CN112121853B - Mesoporous hollow silica nanosphere loaded with prolinol catalyst as well as preparation method and application of mesoporous hollow silica nanosphere - Google Patents
Mesoporous hollow silica nanosphere loaded with prolinol catalyst as well as preparation method and application of mesoporous hollow silica nanosphere Download PDFInfo
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Abstract
The invention discloses mesoporous hollow silica nanospheres loaded with prolinol catalyst and a preparation method and application thereof, firstly mesoporous silica with super-large specific surface area is prepared, a shell layer is very thin, the maximization of the loading capacity is ensured, the mesoporous hollow silica nanospheres are effectively combined with the prolinol catalyst, the defect that the silica is not easy to activate is overcome, the mesoporous silica and the shell layer are effectively combined and successfully used for Michael/Michael/aldol series reaction with strict catalysis requirements, a good result (ee is close to 100%, dr is 98) is obtained, the catalytic effect is decreased after the mesoporous hollow silica nanospheres are recycled 8, and the method for combining the structural stability and the hydrolysis method of the silica spheres with organic groups is very suitable.
Description
Technical Field
The invention belongs to the fields of high polymer materials and heterogeneous catalysis, and relates to a catalyst-loaded mesoporous hollow silica nanosphere with an ultra-large specific surface area, a preparation method and application in asymmetric tandem reaction.
Background
In recent years, hollow nanospheres have received increasing attention and research due to their unique characteristics, such as low density, good thermal stability and surface permeability, and large internal space. Many materials such as inorganic materials (zeolite, hydroxyapatite, titanium dioxide, aluminum oxide, gallium nitride, etc.) and organic polymer materials (polystyrene, etc.) have been made into hollow sphere structures and exhibit special functions which conventional materials do not have, and thus, they are widely used in many fields such as drug sustained-release/controlled-release systems, chromatographic separations, catalysts, coatings, microreactors, and photoelectric materials. In addition, the hollow silica ball may be coated with biochemical enzyme for enzyme catalysis reaction and may be used as micro reactor for some specific reaction. At present, the methods for preparing the hollow nanospheres mainly comprise a spray reaction method, a template method, a microemulsion polymerization method, an interfacial polycondensation method and the like.
The silicon dioxide hollow mesoporous nanospheres have the advantages that a large number of mesopores exist on the surface of the nanospheres with the activating functional groups, the inner surface and the outer surface of the nanospheres can be communicated, small molecules can freely come in and go out of the interior of the nanospheres, the number of the small molecules cannot be as large as that of micropores and as large as that of macropores, the nanospheres cannot be collapsed due to the large number of the small molecules, and the skeleton stability of the nanospheres is affected. Meanwhile, the skeleton of the nanosphere is of an organic structure, the hardness can be adjusted, and a large number of unpolymerized chain end active sites exist on the inner surface and the outer surface of the nanosphere, so that a good environment is provided for targeted slow release of medicines, solid loading of catalysts and the like.
The mesoporous silica nanosphere can provide 30-150m 2 g -1 The specific surface area of the nanosphere is far insufficient for catalytic reaction with large load demand, in order to improve the specific surface area, besides through mesoporous pores, the method for reducing the shell thickness is also a common method, but the nanosphere has limited supporting force, and the collapse or the fracture of the nanosphere can be caused by the excessively thin shell thickness.
Prolinol catalysts are commonly used in a variety of chiral catalytic reactions. Because the addition amount of the prolinol catalyst in the catalytic reaction is large (10-30 mol%), the prolinol catalyst is difficult to separate, recycle and reuse after the reaction is finished, the subsequent separation cost is increased, the environment is polluted, and the development of green chemistry is hindered. Based on the concept of green chemistry, the supported recovery strategy of prolinol catalyst is receiving more and more attention.
The asymmetric series reaction has extremely high requirements on the structure of a heterogeneous catalyst, and the heterogeneous reaction system has serious mass transfer limitation, high-performance green circulation and other key technical and scientific problems.
