CN117603420A - (R) -TPBBP-COF catalyst and preparation method and application thereof - Google Patents
(R) -TPBBP-COF catalyst and preparation method and application thereof Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 58
- 238000002360 preparation method Methods 0.000 title claims abstract description 31
- 238000006243 chemical reaction Methods 0.000 claims abstract description 80
- 239000007787 solid Substances 0.000 claims abstract description 44
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 24
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims abstract description 22
- 238000000034 method Methods 0.000 claims abstract description 20
- 239000011259 mixed solution Substances 0.000 claims abstract description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000007788 liquid Substances 0.000 claims abstract description 9
- AUHZEENZYGFFBQ-UHFFFAOYSA-N mesitylene Substances CC1=CC(C)=CC(C)=C1 AUHZEENZYGFFBQ-UHFFFAOYSA-N 0.000 claims abstract description 7
- 125000001827 mesitylenyl group Chemical group [H]C1=C(C(*)=C(C([H])=C1C([H])([H])[H])C([H])([H])[H])C([H])([H])[H] 0.000 claims abstract description 7
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 5
- 238000002156 mixing Methods 0.000 claims abstract description 4
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 105
- 239000012074 organic phase Substances 0.000 claims description 23
- 238000001816 cooling Methods 0.000 claims description 22
- 239000000243 solution Substances 0.000 claims description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 21
- 238000010992 reflux Methods 0.000 claims description 19
- 239000012043 crude product Substances 0.000 claims description 18
- 238000002390 rotary evaporation Methods 0.000 claims description 18
- 238000001291 vacuum drying Methods 0.000 claims description 18
- 238000004440 column chromatography Methods 0.000 claims description 17
- 238000003756 stirring Methods 0.000 claims description 17
- 239000012044 organic layer Substances 0.000 claims description 16
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 15
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 14
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 14
- 238000010438 heat treatment Methods 0.000 claims description 13
- 238000005303 weighing Methods 0.000 claims description 13
- ILAHWRKJUDSMFH-UHFFFAOYSA-N boron tribromide Chemical compound BrB(Br)Br ILAHWRKJUDSMFH-UHFFFAOYSA-N 0.000 claims description 12
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 12
- 239000003480 eluent Substances 0.000 claims description 11
- 239000000047 product Substances 0.000 claims description 11
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 10
- 238000001914 filtration Methods 0.000 claims description 10
- 239000000706 filtrate Substances 0.000 claims description 9
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 8
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 8
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 8
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 8
- 229910052794 bromium Inorganic materials 0.000 claims description 8
- PPTXVXKCQZKFBN-UHFFFAOYSA-N (S)-(-)-1,1'-Bi-2-naphthol Chemical compound C1=CC=C2C(C3=C4C=CC=CC4=CC=C3O)=C(O)C=CC2=C1 PPTXVXKCQZKFBN-UHFFFAOYSA-N 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 7
- 239000003208 petroleum Substances 0.000 claims description 7
- 229910021591 Copper(I) chloride Inorganic materials 0.000 claims description 6
- RDHPKYGYEGBMSE-UHFFFAOYSA-N bromoethane Chemical compound CCBr RDHPKYGYEGBMSE-UHFFFAOYSA-N 0.000 claims description 6
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 claims description 6
- 229940045803 cuprous chloride Drugs 0.000 claims description 6
- RLOWWWKZYUNIDI-UHFFFAOYSA-N phosphinic chloride Chemical compound ClP=O RLOWWWKZYUNIDI-UHFFFAOYSA-N 0.000 claims description 6
- 239000012295 chemical reaction liquid Substances 0.000 claims description 5
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 5
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- VXWBQOJISHAKKM-UHFFFAOYSA-N (4-formylphenyl)boronic acid Chemical compound OB(O)C1=CC=C(C=O)C=C1 VXWBQOJISHAKKM-UHFFFAOYSA-N 0.000 claims description 4
- 239000008346 aqueous phase Substances 0.000 claims description 4
- 238000007872 degassing Methods 0.000 claims description 4
- 238000007710 freezing Methods 0.000 claims description 4
- 230000008014 freezing Effects 0.000 claims description 4
- 239000010410 layer Substances 0.000 claims description 4
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 4
- 238000010791 quenching Methods 0.000 claims description 4
- 230000000171 quenching effect Effects 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 3
- 230000020477 pH reduction Effects 0.000 claims description 3
- 239000000843 powder Substances 0.000 claims description 3
- 239000002994 raw material Substances 0.000 claims description 3
- 238000010025 steaming Methods 0.000 claims description 3
- UIGXGNUMMVHJKX-UHFFFAOYSA-N (4-formylphenoxy)boronic acid Chemical compound OB(O)OC1=CC=C(C=O)C=C1 UIGXGNUMMVHJKX-UHFFFAOYSA-N 0.000 claims description 2
- XVMSFILGAMDHEY-UHFFFAOYSA-N 6-(4-aminophenyl)sulfonylpyridin-3-amine Chemical compound C1=CC(N)=CC=C1S(=O)(=O)C1=CC=C(N)C=N1 XVMSFILGAMDHEY-UHFFFAOYSA-N 0.000 claims description 2
- 230000015572 biosynthetic process Effects 0.000 claims description 2
