CN112341324A - Method for synthesizing aryl propionic acid by carbon dioxide carboxylation without metal catalysis - Google Patents

Method for synthesizing aryl propionic acid by carbon dioxide carboxylation without metal catalysis Download PDF

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CN112341324A
CN112341324A CN202011386158.9A CN202011386158A CN112341324A CN 112341324 A CN112341324 A CN 112341324A CN 202011386158 A CN202011386158 A CN 202011386158A CN 112341324 A CN112341324 A CN 112341324A
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diselenide
carbon dioxide
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propionic acid
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景苏
程飞虹
吉玮
顾蓉
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Nanjing Tech University
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/15—Preparation of carboxylic acids or their salts, halides or anhydrides by reaction of organic compounds with carbon dioxide, e.g. Kolbe-Schmitt synthesis
    • 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
    • B01J31/0272—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing elements other than those covered by B01J31/0201 - B01J31/0255
    • B01J31/0275—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing elements other than those covered by B01J31/0201 - B01J31/0255 also containing elements or functional groups covered by B01J31/0201 - B01J31/0269
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C391/00—Compounds containing selenium
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
    • B01J2231/30—Addition reactions at carbon centres, i.e. to either C-C or C-X multiple bonds
    • B01J2231/32—Addition reactions to C=C or C-C triple bonds
    • B01J2231/321—Hydroformylation, metalformylation, carbonylation or hydroaminomethylation

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Abstract

The invention relates to the field of carbon dioxide fixation and conversion, and particularly discloses a method for synthesizing aryl propionic acid by carboxylation of carbon dioxide without metal catalysis. The method directly uses styrene as a raw material, uses diselenide as a catalyst to realize the carboxylation reaction of olefin and carbon dioxide, and compared with the generation of metal catalyst residues or halogen-containing byproducts in the traditional synthetic method, the byproduct only contains water, and uses micromolecular diselenide as a catalyst to replace the traditional metal catalyst, thereby avoiding metal residues.

Description

Method for synthesizing aryl propionic acid by carbon dioxide carboxylation without metal catalysis
Technical Field
The invention relates to the field of carbon dioxide fixation and conversion, in particular to a method for synthesizing aryl propionic acid by carbon dioxide carboxylation without metal catalysis.
Background
With increasing concern about climate change, carbon dioxide (CO)2) The fixation and conversion of this greenhouse gas has become a focus of research by chemists. CO 22Is a carbon-carbon (C1) resource which is non-toxic, difficult to burn, renewable, abundant in source and low in cost. In organic synthesis, CO is used2The method has high research value for replacing poisonous phosgene or carbon monoxide. In recent years, people pay more and more attention to the development of a green sustainable strategy in the direction of organic synthesis. There are two main directions for the conversion and utilization of carbon dioxide, first to a new generation of dyes, such as methanol or hydrocarbons. However, compounds such as methanol have low market value and the use of carbon dioxide to produce them is not economically feasible and competitive. Compared with methanol and low-carbon alkane with low additional value, the design and synthesis of carboxylic acid or carbonate with high additional value are obviously more meaningful. The direct conversion of carbon dioxide to carboxylic acids by catalysis is most attractive in a variety of different synthetic processes because the carboxylic acid backbone is widely present in a variety of organic natural products as well as in drug molecules, of which arylpropionic acid-based nonsteroidal anti-inflammatory drugs are very widely used in life.
Through years of development, as shown in fig. 1, the main synthetic strategies at present are: (1) by reacting halogenated compounds with CO under the action of metal catalyst and stoichiometric reducing agent2Reacting to generate corresponding carboxylic acid; (2) by reacting an olefin with a stoichiometric amount of an organometallic reagent and CO2To produce an olefin difunctional product. However, both of these strategies have certain limitations, such as the need for specific ligands in the former, the sensitivity of the latter to air and water, limited applicability of the substrate, and the like. In addition to the above drawbacks, the use of transition metals increases the risk of metal residues, hindering their industrial application. In recent years, organic selenium compounds have been widely used in catalytic processes. Due to the continuing interest in organoselenium catalysts in our topic group, we wanted to know if C (sp) can be achieved with organoselenium catalysts2) -H bond to CO2Thereby obtaining the aryl propionic acid under transition metal-free and mild conditions.