Disclosure of Invention
In view of this, the prolinol catalyst is loaded on the mesoporous hollow silica nanospheres, so that the prolinol catalyst is convenient to recover, and the cost and the environmental pollution are reduced. The catalyst prepared by the invention obtains better effect in catalyzing Michael/Michael/aldol asymmetric series reaction.
In order to solve the problems, the invention prepares mesoporous silica with an ultra-large specific surface area, activates the mesoporous silica, and effectively combines the mesoporous silica with a prolinol catalyst to prepare mesoporous hollow silica nanospheres loaded with the prolinol catalyst, as shown in fig. 1.
The method specifically comprises the following steps:
(1) Preparation of hollow mesoporous silica with super large specific surface area
Weighing hexadecyl trimethyl ammonium bromide and 1,3, 5-triisopropylbenzene, dissolving in a mixed solution of ethanol, deionized water and ammonia water, adding dispersed PS/AA, keeping the temperature at 60 ℃ for heating in a water bath, magnetically stirring for 30min at 400r/min, dropwise adding tetraethyl orthosilicate within 15min, keeping the rotating speed for continuing reaction for 2h, then carrying out centrifugal separation on milky white solution to obtain solid particles, and washing, drying and roasting to obtain the hollow mesoporous silica nanospheres; wherein the mass ratio of the hexadecyl trimethyl ammonium bromide to the 1,3, 5-triisopropylbenzene is 7-10, the mass ratio of the hexadecyl trimethyl ammonium bromide to the PS/AA is 7-10.
(2) Modification of hollow mesoporous silica with super large specific surface area
Adding absolute ethyl alcohol, the prepared hollow mesoporous silica nanospheres, deionized water and 5-methoxy-1-pentene into a beaker, stirring to form an emulsion, slowly dropwise adding ammonia water, adding the mixed solution into a double-neck flask, stirring by using a power-enhanced electric stirrer to hydrolyze the surfaces of microspheres, then centrifugally separating, washing, and ventilating and drying at room temperature to obtain the modified hollow mesoporous silica nanospheres.
(3) Preparation of mesoporous hollow silica nanosphere loaded with prolinol catalyst
Adding 100mg of modified mesoporous silica nanosphere into 25mL of ethanol/0.5% of PVA aqueous solution, wherein v/v =1/10, adding 0.04mmol of initiator KPS, argon protection, adding 10mL of deionized water, stirring for dissolving, dropwise adding a mixed solution of prolinol catalyst and acrylic acid, wherein the molar ratio of the prolinol catalyst to the acrylic acid is 1.
The catalyst prepared by the invention is used for alpha, beta-unsaturated aldehyde and benzofuranone Michael/Michael/aldol series reaction.
The invention firstly prepares the mesoporous silicon dioxide with ultra-large specific surface area, the shell layer is very thin and has 450-650m 2 The ultra-large specific surface area of/g ensures the maximization of the loading capacity. Then effectively combined with prolinol catalyst, overcomes the defect that the silicon dioxide is not easy to activate, and hasThe two are effectively combined and successfully used for catalyzing the harsh Michael/Michael/aldol tandem reaction.
The silicon dioxide is used as an inorganic material, the surface is not easy to generate organic reaction, the 5-methoxy-1-pentene is added to hydrolyze on the surface of the microsphere, double bonds are grafted, and the silicon dioxide spheres with the surface modified into the double bonds can participate in polymerization reaction to achieve the purpose of activation.
The invention takes Boc-L-proline methyl ester as raw material to synthesize alpha, alpha-distyryl prolinol Pro through nucleophilic addition reaction and the like. Polymerizing with the modified silicon dioxide spheres to prepare the mesoporous silicon dioxide nanosphere catalyst with the super large specific surface area. And the morphology and the catalytic performance of the catalyst are regulated and controlled by changing the preparation conditions such as the addition of different substances.
With N 2 The structure, the morphology and the like of the material are characterized by means of adsorption-desorption, SEM, TEMMapping and the like.
