CN110681381B - anti-Malassezia hydroamination catalyst and preparation method and application thereof - Google Patents
anti-Malassezia hydroamination catalyst and preparation method and application thereof Download PDFInfo
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Abstract
An anti-Malassezia hydroamination catalyst, a preparation method and an application thereof, which belong to the technical field of green catalysis and related chemistry. The catalyst consists of atomically dispersed Pt and composite oxide. The catalyst is prepared by inducing a Pt salt precursor on the surface of hydrotalcite, and then carrying out high-temperature roasting topological transformation and reduction, and has the advantages that Pt is atomically dispersed and the proportion of various Pt active centers can be regulated. The catalyst is applied to hydrogen amination reaction, substrate olefin, amine and the catalyst are added into a solvent, the reaction temperature is 30-120 ℃, the reaction pressure is autogenous pressure, and the reaction time is 0.5-48 h. The invention has the obvious advantages of simple and easy preparation method of the catalyst, high selectivity and high activity of catalytic anti-Ma hydrogen amination, cheap and easily obtained reaction raw materials, mild reaction conditions and high atom utilization rate.
Description
Technical Field
The invention belongs to the technical field of green catalysis and related chemistry, and particularly provides a reverse-maleated hydrogen amination catalyst and a preparation method and application thereof.
Background
The C-N bond widely exists in fine chemicals, drug intermediates and biological macromolecules, so that the development of an effective method for constructing the C-N bond has important theoretical significance and potential application value. The addition reaction of carbon-carbon unsaturated bond and N-H bond, namely the hydroamination reaction, has the advantages of cheap and easily obtained raw materials, mild reaction conditions, 100 percent of atom utilization rate and the like, and provides the most economic and effective method for synthesizing the amine.
The hydroamination catalyst is mainly a rare earth metal complex (J.Am.chem.Soc.1989,111,4108-4110), an organic acid (org.Lett.2002,4, 1471-. Thus, transition metal complexes such as Au (org. Lett.2006,8, 3537-. However, the anti-Markov hydroamination reaction, which has been classified as ten major catalytic challenges, remains a challenge, and Rh (chem. Eur. J.1999,5, 1306-.
Therefore, the development of a catalyst which is simple, feasible and effective in catalyzing the anti-Markov hydrogen amination reaction is of great significance.
Disclosure of Invention
The invention aims to provide a reverse-Maltese hydroamination catalyst, a preparation method and application thereof.
The content of Pt in the catalyst is 0.01-20 wt%, the Pt is in a single atom, two-dimensional cluster, three-dimensional cluster or nano-particle dispersion state, and various Pt active centers are electron-deficient Pt centers (Pt)δ+) Metallic Pt center (Pt)0) Rich electron state Pt center (Pt)δ-) Preferably contains at least an electron deficient Pt center (Pt)δ+) Metallic Pt center (Pt)0) (ii) a The composite oxide in the catalyst is preferably zinc-aluminum, zinc-titanium, zinc-gallium, magnesium-aluminum and magnesium-gallium composite oxide.
The catalyst is prepared by taking hydrotalcite (LDHs) as a precursor to load Pt. Hydrotalcite layer divalent cationIs selected as Zn2+Or Mg2+The higher cation is preferably Al3+、Ti4+Or Ga3+The molar ratio thereof is preferably Zn2+(or Mg)2+):Al3+(or Ti)4+、Ga3+) 1, loading a hydrotalcite precursor on a Pt salt, wherein the Pt salt is preferably sodium chloroplatinate, platinum acetylacetonate or platinum tetraammine nitrate, calcining the Pt salt in a muffle furnace at a heating rate of 1-10 ℃/min and at 530 ℃ and 560 ℃ for 2-3 hours, and then calcining the calcined Pt salt in H2Reducing in the atmosphere, controlling the reduction temperature at 300-900 ℃, the reduction heat preservation time at 1-5 h, and the heating rate at 1-10 ℃/min to obtain the corresponding catalyst. The Pt center species can be determined by CO in-situ infrared and XPS characterization.
The catalyst is used for anti-Markov hydrogen amination reaction of olefin and amine, substrates of olefin, amine and catalyst are added into a solvent, the reaction temperature is 30-120 ℃, the reaction pressure is autogenous pressure, and the reaction time is 0.5-48 h.
The specific reaction is as follows:
the solvent is preferably isopropanol, toluene or acetonitrile.
The mol ratio of the Pt addition amount to the added amine in the catalyst is preferably 1:50-1: 10000.
