CN116747878A - Magnetic nano microsphere and preparation method and application thereof - Google Patents

Magnetic nano microsphere and preparation method and application thereof Download PDF

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CN116747878A
CN116747878A CN202311029566.2A CN202311029566A CN116747878A CN 116747878 A CN116747878 A CN 116747878A CN 202311029566 A CN202311029566 A CN 202311029566A CN 116747878 A CN116747878 A CN 116747878A
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nhco
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magnetic nano
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CN116747878B (en
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张振华
钱星彤
李雅璇
吴燕华
卢欢
畅温旭
冯冀尧
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China Agricultural University
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    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
    • B01J23/8906—Iron and noble metals
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J31/0274—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing elements other than those covered by B01J31/0201 - B01J31/0255 containing silicon
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/0272—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing elements other than those covered by B01J31/0201 - B01J31/0255
    • B01J31/0275—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing elements other than those covered by B01J31/0201 - B01J31/0255 also containing elements or functional groups covered by B01J31/0201 - B01J31/0269
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    • C07C209/04—Preparation of compounds containing amino groups bound to a carbon skeleton by substitution of functional groups by amino groups
    • C07C209/14—Preparation of compounds containing amino groups bound to a carbon skeleton by substitution of functional groups by amino groups by substitution of hydroxy groups or of etherified or esterified hydroxy groups
    • C07C209/18—Preparation of compounds containing amino groups bound to a carbon skeleton by substitution of functional groups by amino groups by substitution of hydroxy groups or of etherified or esterified hydroxy groups with formation of amino groups bound to carbon atoms of six-membered aromatic rings or from amines having nitrogen atoms bound to carbon atoms of six-membered aromatic rings
    • 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
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    • C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
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Abstract

The application discloses a magnetic nano microsphere, a preparation method and application thereof, wherein the magnetic nano microsphere uses Fe 3 O 4 Denoted by @ Pd @ Si-R', which has a core-shell structure, expressed as Fe 3 O 4 Pd is supported on the core as a core, and modified silicon compounds Si-R' are used as shells. The application provides a magnetic nano microsphere which can realize the catalytic effect of high-efficiency separation and recovery. The catalyst is used for the reaction process of preparing N-ethylaniline by catalyzing nitrobenzene to reduce and alkylate and preparing primary amine by azide reduction in a Suzuki reaction, and realizes the multiple recovery of the catalyst. Meanwhile, the magnetic full-automatic organic synthesis is realized.

Description

Magnetic nano microsphere and preparation method and application thereof
Technical Field
The application belongs to the field of magnetic materials, and particularly relates to a magnetic nanoparticle, a preparation method and application thereof.
Background
The magnetic nano catalyst has wide application in organic synthesis catalytic reaction, and the excellent dispersibility and easy separation capability enable the magnetic nano catalyst to be between homogeneous phase and heterogeneous phase boundaries, and the size and the surface property enable the magnetic nano catalyst to show unique catalytic performance.
In the prior art, fe 3 O 4 @Pd (Mag-Core) or Fe 3 O 4 @SiO 2 The magnetic nano catalyst in the form of Pd (Mag-Shell-Core) is reacted under magnetic stirring, and the magnetic nano catalyst is difficult to recycle.
Disclosure of Invention
In order to solve the technical problems, the application provides a magnetic nano microsphere which uses Fe 3 O 4 Denoted by @ Pd @ Si-R', which has a core-shell structure, expressed as Fe 3 O 4 Pd is loaded on the core and takes a modified silicon compound Si-R' as a shell;
wherein R' is selected from the group consisting of-C 1-12 Alkyl, -C 6-20 Aryl, -NHCO-C 6-20 Aryl, - (CH) 2 ） n -COOH、-（CH 2 ） n -CN、-（CH 2 ） n -Cl、-（CH 2 ） n -NR 1 R 2 、-（CH 2 ） n -NHCO-（CH 2 ） n -COOH、-NHCH 2 CH 2 -NH-CH 2 CH 2 -NH 2 、-NHCO-（CH 2 ） n -OH；
Wherein n is the same or different and is an integer selected from 0 to 10 independently of each other;
R 1 and R is 2 Identical or different, independently of one another, from H, C 1-12 An alkyl group.
