CN117586468A - (R) -BNBA-TP-COF polymer and preparation method and application thereof - Google Patents

(R) -BNBA-TP-COF polymer and preparation method and application thereof Download PDF

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CN117586468A
CN117586468A CN202311589322.XA CN202311589322A CN117586468A CN 117586468 A CN117586468 A CN 117586468A CN 202311589322 A CN202311589322 A CN 202311589322A CN 117586468 A CN117586468 A CN 117586468A
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bnba
compound
reaction
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蒋海坪
姚子辉
谭竣峰
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Shandong Normal University
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G12/00—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen
    • C08G12/02—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes
    • C08G12/04—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with acyclic or carbocyclic compounds
    • C08G12/06—Amines
    • C08G12/08—Amines aromatic
    • 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
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/36—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring increasing the number of carbon atoms by reactions with formation of hydroxy groups, which may occur via intermediates being derivatives of hydroxy, e.g. O-metal
    • C07C29/38—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring increasing the number of carbon atoms by reactions with formation of hydroxy groups, which may occur via intermediates being derivatives of hydroxy, e.g. O-metal by reaction with aldehydes or ketones
    • C07C29/42—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring increasing the number of carbon atoms by reactions with formation of hydroxy groups, which may occur via intermediates being derivatives of hydroxy, e.g. O-metal by reaction with aldehydes or ketones with compounds containing triple carbon-to-carbon bonds, e.g. with metal-alkynes
    • 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
    • B01J2231/34—Other additions, e.g. Monsanto-type carbonylations, addition to 1,2-C=X or 1,2-C-X triplebonds, additions to 1,4-C=C-C=X or 1,4-C=-C-X triple bonds with X, e.g. O, S, NH/N
    • B01J2231/341—1,2-additions, e.g. aldol or Knoevenagel condensations
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
    • C07B2200/00—Indexing scheme relating to specific properties of organic compounds
    • C07B2200/07—Optical isomers

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Abstract

The invention relates to a porous organic polymer material, in particular to a two-dimensional chiral (R) -BNBA-TP-COF polymer, a preparation method thereof and application thereof as a chiral catalyst in catalytic synthesis of propargyl alcohol. The structural formula of the (R) -BNBA-TP-COF polymer is shown as the formula (I):the (R) -BNBA-TP-COF polymer provided by the invention is used as a catalyst for catalyzing asymmetric addition reaction of phenylacetylene and benzaldehyde, has high catalytic activity and enantioselectivity, can be recycled, and can still keep high catalytic activity and enantiomer for a plurality of timesSelectivity.

Description

(R) -BNBA-TP-COF polymer and preparation method and application thereof
Technical Field
The invention relates to a porous organic polymer material, in particular to a two-dimensional chiral (R) -BNBA-TP-COF polymer, a preparation method thereof and application thereof as a chiral catalyst in catalytic synthesis of propargyl alcohol.
Background
The disclosure of this background section is only intended to increase the understanding of the general background of the invention and is not necessarily to be construed as an admission or any form of suggestion that this information forms the prior art already known to those of ordinary skill in the art.
Propiolic alcohol with optical activity is a precursor for synthesizing a plurality of chiral compounds, and is widely applied to synthesis of natural products, medicines and complex macromolecular compounds on one hand; on the other hand, the two flexible and changeable functional groups of alkynyl and hydroxyl can be converted through the functional groups, so that the functional groups have great potential application value in the aspect of molecular diversity.
The propargyl alcohol can be prepared through the addition reaction of terminal alkyne to aldehyde or ketone, the prior art reports that 1,1' -Binaphthol (BINOL) can catalyze asymmetric addition of phenylacetylene and benzaldehyde to generate the propargyl alcohol, but BINOL serving as a homogeneous catalyst has the defects of difficult separation, unsustainable utilization, low production efficiency and the like, and in contrast, the heterogeneous chiral catalyst has the advantage of recycling, and has wide development prospect, so that the heterogeneous chiral catalyst for catalyzing and synthesizing the propargyl alcohol has important significance.
Disclosure of Invention
In order to overcome the problems, the invention provides a two-dimensional chiral (R) -BNBA-TP-COF polymer, a preparation method thereof and application thereof as a chiral catalyst in catalytic synthesis of propargyl alcohol.
