Synthetic method of photoelectric functional material 2-(4-fluorophenyl) propionic acid-2-propenyl ester

Abstract

The invention discloses a photoelectric functional material 2-(4-fluorophenyl) propionic acid-2-propenyl ester synthesis method, which comprises: 1, adding alkaline earth metal, an initiator and a solvent I into a reaction bottle, carrying out heating reflux in an inert gas atmosphere, firstly dropwise adding a p-bromofluorobenzene solution, observing the change of the reaction solution, determining the initiation success, then dropwise adding the residual p-bromofluorobenzene solution, and carrying out heating reflux in an inert gas atmosphere, adding dropwise under a controlled reflux condition, carrying out heat preservation and stirring after dropwise adding, then cooling in an inert atmosphere, dropwise adding a 3-pentanone solution, controlling the temperature until the reaction is finished, and carrying out post-treatment to obtain an intermediate 1; and 2, dissolving the intermediate 1 in a solvent II, cooling in a nitrogen atmosphere, dropwise adding an alkyl metal solution, heating after dropwise adding, cooling, dropwise adding methacrylic anhydride, controlling the temperature until the reaction is finished, adding a polymerization inhibitor into the reaction liquid, and carrying out post-treatment to obtain the 2-(4-fluorophenyl) propionic acid-2-propenyl ester. According to the invention, the cheap p-bromofluorobenzene is used as the raw material, so that the material cost is saved, and the 2-(4-fluorophenyl) propionic acid-2-propenyl ester with high purity and high yield is prepared.

Description

Technical Field

[0001] The invention relates to the technical field of compound synthesis, in particular to the technical field of organic photoelectric functional material compounds, and specifically to a method for synthesizing photoelectric functional material 2-(4-fluorophenyl) propionic acid-2-propylene ester. Background Art

[0002] Organic optoelectronic materials include small molecule materials, polymer materials, light-emitting layer materials, transport layer materials and packaging materials. These materials have a decisive influence on the performance and life of OLED devices. Researchers continue to develop new functional layer materials by optimizing material structure, improving luminous efficiency and extending service life. 2-(4-Fluorophenyl)propanoic acid 2-propen-1-yl ester is an organic compound that may have multiple uses in chemical synthesis: synthetic intermediates, material modifiers, drug synthesis, polymerization reactions, coupling reactions, etc.

[0003] 2-(4-fluorophenyl)propionic acid-2-propylene ester may be used to prepare OLED light-emitting layer materials or their precursor materials due to its specific electronic structure, which helps to improve the luminous efficiency and stability of the device; it can also be used to prepare carrier transport materials. In OLED, effective carrier (electron and hole) transport is crucial to improving device performance. In the OLED structure, the electron blocking layer is used to limit the movement direction of the carriers, thereby improving the luminous efficiency. The fluorophenyl group of 2-(4-fluorophenyl)propionic acid-2-propylene ester can provide specific electronic properties, making it suitable for the preparation of electron or hole blocking layer materials.

[0004] There is no literature report on the synthesis of 2-(4-fluorophenyl)propionic acid-2-propylene ester in the prior art. Currently, JP2015107923A reports a method for synthesizing aliphatic acrylate compounds, but the yield is low. Therefore, developing a new method for synthesizing 2-(4-fluorophenyl)propionic acid-2-propylene ester to replace the above existing synthesis process is of great significance for realizing the synthesis of 2-(4-fluorophenyl)propionic acid-2-propylene ester and the research and development of related materials. Summary of the invention

[0005] In view of this, the purpose of the present invention is to develop a method for preparing 2-(4-fluorophenyl)propionic acid-2-propylene ester with high yield and purity and low cost.