According to an embodiment of the application, n is identical or different and is independently an integer from 0 to 6.
According to an embodiment of the application, R' is selected from-C 1-10 Alkyl, -C 6-14 Aryl, -NHCO-C 6-14 Aryl, - (CH) 2 ） n -COOH、-（CH 2 ） n -CN、-（CH 2 ） n -Cl、-（CH 2 ） n -NR 1 R 2 、-（CH 2 ） n -NHCO-（CH 2 ） n -COOH、-NHCH 2 CH 2 -NH-CH 2 CH 2 -NH 2 、-NHCO-（CH 2 ） n -OH。
According to an embodiment of the application, R' is selected from propyl, - (CH) 2 ） 3 - NHCO-（CH 2 ） 2 -COOH, carboxyl, -NHCO-Ph, pentyl, octyl, decyl, phenyl, -CH 2 -Ph-、-（CH 2 ） 2 -CN、-（CH 2 ） 3 -Cl、-（CH 2 ） 3 -NH 2 、-（CH 2 ） 3 -NEt 2 、-NHCH 2 CH 2 -NH-CH 2 CH 2 -NH 2 、-NHCO-（CH 2 ） 2 -COOH、-NHCO-（CH 2 ） 4 -COOH、-NHCO-Ph、-NHCO-（CH 2 ） 2 -OH。
According to an embodiment of the application, the Fe 3 O 4 Particle diameters of 50nm to 300nm, exemplary 50nm, 100nm、125nm、150nm、200nm、250nm、300nm。
According to an embodiment of the application, the loading of Pd is 1-15 wt%, such as 1wt%, 3wt%, 5wt%, 7wt%, 9wt%, 10wt%, 12wt%, 15wt% based on the mass of the magnetic nanoparticle.
According to an embodiment of the application, the thickness of the shell is 10-300 a nm a.
According to an embodiment of the application, the shell is 100% coated.
According to an embodiment of the present application, the magnetic nanoparticle has a hydrated particle size of 100 to 1100nm, preferably 200 to 1000nm, and more preferably 450 to 800nm.
The application also provides a preparation method of the magnetic nano microsphere, which comprises the following steps:
fe is added to 3 O 4 @Pd magnetic nanoparticles and modified silicon compounds (RO) 3 Si-R' is mixed and reacted in a solvent to prepare the magnetic nano microsphere,
wherein R' has the meaning as above, R is selected from C 1-12 An alkyl group.
According to an embodiment of the application, an alkaline solution is also added to the process to adjust the pH to a pH of 7-12.
According to an embodiment of the present application, the alkali solution is selected from at least one of ammonia water, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, and the like. In the present application, the concentration and content of the alkali solution are not particularly limited, so that the pH of the system is 7 to 12.
According to an embodiment of the present application, the solvent is selected from at least one of water, ethanol, ethylene glycol dimethyl ether, and the like. Preferably a mixture of water and ethanol.
According to an embodiment of the application, the Fe 3 O 4 @Pd magnetic nanoparticles and modified silicon compounds (RO) 3 The mass ratio of Si to R' is 0.05-1:1, preferably 0.2-0.6:1.
According to an embodiment of the application, the Fe 3 O 4 The mass volume ratio of the@Pd magnetic nano-particles to the solvent is 1-10 (mg): 1 (mL), preferably 1-6 (mg): 1 (mL).
According to an embodiment of the application, the temperature of the reaction is 30-90 ℃, preferably 40-80 ℃.
According to an embodiment of the application, the reaction time is 0.5-10h, preferably 1-8h.
According to an embodiment of the application, the Fe 3 O 4 The preparation method of the Pd magnetic nano-particles is a conventional technology in the field. Illustratively, the Fe 3 O 4 The preparation method of the@Pd magnetic nanoparticle comprises the following steps:
metal palladium salt and Fe 3 O 4 Mixing in water, reacting at room temperature, adding a reducing agent, and reacting overnight to obtain the Fe 3 O 4 @pd magnetic nanoparticles.
