solution of sulfuric acid, stirring for 10-15 hours at the reaction temperature of 70-80 ℃, adjusting the pH value to 7-9, extracting by using dichloromethane, performing column separation to obtain a white solid, wherein the mol ratio of the potassium carbonate to the 3, 5-dicyano fluorobenzene is 1: 0.8-1.0, wherein the molar ratio of the dimethyl 5-hydroxyisophthalate to the sodium hydroxide is 1: 5-8, and the molar ratio of the dimethyl 5-hydroxyisophthalate to the methanol of the sulfuric acid is 1: 5-8;
secondly, mixing the white solid obtained in the first step with 10-60 ml of hydrazine hydrate, refluxing and stirring at 80-100 ℃ for 10-15 hours, performing suction filtration after the reaction is finished, washing the obtained filter cake with ethanol, and drying the washed filter cake in vacuum to obtain white powder;
thirdly, adding the white powder obtained in the second step and 2-pyridylaldehyde into 40-160 ml of ethanol according to a molar ratio of 1: 4-5 for mixing, then adding 5-6 drops of glacial acetic acid, refluxing the mixed solution at 80-100 ℃ for 10-15 hours, after the reaction is stopped, performing suction filtration, washing the obtained filter cake with methanol, and performing vacuum drying on the washed filter cake to obtain yellow powder, namely a ligand H4TPO；
Step four, ligand H obtained in the step three4Adding TPO and metal cobalt salt into a mixed solvent of methanol and acetonitrile according to a molar ratio of 1: 2-4, stirring for 4-6 hours at room temperature, stirring and filtering, standing filtrate at room temperature for 2 weeks, and precipitating an orange solid in the solution to obtain a target compound Co-TPO, wherein the volume ratio of methanol to acetonitrile is 1: 8 to 10.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710937122.7A CN107814760B (en) | 2017-10-10 | 2017-10-10 | Preparation method and application of metal organic cage-shaped compound for preparing aniline by catalytic reduction of nitrobenzene |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710937122.7A CN107814760B (en) | 2017-10-10 | 2017-10-10 | Preparation method and application of metal organic cage-shaped compound for preparing aniline by catalytic reduction of nitrobenzene |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN107814760A CN107814760A (en) | 2018-03-20 |
| CN107814760B true CN107814760B (en) | 2020-07-24 |
Family
ID=61607845
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710937122.7A Active CN107814760B (en) | 2017-10-10 | 2017-10-10 | Preparation method and application of metal organic cage-shaped compound for preparing aniline by catalytic reduction of nitrobenzene |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107814760B (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110467636B (en) * | 2019-08-17 | 2021-06-15 | 大连理工大学 | Preparation method and application of metal organic triangular prism-shaped compound for preparing amino aromatic hydrocarbon by catalytic reduction of nitroarene |
| CN111303216B (en) * | 2019-11-26 | 2022-07-22 | 大连理工大学 | Preparation method and application of metal organic ternary cyclic compound |
| CN111153937A (en) * | 2020-01-07 | 2020-05-15 | 大连理工大学 | Preparation method and application of cobalt metal organic macrocyclic compound |
| CN111423365B (en) * | 2020-04-03 | 2020-11-20 | 华东师范大学 | Bifunctional group pillar aromatic hydrocarbon derivative ligand, metal organic cage and preparation method |
| CN111454249B (en) * | 2020-04-23 | 2022-06-14 | 大连理工大学 | Preparation method and application of metal organic cage-shaped compound |
| CN113582892B (en) * | 2021-08-01 | 2022-04-12 | 大连理工大学 | Preparation method and application of metal organic cage-shaped compound for catalyzing ethanol cracking |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103724255A (en) * | 2014-01-07 | 2014-04-16 | 大连理工大学 | Preparation method of compounds used for detecting explosive RDX (Research Department eXplosive) and based on acylamino dihydropyridine structure |
| CN104324762A (en) * | 2014-10-09 | 2015-02-04 | 济南大学 | Preparation method and applications of ternary composite material |