[0006] In order to achieve the above object, the present invention adopts the following technical solution: The technical solution of the present invention is as follows: A method for synthesizing 2-(4-fluorophenyl)propionic acid-2-propylene ester, a photoelectric functional material, wherein the synthesis steps are as follows: Step 1, add alkaline earth metal, initiator, and solvent I to a reaction bottle, heat and reflux under an inert gas atmosphere, first drop a portion of the p-bromofluorobenzene solution, observe the change of the reaction solution, determine that the initiation is successful, then drop the remaining p-bromofluorobenzene solution, drop it under controlled reflux conditions, keep it warm and stir after dropping, determine the control, then cool it down under an inert atmosphere, drop the 3-pentanone solution, control the temperature until the reaction is completed, and obtain intermediate 1 through post-treatment; Step 2: Dissolve the intermediate 1 in solvent II, cool it down in a nitrogen atmosphere, drop the alkyl metal solution, raise the temperature after the dropwise addition, cool it down again and drop methacrylic anhydride, control the temperature until the reaction is complete, add a polymerization inhibitor to the reaction solution, and then post-treat to obtain 2-(4-fluorophenyl)propionic acid-2-propylene ester.

[0007] The synthesis method of the photoelectric functional material 2-(4-fluorophenyl)propionic acid-2-propylene ester described in the present invention has the following synthesis route:

[0008] As a preferred embodiment of the present invention, the alkaline earth metal in step one can be selected from at least one of beryllium, magnesium, calcium and strontium; further preferably, the alkaline earth metal in step one is selected from one of magnesium and calcium.

[0009] As a preferred embodiment of the present invention, the initiator in step 1 can be selected from at least one of azobisisobutyronitrile, dodecyl peroxide, iodine and sodium persulfate.

[0010] As a preferred embodiment of the present invention, the solvent I in step 1 can be selected from at least one of 1,2-dioxane, tetrahydrofuran, methanol and acetonitrile.

[0011] As a preferred embodiment of the present invention, the solvent II in step 2 can be selected from at least one of ethanol, tetrahydrofuran, 2-methyltetrahydrofuran and 2,2-dimethylcyclopentanone.

[0012] As a preferred embodiment of the present invention, the alkyl metal solution in step 2 can be selected from at least one of butyl lithium, triethyl aluminum, and dimethyl copper lithium; further preferably, the alkyl metal solution can be selected from one of butyl lithium and dimethyl copper lithium.

[0013] As a preferred embodiment of the present invention, the polymerization inhibitor in step 2 can be selected from at least one of methylene blue, cuprous chloride, ferric chloride, and hydroquinone; further preferably, the polymerization inhibitor can be selected from one of cuprous chloride, ferric chloride, and hydroquinone.

[0014] As a preferred embodiment of the present invention, in the step 1, a portion of the p-bromofluorobenzene solution is first added dropwise, which does not exceed 20% of the amount of the p-bromofluorobenzene solution required for the reaction.

[0015] As a preferred embodiment of the present invention, the step 1 determines whether the reaction is initiated mainly through the temperature, color, and presence of bubbles in the reaction solution.

[0016] As a preferred embodiment of the present invention, the alkyl metal solution is added dropwise in the step 2 continuously and slowly, and the temperature of the reaction solution is kept below 20°C during the addition.

[0017] As a preferred embodiment of the present invention, the addition of the polymerization inhibitor in step 2 needs to be done at the end of the reaction.

[0018] As a preferred embodiment of the present invention, the solubility of the p-bromochlorobenzene solution can be selected from 0.5-5 mol / L; further preferably, the solubility of the p-bromochlorobenzene solution can be selected from 0.5-3 mol / L.

[0019] As a preferred embodiment of the present invention, the concentration of the alkyl metal solution is 1-4 mol / L; more preferably, the concentration of the alkyl metal solution is 1-3 mol / L.

[0020] As a preferred embodiment of the present invention, the molar ratio of p-bromofluorobenzene to alkaline earth metal is 1:(1.0-3.0); further preferably, the molar ratio of p-bromofluorobenzene to alkaline earth metal is 1:(1.0-2.0).

[0021] As a preferred embodiment of the present invention, the weight ratio of p-bromofluorobenzene to the initiator is 1:(0.005-0.01); further preferably, the weight ratio of p-bromofluorobenzene to the initiator is 1:(0.005-0.01).

[0022] As a preferred embodiment of the present invention, the molar ratio of p-bromofluorobenzene to 3-pentanone is 1:(0.8-1.5); more preferably, the molar ratio of p-bromofluorobenzene to 3-pentanone is 1:(0.9-1.3).

