WO2021114893A1 - Method for preparing 5-acetyl acetylaminobenzimidazolone - Google Patents
Method for preparing 5-acetyl acetylaminobenzimidazolone Download PDFInfo
- Publication number
- WO2021114893A1 WO2021114893A1 PCT/CN2020/123240 CN2020123240W WO2021114893A1 WO 2021114893 A1 WO2021114893 A1 WO 2021114893A1 CN 2020123240 W CN2020123240 W CN 2020123240W WO 2021114893 A1 WO2021114893 A1 WO 2021114893A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- aminobenzimidazolone
- acetoacetamidobenzimidazolone
- temperature
- sodium hydrosulfide
- preparing
- Prior art date
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D235/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, condensed with other rings
- C07D235/02—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, condensed with other rings condensed with carbocyclic rings or ring systems
- C07D235/04—Benzimidazoles; Hydrogenated benzimidazoles
- C07D235/24—Benzimidazoles; Hydrogenated benzimidazoles with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached in position 2
- C07D235/26—Oxygen atoms
Definitions
- the invention belongs to the technical field of fine chemical technology, and specifically relates to a preparation method of 5-acetoacetamidobenzimidazolone.
- 5-acetoacetamidobenzimidazolone (AABI) is an important chemical intermediate. Its series of products are widely used in medicine, pesticides, special materials and other fields, and benzimidazole prepared with it as a coupling component Ketone organic pigments have good heat resistance, light resistance, weather resistance, solvent resistance and other excellent properties, which make the market demand huge. However, the domestic production level of 5-acetoacetamidobenzimidazolone is not high, so this product has a good market prospect.
- the existing preparation method mainly uses 5-aminobenzimidazolone and diketene as raw materials to undergo acylation reaction to prepare 5-acetoacetylaminobenzimidazolone.
- 5-aminobenzimidazolone is easily oxidized and has low solubility in water. Therefore, most of the existing processes are to dissolve 5-aminobenzimidazolone under acidic conditions in alcohol solvents, while adding antioxidants to avoid amino groups. Oxidation.
- Chinese patent CN101307023A discloses a method for preparing 5-acetoacetaminobenzimidazolone from 5-aminobenzimidazolone and diketene, phosphoric acid, liquid caustic soda, and water.
- the 5-acetoacetaminobenzimidazolone produced by this process Although the product purity is relatively high, the total yield is only 75%, and there is still a lot of room for improvement.
- the addition of concentrated phosphoric acid produces a large amount of phosphorus-containing wastewater during the production process, which increases the cost of environmental protection treatment in the later stage and is not conducive to the concept of green chemistry. Therefore, solving the existing problems in the process of synthesizing 5-acetoacetamidobenzimidazolone is of great significance for protecting the environment and reducing production costs.
- the purpose of the present invention is to provide a method for preparing 5-acetoacetamidobenzimidazolone with low production cost, environmental protection, high product quality and high yield.
- the technical solution adopted by the present invention to solve its technical problems is: a preparation method of 5-acetoacetamidobenzimidazolone, which includes the following steps:
- step 2) Add diketene dropwise to the intermediate filtrate of step 1) at a certain temperature, after keeping it for a certain period of time, cooling, filtering, and drying to obtain 5-acetoacetamidobenzimidazolone.
- the mass concentration of the sodium hydrosulfide solution in the step 1) is 15-30%.
- the mass ratio of solvent water, 5-aminobenzimidazolone, sodium hydrosulfide solution and activated carbon is: (21.4-28.5):1:(0.21-0.36):(0.1-0.22) .
- the temperature in the step 1) is 60-85° C., and the time is 0.5-1 h.
- the mass ratio of diketene to 5-aminobenzimidazolone in step 2) is (0.7-0.95):1.
- the holding temperature is 60-85°C
- the holding time is 0.5-1.5h.
- the temperature is lowered to 45° C. and filtered.
- the present invention has the following beneficial effects: Compared with the existing method, the present invention adopts sodium hydrosulfide solution, which can not only accelerate the dissolution of 5-aminobenzimidazolone, but also prevent the oxidation of 5-aminobenzimidazolone.
- Sodium hydrosulfide The H 2 S gas produced by hydrolysis at high temperature can be absorbed by sodium hydroxide solution to generate sodium hydrosulfide solution, which can be recycled to avoid exhaust gas emission. Water is used as solvent to reduce the cost when alcohol is used as solvent. , To avoid the hidden dangers of product drying, and the reaction time is short.
- the purity of the obtained product is greater than or equal to 99.2%, and the yield is greater than or equal to 85%, which not only ensures the quality but also improves the yield.
- a preparation method of 5-acetoacetamidobenzimidazolone includes the following steps:
- step 2) Add diketene dropwise to the intermediate filtrate of step 1) at a certain temperature.
- the mass ratio of diketene to 5-aminobenzimidazolone is (0.7-0.95): 1, after holding at 60-85°C for 0.5-1.5h, The temperature is lowered to 45° C. and filtered, and dried to obtain 5-acetoacetamidobenzimidazolone.
- the 5-acetoacetaminobenzimidazolone obtained in this example was detected by liquid chromatography.
- the purity of the 5-acetoacetaminobenzimidazolone prepared by the present invention was 99.36%, the raw material peak was 0.025%, and the acetic anhydride peak was 0.183%. , In line with industry standards.
- the 5-acetoacetaminobenzimidazolone obtained in this example was detected by liquid chromatography.
- the purity of the 5-acetoacetaminobenzimidazolone prepared by the present invention was 99.41%, the raw material peak was 0.011%, and the acetic anhydride peak was 0.17%. , In line with industry standards.
- the 5-acetoacetaminobenzimidazolone obtained in this example was detected by liquid chromatography.
- the purity of the 5-acetoacetaminobenzimidazolone prepared by the present invention was 99.43%, the raw material peak was 0.015%, and the acetic anhydride peak was 0.181%. , In line with industry standards.
- the 5-acetoacetaminobenzimidazolone obtained in this example was detected by liquid chromatography.
- the purity of the 5-acetoacetaminobenzimidazolone prepared by the present invention was 99.40%, the raw material peak was 0.023%, and the acetic anhydride peak was 0.179%. , In line with industry standards.
- the present invention is not limited to the above-mentioned embodiments.
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Nitrogen Condensed Heterocyclic Rings (AREA)
- Plural Heterocyclic Compounds (AREA)
Abstract
Disclosed is a method for preparing 5-acetyl acetylaminobenzimidazolone, comprising using water as a solvent, adding 5-aminobenzimidazolone, a sodium hydrosulfide solution, activated carbon and mixing same, reacting same at a certain temperature for a certain time, and filtering same to obtain an intermediate filtrate; and adding diketene dropwise into the intermediate filtrate at a certain temperature, maintaining the temperature for a certain time, and cooling, filtering, and drying the mixture to obtain the 5-acetyl acetylaminobenzimidazolone. The use of the sodium hydrosulfide solution can not only accelerate the dissolution of the 5-aminobenzimidazolone, but can also prevent oxidation of the 5-aminobenzimidazolone; H2S gas generated from hydrolysis of sodium hydrosulfide at a high temperature is absorbed by a sodium hydroxide solution and then formed into a sodium hydrosulfide solution, such that same can be recycled and the emission of waste gas is avoided; and the use of water as a solvent reduces costs compared to when alcohol is used as a solvent, and prevents safety hazards when a product is dried, with the reaction time being short. The product has a purity of ≥99.2%, and a yield of ≥85%, ensuring both quality and improvement of the yield.
Description
本发明属于精细化工工艺技术领域，具体涉及一种5-乙酰乙酰氨基苯并咪唑酮的制备方法。The invention belongs to the technical field of fine chemical technology, and specifically relates to a preparation method of 5-acetoacetamidobenzimidazolone.
5-乙酰乙酰氨基苯并咪唑酮（AABI）是一种重要的化工中间体，其系列产品被广泛的应用于医药、农药、特殊材料等领域，并且以其作为偶合组分制备的苯并咪唑酮类有机颜料具有较好的耐热、耐光、耐气候、耐溶剂等优良性能，使其市场需求量巨大。而国内5-乙酰乙酰氨基苯并咪唑酮的生产水平不高，因此该产品具有较好的市场前景。5-acetoacetamidobenzimidazolone (AABI) is an important chemical intermediate. Its series of products are widely used in medicine, pesticides, special materials and other fields, and benzimidazole prepared with it as a coupling component Ketone organic pigments have good heat resistance, light resistance, weather resistance, solvent resistance and other excellent properties, which make the market demand huge. However, the domestic production level of 5-acetoacetamidobenzimidazolone is not high, so this product has a good market prospect.
现有制备方法中主要是以5-氨基苯并咪唑酮和双乙烯酮为原料发生酰化反应制备5-乙酰乙酰氨基苯并咪唑酮。5-氨基苯并咪唑酮作为重要原料，氨基易被氧化，在水中溶解度低，因此现存工艺大多是在醇溶剂酸性条件下溶解5-氨基苯并咪唑酮，同时加入抗氧剂来避免氨基的氧化。中国专利CN101307023A公开了一种以5-氨基苯并咪唑酮和双乙烯酮、磷酸、液碱、水制备5-乙酰乙酰氨基苯并咪唑酮的方法，该工艺生产的5-乙酰乙酰氨基苯并咪唑酮虽然产品纯度较高，但是总收率仅75%，仍旧有很大的提升空间，浓磷酸的加入，使得生产过程中产生了大量含磷废水，增加了后期环保处理成本，不利于绿色化学理念的推广；因此解决现有合成5-乙酰乙酰氨基苯并咪唑酮工艺中存在的问题对于保护环境、降低生产成本具有很重要的意义。The existing preparation method mainly uses 5-aminobenzimidazolone and diketene as raw materials to undergo acylation reaction to prepare 5-acetoacetylaminobenzimidazolone. As an important raw material, 5-aminobenzimidazolone is easily oxidized and has low solubility in water. Therefore, most of the existing processes are to dissolve 5-aminobenzimidazolone under acidic conditions in alcohol solvents, while adding antioxidants to avoid amino groups. Oxidation. Chinese patent CN101307023A discloses a method for preparing 5-acetoacetaminobenzimidazolone from 5-aminobenzimidazolone and diketene, phosphoric acid, liquid caustic soda, and water. The 5-acetoacetaminobenzimidazolone produced by this process Although the product purity is relatively high, the total yield is only 75%, and there is still a lot of room for improvement. The addition of concentrated phosphoric acid produces a large amount of phosphorus-containing wastewater during the production process, which increases the cost of environmental protection treatment in the later stage and is not conducive to the concept of green chemistry. Therefore, solving the existing problems in the process of synthesizing 5-acetoacetamidobenzimidazolone is of great significance for protecting the environment and reducing production costs.
本发明的目的在于提供一种生产成本低、绿色环保、产品质量及收率高的5-乙酰乙酰氨基苯并咪唑酮的制备方法。The purpose of the present invention is to provide a method for preparing 5-acetoacetamidobenzimidazolone with low production cost, environmental protection, high product quality and high yield.
本发明解决其技术问题所采用的技术方案是：一种5-乙酰乙酰氨基苯并咪唑酮的制备方法，包括以下步骤：The technical solution adopted by the present invention to solve its technical problems is: a preparation method of 5-acetoacetamidobenzimidazolone, which includes the following steps:
1）以水为溶剂，加入5-氨基苯并咪唑酮、硫氢化钠溶液、活性炭混合并在一定温度反应一定时间，过滤得中间体滤液；1) Using water as the solvent, add 5-aminobenzimidazolone, sodium hydrosulfide solution, activated carbon and mix and react at a certain temperature for a certain time, and filter to obtain the intermediate filtrate;
2）在一定温度下向步骤1）中间体滤液中滴加双乙烯酮，保温一定时间后，降温过滤、烘干，得到5-乙酰乙酰氨基苯并咪唑酮。2) Add diketene dropwise to the intermediate filtrate of step 1) at a certain temperature, after keeping it for a certain period of time, cooling, filtering, and drying to obtain 5-acetoacetamidobenzimidazolone.
具体的，所述步骤1）中硫氢化钠溶液的质量浓度为15-30%。Specifically, the mass concentration of the sodium hydrosulfide solution in the step 1) is 15-30%.
具体的，所述步骤1）中溶剂水、5-氨基苯并咪唑酮、硫氢化钠溶液以及活性炭的质量比为：（21.4-28.5）：1：（0.21-0.36）：（0.1-0.22）。Specifically, in the step 1), the mass ratio of solvent water, 5-aminobenzimidazolone, sodium hydrosulfide solution and activated carbon is: (21.4-28.5):1:(0.21-0.36):(0.1-0.22) .