- 238000003786 synthesis reaction Methods 0.000 claims 1
- 238000006555 catalytic reaction Methods 0.000 abstract description 11
- LXCYSACZTOKNNS-UHFFFAOYSA-N diethoxy(oxo)phosphanium Chemical compound CCO[P+](=O)OCC LXCYSACZTOKNNS-UHFFFAOYSA-N 0.000 abstract description 5
- 230000003197 catalytic effect Effects 0.000 abstract description 4
- 150000001412 amines Chemical class 0.000 abstract description 3
- 238000007210 heterogeneous catalysis Methods 0.000 abstract description 3
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 abstract 1
- 239000013310 covalent-organic framework Substances 0.000 description 42
- 238000007036 catalytic synthesis reaction Methods 0.000 description 5
- 230000002194 synthesizing effect Effects 0.000 description 5
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 description 4
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- 230000004087 circulation Effects 0.000 description 3
- 101150021494 cof gene Proteins 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 238000000634 powder X-ray diffraction Methods 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- NBBJYMSMWIIQGU-UHFFFAOYSA-N Propionic aldehyde Chemical compound CCC=O NBBJYMSMWIIQGU-UHFFFAOYSA-N 0.000 description 2
- 150000001299 aldehydes Chemical class 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
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- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- 230000005311 nuclear magnetism Effects 0.000 description 2
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 description 2
- 238000010587 phase diagram Methods 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 238000001144 powder X-ray diffraction data Methods 0.000 description 2
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- 101001018064 Homo sapiens Lysosomal-trafficking regulator Proteins 0.000 description 1
- 102100033472 Lysosomal-trafficking regulator Human genes 0.000 description 1
- 235000010703 Modiola caroliniana Nutrition 0.000 description 1
- 244000038561 Modiola caroliniana Species 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- 108091005461 Nucleic proteins Proteins 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
- XCSGPAVHZFQHGE-UHFFFAOYSA-N alachlor Chemical compound CCC1=CC=CC(CC)=C1N(COC)C(=O)CCl XCSGPAVHZFQHGE-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
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- ZTQSAGDEMFDKMZ-UHFFFAOYSA-N butyric aldehyde Natural products CCCC=O ZTQSAGDEMFDKMZ-UHFFFAOYSA-N 0.000 description 1
- 150000001720 carbohydrates Chemical class 0.000 description 1
- 235000014633 carbohydrates Nutrition 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
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- 238000004128 high performance liquid chromatography Methods 0.000 description 1
- 238000007172 homogeneous catalysis Methods 0.000 description 1
- 239000002815 homogeneous catalyst Substances 0.000 description 1
- 150000002466 imines Chemical class 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
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- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 1
- DCWXELXMIBXGTH-UHFFFAOYSA-N phosphotyrosine Chemical compound OC(=O)C(N)CC1=CC=C(OP(O)(O)=O)C=C1 DCWXELXMIBXGTH-UHFFFAOYSA-N 0.000 description 1
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses an (R) -TPBBP-COF catalyst, a preparation method and application thereof, and belongs to the technical field of COF catalysts. The invention adds the prepared (R) -BINOLPA-DA and TAPB into the mixed solution of ethanol, mesitylene and dilute acetic acid, and after ultrasonic mixing, uses liquid nitrogen to freeze and degas, after reaction, centrifugally collects solid, washes and dries in vacuum to obtain the (R) -TPBBP-COF catalyst. The (R) -TPBBP-COF prepared by the method has good asymmetric catalytic property, and can effectively catalyze asymmetric reactions of aldehyde, amine and diethyl phosphite to obtain chiral alpha-aminophosphonate by using the (R) -TPBBP-COF as a catalyst, and the yield and the stereoselectivity of the catalytic reaction are high, thus heterogeneous catalysis is realized, and the catalyst can be repeatedly used for more than five times, so that the catalyst is easy to recycle, the utilization rate of the catalyst is improved, and the cost is reduced.
Description
Technical Field
The invention belongs to the technical field of COF catalysts, and particularly relates to an (R) -TPBBP-COF catalyst, and a preparation method and application thereof.
Background
Chirality is a fundamental feature of nature, and most of important biomolecules such as nucleic acids, proteins, and carbohydrates involved in vital activities are chiral. In recent years, the demand for chiral compounds such as chiral medicines and chiral pesticides has been increasing, and the development of asymmetric synthesis has been greatly promoted. Currently, great progress has been made in the field of asymmetric catalytic synthesis, in which thousands of chiral ligand molecules and chiral catalysts have been synthesized and reported, and asymmetric catalytic synthesis has been applied to almost all types of organic reactions and has begun to become an important method for synthesizing chiral substances industrially, particularly in the pharmaceutical industry.
Chiral alpha-aminophosphonates have important applications in modern pharmaceutical chemistry as antibiotics and antibacterial drugs, such as alachlor and phosphotyrosine. At present, chiral phosphoric acid catalyzes the selective addition reaction of phosphite and imine to be one of the most direct strategies for preparing optically active alpha-aminophosphonate. Therefore, the chiral COFs containing phosphoric acid is used for catalyzing and synthesizing the alpha-amino phosphonate ester with high feasibility.
At present, homogeneous catalysis is the main stream of asymmetric catalysis for synthesizing alpha-aminophosphonate, but the homogeneous catalyst has the problems of difficult separation, difficult recycling and the like, and in contrast, the heterogeneous chiral catalyst has the advantage of repeated utilization, meets the requirement of sustainable development and has wide development prospect, so the invention provides the (R) -TPBBP-COF catalyst and the preparation method and application thereof.
Disclosure of Invention
The invention aims to provide an (R) -TPBBP-COF catalyst, a preparation method and application thereof, and the prepared catalyst is applied to catalytic synthesis of alpha-aminophosphonate, has good catalytic efficiency, can be repeatedly used for many times, and has wide application prospect.
In order to achieve the above purpose, the invention provides an (R) -TPBBP-COF catalyst, wherein the structural formula of the (R) -TP BBP-COF catalyst is as follows:
the (R) -TPBBP-COF catalyst takes TAPB and (R) -BINOLPA-DA as reaction raw materials, and the structural formulas of the TAPB and the (R) -BINOLPA-DA are respectively as follows:
the invention also provides a preparation method of the (R) -TPBBP-COF catalyst, which comprises the steps of adding TAPB and (R) -BINOLPA-DA into a mixed solution of ethanol, mesitylene and dilute acetic acid, carrying out ultrasonic mixing uniformly, freezing and degassing by liquid nitrogen, reacting for 72 hours at 120 ℃, cooling to room temperature after the reaction is finished, standing for 48 hours, centrifuging to collect solids, repeatedly washing by ethanol, and carrying out vacuum drying to obtain purple black powder, namely the (R) -TPBBP-COF catalyst;
wherein, the mol mass ratio of TAPB and (R) -BINOLPA-DA is 1:1.5; the volume ratio of ethanol, mesitylene and dilute acetic acid is 15:5:2.
preferably, the preparation method of the (R) -BINOLPA-DA comprises the following steps: under the protection of nitrogen atmosphere, weighing a proper amount of (R) -BINOLDH-DA, placing into a two-neck flask, adding anhydrous pyridine, refluxing at 100-105deg.C for 12-14h, cooling to 0deg.C, and dripping POCl 3 Heating to 100-105 ℃ for continuous reaction for 45-48h, cooling the reaction system to 0 ℃, adding water, heating and refluxing for 48h at 100 ℃, recovering to room temperature after the reaction is finished, adding hydrochloric acid into the reaction system for acidification, separating liquid, taking an organic phase, extracting for multiple times by using dichloromethane, merging organic layers, performing rotary evaporation to obtain a yellow solid crude product, performing column chromatography on the crude product, performing rotary evaporation and vacuum drying to obtain a pale yellow product (R) -BINOLPA-DA;
wherein, (R) -BINOLDH-DA and POCl 3 And anhydrous pyridine in a mass to volume ratio of 0.56mg:457 μl:20mL; the eluent used in the column chromatography is a mixed solution of dichloromethane and petroleum ether with the volume ratio of 1:1.
Preferably, the preparation method of the (R) -BINOLDH-DA comprises the following steps: adding a proper amount of boron tribromide into dichloromethane, stirring at room temperature for reaction for 22-24 hours, then dropwise adding (R) -BINOLDE-DA for reaction, cooling to 0 ℃ after the reaction is finished, dropwise adding water for quenching reaction, continuously stirring for 1-1.5 hours, finally adding a dichloromethane solution into a reaction system, separating liquid to obtain an organic phase, extracting the aqueous phase with ethyl acetate for multiple times, merging the organic layers, performing rotary evaporation and vacuum drying to obtain yellow solid (R) -BINOLDH-DA;
wherein, the adding ratio of boron tribromide, methylene dichloride and (R) -BINOLDE-DA is 570 mu L:10mL:0.62mg.
Preferably, the preparation method of the (R) -BINOLDE-DA comprises the following steps: under the protection of nitrogen atmosphere, weighing a proper amount of (R) -DCDB, 4-formylphenylboric acid and anhydrous K 2 CO 3 、Pd[P(Ph)3]4 placing the mixture into a two-mouth flask, adding tetrahydrofuran/water mixed solution, heating and refluxing for 36 hours at 80 ℃ to react, separating the solution after the reaction is finished, taking an upper organic layer, extracting a water layer with dichloromethane for a plurality of times, merging the organic layers, performing rotary evaporation to obtain an orange solid crude product, performing column chromatography on the crude product, performing rotary evaporation and vacuum drying to obtain pale yellow solid (R) -BINOLD E-DA;
wherein, (R) -DCDB, 4-formylphenylboronic acid, anhydrous K 2 CO 3 、Pd[P(Ph)3]4 in a molar ratio of 1:2:6:0.06; the eluent used in the column chromatography is a mixed solution of dichloromethane and petroleum ether with the volume ratio of 1:1.