The molar ratio of the olefin to the amine is preferably from 1: 1to 5: 1.
The substrate olefin is preferably terminal olefin, preferably hexene, n-octene, styrene, methylstyrene, nitrostyrene, methoxystyrene.
The substrate amine is an N-H organic substance, and the amine (secondary amine) with at least one active hydrogen is preferably 3-hexylamine, pyrrolidine and aniline.
After the reaction is finished, the anti-Ma hydrogen amination product is obtained through post-treatment.
The post-treatment step is preferably: filtering, and purifying the filtrate by recrystallization, distillation, reduced pressure distillation, thin-layer chromatography or column chromatography to obtain the anti-Markov hydrogen amination product.
The invention has the obvious advantages of simple and easy preparation method of the catalyst, high selectivity and high conversion number of catalytic anti-Ma hydrogen amination, cheap and easily obtained reaction raw materials, mild reaction conditions and high atom utilization rate.
Drawings
FIG. 1 is an infrared spectrum of example 1.
The specific implementation mode is as follows:
the present invention will be further illustrated with reference to the following examples, but the present invention is not limited to the following examples. In the preparation of hydrotalcite (LDHs) precursor, metal ion salt in hydrotalcite is dissolved in water, and then mixed with sodium hydroxide and Na2CO3The mixed solution is dripped into water, the pH is controlled to be 9-11 in the dripping process, the mixed solution is stirred and crystallized for 12 hours at the temperature of 60 ℃, and then the mixed solution is washed.
Example 1
Step A: 0.01mol of Zn (NO)3)2·6H2O、0.005mol Al(NO3)3·9H2Dissolving O in 200ml deionized water to prepare mixed salt solution, and taking 0.05mol NaOH and 0.1mol Na2CO3Dissolving the mixture in 200ml of deionized water to prepare an alkali solution, simultaneously dropwise adding the salt solution and the alkali solution into a four-neck flask containing 200ml of deionized water at room temperature, controlling the pH to be about 10 in the dropwise adding process, stirring and crystallizing at 60 ℃ for 12 hours, filtering and washing a product until the pH is 7, and drying in an oven at 60 ℃ for 10 hours to obtain ZnAl-LDHs.
And B: weighing 2g of ZnAl-LDHs (prepared in step A), and soaking in an equal volume of solution containing 0.0040g of Na2[PtCl6]·6H2And (3) uniformly shaking the O aqueous solution, washing to remove physical adsorption ions, and drying at 80 ℃ for 12h to obtain the Pt/ZnAl-LDHs. Heating the obtained Pt/ZnAl-LDHs in a muffle furnace at 5 ℃/min, preserving the temperature at 550 ℃ for 120min, cooling to room temperature, and putting the obtained product in a tube furnace H2Reducing for 120min at 550 ℃ to obtain the Pt/ZnAl-MMO. FIG. 1 is an in-situ CO adsorption infrared spectrogram, 2070cm, of catalyst Pt/ZnAl-MMO-1Is an electron-deficient Pt center, 2020cm-1Is a metallic Pt center.
And C: accurately weighing 0.6mmol of styrene, 0.3mmol of pyrrolidine, 35mg of catalyst and 1.5mL of isopropanol as solvent into a schlenk reaction bottle, sealing, filling nitrogen to replace air in the reactor, and repeating for 5 times. The reaction temperature is 60 ℃, the reaction time is 8 hours, then the reaction mixture is cooled to room temperature, and the gas chromatography analysis is adopted, the anti-Markov selectivity is 90%, and the conversion number is 327. The product was isolated and purified by distillation under reduced pressure at 0.1Torr, 55 ℃.1H NMR(400MHz)δ/ppm＝1.80-1.83(td,J＝5.6Hz,J＝11.1Hz,4H),2.55(bs,4H), 2.56-2.65(m,2H),2.81-2.85(m,2H),7.20-7.26(m,3H),7.20-7.31(m,2H)。
Example 2
Step A: 0.01mol of Zn (NO)3)2·6H2O、0.005mol Al(NO3)3·9H2Dissolving O in 200ml deionized water to prepare mixed salt solution, and taking 0.05mol NaOH and 0.1mol Na2CO3Dissolving the mixture in 200ml of deionized water to prepare an alkali solution, simultaneously dropwise adding the salt solution and the alkali solution into a four-neck flask containing 200ml of deionized water at room temperature, controlling the pH to be about 10 in the dropwise adding process, stirring and crystallizing at 60 ℃ for 12 hours, filtering and washing a product until the pH is 7, and drying in an oven at 60 ℃ for 10 hours to obtain ZnAl-LDHs.