In order to achieve the technical purpose, the invention adopts the following technical scheme:
in a first aspect of the invention, there is provided an (R) -BNBA-TP-COF polymer having the structural formula shown in formula (I):
in a second aspect of the present invention, there is provided a process for preparing the above (R) -BNBA-TP-COF polymer, comprising the steps of:
adding ligand TP and (R) -BINOLDH-DA into a mixed solution of ethanol and mesitylene, dropwise adding a catalyst acetic acid solution, uniformly mixing, putting the mixed solution into a liquid nitrogen bath, freezing, thawing, circularly degassing for 3 times, sealing, and performing solvothermal reaction to obtain (R) -BNBA-TP-COF polymer;
in a third aspect of the invention, there is provided the use of the (R) -BNBA-TP-COF polymer as described above as a catalyst.
The invention has the beneficial effects that:
(1) The (R) -BNBA-TP-COF polymer provided by the invention has high crystallinity, large porosity and good chemical stability.
(2) The invention provides (R) -BNBA-TP-COF polymer and tetraisopropyl titanate (Ti (OiPr) 4 ) The synergistic catalytic system has more efficient catalytic activity and enantioselectivity, can be reused, and can still keep higher catalytic activity and enantioselectivity for a plurality of times. This is due to the hydroxyl groups on the (R) -BNBA-TP-COF polymer and Ti (OiPr) 4 The method is effectively combined, so that the method is used as Lewis acid to catalyze asymmetric addition reaction of phenylacetylene and benzaldehyde, phenylacetylene and diethyl zinc generate alkynyl zinc, and under the catalysis of a ligand, the steric hindrance is influenced, so that the probability of attacking the alkynyl zinc from one side of aldehyde is increased, and a single-configuration propargyl alcohol product is obtained. The specific mechanism is shown in the following formula:
(3) The invention uses the polymer (R) -BNBA-TP-COF as the catalyst of propargyl alcohol, has low price, high yield and purity, is easy to separate, avoids resolution and racemization in a synthetic route, does not use special and toxic harmful reagents in the experimental process, and has mild reaction conditions.
Drawings
The accompanying drawings, which are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description serve to explain the invention.
FIG. 1 is a scanning electron microscope image of (R) -BNBA-TP-COF prepared in example 2;
FIG. 2 is a thermogram of (R) -BNBA-TP-COF prepared in example 2;
FIG. 3 is a PXRD pattern of (R) -BNBA-TP-COF prepared in example 2;
FIG. 4 is a solid nuclear magnetic resonance spectrum of (R) -BNBA-TP-COF prepared in example 2;
FIG. 5 is a diagram of N of (R) -BNBA-TP-COF prepared in example 2 2 Sucking the attached drawings;
FIG. 6 shows the (R) -BNBA-TP-COF polymer and Ti (OiPr) in Experimental example 1 4 A liquid phase diagram of the synergistic catalysis;
FIG. 7 shows the (R) -BNBA-TP-COF polymer and Ti (OiPr) in Experimental example 1 4 A synergistic catalyzed nuclear magnetic pattern;
FIG. 8 shows the (R) -BNBA-TP-COF polymer and Ti (OiPr) in Experimental example 1 4 PXRD pattern after 5 synergistic catalysis.
Detailed Description
It should be noted that the following detailed description is exemplary and is intended to provide further explanation of the invention. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs.
It is noted that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of exemplary embodiments according to the present invention. As used herein, the singular is also intended to include the plural unless the context clearly indicates otherwise, and furthermore, it is to be understood that the terms "comprises" and/or "comprising" when used in this specification are taken to specify the presence of stated features, steps, operations, devices, components, and/or combinations thereof.
In a first exemplary embodiment of the present invention, there is provided an (R) -BNBA-TP-COF polymer having a structural formula shown in formula (I):
in a second exemplary embodiment of the present invention, there is provided a method for preparing the above (R) -BNBA-TP-COF polymer, comprising the steps of:
adding ligand TP and (R) -BINOLDH-DA into a mixed solution of ethanol and mesitylene, dropwise adding a catalyst acetic acid solution, uniformly mixing, putting the mixed solution into a liquid nitrogen bath, freezing, thawing, circularly degassing for 3 times, sealing, and performing solvothermal reaction to obtain (R) -BNBA-TP-COF polymer;
in one or more embodiments, the molar ratio of ligand TP to (R) -BINOLDH-DA is from 2:2 to 4, preferably 2:3.
