CN113457736B - 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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CN113457736B
CN113457736B CN202110733711.XA CN202110733711A CN113457736B CN 113457736 B CN113457736 B CN 113457736B CN 202110733711 A CN202110733711 A CN 202110733711A CN 113457736 B CN113457736 B CN 113457736B
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chitosan
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catalytic material
copper
group
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CN113457736A (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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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • 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
    • B01J35/51—
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/0201—Impregnation
    • B01J37/0207—Pretreatment of the support
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic System
    • C07F7/02—Silicon compounds
    • C07F7/08—Compounds having one or more C—Si linkages
    • C07F7/0803—Compounds with Si-C or Si-Si linkages
    • 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
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic System
    • C07F7/02—Silicon compounds
    • C07F7/08—Compounds having one or more C—Si linkages
    • C07F7/0803—Compounds with Si-C or Si-Si linkages
    • C07F7/0825—Preparations of compounds not comprising Si-Si or Si-cyano linkages
    • C07F7/0827—Syntheses with formation of a Si-C bond
    • C07F7/0829—Hydrosilylation reactions
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
    • B01J2231/30—Addition reactions at carbon centres, i.e. to either C-C or C-X multiple bonds
    • B01J2231/32—Addition reactions to C=C or C-C triple bonds
    • B01J2231/323—Hydrometalation, e.g. bor-, alumin-, silyl-, zirconation or analoguous reactions like carbometalation, hydrocarbation

Abstract

The application relates to an application of chitosan/cellulose composite microsphere immobilized copper in catalyzing silicon addition reaction of alpha, beta-unsaturated carbonyl compounds, wherein the catalytic material takes chitosan/cellulose composite microsphere as a carrier, copper is used as an active ingredient, when the catalyst is applied, chitosan/cellulose immobilized copper catalytic material (CC@Cu) is used as a catalyst, a bisboronic acid pinacol dimethyl silicon reagent is used as a silicon reagent, pure water is used as a solvent, the silicon addition reaction is carried out on alpha, beta-unsaturated carbonyl compounds containing different substituent groups to obtain an organosilicon compound, potassium bromide and peracetic acid are directly added on the basis of separating and purifying the organosilicon compound, and the beta-hydroxyl compound is obtained by oxidation. The CC@Cu catalytic material is applied to a silicon addition reaction, and has the advantages of small consumption, mild reaction conditions, high product yield and high conversion rate; pure water is used as a solvent, and the process is carried out at room temperature, so that the process is simple and easy to operate; can be repeatedly used for a plurality of times.

Description

Application of chitosan/cellulose composite microsphere immobilized copper in catalyzing silicon addition reaction of alpha, beta-unsaturated carbonyl compound
Technical Field
The application relates to a preparation method of a catalytic material and application thereof in an organosilicon compound, in particular to a shell polymersugar/Cellulose composite microsphere immobilized copper catalytic material (Chitosan/Cellulose-Cu) 2+ =cc@cu) and use in the hydrosilylation reaction of α, β -unsaturated carbonyl compounds.
Background
The organosilicon compound is an important intermediate, and is widely applied to the synthesis of natural products and drug molecules, because the C-Si bond is relatively stable and can be used as a protecting group in the synthesis process, and decomposition or side reaction can not occur. Compared with the traditional reported preparation method using strong alkali, the strategy of direct silicon addition of unsaturated carbonyl compounds under the action of a catalyst is more direct and effective, and has gained wide attention in recent years. The catalysts used in the reactions for catalyzing the hydrosilylation in the literature are Pd (chem. Commun.,2016,52,5609-5612), rh (Angew. Chem. Int. Ed.2006,45, 5675-5677), etc., but noble metals are used in many cases in these reports, and the cost is high and not suitable for practical production. Copper as a widely available, inexpensive and readily available transition metal has therefore shown its unique advantages in the reaction of catalyzing the hydrosilylation, in 2010, literature (J.am. Chem. Soc.2010,132, 2898-2900) reported the use of CuCl as a catalyst, the addition of a strong base NaOt-Bu, the realization of (dimethylbenzyll) bisboronic acid pinacol ester Me without the need for a proton source at low temperatures of-78 DEG C 2 The beta-silicon addition reaction of PhSi-Bpin on alpha, beta-unsaturated carbonyl compound uses metal monovalent copper salt, and does not need proton source, but is accompanied by the use of strong alkali, low temperature condition and the need of using NHC ligand, and the post-treatment is complex and not friendly to environment. In 2015, the use of Cu (acac) was reported in the literature (J.am. Chem. Soc.2015,137, 15422-15425) 2 For the action of the catalyst and the special chiral bipyridine ligand, H is used as 2 O is a solvent, and under the condition of room temperature, the method is simple, but the ligand preparation method is complex, the commercialization is not realized, the reaction cost is limited, the actual production is not facilitated, and meanwhile, the problem that the catalyst cannot be recycled exists; in 2018, cu was used in the literature (J.Chin. Chem. Soc.2018,65,81-86) 2 (OH) 2 CO 3 Simultaneous addition of 2, 2-bipyridine ligand and surfactant Triton X-100 phase to catalystThe interaction takes pure water as a solvent and reacts at room temperature, but the problems of limited reaction cost, 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 method is greatly limited to be applied to actual production. Therefore, development of a new environment-friendly method for preparing organosilicon compounds by a direct silicon addition strategy, which is simple and easy to operate, mild in condition and low in cost, is highly urgent.
The conversion of organosilicon compounds to beta-hydroxy compounds is an important application of organosilicon compounds, since the beta-hydroxy structure is widely present in the natural product structure, if the strategy of "one-pot method" can be adopted, the silicon addition of the substrate is realized first, and then the substrate is continuously converted into the beta-hydroxy compound without separation, so that the synthesis steps of the natural product are simplified, and the method has very important application value. In addition, the organic silicide itself has wide practical applications in organic synthesis and material chemistry, such as monomers for polymerization, precursors for anticancer drugs, coupling agents, and the like.
Disclosure of Invention
The application 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 prepare an organosilicon 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 organosilicon 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 ligands are used as catalysts, the operation process is complex, strong alkali (potassium tert-butoxide and the like), low temperature (-78 ℃) and strict anhydrous and other harsh conditions are needed, and the production cost is high; when the existing beta-hydroxyl compound is prepared by taking an organosilicon compound as a starting point, the organosilicon compound is required to be separated and purified from a reaction product after synthesis, continuous production is avoided, and the process route is complex and the production efficiency is low. The application prepares the organic silicon compound by the chitosan/cellulose composite microsphere immobilized copper catalytic material, utilizes the unique compatibility and space structure of the chitosan/cellulose composite microsphere immobilized copper catalytic material, has 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 bisboronic acid pinacol dimethyl silicon reagent and a chitosan/cellulose composite microsphere immobilized copper catalytic material CC@Cu into water according to the mol ratio of 1:1.2:0.01, wherein the dosage ratio of the CC@Cu to the water is 0.002mmol:1ml, stirred at room temperature for 12h, the hydrosilylation reaction took place:
wherein R1 is a phenylketone group, a p-methoxyphenylketone group, a p-methylbenzketone group, a p-halophenylketone group, an acetyl group, a formaldehyde group, a methyl ester group, an ethyl ester group or a cyano group; r2 is phenyl, p-methylphenyl, p-halophenyl, o-halophenyl, p-methoxyphenyl, methyl, tert-butyl, acetyl, p-halophenyl;
2) Filtering the CC@Cu, spin-drying a filtrate solvent after extraction, and separating a product by a thin layer chromatography method to obtain an organosilicon 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-forming agent and a crosslinking agent, crosslinking to form composite microspheres, and immersing in Cu 2+ The relative content of copper in the CC@Cu catalyst obtained in the aqueous solution of (2) is 1.75X10 -3 mol/g, the molar ratio of C=O and chitosan unit in the aldehyde or ketone containing solution is 8-12: 1.
in the foregoing application, the preparation method of cc@cu includes the following steps:
1) The cellulose particles are stirred uniformly in chitosan solution, and the mass ratio of cellulose to chitosan is 400mg:1.5g, the prepared mixed solution is slowly dripped into sodium hydroxide solution by a syringe to form transparent microspheres;
2) The microbeads are recovered by filtration, washed thoroughly with distilled water and ethanol, added to a solution containing ethanol and aldehyde or ketone, stirred at 50 ℃ for 12 hours, crosslinked, the molar ratio of c=o and chitosan units in the solution containing aldehyde or ketone being 8-12: 1, a step of;
3) Filtering out the yellow-brown composite microbeads after crosslinking, washing with water and ethanol, and drying at room temperature;
4) Soaking and suspending the dried microspheres in water at 50 ℃ for 1 hour; cu is added with 2+ Adding the aqueous solution of (2) into the suspension, slowly stirring for 12 hours, and adsorbing copper ions;
5) Separation of loaded Cu by filtration 2+ Washing with water and ethanol to remove free copper ions and anions, and finally oven drying the CC@Cu at 50 ℃ for 12 hours to obtain the CC@Cu catalytic material.
In the foregoing application, the α, β -unsaturated carbonyl compound I is chalcone.
In the aforementioned application, in step 2): and filtering the CC@Cu, fully washing with water and ethanol for 3 times, and then drying for repeated use.
In the aforementioned application, the molar ratio of c=o and chitosan units in the aldehyde or ketone containing solution is 8:1.
in the foregoing application, after the cc@cu cycle is continuously used for 6 times, 7 th time is applied to the boron addition reaction of the chalcone, and the yield of the product is 80%.
The possible reaction mechanism is presumed to be as follows:
first, pinacol dimethyl silicon biborate reagent [ PhMe 2 Si-B(pin)]Cleavage of Si-B bond (chitosan in the catalytic material contains a large amount of amino groups and provides an alkaline environment for the reaction) under the catalysis of active copper in the CC@Cu catalytic material, and the catalyst reacts with bivalent copper to form copper silane-based complex and byproduct Bpin-OH, whereinThe intermediate is subjected to conjugate addition with an alpha, beta-unsaturated carbonyl compound under the guiding action of carbonyl, then subjected to six-membered ring transition rearrangement, and subjected to protonation process under the action of water provided with a proton source to generate a target product, and the regeneration of a catalytic material is realized, wherein in the reaction, the water is the proton source and also is a solvent.
Compared with the traditional method, the application has the following advantages:
1. the chitosan/cellulose composite microsphere has good biocompatibility, is environment-friendly, can be used for participating in pure water reaction, has good effect of immobilized metallic copper, has longer service life, can be conveniently separated from other components in a reaction system by a solid-liquid separation method after the reaction is completed, and can be repeatedly used after simple regeneration, so that the production cost can be greatly reduced, and various environmental pollution problems can be obviously reduced.
2. The method can realize higher conversion rate of the reactant by using lower catalyst consumption;
3. the method has mild reaction conditions, takes pure water as a solvent, and is simple and easy to operate, and the reaction is carried out at room temperature;
4. the method has wide application, can be used for the silicon addition of various alpha, beta-unsaturated carbonyl compounds, and successfully prepares corresponding organosilicon compounds and beta-hydroxyl compounds.
5. The method can adopt a one-pot strategy, and the initial raw materials directly prepare the carbonyl-containing beta-hydroxy compound through continuous silicon addition reaction and oxidation reaction.
6. When only chitosan loaded cupric oxide is used as a catalyst, chalcone is used as a template substrate, chitosan loaded cupric hydroxide is used as a catalyst, 2-bipyridine is used as a ligand, and B is carried out in pure water during the boron addition reaction of alpha, beta-unsaturated receptors 2 (pin) 2 In pure water, wherein chitosan is immobilized with copper hydroxide (CS@Cu (OH) 2 ) And chitosan-supported copper oxide (CS@CuO) prepared according to literature (Carbohydrate Polymer 2015,134, 190-204), chitosan-supported copper cyanide (CS@CuCN), chitosan-supported copper sulfate (CS@CuSO) 4 ) Chitosan-supported copper chloride (CS@CuCl) 2 ) Chitosan immobilized copper fluoride (CS@CuF) 2 ) And chitosan immobilized copper bromide (CS@CuBr) 2 ) Prepared according to literature (GreenChem.2014, 16, 3007-3012). Chitosan pair Cu 2+ Is adsorbed by amino group [ (2)]Mainly, the main adsorption reactions include:
protonation of the amino group:
matching:
hydrogen bond adsorption:
electrostatic attraction:
at lower pH, -NH formed in the reaction of protonation 3 + The number is high, and the catalyst is used for the co-adsorption of Cu 2+ Of (2) NH 2 Less. The catalyst recovered after the reaction was checked by ICP (CS@Cu (OH) 2 ) 1.6% of copper is found to fall off, and considering that copper hydroxide is insoluble in water, it is presumed that the generation of (pin) BOH byproducts causes the change of the pH value of the system, and the type of cupric salt is further screened, and copper is found to fall off more seriously when cupric salt with better water solubility (such as copper sulfate and cupric chloride) is used, so that the pH value of the reaction system is adjusted by adopting a strategy of adding ligand, and finally, pyridine ligand containing amide bonds is found to well inhibit the fall off of copper and play a role of stabilizing a catalyst.
After the chitosan and cellulose are subjected to composite crosslinking, the density of the catalyst carrier is improved, the micropore structure is increased, and primary amine (R' NH) on the chitosan is increased 2 ) With aldehyde ketone (R) 2 C=o) to form an imine (R) containing a carbon-nitrogen double bond 2 C=NR') the aldehyde ketone forms a bridge connection between different amino positions inside and among chitosan molecules, while the Schiff base reaction is reducedThe amino group on the surface of the chitosan is reduced, but because the surface of the chitosan is rich in hydroxyl groups, N atoms in C=N double bonds formed by Schiff base reaction and O atoms in adjacent OH are very easy to be combined with Cu 2+ Complexing occurs to form a conjugate plane (Xie X J, qin Y.Sens practitioners B,2011,156 (1): 213), and the crosslinking also improves the acid resistance of chitosan, and the complexing effect on copper ions is stronger through chemical adsorption and physical adsorption.
7. When chitosan is crosslinked with an aldehyde or ketone, the aldehyde or ketone has-c=o relative to-NH of the chitosan unit due to acetalization reaction 2 With a large excess, sufficient imide groups are formed for forming stable complexes with copper ions. However, when the amount of the crosslinking compound microsphere is too large, the O atom adjacent to the N atom in the C=N double bond in OH is reduced due to the acetal reaction, and the yield of the reactant is reduced, so that when the crosslinking compound microsphere of the chitosan and the cellulose is prepared, the molar ratio of the C=O and the chitosan in the aldehyde or ketone solution in the crosslinking agent is 8-12: 1 is preferably 1.
Drawings
FIG. 1 is an infrared spectrogram of cross-linked chitosan/cellulose composite microsphere CC@Cu and cross-linked chitosan/cellulose microsphere loaded with bivalent copper ions;
FIG. 2 is a schematic diagram of the mechanism of the cross-linking reaction of chitosan with ketones or aldehydes.
Detailed Description
The principles and features of the present application are described below in connection with specific embodiments, examples of which are provided for illustration only and are not intended to limit the scope of the application.
Example 1:
the active component of the CC@Cu catalytic material provided by the embodiment of the application is copper, and the carrier is chitosan/cellulose composite microspheres; meanwhile, the relative content of the active component copper in the CC@Cu catalytic material is 1.75mmol/g.
Wherein the carrier is chitosan/cellulose composite microsphere, the chitosan/cellulose composite microsphere is formed by adding cellulose into acid solution of chitosan, then adding into alkaline solution to suspend to form microsphere, and then adding pore-forming agent and cross-linking agent to crosslink.
Example 2:
the embodiment of the application also provides a preparation method of the CC@Cu catalytic material, which comprises the following three steps:
1) Preparation of chitosan/cellulose microspheres: cellulose particles (400 mg) were added to 100ml of chitosan solution (100 ml of water, 1.5g of chitosan, 3.0ml of acetic acid) to be stirred uniformly, to obtain a viscous liquid. The prepared mixed solution was slowly dropped into 100mL of sodium hydroxide solution (prepared from 15g of sodium hydroxide and 100mL of distilled water) by a syringe to form transparent microspheres. The hydroxyl and amino groups in chitosan molecules have good reactivity, the chitosan can be conveniently grafted and modified, metal ions can be adsorbed by the chitosan through coordination, ion exchange and electrostatic interaction, 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 groups, and the molecular formula of the chitosan is (C 6 H 11 NO 4 ) N, molecular weight of the unit is: 161.2,1.5g chitosan contained 0.009 mol of monomer units. 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, improves the pore structure and the surface characteristics of the adsorbent, and is beneficial to improving the adsorption performance.
2) Preparation of crosslinked chitosan/cellulose microspheres: the microbeads were recovered by filtration, washed thoroughly with distilled water and ethanol, stirred in a cross-linking solution containing ethanol (100 mL) and succinaldehyde (chitosan unit: succinaldehyde=1 mol:4 mol) at 50 ℃ for 12 hours, the cross-linked yellowish-brown composite microbeads were filtered off, washed with water and ethanol, and dried at room temperature. In the step, porous crosslinked chitosan/cellulose composite microspheres are prepared by ethanol pore-forming and succinyl aldehyde crosslinking, and amino groups are reduced after crosslinking, so that the chemical stability of chitosan in an acidic medium can be improved.
3) Preparation of divalent copper ion-loaded crosslinked chitosan/cellulose microspheres (CC@Cu): the crosslinked and dried microspheres (1.0 g) were suspended in 50℃water (20 ml) and soaked for 1 hour. 10mL of a copper sulfate solution (prepared from 100mg of copper sulfate pentahydrate, about 0.0004 mol) was added to the suspension and stirred for 12 hours, and the Cu-loaded was separated by filtration 2+ Is washed with water and ethanol to remove free copper and sulfate ions. Finally, chitosan/cellulose-Cu is added 2+ And (CC@Cu) the catalytic material is dried in an oven at 50 ℃ for 12 hours to obtain the CC@Cu catalytic material.
Fig. 1 is an infrared spectrum of chitosan/cellulose composite microsphere (CC) and cc@cu catalytic material, with the upper line representing the infrared spectrum before the chitosan/cellulose composite microsphere (CC) is loaded with Cu and the lower line representing the infrared spectrum after the chitosan/cellulose composite microsphere (CC) is loaded with Cu.
Chitosan/cellulose composite microsphere (CC) through-NH of chitosan 2 The ketone group of the radical is condensed with succinaldehyde to form an imine group (c=n), as in the I and IV processes of fig. 2. At 1636cm -1 Stretching of the carrier imine group was observed at 3422.15cm -1 Stretching of the carrier N-H groups was observed. On the characterization curve of the catalyst CC@Cu, the imine group is in a belt of 1621cm -1 The vibration at this point is reduced, which can be attributed to the coordination of the copper ions with the ligand imide groups. The N-H radical is 3422.15cm -1 The vibration of the position disappears, which is attributed to the complexation of copper ions with N-H groups, all of which participate in the complexation with copper ions, and copper is not easy to fall off due to pH change after the copper ions are coordinated with ligand imino groups. In FIG. 1 (CC) and CC@Cu at 1110cm -1 A strong new characteristic peak is observed, which is derived from the stretching vibration of the C-O-C-O-C group, which indicates that the carbonyl group in the succinaldehyde and the hydroxyl group on the chitosan glucosamine ring are also subjected to acetalization reaction, such as the II process in FIG. 2, and in theory, the carbonyl group and the hydroxyl group can be subjected to acetalization reaction. Mixing together one mole of aldehyde and one mole of alcohol results in a reversible reaction equilibrium, 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 the fact that an-OH group and an-OR group are attached to the same carbon atom. Hemiacetals are generally too unstable to be isolated and can be reacted with another mole of alcohol to form one mole of acetal by a second reaction catalyzed by small amounts of gaseous hydrochloric acid. Acetals are characterized in that two-OR groups are linked to the same CH group. The acetalation reaction most likely occurs in chitosan C where the carbonyl group and steric hindrance are relatively weak 6 Between hydroxy groups, shrinkingCharacteristic peaks of aldehyde should appear in 1105-116 cm of cross-linked chitosan fiber infrared spectrogram -1 Section, thus 1110cm -1 The presence of the characteristic peaks suggests that the crosslinking reaction occurs not only between succinaldehyde and primary amine but also between succinaldehyde and hydroxyl groups. But here the peak intensity ratio is 1621-1636 cm -1 The same is true (Schiff base characteristic peak), indicating that Schff base reaction and acetalation reaction predominate in the crosslinking reaction. The structural schematic diagram of the reaction of succinaldehyde and hydroxyl groups on the chitosan molecular ring is shown as II in fig. 2, and it can be seen from the figure that one butanedialdehyde molecule can react with four hydroxyl groups to form a crosslinked structure. No band stretching attributable to succinaldehyde carbon groups was observed in (CC) and CC@Cu (at 1750cm -1 Left to right), it was confirmed that all ketone groups of succinaldehyde participate in schiff base reaction and acetalation reaction. In the crosslinking reaction, only the carbonyl group at one end reacts with the amino group on the chitosan molecular ring, and the carbonyl group at the other end is not reacted, so that an n=c—o=o structure is formed (see the IV process in fig. 2). At 3422.15cm -1 It 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 carry out the entire-NH group 2 Conversion to-c=n.
Examples 3 to 5
The cc@cu catalytic material was prepared by the method of example 2, except that in step 2) of example 3, the chitosan unit body: succinaldehyde = 1mol:1mol, at which time the microspheres are transparent, fragile, i.e. this proportion is excluded, possibly due to incomplete crosslinking; chitosan unit in step 2) of example 4: succinaldehyde=1 mol:2mol, possibly incompletely crosslinked, transparent and easily denatured; chitosan unit in step 2) of example 5: succinaldehyde=1 mol:6mol, and the microsphere is brown solid and stable in shape. When succinaldehyde-c=o and chitosan unit-NH were analyzed by infrared spectroscopy of the catalytic material in combination with fig. 2 and example 2 2 Is 2:1 or 4: the crosslinking at 1 is incomplete, which is attributable to the fact that all ketone groups of succinaldehyde participate in the schiff base reaction and acetalization reaction, which are dominant, even though-c=o of succinaldehyde is relative to-NH of chitosan unit 2 Excessive amount of-NH-not guaranteed 2 Schiff base reaction all occurs; a significant portion of the-c=o of succinaldehyde was consumed by the acetalization reaction.
