CN113457736A - Application of chitosan/cellulose composite microsphere immobilized copper in catalyzing silicon addition reaction of alpha, beta-unsaturated carbonyl compound - Google Patents

Application of chitosan/cellulose composite microsphere immobilized copper in catalyzing silicon addition reaction of alpha, beta-unsaturated carbonyl compound Download PDF

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CN113457736A
CN113457736A CN202110733711.XA CN202110733711A CN113457736A CN 113457736 A CN113457736 A CN 113457736A CN 202110733711 A CN202110733711 A CN 202110733711A CN 113457736 A CN113457736 A CN 113457736A
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silicon
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CN113457736B (en
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朱磊
韩彪
张泽浪
赵雪
李铭超
李博解
张瑶瑶
何边阳
汪连生
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Hubei Engineering University
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    • 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
    • B01J31/06—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
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    • B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
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    • B01J37/0201—Impregnation
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    • C07F7/081—Compounds with Si-C or Si-Si linkages comprising at least one atom selected from the elements N, O, halogen, S, Se or Te
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    • C07F7/0825—Preparations of compounds not comprising Si-Si or Si-cyano linkages
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    • B01J2231/30—Addition reactions at carbon centres, i.e. to either C-C or C-X multiple bonds
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Abstract

The invention relates to an application of chitosan/cellulose composite microsphere immobilized copper in catalyzing a silicon addition reaction of an alpha, beta-unsaturated carbonyl compound, wherein a chitosan/cellulose composite microsphere is used as a carrier of a catalytic material, an active ingredient is copper, the chitosan/cellulose immobilized copper catalytic material (CC @ Cu) is used as a catalyst, a pinacolato dimethyl silicon diboron is used as a silicon reagent, and pure water is used as a solvent, the silicon addition reaction is respectively carried out on the alpha, beta-unsaturated carbonyl compounds containing different substituent groups to obtain an organic silicon compound, and potassium bromide and peracetic acid are further directly added on the basis of separating and purifying the organic silicon compound to obtain the beta-hydroxy compound through oxidation. The CC @ Cu catalytic material is applied to the silicon addition reaction, and has the advantages of small using amount, mild reaction condition, high product yield and high conversion rate; pure water is used as a solvent, and the method is carried out at room temperature, and is simple, convenient and easy to operate; can be repeatedly used.

Description

Application of chitosan/cellulose composite microsphere immobilized copper in catalyzing silicon addition reaction of alpha, beta-unsaturated carbonyl compound
Technical Field
The invention relates to preparation of a catalytic material and application of the catalytic material in an organic silicon compound, in particular to a Chitosan/Cellulose composite microsphere copper-supported solid catalytic material (Chitosan/Cellulose-Cu)2+CC @ Cu) and its use in the hydrosilylation reaction of α, β -unsaturated carbonyl compounds.
Background
The organic silicon compound is an important intermediate and is widely applied to the synthesis of natural products and drug molecules, and because the C-Si bond is relatively stable, the organic silicon compound can be used as a protective group in the synthesis process, and can not be decomposed or subjected to side reaction. Compared with the traditional reported preparation method using strong base, the method has the advantages that the strategy of direct silicon addition of unsaturated carbonyl compounds under the action of a catalyst is more direct and effective, and the method has attracted much attention in recent years. Catalysts used for catalyzing the reaction of silicon addition in the literature are Pd (chem.Commun.,2016,52,5609- -5612), Rh (Angew.chem.Int.Ed.2006,45, 5675-5677) and the like, but in these reports, noble metals are mostly used, so that the cost is high and the catalysts are not suitable for practical production. Therefore, copper as a transition metal with wide source, low cost and easy availability shows unique advantages in the reaction of catalyzing silicon addition, and in 2010, the document (J.Am.chem.Soc.2010,132, 2898-2900) reports that (dimethyl phenyl silane) diboronic acid pinacol ester M is realized under the low-temperature condition of-78 ℃ without the existence of a proton source by using CuCl as a catalyst and adding strong base NaOt-Bue2The beta-silicon addition reaction of PhSi-Bpin to alpha, beta-unsaturated carbonyl compound, the method uses metal cuprous salt, and does not need proton source, but the method is accompanied by the use of strong base, low temperature condition and the need of using NHC ligand with high price, the post-treatment is complex, and the method is not friendly to environment. In 2015, the use of Cu (acac) was reported in the literature (J.Am.chem.Soc.2015,137,15422-15425)2Acting as catalyst with special chiral bipyridine ligand, with H2O is a solvent, and the organic silicon compound is prepared under the catalysis at room temperature, but the method is simple, the ligand preparation method is complex, the commercialization is not realized, the reaction cost is limited, the actual production is not facilitated, and the problem that the catalyst cannot be recycled exists; in 2018, Cu was used in literature (j.chi.chem.soc.2018, 65, 81-86)2(OH)2CO32, 2-bipyridyl ligand and surfactant Triton X-100 are added into the catalyst at the same time for interaction, and pure water is used as a solvent for reaction at room temperature, but the problems of reaction cost limitation, incapability of recycling the catalyst and the like exist. Although the activity of the reaction is improved, the method also has the problems of limited reaction conditions, high cost, environmental pollution, incapability of recycling the catalyst and the like, and the application of the method in actual production is greatly limited. Therefore, the development of a new green and environment-friendly method for preparing an organosilicon compound by a direct silicon addition strategy, which is simple, convenient and easy to operate, mild in condition and low in cost, is very urgently needed.
The conversion of organosilicon compounds to beta-hydroxy compounds is an important application of organosilicon compounds, because the beta-hydroxy structure is widely existed in the structure of natural products, if the strategy of 'one-pot method' is adopted, the silicon addition of substrates is firstly realized, and then the substrates are continuously converted into the beta-hydroxy compounds without separation, so that the synthetic steps of the natural products are simplified, and the method has very important application value. In addition, the organosilicates themselves have wide practical applications in organic synthesis and material chemistry, such as monomers for polymerization reactions, precursors of anticancer drugs, coupling agents, and the like.
Disclosure of Invention
The invention provides a preparation method of a chitosan/cellulose composite microsphere immobilized copper metal catalytic material (CC @ Cu) and a method for applying the chitosan/cellulose composite microsphere immobilized copper metal catalytic material to the preparation of an organic silicon compound and a beta-hydroxy compound, aiming at overcoming the following defects in the prior art to at least a certain extent: when noble metal is used as a catalyst for synthesizing an organic silicon compound or an expensive silicon reagent is used as a synthesis raw material, the cost is high, and industrialization cannot be realized; when monovalent copper and nitrogen carbene ligand are used as catalysts, the operation process is complex, strong alkali (potassium tert-butoxide and the like) is needed, the temperature is low (-78 ℃), strict anhydrous and other harsh conditions are needed, and the production cost is high; when the existing beta-hydroxy compound is prepared by taking the organic silicon compound as a starting point, the organic silicon compound needs to be separated and purified from a reaction product after being synthesized, and continuous production is not carried out, so that the process route is complex and the production efficiency is low. The organic silicon compound is prepared from the chitosan/cellulose composite microsphere copper-supported catalytic material, and the unique compatibility and spatial structure of the chitosan/cellulose composite microsphere copper-supported catalytic material are utilized, so that the organic silicon compound has a larger specific surface area and higher catalytic activity, can realize catalytic reaction in pure water, can be recycled for multiple times, accords with the concept of green chemistry, and is very suitable for industrial application.