Disclosure of Invention
The purpose of the invention is as follows: aiming at the defects of the prior art, the invention provides a preparation method for synthesizing an arylpropionic acid compound by carboxylation of carbon dioxide under the condition of no metal catalysis, and organic micromolecule diselenide is used for replacing the traditional transition metal catalyst to realize CO2The important medical intermediate 2-aryl propionic acid is synthesized at room temperature.
In order to solve the technical problems, the invention discloses a preparation method for synthesizing an aryl propionic acid compound by carbon dioxide carboxylation without metal catalysis, which has the following reaction formula:
Figure BDA0002809579140000021
the preparation method comprises the steps of sequentially adding diselenide catalyst and styrene into a reaction solvent for mixing to obtain a mixed solution; vacuumizing at room temperature, introducing carbon dioxide, and stirring in the atmosphere of carbon dioxide; adding hydrogen peroxide, and stirring for reaction to obtain the final product.
Wherein the dosage ratio of the diselenide catalyst to the styrene compound is 0.02-0.08 mmol: 0.2-0.4 mmol, preferably 0.08 mmol: 0.4 mmol.
Wherein the dosage ratio of the diselenide catalyst to the solvent in the mixed solution is 0.02-0.08 mmol: 1-2 mL, preferably 0.08 mmol: 2 mL.
Wherein the diselenide catalyst is any one of diphenyl diselenide, dibenzyl diselenide, bis (4-bromobenzyl) diselenide, bis (2-bromobenzyl) diselenide and dipropyl diselenide; wherein, the bis (4-bromobenzyl) diselenide is shown as a formula I:
Figure BDA0002809579140000022
wherein the styrene compound is any one of 6-methoxy-2-naphthylene, 3, 4-dimethoxystyrene, 2, 4-dimethylstyrene, 2-methylstyrene, 3-methylstyrene, 4-bromostyrene, 4-chlorostyrene, 4-methoxystyrene, 4-hydroxystyrene, 4-vinylbiphenyl, 4-tert-butylstyrene and styrene, and is preferably 4-tert-butylstyrene.
Wherein, the solvent of the mixed solution of the diselenide catalyst and the styrene compound is any one of acetonitrile, ethanol and dimethyl sulfoxide.
Wherein the amount of the carbon dioxide is controlled to enable the pressure of the reaction system to be 80-120 KPa, and preferably 100 KPa.
Further preferably, the dosage ratio of the diselenide catalyst to the carbon dioxide is 0.02-0.08 mmol: 100 KPa.
Wherein, the mixed solution of the diselenide catalyst and the styrene compound is stirred for 1 to 3 hours, preferably 2 hours, at room temperature under the atmosphere of carbon dioxide.
Wherein the dosage ratio of the diselenide catalyst to the hydrogen peroxide is 0.02-0.08 mmol: 0.1-0.5 mL, preferably 0.08 mmol: 0.1 mL.
Wherein, after adding hydrogen peroxide, stirring for 8-16h at room temperature in the atmosphere of carbon dioxide.
After the reaction is finished, removing the reaction solvent in the reaction solution, adding water for dilution, extracting to obtain an organic phase, then spin-drying the organic phase, and purifying the obtained solid to obtain the aryl propionic acid compound.
Wherein, the method for removing the reaction solvent is an extraction method and a method for processing by adopting a vacuum rotary evaporator.
Wherein the purification method is thin layer chromatography or column chromatography, the developing solvent used in the thin layer chromatography is n-hexane and ethyl acetate, and the volume ratio of n-hexane to ethyl acetate is 2: 1-6: 1.