Preferably, the preparation method of the (R) -DCDB comprises the following steps: weighing a proper amount of (R) -DCDE, placing into a three-neck flask, adding dichloromethane, cooling to 0 ℃, slowly adding dropwise bromine under stirring, reacting at 0 ℃ for 24 hours, and adding Na 2 S 2 O 3 The quenching reaction of the aqueous solution of (2) is continued to be stirred for 2 hours, the organic phase is separated and taken out, the organic phase is washed by saturated NaCl solution for a plurality of times, and the yellow solid (R) -DCDB is obtained after the organic phase is combined, rotary evaporated and vacuum dried;
wherein, (R) -DCDE, liquid bromine and Na 2 S 2 O 3 The molar ratio of (2) is 1:24:7.4.
preferably, the preparation method of the (R) -DCDE comprises the following steps: placing (R) -DBDE and cuprous chloride in a three-neck flask under the protection of nitrogen atmosphere, adding DMF, refluxing at 110-120 ℃ for 45-48h for reaction, filtering while the reaction is hot, pouring the filtrate into water, and filtering again to obtain pale yellow solid; performing column chromatography on the crude product by using dichloromethane as an eluent, performing rotary evaporation and vacuum drying to obtain yellow solid (R) -DCDE;
wherein, the addition ratio of (R) -DBDE, cuprous chloride and DMF is 4.97g:2.20g:15mL.
Preferably, the preparation method of the (R) -DBDE comprises the following steps: weighing proper amount of (R) -DB and anhydrous K 2 CO 3 Placing bromoethane into a two-mouth flask, adding acetone, heating and refluxing for 48 hours, cooling to room temperature after the reaction is finished, filtering to obtain filtrate, steaming in a rotary manner and drying in vacuum to obtain yellow solid (R) -DBDE;
wherein, (R) -DB, anhydrous K 2 CO 3 The molar ratio of bromoethane is 1:4:6.
preferably, the preparation method of the (R) -DB comprises the following steps: weighing a proper amount of (R) -1,1' -bi-2-naphthol, placing into a three-neck flask, adding dichloromethane, cooling to 0 ℃, slowly adding dropwise bromine under stirring, reacting at 0 ℃ for 24 hours, and adding Na 2 S 2 O 3 The reaction is quenched and stirred for 2 hours, after the reaction is finished, the reaction liquid is changed from orange to light yellow, the reaction liquid is filtered, the organic phase is washed by saturated NaCl solution and then is combined with the organic phase to be distilled in a rotary way and dried in vacuum, and light yellow solid (R) -DB is obtained;
wherein, (R) -1,1' -bi-2-naphthol, liquid bromine and Na 2 S 2 O 3 The molar ratio of (2) is 10:25.2:7.4.
the invention also provides application of the (R) -TPBBP-COF catalyst in synthesizing chiral alpha-amino phosphonate.
Therefore, the (R) -TPBBP-COF catalyst and the preparation method and application thereof provided by the invention have the following beneficial effects compared with the prior art:
(1) The (R) -TPBBP-COF prepared by the invention can be used as a catalyst to effectively catalyze asymmetric reactions of aldehyde, amine and diethyl phosphite to obtain chiral product alpha-aminophosphonate, and the yield and stereoselectivity of the catalytic reaction are high, heterogeneous catalysis is realized, and the catalyst can be repeatedly used for more than five times, so that the catalyst is easy to recycle, the utilization rate of the catalyst is improved, and the cost is reduced;
(2) The (R) -TPBBP-COF prepared by the method is used as the catalyst of the alpha-aminophosphonate, 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, has mild reaction conditions, and meets the requirements of energy conservation and environmental protection.
The technical scheme of the invention is further described in detail through the drawings and the embodiments.
Drawings
FIG. 1 is a scanning electron microscope image of (R) -TPBBP-COF prepared in example 2 of the present invention;
FIG. 2 is a thermogram of (R) -TPBBP-COF prepared in example 2 of the present invention;
FIG. 3 is a PXRD pattern of (R) -TPBBP-COF prepared in example 2 of the present invention;
FIG. 4 is a solid nuclear magnetic resonance spectrum of (R) -TPBBP-COF prepared in example 2 of the present invention;
FIG. 5 is a sample of N of (R) -TPBBP-COF prepared in example 2 of the present invention 2 Sucking the attached drawings;
FIG. 6 is a PXRD pattern of 5 times of catalysis of (R) -TPBBP-COF prepared in example 2 of the present invention;
FIG. 7 is a liquid phase diagram of the (R) -TPBBP-COF catalysis prepared in example 2 of the present invention;
FIG. 8 is a mass spectrum of the (R) -TPBBP-COF catalysis prepared in example 2 of the present invention;
FIG. 9 is a nuclear magnetic resonance diagram of (R) -TPBBP-COF catalysis prepared in example 2 of the present invention.