Preferably, the metallic palladium salt is, for example, sodium chloropalladate.
Also exemplary, the Fe 3 O 4 The preparation method of the@Pd magnetic nanoparticle comprises the following steps: metal palladium salt and Fe 3 O 4 Dispersing magnetic nano particles with water, regulating pH of the system with alkali solution, reacting at room temperature, adding a reducing agent under cooling with ice water bath, stirring overnight, magnetically separating, and washing with water for 3 times to obtain Fe 3 O 4 @Pd。
As an exemplary embodiment of the present application, the magnetic nanoparticle is prepared as follows: fe is added to 3 O 4 @Pd magnetic nanoparticles and modified silicon compounds (RO) 3 Dispersing Si-R' in a mixed solution of water and alcohol, regulating the pH of the system by using alkali solution, reacting at room temperature, magnetically separating, and washing for 3 times to obtain the magnetic nano microsphere Fe 3 O 4 @Pd@Si-R’。
The application also provides application of the magnetic nano microsphere as a transition metal Pd catalyst, and the application is exemplified by a Pd catalyst-catalyzed coupling reaction (such as a C-C bond coupling reaction and a C-N bond coupling reaction), a Pd catalyst-catalyzed reduction reaction and the like, for example, the magnetic nano microsphere is used as a catalyst for a Suzuki reaction, is used for catalyzing nitrobenzene to prepare aniline, N-alkylaniline and/or N, N-dialkylaniline by reduction alkylation, and is used for catalyzing azide compounds to reduce primary amines. Preferably as a magnetic catalyst for high throughput automated organic synthesis reactions.
The beneficial effects of the application are that
The application provides a magnetic nano microsphere which can realize the catalytic effect of high-efficiency separation and recovery. The catalyst is used for the reaction process of preparing aniline, N-alkylaniline and N, N-dialkylaniline by catalyzing reduction alkylation of nitrobenzene and preparing primary amine by azide reduction, and realizes multiple recovery of the catalyst. Meanwhile, high-flux automatic organic synthesis is realized.
The term "C 1-12 Alkyl "denotes straight-chain and branched alkyl having 1,2, 3, 4, 5, 6, 7, 8, 9, 10, 11 or 12 carbon atoms," C 1-6 Alkyl "means straight and branched alkyl groups having 1,2, 3, 4, 5 or 6 carbon atoms. The alkyl group is, for example, methyl, ethyl, propyl, butyl, pentyl, hexyl, isopropyl, isobutyl, sec-butyl, tert-butyl, isopentyl, 2-methylbutyl, 1-ethylpropyl, 1, 2-dimethylpropyl, neopentyl, 1-dimethylpropyl, 4-methylpentyl, 3-methylpentyl, 2-methylpentyl, 1-methylpentyl, 2-ethylbutyl, 1-ethylbutyl, 3-dimethylbutyl, 2-dimethylbutyl, 1-dimethylbutyl, 2, 3-dimethylbutyl, 1, 3-dimethylbutyl, or 1, 2-dimethylbutyl, or the like, or an isomer thereof.
The term "C 6-20 Aryl "is understood to mean preferably a mono-, bi-or tricyclic hydrocarbon ring, preferably" C ", of monovalent aromatic or partly aromatic nature having 6 to 20 carbon atoms 6-14 Aryl group). The term "C 6-14 Aryl "is understood to mean preferably a mono-, bi-or tricyclic hydrocarbon ring (" C ") having a monovalent aromatic or partially aromatic character of 6, 7, 8, 9, 10, 11, 12, 13 or 14 carbon atoms 6-14 Aryl), in particular a ring having 6 carbon atoms ("C) 6 Aryl "), such as phenyl; or biphenyl, or a ring having 9 carbon atoms ("C 9 Aryl "), e.g. indanyl or indenyl, or a ring having 10 carbon atoms (" C 10 Aryl "), such as tetralin, dihydronaphthyl or naphthyl, or a ring having 13 carbon atoms (" C " 13 Aryl "), examplesSuch as fluorenyl, or a ring having 14 carbon atoms ("C 14 Aryl "), such as anthracenyl. When said C 6-20 When the aryl group is bonded to another group, the bonding position may be a phenyl group or a group bonded to a phenyl group.