Example 6:
the embodiment of the application also provides a method for applying the CC@Cu catalytic material to the silicon addition reaction between the alpha, beta-unsaturated carbonyl compound and the bisboronic acid pinacol dimethyl silicon reagent, which comprises the following specific steps: the alpha, beta-unsaturated carbonyl compound I, the bisboronic acid pinacol dimethyl silicon reagent and the CC@Cu catalytic material (prepared in example 2) are added into a mixed solvent of 1.0ml of water according to the mol ratio of 1:1.2:0.01,the ratio of CC@Cu to water was 0.002mmol:1ml, stirring at room temperature for 12h; filtering the CC@Cu catalytic material, extracting, spin-drying the solvent, and separating by thin layer chromatography to obtain the organosilicon compound II. Meanwhile, the CC@Cu catalytic material is firstly applied to the silicon addition reaction between an alpha, beta-unsaturated carbonyl compound and a bisboronic acid pinacol dimethyl silicon reagent. The silicon addition reaction is as follows:
wherein R1 is a benzophenone group, a p-methoxy benzophenone group, a p-methyl benzophenone group, a p-halogenophenone group, an acetyl group, a formaldehyde group, a methyl ester group, an ethyl ester group or a cyano group; r2 is phenyl, p-methylphenyl, p-halophenyl, o-halophenyl, p-methoxyphenyl, methyl, tertiary butyl, acetyl and p-halophenyl, for example, the alpha, beta-unsaturated carbonyl compound is chalcone, and after the reaction, the CC@Cu catalytic material is filtered, fully washed for a plurality of times by water and ethanol, and then dried, so that the catalyst can be reused.
Application example 1:
the CC@Cu catalytic material provided in the above example 2 is applied to a silicon addition reaction of chalcone and a bisboronic acid pinacol dimethyl silicon reagent, wherein the chalcone is 0.20mmol, the bisboronic acid pinacol dimethyl silicon 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 after the reaction is finished, filtering is carried outThe whole reaction system was washed with 10mL of ethyl acetate, extracted with ethyl acetate (3X 10 mL), and the organic phase was separated and then extracted with anhydrous Na 2 SO 4 Drying, filtration, and rotary evaporation to remove the solvent. The residue was purified by ethyl acetate/petroleum ether mixed solvent=9: 1 column chromatography purification gave organosilicon compound II-1 (58.6 mg) in 85% yield.
The nuclear magnetic hydrogen spectrum and the carbon spectrum of the target product are shown as follows:
1 H 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).
13 C 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 catalysis condition of the CC@Cu catalysis material provided by the embodiment 2 of the application, 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 bisboronic acid pinacol dimethylsiloxane reagent in the above reaction procedure with a yield of 68%.
more-NH in catalyst 2 The catalytic efficiency cannot be improved, and more-NH is contained in chitosan along with the increase of the dosage of succinaldehyde 2 The Schiff base reaction is carried out, and the chitosan is crosslinked more completely, so that copper ions are combined with a catalyst more firmly in the silicon addition reaction, the copper ions are not fallen 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 increased still further, the yield is lowered, probably due to the reduced hydroxyl groups on the glucosamine ring of chitosan by the acetalization reaction, and there is insufficient coordination between the O atom in the adjacent OH and the N atom in the c=n double bond and Cu 2+ Complexation occurs.
Application example 2:
the CC@Cu catalytic material provided in the above example 2 was applied to a hydrosilylation reaction of (1-phenyl-3- (p-tolyl) prop-2-en-1-one with a bisboronic acid pinacol dimethylsilicon reagent, wherein (1-phenyl-3- (p-tolyl) prop-2-en-1-one was 0.20mmol, bisboronic acid pinacol dimethylsilicon reagent was 0.24mmol, catalytic material was 0.002mmol, water was 1.0mL, and the reaction time was 12 hours at room temperature, thereby obtaining a hydrosilylation product, after the reaction was completed, the whole reaction system was filtered, washed with 10mL of ethyl acetate, extracted with 3X 10mL of ethyl acetate, and after the organic phase was separated, anhydrous Na was used 2 SO 4 Drying, filtration, and rotary evaporation to remove the solvent. The residue was purified by ethyl acetate/petroleum ether mixed solvent=9: 1 column chromatography purification gave organosilicon compound II-2 (50.2 mg) in 70% yield.
The nuclear magnetic hydrogen spectrum and the carbon spectrum of the target product are shown as follows:
1 H 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).
13 C 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 catalysis condition of the CC@Cu catalytic material provided by the embodiment of the application, the conversion rate of the (1-phenyl-3- (p-tolyl) prop-2-en-1-one is also very high, and the yield of the silicon addition product reaches 70%.
Application example 3:
the CC@Cu catalytic material provided in the above example 2 was applied to the hydrosilylation reaction of (E) -3- (4-bromophenyl) -1-phenylprop-2-en-1-one with pinacol dimethyl silicon reagent, wherein (E) -3- (4-bromophenyl) -1-phenylprop-2-en-1-one was 0.20mmol, and the reaction was carried out in a column reactorThe reaction time at room temperature is 12h, thus obtaining a silicon addition product, after the reaction is finished, the whole reaction system is filtered, washed with 10mL of ethyl acetate, extracted with 3X 10mL of ethyl acetate, and the organic phase is separated, and then anhydrous Na is used 2 SO 4 Drying, filtration, and rotary evaporation to remove the solvent. The residue was purified by ethyl acetate/petroleum ether mixed solvent=9: 1 column chromatography purification gave organosilicon compound II-3 (67.7 mg) in 80% yield.
The nuclear magnetic hydrogen spectrum and the carbon spectrum of the target product are shown as follows:
1 H 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).
13 C 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 catalysis condition of the CC@Cu catalysis material provided by the embodiment of the application, the conversion rate of (E) -3- (4-bromophenyl) -1-phenylpropan-2-en-1-one is also very high, and the yield of the silicon addition product reaches 80%.
