CN114292197A - Organic ligand L, preparation method thereof, chiral catalyst and application - Google Patents
Organic ligand L, preparation method thereof, chiral catalyst and application Download PDFInfo
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- CN114292197A CN114292197A CN202111405390.7A CN202111405390A CN114292197A CN 114292197 A CN114292197 A CN 114292197A CN 202111405390 A CN202111405390 A CN 202111405390A CN 114292197 A CN114292197 A CN 114292197A
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- 239000013110 organic ligand Substances 0.000 title claims abstract description 28
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- 238000006243 chemical reaction Methods 0.000 claims abstract description 16
- 150000003568 thioethers Chemical class 0.000 claims abstract description 14
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 9
- 238000006555 catalytic reaction Methods 0.000 claims abstract description 6
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- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 18
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 18
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 18
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- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 12
- 239000013067 intermediate product Substances 0.000 claims description 10
- 239000002904 solvent Substances 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 8
- HLHBIMJNCKZZQO-NHCUHLMSSA-N (4s)-4-phenyl-2-[6-[(4s)-4-phenyl-4,5-dihydro-1,3-oxazol-2-yl]pyridin-2-yl]-4,5-dihydro-1,3-oxazole Chemical compound C1([C@@H]2N=C(OC2)C=2N=C(C=CC=2)C=2OC[C@@H](N=2)C=2C=CC=CC=2)=CC=CC=C1 HLHBIMJNCKZZQO-NHCUHLMSSA-N 0.000 claims description 7
- 239000000047 product Substances 0.000 claims description 7
- ITMCEJHCFYSIIV-UHFFFAOYSA-M triflate Chemical compound [O-]S(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-M 0.000 claims description 7
- BQTRMYJYYNQQGK-UHFFFAOYSA-N 1-(bromomethyl)-4-iodobenzene Chemical compound BrCC1=CC=C(I)C=C1 BQTRMYJYYNQQGK-UHFFFAOYSA-N 0.000 claims description 6
- YSIIHTHHMPYKFP-UHFFFAOYSA-N 2,5-dimethoxyterephthalaldehyde Chemical compound COC1=CC(C=O)=C(OC)C=C1C=O YSIIHTHHMPYKFP-UHFFFAOYSA-N 0.000 claims description 6
- UVAJHKGWZQPAEZ-UHFFFAOYSA-N C12=CC=C(N1)C=C1C=CC(=N1)C=C1C=CC(N1)=CC=1C=CC(N1)=C2.NC2=CC=CC=C2 Chemical compound C12=CC=C(N1)C=C1C=CC(=N1)C=C1C=CC(N1)=CC=1C=CC(N1)=C2.NC2=CC=CC=C2 UVAJHKGWZQPAEZ-UHFFFAOYSA-N 0.000 claims description 5
- 229910021595 Copper(I) iodide Inorganic materials 0.000 claims description 5
- LSXDOTMGLUJQCM-UHFFFAOYSA-M copper(i) iodide Chemical compound I[Cu] LSXDOTMGLUJQCM-UHFFFAOYSA-M 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 5
- YNHIGQDRGKUECZ-UHFFFAOYSA-N dichloropalladium;triphenylphosphanium Chemical compound Cl[Pd]Cl.C1=CC=CC=C1[PH+](C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1[PH+](C=1C=CC=CC=1)C1=CC=CC=C1 YNHIGQDRGKUECZ-UHFFFAOYSA-N 0.000 claims description 4
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- GBRBMTNGQBKBQE-UHFFFAOYSA-L copper;diiodide Chemical compound I[Cu]I GBRBMTNGQBKBQE-UHFFFAOYSA-L 0.000 description 1
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Abstract
The invention relates to an organic ligand L, a preparation method thereof, a chiral catalyst synthesized by the organic ligand L and application of the chiral catalyst. The chiral catalyst provided by the invention has high utilization rate and mild reaction conditions, and can effectively reduce the catalysis cost. The asymmetric thioether oxidation reaction is adopted for catalysis, heterogeneous catalysis is realized, the catalyst is less in consumption and easy to recover, the utilization rate of the catalyst is improved, and the cost is reduced.
Description
Technical Field
The invention belongs to the technical field of catalyst preparation, and particularly relates to an organic ligand L, a preparation method thereof, a chiral catalyst synthesized by the organic ligand L and application of the chiral catalyst.