Drawings
FIG. 1 is a flow chart of the preparation of the magnetic nanoparticle of the present application.
FIG. 2 is a graph showing the yields of the products produced by the catalytic reactions performed multiple times on the catalyst after the separation and recovery reactions of comparative application examples 2 and 4 and application example 31.
Fig. 3a is a schematic and actual view showing the reaction formula and the reaction result in the automated azide reduction reaction in application example 47, and fig. 3b is a schematic and actual view showing the process of the automated azide reduction reaction in application example 47.
Detailed Description
The technical scheme of the application will be further described in detail below with reference to specific embodiments. It is to be understood that the following examples are illustrative only and are not to be construed as limiting the scope of the application. All techniques implemented based on the above description of the application are intended to be included within the scope of the application.
Unless otherwise indicated, the starting materials and reagents used in the following examples were either commercially available or may be prepared by known methods.
Example 1
Fe 3 O 4 The specific scheme for the synthesis of @ Pd @ PTEO (i.e., MNP-01) is shown below:
the first step: 1 mmol of sodium chloropalladate and 1 g of Fe are added to 50 mL of water 3 O 4 After stirring the magnetic nanoparticles (200 nm) at room temperature for 1 h, the system pH was adjusted to 12 with 1M NaOH aqueous solution. Reaction 6 h was sonicated and mechanically stirred. 1 mmol of sodium borohydride was added under cooling in an ice-water bath, and the reaction was stirred overnight. Finally, fe is prepared 3 O 4 @Pd magnetic nanoparticlesThe particles were magnetically separated and washed 3 times. XPS detects Pd content of 5wt%.
And a second step of: 500 mg of Fe is added into a 500 mL three-neck round bottom flask 3 O 4 The @ Pd magnetic nanoparticles were dispersed with 100 mL water and 200 mL ethanol and the system was basicity adjusted by adding 5 mL ammonia. 2 g triethoxypropyl silane was added and reacted overnight with mechanical stirring. Fe obtained 3 O 4 Magnetic attraction separation is carried out on the magnetic nano particles @ Pd @ PTEO and ethanol washing is carried out for 3 times. XPS detects Fe 3 O 4 Pd content in @ Pd @ PTEO is 3 wt%.
Example 2
Fe 3 O 4 The specific synthesis scheme of @ Pd @ APTES (MNP-09) is as follows:
the first step: the same as in example 1, first step
And a second step of: 500 mg of Fe is added into a 500 mL three-neck round bottom flask 3 O 4 The @ Pd magnetic nanoparticles were dispersed with 100 mL water and 250 mL ethanol and the system was basicity adjusted by adding 5 mL ammonia. Adding 2 g triethoxypropylamino silane, reacting 12 h under mechanical stirring, magnetically separating the obtained product, and washing with ethanol for 3 times to obtain Fe 3 O 4 @Pd@APTES。
Example 3
Fe 3 O 4 The specific scheme for the synthesis of @ Pd @ Si-COOH (MNP-12) is shown below:
into a 250 mL three neck round bottom flask was charged 500 mg of Fe prepared in example 2 3 O 4 @Pd@APTES was dispersed with 100 mL of DMF, succinic anhydride (1.1 equiv) was added dropwise, and then reacted by heating at 60℃under stirring 2 h. Fe obtained 3 O 4 Magnetic attraction separation is carried out on the magnetic nano particles of@Pd@Si-COOH, and the magnetic nano particles are washed 3 times.
Example 4
Fe 3 O 4 The specific synthetic procedure for the @ Pd @ Si-NHCO-Ph (i.e., MNP-14) is as follows:
the first step: 5 mmol of triethoxypropylaminosilane and EDCI (1.0 equiv.) are placed in a 50 mL round bottom flask and dispersed with 10 mL dichloromethane, 5 mmol of benzoic acid are added dropwise with stirring and cooling in an ice water bath, after reaction 2 h at room temperature, after extraction of the system 3 times with 10 mL water, the organic phase is collected and dried by spinning to give N- (3- (triethoxysilyl) propyl) benzamide.