The technical scheme for solving the technical problems is as follows:
the application of chitosan/cellulose composite microsphere immobilized copper in catalyzing the silicon addition reaction of alpha, beta-unsaturated carbonyl compounds comprises the following steps:
1) adding an alpha, beta-unsaturated carbonyl compound I, a bis (pinacolato) diboron dimethyl silicon reagent and a chitosan/cellulose composite microsphere immobilized copper catalytic material CC @ Cu into water according to a molar ratio of 1:1.2:0.01, wherein the ratio of the CC @ Cu to the water is 0.002 mmol: 1ml, stirred at room temperature for 12h, to effect a hydrosilylation reaction:
Figure BDA0003140700190000031
wherein R1 is a phenylketonic group, a p-methoxyphenylketonic group, a p-methylphenylketonic group, a p-halophenylketonic group, an acetyl group, a carboxaldehyde group, a carbomethoxy group, an carbethoxy group or a cyano group; r2 is phenyl, p-methylphenyl, p-halophenyl, o-halophenyl, p-methoxyphenyl, methyl, t-butyl, acetyl, p-halomethylphenyl;
2) filtering the CC @ Cu, extracting, then carrying out spin-drying on a filtrate solvent, and separating a product by using a thin-layer chromatography method to obtain an organic silicon compound II;
the CC @ Cu is prepared by mixing a mixed solution of chitosan and cellulose, forming microspheres in an alkaline solution, adding a pore-foaming agent and a cross-linking agent, crosslinking to form composite microspheres, and immersing in Cu2+In an aqueous solution of 1.75X 10 relative to the copper in said CC @ Cu-3mol/g, wherein the molar ratio of C ═ O to chitosan units in the solution containing aldehyde or ketone is 8-12: 1.
in the application, the preparation method of CC @ Cu comprises the following steps:
1) uniformly stirring the cellulose particle chitosan solution, wherein the mass ratio of cellulose to chitosan is 400 mg: 1.5g, slowly dripping the prepared mixed solution into a sodium hydroxide solution by using an injector to form transparent microspheres;
2) and (2) recovering the microbeads through filtration, fully washing the microbeads by using distilled water and ethanol, adding the microbeads into a solution containing ethanol and aldehyde or ketone, stirring the solution at 50 ℃ for 12 hours, and crosslinking the solution, wherein the molar ratio of C ═ O to chitosan unit bodies in the solution containing aldehyde or ketone is 8-12: 1;
3) filtering out the crosslinked yellow-brown composite microbeads, washing with water and ethanol, and drying at room temperature;
4) soaking the dried microspheres in water at 50 ℃ for suspension for 1 hour; mixing Cu2+Adding the aqueous solution into the suspension, and slowly stirring for 12 hours to adsorb copper ions;
5) separation of loaded Cu by filtration2+The microspheres are washed with water and ethanol to remove free copper ions and anions, and finally, the CC @ Cu is dried in an oven at 50 ℃ for 12 hours to obtain the CC @ Cu catalytic material.
In the aforementioned application, the α, β -unsaturated carbonyl compound I is chalcone.
In the foregoing application, in step 2): the CC @ Cu was filtered, washed thoroughly 3 times with water and ethanol, and then dried for reuse.
In the aforementioned applications, the molar ratio of C ═ O to chitosan units in the solution containing the aldehyde or ketone is 8: 1.
in the application, after the CC @ Cu is recycled for 6 times and is applied to the boron addition reaction of the chalcone for 7 times, the yield of the product is 80%.
The possible reaction mechanism is presumed to be as follows:
first, bis-boronic acid pinacol dimethyl silicon reagent [ PhMe2Si-B(pin)]The method comprises the steps of breaking Si-B bonds under the catalysis of active copper in a CC @ Cu catalytic material (chitosan in the catalytic material contains a large number of amino groups to provide an alkaline environment for reaction), reacting with bivalent copper to form a copper-silicon alkyl complex and a byproduct Bpin-OH, carrying out conjugate addition on an intermediate and an alpha, beta-unsaturated carbonyl compound under the guiding action of a carbonyl group, carrying out six-membered ring transition rearrangement, carrying out protonation under the action of water to provide a proton source to generate a target product, and realizing regeneration of the catalytic material, wherein in the reaction, water is the proton source and is also a solvent.
Compared with the traditional method, the method has the following advantages:
1. the chitosan/cellulose composite microsphere has good biocompatibility, is green and environment-friendly, can be used for participating in pure water reaction, has good effect of immobilizing metal copper, and has longer service life, and the chitosan/cellulose composite microsphere copper-immobilized catalytic material can be conveniently separated from other components in a reaction system by a solid-liquid separation method after the reaction is finished, and can be reused by simple regeneration, so that the production cost can be greatly reduced, and meanwhile, various environmental pollution problems can be obviously reduced.
2. The method can realize higher conversion rate of reactants only by using lower catalyst dosage;
3. the method has mild reaction conditions, takes pure water as a solvent, carries out reaction at room temperature, and is simple and easy to operate;
4. the method has wide applicability, can be used for the silicon addition of various different types of alpha, beta-unsaturated carbonyl compounds, and successfully prepares corresponding organic silicon compounds and beta-hydroxy compounds.
5. The method can adopt a one-pot method strategy, and the beta-hydroxy compound containing carbonyl can be directly prepared from the starting raw materials through continuous silicon addition reaction and oxidation reaction.
6. When only chitosan-loaded bivalent copper is used as a catalyst, and alpha, beta-unsaturated receptor boron addition reaction is carried out in pure water, chalcone is used as a template substrate, chitosan-loaded copper hydroxide is used as a catalyst, 2-bipyridine is used as a ligand, and the catalyst and B are reacted with each other2(pin)2Reacting in pure water, wherein the chitosan is used for immobilizing copper hydroxide (CS @ Cu (OH)2) And chitosan-supported copper oxide (CS @ CuO) prepared according to the literature (Carbohydrate polymers2015,134,190-204), chitosan-supported copper cyanide (CS @ CuCN), chitosan-supported copper sulfate (CS @ CuSO)4) Chitosan-immobilized copper chloride (CS @ CuCl)2) Chitosan-immobilized copper fluoride (CS @ CuF)2) And chitosan-immobilized copper bromide (CS @ CuBr)2) Prepared according to the literature (GreenChem.2014,16, 3007-3012). Chitosan to Cu2+The adsorption of (2) is carried out by reacting with an amino group]Mainly, the main adsorption reactions include:
protonation of amino group:
Figure BDA0003140700190000051
matching:
Figure BDA0003140700190000052
hydrogen bond adsorption:
Figure BDA0003140700190000053
electrostatic attraction:
Figure BDA0003140700190000054
at lower pH, -NH formed by participation in protonation3 +A large number of them are used for adsorbing Cu2+Of (2) is-NH2Less. Through ICP detection of the catalyst recovered after the reaction (CS @ Cu (OH))2) It was found that 1.6% of copper was dropped, and it is presumed that the formation of (pin) BOH by-product may cause the change of pH value of the system in consideration of the insolubility of copper hydroxide in water, and further, the kind of divalent copper salt was screened, and it was found that the dropping of copper was more serious when copper salt having good water solubility (such as copper sulfate and copper chloride) was used, and therefore, the pH value of the reaction system was adjusted by using a strategy of adding a ligand, and it was finally found that the pyridine ligand having an amide bond can well inhibit the dropping of copper and functions as a stable catalyst.