Wherein, the preparation method of the bis (4-bromobenzyl) diselenide comprises the following steps:
(i) adding benzyl bromide and potassium selenocyanate into absolute ethyl alcohol, and stirring;
(ii) and (e) adding sodium hydroxide into the mixed solution obtained in the step (i), and stirring to obtain the sodium hydroxide-sodium chloride-zinc mixed solution.
Both steps (i) and (ii) are carried out at room temperature.
In the step (i), the dosage ratio of the p-bromobenzyl bromide to the potassium selenocyanate is 6 mmol: 10 mmol; the concentration of p-bromo benzyl bromide is 0.075 mmol/mL; the stirring time is 2h, and the stirring speed is 800 r/min.
In the step (ii), the dosage ratio of the p-bromobenzyl bromide to the sodium hydroxide is 6 mmol: 25mmol, the stirring time is 2h, and the stirring speed is 800 r/min.
After completion of step (ii), the reaction mixture was subjected to removal of the solvent under reduced pressure, 20mL of water was added to dilute the reaction, and then ether (3X 25mL) was added to extract the organic phase several times, and the resulting upper organic phase was dried over anhydrous magnesium sulfate, filtered, and the ether was removed by a vacuum rotary evaporator to obtain bis (4-bromobenzyl) diselenide as a yellow solid.
Has the advantages that: compared with the prior art, the invention has the following advantages:
(1) the method directly uses styrene as a raw material, uses diselenide as a catalyst to realize the carboxylation reaction of olefin and carbon dioxide, and compared with the generation of metal catalyst residues or halogen-containing byproducts in the traditional synthetic method, the byproduct only contains water, and uses micromolecular diselenide as a catalyst to replace the traditional metal catalyst, thereby avoiding metal residues.
(2) The aryl propionic acid compound is directly obtained from styrene and carbon dioxide through catalysis, and the prepared aryl propionic acid compound plays an important role in the synthesis of a plurality of organic natural products and bioactive molecules.
(3) The preparation method provided by the invention has the advantages of simple operation, environmental protection and high atom economy.
(4) In practical application, the preparation method provided by the invention has the highest yield of 94%, and medium to good yields can be obtained from expanded partial substrates. Therefore, the target compound can be synthesized quickly and efficiently.
Drawings
The foregoing and/or other advantages of the invention will become further apparent from the following detailed description of the invention when taken in conjunction with the accompanying drawings.
FIG. 1 is a diagram of a reaction pathway in the prior art;
FIG. 2 shows the preparation of bis (4-bromobenzyl) diselenide, a catalyst obtained in example 1 of the present invention1H-NMR chart;
FIG. 3 shows the preparation of bis (4-bromobenzyl) diselenide, a catalyst obtained in example 1 of the present invention13C-NMR chart;
FIG. 4 shows the preparation of bis (4-bromobenzyl) diselenide, a catalyst obtained in example 1 of the present invention77Se-NMR chart;
FIG. 5 is an infrared spectrum of the catalyst bis (4-bromobenzyl) diselenide obtained in example 1 of the present invention;
FIG. 6 shows the preparation of 2- (4-tert-butylphenyl) propionic acid, a product obtained in examples 2, 3,4 and 5 according to the present invention1H-NMR chart;
FIG. 7 shows the preparation of 2- (6-methoxy-2-naphthyl) propionic acid, a product obtained in example 8 of the present invention1H-NMR chart.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1: synthesis method of catalyst bis (4-bromobenzyl) diselenide
Figure BDA0002809579140000051
(i) Under the condition of room temperature, 6mmol of p-bromobenzyl bromide and 10mmol of potassium selenocyanate are sequentially added into 80mL of absolute ethyl alcohol, and stirred for 2 hours at the speed of 800 r/min.
(ii) Then 25mmol of sodium hydroxide is added, and the mixture is continuously mixed at 800r/min and stirred for 2 hours to obtain a reaction mixture.
(iii) The reaction mixture was subjected to removal of the solvent under reduced pressure, 20mL of water was added to dilute the reaction, and then ether (3X 25mL) was added to extract the organic phase multiple times, the resulting upper organic phase was dried over anhydrous magnesium sulfate and filtered, and the ether was removed by a vacuum rotary evaporator to give bis (4-bromobenzyl) diselenide as a yellow solid, which was obtained1H-NMR chart,13C-NMR chart and77Se-NMR patterns are shown in FIG. 2, FIG. 3 and FIG. 4, respectively, and infrared is shown in FIG. 5.
Example 2 (with synthetic bis (4-bromobenzyl) diselenide as catalyst)
Figure BDA0002809579140000052
Adding 4-tert-butylstyrene (0.4mmol), bis (4-bromobenzyl) diselenide (0.08mmol) and acetonitrile (2mL) into a 10mL Schlenk tube at room temperature, vacuumizing, introducing carbon dioxide (100KPa), mixing, stirring at 800r/min for 2 hours, adding hydrogen peroxide (0.1mL), mixing and stirring for catalytic reaction, removing the solvent in the reaction solution by using a vacuum rotary evaporator after reacting for 16 hours, adding 10mL of water for dilution, adding ethyl acetate (3X 15mL) for extracting an organic phase for multiple times, spin-drying the obtained upper organic phase, separating a product by adopting a thin layer chromatography, the developing solvent used in thin layer chromatography is n-hexane and ethyl acetate, and the volume ratio of n-hexane and ethyl acetate is 4: 1, and the obtained product is white solid (63.8mg, 0.31mmol), and its nuclear magnetism is shown in FIG. 6, and the yield is 77%. The method provided by the invention can quickly and efficiently synthesize the target compound.
Example 3 replacement of catalyst for Diphenyl diselenide
Figure BDA0002809579140000061
Adding 4-tert-butylstyrene (0.4mmol), diphenyl diselenide (0.08mmol) and acetonitrile (2mL) into a 10mL Schlenk tube at room temperature, vacuumizing, introducing carbon dioxide (100KPa), mixing, stirring at 800r/min for 2 hours, adding hydrogen peroxide (0.1mL), mixing, stirring, carrying out catalytic reaction for 16 hours, removing the solvent in the reaction solution by using a vacuum rotary evaporator, adding 10mL of water for dilution, adding ethyl acetate (3X 15mL) for multiple times to extract an organic phase, carrying out spin drying on the obtained upper organic phase, and separating a product by adopting a thin layer chromatography, wherein the developing agents selected during the thin layer chromatography are n-hexane and ethyl acetate, the volume ratio of the n-hexane to the ethyl acetate is 4: 1, and the obtained product is a white solid (75.8mg and 0.368mmol) with the nuclear magnetic field nuclear magnetic chromatography yield of 92% as shown in FIG. 6. The method provided by the invention can quickly and efficiently synthesize the target compound.
Example 4 (varying amounts of catalyst Diphenyl diselenide)
Figure BDA0002809579140000062
Adding 4-tert-butylstyrene (0.4mmol), diphenyl diselenide (0.04mmol) and acetonitrile (2mL) into a 10mL Schlenk tube at room temperature, vacuumizing, introducing carbon dioxide (100KPa), mixing, stirring at 800r/min for 2 hours, adding hydrogen peroxide (0.1mL), mixing, stirring, carrying out catalytic reaction for 16 hours, removing the solvent in the reaction solution by using a vacuum rotary evaporator, adding 10mL of water for dilution, adding ethyl acetate (3X 15mL) for multiple times to extract an organic phase, carrying out spin drying on the obtained upper organic phase, and separating a product by adopting a thin layer chromatography, wherein the developing agents selected during the thin layer chromatography are n-hexane and ethyl acetate, the volume ratio of the n-hexane to the ethyl acetate is 4: 1, and the obtained product is a white solid (47.79mg and 0.232mmol) as shown in FIG. 6, and the yield is 58%. The method provided by the invention can quickly and efficiently synthesize the target compound.