Application example 4:
the CC@Cu catalytic material provided in the above example 2 was applied to a hydrosilylation reaction of (penta) -3- (4-chlorophenyl) -1-phenylprop-2-en-1-one with a dithiopinacol dimethylsilicon reagent, wherein 0.20mmol of (penta) -3- (4-chlorophenyl) -1-phenylprop-2-en-1-one, 0.24mmol of the dithiopinacol dimethylsilicon reagent, 0.002mmol of the catalytic material, 1.0mL of water, and a room temperature reaction time of 12 hours, thereby obtaining a hydrosilylation product, after the reaction was completed, the whole reaction system was filtered, washed with 10mL of ethyl acetate, extracted with 3X 10mL of ethyl acetate, and after the organic phase was separated, anhydrous Na was used 2 SO 4 Drying, filtering, and rotary steamingThe solvent was removed. The residue was purified by ethyl acetate/petroleum ether mixed solvent=9: 1 column chromatography gave organosilicon compound II-4 (56.8 mg) in 75% yield.
The nuclear magnetic hydrogen spectrum and the carbon spectrum of the target product are shown as follows:
1 H 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).
13 C 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 condition of the CC@Cu catalysis material provided by the embodiment of the application, the conversion rate of (penta) -3- (4-chlorophenyl) -1-phenylprop-2-en-1-one is also very high, and the yield of the silicon addition product reaches 75%.
Application example 5:
the CC@Cu catalytic material provided in the above example 2 was applied to the hydrosilylation reaction of (penta) -1-phenyl-3- (4- (trifluoromethyl) phenyl) prop-2-en-1-one with pinacol dimethyl silicon reagent, wherein 0.20mmol of (penta) -1-phenyl-3- (4- (trifluoromethyl) phenyl) prop-2-en-1-one, 0.24mmol of pinacol dimethyl silicon reagent, 0.002mmol of catalytic material, 1.0mL of water and a reaction time of 12 hours at room temperature, thereby obtaining a hydrosilylation product, after the reaction was completed, the whole reaction system was filtered, washed with 10mL of ethyl acetate, extracted with 3X 10mL of ethyl acetate, and after the organic phase was separated, anhydrous Na was used 2 SO 4 Drying, filtration, and rotary evaporation to remove the solvent. The residue was purified by ethyl acetate/petroleum ether mixed solvent=9: 1 column chromatography purification gave organosilicon compound II-5 (66.0 mg) in 80% yield.
The nuclear magnetic hydrogen spectrum and the carbon spectrum of the target product are shown as follows:
1 H 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).
13 C 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 catalysis condition of the CC@Cu catalysis material provided by the embodiment of the application, the conversion rate of (penta) -1-phenyl-3- (4- (trifluoromethyl) phenyl) prop-2-en-1-one is also very high, and the yield of a silicon addition product reaches 80%.
Application example 6:
the CC@Cu catalytic material provided in the above example 2 was applied to a hydrosilylation reaction of (E) -3- (4-methoxyphenyl) -1-phenylpropan-2-en-1-one with a bisboronic acid pinacol dimethylsilicon reagent, wherein 0.20mmol of (E) -3- (4-methoxyphenyl) -1-phenylpropan-2-en-1-one, 0.24mmol of the bisboronic acid pinacol dimethylsilicon reagent, 0.002mmol of the catalytic material, 1.0mL of water and a reaction time of 12 hours at room temperature were used to obtain a hydrosilylation product, after the reaction was completed, the whole reaction system was filtered, washed with 10mL of ethyl acetate and extracted with 3X 10mL of ethyl acetate, and after the organic phase was separated, anhydrous Na was used 2 SO 4 Drying, filtration, and rotary evaporation to remove the solvent. The residue was purified by ethyl acetate/petroleum ether mixed solvent=9: 1 column chromatography purification gave organosilicon compound II-6 (61.4 mg) in 82% yield.
The nuclear magnetic hydrogen spectrum and the carbon spectrum of the target product are shown as follows:
1 H 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).
13 C 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 condition of the CC@Cu catalytic material provided by the embodiment of the application, the conversion rate of (E) -3- (4-methoxyphenyl) -1-phenylpropan-2-en-1-one is high, and the yield of the silicon addition product reaches 82%.
Application example 7:
the CC@Cu catalytic material provided in the above example 2 was applied to the hydrosilylation reaction of (penta) -3- (4-chlorophenyl) -1- (p-tolyl) prop-2-en-1-one with pinacol dimethyl silicon reagent, wherein 0.20mmol of (penta) -3- (4-chlorophenyl) -1- (p-tolyl) prop-2-en-1-one, 0.24mmol of pinacol dimethyl silicon reagent, 0.002mmol of catalytic material, 1.0mL of water, and a room temperature reaction time of 12 hours, to thereby obtain a hydrosilylation product, after the reaction was completed, the whole reaction system was filtered, washed with 10mL of ethyl acetate, and extracted with ethyl acetate (3X 10 mL), and after the organic phase was separated, anhydrous Na was used 2 SO 4 Drying, filtration, and rotary evaporation to remove the solvent. The residue was purified by ethyl acetate/petroleum ether mixed solvent=9: 1 column chromatography purification gave organosilicon compound II-7 (48.7 mg) in 62% yield.
The nuclear magnetic hydrogen spectrum and the carbon spectrum of the target product are shown as follows:
1 H 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).
13 C 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 catalysis condition of the CC@Cu catalysis material provided by the embodiment of the application, the conversion rate of (penta) -3- (4-chlorophenyl) -1- (p-tolyl) prop-2-en-1-one is also very high, and the yield of the silicon addition product reaches 62%.