And B: weighing 2g of ZnAl-LDHs (prepared in step A), and soaking in an equal volume of solution containing 0.0040g of Na2[PtCl6]·6H2And (3) uniformly shaking the O aqueous solution, washing to remove physical adsorption ions, and drying at 80 ℃ for 12h to obtain the Pt/ZnAl-LDHs. Putting the obtained Pt/ZnAl-LDHs into a tube furnace H2Reducing at 550 ℃ for 120min to obtain the catalyst.
And C: accurately weighing 0.6mmol of styrene, 0.3mmol of pyrrolidine, 35mg of catalyst and 1.5mL of isopropanol as solvent into a schlenk reaction bottle, sealing, filling nitrogen to replace air in the reactor, and repeating for 5 times. The reaction temperature is 60 ℃, the reaction time is 8 hours, then the reaction mixture is cooled to room temperature, and the gas chromatography is adopted, so that the anti-Markov selectivity is 85%, and the conversion number is 225.
Example 3
Step A: 0.01mol of Zn (NO)3)2·6H2O、0.005mol Al(NO3)3·9H2Dissolving O in 200ml deionized water to prepare mixed salt solution, and taking 0.05mol NaOH and 0.1mol Na2CO3Dissolving the mixture in 200ml of deionized water to prepare an alkali solution, simultaneously dropwise adding the salt solution and the alkali solution into a four-neck flask containing 200ml of deionized water at room temperature, controlling the pH to be about 10 in the dropwise adding process, stirring and crystallizing at 60 ℃ for 12 hours, filtering and washing a product until the pH is 7, and drying in an oven at 60 ℃ for 10 hours to obtain ZnAl-LDHs.
And B: weighing 2g of ZnAl-LDHs (prepared in step A), and soaking in an equal volume of solution containing 0.0040g of Na2[PtCl6]·6H2And (3) uniformly shaking the O aqueous solution, washing to remove physical adsorption ions, and drying at 80 ℃ for 12h to obtain the Pt/ZnAl-LDHs. The obtained Pt/ZnAl-LDHs is put in NaBH4Reduced in solution and then in tube furnace H2Roasting at 550 ℃ for 120min in the atmosphere to obtain the catalyst.
And C: accurately weighing 0.6mmol of styrene, 0.3mmol of pyrrolidine, 35mg of catalyst and 1.5mL of isopropanol as solvent into a schlenk reaction bottle, sealing, filling nitrogen to replace air in the reactor, and repeating for 5 times. The reaction temperature was 60 ℃ and the reaction time was 8h, then cooled to room temperature and analyzed by gas chromatography with an inverse Markov selectivity of 36% and a conversion number of 46.
Example 4
Step A: 0.01mol of Zn (NO)3)2·6H2O、0.005mol Al(NO3)3·9H2Dissolving O in 200ml deionized water to prepare mixed salt solution, and taking 0.05mol NaOH and 0.1mol Na2CO3Dissolving the mixture in 200ml of deionized water to prepare an alkali solution, simultaneously dropwise adding the salt solution and the alkali solution into a four-neck flask containing 200ml of deionized water at room temperature, controlling the pH to be about 10 in the dropwise adding process, stirring and crystallizing at 60 ℃ for 12 hours, filtering and washing a product until the pH is 7, and drying in an oven at 60 ℃ for 10 hours to obtain ZnAl-LDHs.
And B: weighing 2g of ZnAl-LDHs (prepared in step A), and soaking in an equal volume of solution containing 0.0040g of Na2[PtCl6]·6H2And (3) uniformly shaking the O aqueous solution, washing to remove physical adsorption ions, and drying at 80 ℃ for 12h to obtain the Pt/ZnAl-LDHs. Heating the obtained Pt/ZnAl-LDHs in a muffle furnace at 5 ℃/minKeeping the temperature at 550 ℃ for 120min, cooling to room temperature, and putting the mixture in a tube furnace H2Reducing at 550 ℃ for 120min to obtain the catalyst.