| CN107098786A (en) * | 2017-05-15 | 2017-08-29 | 大连理工大学 | A kind of preparation method of aromatic amine compounds |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US10201803B2 (en) * | 2015-06-09 | 2019-02-12 | The Regents Of The University Of California | Polymer-metal organic framework materials and methods of using the same |
-
2017
- 2017-10-10 CN CN201710937122.7A patent/CN107814760B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103724255A (en) * | 2014-01-07 | 2014-04-16 | 大连理工大学 | Preparation method of compounds used for detecting explosive RDX (Research Department eXplosive) and based on acylamino dihydropyridine structure |
| CN104324762A (en) * | 2014-10-09 | 2015-02-04 | 济南大学 | Preparation method and applications of ternary composite material |
| CN107098786A (en) * | 2017-05-15 | 2017-08-29 | 大连理工大学 | A kind of preparation method of aromatic amine compounds |
Also Published As
| Publication number | Publication date |
|---|---|
| CN107814760A (en) | 2018-03-20 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107814760B (en) | Preparation method and application of metal organic cage-shaped compound for preparing aniline by catalytic reduction of nitrobenzene | |
| CN114195827B (en) | Carboxyl substituted ruthenium complex and preparation method and application thereof | |
| CN110483585A (en) | A kind of preparation method and applications of the organic cage compound of metal of adjustable high-efficient selective catalytic reduction nitrobenzaldehyde | |
| CN110467636B (en) | Preparation method and application of metal organic triangular prism-shaped compound for preparing amino aromatic hydrocarbon by catalytic reduction of nitroarene | |
| CN102010447A (en) | Preparation method and application of ruthenium and rhodium transition metal complex functional ionic liquid | |
| CN111686821A (en) | Ruthenium complex and molybdenum-sulfur cluster dye-sensitized photocatalytic hydrogen production system reaction liquid | |
| CN107570172A (en) | A kind of preparation method and applications of ruthenium/nickel alloy nanocatalyst | |
| CN115449082B (en) | Metal organic coordination supermolecule sphere, preparation method and application thereof | |
| CN111574569B (en) | Coordination compound of rhodium, preparation method and application thereof | |
| CN107501564B (en) | Three-dimensional N-heterocyclic carbine metal coordination polymer and preparation method thereof and and application | |
| CN114716459B (en) | Carboxyl substituted ruthenium complex, preparation method and application thereof | |
| WO2012073268A1 (en) | Process for the synthesis of precursor complexes of titanium dioxide sensitization dyes based on ruthenium polypyridine complexes | |
| CN113045440B (en) | Preparation method of 1-aminoanthraquinone | |
| CN113234031B (en) | D-A type aggregation-induced emission compound and preparation method and application thereof | |
| CN114891231A (en) | Synthesis method and application of bifunctional metal-organic framework for selective oxidation of inert C-H bond | |
| Pruchnik et al. | Synthesis and structural characterization of new rhodium formato complexes containing [Rh2] 4+ and [Rh4] 6+ cores | |
| CN108948055B (en) | 8-methylquinoline gem-diboron compound and preparation method thereof | |
| CN101134742B (en) | Method for synthesizing 2,2'-biquinoline | |
| CN107540660A (en) | It is a kind of using terpyridyl derivative as the iron complex and its synthetic method of part and application | |
| CN113999120A (en) | Preparation method of halogenated aniline compound | |
| CN112608245A (en) | Cationic water-soluble inclined column [6] arene and synthetic method thereof | |
| CN113896675A (en) | Organic luminescent material based on carbazole-triphenylamine derivative and preparation method thereof | |
| CN102827169A (en) | Novel porphyrin ligand and metal complex, preparation method and application for novel porphyrin ligand | |
| CN112110887A (en) | Synthetic method and application of 3-position formyl substituted 2H-chromene derivative | |
| CN113354956A (en) | Near-infrared squarylium dye connected with oxygen ether chain, and preparation and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |