CN108822029B - Method for preparing tetrahydroquinoline compound and acid-base carrier loaded Ni metal catalyst - Google Patents
Method for preparing tetrahydroquinoline compound and acid-base carrier loaded Ni metal catalyst Download PDFInfo
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- CN108822029B CN108822029B CN201810430413.1A CN201810430413A CN108822029B CN 108822029 B CN108822029 B CN 108822029B CN 201810430413 A CN201810430413 A CN 201810430413A CN 108822029 B CN108822029 B CN 108822029B
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D215/00—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems
- C07D215/02—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom
- C07D215/04—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, directly attached to the ring carbon atoms
- C07D215/06—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, directly attached to the ring carbon atoms having only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, attached to the ring nitrogen atom
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/755—Nickel
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/80—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with zinc, cadmium or mercury
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Abstract
A method for efficiently preparing tetrahydroquinoline compound and an acid-base carrier loaded Ni metal catalyst, belonging to the field of biomass ethanol conversion. An application of a metal active center and solid acid-base carrier synergistic catalyst in the synthesis of 1,2,3, 4-tetrahydroquinoline belongs to the technical field of biomass ethanol conversion. The catalyst consists of uniformly dispersed nickel nano particles and a nickel-aluminum (zirconium) composite oxide. The catalyst is prepared by nickel-containing hydrotalcite (NiAl-LDHs, NiAlZr-LDHs) in-situ topological transformation, and has the advantages that strong interface interaction exists between Ni nano particles and a carrier, the reaction lasts for 16h at 125 ℃, and the yield of 1,2,3, 4-tetrahydroquinoline catalyzed by Ni-NiAl-LDO can reach 97%; after the reaction is carried out for 26 hours, the yield of N-ethyl-1, 2,3, 4-tetrahydroquinoline catalyzed by Ni-NiAlZr-LDO is as high as 95%.
Description
Technical Field
The invention belongs to the field of biomass ethanol conversion, and particularly provides an acid-base carrier loaded Ni metal catalyst and application thereof in preparation of tetrahydroquinoline in a biomass ethanol hydrogen transfer process.
Background
The 1,2,3, 4-tetrahydroquinoline compounds are important nitrogen-containing heterocyclic compounds, are important structural units for forming a plurality of natural products and bioactive molecules, and are structural fragments for forming a plurality of novel functional materials. Compounds containing tetrahydroquinoline building blocks exhibit a variety of biological activities such as antiarrhythmic, antitumor, immunoprotective, cholesterin protein inhibitory, selective estrogen modulation, PPAR α/γ agonism, antiparasitic, glucocorticoid receptor antagonistic, prevention and treatment of arteriosclerosis, and the like. The tetrahydroquinoline structural unit also has a chromophore with good electron donating capability, and can be used as an intermediate for the synthesis of disperse dyes. In addition, tetrahydroquinoline can also be used for membrane lipid compounds. Therefore, the research on new methods for synthesizing 1,2,3, 4-tetrahydroquinoline derivatives has been focused. At present, 1,2,3, 4-tetrahydroquinoline derivatives are mainly prepared by hydrogenation reduction of quinoline compounds, ring closing conversion reaction and by multi-molecule condensation reaction strategy. At present, the quinoline compounds are mainly composed of benzeneAmine compounds and alcohol compounds Skraup-Doebner-Von Miller method (Karl Kirchner et al.J.Am.chem.Soc.2016,138,15543-15546) and o-aminobenzyl alcohol and alcohol compounds
Synthesized by the method (Zi-Sheng Chao et al RSC adv.2017,7, 24950 and 24962). The reaction process needs additional oxygen for oxidation.
Disclosure of Invention
The invention aims to provide a method for efficiently preparing a tetrahydroquinoline compound and a non-noble metal catalyst.
The acid-base carrier loaded Ni metal catalyst consists of one or more of uniformly dispersed nickel nano particles and a nickel-aluminum-zirconium/zinc-aluminum-zirconium/nickel-aluminum/zinc-aluminum composite oxide carrier. The catalyst is prepared by roasting and reducing a hydrotalcite precursor, and has the advantage that strong interfacial interaction exists between Ni nano particles and a carrier, so that the tetrahydroquinoline compound is efficiently prepared.
The catalyst is prepared by taking hydrotalcite (LDHs) containing Ni as a precursor, and divalent cations M of hydrotalcite laminate2+Selection of Ni2+Or Ni2+And Zn2+Of trivalent cation M3+Selection of Al3+Tetravalent cation M4+Selection of Zr4+In a molar ratio of M2+/(M3++M4+) (2-4): 1, then the hydrotalcite precursor is reacted with H2Reducing in the atmosphere, controlling the reduction temperature at 400-; the Ni metal content of the catalyst is 10-70 wt%, the average particle size of the nickel nano-particles is 3-15nm, the interaction between the Ni metal particles and the carrier interface can be adjusted through Zn, and further the carrier acid-base property can be adjusted. The molar ratio of zinc oxide to aluminum oxide can be controlled to be (0-3)/1, and the ratio of zinc oxide to aluminum oxide can be controlled to be 0/1 or (1-3)/1.
Tetravalent cation M4+With trivalent cations M3+The ratio of (A) to (B) is adjustable, and is generally (0-0.3) to 1. Preferably, the molar ratio of the zirconium oxide to the aluminum oxide is controlled to be 0 or (C)0.05-0.2)/1。
The method for preparing the tetrahydroquinoline compound by using the catalyst comprises the steps of adding a substrate 2-aminobenzyl alcohol, wherein the mass ratio of the added amount of the catalyst to the added substrate 2-aminobenzyl alcohol is 0.05: 1-0.20: 1, the reaction temperature is 100-200 ℃, the reaction pressure is autogenous pressure, the reaction time is 0.5-36h, and the reaction solvent is ethanol; one or two of 1,2,3, 4-tetrahydroquinoline and N-ethyl-1, 2,3, 4-tetrahydroquinoline are generated by reaction.
Preferably, the Zr content and the Zn content in the catalyst are adjusted to obtain 1,2,3, 4-tetrahydroquinoline, N-ethyl-1, 2,3, 4-tetrahydroquinoline or different proportions of the two. If Zr and Zn are not contained, 1,2,3, 4-tetrahydroquinoline is basically generated; when the Zr/Al molar ratio is larger than 1/7, the N-ethyl-1, 2,3, 4-tetrahydroquinoline is basically generated, and when the Zr content and the Zn content are adjusted, the 1,2,3, 4-tetrahydroquinoline and the N-ethyl-1, 2,3, 4-tetrahydroquinoline products with different proportions can be obtained.
The invention has the obvious advantages that the tetrahydroquinoline compound is prepared by the one-step method of catalyzing 2-aminobenzyl alcohol and ethanol reaction by the Ni metal particle catalyst for the first time, the reaction lasts for 16h at 125 ℃, and the yield of 1,2,3, 4-tetrahydroquinoline catalyzed by Ni-NiAl-LDO can reach 97 percent; after the reaction is carried out for 26 hours, the yield of N-ethyl-1, 2,3, 4-tetrahydroquinoline catalyzed by Ni-NiAlZr-LDO is as high as 95%. .
Detailed Description
The present invention will be further illustrated with reference to the following examples, but the present invention is not limited to the following examples.
Example 1
Step A: 200mL of deionized water was measured into a four-neck flask. Accurately weighing Ni (NO)3)2·6H2O 48mmol，Al(NO3)3·9H2Dissolving O16 mmol in 200mL deionized water to form solution A; accurately weighing Na2CO36.5mmol and 120mmol NaOH are dissolved in 200mL deionized water to form a solution B, the solution A, B is simultaneously dropped into four mouths of coprecipitation and put into a four mouth flask, the temperature is raised to 80 ℃, and magnetic stirring is carried out for 18 hours. After the reaction is finished, filtering and washing the mixture by deionized water until the filtrate is neutral, filtering and washing the mixture for 1 time by absolute ethyl alcohol, and placing the mixtureDried in an oven overnight. Obtaining the NiAl-LDHs.