In one or more embodiments, the volume ratio of ethanol to mesitylene is from 2 to 4:1, preferably 3:1.
In one or more embodiments, the concentration of the ligand (R) -BINOLDH-DA in the mixed solution of ethanol and mesitylene is 0.01 to 0.02mol/L, preferably 0.015mol/L.
In one or more embodiments, the solvothermal temperature is 110 to 130 ℃, preferably 120 ℃; the time of solvothermal is 70 to 75 hours, preferably 72 hours.
In one or more embodiments, the method of preparing the ligand (R) -binolldh-DA comprises the steps of:
(1) Dissolving the compound 1 in dichloromethane, placing the whole reaction system in ice-water bath, slowly adding dropwise bromine under stirring, reacting for 20-25 h, and adding Na 2 S 2 O 3 The water solution of (2) is quenched to obtain a compound 2 after the reaction is finished;
(2) Compound 2, anhydrous K 2 CO 3 Adding bromoethane into acetone, heating and refluxing for reaction for 45-50 h, cooling to room temperature after the reaction is finished, filtering to obtain filtrate, and performing rotary evaporation and vacuum drying to obtain a compound 3;
(3) Adding the compound 3 and cuprous chloride into N, N-Dimethylformamide (DMF) in an inert gas atmosphere, refluxing for 45-50 h at 100-130 ℃, filtering while the reaction is finished, pouring filtrate into water, filtering again to obtain a crude compound 4, and purifying by column chromatography to obtain the compound 4;
(4) Dissolving the compound 4 in dichloromethane, placing the whole reaction system in ice-water bath, slowly adding dropwise bromine under stirring, reacting for 20-25 h, and adding Na 2 S 2 O 3 The water solution of (2) is quenched to obtain a compound 5 after the reaction is finished;
(5) Under inert gas atmosphere, 5, 4-formylphenylboronic acid, anhydrous K 2 CO 3 And catalyst Pd [ P (Ph) 3 ] 4 Adding the mixture of tetrahydrofuran and water into the mixture, carrying out reflux reaction for 35-40 h at 75-85 ℃, separating the mixture while the mixture is hot after the reaction is finished, taking an upper organic layer, extracting a water phase by using dichloromethane, combining the water phase with the organic phase, and purifying the mixture by using column chromatography after rotary evaporation to obtain a compound 6;
(6) Dissolving boron tribromide in dichloromethane, and marking as a mixed solution A; compound 6 was dissolved in dichloromethane and noted as mixed solution B; slowly dripping the mixed solution B into the mixed solution A under the stirring condition, reacting for 20-30 hours at room temperature, putting the reaction system into an ice-water bath after the reaction is finished, dripping water to quench the reaction, adding dichloromethane into the reaction system, separating liquid to obtain an organic phase, extracting the aqueous phase with ethyl acetate, merging the organic layers, performing rotary evaporation and vacuum drying to obtain a ligand (R) -BINOLDH-DA;
preferably, the molar ratio of compound 1 to liquid bromine in step (1) is from 10:24 to 26, preferably 10:25.2.
Preferably, compound 2, anhydrous K in step (2) 2 CO 3 The molar ratio of bromoethane is 1:3-5:5-7, preferably 1:4:6.
Preferably, the molar ratio of compound 3 to cuprous chloride in step (3) is 1:2 to 2.5, preferably 1:2.2.
Preferably, the molar ratio of compound 4 to liquid bromine in step (4) is from 1:20 to 25, preferably 1:24.
Preferably, in step (5), compound 5, 4-formylphenylboronic acid, anhydrous K 2 CO 3 And catalyst Pd [ P (Ph) 3 ] 4 The molar ratio of (2) is 1:1.5-2.5:5-7:0.05-0.07, preferably 1:2:6:0.06.
Preferably, the molar ratio of boron tribromide to compound 6 in step (6) is from 5 to 7:1, preferably 6:1.
In a third exemplary embodiment of the present invention, there is provided the use of the (R) -BNBA-TP-COF polymer as described above as a catalyst.
In one or more embodiments, the use includes catalyzing the asymmetric addition of phenylacetylene to benzaldehyde to produce 1, 3-diphenylprop-2-en-1-ol.
In one or more embodiments, the use includes the (R) -BNBA-TP-COF polymer described above with tetraisopropyl titanate (Ti (OiPr) 4 ) Synergistic catalysis of asymmetric addition of phenylacetylene to benzaldehyde to produce 1, 3-diphenylprop-2-en-1-ol.
Preferably, the (R) -BNBA-TP-COF polymer is blended with Ti (OiPr) 4 The preparation method of the synergistic catalytic system comprises the following steps: dissolving (R) -BNBA-TP-COF polymer in mixed solution of dichloromethane and toluene, adding Ti (OiPr) 4 Stirring for 1.5-2.5 h at normal temperature, and centrifuging to obtain (R) -BNBA-TP-COF polymer and Ti (OiPr) 4 A synergistic catalytic system.
Further preferably, the (R) -BNBA-TP-COF polymer is blended with Ti (OiPr) 4 The molar ratio of (2) is 1:4-6, preferably 1:5.
In order to enable those skilled in the art to more clearly understand the technical scheme of the present invention, the technical scheme of the present invention will be described in detail with reference to specific embodiments.
Example 1
Preparation of ligand (R) -BINOLDH-DA, see formula:
(1) Compound 1 (10.0 mmol,2.86 g) was weighed into a 100mL three-necked flask, and addedDichloromethane (20 mL) was added, cooled to 0deg.C, bromine (25.2 mmol,4.00 g) was slowly added dropwise with stirring, and after 24h reaction at 0deg.C, na was added 2 S 2 O 3 The reaction was quenched with (7.4 mmol,1.20 g) of water and stirring was continued for 2h. After the reaction was completed, the reaction solution was changed from orange to pale yellow. The reaction solution was filtered, the filtrate was transferred to a separatory funnel, the organic phase was washed three times with saturated NaCl solution, and the organic phases were combined, evaporated in vacuo to give compound 2 as a pale yellow solid.
(2) Compound 2 (10.0 mmol,4.44 g), anhydrous K, was weighed out 2 CO 3 (40.0 mmol,5.50 g) and bromoethane (60.0 mmol,7.00 g) were placed in a 100mL two-necked flask, and acetone (40 mL) was added thereto and heated under reflux for 48h. After the reaction, cooling to room temperature, filtering to obtain filtrate, rotary evaporating and vacuum drying to obtain yellow solid compound 3.
(3)N 2 Compound 3 (10.0 mmol,4.97 g) and cuprous chloride (22.0 mmol,2.20 g) were placed in a 100mL three-necked flask under protection, DMF (15 mL) was added and the mixture was refluxed at 110℃for 48h. After the reaction was completed, the mixture was filtered while it was still hot, and the filtrate was poured into water (300 mL) and filtered again to obtain a pale yellow solid. The crude product was subjected to column chromatography (eluent dichloromethane), rotary evaporation and vacuum drying to give compound 4 as a yellow solid.
(4) Compound 4 (1.0 mmol,0.41 g) was weighed into a 100mL three-necked flask, methylene chloride (30 mL) was added, cooled to 0℃and bromine (24.0 mmol,1.25 mL) was slowly added dropwise with stirring, reacted at 0℃for 24h, and then Na was added 2 S 2 O 3 The reaction was quenched with (7.4 mmol,1.20 g) of water and stirring was continued for 2h. The organic phase was separated, washed three times with saturated NaCl solution, combined with the organic phase, rotary distilled and dried in vacuo to give compound 5 as a yellow solid.
(5) Under nitrogen, compound 5 (1.0 mmol,0.57 g), 4-formylphenylboronic acid (2.0 mmol,0.36 g), anhydrous K were weighed out 2 CO 3 (6.0mmol，0.82g)、Pd[P(Ph) 3 ] 4 (0.06 mmol,0.08 g) was placed in a 100mL two-necked flask, and a tetrahydrofuran/water (3:1, total volume: 40 mL) mixed solvent was added thereto and heated at 80℃under reflux for 36h. Separating the solution while the reaction is hot after the reaction is finished, taking an upper organic layer and waterThe layers were extracted three times with dichloromethane (20 mL) and the organic layers were combined and evaporated in vacuo to give an orange solid. The crude product was subjected to column chromatography (eluent dichloromethane: petroleum ether=1:1), rotary evaporation and vacuum drying to give compound 6 as a pale yellow solid.
(6) Boron tribromide (6.0 mmol, 570. Mu.L) was weighed into a 50mL two-necked flask, methylene chloride (10 mL) was added and stirred at room temperature, a solution of compound 6 (1.0 mmol,0.62 mg) in methylene chloride (10 mL) was slowly added dropwise and reacted at room temperature for 24h. After the reaction, the mixture was cooled to 0℃and quenched by dropwise addition of water, followed by stirring for 1 hour. Dichloromethane (20 mL) was added to the reaction system, the organic phase was separated, the aqueous phase was extracted three times with ethyl acetate, the organic layers were combined, rotary distilled and dried under vacuum to give a yellow solid (R) -binolh-DA.
EXAMPLE 2 preparation of (R) -BNBA-TP-COF Polymer
Ligand TP (0.10 mmol,20.00 mg), (R) -BINOLDH-DA (0.15 mmol,80.40 mg) was weighed into a 50mL pressure-resistant tube, a mixed solution of ethanol and mesitylene (the volume ratio of ethanol to mesitylene is 3:1, 10mL total) was added dropwise with a catalyst acetic acid solution (6M, 0.2 mL), and the mixture was stirred for 10min to mix uniformly. Freezing and degassing with liquid nitrogen for three times, sealing, heating at 120deg.C for 72 hr, and cooling to room temperature. The solid was collected by centrifugation, repeatedly washed with dichloromethane and ethanol, and dried under vacuum to give the purplish black product (R) -BNBA-TP-COF.
Characterization of the (R) -BNBA-TP-COF Polymer prepared in this example
The structure of (R) -BNBA-TP-COF was simulated by the Materials Studio (ver.8.0) software, and the result shows that (R) -BNBA-TP-COF is crystallized in chiral space group R 3 The cell parameters after Pawley refinement are as follows by adopting an AB staggered stacking modeThe values of the refinement coefficients Rwp and Rp are 3.44% and 2.57%, respectively, α=β=90°, γ=120°, the unit cell parameters and the atomic coordinates of which are shown in table 1.
Table 1 shows the unit cell parameters and atomic coordinates of (R) -BNBA-TP-COF
FIG. 1 is a scanning electron microscope image of (R) -BNBA-TP-COF polymer, FIG. 2 is a thermogravimetric image of (R) -BNBA-TP-COF polymer, FIG. 3 is a PXRD image of (R) -BNBA-TP-COF polymer, FIG. 4 is a solid core magnetism of (R) -BNBA-TP-COF polymer, FIG. 5 is a BET N of (R) -BNBA-TP-COF polymer 2 The image is adsorbed. It can be seen from FIGS. 1 and 5 that the (R) -BNBA-TP-COF polymer prepared in this example has a porous structure. It can be seen from FIGS. 2 to 4 that the (R) -BNBA-TP-COF polymer is a crystalline porous material having high thermal stability.
Experimental example 1
Experimental example 2 (R) -BNBA-TP-COF Polymer and Ti (OiPr) 4 Synergistic catalysis of asymmetric addition of phenylacetylene to benzaldehyde to produce 1, 3-diphenylprop-2-en-1-ol.