And a second step of: the same as in preparation example 1
And a third step of: 500 mg of Fe is added into a 500 mL three-neck round bottom flask 3 O 4 The @ Pd magnetic nanoparticles were dispersed with 100 mL water and 250 mL ethanol and the system was basicity adjusted by adding 5 mL ammonia. Adding 2 g modified silane raw material, reacting 12 h under mechanical stirring, magnetically separating the prepared product, and washing with water for 3 times to obtain Fe 3 O 4 @Pd@Si-NHCO-Ph。
Examples 5 to 13
Examples 5-13 differ from example 1 in that the propyl group of example 1 was replaced with R' in Table 1 below.
Example 14
Example 14 differs from example 2 in that R 'in Table 1 is used instead of R' in example 1.
Example 15
Example 15 differs from example 3 in that R 'in Table 1 is used instead of R' in example 1.
TABLE 1 hydration particle size table of magnetic nanoparticle prepared with each R' group in examples 1 to 15
In the table 1, the contents of the components,
[a] dynamic Light Scattering (DLS) test
Examples 16 to 18
Examples 16 to 18 differ from example 1 in that Fe is used 3 O 4 The particle sizes of the obtained products were 50nm, 125 nm and 300nm, respectively, and the hydrated particle sizes of the obtained products are shown in Table 2 below.
TABLE 2 hydrated particle size of magnetic nanoparticle of examples 1, 16-18
Magnetic bead numbering Fe 3 O 4 Size (nm) Particle size of hydration (nm) [a]
Example 1 MNP-1 200 475.45
Example 16 MNP-16 50 213.47
Example 17 MNP-17 125 357.83
Example 18 MNP-18 300 768.25
[a] Dynamic Light Scattering (DLS) test
Examples 19 to 21
Examples 19-21 differ from example 1 in that the molar ratio of sodium chloropalladate to sodium borohydride used was 0.3 mmol,1 mmol,2 mmol, respectively, and the hydrated particle size of the resulting product is shown in Table 3 below.
TABLE 3 hydrated particle size of each magnetic nanoparticle of examples 1 and 19-21
Magnetic bead numbering Pd loading (wt%) [b] Particle size of hydration (nm) [a]
Example 1 MNP-1 3 475.45
Example 19 MNP-19 1 482.56
Example 20 MNP-20 10 553.18
Example 21 MNP-21 15 658.51
[a] Dynamic Light Scattering (DLS) test; [b] x-ray photoelectron spectroscopy (XPS) test
In the table, the Pd loading is based on the mass of the magnetic nanoparticle.
Application examples 1-15 catalytic Suzuki coupling reactions
To a reaction flask of 10 mL were added 3 mol% (relative to bromobenzene) of the magnetic nanoparticle catalyst of examples 1-15 and 10 mol% (relative to bromobenzene) of the ligand triphenylphosphine, respectively, and 2 mL of 1, 4-dioxane was added for dispersion. 0.1 mmol of bromobenzene and cesium carbonate (the content of cesium carbonate is 1.5 times that of bromobenzene) are added under the protection of nitrogen, and p-methoxyphenylboric acid (the content of p-methoxyphenylboric acid is 1.1 times that of bromobenzene) is added under stirring, and the mixture is heated to 70 ℃ for reaction for 8 hours. After TLC detection of the reaction results, 20. Mu.l of the system was taken, ethyl acetate was diluted to 1 mL, and GC-MS detection was performed to obtain the yield.
The specific process is as follows:
TABLE 4 yields of the products in application examples 1-15
Application examples 16-30 catalytic reduction alkylation of nitrobenzene to prepare aniline, N-ethylaniline and N, N-diethylaniline
To a 25 mL reaction flask was added 3 mol% (relative to nitrobenzene) of the magnetic nanoparticle catalyst of examples 1-15, respectively, and dispersed with 5 mL ethanol. 0.1 mmol of nitrobenzene was added and the reaction was carried out at room temperature under hydrogen. After TLC detection of the reaction results, 20. Mu.l of the system was taken, ethyl acetate was diluted to 1 mL, and GC-MS detection was performed to obtain the yield.