And B: precursor of NiAl-LDHs in H2Reducing for 1h at the temperature of 400 ℃ to obtain the catalyst.
30mg of catalyst, 0.5mmol of 2-aminobenzyl alcohol and 3mL of ethanol are weighed into a reaction tube and stirred uniformly. The reaction was started at room temperature to 125 ℃ and ended after 24 h. The reaction product was analyzed by gas chromatography. The yield of tetrahydroquinoline reaches 97 percent.
Example 2
Step A: 200mL of deionized water was measured into a four-neck flask. Accurately weighing Ni (NO)3)2·6H2O 48mmol，Al(NO3)3·9H2O 14mmol，ZrO(NO3)2·2H2O2 mmol is dissolved in 200mL deionized water to form a solution A; accurately weighing Na2CO310mmol of NaOH and 120mmol of NaOH are dissolved in 200mL of deionized water to form a solution B, the solution A, B is simultaneously dropped into a four-neck coprecipitation in a four-neck flask, the temperature is raised to 80 ℃, and the magnetic stirring is carried out for 18 hours. After the reaction is finished, filtering and washing the mixture by deionized water until the filtrate is neutral, filtering and washing the mixture by absolute ethyl alcohol for 1 time, and putting the mixture into an oven for overnight drying. Obtaining the NiAlZr-LDHs.
And B: the product NiAlZr-LDHs precursor of the step A is reacted in H2Reducing for 1h at the temperature of 400 ℃ to obtain the catalyst.
30mg of catalyst, 0.5mmol of 2-aminobenzyl alcohol and 3mL of ethanol are weighed into a reaction tube and stirred uniformly. The reaction was started by raising the temperature from room temperature to 125 ℃ and ended after 26 hours. The reaction product was analyzed by gas chromatography. The yield of the N-ethyl-1, 2,3, 4-tetrahydroquinoline reaches 95 percent.
Example 3
Step A: 200mL of deionized water was measured into a four-neck flask. Accurately weighing Ni (NO)3)2·6H2O 18mmol，Zn(NO3)2·6H2O 24mmol,Al(NO3)3·9H2Dissolving O16 mmol in 200mL deionized water to form solution A; accurately weighing Na2CO310mmol, NaOH120mmol and dissolved in 200mL deionized water to form solution B, and A, B was added dropwise simultaneouslyAdding four mouths of the mixture to coprecipitate the mixture in a four-mouth flask, heating the mixture to 80 ℃, and magnetically stirring the mixture for 18 hours. After the reaction is finished, filtering and washing the mixture by deionized water until the filtrate is neutral, filtering and washing the mixture by absolute ethyl alcohol for 1 time, and putting the mixture into an oven for overnight drying. Obtaining the NiZnAl-LDHs.
And B: the product NiZnAl-LDHs precursor of the step A is put in H2Reducing for 1h at 700 ℃ to obtain the catalyst.
30mg of catalyst, 0.5mmol of 2-aminobenzyl alcohol and 3mL of ethanol are weighed into a reaction tube and stirred uniformly. The reaction was started by raising the temperature from room temperature to 125 ℃ and ended after 12 hours. The reaction product was analyzed by gas chromatography. The yield of tetrahydroquinoline reaches 84 percent.
Example 4
Step A: 200mL of deionized water was measured into a four-neck flask. Accurately weighing Ni (NO)3)2·6H2O 18mmol，Zn(NO3)2·6H2O 24mmol,Al(NO3)3·9H2O 14 mmol，ZrO(NO3)2·2H2O2 mmol is dissolved in 200mL deionized water to form a solution A; accurately weighing Na2CO310mmol of NaOH and 120mmol of NaOH are dissolved in 200mL of deionized water to form a solution B, the solution A, B is simultaneously dropped into a four-neck coprecipitation in a four-neck flask, the temperature is raised to 80 ℃, and the magnetic stirring is carried out for 18 hours. After the reaction is finished, filtering and washing the mixture by deionized water until the filtrate is neutral, filtering and washing the mixture by absolute ethyl alcohol for 1 time, and putting the mixture into an oven for overnight drying. Obtaining the NiZnAlZr-LDHs.