[0023] As a preferred embodiment of the present invention, the molar ratio of the intermediate 1 to the alkyl metal is 1:(1.0-3.0); further preferably, the molar ratio of the intermediate 1 to the alkyl metal is 1:(1.0-2.0).

[0024] As a preferred embodiment of the present invention, the molar ratio of intermediate 1 to methacrylic anhydride is 1:(1.0-1.5); more preferably, the molar ratio of intermediate 1 to methacrylic anhydride is 1:(1.0-1.3).

[0025] As a preferred embodiment of the present invention, the weight ratio of the intermediate 1 to the polymerization inhibitor is 1:(0.01-0.1); further preferably, the weight ratio of the intermediate 1 to the polymerization inhibitor is 1:(0.03-0.1).

[0026] Compared with the prior art, the present invention has the following beneficial effects: The present invention uses the synthetic route for the first time to prepare the target product with high yield. At the same time, the present invention uses cheap p-bromofluorobenzene as a raw material, which greatly saves material costs. In addition, the free radical reaction is accelerated by adding an initiator, so as to prepare 2-(4-fluorophenyl) propionic acid-2-propylene ester with high purity and high yield. BRIEF DESCRIPTION OF THE DRAWINGS

[0027] Figure 1 is the hydrogen nuclear magnetic resonance spectrum of 2-(4-fluorophenyl)propanoate of the present invention; Figure 2 It is the hydrogen nuclear magnetic resonance spectrum of intermediate 1 of the present invention. DETAILED DESCRIPTION

[0028] The technical scheme of the present invention is further described below in conjunction with specific embodiments, but the present invention is not limited to these embodiments, and in order to better illustrate the content of the present application, numerous specific details are given in the specific embodiments below. It should be understood by those skilled in the art that without certain specific details, the present application can be implemented equally. In the embodiments, some methods, means, instruments, equipment, etc. well known to those skilled in the art are not described in detail, so as to highlight the purpose of the present application under the premise of not conflicting, the technical features disclosed in the embodiments of the present application can be arbitrarily combined, and the obtained technical scheme belongs to the content disclosed in the embodiments of the present application.

[0029] Example 1 Preparation of intermediate 1: Take a dry three-necked flask, add magnesium (58g, 2.23mol), iodine (2.8g) and tetrahydrofuran (100ml) and mix evenly, replace with nitrogen 3 times, start to heat until the solution refluxes, then slowly drop the tetrahydrofuran solution of p-bromofluorobenzene (110ml, 1M) into the above reaction flask, a large number of bubbles appear in the reaction solution and reflux violently, and the reaction solution is accompanied by fading. At this time, stop dropping the p-bromofluorobenzene solution. Keep stirring at this temperature, and continue to drop the p-bromofluorobenzene solution (2.19L) when the reflux slows down. Control the temperature of the reaction solution at about 80℃ during the dropwise addition, and keep warm and stir for 0.5 hours after the dropwise addition. Cool the reaction solution to 20℃ under nitrogen protection, dissolve 3-pentanone (199.6g, 1.294mol) in 1.2L tetrahydrofuran, control the temperature below 20℃ and dropwise, and add the solution after the dropwise addition is complete. Naturally heat and stir for 10h until the reaction is completed. The reaction solution was added dropwise into an aqueous solution of ammonium chloride (mass fraction 10%), stirred for 30 min after the addition, the reaction solution became turbid, and filtered through diatomaceous earth. The mother liquor was concentrated to a solvent-free state and directly distilled to obtain intermediate 1 (388.1 g, yield 93%).