具体的，所述步骤1）中的温度为60-85℃，时间为0.5-1h。Specifically, the temperature in the step 1) is 60-85° C., and the time is 0.5-1 h.
具体的，所述步骤2）中的双乙烯酮与5-氨基苯并咪唑酮的质量比为（0.7-0.95）：1。Specifically, the mass ratio of diketene to 5-aminobenzimidazolone in step 2) is (0.7-0.95):1.
具体的，所述步骤2）中保温温度为60-85℃，保温时间为0.5-1.5h。Specifically, in the step 2), the holding temperature is 60-85°C, and the holding time is 0.5-1.5h.
具体的，所述步骤2）中降温至45℃以下过滤。Specifically, in the step 2), the temperature is lowered to 45° C. and filtered.
本发明具有以下有益效果：本发明与现有方法相比，采用硫氢化钠溶液，既能加快5-氨基苯并咪唑酮的溶解，又能防止5-氨基苯并咪唑酮氧化，硫氢化钠在高温下水解产生的H
2S气体经氢氧化钠溶液吸收后又可以生成硫氢化钠溶液，使之循环使用，避免了废气的排放，以水为溶剂，降低了醇类作为溶剂时的成本，避免了产品烘干时的安全隐患，反应所需时间短。所得产品纯度≥99.2%，收率≥85%，既保证了质量又提高了收率。
The present invention has the following beneficial effects: Compared with the existing method, the present invention adopts sodium hydrosulfide solution, which can not only accelerate the dissolution of 5-aminobenzimidazolone, but also prevent the oxidation of 5-aminobenzimidazolone. Sodium hydrosulfide The H 2 S gas produced by hydrolysis at high temperature can be absorbed by sodium hydroxide solution to generate sodium hydrosulfide solution, which can be recycled to avoid exhaust gas emission. Water is used as solvent to reduce the cost when alcohol is used as solvent. , To avoid the hidden dangers of product drying, and the reaction time is short. The purity of the obtained product is greater than or equal to 99.2%, and the yield is greater than or equal to 85%, which not only ensures the quality but also improves the yield.
以下是本发明的具体实施例，对本发明的技术方案做进一步描述，但是本发明的保护范围并不限于这些实施例。凡是不背离本发明构思的改变或等同替代均包括在本发明的保护范围之内。The following are specific embodiments of the present invention to further describe the technical solutions of the present invention, but the protection scope of the present invention is not limited to these embodiments. Any changes or equivalent substitutions that do not deviate from the concept of the present invention are included in the protection scope of the present invention.
一种5-乙酰乙酰氨基苯并咪唑酮的制备方法，包括以下步骤：A preparation method of 5-acetoacetamidobenzimidazolone includes the following steps:
1）以水为溶剂，加入5-氨基苯并咪唑酮、质量浓度15-30%的硫氢化钠溶液、活性炭混合并在60-85℃反应0.5-1h，过滤得中间体滤液；水、5-氨基苯并咪唑酮、硫氢化钠溶液以及活性炭的质量比为：（21.4-28.5）：1：（0.21-0.36）：（0.1-0.22）。1) Using water as the solvent, add 5-aminobenzimidazolone, sodium hydrosulfide solution with a mass concentration of 15-30%, and activated carbon to mix and react at 60-85°C for 0.5-1h, and filter to obtain the intermediate filtrate; water, 5 -The mass ratio of aminobenzimidazolone, sodium hydrosulfide solution and activated carbon is: (21.4-28.5): 1: (0.21-0.36): (0.1-0.22).
2）在一定温度下向步骤1）中间体滤液中滴加双乙烯酮，双乙烯酮与5-氨基苯并咪唑酮的质量比为（0.7-0.95）：1，60-85℃保温0.5-1.5h后，降温至45℃以下过滤，烘干，得到5-乙酰乙酰氨基苯并咪唑酮。2) Add diketene dropwise to the intermediate filtrate of step 1) at a certain temperature. The mass ratio of diketene to 5-aminobenzimidazolone is (0.7-0.95): 1, after holding at 60-85°C for 0.5-1.5h, The temperature is lowered to 45° C. and filtered, and dried to obtain 5-acetoacetamidobenzimidazolone.