Detailed Description
The following description of the present invention will be made clearly and fully, but the embodiments described are only some, but not all, of the embodiments of the present invention. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
The invention provides an (R) -TPBBP-COF catalyst, which has the structural formula:
the invention simulates the structure of (R) -TPBBP-COF by the software of MaterialsStudio (ver.8.0), and the result shows that (R) -TPBBP-COF is crystallized in chiral space group P 3 Adopts AA crossingThe cell parameters after Pawley refinement wereThe values of the refinement coefficients Rwp and Rp are 2.04% and 2.01%, respectively, α=γ=90°, β=120°, and the unit cell parameters and atomic coordinates are shown in table 1.
TABLE 1 unit cell parameters and atomic coordinates of (R) -TPBBP-COF
The invention also provides a preparation method of the (R) -TPBBP-COF catalyst, wherein the (R) -TPBBP-COF catalyst takes TAPB and (R) -BINOLPA-DA as reaction raw materials, and the structural formulas of the TAPB and the (R) -BINOLPA-DA are respectively as follows:
the preparation method comprises the following steps: the molar mass ratio is 1:1.5 TAPB and (R) -BINOLPA-DA added in a volume ratio of 15:5:2, in the mixed solution of ethanol, mesitylene and dilute acetic acid, carrying out ultrasonic treatment for 10min to uniformly mix. Freezing and degassing for three times by using liquid nitrogen, reacting for 72 hours at 120 ℃, collecting solid after the reaction is finished, and washing by using ethanol to obtain the black powder which is the (R) -TPBBP-COF catalyst.
Further, the preparation method of the (R) -BINOLPA-DA comprises the following steps: under the protection of nitrogen atmosphere, 0.56mg of (R) -BINOLDH-DA is weighed, 20mL of anhydrous pyridine is added, reflux is carried out for 12-14h at 100-105 ℃, then the temperature is reduced to 0 ℃, and 457 mu L of POCl is added dropwise 3 Heating to 100-105deg.C, reacting for 45-48 hr, cooling to 0deg.C, adding water, heating at 100deg.C for reflux for 48 hr, recovering to room temperature, adding hydrochloric acid to acidify, separating, and collecting organic phaseExtracting with dichloromethane for three times, mixing organic layers, rotary evaporating to obtain yellow solid crude product, subjecting the crude product to column chromatography, rotary evaporating, and vacuum drying to obtain pale yellow product (R) -BINOLPA-DA.
Further, the preparation method of the (R) -BINOLDH-DA comprises the following steps: taking 570 mu L of boron tribromide, adding 10mL of dichloromethane, stirring at room temperature for reaction for 22-24 hours, then dropwise adding 0.62mg of (R) -BINOLDE-DA for reaction, cooling to 0 ℃ after the reaction is finished, dropwise adding water for quenching reaction, continuously stirring for 1-1.5 hours, finally adding a dichloromethane solution into a reaction system, separating to obtain an organic phase, extracting the aqueous phase with ethyl acetate three times, merging the organic layers, performing rotary evaporation and vacuum drying to obtain yellow solid (R) -BINOLDH-DA.
Further, the preparation method of the (R) -BINOLDE-DA comprises the following steps: under the protection of nitrogen atmosphere, weighing the following components in a molar ratio of 1:2:6:0.06 (R) -DCDB, 4-formylphenylboronic acid, anhydrous K 2 CO 3 、Pd[P(Ph)3]4, placing the mixture into a two-neck flask, adding tetrahydrofuran/water mixed solution, heating and refluxing for 36h at 80 ℃ to perform reaction, separating the solution after the reaction is finished to obtain an upper organic layer, extracting a water layer by using dichloromethane, merging the organic layers, performing rotary evaporation to obtain an orange solid crude product, and performing column chromatography on the crude product, wherein an eluent used by the column chromatography is dichloromethane: petroleum ether = 1:1, rotary evaporation and vacuum drying to give (R) -BINOLDE-DA as a pale yellow solid.
Further, the preparation method of the (R) -DCDB comprises the following steps: taking a molar ratio of 1:24:7.4 (R) -DCDE, liquid bromine, na 2 S 2 O 3 Firstly placing (R) -DCDE in a 100mL three-neck flask, adding dichloromethane, cooling to 0 ℃, slowly adding dropwise bromine under stirring, then reacting at 0 ℃ for 24 hours, and adding Na 2 S 2 O 3 The reaction was quenched with aqueous solution of (2) and stirred for 2h, the organic phase was separated, washed three times with saturated NaCl solution, the organic phases were combined, distilled off in vacuo and dried in vacuo to give (R) -DCDB as a yellow solid.
Further, the preparation method of the (R) -DCDE comprises the following steps: under the protection of nitrogen atmosphere, 4.97g of (R) -DBDE and 2.20g of cuprous chloride are placed in a 100mL three-neck flask, 15mL of DMF is added, reflux is carried out for 45-48h at 110-120 ℃ for reaction, filtration is carried out while the reaction is hot after the reaction is finished, the filtrate is poured into water, and the light yellow solid is obtained by filtration again; column chromatography is carried out on the crude product by using methylene dichloride as an eluent, and yellow solid (R) -DCDE is obtained after rotary evaporation and vacuum drying.