Background
The information in this background section is only for enhancement of 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 that is already known to a person of ordinary skill in the art.
Compared with achiral COF synthesis and its rapid development of photocatalysis, Chiral Covalent Organic Framework (CCOF) synthesis and CCOF-based asymmetric photocatalysis have not attracted attention. Recent studies have shown that organic catalysts, metal nanoparticles and metal ion-supported CCOFs can effectively promote the heterogeneity of asymmetric organic transformations. The chiral entities are highly orderly arranged in a definite internal channel, and a rigid COF skeleton is added, so that a tenacious chiral closed space can be endowed to CCOF, and the optical purity of a product under the reaction condition is ensured. These attractive intrinsic characteristics give CCOFs great potential in photocatalytic energy conversion and environmental remediation, which are believed to match or even exceed the performance of traditional photocatalytic semiconductors. CCOFs are therefore an ideal platform for asymmetric photocatalysis. However, the inventors found that: so far, there are very few reports of chiral COF photocatalysis, and therefore, developing a strategy for constructing chiral COF photocatalysis is an important subject to be solved and challenged urgently in the field.
Disclosure of Invention
In order to solve the problems, the invention provides an organic ligand L and a preparation method thereof, as well as a chiral catalyst synthesized by the organic ligand L and application of the chiral catalyst. The chiral catalyst provided by the invention has high utilization rate and mild reaction conditions, and can effectively reduce the catalysis cost.
In order to achieve the technical purpose, the invention adopts the following technical scheme:
in a first aspect of the present invention, there is provided an organic ligand L, chemically designated N, N-diethyl-N- (4-ethynylbenzyl) ethylamine, having the chemical formula:
in a second aspect of the present invention, a method for synthesizing the organic ligand L is provided, which comprises the following steps:
(1) taking 4-iodobenzyl bromide, triethylamine, trimethylsilyne and cuprous iodide as raw materials, taking bis (triphenylphosphine) palladium dichloride as a catalyst, heating in an acetonitrile solution, and separating a product to obtain an intermediate product A, wherein the intermediate product A has the following structure:
(2) reacting the intermediate product A with potassium hydroxide, and taking methanol and dichloromethane as solvents to prepare an organic ligand L; the structural formula of the organic ligand L is as follows:
in a third aspect of the invention, the application of the organic ligand L in the preparation of heterogeneous catalyst (R) -DTP-COF-QA is provided.
In a fourth aspect of the present invention, there is provided a chiral catalyst (R) -DTP-COF-QA, which has the following structural formula:
in a fifth aspect of the present invention, there is provided a method for preparing a chiral catalyst (R) -DTP-COF-QA, comprising:
cuprous trifluoromethanesulfonate and (S, S) -2, 6-bis (4-phenyl-2-oxazoline-2-yl) pyridine are uniformly mixed in a solvent; then adding 2, 5-dimethoxybenzene-1, 4-dicarbaldehyde, 5,10,15, 20-tetra (4-aminobenzene) -21H, 23H-porphyrin and N, N-diethyl-N- (4-ethynylbenzyl) ethylamine, and stirring at room temperature for 48-50H; then adding acetic acid, and stirring for 24-48h to obtain (R) -DTP-COF-QA.
In a sixth aspect of the invention, the application of the chiral catalyst (R) -DTP-COF-QA in catalyzing the asymmetric thioether oxidation reaction is provided.
The seventh aspect of the invention provides a method for recovering the chiral catalyst (R) -DTP-COF-QA, after the asymmetric thioether oxidation reaction is finished, centrifugal separation is carried out to obtain the catalyst (R) -DTP-COF-QA.
The invention has the beneficial effects that:
(1) the chiral catalyst (R) -DTP-COF-QA prepared by the method has the advantages of low reaction temperature, good reaction effect and reduced energy consumption.
(2) The asymmetric thioether oxidation reaction is adopted for catalysis, heterogeneous catalysis is realized, the catalyst is less in consumption and easy to recover, the utilization rate of the catalyst is improved, and the cost is reduced.
(3) The method is simple, low in cost, strong in practicability and easy to popularize.
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this specification, are included to provide a further understanding of the invention, and are incorporated in and constitute a part of this specification, illustrate exemplary embodiments of the invention and together with the description serve to explain the invention and not to limit the invention.
