Preparation method of organic non-fullerene receptor intermediate
By simplifying the process conditions, purifying the organic non-fullerene acceptor intermediates by filtration, extraction and distillation, the problems of cumbersome preparation process, high cost and low yield in the prior art are solved, and efficient and low-cost industrial production is achieved.
Patent Information
- Application Number
- CN202510666449.X
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-05-22
- Publication Date
- 2025-09-02
AI Technical Summary
In the prior art, the preparation process of organic solar cell acceptor materials is complicated, has high cost, low yield and difficult purification, which limits the development of organic solar cells.
Using simplified process conditions, the organic non-fullerene acceptor intermediates were purified by filtration, extraction, distillation and recrystallization to avoid column chromatography and achieve large-scale production.
It greatly shortens production time, reduces costs, is suitable for industrial production, improves output and purity, and simplifies the process flow.
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Figure CN120574255A_ABST
Abstract
Description
Technical Field
[0001] The present invention relates to the field of preparation of organic solar cell acceptor materials, and in particular to a method for preparing an organic non-fullerene acceptor intermediate. Background Art
[0002] Among the emerging photovoltaic technologies, organic solar cells are highly favored due to their low cost, light weight, flexibility, and solution processing capabilities. Over the past few decades, researchers around the world have made tremendous efforts in device engineering and chemical structure modification of active layer materials, which has increased the energy conversion efficiency of single-cell organic solar cells from 1% to 21%, demonstrating great potential for commercial applications. Currently, the non-fullerene acceptor materials that maintain the energy conversion efficiency of organic solar cells are still derivatives of the Y6 series. As key materials in organic solar cells, their synthesis generally adopts fragment synthesis, specifically splitting the non-fullerene acceptor molecule into several important intermediate fragments, synthesizing them separately, and then splicing them into complete acceptor molecules. However, its production and preparation are still constrained by factors such as high cost, low yield, complex process, and difficult purification, which has limited the development of organic solar cells. Summary of the Invention
[0003] The technical problem to be solved by the present invention is to overcome the deficiencies of the prior art and provide a method for preparing an organic non-fullerene acceptor intermediate with low cost, high yield and simple process.
[0004] To solve the above technical problems, the present invention proposes a technical solution: a method for preparing an organic non-fullerene acceptor intermediate, comprising:
[0005] S1:
[0006]
[0007] According to the above reaction formula, compound 1 and compound A are mixed and stirred at a temperature of -30 to -20°C using dichloromethane as solvent, and metal chloride is added in batches and reacted at room temperature to obtain compound 2, where R2 is C n H 2n+1 , n=1~50;
[0008] The structural formula of the compound A is The equivalent ratio of compound 1, compound A and metal chloride is 1:1:1-1.5;
[0009] S2:
[0010]
[0011] According to the above reaction formula, compound 2, compound B and alkaline solution are added to a reaction kettle with α as solvent, the temperature is raised to 60-80°C for reaction, an alkaline regulator is added, the reaction is continued, and compound 3 is obtained after extraction;
[0012] The structural formula of the compound B is Where R3 is C n H 2n+1 , n=1~4;
[0013] The solvent α is any one of N,N-dimethylformamide, N,N-dimethylacetamide, tetrahydrofuran, 2-methyltetrahydrofuran, 2,5-dimethyltetrahydrofuran and 1,4-dioxane;
[0014] The equivalent ratio of compound 2, compound B and alkali solution is 1:1-1.5:1-2;
[0015] S3:
[0016]
[0017] According to the above reaction formula, compound 3 and sodium hydroxide are added to a reaction kettle with a monohydric alcohol as a solvent, the temperature is raised to 60-80°C, and refluxed for 18-24 hours. The reaction is monitored by TLC until the end point, the solvent is removed, 1-1.5 times the volume of the solvent is added with water, the pH is adjusted to 1-2, the mixture is stirred, filtered, and dried to obtain compound 4;
[0018] The equivalent ratio of compound 3 and sodium hydroxide is 1:2-2.5;
[0019] S4:
[0020]
[0021] Compound 4, tetramethylethylenediamine, and cuprous oxide were added to a reaction kettle using β as solvent, and the temperature was raised to 130-140°C. The reaction was allowed to proceed for 4-6 hours. The reaction was monitored by TLC until the end point. An acidifying agent was added to acidify the mixture, and the mixture was extracted with petroleum ether. The resulting organic phase was filtered through diatomaceous earth, and the filter cake was washed with petroleum ether. The organic solvent was removed under reduced pressure and dried to obtain compound 5.