And C: accurately weighing 0.6mmol of styrene, 0.3mmol of 3-hexylamine, 35mg of catalyst and 1.5mL of isopropanol as a solvent into a schlenk reaction bottle, sealing, filling nitrogen to replace air in the reactor, and repeating for 5 times. The reaction temperature was 60 ℃ and the reaction time was 8h, then cooled to room temperature, and analyzed by gas chromatography with an anti-Markov selectivity of 88% and a conversion number of 168. The product was isolated and purified by distillation under reduced pressure at 0.1Torr, 95 ℃.1H NMR(400MHz)δ/ppm＝0.92-0.97(t,J＝9.6Hz,3H),1.05-1.09(t,J＝9.6Hz, 3H),1.32-1.35(m,2H),1.45-1.48(m,2H),2.49-2.54(t,J＝10.0Hz,2H),2.58-2.65(dd, J＝9.6,9.2Hz,2H),2.71-2.76(m,4H),7.19-7.22(m,3H),7.26-7.33(m,2H).
Example 5
Step A: 0.01mol of Zn (NO)3)2·6H2O、0.005mol Al(NO3)3·9H2Dissolving O in 200ml deionized water to prepare mixed salt solution, and taking 0.05mol NaOH and 0.1mol Na2CO3Dissolving the mixture in 200ml of deionized water to prepare an alkali solution, simultaneously dropwise adding the salt solution and the alkali solution into a four-neck flask containing 200ml of deionized water at room temperature, controlling the pH to be about 10 in the dropwise adding process, stirring and crystallizing at 60 ℃ for 12 hours, filtering and washing a product until the pH is 7, and drying in an oven at 60 ℃ for 10 hours to obtain ZnAl-LDHs.
And B: weighing 2g of ZnAl-LDHs (prepared in step A), and soaking in an equal volume of solution containing 0.0040g of Na2[PtCl6]·6H2And (3) uniformly shaking the O aqueous solution, washing to remove physical adsorption ions, and drying at 80 ℃ for 12h to obtain the Pt/ZnAl-LDHs. Heating the obtained Pt/ZnAl-LDHs in a muffle furnace at 5 ℃/min, preserving the temperature at 550 ℃ for 120min, cooling to room temperature, and putting the obtained product in a tube furnace H2Reducing for 120min at 550 ℃ to obtain the Pt/ZnAl-MMO.
And C: accurately weighing 0.6mmol of styrene, 0.3mmol of aniline, 35mg of catalyst and 1.5mL of isopropanol as solvent into a schlenk reaction bottle, sealing, filling nitrogen to replace air in the reactor, and repeating for 5 times. The reaction temperature is 60 ℃, andthe reaction time was 8h, then cooled to room temperature and the conversion number was 296, with an inverse Markov selectivity of 91% as determined by gas chromatography. Separating and purifying the product by silica gel column chromatography under the specific condition of (CHCl)3:NH3 in MeOH(7mol/L)＝20:0.5)。1H NMR(400MHz)δ/ppm＝2.78-2.83(t, J＝7.0Hz,2H),3.41(t,J＝7.0Hz,2H),3.35(s,1H),6.62(dd,3J＝8.6,1.0Hz,2H),6.58(tt, J＝7.3,1.0Hz,1H),7.19(dd,J＝8.6,7.3Hz,2H),7.21-7.36(m,5H).
Example 6
Step A: 0.01mol of Zn (NO)3)2·6H2O、0.005mol Al(NO3)3·9H2Dissolving O in 200ml deionized water to prepare mixed salt solution, and taking 0.05mol NaOH and 0.1mol Na2CO3Dissolving the mixture in 200ml of deionized water to prepare an alkali solution, simultaneously dropwise adding the salt solution and the alkali solution into a four-neck flask containing 200ml of deionized water at room temperature, controlling the pH to be about 10 in the dropwise adding process, stirring and crystallizing at 60 ℃ for 12 hours, filtering and washing a product until the pH is 7, and drying in an oven at 60 ℃ for 10 hours to obtain ZnAl-LDHs.
And B: weighing 2g of ZnAl-LDHs (prepared in step A), and soaking in an equal volume of solution containing 0.0040g of Na2[PtCl6]·6H2And (3) uniformly shaking the O aqueous solution, washing to remove physical adsorption ions, and drying at 80 ℃ for 12h to obtain the Pt/ZnAl-LDHs. Heating the obtained Pt/ZnAl-LDHs in a muffle furnace at 5 ℃/min, preserving the temperature at 550 ℃ for 120min, cooling to room temperature, and putting the obtained product in a tube furnace H2Reducing for 120min at 550 ℃ to obtain the Pt/ZnAl-MMO.