Further, the preparation method of the (R) -DBDE comprises the following steps: weighing the molar ratio of 1:4:6 (R) -DB, anhydrous K 2 CO 3 And placing bromoethane into a two-mouth flask, adding acetone, heating and refluxing for 48 hours, cooling to room temperature after the reaction is finished, filtering to obtain filtrate, and performing rotary evaporation and vacuum drying to obtain yellow solid (R) -DBDE.
Further, the preparation method of the (R) -DB comprises the following steps: the molar ratio is weighed to be 10:25.2:7.4 (R) -1,1' -bi-2-naphthol, liquid bromine, na 2 S 2 O 3 Firstly placing (R) -1,1' -bi-2-naphthol into a 100mL three-neck flask, firstly adding dichloromethane, cooling to 0 ℃, slowly adding dropwise bromine under stirring, reacting at 0 ℃ for 24 hours, and then adding Na 2 S 2 O 3 The reaction was quenched and stirring was continued for 2h, the reaction was changed from orange to pale yellow, the reaction was filtered, the organic phases were combined after washing with saturated NaCl solution, and dried in vacuo to give (R) -DB as a pale yellow solid.
The invention also provides application of the (R) -TPBBP-COF catalyst in synthesizing chiral alpha-amino phosphonate.
Wherein, the preparation of the alpha-aminophosphonic acid is realized by the reaction of benzaldehyde, aniline and diethyl phosphite under the condition of room temperature, and the specific reaction equation is as follows:
in order to make the technical solution of the present invention more clearly understood by those skilled in the art, the technical solution of the present invention will be further described with reference to specific embodiments and drawings.
Example 1
Preparation of (R) -BINOLPA-DA:
(1) (R) -1,1' -bi-2-naphthol (10.0 mmol,2.86 g) was weighed into a 100mL three-necked flaskDichloromethane (20 mL) was added first, 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 an aqueous solution of (7.4 mmol,1.20 g) and stirred for 2h, after which the reaction mixture turned 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, distilled off in a rotary manner and dried in vacuo to give (R) -DB as a pale yellow solid.
(2) Weighing (R) -DB (10.0 mmol,4.44 g), anhydrous K 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 is finished, cooling to room temperature, filtering to obtain filtrate, rotary steaming and vacuum drying to obtain yellow solid (R) -DBDE.
(3) (R) -DBDE (10.0 mmol,4.97 g) and cuprous chloride (22.0 mmol,2.20 g) were placed in a 100mL three-necked flask under nitrogen atmosphere, DMF (15 mL) was added and 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 distilled and dried in vacuo to give (R) -DCDE as a yellow solid.
(4) (R) -DCDE (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 24 hours, 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 (R) -DCDB as a yellow solid.
(5) Under the protection of nitrogen atmosphere, (R) -DCDB (1.0 mmol,0.57 g), 4-formylphenylboronic acid (2.0 mmol,0.36 g) and anhydrous K are weighed 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, 40 mL) mixed solvent was added thereto and heated at 80℃under reflux for 36h. Separating the solution when the reaction is hot after the reaction is finished, taking an upper organic layer,the aqueous layer was 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 distilled and dried under vacuum to give (R) -BINOLDE-DA 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 thereto and stirred at room temperature, and a solution of (R) -BINOLDE-DA (1.0 mmol,0.62 mg) in methylene chloride (10 mL) was slowly added dropwise thereto and reacted at room temperature for 24 hours. 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.
(7) Under the protection of nitrogen atmosphere, (R) -BINOLDH-DA (1.0 mmol,0.56 mg) was weighed into a 50mL two-necked flask, and anhydrous pyridine (20 mL) was added thereto to reflux at 100℃for 12 hours. Then cooling to 0 ℃, and dripping POCl into the reaction system 3 (4.9 mmol, 457. Mu.L) and heated to 100deg.C for a further 48h. The reaction was cooled to 0deg.C, water (4.5 mL) was added and the mixture was heated at 100deg.C to reflux for 48h. And after the reaction is finished, the temperature is restored to the room temperature, and hydrochloric acid is added into the reaction system for acidification. The organic phase was separated, extracted three times with dichloromethane, and the combined organic layers were evaporated by rotary evaporation to give a yellow solid. The crude product was subjected to column chromatography (ethyl acetate: petroleum ether=1:1 as eluent), rotary distilled and dried under vacuum to give the pale yellow product (R) -BINOLPA-DA.
Example 2
Preparation of (R) -TPBBP-COF catalyst:
TAPB (0.10 mmol,35.10 mg) and (R) -BINOLPA-DA (0.15 mmol,92.40 mg) were weighed into a 10mL pressure-resistant tube, and mixed solvents of acetic acid (6M, 0.2 mL) and ethanol/mesitylene (3:1, 2 mL) were added and sonicated for 10min to mix well. Freezing and degassing with liquid nitrogen for three times, heating at 120deg.C for 72 hr, cooling to room temperature after the reaction is completed, and standing for 48 hr. And (3) centrifugally collecting the solid, repeatedly washing with ethanol, and drying in vacuum to obtain the mauve product (R) -TPBBP-COF.