Example 5 replacement of catalyst for dibenzyl diselenide
Figure BDA0002809579140000071
Adding 4-tert-butylstyrene (0.4mmol), dibenzyl diselenide (0.08mmol) and acetonitrile (2mL) into a 10mL Schlenk tube at room temperature, vacuumizing, introducing carbon dioxide (100KPa), mixing, stirring at 800r/min for 2 hours, adding hydrogen peroxide (0.1mL), mixing and stirring for catalytic reaction, removing the solvent in the reaction solution by using a vacuum rotary evaporator after reacting for 16 hours, adding 10mL of water for diluting, adding ethyl acetate (3X 15mL) for extracting an organic phase for multiple times, spin-drying the obtained upper organic phase, and separating a product by adopting a thin layer chromatography, wherein nuclear magnetism and ethyl acetate are used as developing agents during the thin layer chromatography, the volume ratio of the n-hexane to the ethyl acetate is 4: 1, and the obtained product is a white solid (77.5mg, 0.376mmol) which is shown in FIG. 6 and has the yield of 94%. The method provided by the invention can quickly and efficiently synthesize the target compound.
Example 6 (No catalyst diselenide)
Adding 4-tert-butylstyrene (0.4mmol) and acetonitrile (2mL) into a 10mL Schlenk tube at room temperature, vacuumizing, introducing carbon dioxide (100KPa), mixing, stirring at 800r/min for 2 hours, adding hydrogen peroxide (0.1mL), mixing and stirring for catalytic reaction, reacting for 16 hours, removing a solvent in a reaction solution by using a vacuum rotary evaporator, adding 10mL of water for dilution, adding ethyl acetate (3X 15mL) for extracting an organic phase for multiple times, spin-drying an obtained upper organic phase, separating a product by adopting a thin-layer chromatography, selecting a developing agent for the thin-layer chromatography, namely n-hexane and ethyl acetate, wherein the volume ratio of the n-hexane to the ethyl acetate is 4: 1, and the reaction system does not react, so that the diselenide catalyst is indispensable.
Example 7 (No Hydrogen peroxide Water participating in the reaction)
Figure BDA0002809579140000072
Adding 4-tert-butylstyrene (0.4mmol), dibenzyl diselenide (0.08mmol) and acetonitrile (2mL) into a 10mL Schlenk tube at room temperature, mixing, directly adding a carbon dioxide balloon (about 30mL), stirring at the speed of 800r/min for reaction for 16 hours, removing a solvent in a reaction solution by using a vacuum rotary evaporator, adding 10mL of water for dilution, adding ethyl acetate (3X 15mL) for extracting an organic phase for multiple times, spin-drying the obtained upper organic phase, separating a product by adopting a thin-layer chromatography method, wherein developing agents selected during the thin-layer chromatography are n-hexane and ethyl acetate, the volume ratio of the n-hexane to the ethyl acetate is 4: 1, only trace (< 2%) target products are obtained, and the fact that oxygen in the air hardly pushes a reaction system to proceed and a cocatalyst is indispensable.
Example 8 (substrate exchange, direct Synthesis of the drug molecule naproxen)
Figure BDA0002809579140000081
Adding 6-methoxy-2-naphthylethylene (0.4mmol), dibenzyl diselenide (0.08mmol) and acetonitrile (2mL) into a 10mL Schlenk tube at room temperature, vacuumizing, introducing carbon dioxide (100KPa), mixing, stirring at 800r/min for 0.5 hr, adding hydrogen peroxide (0.1mL), mixing, stirring, performing catalytic reaction for 16 hr, removing solvent from the reaction solution with vacuum rotary evaporator, diluting with 10mL water, adding ethyl acetate (3 × 15mL), extracting the organic phase for several times, spin drying the upper organic phase, separating the product by thin layer chromatography, the developing solvent used in thin layer chromatography is n-hexane and ethyl acetate, and the volume ratio of n-hexane to ethyl acetate is 4: 1, and the obtained product is white solid (59.8mg, 0.26mmol), and its nuclear magnetism is shown in FIG. 7, with yield of 65%. The method provided by the invention can quickly and efficiently synthesize the target compound.