[0022] The solvent β is any one of N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, and dimethyl sulfoxide;
[0023] The equivalent ratio of the compound 4, tetramethylethylenediamine and cuprous oxide is 1:0.1-0.3:0.05-0.1;
[0024] S5:
[0025]
[0026] Compound 5 was added to a reaction kettle using tetrahydrofuran as solvent, filled with inert gas, cooled to -78°C to -40°C, and compound C was added. The mixture was stirred for 1 to 2 hours, and then compound D was added. After reacting at room temperature for 6 to 18 hours, a quenching agent was added, and the reaction solution was poured into water, extracted with petroleum ether, and the organic solvent was removed under reduced pressure to obtain compound 6.
[0027] The compound C is one of n-butyl lithium or lithium diisopropylamide;
[0028] The structural formula of the compound D is Where R1=C n H 2n+1 , n=1~4;
[0029] The feed equivalent ratio of the compound 5, compound C and compound D is 1:1-1.3:1-1.3.
[0030] In one embodiment, the metal chloride is anhydrous aluminum trichloride, ferric chloride, tin tetrachloride, boron trifluoride, titanium tetrachloride or zinc chloride.
[0031] In one embodiment, the monohydric alcohol is ethanol, methanol or isopropanol.
[0032] In one embodiment, the acidifying agent is hydrochloric acid, sulfuric acid, acetic acid or oxalic acid.
[0033] In one embodiment, the alkali solution is anhydrous potassium carbonate, anhydrous sodium carbonate, sodium bicarbonate, potassium bicarbonate, sodium hydroxide, anhydrous cesium carbonate, potassium hydroxide, triethylamine or diisopropylethylamine.
[0034] In one embodiment, the alkaline regulator is sodium hydroxide, potassium hydroxide, triethylamine, diisopropylethylamine or cesium hydroxide.
[0035] Compared with the prior art, the advantages of the present invention are as follows: the preparation process of the non-fullerene acceptor materials of the Y6 series in the prior art is cumbersome. For example, the synthesis process of the key intermediate of Y6, tributyl (6-undecylthieno [3,2-b] thiophene-2-yl) stannane, is the most complicated. Almost every step requires column chromatography purification before proceeding to the next step. If purification is not performed, impurities will participate in the reaction, affecting the purification and separation of the next step, and even destroying the structure of the product in the next step. In addition, column chromatography of the product synthesized in each step takes a long time. A purification time of 1 to 2 hours is required for a ten-gram level. For a kilogram level or even an industrial production level, the required purification time is even longer. Considering the economic and time costs, it is unrealistic to still use column chromatography for purification of large-scale synthesis. In the present invention, the synthesis and purification of the organic non-fullerene acceptor intermediate are both optimized. By optimizing the process conditions, simple and rapid post-treatment methods such as filtration, extraction, distillation, and recrystallization are primarily employed during the purification process to remove most impurities, enabling kilogram-level production. This significantly shortens production time, enables continuous industrial production, and is suitable for large-scale production. Furthermore, the impurity removal method provided by the present invention is simple, does not require large-scale equipment, and is less constrained by external factors such as economic equipment and manpower. BRIEF DESCRIPTION OF THE DRAWINGS
[0036] In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the following briefly introduces the drawings required for use in the embodiments or the description of the prior art. Obviously, the drawings described below are some embodiments of the present invention. For ordinary technicians in this field, other drawings can be obtained based on these drawings without paying any creative work.
[0037] Figure 1 This is the TLC chart of the reaction endpoint of S1 in Example 6 of the present invention;
[0038] Figure 2 This is the TLC chart of the reaction endpoint of S2 in Example 6 of the present invention;
[0039] Figure 3 This is the TLC chart of the reaction endpoint of S3 in Example 6 of the present invention;
[0040] Figure 4 This is the TLC chart of the reaction endpoint of S4 in Example 6 of the present invention;
[0041] Figure 5 This is the TLC chart of the reaction endpoint of S5 in Example 6 of the present invention;
[0042] Figure 6 1HNMR diagram of the product compound 5 in Comparative Example 4 of the present invention;
[0043] Figure 7This is the HNMR spectrum of compound 5, the product of Example 4 of the present invention. DETAILED DESCRIPTION
[0044] In order to facilitate understanding of the present invention, the present invention will be described more comprehensively and meticulously below in conjunction with preferred embodiments, but the protection scope of the present invention is not limited to the following specific embodiments.
[0045] Unless otherwise defined, all technical terms used hereinafter have the same meanings as those generally understood by those skilled in the art. The technical terms used herein are only for the purpose of describing specific embodiments and are not intended to limit the scope of protection of the present invention.
[0046] Unless otherwise specified, all reagents and raw materials used in the present invention are commercially available products or products that can be prepared by known methods.
[0047] See also Figure 1-7 , a method for preparing an organic non-fullerene acceptor intermediate, comprising:
[0048] S1:
[0049]
[0050] According to the above reaction formula, compound 1 and compound A are mixed and stirred at a temperature of -30 to -20°C using dichloromethane as solvent, and metal chloride is added in batches and reacted at room temperature to obtain compound 2, where R2 is C n H 2n+1 , n=1~50;
[0051] The structural formula of the compound A is The equivalent ratio of compound 1, compound A and metal chloride is 1:1:1-1.5;
[0052] Specifically, the metal chloride is anhydrous aluminum trichloride, ferric chloride, tin tetrachloride, boron trifluoride, titanium tetrachloride or zinc chloride.
[0053] In the reaction and purification process, compound 1 and compound A can be fully mixed at low temperature, and then reacted with a metal chloride at room temperature to obtain compound 2.
[0054] S2:
[0055]
[0056] According to the above reaction formula, compound 2, compound B and alkaline solution are added to a reaction kettle with α as solvent, the temperature is raised to 60-80°C for reaction, an alkaline regulator is added, the reaction is continued, and compound 3 is obtained after extraction;
[0057] The structural formula of the compound B is Where R3 is C n H 2n+1 , n=1~4;
[0058] The solvent α is any one of N,N-dimethylformamide, N,N-dimethylacetamide, tetrahydrofuran, 2-methyltetrahydrofuran, 2,5-dimethyltetrahydrofuran and 1,4-dioxane;
[0059] The equivalent ratio of compound 2, compound B and alkali solution is 1:1-1.5:1-2;
[0060] Specifically, the alkali solution is anhydrous potassium carbonate, anhydrous sodium carbonate, sodium bicarbonate, potassium bicarbonate, sodium hydroxide, anhydrous cesium carbonate, potassium hydroxide, triethylamine or diisopropylethylamine.
[0061] The alkaline regulator is sodium hydroxide, potassium hydroxide, triethylamine, diisopropylethylamine or cesium hydroxide.
[0062] In the above reaction, compound 3 can be obtained by extraction, which simplifies the process flow.
[0063] S3:
[0064]
[0065] According to the above reaction formula, compound 3 and sodium hydroxide are added to a reactor with a monohydric alcohol as a solvent, the temperature is raised to 60-80°C, and refluxed for 18-24 hours. The reaction is monitored by TLC until the end point, the solvent is removed, 1-1.5 times the solvent amount of water is added, the pH is adjusted to 1-2, stirred, filtered, and dried to obtain compound 4.
[0066] The equivalent ratio of compound 3 and sodium hydroxide is 1:2-2.5;
[0067] Specifically, the monohydric alcohol is ethanol, methanol or isopropanol.
[0068] In the above reaction, after the reaction is completed, the solvent is first removed, and then water is added to adjust to strong acidity, and then filtered and dried to obtain compound 4. The process is simple and time-saving.
[0069] S4:
[0070]
[0071] Compound 4, tetramethylethylenediamine, and cuprous oxide were added to a reaction kettle using β as solvent. The temperature was raised to 130-140°C and the reaction was carried out for 4-6 hours. The reaction was monitored by TLC until the end point. An acidifying agent was added to acidify the mixture, and the mixture was extracted with petroleum ether. The obtained organic phase was filtered through diatomaceous earth, and the filter cake was washed with petroleum ether. The organic solvent was removed under reduced pressure and dried to obtain compound 5.
[0072] The solvent β is any one of N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, and dimethyl sulfoxide;
[0073] The equivalent ratio of the compound 4, tetramethylethylenediamine and cuprous oxide is 1:0.1-0.3:0.05-0.1;
[0074] Specifically, the acidifying agent is hydrochloric acid, sulfuric acid, acetic acid or oxalic acid.