The embodiment uses scanning electron microscope, thermogravimetry, PXRD, solid nuclear magnetism and N 2 The adsorption characterizes the compound, and the results are shown in figures 1,2, 3, 4 and 5, respectively, and the polymer has a pore structure, and can be confirmed by figures 1 and 5, and the thermal weight (figure 2), PXRD (figure 3) and solid nuclear magnetism (figure 4) of the catalyst (R) -TPBBP-COF indicate that the COF is a crystalline porous material with high thermal stability.
Example 3
Catalytic synthesis of chiral alpha-aminophosphonate by using (R) -TPBBP-COF catalyst
The reaction equation in this example is as follows:
catalyst (R) -TPBBP-COF (0.0125 mmol,31.0 mg), aniline (0.25 mmol, 23. Mu.L), benzaldehyde (0.25 mmol, 25.5. Mu.L) and diethyl phosphite (0.25 mmol, 30. Mu.L) were placed in a flask, tetrahydrofuran (3 mL) was added, and stirred at 0deg.C for 5 hours to obtain chiral α -phosphoramidate 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. 7 (liquid phase diagram), fig. 8 (mass spectrum diagram), fig. 9 (nuclear magnetic diagram), respectively, and fig. 7-9 demonstrate the formation of α -phosphoramidate product.
Experimental example 4
Performance verification of (R) -TPBBP-COF catalytic synthesis of alpha-phosphoramidate
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 2, the yield and the ee value of the product are basically consistent after the catalyst is circulated twice as shown in the table 2, 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-time cyclic 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 6, the (R) -TPBBP-COF still keeps the original framework, further the stability of the catalyst is verified, and the original structural framework can be maintained after multiple times of cyclic catalysis.
TABLE 2 yield and stereoselectivity of 5 cycles of (R) -TPBBP-COF catalytic reaction
a: yield was determined by isolation b: ee value is determined by liquid chromatography
The (R) -TPBBP-COF prepared by the preparation method provided by the invention can be used as a catalyst to effectively catalyze asymmetric reactions of aldehyde, amine and diethyl phosphite to obtain chiral product alpha-aminophosphonate, the yield and stereoselectivity of the catalytic reaction are high, heterogeneous catalysis is realized, the method can be repeatedly used for more than five times, the framework structure is not changed, the yield is not obviously reduced after repeated use for many times, and the method has good stability and catalytic efficiency.
Finally, it should be noted that: the above embodiments are only for illustrating the technical solution of the present invention and not for limiting it, and although the present invention has been described in detail with reference to the preferred embodiments, it will be understood by those skilled in the art that: the technical scheme of the invention can be modified or replaced by the same, and the modified technical scheme cannot deviate from the spirit and scope of the technical scheme of the invention.
Claims (10)
1. The (R) -TPBBP-COF catalyst is characterized by comprising the following structural formula:
the (R) -TPBBP-COF catalyst takes TAPB and (R) -BINOLPA-DA as reaction raw materials, and the structural formulas of the TAPB and the (R) -BINOLPA-DA are respectively as follows:
2. a process for the preparation of the (R) -TPBBP-COF catalyst according to claim 1, characterized in that: adding TAPB and (R) -BINOLPA-DA into a mixed solution of ethanol, mesitylene and dilute acetic acid, carrying out ultrasonic mixing, freezing and degassing by using liquid nitrogen, reacting at 120 ℃ for 72 hours, cooling to room temperature after the reaction is finished, standing for 48 hours, centrifugally collecting solids, repeatedly washing by using ethanol, and carrying out vacuum drying to obtain purple black powder which is the (R) -TPBBP-COF catalyst;
wherein, the mol mass ratio of TAPB and (R) -BINOLPA-DA is 1:1.5; the volume ratio of ethanol, mesitylene and dilute acetic acid is 15:5:2.
3. the method for preparing the (R) -TPBBP-COF catalyst as claimed in claim 2, wherein: the preparation method of the (R) -BINOLPA-DA comprises the following steps: under the protection of nitrogen atmosphere, weighing a proper amount of (R) -BINOLDH-DA, placing into a two-neck flask, adding anhydrous pyridine, refluxing at 100-105deg.C for 12-14h, cooling to 0deg.C, and dripping POCl 3 Heating to 100-105 ℃ for continuous reaction for 45-48h, cooling the reaction system to 0 ℃, adding water, heating and refluxing for 48h at 100 ℃, recovering to room temperature after the reaction is finished, adding hydrochloric acid into the reaction system for acidification, separating liquid, taking an organic phase, extracting for multiple times by using dichloromethane, merging organic layers, performing rotary evaporation to obtain a yellow solid crude product, performing column chromatography on the crude product, performing rotary evaporation and vacuum drying to obtain a pale yellow product (R) -BINOLPA-DA;
wherein, (R) -BINOLDH-DA and POCl 3 And anhydrous pyridine in a mass to volume ratio of 0.56mg:457 μl:20mL; the eluent used in the column chromatography is a mixed solution of dichloromethane and petroleum ether with the volume ratio of 1:1.