The heterogeneous catalyst prepared by the invention is used for Michael/Michael/aldol asymmetric tandem reaction of cinnamaldehyde and benzofuranone, the yield of reaction products is 38-75%, the ee value is 95- >99%, and the dr value is > 19. After the catalytic reaction is finished, the supported catalyst can be recovered through simple centrifugation, and the catalytic activity is slightly reduced after the catalyst is used for 5 times.
Because the asymmetric series reaction has extremely high requirements on the structure of the heterogeneous catalyst and the heterogeneous reaction system has serious mass transfer limitation, the invention enhances the penetrability of the reaction by reducing the thickness of the catalytic carrier, namely the thickness of the silica spheres, simultaneously reduces the relative mass of the microspheres and promotes the loading capacity of the catalyst under the same mass.
Drawings
FIG. 1 is a flow chart of a modified and prolinol catalyst supported silica microsphere
Fig. 2 is the specific surface area, diameter D: thickness T, transmission electron micrograph of the nanospheres of examples 1-3, wherein CTAB (mg), TEOS (mL) to PS (mg) ratio (a: 350, 8, c: 350; it can be seen from the figure that the ratio of the diameter D to the thickness T increases gradually (3.2Gradually increase (56.32 m) 2 g -1 、98.35 m 2 g -1 、479.47m 2 g -1 )。
FIG. 3 is a scanning, transmission electron microscope, pore distribution and particle size distribution diagram (a: SEM spectrum, b: TEM spectrum, c: particle size distribution spectrum, d: pore size distribution spectrum) of the nanospheres prepared in example 3. As can be seen from the figure, the silicon dioxide catalyst with the ultra-large specific surface area is a hollow mesoporous sphere (300 +/-10 nm) with uniform particle size, the interior is hollow obviously, and the spherical shell is full of mesopores with the particle size of 4-20 nm.
Figure 4 is TEMMapping after loading prolinol catalyst.
FIG. 5 is a High Performance Liquid Chromatography (HPLC) chart of the catalytic asymmetric tandem reaction of example 8. According to the figure, the Michael/Michael/aldol asymmetric tandem reaction selectivity of the cinnamaldehyde and the benzofuranone catalyzed by the modified mesoporous silica catalyst with the ultra-large specific surface area is good: enantioselectivity (ee) was close to 100%, diastereoselectivity (Dr) 98:2.
Detailed Description
The following examples are presented to enable one of ordinary skill in the art to more fully understand the present invention and are not intended to limit the invention in any way. In the following examples, unless otherwise specified, the experimental methods used were all conventional methods, and materials, reagents and the like used were all available from chemical reagent companies.
Preparation of hollow mesoporous silica with super large specific surface area
Example 1
0.35g of hexadecyl trimethyl ammonium bromide and 0.15g of 1,3, 5-triisopropylbenzene are weighed and dissolved in a mixed solution of 16mL of ethanol, 64mL of deionized water and 1mL of ammonia water, 20mL (200 mg) of dispersed PS/AA is added, the mixture is heated in a water bath at 60 ℃, and magnetic stirring is carried out for 30min at 400 r/min. And (3) dropwise adding 8mL of tetraethyl orthosilicate within 15min, keeping the rotating speed to continue reacting for 2h, and then carrying out centrifugal separation on the milky white solution to obtain solid particles. Washed with distilled water 2X 8mL times and absolute ethyl alcohol 2X 8mL times, and then dried in an oven at 80 ℃ for 24h. Then placing the dried product in a muffle furnace to roast for 15h at 600 ℃ (the heating rate is 2 ℃ and min -1 ) Cooling to room temperature to obtain hollowMesoporous silica nanospheres.