[0075] After the reaction, the product was acidified and then extracted, and the filter cake was washed with an extractant to obtain compound 5.
[0076] S5:
[0077]
[0078] Compound 5 was added to a reaction kettle using tetrahydrofuran as solvent, filled with inert gas, cooled to -78°C to -40°C, and compound C was added. The mixture was stirred for 1 to 2 hours, and then compound D was added. After reacting at room temperature for 6 to 18 hours, a quenching agent was added, and the reaction solution was poured into water, extracted with petroleum ether, and the organic solvent was removed under reduced pressure to obtain compound 6.
[0079] The compound C is one of n-butyl lithium or lithium diisopropylamide;
[0080] The structural formula of the compound D is Where R1=C n H 2n+1 , n=1~4;
[0081] The feed equivalent ratio of the compound 5, compound C and compound D is 1:1-1.3:1-1.3.
[0082] After the reaction, the mixture was extracted with petroleum ether and the organic solvent was removed under reduced pressure to obtain compound 6.
[0083] Example 1 and Comparative Example 1
[0084] Example 1
[0085] The reaction formula of S1 is as follows:
[0086]
[0087] According to the reaction formula, 1 kg of compound 1 and 1.0 equivalent of dodecanoyl chloride were added to a 5 L reactor, 6 V of dichloromethane was added, stirring was started, the temperature was lowered to -30 ° C, 1.05 equivalents of anhydrous aluminum chloride were added in batches, and after the addition of aluminum chloride, the temperature was returned to room temperature and the reaction was carried out for 12 hours. The reaction was monitored by TLC until the end point.
[0088] The obtained reaction solution was decompressed to remove half of the dichloromethane, the reaction solution was discharged, poured into 6V volume of water, stirred for 30 minutes, allowed to stand to separate, the organic phase was collected, and the solvent was removed under reduced pressure to obtain a black oily compound 2 (1.7 kg, yield 80%).
[0089] Comparative Example 1: The reaction was carried out in the same manner as in Example 1. After the reaction reached the endpoint as monitored by TLC, the reaction solution was discharged and poured into 6V volume of water. The mixture was extracted three times with dichloromethane. The organic solvent was removed under reduced pressure. The crude product was purified by column chromatography for 2 days to obtain Compound 2 (1.12 kg, yield 53%) as a yellow oil.
[0090] Example 2 and Comparative Example 2
[0091] The S2 reaction formula is as follows:
[0092]
[0093] Example 2: According to the reaction formula, 1 kg of compound 2 obtained in Example 1 was added to a 5 L reactor, followed by the addition of 1.5 V of N,N-dimethylformamide and 1.1 equivalents of anhydrous potassium carbonate. The mixture was stirred for 30 minutes, and 1.0 equivalents of ethyl mercaptoacetate was added. The temperature was raised to 60°C, and the reaction was allowed to proceed for 24 hours. The reaction was monitored by TLC until the end point.
[0094] 1.5V volume of 1M sodium hydroxide aqueous solution was added, stirring was continued for 2 hours, 3V volume of dichloromethane was added for extraction, and the organic solvent was removed under reduced pressure to obtain black oily compound 3 (0.84 kg, yield 79%).
[0095] Comparative Example 2: According to the reaction formula, 1 kg of compound 2 obtained in Comparative Example 1 was taken and reacted in the manner of Example 2. The reaction was monitored by TLC until the end point. A 1.5 V volume of 1 M sodium hydroxide aqueous solution was added and stirring was continued for 2 hours. The mixture was extracted three times with dichloromethane and the organic solvent was removed under reduced pressure. The crude product was purified by column chromatography for 1 day to obtain a yellow oily liquid (0.90 kg, yield 85%).
[0096] Example 3 and Comparative Example 3
[0097] The S3 reaction formula is as follows:
[0098]
[0099] Example 3: According to the reaction formula, 0.8 kg of compound 3 obtained in Example 2 was added to a 5 L reactor, and 4 V volume of ethanol was added, stirred evenly, and then 2.0 equivalents of sodium hydroxide was added. The temperature was raised to 90 ° C. and the reaction was reacted for 20 hours. The reaction was monitored by TLC until the end point.
[0100] Most of the ethanol was distilled off under reduced pressure, 4V volume of water was added, stirred for 1 hour, and then concentrated hydrochloric acid was added to acidify to pH 1-2, stirred for 1 hour, filtered, and dried to obtain yellow solid compound 4 (0.55 kg, yield 74%).