[0030] Preparation of 2-(4-fluorophenyl)propionic acid-2-propylene ester: Add intermediate 1 (235.9 g, 1.294 mol) into a three-necked flask, add tetrahydrofuran and mix evenly (230 ml), replace with nitrogen 3 times, cool to -20 °C, control the temperature at -20 to -10 °C, add n-butyl lithium (673 ml, 1.682 mol, 2.4 M in THF), and naturally heat to 20 °C after the dropwise addition. The reaction solution will turn red. Continue stirring for 1 h, cool to -10 °C, and start to add methacrylic anhydride (199.6 g, 1.294 mol). Control the temperature at -10-0 °C. The color gradually disappears during the dropwise addition. After the dropwise addition is completed, the reaction solution turns yellow and continues to stir until the reaction is completed. At this time, it is necessary to add hydroquinone (2.1 g), and then drop an aqueous solution of ammonium chloride (100 g plus 500 ml of water) into the reaction solution and control the temperature to 0-10°C. After stirring for 10 minutes, let it stand to separate the layers. After the aqueous phase passes through diatomaceous earth, it is extracted three times with 500 ml of ethyl acetate. The organic phases are combined and concentrated to obtain a crude product. The crude product is directly and rapidly distilled under reduced pressure to obtain a crude product, which is then rectified again (positive boiling top temperature 99°C, pump pressure 148 Pa) to obtain 2-(4-fluorophenyl)propionic acid-2-propylene ester (261 g, yield 91%).

[0031] Example 2 Preparation of intermediate 1: Take a dry three-necked flask, add magnesium (58g, 2.23mol), azobisisobutyronitrile (3.6g) and tetrahydrofuran (100ml) and mix evenly, replace with nitrogen 3 times, start to heat until the solution refluxes, then slowly drop a tetrahydrofuran solution of p-bromofluorobenzene (110ml, 1M) into the above reaction flask, a large number of bubbles appear in the reaction solution and reflux violently, and the reaction solution is accompanied by fading. At this time, stop dropping the p-bromofluorobenzene solution. Keep stirring at this temperature, and continue to drop the p-bromofluorobenzene solution (2.19L) when the reflux slows down. Control the temperature of the reaction solution at about 80°C during the dropwise addition, and keep warm and stir for 0.5 hours after the dropwise addition. The reaction solution was cooled to 20°C under nitrogen protection, 3-pentanone (199.6 g, 1.294 mol) was dissolved in 1.2 L tetrahydrofuran, and the temperature was controlled below 20°C and added dropwise. After the addition was completed, the temperature was naturally raised and stirred for 10 hours until the reaction was completed. The reaction solution was restored to room temperature, and a 10% ammonium chloride aqueous solution was prepared. The temperature was controlled below 30°C, and the reaction solution was dropped into the ammonium chloride aqueous solution. After the dropwise addition, the reaction solution was stirred for 30 minutes. The reaction solution was turbid and filtered through diatomaceous earth. The mother liquor was concentrated to solvent-free and directly distilled to obtain intermediate 1 (328.86 g, yield 78.8%).

[0032] Preparation of 2-(4-fluorophenyl)propionic acid-2-propylene ester: Add intermediate 1 (235.9 g, 1.294 mol) into a three-necked flask, add tetrahydrofuran and mix evenly (230 ml), replace with nitrogen 3 times, cool to -20 °C, control the temperature at -20 to -10 °C, add n-butyl lithium (673 ml, 1.682 mol, 2.4 M in THF), and naturally heat to 20 °C after the dropwise addition. The reaction solution will turn red. Continue stirring for 1 h, cool to -10 °C, and start to add methacrylic anhydride (199.6 g, 1.294 mol) dropwise. Control the temperature at -10-0 °C. The color gradually disappears during the dropwise addition. After the dropwise addition is completed, the reaction solution turns yellow and continues to stir until the reaction is completed. At this time, it is necessary to add hydroquinone (2.1 g), and then drop an aqueous solution of ammonium chloride (100 g plus 500 ml of water) into the reaction solution and control the temperature to 0-10°C. After stirring for 10 minutes, let it stand to separate the layers. After the aqueous phase passes through diatomaceous earth, it is extracted three times with 500 ml of ethyl acetate. The organic phases are combined and concentrated to obtain a crude product. The crude product is directly and rapidly distilled under reduced pressure to obtain a crude product, which is then rectified again (positive boiling top temperature 99°C, pump pressure 148 Pa) to obtain 2-(4-fluorophenyl)propionic acid-2-propylene ester (253 g, yield 88%).