After chitosan and cellulose composite crosslinking, the density of the catalyst carrier is improved, the microporous structure is increased, and primary amine (R' NH) on chitosan is added2) With an aldehyde ketone (R)2C ═ O) is subjected to Schiff base reaction to generate imine (R) containing carbon-nitrogen double bond2C ═ NR'), the aldone forms bridge connection in the chitosan molecule and different amino sites between the molecules, the Schiff base reaction reduces the amino groups on the chitosan surface, but because the chitosan surface is rich in hydroxyl groups, the N atom in the C ═ N double bond formed by the Schiff base reaction and the O atom in the adjacent OH are easy to react with Cu2+Complexing to form conjugate plane (Xie X J, Qin Y. Sens initiators B,2011,156(1):213), cross-linking also improves the acid resistance of chitosan, and the complexing effect to copper ions is stronger through chemical adsorption and physical adsorption.
7. When chitosan is crosslinked with aldehyde or ketone, the acetalization reaction occurs, and the-C ═ O of aldehyde or ketone is relative to-NH of chitosan unit2In large excess, sufficient imine groups are formed for the formation of stable complexes with copper ions. When the amount of the compound is too excessive, the O atoms in OH adjacent to N atoms in C ═ N double bonds are reduced due to an acetalization reaction, and the yield of reactants is reduced, so that when the CC @ Cu is prepared into the crosslinked composite microspheres of chitosan and cellulose, the molar ratio of the C ═ O to the chitosan unit bodies in the solution of aldehyde or ketone in the crosslinking agent is 8-12: 1 is preferred.
Drawings
FIG. 1 is an infrared spectrum of a cross-linked chitosan/cellulose composite microsphere CC @ Cu loaded with divalent copper ions and a cross-linked chitosan/cellulose microsphere;
FIG. 2 is a diagram showing the mechanism of the cross-linking reaction of chitosan with a ketone or aldehyde.
Detailed Description
The principles and features of this invention are described below in conjunction with specific embodiments, which are set forth merely to illustrate the invention and are not intended to limit the scope of the invention.
Example 1:
the CC @ Cu catalytic material provided by the embodiment of the invention has the active ingredient copper and the carrier chitosan/cellulose composite microspheres; meanwhile, the relative content of the active ingredient copper in the CC @ Cu catalytic material is 1.75 mmol/g.
The carrier is chitosan/cellulose composite microspheres, the chitosan/cellulose composite microspheres are composite microspheres formed by adding cellulose into an acid solution of chitosan, then adding an alkaline solution to suspend to form microspheres, and then adding a pore-foaming agent and a crosslinking agent to crosslink.
Example 2:
the embodiment of the invention also provides a preparation method of the CC @ Cu catalytic material, which comprises the following three steps:
1) preparing chitosan/cellulose microspheres: cellulose particles (400mg) were added to 100ml of chitosan solution (100ml of water, 1.5g of chitosan, 3.0ml of acetic acid) to be uniformly stirred to obtain viscous liquid. The mixed solution thus obtained was slowly dropped (prepared from 15g of sodium hydroxide and 100mL of distilled water) into 100mL of a sodium hydroxide solution with a syringe to form transparent microspheres. The hydroxyl and amino in the chitosan molecule have good reactivity, can be conveniently grafted and modified, the chitosan can adsorb metal ions through coordination, ion exchange and electrostatic action, but the strength and acid resistance of the chitosan microsphere are poor, the chitosan is dissolved in acid due to the hydrophilicity of protonated amino, and the molecular formula of the chitosan is (C)6H11NO4) N, molecular weight of the unit cell: 161.2, 1.5g of chitosan contained 0.009moml of monols. The cellulose has high tensile strength, is similar to the molecular structure of chitosan, has compatibility, can improve the strength by blending the cellulose and the chitosan, simultaneously improves the pore structure and the surface characteristic of the adsorbent, and is beneficial to improving the adsorption performance.
2) Preparing crosslinked chitosan/cellulose microspheres: the microbeads were recovered by filtration, washed thoroughly with distilled water and ethanol, stirred in a crosslinking solution containing ethanol (100mL) and succinaldehyde (chitosan unit: succinaldehyde 1mol:4mol) at 50 ℃ for 12 hours, filtered off the crosslinked yellowish-brown composite microbeads, washed with water and ethanol, and dried at room temperature. In the step, the porous crosslinked chitosan/cellulose composite microspheres are prepared by ethanol pore-forming and succinaldehyde crosslinking, and the amino groups are reduced after crosslinking, so that the chemical stability of the chitosan in an acidic medium can be improved.
3) Preparation of divalent copper ion-loaded crosslinked chitosan/cellulose microspheres (CC @ Cu): the crosslinked dried microspheres (1.0g) were suspended and immersed in water (20ml) at 50 ℃ for 1 hour. 10mL of copper sulfate solution (prepared from 100mg of copper sulfate pentahydrate, ca. 0.0004 mol mL) was added to the suspension and stirred for 12h, and the Cu-loaded was separated by filtration2+The microspheres are washed with water and ethanol to remove free copper ions and sulfate ions. Finally, chitosan/cellulose-Cu is added2+The (CC @ Cu) catalytic material was oven dried at 50 ℃ for 12 hours to obtain the above-described CC @ Cu catalytic material.
Fig. 1 is an infrared spectrum of a chitosan/cellulose composite microsphere (CC) and a CC @ Cu catalytic material, wherein an upper line represents an infrared spectrum before the chitosan/cellulose composite microsphere (CC) is loaded with Cu, and a lower line represents an infrared spectrum after the chitosan/cellulose composite microsphere (CC) is loaded with Cu.
Chitosan/cellulose composite microspheres (CC) passing-NH of chitosan2The condensation of the group with the keto group of succinaldehyde forms an imine group (C ═ N), as in process I and process IV in fig. 2. At 1636cm-1Stretching of the carrier imine group was observed at 3422.15cm-1Stretching of the carrier N-H groups was observed. On the characterization curve of catalyst CC @ Cu, the imine group band was 1621cm-1The vibration is reduced, which can be attributed to the coordination of copper ions to the ligand imine groups. The N-H group is at 3422.15cm-1The vibration disappears, which is attributed to the complexation of copper ions and N-H groups, all the N-H groups participate in the complexation with copper ions, and after the copper ions are coordinated with ligand imine groups, copper is not easy to be removed due to the change of pH valueAnd (6) dropping. In FIG. 1 (CC) and CC @ Cu are at 1110cm-1A strong new characteristic peak is observed, which is derived from the stretching vibration of the C-O-C-O-C group, indicating that the carbonyl group in succinaldehyde also has acetalization reaction with the hydroxyl group on the glucosamine ring of chitosan, as shown in FIG. 2, which can theoretically have acetalization reaction with the hydroxyl group. Mixing together one mole of aldehyde and one mole of alcohol forms a reversible equilibrium of reactions, the product of which is a hemiacetal. Hemiacetals are formed by nucleophilic addition of an alcohol to a carbonyl group and are structurally characterized by an-OH group and an-OR group attached to the same carbon atom. The hemiacetal is generally unstable and cannot be isolated, and can be reacted a second time with another mole of alcohol to form one mole of acetal, catalyzed by a small amount of gaseous hydrochloric acid. Acetals are characterized by the attachment of two-OR groups to the same CH group. The acetalization reaction most likely occurs in the case of chitosan C, where the carbonyl group is relatively sterically less hindered6The characteristic peak of acetal between hydroxyl groups should appear in 1105-1160 cm of the infrared spectrogram of the cross-linked chitosan fiber-1Interval, therefore 1110cm-1The presence of characteristic peaks indicates that the crosslinking reaction occurs not only between succinaldehyde and primary amine, but also between succinaldehyde and hydroxyl groups. But the peak intensity ratio is 1621-1636 cm-1Here (Schiff base characteristic peak) is equally strong, indicating that the Schff base reaction and acetalization reaction predominate in the crosslinking reaction. The schematic structure of the reaction of succinaldehyde with the hydroxyl group on the chitosan molecule ring is shown in fig. 2 as II, and it can be seen from the figure that one succinaldehyde molecule can react with four hydroxyl groups to form a cross-linked structure. We did not observe any band stretching attributable to succinaldehyde carbon groups (at 1750 cm) in (CC) and CC @ Cu-1Left and right), it was confirmed that all the ketone groups of succinaldehyde participated in the schiff base reaction and acetalization reaction. In the crosslinking reaction, only one end of carbonyl group of the butanedialdehyde reacts with amino group on the chitosan molecule ring, and the other end of the carbonyl group does not react, so that the structure of N-C-O is formed (see the IV process in figure 2). At 3422.15cm-1It was observed that the stretching of the N-H groups of the support was also due to the insufficient amount of succinaldehyde, which did not incorporate all the-NH groups2Conversion to-C ═ N.
Examples 3 to 5
The method of example 2 was used to prepare a CC @ Cu catalytic material, except that the chitosan unit in step 2) of example 3: when the succinaldehyde is 1mol:1mol, the microspheres are transparent and fragile and easy to deform due to incomplete crosslinking, namely the ratio is excluded; chitosan unit in step 2) of example 4: succinaldehyde is 1mol:2mol, may crosslink incompletely, the microballoons are transparent, easy to change; chitosan unit in step 2) of example 5: the succinaldehyde accounts for 1mol to 6mol, and the microspheres are in a brown solid shape and have stable shapes. Infrared spectroscopic analysis of catalytic materials in conjunction with FIG. 2 and example 2 when-C ═ O of succinaldehyde and-NH of chitosan monoliths2Is that 2: 1 or 4:1, the crosslinking is incomplete, and all ketone groups attributable to the succinaldehyde participate in Schiff base reaction and acetalization reaction, which are dominant, even though-C ═ O of the succinaldehyde is relative to-NH of the chitosan unit body2Excess or no guarantee of-NH2All undergo Schiff base reaction; a significant portion of the-C ═ O of succinaldehyde is consumed by the aldolization reaction.
Example 6:
the embodiment of the invention also provides a method for applying the CC @ Cu catalytic material to a silicon addition reaction between an alpha, beta-unsaturated carbonyl compound and a bis (pinacol) diboron dimethyl silicon reagent, which comprises the following specific steps: alpha, beta-unsaturated carbonyl compound I, pinacol dimethyl silicon diboride and CC @ Cu catalytic material (prepared in example 2) are added into a mixed solvent of 1.0ml of water according to the molar ratio of 1:1.2:0.01,the ratio of the amount of CC @ Cu to the amount of water is 0.002 mmol: 1ml, stirring for 12 hours at room temperature; filtering the CC @ Cu catalytic material, extracting, then spin-drying the solvent, and separating by thin-layer chromatography to obtain the organic silicon compound II. Meanwhile, the CC @ Cu catalytic material is applied to the silicon addition reaction between an alpha, beta-unsaturated carbonyl compound and a diboron pinacol dimethyl silicon reagent for the first time. The hydrosilylation reaction was as follows:
Figure BDA0003140700190000101
wherein R1 is a phenylketonic group, a p-methoxyphenylketonic group, a p-methylphenylketonic group, a p-halophenylketonic group, an acetyl group, a carboxaldehyde group, a carboximidic group, an ethanolate group or a cyano group; r2 is phenyl, p-methylphenyl, p-halophenyl, o-halophenyl, p-methoxyphenyl, methyl, tert-butyl, acetyl, p-halomethylphenyl, for example, chalcone is used as the above-mentioned alpha, beta-unsaturated carbonyl compound, after reaction, the CC @ Cu catalytic material is filtered, washed with water and ethanol for many times, and then dried, so that the catalyst can be reused.
Application example 1:
the CC @ Cu catalytic material provided in the embodiment 2 is applied to a silicon addition reaction of chalcone and a pinacol dimethyl silicon diboride, wherein the chalcone is 0.20mmol, the pinacol dimethyl silicon diboride is 0.24mmol, the catalytic material is 0.002mmol, the water is 1.0mL, the room temperature reaction time is 12 hours, so that a silicon addition product is obtained, after the reaction is finished, the whole reaction system is filtered, the ethyl acetate is used for washing by 10mL, the ethyl acetate (3 multiplied by 10mL) is used for extraction, an organic phase is separated, and anhydrous Na is used for2SO4Drying, filtering and rotary evaporation to remove the solvent. The residue was purified by ethyl acetate/petroleum ether mixed solvent ═ 9: purification by 1 column chromatography gave organosilicon compound II-1(58.6mg) in 85% yield.
Figure BDA0003140700190000102
The nuclear magnetic hydrogen spectrum and the carbon spectrum of the target product are as follows:
1H NMR(400MHz,Chloroform-d)；δ＝7.76–7.73(m,2H),7.48–7.44(m,1H),7.42–7.39(m,2H),7.36–7.28(m,5H),3.49(dd,J＝17.1,10.2Hz,1H),3.19–3.05(m,2H),0.26(s,3H),0.20(s,3H).
13C NMR(100MHz,Chloroform-d)；δ＝199.1,142.4,137.1,136.9,134.2,132.8,129.4,128.5,128.1,128.0,127.8,127.7,124.8,39.0,31.1,-3.8,-5.1.
application example 1 shows that, under the catalytic conditions of the CC @ Cu catalytic material provided in example 2 of the present invention, the conversion rate of chalcone is very high, and the yield of the silicon addition product reaches 85%.
The catalytic material prepared in example 5 was applied to the hydrosilylation reaction between an α, β -unsaturated carbonyl compound (chalcone) and a bis-boronic acid pinacol dimethyl silicon reagent according to the above reaction procedure, with a yield of 68%.
more-NH in the catalyst2The catalytic efficiency cannot be improved, and more-NH is contained in the chitosan with the increase of the consumption of the succinaldehyde2The Schiff base reaction is carried out, the chitosan crosslinking is more complete, so that the copper ions are combined with the catalyst more firmly in the silicon addition reaction, the copper ions are not dropped off due to the reduction of the pH value caused by an intermediate product, and the reaction conversion rate is reduced. However, when the amount of succinaldehyde is further increased, the yield is lowered, probably due to the reduction of hydroxyl groups on the glucosamine ring of chitosan by the aldolization reaction, and thus there is not enough O atom adjacent to OH to coordinate N atom in C ═ N double bond with Cu2+Complexation occurs.
Application example 2:
the CC @ Cu catalytic material provided in the embodiment 2 is applied to the silicon addition reaction of (1-phenyl-3- (p-tolyl) prop-2-en-1-one and pinacol dimethyl silicon diboron borate, wherein the (1-phenyl-3- (p-tolyl) prop-2-en-1-one is 0.20mmol, the pinacol dimethyl silicon diboron borate is 0.24mmol, the catalytic material is 0.002mmol, the water is 1.0mL, and the reaction time at room temperature is 12h, so that a silicon addition product is obtained, after the reaction is finished, the whole reaction system is filtered, ethyl acetate is used for washing by 10mL, then ethyl acetate (3X 10mL) is used for extraction, an organic phase is separated, and anhydrous Na is used for2SO4Drying, filtering and rotary evaporation to remove the solvent. The residue was purified by ethyl acetate/petroleum ether mixed solvent ═ 9: purification by column chromatography 1 gave organosilicon compound II-2(50.2mg) in 70% yield.
Figure BDA0003140700190000121
The nuclear magnetic hydrogen spectrum and the carbon spectrum of the target product are as follows:
1H NMR(400MHz,Chloroform-d)；δ＝7.79(d,J＝7.6Hz,2H),7.52–7.46(m,3H),7.40–7.33(m,5H),7.00(d,J＝7.8Hz,2H),6.89(d,J＝7.7Hz,2H),3.49(dd,J＝17.0,10.4Hz,1H),3.21–3.04(m,2H),2.27(s,3H),0.30(s,3H),0.23(s,3H).
13C NMR(100MHz,Chloroform-d)；δ＝199.2,139.1,137.1,137.1,134.2,134.1,132.8,129.3,128.9,128.5,128.0,127.8,127.6,77.3,39.0,30.6,21.0,-3.7,-5.2.
application example 2 shows that under the catalytic conditions of the CC @ Cu catalytic material provided by the embodiment of the invention, the conversion rate of (1-phenyl-3- (p-tolyl) prop-2-en-1-one is also high, and the yield of the silicon addition product reaches 70%.
Application example 3:
the CC @ Cu catalytic material provided by the embodiment 2 is applied to the silicon addition reaction of (E) -3- (4-bromophenyl) -1-phenylprop-2-en-1-one and a pinacol dimethyl silicon diboride, wherein the amount of (E) -3- (4-bromophenyl) -1-phenylprop-2-en-1-one is 0.20mmol, the amount of pinacol dimethyl silicon diboride is 0.24mmol, the amount of the catalytic material is 0.002mmol, the amount of water is 1.0mL, the room temperature reaction time is 12h, so that a silicon addition product is obtained, after the reaction is finished, the whole reaction system is filtered, ethyl acetate is used for washing by 10mL, then ethyl acetate (3 x 10mL) is used for extraction, after an organic phase is separated, anhydrous Na is used for2SO4Drying, filtering and rotary evaporation to remove the solvent. The residue was purified by ethyl acetate/petroleum ether mixed solvent ═ 9: purification by 1 column chromatography gave organosilicon compound II-3(67.7mg) in 80% yield.
Figure BDA0003140700190000131
The nuclear magnetic hydrogen spectrum and the carbon spectrum of the target product are as follows:
1H NMR(400MHz,Chloroform-d)；δ＝7.79–7.77(m,2H),7.54–7.49(m,1H),7.44–7.33(m,7H),7.28–7.26(m,2H),3.46(dd,J＝17.2,10.6Hz,1H),3.22–3.03(m,2H),0.30(s,3H),0.25(s,3H).
13C NMR(100MHz,Chloroform-d)；δ＝198.7,141.6,136.9,136.3,134.2,133.0,131.1,129.5,129.3,128.5,127.9,127.9,118.4,38.7,30.8,-4.0,-5.2.
application example 3 shows that, under the catalytic conditions of the CC @ Cu catalytic material provided by the embodiment of the invention, the conversion rate of (E) -3- (4-bromophenyl) -1-phenylprop-2-en-1-one is also high, and the yield of the silicon addition product reaches 80%.
Application example 4:
the CC @ Cu catalytic material provided by the embodiment 2 is applied to the silicon addition reaction of (amyl) -3- (4-chlorphenyl) -1-phenylprop-2-ene-1-ketone and a pinacol dimethyl silicon diboron reagent, wherein the thickness of the (amyl) -3- (4-chlorphenyl) -1-phenylprop-2-ene-1-ketone is 0.20mmol, the pinacol dimethyl silicon diboron reagent is 0.24mmol, the catalytic material is 0.002mmol, the water is 1.0mL, the room temperature reaction time is 12h, so that a silicon addition product is obtained, after the reaction is finished, the whole reaction system is filtered, ethyl acetate is used for washing, then ethyl acetate (3 x 10mL) is used for extraction, an organic phase is separated, and anhydrous Na is used2SO4Drying, filtering and rotary evaporation to remove the solvent. The residue was purified by ethyl acetate/petroleum ether mixed solvent ═ 9: purification by column chromatography 1 gave organosilicon compound II-4(56.8mg) in 75% yield.
Figure BDA0003140700190000132
The nuclear magnetic hydrogen spectrum and the carbon spectrum of the target product are as follows:
1H NMR(400MHz,Chloroform-d)；δ＝7.80–7.78(m,2H),7.54–7.50(m,1H),7.45–7.34(m,7H),7.15–7.13(m,2H),6.90–6.88(m,2H),3.48(dd,J＝17.2,10.6Hz,1H),3.23–3.08(m,2H),0.30(s,3H),0.26(s,3H).
13C NMR(100MHz,Chloroform-d)；δ＝198.8,141.0,136.9,136.3,134.2,133.0,130.4,129.5,128.9,128.6,128.2,127.94,127.90,38.7,30.7,-4.0,-5.2.
application example 4 shows that under the catalysis conditions of the CC @ Cu catalytic material provided by the embodiment of the invention, the conversion rate of (amyl) -3- (4-chlorphenyl) -1-phenylpropan-2-en-1-one is also high, and the yield of the silicon addition product reaches 75%.
Application example 5:
the CC @ Cu catalytic material provided in the embodiment 2 is applied to the silicon addition reaction of (amyl) -1-phenyl-3- (4- (trifluoromethyl) phenyl) prop-2-ene-1-one and a pinacol dimethyl silicon diboron reagent, wherein the concentration of (amyl) -1-phenyl-3- (4- (trifluoromethyl) phenyl) prop-2-ene-1-one is 0.20mmol, the concentration of the pinacol dimethyl silicon diboron reagent is 0.24mmol, the concentration of the catalytic material is 0.002mmol, the concentration of water is 1.0mL, the room temperature reaction time is 12h, so that a silicon addition product is obtained, after the reaction is finished, the whole reaction system is filtered, 10mL of ethyl acetate is used for washing, then ethyl acetate (3X 10mL) is used for extraction, an organic phase is separated, and anhydrous Na is used for2SO4Drying, filtering and rotary evaporation to remove the solvent. The residue was purified by ethyl acetate/petroleum ether mixed solvent ═ 9: purification by column chromatography 1 gave organosilicon compound II-5(66.0mg) in 80% yield.
Figure BDA0003140700190000141
The nuclear magnetic hydrogen spectrum and the carbon spectrum of the target product are as follows:
1H NMR(400MHz,Chloroform-d)；δ＝7.82–7.80(m,2H),7.55–7.51(m,1H),7.44–7.34(m,9H),7.08(d,J＝8Hz,2H),3.56(dd,J＝17.4,10.5Hz,1H),3.28–3.18(m,2H),0.32(s,3H),0.27(s,3H).
13C NMR(100MHz,Chloroform-d)；δ＝198.5,147.0,136.8,136.0,134.1,133.1,129.6,128.6,128.0,127.9,127.71,127.14,126.8,125.8,125.10,125.06,125.0,124.99,123.1,38.5,31.5,-4.0,-5.2.
application example 5 shows that under the catalytic conditions of the CC @ Cu catalytic material provided by the embodiment of the invention, the conversion rate of (amyl) -1-phenyl-3- (4- (trifluoromethyl) phenyl) prop-2-en-1-one is also high, and the yield of the silicon addition product reaches 80%.
Application example 6:
the CC @ Cu catalytic material provided in example 2 above was applied to (E) -3- (4-methoxyphenyl) -1-phenylprop-2-en-1-one and pinacol diboronAnd (2) performing a silicon addition reaction on a dimethyl silicon reagent, wherein (E) -3- (4-methoxyphenyl) -1-phenylpropan-2-en-1-one is 0.20mmol, a pinacol diboron dimethyl silicon reagent is 0.24mmol, a catalytic material is 0.002mmol, water is 1.0mL, and the reaction time at room temperature is 12 hours, so as to obtain a silicon addition product, filtering the whole reaction system after the reaction is finished, washing the reaction system with 10mL of ethyl acetate, extracting the reaction system with 3 x 10mL of ethyl acetate, separating an organic phase, and then using anhydrous Na2SO4Drying, filtering and rotary evaporation to remove the solvent. The residue was purified by ethyl acetate/petroleum ether mixed solvent ═ 9: purification by 1 column chromatography gave organosilicon compound II-6(61.4mg) in 82% yield.
Figure BDA0003140700190000151
The nuclear magnetic hydrogen spectrum and the carbon spectrum of the target product are as follows:
1H NMR(400MHz,Chloroform-d)；δ＝7.80–7.78(m,2H),7.52–7.45(m,3H),7.41–7.33(m,5H),6.93–6.88(m,2H),6.75–6.72(m,2H),3.75(s,3H),3.46(dd,J＝17.0,10.5Hz,1H),3.21–3.01(m,2H),0.30(s,3H),0.24(s,3H).
13C NMR(100MHz,Chloroform-d)；δ＝199.4,157.0,137.1,137.0,134.21,134.19,132.8,129.3,128.6,128.5,128.0,127.8,113.6,55.2,39.2,30.1,-3.8,-5.2.
application example 6 shows that under the catalytic conditions of the CC @ Cu catalytic material provided by the embodiment of the invention, the conversion rate of (E) -3- (4-methoxyphenyl) -1-phenylprop-2-en-1-one is also high, and the yield of the silicon addition product reaches 82%.
Application example 7:
the CC @ Cu catalytic material provided by the embodiment 2 is applied to the silicon addition reaction of (amyl) -3- (4-chlorphenyl) -1- (p-tolyl) prop-2-ene-1-ketone and a pinacol dimethyl silicon diboron reagent, wherein the (amyl) -3- (4-chlorphenyl) -1- (p-tolyl) prop-2-ene-1-ketone is 0.20mmol, the pinacol dimethyl silicon diboron reagent is 0.24mmol, the catalytic material is 0.002mmol, the water is 1.0ml, the room temperature reaction time is 12 hours, so that a silicon addition product is obtained, and the reaction is finishedThen, the whole reaction system was filtered, washed with 10mL of ethyl acetate, extracted with ethyl acetate (3X 10mL), and the organic phase was separated and purified with anhydrous Na2SO4Drying, filtering and rotary evaporation to remove the solvent. The residue was purified by ethyl acetate/petroleum ether mixed solvent ═ 9: purification by column chromatography 1 gave organosilicon compound II-7(48.7mg) in 62% yield.
Figure BDA0003140700190000161
The nuclear magnetic hydrogen spectrum and the carbon spectrum of the target product are as follows:
1H NMR(400MHz,Chloroform-d)；δ＝7.70–7.68(m,2H),7.44–7.33(m,5H),7.20–7.18(m,2H),7.14–7.10(m,2H),6.90–6.86(m,2H),3.44(dd,J＝16.9,10.4Hz,1H),3.19–3.04(m,2H),2.38(s,3H),0.29(s,3H),0.23(s,3H).
13C NMR(100MHz,Chloroform-d)；δ＝198.4,143.8,141.1,136.4,134.4,134.2,130.3,129.5,129.2,128.9,128.2,128.1,127.9,38.5,30.8,21.7,-4.0,-5.2.
application example 7 shows that under the catalytic conditions of the CC @ Cu catalytic material provided by the embodiment of the invention, the conversion rate of (amyl) -3- (4-chlorphenyl) -1- (p-tolyl) prop-2-ene-1-ketone is also high, and the yield of the silicon addition product reaches 62%.
Application example 8:
the CC @ Cu catalytic material provided in the embodiment 2 is applied to the silicon addition reaction of (amyl) -3- (4-fluorophenyl) -1- (p-tolyl) prop-2-ene-1-one and a pinacol dimethyl silicon diboron reagent, wherein 0.20mmol of (amyl) -3- (4-fluorophenyl) -1- (p-tolyl) prop-2-ene-1-one, 0.24mmol of pinacol dimethyl silicon diboron reagent, 0.002mmol of catalytic material, 1.0mL of water and the reaction time at room temperature is 12h to obtain a silicon addition product, after the reaction is finished, the whole reaction system is filtered, washed by 10mL of ethyl acetate, extracted by 3X 10mL of ethyl acetate, an organic phase is separated, and then anhydrous Na is used for2SO4Drying, filtering and rotary evaporation to remove the solvent. The residue was purified by ethyl acetate/petroleum ether mixed solvent ═ 9: 1 column layerThe resulting mixture was purified by precipitation to give organosilicon compound II-8(51.2mg) in a yield of 68%.
Figure BDA0003140700190000171
The nuclear magnetic hydrogen spectrum and the carbon spectrum of the target product are as follows:
1H NMR(400MHz,Chloroform-d)；δ＝7.70–7.67(m,2H),7.43–7.32(m,5H),7.19(d,J＝8.1Hz,2H),6.91–6.82(m,4H),6.90–6.86(m,2H),3.43(dd,J＝17.0,10.6Hz,1H),3.19–3.03(m,2H),2.38(s,3H),0.29(s,3H),0.24(s,3H).