[0101] Comparative Example 3: According to the reaction formula, 0.8 kg of compound 3 obtained in Comparative Example 2 was taken and reacted according to Example 3. The reaction was monitored by TLC until the end point. Most of the ethanol was distilled off under reduced pressure, 4 V volume of water was added, and stirred for 1 hour. Concentrated hydrochloric acid was then added to acidify to pH 1-2, stirred for 1 hour, filtered, and dried to obtain a yellow solid crude product. The product was purified by column chromatography for 2 days to obtain white solid compound 4 (0.65 kg, yield 88%).
[0102] Example 4 and Comparative Example 4
[0103] The S4 reaction formula is as follows:
[0104]
[0105] Example 4: According to the reaction formula, 0.5 kg of compound 4 obtained in Example 3 was taken and added to a 2 L three-necked flask, and then 3 V volume of N, N-dimethylformamide and 0.05 equivalent of cuprous oxide were added. The mixture was evacuated three times, and 0.1 equivalent of tetramethylethylenediamine was added. The temperature was raised to 140 ° C. and the reaction was reacted for 6 hours. The reaction was monitored by TLC until the end point.
[0106] The mixture was poured into 3V volume of 1N hydrochloric acid solution, extracted three times with petroleum ether, the upper liquid was collected, filtered through diatomaceous earth, the filter cake was rinsed with petroleum ether, the organic solvent was removed under reduced pressure, and dried to obtain a colorless to light yellow oily compound 5 (0.37 kg, yield 86%). The NMR results are as follows Figure 7 As shown, combined with the diagram, it can be seen that the purity and yield of compound 5 obtained by the method of the present application are similar to those of the comparative example, but the efficiency of the present application is greatly improved.
[0107] Comparative Example 4: According to the reaction formula, 0.5 kg of compound 4 obtained in Comparative Example 3 was taken and reacted in the same manner as in Example 4. The reaction was monitored by TLC until the end point, and then poured into a 3V volume of 1N hydrochloric acid solution. The dichloromethane was extracted three times, and the dichloromethane was back-extracted with water five times to obtain an organic phase. The organic solvent was removed under reduced pressure, and the resulting yellow oily crude product was purified by column chromatography for 3 hours to obtain a colorless to light yellow oily compound 5 (0.39 kg, yield 90%). The nuclear magnetic resonance results are as follows Figure 6 shown.
[0108] Example 5 and Comparative Example 5
[0109] The reaction formula of S5 is as follows:
[0110]
[0111] Example 5: According to the reaction formula, 0.3 kg of compound 5 obtained in Example 4 was taken and added to a 2 L three-necked flask, followed by a 5 V volume of tetrahydrofuran. The mixture was ventilated three times and cooled to -78 ° C. 1.1 equivalents of n-butyl lithium was slowly added dropwise with a syringe. After the addition was complete, the mixture was stirred for 2 hours, and then 1.2 equivalents of n-tributyltin chloride were injected with a syringe. The mixture was reacted at room temperature for 12 hours. TLC monitored the complete reaction of the raw materials. 100 mL of water was injected to quench the reaction. The reaction solution was poured into a 5 V volume of water, extracted three times with petroleum ether, and the organic solvent was removed under reduced pressure to obtain a colorless to light yellow oily liquid compound 6 (0.57 kg, yield 96%).
[0112] Comparative Example 5: According to the reaction formula, 0.3 kg of compound 5 obtained in Comparative Example 4 was taken and reacted in the same manner as in Example 5. The reaction of the raw materials was completed by TLC monitoring. 100 mL of water was injected to quench the reaction. The reaction solution was poured into 2 V volume of water, extracted three times with petroleum ether, and the organic solvent was removed under reduced pressure. The crude product was purified by column chromatography for 3 hours to obtain a colorless oily liquid compound 6 (0.56 kg, yield 94%).
[0113] By comparing the above experimental data, it can be seen that the method provided by the present invention greatly shortens the time, manpower and material resources required for post-reaction treatment and purification, and reduces the wastewater and waste residue generated by column chromatography purification. Compared with Comparative Example 1, the yield and purity of the final intermediate obtained in Example 5 and the final intermediate obtained in the comparative example are similar, but the method of the present application greatly improves efficiency, saves time and equipment costs.
[0114] Example 6 Kilogram-level scale-up experiment
[0115] See also Figure 1-5 .