[0033] Example 3 Preparation of intermediate 1: Take a dry three-necked flask, add magnesium (58g, 2.23mol), iodine (2.8g) and tetrahydrofuran (100ml) and mix evenly, replace with nitrogen 3 times, start to heat up until the solution refluxes, slowly drop a tetrahydrofuran solution of p-bromofluorobenzene (200ml, 1M) into the above reaction flask, at this time, a large number of bubbles appear in the reaction solution and reflux violently, and the reaction solution is accompanied by fading. At this time, stop dropping the p-bromofluorobenzene solution. Keep stirring at this temperature, and continue to drop the p-bromofluorobenzene solution (2.1L) when the reflux slows down. Control the temperature of the reaction solution at about 80°C during the dropwise addition, and keep warm and stir for 0.5 hours after the dropwise addition. The reaction liquid was cooled to 20°C under nitrogen protection, 3-pentanone (199.6 g, 1.294 mol) was dissolved in 1.2 L tetrahydrofuran, and the temperature was controlled below 20°C. After the addition was completed, the temperature was naturally raised and stirred for 10 hours until the reaction was completed; the reaction liquid was restored to room temperature, and a 10% ammonium chloride aqueous solution was prepared, and the temperature was controlled below 30°C. The reaction liquid was dripped into the ammonium chloride aqueous solution, and stirred for 30 minutes after the dripping. The reaction liquid was turbid and filtered through diatomaceous earth. The mother liquor was concentrated to solvent-free and directly distilled to obtain intermediate 1 (371.42 g, yield 89%).

[0034] Preparation of 2-propenyl (4-fluorophenyl) propionate: Add intermediate 1 (235.9 g, 1.294 mol) into a three-necked flask, add tetrahydrofuran and mix evenly (230 ml), replace with nitrogen 3 times, cool to -20 °C, control the temperature at -20 to -10 °C, add n-butyl lithium (673 ml, 1.682 mol, 2.4 M in THF), and naturally heat to 20 °C after the dropwise addition. The reaction solution will turn red. Continue stirring for 1 h, cool to -10 °C, and start to add methacrylic anhydride (154.25 g, 1 mol) dropwise. Control the temperature at -10-0 °C. The color gradually disappears during the dropwise addition. After the dropwise addition is completed, the reaction solution turns yellow and continues to stir until the reaction is completed. At this time, cuprous chloride (2.1 g) needs to be added, and then an aqueous solution of ammonium chloride (100 g plus 500 ml of water) is dripped into the reaction solution and the temperature is controlled at 0-10°C. After stirring for 10 minutes, the mixture is allowed to stand for stratification. After the aqueous phase is passed through diatomaceous earth, it is extracted three times with 500 ml of ethyl acetate. The organic phases are combined and concentrated to obtain a crude product. The crude product is directly and rapidly distilled under reduced pressure to obtain a crude product, which is then rectified again (positive boiling top temperature 99°C, pump pressure 148 Pa) to obtain 2-(4-fluorophenyl)propionic acid-2-propenyl ester (250.2 g, yield 87%).

[0035] Comparative Example 1 Compared with Example 1, the first dropwise addition amount of p-bromofluorobenzene was changed, and the "p-bromofluorobenzene (110 ml, 1 M) tetrahydrofuran solution" was replaced with "p-bromofluorobenzene (666 ml, 1 M) tetrahydrofuran solution", and the other steps remained unchanged to prepare intermediate 1 (217.01 g, yield 52%).

[0036] Comparative Example 2 Compared with Example 1, in step 2, no polymerization inhibitor was added, and the other steps remained unchanged to prepare 2-(4-fluorophenyl)propionic acid-2-propenyl ester (204.2 g, yield 71%).

[0037] The diatomite in the embodiments of the present invention was purchased from Changbaishan Filter Aid Co., Ltd. in Linjiang City, with a mesh size of 200 meshes.

[0038] In summary, the present invention uses cheap p-bromofluorobenzene as a raw material, which greatly saves material costs. In addition, the addition of an initiator accelerates the free radical reaction, thereby preparing 2-(4-fluorophenyl)propionic acid-2-propylene ester with high purity and high yield.

[0039] Although the present invention has been described and illustrated with specific embodiments, it will be apparent to those skilled in the art that many other changes and modifications may be made without departing from the spirit and scope of the present invention. Therefore, all such changes and modifications within the scope of the present invention are consciously included in the appended claims.