FIG. 1 shows an organic ligand L according to the invention1HNMR；
FIG. 2 is an infrared spectrum of an organic ligand L of the present invention;
FIG. 3 is an infrared spectrum of (R) -DTP-COF-QA and ligand of the present invention;
FIG. 4 is a PXRD spectrum of (R) -DTP-COF-QA of the present invention;
FIG. 5 is a circular dichroism spectrum of (R) -DTP-COF-QA of the present invention;
FIG. 6 is a PXRD spectrum after five cycles of the (R) -DTP-COF-QA of the present invention.
Detailed Description
It is to be understood that the following detailed description is exemplary and is intended to provide further explanation of the invention as claimed. 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 invention. As used herein, the singular forms "a", "an" and "the" are intended to include the plural forms as well, and it should be understood that when the terms "comprises" and/or "comprising" are used in this specification, they specify the presence of stated features, steps, operations, devices, components, and/or combinations thereof, unless the context clearly indicates otherwise.
In one exemplary embodiment of the present invention, there is provided an organic ligand L, chemically designated as N, N-diethyl-N- (4-ethynylbenzyl) ethylamine, having the chemical formula:
in another embodiment of the present invention, a method for synthesizing the organic ligand L is provided, which comprises the following steps:
(1) taking 4-iodobenzyl bromide, triethylamine, trimethylsilyne and cuprous iodide as raw materials, taking bis (triphenylphosphine) palladium dichloride as a catalyst, heating to 80-90 ℃ (preferably 82 ℃) in acetonitrile solution for reaction, separating a product by silica gel column chromatography, and removing a solvent by reduced pressure distillation to obtain an intermediate product A, wherein the intermediate product A has the following structure:
(2) reacting the intermediate A with potassium hydroxide, and taking methanol and dichloromethane as solvents to prepare an organic ligand L; the structural formula of the organic ligand L is as follows:
preferably, in another embodiment of the present invention, in the step (1), the molar ratio of 4-iodobenzyl bromide, triethylamine, trimethylsilyne and cuprous iodide is 3:3.5:3.5: 0.4;
preferably, in another embodiment of the present invention, in the step (2), the molar ratio of the intermediate product a to the potassium hydroxide is 1: 3.
In another embodiment of the invention, the application of the organic ligand L in the preparation of chiral catalyst (R) -DTP-COF-QA is provided.
In another embodiment of the present invention, there is provided a method for preparing a chiral catalyst (R) -DTP-COF-QA, comprising the steps of:
cuprous trifluoromethanesulfonate and (S, S) -2, 6-bis (4-phenyl-2-oxazoline-2-yl) pyridine are placed in a round-bottom flask, chloroform is used as a solvent, and the mixture is stirred and dissolved. 2, 5-dimethoxybenzene-1, 4-dicarbaldehyde, 5,10,15, 20-tetrakis (4-aminophenyl) -21H, 23H-porphyrin, N-diethyl-N- (4-ethynylbenzyl) ethylamine were added to a round-bottomed flask and stirred at room temperature for 48H. Finally adding acetic acid, and stirring for 24-48h to obtain (R) -DTP-COF-QA.
In some embodiments, the cuprous triflate, (S, S) -2, 6-bis (4-phenyl-2-oxazolin-2-yl) pyridine, 2, 5-dimethoxybenzene-1, 4-dicarbaldehyde, 5,10,15, 20-tetrakis (4-aminobenzene) -21H, 23H-porphyrin, N-diethyl-N- (4-ethynylbenzyl) ethylamine are in a molar ratio of 1:1:9:6:3.7 to improve reaction efficiency and yield.
Preferably, the chloroform solvent is in an amount of 25mL to effectively dissolve cuprous trifluoromethanesulfonate and (S, S) -2, 6-bis (4-phenyl-2-oxazolin-2-yl) pyridine.
Preferably, the room temperature is 15-25 ℃, and the reaction can be carried out in different seasons and regions.
The chiral catalyst (R) -DTP-COF-QA is applied to catalyzing the asymmetric thioether oxidation reaction.
The application method specifically comprises the following steps:
the thioethers, H, are reacted at 15 ℃ under 660nm light2And O, (R) -DTP-COF-QA is stirred for 16h to obtain the corresponding product.
Wherein the molar ratio of the thioether to the catalyst (R) -DTP-COF-QA is 1: 0.02. The asymmetric thioether oxidation reaction is adopted for catalysis, heterogeneous catalysis is realized, the catalyst is less in consumption and easy to recover, the utilization rate of the catalyst is improved, and the cost is reduced.