Example 2
0.35g of cetyltrimethylammonium bromide (CTAB) and 0.10g of 1,3, 5-triisopropylbenzene are weighed and dissolved in a mixed solution of 16mL of ethanol, 64mL of deionized water and 1mL of ammonia water, dispersed PS/AA (400 mg) is added, water bath heating at 60 ℃ is kept, and magnetic stirring is carried out for 30min at 400 r/min. Dropwise adding 8mL of tetraethyl orthosilicate (TEOS) within 15min, keeping the rotating speed to continue reacting for 2h, and then carrying out centrifugal separation on the milky white solution to obtain solid particles. Washed with distilled water 2X 8mL times and absolute ethanol 2X 8mL times, and then dried in an oven at 80 ℃ for 24h. Then placing the dried product in a muffle furnace to roast for 15h at 350 ℃ (the heating rate is 3 ℃ and min -1 ) And cooling to room temperature to obtain the hollow mesoporous silica nanospheres.
Example 3
0.35g of hexadecyl trimethyl ammonium bromide and 0.20g of 1,3, 5-triisopropylbenzene are weighed and dissolved in a mixed solution of 16mL of ethanol, 64mL of deionized water and 1mL of ammonia water, dispersed PS/AA (1000 mg) is added, water bath heating at 60 ℃ is kept, and magnetic stirring is carried out for 30min at 400 r/min. And (3) dropwise adding 8mL of tetraethyl orthosilicate within 15min, keeping the rotating speed to continue reacting for 2h, and then carrying out centrifugal separation on the milky white solution to obtain solid particles. Washed with distilled water 2X 8mL times and absolute ethyl alcohol 2X 8mL times, and then dried in an oven at 80 ℃ for 24h. Then placing the dried product in a muffle furnace to roast for 15h at 800 ℃ (the heating rate is 3 ℃ and min) -1 ) And cooling to room temperature to obtain the hollow mesoporous silica nanospheres.
Example 4
0.50g of hexadecyl trimethyl ammonium bromide and 0.25g of 1,3, 5-triisopropylbenzene are weighed and dissolved in a mixed solution of 16mL of ethanol, 64mL of deionized water and 1mL of ammonia water, dispersed PS/AA (1200 mg) is added, water bath heating at 60 ℃ is kept, and magnetic stirring is carried out for 30min at 400 r/min. And (3) dropwise adding 20mL of tetraethyl orthosilicate within 15min, keeping the rotating speed to continue reacting for 2h, and then carrying out centrifugal separation on the milky white solution to obtain solid particles. Washed with distilled water 2X 8mL times and absolute ethyl alcohol 2X 8mL times, and then dried in an oven at 80 ℃ for 24h. Then thePlacing the dried product in a muffle furnace to roast at 1000 ℃ for 15h (the heating rate is 5 ℃ min) -1 ) And cooling to room temperature to obtain the hollow mesoporous silica nanosphere.
Modification of hollow mesoporous silica with super large specific surface area
Example 5
75 ml of absolute ethyl alcohol, 50mg of the hollow mesoporous silica spheres prepared in example 3, 3 ml of deionized water and 0.025g of 5-methoxy-1-pentene were weighed into a beaker, stirred for 20min to form an emulsion, and 15ml of ammonia water was added dropwise (5-8 drops/min). Adding the mixed solution into a double-mouth flask, stirring with a power-increasing electric stirrer at about 45 deg.C and 350 r.min -1 And stirring for 2 hours to hydrolyze the surfaces of the microspheres. And (3) centrifugally separating the stirred solution, washing the solution by distilled water for 3X 10mL times and washing the solution by absolute ethyl alcohol for 2X 10mL times, and then ventilating and drying the solution at room temperature for later use to obtain the modified hollow mesoporous silica nanosphere.