And C: accurately weighing 0.6mmol of 1-octene, 0.3mmol of pyrrolidine, 35mg of catalyst and 1.5mL of isopropanol as solvent into a schlenk reaction bottle, sealing, filling nitrogen to replace air in the reactor, and repeating for 5 times. The reaction temperature was 60 ℃ and the reaction time was 8h, then cooled to room temperature and analyzed by gas chromatography with an anti-Markov selectivity of 83% and a conversion number of 61. The product was isolated and purified by distillation under reduced pressure at 0.1Torr at 50 ℃.1H NMR(400MHz)δ/ppm＝0.83-0.85(t,J＝7Hz,3H),1.26(br,10H),1.51(br, 2H),1.73-1.78(m,4H),2.42-2.49(m,6H)。
Claims (6)
1. The application of a catalyst for anti-Malassezia amination is characterized in that the catalyst is used for anti-Malassezia amination reaction of olefin and amine, and the catalyst consists of a plurality of Pt centers and composite oxides which are dispersed at an atomic level;
the content of Pt in the catalyst is 0.01-20 wt%, the Pt is in a single atom, two-dimensional cluster, three-dimensional cluster or nano-particle dispersion state, and various Pt active centers are electron-deficient Pt centersδ+Metallic Pt center Pt0Rich electron Pt center Ptδ-Two or more kinds of them, at least containing Pt as electron deficient Pt centerδ+Metallic Pt center Pt0；
The composite oxide in the catalyst is a zinc-aluminum composite oxide;
the catalyst is prepared by taking hydrotalcite as a precursor to load Pt, inducing a Pt salt precursor on the surface, and then roasting at high temperature for topological transformation and reduction;
zn is selected from divalent cations of hydrotalcite laminate2+High valence cation selected from Al3+In a molar ratio of Zn2+:Al3+The molar ratio of (0-5): 1, which is not 0:1, loading a hydrotalcite precursor with a Pt salt selected from sodium chloroplatinate, platinum acetylacetonate or platinum tetraammine nitrate, calcining the Pt salt in a muffle furnace at a heating rate of 1-10 ℃/min and a temperature of 530-2Reducing in the atmosphere, controlling the reduction temperature at 300-900 ℃, the reduction heat preservation time at 1-5 h, and the heating rate at 1-10 ℃/min to obtain the corresponding catalyst.
2. Use according to claim 1, characterized in that the substrates olefin and amine and the catalyst are added to the solvent at a reaction temperature of 30-120 ℃, a reaction pressure of autogenous pressure and a reaction time of 0.5-48 h.
3. Use according to claim 2, characterized in that the solvent is selected from isopropanol, toluene or acetonitrile; the substrate olefin is terminal olefin, and the amine is an organic matter containing N-H; the molar ratio of the added amount of the catalyst Pt to the added amine is 1:50-1: 10000; the mol ratio of the olefin to the amine is 1:1-5: 1.
4. Use according to claim 2, wherein the substrate olefin is selected from hexene, n-octene, styrene, methylstyrene, nitrostyrene or methoxystyrene; the amine is 3-hexylamine, pyrrolidine or aniline.
5. Use according to claim 2, characterized in that after the reaction has ended, the product of the anti-mahalanobis amination is obtained by work-up.
6. Use according to claim 5, characterized in that said post-processing step comprises: filtering, and purifying the filtrate by recrystallization, distillation, thin-layer chromatography or column chromatography to obtain the anti-mahalanobis hydroamination product.
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| PCT/CN2019/112639 WO2021056647A1 (en) | 2019-09-27 | 2019-10-23 | Catalyst for anti-markovnikov hydroamination, preparation method therefor and use thereof |
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| WO2005077885A1 (en) * | 2004-02-06 | 2005-08-25 | Yale University | Ruthenium-catalyzed hydroamination of olefins |
| US9120732B2 (en) * | 2010-12-31 | 2015-09-01 | California Institute Of Technology | Catalytic anti-markovnikov oxidation and hydration of olefins |
| CN107051434A (en) * | 2017-01-15 | 2017-08-18 | 北京化工大学 | The propane dehydrogenation catalyst and preparation method and application of a kind of stable high dispersive |
| WO2018209666A1 (en) * | 2017-05-19 | 2018-11-22 | 北京化工大学 | Preparation method for single-atom dispersed palladium-based catalyst and catalytic application thereof |
| CN110229045B (en) * | 2019-06-26 | 2020-10-27 | 北京化工大学 | Method for efficiently hydrogenating and converting furfuryl alcohol and high-dispersion supported Pt catalyst |
-
2019
- 2019-09-27 CN CN201910927003.2A patent/CN110681381B/en active Active
- 2019-10-23 WO PCT/CN2019/112639 patent/WO2021056647A1/en active Application Filing
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| CN110681381A (en) | 2020-01-14 |
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