The specific process is as follows:
TABLE 4 yields of the products in application examples 16-30
In Table 4, comparative application example 1 was conducted in the same manner as in application example 15 using Pd/C as a catalyst.
Application examples 31-45 catalytic reduction of azides to primary amines
To a reaction flask of 10 mL was added 0.5 mol% of the magnetic nanoparticle catalyst of examples 1-15, respectively, and 1 mL ethanol was added for dispersion. 0.015 mmol of phenylpropyl azide was added, hydrazine hydrate (2 times the content of phenylpropyl azide) was added with stirring, and the mixture was heated to 40℃for 45 min. After TLC detection of the reaction results, 20. Mu.l of the system was taken, ethyl acetate was diluted to 1 mL, and GC-MS detection was performed to obtain the yield.
The specific process is as follows:
TABLE 5 yields of the products in application examples 31-45
In Table 5, comparative application examples 2 to 5 were each carried out as Pd/C, fe 3 O 4 、Fe 3 O 4 @Pd、Fe 3 O 4 @Pd@SiO 2 The rest of the procedure was the same as in application example 31, except that it was catalyst.
Application example 46
Recovery experiments:
the catalysts after the reaction (Pd/C, fe respectively) were recovered by separating comparative examples 2, 4 and example 31 3 O 4 @Pd，Fe 3 O 4 @Pd@PTEO), the reaction was continued according to application example 31 after washing 3 times with ethanol, a plurality of recovery reactions were achieved, and the yield was calculated for the produced product, and the experimental results are shown in FIG. 2. As can be seen from FIG. 2, the Pd/C is lost in productivity after the third reaction cycle, and the catalyst Pd/C, fe after the fourth reaction cycle 3 O 4 The catalyst activity of @ Pd is obviously reduced, and Fe 3 O 4 The shell layer of the application can realize the protection of the catalytic active substance transition metal palladium.
Application example 47 automated azide reduction reaction
Fig. 3a is a schematic and actual view showing the reaction formula and the reaction result in the automated azide reduction reaction in application example 47, and fig. 3b is a schematic and actual view showing the process of the automated azide reduction reaction in application example 47.
In FIG. 3a or FIG. 3b, R 1 Represents hydrazine hydrate, R 2 Represents an azide compound, C represents a catalyst, and P represents a prepared product.
The first step: and (5) prefabricating the plate. In a 96-well reaction plate, 20 microliters of hydrazine hydrate and 300 microliters of ethanol are preloaded per well; a96-well magnetic catalyst plate was preloaded with 600. Mu.l of the catalyst Fe of example 1 3 O 4 Pd@PTEOethanolSolution (4 mg/mL) per well; in a 96-well recovery plate, 800 microliters of ethanol per well were preloaded.
And a second step of: and (5) transferring liquid. The pipetting is set at 300 microliters. 48 azide (specific azide is shown in Table 6 below) in ethanol (2 mL 1 mol/L) was transferred to a reaction plate 96 well (48X 2)
And a third step of: magnetic solid transfer. The magnetic rod (containing the magnetic rod sleeve) is arranged in the magnetic catalyst plate, the magnetic attraction is 30 and s, the magnetic rod (containing the magnetic rod sleeve) is put forward and then is transferred into the reaction plate, only the magnetic rod is moved out, and the magnetic catalyst is dispersed in the reaction liquid by the magnetic rod sleeve.
Fourth step: the reaction was slapped. Setting the reaction temperature at 40 ℃ and the reaction time at 30 min. The magnetic rod sleeve is vertically flapped up and down, and the reaction solution is fully and uniformly mixed.