Prolinanol catalyst monomer preparation
Example 6
1) Synthesis of Compound 1d
2) Synthesis of Compound 2d (Pro)
Preparation of mesoporous hollow silica nanosphere loaded with prolinol catalyst
Example 7
In a 50mL two-necked round-bottomed flask, modified mesoporous silica nanospheres (100 mg) were added to 25mL ethanol/0.5% PVA aqueous solution (v/v = 1/10) and initiator KPS (0.04 mmol), argon protected, 10mL deionized water was added. Stirring for dissolving, dropwise adding a mixed solution (dropwise adding for 2 min) of prolinol catalyst (Pro, 0.20 mmol) and AA (0.20 mmol) to form white emulsion, stirring to emulsify uniformly, heating to 70 ℃, and continuing to react for 24h. The mixture was cooled to room temperature, the supernatant was centrifuged, and the lower solid was washed with deionized water (10 mL. Times.4) and absolute ethanol (10 mL. Times.4), respectively. Vacuum drying to obtain white silica nanosphere-supported multifunctional organic catalyst (138.9 mg). The TEMMapping diagram is shown in fig. 4.
Step of catalyzing alpha, beta-unsaturated aldehyde and benzofuranone Michael/Michael/aldol tandem reaction
Example 8
Taking cinnamaldehyde as an example: a25 mL catalytic test tube was charged with the modified mesoporous silica catalyst (27.0 mg, 20 mol%) and 1mL of toluene, stirred and dispersed for 5min, then cinnamaldehyde (39.4 mg, 0.3mmol) was added, stirring was continued for 5min, benzofuranone (13.4 mg, 0.1mmol) was added, and reaction was carried out at 40 ℃ for 30h. After the reaction, the heterogeneous catalyst was centrifuged, washed with toluene (5 mL. Times.3), the supernatants combined, concentrated under reduced pressure and the crude product purified on a silica gel column (V) Petroleum ether /V Ethyl acetate = 6). Detecting the enantioselectivity of the catalytic product by High Performance Liquid Chromatography (HPLC) 1 Detection of catalytic products by HNMRNon-corresponding selectivity of (a).
The comparative tables for the catalytic effects of the catalysts prepared respectively using the silica spheres prepared in examples 1 to 3 at the same organic amount are as follows:
the catalyst prepared by the invention is adopted to carry out the reaction, so that the catalyst is convenient to recover and has small dosage.
Finally, it is noted that the above-mentioned preferred embodiments illustrate rather than limit the invention, and that, although the invention has been described in detail with reference to the above-mentioned preferred embodiments, it will be understood by those skilled in the art that various changes in form and detail may be made therein without departing from the scope of the invention as defined by the appended claims.
Claims (8)
1. A preparation method of mesoporous hollow silica nanospheres loaded with prolinol catalyst comprises the following steps:
(1) Preparation of hollow mesoporous silica with super large specific surface area
Weighing hexadecyl trimethyl ammonium bromide and 1,3, 5-triisopropylbenzene, dissolving in a mixed solution of ethanol, deionized water and ammonia water, adding dispersed PS/AA, keeping the temperature at 60 ℃ for heating in a water bath, magnetically stirring for 30min at 400r/min, dropwise adding tetraethyl orthosilicate within 15min, keeping the rotating speed for continuing reaction for 2h, then carrying out centrifugal separation on milky white solution to obtain solid particles, and washing, drying and roasting to obtain the hollow mesoporous silica nanospheres; wherein the mass ratio of the hexadecyl trimethyl ammonium bromide to the 1,3, 5-triisopropylbenzene is 7-10, the mass ratio of the hexadecyl trimethyl ammonium bromide to the PS/AA is 7-10;
(2) Modification of hollow mesoporous silica with super large specific surface area
Adding absolute ethyl alcohol, prepared hollow mesoporous silica nanospheres of 100mg, deionized water and 0.2mmol of 5-methoxy-1-pentene into a beaker, stirring to form emulsion, slowly dropwise adding ammonia water, adding the mixed solution into a double-neck flask, stirring by a power-enhanced electric stirrer to hydrolyze the surfaces of microspheres, then centrifugally separating, washing, and ventilating and drying at room temperature to obtain modified hollow mesoporous silica nanospheres;
(3) Preparation of mesoporous hollow silica nanosphere loaded with prolinol catalyst
Adding 100mg of modified mesoporous silica nanospheres into 25mL of ethanol/0.5% of PVA aqueous solution, wherein v/v =1/10, adding 0.04mmol of initiator KPS, argon protection, adding 10mL of deionized water, stirring for dissolving, dropwise adding a mixed solution of prolinol catalyst and acrylic acid, wherein the molar ratio of the prolinol catalyst to the acrylic acid is 1;
the prolinol catalyst: boc-L-proline methyl ester is used as a raw material, and alpha, alpha-distyryl prolinol Pro is synthesized through a nucleophilic addition reaction.