[0116] S1: In a 10L reactor, 3kg of compound 1 and 1.0 equivalent of dodecanoyl chloride were added, 6V of dichloromethane was added, stirring was started, the temperature was lowered to -30°C, 1.05 equivalents of anhydrous aluminum chloride were added in batches, after the addition of aluminum chloride, the temperature was returned to room temperature, the reaction was carried out for 12 hours, and the reaction was monitored by TLC until the end point. The results were as follows: Figure 1 shown.
[0117] The obtained reaction solution was removed by reducing pressure and half of the dichloromethane was removed. The reaction solution was discharged and poured into 6V volume of water, stirred for 30 minutes, allowed to stand and separate, the organic phase was collected, and the solvent was removed by reducing pressure to obtain black oily compound 2 (3.4 kg, yield 80%).
[0118] S2: Take 3 kg of the obtained compound 2 and add it to a 10 L reactor. Then add 1.5 V volume of N, N-dimethylformamide and 1.1 equivalents of anhydrous potassium carbonate. Start stirring. After 30 minutes, add 1.0 equivalent of ethyl mercaptoacetate. Heat to 60 ° C and react for 24 hours. Monitor the reaction by TLC until the end point. The results are as follows: Figure 2 shown.
[0119] 1.5V volume of 1M sodium hydroxide aqueous solution was added, stirring was continued for 2 hours, 3V volume of dichloromethane was added for extraction, and the organic solvent was removed under reduced pressure to obtain black oily compound 3 (2.52 kg, yield 79%).
[0120] S3: Take 2.4 kg of the obtained compound 3 and add it to a 10 L reactor. Then add 4 V of ethanol and stir evenly. Then add 2.0 equivalents of sodium hydroxide and heat to 90 ° C. and react for 20 hours. The reaction is monitored by TLC until the end point. The results are as follows: Figure 3 shown.
[0121] Most of the ethanol was distilled off under reduced pressure, 4V volume of water was added, stirred for 1 hour, and then concentrated hydrochloric acid was added to acidify to pH 1-2, stirred for 1 hour, filtered, and dried to obtain yellow solid compound 4 (1.65 kg, yield 74%).
[0122] S4: 1.5 kg of the obtained compound 4 was added to a 5 L reactor, and then 3 V of N, N-dimethylformamide and 0.05 equivalents of cuprous oxide were added. The reaction was evacuated three times, and 0.1 equivalents of tetramethylethylenediamine were added. The temperature was raised to 140 ° C and the reaction was carried out for 6 hours. The reaction was monitored by TLC until the end point. The results were as follows: Figure 4 shown.
[0123] The mixture was poured into 3V volume of 1N hydrochloric acid solution and extracted with petroleum ether three times. The upper liquid was collected and filtered through diatomaceous earth. The filter cake was rinsed with petroleum ether. The organic solvent was removed under reduced pressure and dried to obtain a colorless to light yellow oily compound 5 (1.1 kg, yield 86%).
[0124] S5: Take 0.9 kg of the obtained compound 5 and add it to a 5 L three-necked flask, then add 5 V volume of tetrahydrofuran, replace the argon three times, cool to -78 ° C, slowly add 1.1 equivalents of n-butyl lithium with a syringe, stir for 2 hours after the addition is complete, and then inject 1.2 equivalents of n-tributyltin chloride with a syringe. React at room temperature for 12 hours. TLC monitors the reaction of the raw materials. The results are as follows Figure 5 300 mL of water was injected to quench the reaction, and the reaction solution was poured into 5 V of water, extracted three times with petroleum ether, and the organic solvent was removed under reduced pressure to obtain a colorless to light yellow oily liquid compound 6 (1.7 kg, yield 96%).
[0125] As can be seen from Example 6, the method provided by the present invention still maintains good stability in kilogram-scale scale-up experiments, not only simplifying the post-processing purification steps, but also improving the yield to a certain extent. The continuous feeding method and the fact that the purity equivalent to that obtained by column chromatography purification are obtained during the intermediate preparation process without the use of column chromatography and more advanced purification methods indicate that the method provided by the present invention is suitable for industrial production. The technology provided by the present invention can be applied to industrial-scale scale-up, further improving the production and market supply of key intermediates of non-fullerene acceptor materials.