4. The method for preparing the (R) -TPBBP-COF catalyst according to claim 3, wherein said method for preparing the (R) -BINOLDH-DA comprises the following steps: adding a proper amount of boron tribromide into dichloromethane, stirring at room temperature for reaction for 22-24 hours, then dropwise adding (R) -BINOLDE-DA for reaction, cooling to 0 ℃ after the reaction is finished, dropwise adding water for quenching reaction, continuously stirring for 1-1.5 hours, finally adding a dichloromethane solution into a reaction system, separating liquid to obtain an organic phase, extracting the aqueous phase with ethyl acetate for multiple times, merging the organic layers, performing rotary evaporation and vacuum drying to obtain yellow solid (R) -BINOLDH-DA;
wherein, the adding ratio of boron tribromide, methylene dichloride and (R) -BINOLDE-DA is 570 mu L:10mL:0.62mg.
5. The method for preparing the (R) -TPBBP-COF catalyst according to claim 4, wherein said method for preparing the (R) -BINOLDE-DA comprises the following steps: under the protection of nitrogen atmosphere, weighing a proper amount of (R) -DCDB, 4-formylphenylboric acid and anhydrous K 2 CO 3 、Pd[P(Ph)3]4 placing the mixture into a two-neck flask, adding tetrahydrofuran/water mixed solution, heating and refluxing for 36 hours at 80 ℃ to react, separating the solution after the reaction is finished, taking an upper organic layer, extracting a water layer with dichloromethane for multiple times, merging the organic layers, performing rotary evaporation to obtain an orange solid crude product, performing column chromatography on the crude product, performing rotary evaporation and vacuum drying to obtain pale yellow solid (R) -BI NOLDE-DA;
wherein, (R) -DCDB, 4-formylphenylboronic acid, anhydrous K 2 CO 3 、Pd[P(Ph)3]4 in a molar ratio of 1:2:6:0.06; the eluent used in the column chromatography is a mixed solution of dichloromethane and petroleum ether with the volume ratio of 1:1.
6. The method for preparing the (R) -TPBBP-COF catalyst according to claim 5, wherein said method for preparing the (R) -DCDB comprises the steps of: weighing a proper amount of (R) -DCDE, placing into a three-neck flask, adding dichloromethane, cooling to 0 ℃, slowly adding dropwise bromine under stirring, reacting at 0 ℃ for 24 hours, and adding Na 2 S 2 O 3 The reaction is quenched by water solution of (2) and is stirred for 2 hours, the organic phase is separated and taken out, washed by saturated NaCl solution for a plurality of times, and the organic phase is combined, distilled and dried in vacuumDrying to obtain yellow solid (R) -DCDB;
wherein, (R) -DCDE, liquid bromine and Na 2 S 2 O 3 The molar ratio of (2) is 1:24:7.4.
7. the method for preparing the (R) -TPBBP-COF catalyst according to claim 6, wherein the method for preparing the (R) -DCDE comprises the following steps: placing (R) -DBDE and cuprous chloride in a three-neck flask under the protection of nitrogen atmosphere, adding DMF, refluxing at 110-120 ℃ for 45-48h for reaction, filtering while the reaction is hot, pouring the filtrate into water, and filtering again to obtain pale yellow solid; performing column chromatography on the crude product by using dichloromethane as an eluent, performing rotary evaporation and vacuum drying to obtain yellow solid (R) -DCDE;
wherein, the addition ratio of (R) -DBDE, cuprous chloride and DMF is 4.97g:2.20g:15mL.
8. The method for preparing the (R) -TPBBP-COF catalyst according to claim 4, wherein said method for preparing the (R) -DBDE comprises the following steps: weighing proper amount of (R) -DB and anhydrous K 2 CO 3 Placing bromoethane into a two-mouth flask, adding acetone, heating and refluxing for 48 hours, cooling to room temperature after the reaction is finished, filtering to obtain filtrate, steaming in a rotary manner and drying in vacuum to obtain yellow solid (R) -DBDE;
wherein, (R) -DB, anhydrous K 2 CO 3 The molar ratio of bromoethane is 1:4:6.
9. the method for preparing a (R) -TPBBP-COF catalyst according to claim 4, wherein the method for preparing (R) -DB comprises: weighing a proper amount of (R) -1,1' -bi-2-naphthol, placing into a three-neck flask, adding dichloromethane, cooling to 0 ℃, slowly adding dropwise bromine under stirring, reacting at 0 ℃ for 24 hours, and adding Na 2 S 2 O 3 The reaction is quenched and stirred for 2 hours, after the reaction is finished, the reaction liquid is changed from orange to light yellow, the reaction liquid is filtered, the organic phase is washed by saturated NaCl solution and then is combined with the organic phase to be distilled in a rotary way and dried in vacuum, and light yellow solid (R) -DB is obtained;
wherein, (R) -1,1' -bi-2-naphthol, liquid bromine and Na 2 S 2 O 3 The molar ratio of (2) is 10:25.2:7.4.
10. use of the (R) -TPBBP-COF catalyst prepared by the preparation method according to any one of claims 2 to 9 for the synthesis of chiral alpha-aminophosphonates.
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