2. The preparation method of the prolinol catalyst supported mesoporous hollow silica nanosphere according to claim 1, characterized in that: the washing in the step (1) comprises two times of distilled water washing and two times of absolute ethyl alcohol washing.
3. The preparation method of the prolinol catalyst supported mesoporous hollow silica nanosphere according to claim 1, characterized in that: the roasting temperature of the roasting in the step (1) is 350-800 ℃, and the roasting temperature rise rate is 3-5 ℃ per minute -1 。
4. The preparation method of the prolinol catalyst supported mesoporous hollow silica nanosphere according to claim 1, characterized in that: the prolinol catalyst is prepared by the following method:
adding 0.4g of magnesium powder into a three-necked bottle with a magnetic stirring device, protecting with Ar, adding 30mL of THF and 1.0g of 4-chlorostyrene, dropwise adding 1, 2-dibromoethane to initiate reaction, and dropwise adding 1.3g of 4-chlorostyrene at 60 ℃ to react for 2 hours; under ice bath, adding 1.1g Boc-proline methyl ester into the reaction system, reacting for 1h, adding saturated ammonium chloride solution to quench the reaction, extracting with dichloromethane, collecting an organic phase, and adding anhydrous Na 2 SO 4 Drying, suction filtering, spin drying to obtain light yellow viscous liquid, purifying with silica gel column, eluting with petroleum ether and ethyl acetate, and purifying with silica gel column Petroleum ether /V Ethyl acetate 1, obtaining a white solid 1d;
into a single-necked flask equipped with a magnetic stirring device, 0.5g of the white solid 1d,0.8g of KOH, and 5mL of CH were charged 3 OH and 15mL DMSO react for 2h at 65 ℃, 20mL water is added for quenching reaction, n-hexane is used for extraction, organic phases are combined, and anhydrous Na 2 SO 4 Drying, suction filtering, spin drying to obtain light yellow oily liquid, purifying with silica gel column, eluting with dichloromethane and methanol, and purifying with silica gel column Methylene dichloride /V Methanol 1, to obtain a white solid 2d.
5. Mesoporous hollow silica nanospheres carrying prolinol catalyst prepared by the method of any of claims 1 to 4.
6. The use of the prolinol catalyst-loaded mesoporous hollow silica nanospheres of claim 5 as catalysts in asymmetric tandem reactions.
7. Use according to claim 6, characterized in that: the asymmetric tandem reaction is a Michael/Michael/aldol tandem reaction of alpha, beta-unsaturated aldehyde and benzofuranone.
8. Use according to claim 7, characterized in that: the alpha, beta-unsaturated aldehyde and benzofuranone Michael/Michael/aldol series reaction comprises the following steps:
adding 27.0mg of mesoporous hollow silica nanosphere loaded with prolinol catalyst and 1mL of toluene into a catalytic test tube, stirring and dispersing for 5min, adding 39.4mg of cinnamaldehyde, continuing stirring for 5min, adding 13.4mg of benzofuranone, reacting for 30h at 40 ℃, after the reaction is finished, centrifugally separating the mesoporous hollow silica nanosphere loaded with the prolinol catalyst, washing with toluene, combining supernate, concentrating under reduced pressure, purifying a crude product with a silica gel column, selecting petroleum ether and ethyl acetate as eluent, and purifying V Petroleum ether /V Ethyl acetate 1 to obtain a white solid product.
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