13C NMR(100MHz,Chloroform-d)；δ＝198.6,161.8,159.3,143.7,138.0,136.6,134.5,134.2,129.4,129.2,128.9,128.8,128.1,127.8,115.0,114.8,38.8,30.4,21.6,-4.0,-5.1.
application example 8 shows that the conversion rate of (amyl) -3- (4-fluorophenyl) -1- (p-tolyl) prop-2-en-1-one is also high under the catalytic conditions of the CC @ Cu catalytic material provided by the embodiment of the invention, and the yield of the silicon addition product reaches 68%.
Application example 9:
the CC @ Cu catalytic material provided by the embodiment 2 is applied to the silicon addition reaction of (amyl) -3- (4-chlorphenyl) -1- (4-fluorophenyl) prop-2-ene-1-ketone and a pinacol dimethyl silicon diboron reagent, wherein 0.20mmol of (amyl) -3- (4-chlorphenyl) -1- (4-fluorophenyl) prop-2-ene-1-ketone, 0.24mmol of pinacol dimethyl silicon diboron reagent, 0.002mmol of catalytic material, 1.0mL of water and the reaction time at room temperature is 12h to obtain a silicon addition product, after the reaction is finished, the whole reaction system is filtered, 10mL of ethyl acetate is used for washing, ethyl acetate (3X 10mL) is used for extraction, an organic phase is separated, and anhydrous Na is used for2SO4Drying, filtering and rotary evaporation to remove the solvent. The residue was purified by ethyl acetate/petroleum ether mixed solvent ═ 9: purification by 1 column chromatography gave organosilicon compound II-9(57.2mg) in a yield of 72%.
Figure BDA0003140700190000181
The nuclear magnetic hydrogen spectrum and the carbon spectrum of the target product are as follows:
1H NMR(400MHz,Chloroform-d)；δ＝7.82–7.78(m,2H),7.44–7.33(m,5H),7.15–7.12(m,2H),7.08–7.03(m,2H),6.95–6.86(m,2H),3.42(dd,J＝17.1,10.6Hz,1H),3.18–3.02(m,2H),0.29(s,3H),0.25(s,3H).
13C NMR(100MHz,Chloroform-d)；δ＝197.2,166.9,164.3,140.9,136.3,134.1,133.30,133.28,130.6,130.51,130.46,129.5,128.8,128.3,127.9,115.7,115.5,38.7,30.8,-4.0,-5.3.
application example 9 shows that the conversion rate of (amyl) -3- (4-chlorophenyl) -1- (4-fluorophenyl) prop-2-en-1-one is also high under the catalysis conditions of the CC @ Cu catalytic material provided by the embodiment of the invention, and the yield of the silicon addition product reaches 72%.
Application example 10:
the CC @ Cu catalytic material provided by the embodiment 2 is applied to the silicon addition reaction of trans-1-phenyl-2-butene-1-one and a pinacol dimethyl silicon diborate, wherein the trans-1-phenyl-2-butene-1-one is 0.20mmol, the pinacol dimethyl silicon diborate is 0.24mmol, the catalytic material is 0.002mmol, the water is 1.0mL, and the reaction time at room temperature is 12 hours, so that a silicon addition product is obtained, after the reaction is finished, the whole reaction system is filtered, washed by 10mL of ethyl acetate, extracted by ethyl acetate (3X 10mL), an organic phase is separated, and anhydrous Na is used for removing the organic phase2SO4Drying, filtering and rotary evaporation to remove the solvent. The residue was purified by ethyl acetate/petroleum ether mixed solvent ═ 9: purification by 1 column chromatography gave organosilicon compound II-10(42.4mg) in 75% yield.
Figure BDA0003140700190000191
The nuclear magnetic hydrogen spectrum and the carbon spectrum of the target product are as follows:
1H NMR(400MHz,Chloroform-d)；δ＝7.83–7.81(m,2H),7.55–7.51(m,3H),7.43–7.37(m,5H),3.02(dd,J＝15.8,3.3Hz,1H),2.68–2.61(m,1H),1.63–1.59(m,1H),0.98(d,J＝7.3Hz,3H),0.33(d,J＝3.3Hz,6H).
13C NMR(100MHz,Chloroform-d)；δ＝200.7,137.6,137.1,134.0,132.8,129.2,128.5,128.1,127.9,40.7,15.9,14.6,-4.7,-5.4.
application example 10 shows that under the catalytic conditions of the CC @ Cu catalytic material provided in the present invention, the conversion rate of trans-1-phenyl-2-buten-1-one is also high, and the yield of the silicon addition product reaches 75%.
Application example 11:
the CC @ Cu catalytic material provided by the embodiment 2 is applied to the silicon addition reaction of trans-benzylidene acetone and a bis-boronic acid pinacol dimethyl silicon reagent, wherein the trans-benzylidene acetone is 0.20mmol, the bis-boronic acid pinacol dimethyl silicon reagent is 0.24mmol, the catalytic material is 0.002mmol, water is 1.0mL, the room temperature reaction time is 12 hours, so that a silicon addition product is obtained, after the reaction is finished, the whole reaction system is filtered, washed by 10mL of ethyl acetate, extracted by ethyl acetate (3 x 10mL), an organic phase is separated, and then anhydrous Na is used2SO4Drying, filtering and rotary evaporation to remove the solvent. The residue was purified by ethyl acetate/petroleum ether mixed solvent ═ 9: purification by column chromatography 1 gave organosilicon compound II-11(45.2mg) in 80% yield.
Figure BDA0003140700190000201
The nuclear magnetic hydrogen spectrum and the carbon spectrum of the target product are as follows:
1H NMR(400MHz,Chloroform-d)；δ＝7.42–7.32(m,5H),7.22–7.17(m,2H),7.11–7.06(m,1H),6.95–6.93(m,2H),2.96–2.87(m,2H),2.68–2.59(m,1H),1.95(s,3H),0.24(s,3H)),0.22(s,3H).
13C NMR(100MHz,Chloroform-d)；δ＝208.3,142.0,136.6,134.2,129.4,128.2,127.8,127.6,124.9,44.0,31.4,30.0,-4.0,-5.4.
application example 11 shows that under the catalytic conditions of the CC @ Cu catalytic material provided in the embodiment of the present invention, the conversion rate of trans-benzylidene acetone is also high, and the yield of the silicon addition product reaches 80%.
Application example 12:
the CC @ Cu catalytic material provided by the embodiment 2 is applied to the silicon addition reaction of (E) -3-pentene-2-ketone and a pinacol dimethyl silicon diboride, wherein 0.20mmol of (E) -3-pentene-2-ketone, 0.24mmol of the pinacol dimethyl silicon diboride, 0.002mmol of the catalytic material, 1.0mL of water and the room-temperature reaction time are 12 hours, so that a silicon addition product is obtained, after the reaction is finished, the whole reaction system is filtered, washed by 10mL of ethyl acetate, extracted by ethyl acetate (3 multiplied by 10mL), an organic phase is separated, and then anhydrous Na is used2SO4Drying, filtering and rotary evaporation to remove the solvent. The residue was purified by ethyl acetate/petroleum ether mixed solvent ═ 9: purification by column chromatography 1 gave organosilicon compound II-12(34.4mg) in 78% yield.