The invention provides a thought and a method for synthesizing aryl propionic acid by carbon dioxide carboxylation without metal catalysis, and a method and a way for realizing the technical scheme are many, the above description is only a preferred embodiment of the invention, and it should be noted that, for a person skilled in the art, a plurality of improvements and decorations can be made without departing from the principle of the invention, and the improvements and decorations should be regarded as the protection scope of the invention. All the components not specified in the present embodiment can be realized by the prior art.

Claims (10)

1. A preparation method for synthesizing aryl propionic acid compounds by metal-free catalytic carbon dioxide carboxylation is characterized in that a mixed solution of a diselenide catalyst and a styrene compound is stirred under the atmosphere of carbon dioxide, and hydrogen peroxide is added to be stirred and reacted to obtain the aryl propionic acid compounds.
2. The preparation method according to claim 1, wherein the ratio of the diselenide catalyst to the styrene compound is 0.02-0.08 mmol: 0.2 to 0.4 mmol.
3. The preparation method according to claim 1, wherein the ratio of the diselenide catalyst to the solvent in the mixed solution is 0.02 to 0.08 mmol: 1-2 mL.
4. The preparation method according to claim 1, wherein the diselenide catalyst is any one of diphenyl diselenide, dibenzyldiselenide, bis (4-bromobenzyl) diselenide, bis (2-bromobenzyl) diselenide and dipropyl diselenide; wherein, the bis (4-bromobenzyl) diselenide is shown as a formula I:
Figure FDA0002809579130000011
5. the process according to claim 1, wherein the styrene compound is any one of 6-methoxy-2-naphthylene, 3, 4-dimethoxystyrene, 2, 4-dimethylstyrene, 2-methylstyrene, 3-methylstyrene, 4-bromostyrene, 4-chlorostyrene, 4-methoxystyrene, 4-hydroxystyrene, 4-vinylbiphenyl, 4-tert-butylstyrene and styrene.
6. The method according to claim 1, wherein the solvent of the mixed solution of the diselenide catalyst and the styrene compound is any one of acetonitrile, ethanol and dimethyl sulfoxide.
7. The process according to claim 1, wherein the amount of carbon dioxide is controlled so that the pressure in the reaction system is 80 to 120 KPa.
8. The process according to claim 1, wherein the mixed solution of the diselenide-based catalyst and the styrene-based compound is stirred at room temperature for 1 to 3 hours in an atmosphere of carbon dioxide.
9. The preparation method of claim 1, wherein the dosage ratio of the diselenide catalyst to the hydrogen peroxide is 0.02-0.08 mmol: 0.1-0.5 mL.
10. The preparation method of claim 1, wherein hydrogen peroxide is added and stirred at room temperature for 8-16h under the atmosphere of carbon dioxide.
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CN104892403A (en) * 2015-06-08 2015-09-09 扬州大学 Synthetic method of benzoic anhydride
JP2016132634A (en) * 2015-01-19 2016-07-25 株式会社日本触媒 Method of producing carboxylate
CN111454145A (en) * 2020-05-13 2020-07-28 张明 Preparation method of p-bromomethyl isophenylpropionic acid

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CN102503774A (en) * 2011-10-20 2012-06-20 江苏扬农化工集团有限公司 Method for synthesizing 1,2-cyclohexanediol by cyclohexene under selenium catalysis
JP2016132634A (en) * 2015-01-19 2016-07-25 株式会社日本触媒 Method of producing carboxylate
CN104892403A (en) * 2015-06-08 2015-09-09 扬州大学 Synthetic method of benzoic anhydride
CN111454145A (en) * 2020-05-13 2020-07-28 张明 Preparation method of p-bromomethyl isophenylpropionic acid

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Title
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