Application example 8:
the CC@Cu catalytic material provided in the above example 2 was applied to the hydrosilylation reaction of (penta) -3- (4-fluorophenyl) -1- (p-tolyl) prop-2-en-1-one with pinacol dimethyl silicon reagent, wherein 0.20mmol of (penta) -3- (4-fluorophenyl) -1- (p-tolyl) prop-2-en-1-one, 0.24mmol of pinacol dimethyl silicon reagent, 0.002mmol of catalytic material, 1.0mL of water, and a room temperature reaction time of 12 hours, thereby obtaining a hydrosilylation product, after the reaction was completed, the whole reaction system was filtered, washed with 10mL of ethyl acetate, and extracted with ethyl acetate (3X 10 mL), and after the organic phase was separated, anhydrous Na was used 2 SO 4 Drying, filtration, and rotary evaporation to remove the solvent. The residue was purified by ethyl acetate/petroleum ether mixed solvent=9: 1 column chromatography purification gave organosilicon compound II-8 (51.2 mg) in 68% yield.
The nuclear magnetic hydrogen spectrum and the carbon spectrum of the target product are shown as follows:
1 H 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).
13 C 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 under the catalytic condition of the CC@Cu catalytic material provided by the embodiment of the application, the conversion rate of (penta) -3- (4-fluorophenyl) -1- (p-tolyl) prop-2-en-1-one is also very high, and the yield of a silicon addition product reaches 68%.
Application example 9:
the CC@Cu catalytic material provided in the above example 2 was applied to the hydrosilylation reaction of (penta) -3- (4-chlorophenyl) -1- (4-fluorophenyl) prop-2-en-1-one with pinacol dimethyl silicon reagent, wherein 0.20mmol of (penta) -3- (4-chlorophenyl) -1- (4-fluorophenyl) prop-2-en-1-one, 0.24mmol of pinacol dimethyl silicon reagent, 0.002mmol of catalytic material, 1.0mL of water, and a reaction time of 12 hours at room temperature, thereby obtaining a hydrosilylation product, after the reaction was completed, the whole reaction system was filtered, washed with 10mL of ethyl acetate, extracted with 3X 10mL of ethyl acetate, and after the organic phase was separated, anhydrous Na was used 2 SO 4 Drying, filtration, and rotary evaporation to remove the solvent. The residue was purified by ethyl acetate/petroleum ether mixed solvent=9: 1 column chromatography purification gave organosilicon compound II-9 (57.2 mg) in 72% yield.
The nuclear magnetic hydrogen spectrum and the carbon spectrum of the target product are shown as follows:
1 H 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).
13 C 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 under the catalysis condition of the CC@Cu catalysis material provided by the embodiment of the application, the conversion rate of (penta) -3- (4-chlorophenyl) -1- (4-fluorophenyl) prop-2-en-1-one is also very high, and the yield of the silicon addition product reaches 72%.
Application example 10:
the CC@Cu catalytic material provided in the above example 2 is applied to the silicon addition reaction of trans-1-phenyl-2-butene-1-one and a bisboronic acid pinacol dimethylsiloxane reagent, wherein trans-1-phenyl-2-butene-1-one is 0.20mmol, 0.24mmol of the bisboronic acid pinacol dimethyl silicon reagent, 0.002mmol of a catalytic material, 1.0mL of water and 12 hours of room temperature reaction time, thereby obtaining a silicon addition product, filtering the whole reaction system after the reaction is finished, washing with 10mL of ethyl acetate, extracting with 3X 10mL of ethyl acetate, separating an organic phase, and separating the organic phase by anhydrous Na 2 SO 4 Drying, filtration, and rotary evaporation to remove the solvent. The residue was purified by ethyl acetate/petroleum ether mixed solvent=9: 1 column chromatography purification gave organosilicon compound II-10 (42.4 mg) in 75% yield.
The nuclear magnetic hydrogen spectrum and the carbon spectrum of the target product are shown as follows:
1 H 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).
13 C 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 catalysis condition of the CC@Cu catalytic material provided by the embodiment of the application, the conversion rate of trans-1-phenyl-2-butene-1-one is also very high, and the yield of a silicon addition product reaches 75%.
Application example 11:
the CC@Cu catalytic material provided in the above example 2 was applied to the hydrosilylation reaction of trans-benzylidene acetone with pinacol dimethyl silicon reagent, wherein 0.20mmol of trans-benzylidene acetone, 0.24mmol of pinacol dimethyl silicon reagent, 0.002mmol of catalytic material, 1.0mL of water and 12 hours of room temperature reaction time were used to obtain a hydrosilylation product, after the reaction was completed, the whole reaction system was filtered, washed with 10mL of ethyl acetate, extracted with ethyl acetate (3X 10 mL), and after the organic phase was separated, anhydrous Na was used 2 SO 4 Drying, filtration, and rotary evaporation to remove the solvent. The residue was taken up in ethyl acetate-Petroleum ether mixed solvent = 9:1 column chromatography purification gave organosilicon compound II-11 (45.2 mg) in 80% yield.
The nuclear magnetic hydrogen spectrum and the carbon spectrum of the target product are shown as follows:
1 H 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).
13 C 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 catalysis condition of the CC@Cu catalytic material provided by the embodiment of the application, the conversion rate of trans-benzylidene acetone is also very high, and the yield of a silicon addition product reaches 80%.
Application example 12:
the CC@Cu catalytic material provided in the above example 2 was applied to a hydrosilylation reaction of (E) -3-penten-2-one with a bisboronic acid pinacol dimethylsilicon reagent, wherein (E) -3-penten-2-one 0.20mmol, bisboronic acid pinacol dimethylsilicon reagent 0.24mmol, catalytic material 0.002mmol, water 1.0mL, and a reaction time of 12 hours at room temperature, thereby obtaining a hydrosilylation product, filtering the whole reaction system after the completion of the reaction, washing with 10mL of ethyl acetate, extracting with 3X 10mL of ethyl acetate, separating out an organic phase, and then using anhydrous Na 2 SO 4 Drying, filtration, and rotary evaporation to remove the solvent. The residue was purified by ethyl acetate/petroleum ether mixed solvent=9: 1 column chromatography purification gave organosilicon compound II-12 (34.4 mg) in 78% yield.