Figure BDA0003140700190000202
The nuclear magnetic hydrogen spectrum and the carbon spectrum of the target product are as follows:
1H NMR(400MHz,Chloroform-d)；δ＝7.51–7.48(m,2H),7.38–7.35(m,3H),2.44–2.39(m,1H),2.21–2.14(m,1H),2.07(s,3H),1.54–1.45(m,1H),0.93(d,J＝7.3Hz),0.27(s,6H).
13C NMR(100MHz,Chloroform-d)；δ＝209.5,137.5,133.9,129.1,127.8,45.9,30.0,15.2,14.5,-4.8,-5.3.
application example 12 shows that under the catalytic conditions of the CC @ Cu catalytic material provided by the embodiment of the invention, the conversion rate of (E) -3-penten-2-one is also high, and the yield of the silicon addition product reaches 78%.
Application example 13:
the CC @ Cu catalytic material provided by the embodiment 2 is applied to the silicon addition reaction of trans-cinnamaldehyde and a bis-boronic acid pinacol dimethyl silicon reagent, wherein the trans-cinnamaldehyde accounts for 0.20mmol, the bis-boronic acid pinacol dimethyl silicon reagent accounts for 0.24mmol, the catalytic material accounts for 0.002mmol, water accounts for 1.0ml, the reaction time at room temperature is 12 hours, so that a silicon addition product is obtained, and the reaction is combinedAfter completion of the reaction, the whole reaction system was filtered, washed with 10mL of ethyl acetate, extracted with ethyl acetate (3X 10mL), and the organic phase was separated and then extracted with anhydrous Na2SO4Drying, filtering and rotary evaporation to remove the solvent. The residue was purified by ethyl acetate/petroleum ether mixed solvent ═ 9: purification by column chromatography 1 gave organosilicon compound II-13(40.3mg) in 75% yield.
Figure BDA0003140700190000211
The nuclear magnetic hydrogen spectrum and the carbon spectrum of the target product are as follows:
1H NMR(400MHz,Chloroform-d)；δ＝9.54–9.53(m,1H),7.42–7.33(m,5H),7.23–7.19(m,2H),7.13–7.09(m,1H),6.96–6.94(m,2H),2.91–2.83(m,2H),2.67–2.59(m,1H),0.27(d,J＝11.4Hz,6H).
13C NMR(100MHz,Chloroform-d)；δ＝202.7,141.1,136.2,134.1,129.5,128.3,127.9,127.7,125.2,43.5,30.1,-4.2,-5.5.
application example 13 shows that under the catalytic conditions of the CC @ Cu catalytic material provided in the present invention, the conversion rate of trans-cinnamaldehyde is also high, and the yield of the silicon addition product reaches 75%.
Application example 14:
the CC @ Cu catalytic material provided by the embodiment 2 is applied to a silicon addition reaction of chalcone and a bis-boronic acid pinacol dimethyl silicon reagent, wherein the chalcone is 0.20mmol, the bis-boronic acid pinacol dimethyl silicon reagent is 0.24mmol, the catalytic material is 0.002mmol, water is 1.0mL, the reaction time at room temperature is 12 hours, and after the reaction is finished, the whole reaction system is filtered and washed by 3mL of acetic acid. To the residue were added potassium bromide (24 mg) and peracetic acid (30 mg) directly, the whole was stirred at room temperature for 12 hours, the reaction mixture was diluted with ethyl acetate (10 mL), extracted with ethyl acetate (3X 10mL), and the organic phase was separated and purified with anhydrous Na2SO4Drying, filtering and rotary evaporation to remove the solvent. The residue was purified by column chromatography using ethyl acetate/petroleum ether mixed solvent ═ 4:1 to give a yield of 82%. .
Figure BDA0003140700190000221
Application example 14 shows that, under the catalytic conditions of the CC @ Cu catalytic material provided in the embodiments of the present invention, chalcone can prepare a β -hydroxy compound using a "one-pot" method, and the yield of the conversion product reaches 82%.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.

Claims (5)

1. The application of chitosan/cellulose composite microsphere immobilized copper in catalyzing the silicon addition reaction of alpha, beta-unsaturated carbonyl compounds is characterized by comprising the following steps:
1) adding an alpha, beta-unsaturated carbonyl compound I, a bis (pinacolato) diboron dimethyl silicon reagent and a chitosan/cellulose composite microsphere immobilized copper catalytic material CC @ Cu into water according to a molar ratio of 1:1.2:0.01, wherein the ratio of the CC @ Cu to the water is 0.002 mmol: 1ml, stirred at room temperature for 12h, to effect a hydrosilylation reaction:
Figure FDA0003140700180000011
wherein R1 is a phenylketonic group, a p-methoxyphenylketonic group, a p-methylphenylketonic group, a p-halophenylketonic group, an acetyl group, a carboxaldehyde group, a carbomethoxy group, an carbethoxy group or a cyano group; r2 is phenyl, p-methylphenyl, p-halophenyl, o-halophenyl, p-methoxyphenyl, methyl, t-butyl, acetyl, p-halomethylphenyl;
2) filtering the CC @ Cu, extracting, then carrying out spin-drying on a filtrate solvent, and separating a product by using a thin-layer chromatography method to obtain an organic silicon compound II;
the CC @ Cu is formed by mixing a mixed solution of chitosan and cellulose to form microspheres in an alkaline solution, and then adding a pore-forming agent and crosslinkingCross-linking agent to form composite microsphere, and immersing in Cu2+In an aqueous solution of 1.75X 10 relative to the copper in said CC @ Cu-3mol/g, wherein the molar ratio of C ═ O to chitosan units in the solution containing aldehyde or ketone is 8-12: 1.
2. the use according to claim 1, wherein said CC @ Cu is prepared by a process comprising the steps of:
1) uniformly stirring the cellulose particle chitosan solution, wherein the mass ratio of cellulose to chitosan is 400 mg: 1.5g, slowly dripping the prepared mixed solution into a sodium hydroxide solution by using an injector to form transparent microspheres;
2) and (2) recovering the microbeads through filtration, fully washing the microbeads by using distilled water and ethanol, adding the microbeads into a solution containing ethanol and aldehyde or ketone, stirring the solution at 50 ℃ for 12 hours, and crosslinking the solution, wherein the molar ratio of C ═ O to chitosan unit bodies in the solution containing aldehyde or ketone is 8-12: 1;
3) filtering out the crosslinked yellow-brown composite microbeads, washing with water and ethanol, and drying at room temperature;
4) soaking the dried microspheres in water at 50 ℃ for suspension for 1 hour; mixing Cu2+Adding the aqueous solution into the suspension, and slowly stirring for 12 hours to adsorb copper ions;
5) separation of loaded Cu by filtration2+The microspheres are washed with water and ethanol to remove free copper ions and anions, and finally, the CC @ Cu is dried in an oven at 50 ℃ for 12 hours to obtain the CC @ Cu catalytic material.
3. Use according to claim 1, characterized in that the α, β -unsaturated carbonyl compound I is chalcone.
4. Use according to claim 1, characterized in that in step 2): the CC @ Cu was filtered, washed thoroughly 3 times with water and ethanol, and then dried for reuse.
5. Use according to claim 2, characterized in that the molar ratio of the units of C ═ O and chitosan in the solution containing the aldehyde or ketone is 8: 1.
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