Fifth step: and (5) magnetic attraction separation. After the reaction, the catalyst is moved into a magnetic rod, the magnetic rod (containing a magnetic rod sleeve) is arranged in a reaction plate, the magnetic attraction is 30 s, the magnetic rod (containing the magnetic rod sleeve) is lifted and then is transferred into a recovery plate, the magnetic rod (containing the magnetic rod sleeve) is moved out, and the catalyst is dispersed in the recovery liquid. And (3) separating the reaction system from the catalyst.
Sixth step: and (5) analyzing results. The reaction plate was removed, 20. Mu.l of each well was taken, diluted to 1.1 mL with ethyl acetate, and the reaction was analyzed by GC-MS.
Table 6 shows the catalyst Fe in example 1 3 O 4 Yield of product prepared by automated catalytic azide reduction reaction of @ pd @ pteo.
Table 6: yield table of catalyst automated catalytic azide reduction reaction product in example 1
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The embodiments of the present application have been described above by way of example. However, the scope of the present application is not limited to the above embodiments. Any modifications, equivalent substitutions, improvements, etc. made by those skilled in the art, which fall within the spirit and principles of the present application, are intended to be included within the scope of the present application.

Claims (10)

1. A magnetic nano microsphere is characterized in that Fe is used as the magnetic nano microsphere 3 O 4 Denoted by @ Pd @ Si-R', which has a core-shell structure, expressed as Fe 3 O 4 Pd is loaded on the core and takes a modified silicon compound Si-R' as a shell;
wherein R' is selected from the group consisting of-C 1-12 Alkyl, -C 6-20 Aryl, -NHCO-C 6-20 Aryl, - (CH) 2 ） n -COOH、-（CH 2 ） n -CN、-（CH 2 ） n -Cl、-（CH 2 ） n -NR 1 R 2 、-（CH 2 ） n -NHCO-（CH 2 ） n -COOH、-NHCH 2 CH 2 -NH-CH 2 CH 2 -NH 2 、-NHCO-（CH 2 ） n -OH；
Wherein n is the same or different and is an integer selected from 0 to 10 independently of each other;
R 1 and R is 2 Identical or different, independently of one another, from H, C 1-12 An alkyl group.
2. Microsphere according to claim 1, characterized in that R' is selected from-C 1-10 Alkyl, -C 6-14 Aryl, -NHCO-C 6-14 Aryl, - (CH) 2 ） n -COOH、-（CH 2 ） n -CN、-（CH 2 ） n -Cl、-（CH 2 ） n -NR 1 R 2 、-（CH 2 ） n -NHCO-（CH 2 ） n -COOH、-NHCH 2 CH 2 -NH-CH 2 CH 2 -NH 2 、-NHCO-（CH 2 ） n -OH。
3. The microsphere of claim 1, wherein R' is selected from the group consisting of propyl, - (CH) 2 ） 3 - NHCO-（CH 2 ） 2 -COOH, carboxyl, -NHCO-Ph, pentyl, octyl, decyl, phenyl, -CH 2 -Ph-、-（CH 2 ） 2 -CN、-（CH 2 ） 3 -Cl、-（CH 2 ） 3 -NH 2 、-（CH 2 ） 3 -NEt 2 、-NHCH 2 CH 2 -NH-CH 2 CH 2 -NH 2 、-NHCO-（CH 2 ） 2 -COOH、-NHCO-（CH 2 ） 4 -COOH、-NHCO-Ph、-NHCO-（CH 2 ） 2 -OH；
The Fe is 3 O 4 The particle size of (2) is 50nm-300nm;
based on the mass of the magnetic nano microsphere, the load of Pd is 1-15 wt%.
4. The microsphere of claim 1, wherein the shell has a thickness of 10 to 300 a nm; the shell is 100% coated;
the hydration particle size of the magnetic nano microsphere is 100-1100nm.
5. A method of preparing microspheres according to any one of claims 1-4, wherein the method comprises:
fe is added to 3 O 4 @Pd magnetic nanoparticles and modified silicon compounds (RO) 3 Si-R' is mixed and reacted in a solvent to prepare the magnetic nano microsphere,
wherein R' has the meaning as above, R is selected from C 1-12 An alkyl group.