The reaction is as follows:
finally, the invention also provides a method for recovering the chiral catalyst (R) -DTP-COF-QA, and particularly, after the asymmetric thioether oxidation reaction is finished, the catalyst (R) -DTP-COF-QA is obtained by rapid centrifugation.
The present invention is described in further detail below with reference to specific examples, which are intended to be illustrative of the invention and not limiting.
Example 1: preparation of organic ligand L
The preparation method comprises the following specific steps:
(1) 4-iodobenzyl bromide (890mg,3.0mmol), triethylamine (490. mu.L, 3.5mmol) were heated to 82 ℃ in 50mL acetonitrile under nitrogen at reflux for 3 h. After cooling to room temperature, trimethylsilyne (350. mu.L, 3.5mmol), bis (triphenylphosphine) palladium dichloride (48mg, 0.06mmol), and copper iodide (77mg, 0.4mmol) were added to the reaction system, and heating and refluxing were continued for 10 hours. After the reaction was completed, a brown solution was obtained. The system was evaporated to dryness under reduced pressure, air dried, and purified by silica gel column (dichloromethane and methanol) to obtain 0.7 g of yellow crystalline solid with a yield of 80%.
(2) Intermediate A (145mg,0.5mmol) was added to dichloromethane (15 mL). After dissolution, a methanol solution (15mL) in which KOH (84mg,1.5mmol) was dissolved was added to the mixture, and stirred at room temperature for 24 h. The product was purified by column on silica gel (dichloromethane and methanol) to give 103 mg of a white crystalline solid in 95% yield.
The organic ligand L prepared in this example was subjected to structural characterization, which resulted in1HNMR, IR are shown in FIGS. 1 and 2, respectively.
Example 2: synthesis of (R) -DTP-COF-QA
12mg (0.02mmoL) of cuprous trifluoromethanesulfonate and 8mg (0.02mmoL) of (S, S) -2, 6-bis (4-phenyl-2-oxazolin-2-yl) pyridine were placed in a 50ml round-bottomed flask, and 25ml of chloroform was added thereto and dissolved by stirring. 38.40mg (0.198mmoL) of 2, 5-dimethoxybenzene-1, 4-dicarbaldehyde, 43mg (0.122mmoL) of 5,10,15, 20-tetrakis (4-aminobenzene) -21H, 23H-porphyrin, and 90. mu.l (0.819mmoL) of N, N-diethyl-N- (4-ethynylbenzyl) ethylamine were added to a round-bottomed flask and stirred at room temperature for 48 hours. Finally, 15 mul of acetic acid is added and stirred for 24-48 h. After the reaction, the mixture was centrifuged, washed 3 times with chloroform and 3 times with ethanol to obtain (R) -DTP-COF-QA.
We characterized the polymer by IR, PXRD, CD spectra and the results are shown in figures 3, 4, 5, respectively.
Example 3:
a20 ml vial equipped with a magnetic stir bar was charged with catalyst (R) -DTP-COF-QA (12mg) and the corresponding sulfide (0.3mmol), followed by 2ml of water. The vial was placed on a red LED photoreactor (660nm) and the reaction mixture was stirred at 15 ℃ for 16 hours. After complete consumption of the sulfide, the crude product is filtered through a membrane filter and the yield is determined by gas chromatography. The ee value was determined by chiral HPLC using a Chiralcel OD-H column (95: 5 ═ n-hexane: isopropanol, 0.8mL/min, 254 nm). The catalyst was recovered, and the catalyst was put into the next reaction, and the yield was measured by gas chromatography, and the catalytic effect was as shown in table 1.
TABLE 1 catalytic Effect of the catalyst (R) -DTP-COF-QA
| Entry | R1 | R2 | Yieldb(％) | eec(％) |
| 1 | H | Me | 94 | 99 |
| 2 | 4-OMe | Me | 92 | 92 |
| 3 | 3-Cl | Me | 93 | 88 |
| 4 | 3-Br | Me | 91 | 94 |
| 5 | 4-Cl | Me | 90 | 94 |
| 6 | 4-Br | Me | 90 | 99 |
| 7 | 4-F | Me | 93 | 96 |
| 8 | 4-Me | Me | 87 | 99 |
As can be seen from Table 1, the catalyst (R) -DTP-COF-QA has good chiral catalytic effect when used for catalyzing sulfides, the yield can reach 94%, and the ee value can reach 99%.