Claims

1. A method for synthesizing 2-(4-fluorophenyl)propionic acid-2-propylene ester, a photoelectric functional material, characterized in that: The steps include: Step 1, add alkaline earth metal, initiator, solvent I to the reaction bottle, heat and reflux under an inert gas atmosphere, first drop the p-bromofluorobenzene solution, observe the change of the reaction solution, determine the initiation is successful, then drop the remaining p-bromofluorobenzene solution, drop it under controlled reflux conditions, keep it warm and stir after dropping, determine the control, then cool it down under an inert atmosphere, drop the 3-pentanone solution, control the temperature until the reaction is completed, and obtain intermediate 1 through post-treatment; Step 2: dissolving the intermediate 1 in solvent II, cooling under nitrogen atmosphere, dropping an alkyl metal solution, raising the temperature after dropping, cooling again and dropping methacrylic anhydride, controlling the temperature until the reaction is complete, adding a polymerization inhibitor to the reaction solution, and then post-treating to obtain 2-(4-fluorophenyl)propionic acid-2-propylene ester; Wherein, in step 1, the alkaline earth metal is at least one of beryllium, magnesium, calcium, and strontium; the initiator is at least one of azobisisobutyronitrile, dodecyl peroxide, iodine, and sodium persulfate; the solvent I is at least one of 1,2-dioxane, tetrahydrofuran, methanol, and acetonitrile; In step 2, the solvent II is at least one of ethanol, tetrahydrofuran, 2-methyltetrahydrofuran, and 2,2-dimethylcyclopentanone; In step 2, the alkyl metal solution is at least one of n-butyl lithium, triethylaluminum, and dimethyl copper lithium; In step 2, the polymerization inhibitor is at least one of methylene blue, cuprous chloride, ferric chloride and hydroquinone.

2. The method for synthesizing the optoelectronic functional material 2-(4-fluorophenyl)propionic acid-2-propylene ester according to claim 1, characterized in that: In the step 1, the amount of the p-bromofluorobenzene solution first added dropwise is no more than 20% of the amount of the p-bromofluorobenzene solution required for the reaction.

3. The method for synthesizing the optoelectronic functional material 2-(4-fluorophenyl)propionic acid-2-propylene ester according to claim 1, characterized in that: In the step 2, the alkyl metal solution is added dropwise continuously and slowly, and the temperature of the reaction solution is kept below 20° C. during the addition.

4. The method for synthesizing the optoelectronic functional material 2-(4-fluorophenyl)propionic acid-2-propylene ester according to claim 1, characterized in that: The solubility of the p-bromochlorobenzene solution is 0.5-5 mol / L; the concentration of the alkyl metal solution is 1-4 mol / L.

5. The method for synthesizing the optoelectronic functional material 2-(4-fluorophenyl)propionic acid-2-propylene ester according to claim 1, characterized in that: The molar ratio of p-bromofluorobenzene to alkaline earth metal is 1:(1.0-3.0).

6. The method for synthesizing the optoelectronic functional material 2-(4-fluorophenyl)propionic acid-2-propylene ester according to claim 1, characterized in that: The weight ratio of p-bromofluorobenzene to initiator is 1:(0.005-0.01).

7. The method for synthesizing the optoelectronic functional material 2-(4-fluorophenyl)propionic acid-2-propylene ester according to claim 1, characterized in that: The molar ratio of p-bromofluorobenzene to 3-pentanone is 1:(0.8-1.5).

8. The method for synthesizing the optoelectronic functional material 2-(4-fluorophenyl)propionic acid-2-propylene ester according to claim 1, characterized in that: The molar ratio of intermediate 1 to alkyl metal is 1:(1.0-3.0).

9. The method for synthesizing the optoelectronic functional material 2-(4-fluorophenyl)propionic acid-2-propylene ester according to claim 1, characterized in that: The molar ratio of intermediate 1 to methacrylic anhydride is 1:(1.0-1.5).

10. The method for synthesizing the optoelectronic functional material 2-(4-fluorophenyl)propionic acid-2-propylene ester according to claim 1, characterized in that: The weight ratio of the intermediate 1 to the inhibitor is 1:(0.01-0.1).

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