The equation for the reaction in this experimental example is as follows:
2.1 under the protection of nitrogen, phenylacetylene (0.5 mmol, 51. Mu.L) and Et were measured 2 Zn (1.0 mmol, 102. Mu.L) and 5mL of toluene solvent were placed in a flask, heated at 110℃under reflux for 3h, and cooled to room temperature. The (R) -BNBA-TP-COF polymer (0.05 mmol,96 mg) prepared in example 2 was weighed into a flask, and methylene chloride (4 mL), toluene (1 mL) and Ti (OiPr) were added to the flask 4 (0.25 mmol, 74. Mu.L) and stirred at ambient temperature for 2h; centrifuging after stirring, and placing the centrifuged COF in phenylacetylene and Et 2 To the Zn-reacted system, benzaldehyde (0.5 mmol, 53. Mu.L) was then added and reacted at room temperature for 36 hours to obtain a product. The catalytic reaction yield was isolated and the ee value of the product was determined by HPLC analysis (OD-H chiral column, n-hexane: isopropanol=95:5, flow rate 0.4mL/min, uv wavelength 254 nm) and the results are shown in fig. 6 (liquid phase diagram), fig. 7 (nuclear magnetic diagram), fig. 6 and fig. 7, respectively, demonstrating the formation of propargyl alcohol.
2.2 (R) -BNBA-TP-COF Polymer with Ti (OiPr) 4 Cycle times of the synergistic catalytic synthesis of propynyl alcohol.
The catalyst is directly put into the next circulation reaction after the reaction is finished by tracking the reaction through a dot plate, 5 circulations are used for the catalyst according to the conditions, the yield of the reaction liquid is calculated by separation (propionaldehyde is an internal standard), the ee value of a reaction product is determined by liquid chromatography analysis, the catalytic effect is shown in a table 3, the yield and the ee value of the product are basically consistent after the catalyst is circulated twice as shown in the table 3, only a slight reduction trend is shown after five circulations, the excellent stability of the catalyst is shown, the catalyst can be recycled for more than five times, the utilization rate of the catalyst can be remarkably improved, and the production cost is reduced.
After the five-cycle reaction is completed, the solution is centrifuged, the obtained catalyst is washed three times by ethanol, and is characterized by PXRD after vacuum drying at 90 ℃, as shown in figure 8, the (R) -BNBA-TP-COF still keeps the original framework, further the stability of the catalyst is verified, and the original structural framework can be maintained after multiple-cycle catalysis.
Table 3 2 (R) -BNBA-TP-COF Polymer with Ti (OiPr) 4 Yields and stereoselectivity for 5 cycles of the synergistic catalytic reaction
The above description is only of the preferred embodiments of the present invention and is not intended to limit the present invention, but various modifications and variations can be made to the present invention by those skilled in the art. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims (10)

1. The (R) -BNBA-TP-COF polymer is characterized in that the structural formula is shown as the formula (I):
2. the method for preparing the (R) -BNBA-TP-COF polymer according to claim 1, comprising the following steps:
adding ligand TP and (R) -BINOLDH-DA into a mixed solution of ethanol and mesitylene, dropwise adding a catalyst acetic acid solution, uniformly mixing, putting the mixed solution into a liquid nitrogen bath, freezing, thawing, circularly degassing for 3 times, sealing, and performing solvothermal reaction to obtain (R) -BNBA-TP-COF polymer;
3. process for the preparation of (R) -BNBA-TP-COF polymers according to claim 2, characterized in that the molar ratio of ligand TP to (R) -binolh-DA is 2:2 to 4, preferably 2:3;
or the volume ratio of the ethanol to the mesitylene is 2-4:1, preferably 3:1;
or, the concentration of the ligand (R) -BINOLDH-DA in the mixed solution of ethanol and mesitylene is 0.01-0.02 mol/L, preferably 0.015mol/L.
4. The process for the preparation of (R) -BNBA-TP-COF polymers according to claim 2, characterized in that the solvothermal temperature is 110-130 ℃, preferably 120 ℃; the time of solvothermal is 70 to 75 hours, preferably 72 hours.