Example 4:
after the asymmetric thioether oxidation reaction is finished, centrifugally separating, recovering to obtain the catalyst (R) -DTP-COF-QA, and continuously putting the catalyst into the next reaction. The catalyst was obtained after five cycles (see fig. 6).
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. An organic ligand L, characterized by the chemical structural formula:
2. the process for the preparation of an organic ligand L according to claim 1, characterized in that it comprises the following steps:
(1) taking 4-iodobenzyl bromide, triethylamine, trimethylsilyne and cuprous iodide as raw materials, taking bis (triphenylphosphine) palladium dichloride as a catalyst, heating to 80-90 ℃ in an acetonitrile solution for reaction, separating a product by silica gel column chromatography, and removing a solvent by reduced pressure distillation to obtain an intermediate product A, wherein the intermediate product A has the following structure:
(2) reacting the intermediate product A with potassium hydroxide, and taking methanol and dichloromethane as solvents to prepare an organic ligand L; the structural formula of the organic ligand L is as follows:
3. the preparation method according to claim 2, wherein in the step (1), the molar ratio of 4-iodobenzyl bromide to triethylamine to trimethylsilyne to cuprous iodide is 3:3.5:3.5: 0.4; the heating temperature was 82 ℃.
4. The method according to claim 2, wherein in the step (2), the molar ratio of the intermediate product A to the potassium hydroxide is 1: 3.
5. A preparation method of chiral catalyst (R) -DTP-COF-QA is characterized by comprising the following preparation steps: putting cuprous trifluoromethanesulfonate and (S, S) -2, 6-bis (4-phenyl-2-oxazoline-2-yl) pyridine into a round-bottom flask, taking chloroform as a solvent, and stirring for dissolving; adding 2, 5-dimethoxybenzene-1, 4-dicarbaldehyde, 5,10,15, 20-tetra (4-aminobenzene) -21H, 23H-porphyrin and the organic ligand L in any one of the preceding claims into a round-bottomed flask, and stirring at room temperature; and finally adding acetic acid and stirring to obtain the chiral catalyst (R) -DTP-COF-QA.
6. The preparation method according to claim 5, wherein the molar ratio of the cuprous trifluoromethanesulfonate, (S, S) -2, 6-bis (4-phenyl-2-oxazolin-2-yl) pyridine, 2, 5-dimethoxybenzene-1, 4-dicarboxaldehyde, 5,10,15, 20-tetrakis (4-aminobenzene) -21H, 23H-porphyrin to the organic ligand L is 1:1:9:6: 3.7.
7. The method according to claim 5, wherein the chloroform is contained in an amount of 25 mL; the room temperature is 15-25 ℃.
8. Chiral catalyst (R) -DTP-COF-QA prepared according to the preparation process of any one of claims 5-7.
9. Use of the chiral catalyst (R) -DTP-COF-QA according to claim 8 for the catalysis of asymmetric thioether oxidation reactions.
10. The application of claim 9, wherein the specific application method is as follows: the thioethers, H, are reacted at 15 ℃ under 660nm light2O, (R) -DTP-COF-QA is stirred for 16h to obtain a corresponding product; preferably, the molar ratio of thioether, catalyst (R) -DTP-COF-QA is 1: 0.02.
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|---|---|---|---|---|
| CN104588100A (en) * | 2015-01-09 | 2015-05-06 | 福州大学 | Catalyst for catalyzing thioether oxidation as well as preparation method and application of catalyst |
| CN111978537A (en) * | 2020-07-08 | 2020-11-24 | 山东师范大学 | Chiral catalyst (S) -DTP-COF, and preparation, recycling method and application thereof |
| CN112774733A (en) * | 2021-02-11 | 2021-05-11 | 福州大学 | Cage-shaped supramolecular catalyst for catalyzing thioether oxidation and preparation method and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104588100A (en) * | 2015-01-09 | 2015-05-06 | 福州大学 | Catalyst for catalyzing thioether oxidation as well as preparation method and application of catalyst |
| CN111978537A (en) * | 2020-07-08 | 2020-11-24 | 山东师范大学 | Chiral catalyst (S) -DTP-COF, and preparation, recycling method and application thereof |
| CN112774733A (en) * | 2021-02-11 | 2021-05-11 | 福州大学 | Cage-shaped supramolecular catalyst for catalyzing thioether oxidation and preparation method and application thereof |
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