And B: the product NiZnAlZr-LDHs precursor of the step A is put in H2Reducing for 1h at the temperature of 400 ℃ to obtain the catalyst.
30mg of catalyst, 0.5mmol of 2-aminobenzyl alcohol and 3mL of ethanol are weighed into a reaction tube and stirred uniformly. The reaction was started by raising the temperature from room temperature to 125 ℃ and ended after 12 hours. The reaction product was analyzed by gas chromatography. The yield of the 1,2,3, 4-tetrahydroquinoline reaches 47 percent, and the yield of the N-ethyl-1, 2,3, 4-tetrahydroquinoline reaches 40 percent.
Claims (8)
1. A method for preparing tetrahydroquinoline compounds is characterized in that a substrate 2-aminobenzyl alcohol is added, the mass ratio of the added amount of a catalyst to the added substrate 2-aminobenzyl alcohol is 0.05: 1-0.20: 1, the reaction temperature is 100-200 ℃, the reaction pressure is autogenous pressure, the reaction time is 0.5-36h, and the reaction solvent is ethanol; reacting to generate one or two of 1,2,3, 4-tetrahydroquinoline and N-ethyl-1, 2,3, 4-tetrahydroquinoline;
the catalyst is an acid-base carrier loaded Ni metal catalyst and consists of one or more of uniformly dispersed nickel nano particles and a nickel-aluminum-zirconium/zinc-aluminum-zirconium/nickel-aluminum/zinc-aluminum composite oxide carrier; the catalyst is prepared by roasting and reducing hydrotalcite precursors.
2. The method of claim 1, wherein the ratio of 1,2,3, 4-tetrahydroquinoline, N-ethyl-1, 2,3, 4-tetrahydroquinoline, or both is adjusted by adjusting the Zr content and the Zn content of the catalyst.
3. The method of claim 1, wherein the acidic-basic carrier supports a Ni metal catalyst prepared from Ni-containing hydrotalcite as a precursor, and the hydrotalcite layer divalent cation M2+Selection of Ni2+Or Ni2+And Zn2+Of trivalent cation M3+Selection of Al3+Tetravalent cation M4+Selection of Zr4+In a molar ratio of M2+/(M3++M4+) (2-4): 1, then the hydrotalcite precursor is reacted with H2Reducing in atmosphere, controlling the reduction temperature at 400-.
4. The method of claim 1, wherein the Ni metal content of the catalyst is 10 to 70 wt% and the average particle size of the nickel nanoparticles is 3 to 15 nm.
5. The method according to claim 3, wherein the molar ratio of zinc oxide to aluminum oxide is controlled to be (0-3)/1; tetravalent cation M4+With trivalent cations M3+The ratio of (1) to (0-0.3).
6. The method of claim 3, wherein the ratio of zinc oxide to aluminum oxide is controlled to 0/1 or (1-3)/1; the molar ratio of the zirconia to the alumina is controlled to be 0 or (0.05-0.2)/1.
7. The method of claim 1, wherein in the absence of Zr and Zn, substantially 1,2,3, 4-tetrahydroquinoline is formed; contains Zr, and 1,2,3, 4-tetrahydroquinoline and N-ethyl-1, 2,3, 4-tetrahydroquinoline products with different proportions can be obtained by adjusting the content of Zr and the content of Zn.
8. The method according to claim 7, wherein when Zn is not contained but Zr is contained and the Zr/Al molar ratio is more than 1/7, N-ethyl-1, 2,3, 4-tetrahydroquinoline is substantially produced.
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