6. The method according to claim 5, wherein the method is further characterized by adding an alkali solution to adjust the pH to 7-12;
the alkali solution is at least one selected from ammonia water, sodium hydroxide, potassium hydroxide, sodium carbonate and potassium carbonate.
7. The method of claim 5, wherein the solvent is selected from at least one of water, ethanol, ethylene glycol dimethyl ether.
8. The method according to claim 5, wherein the Fe 3 O 4 @Pd magnetic nanoparticles and modified silicon compounds (RO) 3 The mass ratio of Si-R' is 0.05-1:1;
the Fe is 3 O 4 The mass volume ratio of the@Pd magnetic nano-particles to the solvent is 1-10 (mg): 1 (mL);
the temperature of the reaction is 30-90 ℃, and the time of the reaction is 0.5-10h.
9. Use of the microsphere according to any one of claims 1-4 as a transition metal Pd catalyst, in a coupling reaction catalyzed by a Pd catalyst, in a reduction reaction catalyzed by a Pd catalyst.
10. Use according to claim 9, wherein aniline, N-alkylaniline and/or N, N-dialkylaniline are prepared by catalytic reductive alkylation of nitrobenzene as catalyst for the Suzuki reaction, catalyzing the reduction of azide compounds to primary amines.
CN202311029566.2A 2023-08-16 2023-08-16 Magnetic nano microsphere and preparation method and application thereof Active CN116747878B (en)

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Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR100768632B1 (en) * 2006-10-30 2007-10-18 삼성전자주식회사 Method for dispersing nanoparticles and method for producing nanoparticles thin film using the same
CN101184711A (en) * 2005-05-27 2008-05-21 普罗梅鲁斯有限责任公司 Nucleophilic heterocyclic carbene derivatives of pd(acac)2 for cross-coupling reactions
CN102614896A (en) * 2012-03-08 2012-08-01 昆明理工大学 Preparation method of surface modified nano palladium/iron catalytic reducing agent
CN104667945A (en) * 2015-01-10 2015-06-03 安徽大学 Supported palladium catalyst Fe3O4/SiO2Preparation of Pd and application in Suzuki reaction
CN104971738A (en) * 2015-07-07 2015-10-14 淮阴工学院 Preparation method of magnetic nano palladium catalyst
CN107824198A (en) * 2017-11-09 2018-03-23 武汉工程大学 A kind of preparation method and applications of the magnetic nano-catalyst of supported nano-gold
CN108212211A (en) * 2017-12-30 2018-06-29 武汉工程大学 A kind of preparation method of the magnetic nano-catalyst of supported nano-gold
CN115155614A (en) * 2022-08-09 2022-10-11 国泰新科工业科技(宜兴)有限公司 Preparation method and application of flower-shaped magnetic nano gold catalyst

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101184711A (en) * 2005-05-27 2008-05-21 普罗梅鲁斯有限责任公司 Nucleophilic heterocyclic carbene derivatives of pd(acac)2 for cross-coupling reactions
KR100768632B1 (en) * 2006-10-30 2007-10-18 삼성전자주식회사 Method for dispersing nanoparticles and method for producing nanoparticles thin film using the same
CN102614896A (en) * 2012-03-08 2012-08-01 昆明理工大学 Preparation method of surface modified nano palladium/iron catalytic reducing agent
CN104667945A (en) * 2015-01-10 2015-06-03 安徽大学 Supported palladium catalyst Fe3O4/SiO2Preparation of Pd and application in Suzuki reaction
CN104971738A (en) * 2015-07-07 2015-10-14 淮阴工学院 Preparation method of magnetic nano palladium catalyst
CN107824198A (en) * 2017-11-09 2018-03-23 武汉工程大学 A kind of preparation method and applications of the magnetic nano-catalyst of supported nano-gold
CN108212211A (en) * 2017-12-30 2018-06-29 武汉工程大学 A kind of preparation method of the magnetic nano-catalyst of supported nano-gold
CN115155614A (en) * 2022-08-09 2022-10-11 国泰新科工业科技(宜兴)有限公司 Preparation method and application of flower-shaped magnetic nano gold catalyst

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