5. The method for preparing the (R) -BNBA-TP-COF polymer according to claim 2, wherein the method for preparing the ligand (R) -binolh-DA comprises the steps of:
(1) Dissolving the compound 1 in dichloromethane, placing the whole reaction system in ice-water bath, slowly adding dropwise bromine under stirring, reacting for 20-25 h, and adding Na 2 S 2 O 3 The water solution of (2) is quenched to obtain a compound 2 after the reaction is finished;
(2) Compound 2, anhydrous K 2 CO 3 Adding bromoethane into acetone, addingCarrying out thermal reflux reaction for 45-50 h, cooling to room temperature after the reaction is finished, filtering to obtain filtrate, rotary steaming and vacuum drying to obtain a compound 3;
(3) Adding the compound 3 and cuprous chloride into N, N-Dimethylformamide (DMF) in an inert gas atmosphere, refluxing for 45-50 h at 100-130 ℃, filtering while the reaction is finished, pouring filtrate into water, filtering again to obtain a crude compound 4, and purifying by column chromatography to obtain the compound 4;
(4) Dissolving the compound 4 in dichloromethane, placing the whole reaction system in ice-water bath, slowly adding dropwise bromine under stirring, reacting for 20-25 h, and adding Na 2 S 2 O 3 The water solution of (2) is quenched to obtain a compound 5 after the reaction is finished;
(5) Under inert gas atmosphere, 5, 4-formylphenylboronic acid, anhydrous K 2 CO 3 And catalyst Pd [ P (Ph) 3 ] 4 Adding the mixture of tetrahydrofuran and water into the mixture, carrying out reflux reaction for 35-40 h at 75-85 ℃, separating the mixture while the mixture is hot after the reaction is finished, taking an upper organic layer, extracting a water phase by using dichloromethane, combining the water phase with the organic phase, and purifying the mixture by using column chromatography after rotary evaporation to obtain a compound 6;
(6) Dissolving boron tribromide in dichloromethane, and marking as a mixed solution A; compound 6 was dissolved in dichloromethane and noted as mixed solution B; slowly dripping the mixed solution B into the mixed solution A under the stirring condition, reacting for 20-30 hours at room temperature, putting the reaction system into an ice-water bath after the reaction is finished, dripping water to quench the reaction, adding dichloromethane into the reaction system, separating liquid to obtain an organic phase, extracting the aqueous phase with ethyl acetate, merging the organic layers, performing rotary evaporation and vacuum drying to obtain a ligand (R) -BINOLDH-DA;
6. the process for the preparation of (R) -BNBA-TP-COF polymers according to claim 5, characterized in that in step (1) the molar ratio of compound 1 to liquid bromine is 10:24-26, preferably 10:25.2;
or, in step (2), compound 2, anhydrous K 2 CO 3 The molar ratio of bromoethane is 1:3-5:5-7, preferably 1:4:6;
or, in the step (3), the molar ratio of the compound 3 to the cuprous chloride is 1:2-2.5, preferably 1:2.2;
or, in the step (4), the molar ratio of the compound 4 to the liquid bromine is 1:20-25, preferably 1:24;
or, in step (5), compound 5, 4-formylphenylboronic acid, anhydrous K 2 CO 3 And catalyst Pd [ P (Ph) 3 ] 4 The molar ratio of (2) is 1:1.5-2.5:5-7:0.05-0.07, preferably 1:2:6:0.06;
or, in the step (6), the molar ratio of the boron tribromide to the compound 6 is 5-7:1, preferably 6:1.
7. Use of the (R) -BNBA-TP-COF polymer of claim 1 as a catalyst.
8. The use according to claim 7, wherein said use comprises the above (R) -BNBA-TP-COF polymer and Ti (OiPr) 4 Synergistic catalysis of asymmetric addition of phenylacetylene to benzaldehyde to produce 1, 3-diphenylprop-2-en-1-ol.
9. The use according to claim 8, wherein the (R) -BNBA-TP-COF polymer is combined with Ti (OiPr) 4 The preparation method of the synergistic catalytic system comprises the following steps: dissolving (R) -BNBA-TP-COF polymer in mixed solution of dichloromethane and toluene, adding Ti (OiPr) 4 Stirring for 1.5-2.5 h at normal temperature, and centrifuging to obtain (R) -BNBA-TP-COF polymer and Ti (OiPr) 4 A synergistic catalytic system.
10. The use according to claim 9, wherein the (R) -BNBA-TP-COF polymer is blended with Ti (OiPr) 4 The molar ratio of (2) is 1:4-6, preferably 1:5.
CN202311589322.XA 2023-11-24 2023-11-24 (R) -BNBA-TP-COF polymer and preparation method and application thereof Pending CN117586468A (en)

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