The nuclear magnetic hydrogen spectrum and the carbon spectrum of the target product are shown as follows:
1 H 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).
13 C 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 catalysis condition of the CC@Cu catalytic material provided by the embodiment of the application, the conversion rate of (E) -3-pentene-2-ketone is also very high, and the yield of the silicon addition product reaches 78%.
Application example 13:
the CC@Cu catalytic material provided in the above example 2 is applied to the hydrosilylation reaction of trans-cinnamaldehyde and a bisboronic acid pinacol dimethylsiloxane reagent, wherein 0.20mmol of trans-cinnamaldehyde, 0.24mmol of bisboronic acid pinacol dimethylsiloxane reagent, 0.002mmol of catalytic material, 1.0mL of water and a room temperature reaction time of 12 hours are adopted to obtain a hydrosilylation product, after the reaction is finished, the whole reaction system is filtered, washed with 10mL of ethyl acetate, extracted with 3X 10mL of ethyl acetate, and after an organic phase is separated, anhydrous Na is adopted 2 SO 4 Drying, filtration, and rotary evaporation to remove the solvent. The residue was purified by ethyl acetate/petroleum ether mixed solvent=9: 1 column chromatography purification gave organosilicon compound II-13 (40.3 mg) in 75% yield.
The nuclear magnetic hydrogen spectrum and the carbon spectrum of the target product are shown as follows:
1 H 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).
13 C 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 catalysis condition of the CC@Cu catalytic material provided by the embodiment of the application, the conversion rate of trans-cinnamaldehyde is also very high, and the yield of the silicon addition product reaches 75%.
Application example 14:
the CC@Cu catalytic material provided in the above example 2 was applied to the silicon addition reaction of chalcone and pinacol dimethyl silicon reagent, wherein chalcone 0.20mmol, pinacol dimethyl silicon reagent 0.24mmol, catalytic material 0.002mmol, water 1.0mL, room temperature reaction time 12h, after the reaction was completed, the whole reaction system was filtered and washed with acetic acid 3 mL. 24mg of potassium bromide and 30mg of peracetic acid were directly added to the residue, the whole system was stirred at room temperature for 12 hours, the reaction system was diluted with 10mL of ethyl acetate, and extracted with ethyl acetate (3X 10 mL), and after separating the organic phase, the organic phase was extracted with anhydrous Na 2 SO 4 Drying, filtration, 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 82% yield.
Application example 14 shows that under the catalysis condition of the CC@Cu catalytic material provided by the embodiment of the application, chalcone can be used for preparing the beta-hydroxy compound by using a one-pot method, and the yield of a conversion product reaches 82%.
The foregoing description of the preferred embodiments of the application is not intended to limit the application to the precise form disclosed, and any such modifications, equivalents, and alternatives falling within the spirit and scope of the application are intended to be included within the scope of the application.

Claims (4)

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 bisboronic acid pinacol dimethyl silicon reagent and a chitosan/cellulose composite microsphere immobilized copper catalytic material CC@Cu into water according to the mol ratio of 1:1.2:0.01, wherein the dosage ratio of the CC@Cu to the water is 0.002mmol:1ml, stirring 12h at room temperature, the hydrosilylation reaction:
wherein R1 is a phenylketone group, a p-methoxyphenylketone group, a p-methylbenzketone group, a p-halophenylketone group, an acetyl group, a formaldehyde group, a methyl ester group, an ethyl ester group or a cyano group; r2 is phenyl, p-methylphenyl, p-halophenyl, o-halophenyl, p-methoxyphenyl, methyl, tert-butyl, acetyl, p-halophenyl;
2) Filtering the CC@Cu, spin-drying a filtrate solvent after extraction, and separating a product by a thin layer chromatography method to obtain an organosilicon 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-forming agent and a crosslinking agent, crosslinking to form composite microspheres, and dipping in Cu 2+ The relative content of copper in the CC@Cu catalyst obtained in the aqueous solution of (2) is 1.75X10 -3 mol/g, wherein the molar ratio of C=O to the unit body of chitosan in the solution containing aldehyde or ketone is 8-12: 1, a step of;
the preparation method of the CC@Cu comprises the following steps:
1) Adding cellulose particles into the chitosan solution until the cellulose particles are uniformly stirred, wherein the mass ratio of cellulose to chitosan is 400mg:1.5g, the prepared mixed solution is slowly dripped into sodium hydroxide solution by a syringe to form transparent microspheres;
2) The microbeads are recovered through filtration, distilled water and ethanol are used for fully washing, the microbeads are added into a solution containing ethanol and aldehyde or ketone, and the solution is stirred for 12 hours at 50 ℃, so that crosslinking is carried out, wherein the molar ratio of C=O and chitosan unit bodies in the solution containing aldehyde or ketone is 8-12: 1, a step of;
3) Filtering out the yellow-brown composite microbeads after crosslinking, washing with water and ethanol, and drying at room temperature;
4) Soaking and suspending the dried microspheres in water at 50 ℃ for 1 hour; adding Cu again 2+ Slowly stirring the aqueous solution of (2) for 12h to adsorb copper ions;
5) separation of loaded Cu by filtration 2+ Washing with water and ethanol to remove free copper ions and anions, and finally oven drying the CC@Cu at 50 ℃ for 12 hours to obtain the CC@Cu catalytic material.
2. Use according to claim 1, characterized in that the α, β -unsaturated carbonyl compound I is chalcone.
3. The use according to claim 1, characterized in that in step 2): and filtering the CC@Cu, fully washing with water and ethanol for 3 times, and then drying for repeated use.
4. Use according to claim 1, characterized in that the molar ratio of c=o and chitosan units in the aldehyde or ketone containing solution is 8:1.
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