[0126] The above are only preferred embodiments of the present invention. It should be pointed out that the present invention is not limited to the above embodiments. For ordinary technicians in this technical field, several improvements and modifications can be made without departing from the principles of the present invention. Any modifications, equivalent substitutions, improvements, etc. made within the spirit and principles of the present invention should also be regarded as the scope of protection of the present invention.
Claims
1. A method for preparing an organic non-fullerene acceptor intermediate, characterized in that: include: S1： According to the above reaction formula, compound 1 and compound A are mixed and stirred at a temperature of -30 to -20°C using dichloromethane as solvent, and metal chloride is added in batches and reacted at room temperature to obtain compound 2, where R2 is C n H 2n+1 , n=1~50; The structural formula of the compound A is The equivalent ratio of compound 1, compound A and metal chloride is 1:1:1-1.5; S2： According to the above reaction formula, compound 2, compound B and alkaline solution are added to a reaction kettle with α as solvent, the temperature is raised to 60-80°C for reaction, an alkaline regulator is added, the reaction is continued, and compound 3 is obtained after extraction; The structural formula of the compound B is Where R3 is C n H 2n+1 , n=1~4; The solvent α is any one of N,N-dimethylformamide, N,N-dimethylacetamide, tetrahydrofuran, 2-methyltetrahydrofuran, 2,5-dimethyltetrahydrofuran and 1,4-dioxane; The equivalent ratio of compound 2, compound B and alkali solution is 1:1-1.5:1-2; S3： According to the above reaction formula, compound 3 and sodium hydroxide are added to a reaction kettle with a monohydric alcohol as a solvent, the temperature is raised to 60-80°C, and refluxed for 18-24 hours. The reaction is monitored by TLC until the end point, the solvent is removed, 1-1.5 times the volume of the solvent is added with water, the pH is adjusted to 1-2, the mixture is stirred, filtered, and dried to obtain compound 4; The equivalent ratio of compound 3 and sodium hydroxide is 1:2-2.5; S4： Compound 4, tetramethylethylenediamine, and cuprous oxide were added to a reaction kettle using β as solvent, and the temperature was raised to 130-140°C. The reaction was allowed to proceed for 4-6 hours. The reaction was monitored by TLC until the end point. An acidifying agent was added to acidify the mixture, and the mixture was extracted with petroleum ether. The resulting organic phase was filtered through diatomaceous earth, and the filter cake was washed with petroleum ether. The organic solvent was removed under reduced pressure and dried to obtain compound 5. The solvent β is any one of N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, and dimethyl sulfoxide; The equivalent ratio of the compound 4, tetramethylethylenediamine and cuprous oxide is 1:0.1-0.3:0.05-0.1; S5： Compound 5 was added to a reaction kettle using tetrahydrofuran as solvent, filled with inert gas, cooled to -78°C to -40°C, and compound C was added. The mixture was stirred for 1 to 2 hours, and then compound D was added. After reacting at room temperature for 6 to 18 hours, a quenching agent was added, and the reaction solution was poured into water, extracted with petroleum ether, and the organic solvent was removed under reduced pressure to obtain compound 6. The compound C is one of n-butyl lithium or lithium diisopropylamide; The structural formula of the compound D is Where R1=C n H 2n+1 , n=1~4; The feed equivalent ratio of the compound 5, compound C and compound D is 1:1-1.3:1-1.
3.
2. The method for preparing an organic non-fullerene acceptor intermediate according to claim 1, wherein: The metal chloride is anhydrous aluminum trichloride, ferric chloride, tin tetrachloride, boron trifluoride, titanium tetrachloride or zinc chloride.
3. The method for preparing an organic non-fullerene acceptor intermediate according to claim 1, wherein: The monohydric alcohol is ethanol, methanol or isopropanol.
4. The method for preparing an organic non-fullerene acceptor intermediate according to claim 1, wherein: The acidifying agent is hydrochloric acid, sulfuric acid, acetic acid or oxalic acid.
5. The method for preparing the organic non-fullerene acceptor intermediate according to claim 1, wherein: The alkali solution is anhydrous potassium carbonate, anhydrous sodium carbonate, sodium bicarbonate, potassium bicarbonate, sodium hydroxide, anhydrous cesium carbonate, potassium hydroxide, triethylamine or diisopropylethylamine.
6. The method for preparing an organic non-fullerene acceptor intermediate according to claim 1, wherein: The alkaline regulator is sodium hydroxide, potassium hydroxide, triethylamine, diisopropylethylamine or cesium hydroxide.