实施例1Example 1
室温下向装有搅拌器的四口瓶中加入250g水，10g5-氨基苯并咪唑酮，开动搅拌，加入质量浓度20%的硫氢化钠溶液3.6g，升温至75℃左右，固体全部溶解，加入1.5g活性炭，保温0.5h后抽滤得中间体滤液。滤液倒入另一四口瓶中，升温至80℃向体系中滴加9g双乙烯酮，滴加完毕，产品5-乙酰乙酰氨基苯并咪唑酮即缓慢析出，保温1h，降温至45℃以下，过滤、烘干，得白色5-乙酰乙酰氨基苯并咪唑酮，收率为86.34%。Add 250g of water and 10g of 5-aminobenzimidazolone to a four-necked flask equipped with a stirrer at room temperature, start stirring, add 3.6g of sodium hydrosulfide solution with a mass concentration of 20%, and heat to about 75°C. All the solids are dissolved. 1.5g activated carbon was added, the intermediate filtrate was obtained by suction filtration after holding for 0.5h. Pour the filtrate into another four-necked flask, add 9g diketene dropwise to the system at 80°C, the product 5-acetoacetamidobenzimidazolone will slowly precipitate out, keep it warm for 1h, cool to below 45°C, filter , Drying to obtain white 5-acetoacetamidobenzimidazolone, the yield is 86.34%.
对本实例得到的5-乙酰乙酰氨基苯并咪唑酮进行液相色谱检测，本发明制备的5-乙酰乙酰氨基苯并咪唑酮的纯度为99.36%，原料峰为0.025%，醋酐峰为0.183%，符合行业标准。The 5-acetoacetaminobenzimidazolone obtained in this example was detected by liquid chromatography. The purity of the 5-acetoacetaminobenzimidazolone prepared by the present invention was 99.36%, the raw material peak was 0.025%, and the acetic anhydride peak was 0.183%. , In line with industry standards.
实施例2Example 2
室温下向装有搅拌器的四口瓶中加入214g水，10g5-氨基苯并咪唑酮，开动搅拌，加入质量浓度15%的硫氢化钠溶液3g，升温至68℃左右，固体全部溶解，加入1g活性炭，保温0.8h后抽滤得中间体滤液。滤液倒入另一四口瓶中，60℃向体系中滴加7g双乙烯酮，滴加完毕，产品5-乙酰乙酰氨基苯并咪唑酮即缓慢析出，保温0.5h，降温至45℃以下，过滤、烘干，得白色5-乙酰乙酰氨基苯并咪唑酮，收率为86.79%。Add 214g of water and 10g of 5-aminobenzimidazolone to a four-necked flask equipped with a stirrer at room temperature, start stirring, add 3g of sodium hydrosulfide solution with a mass concentration of 15%, heat up to about 68°C, all solids are dissolved, add 1g of activated carbon was kept for 0.8h and then suction filtered to obtain the intermediate filtrate. The filtrate was poured into another four-necked flask, and 7g of diketene was added dropwise to the system at 60°C. After the addition was completed, the product 5-acetoacetamidobenzimidazolone would slowly precipitate out. After holding for 0.5h, the temperature was lowered to below 45°C, filtered, After drying, white 5-acetoacetamidobenzimidazolone was obtained with a yield of 86.79%.
对本实例得到的5-乙酰乙酰氨基苯并咪唑酮进行液相色谱检测，本发明制备的5-乙酰乙酰氨基苯并咪唑酮的纯度为99.41%，原料峰为0.011%，醋酐峰为0.17%，符合行业标准。The 5-acetoacetaminobenzimidazolone obtained in this example was detected by liquid chromatography. The purity of the 5-acetoacetaminobenzimidazolone prepared by the present invention was 99.41%, the raw material peak was 0.011%, and the acetic anhydride peak was 0.17%. , In line with industry standards.
实施例3Example 3
室温下向装有搅拌器的四口瓶中加入285g水，10g5-氨基苯并咪唑酮，开动搅拌，加入质量浓度25%的硫氢化钠溶液2.5g，升温至60℃左右，固体全部溶解，加入2.2g活性炭，保温1h后抽滤得中间体滤液。滤液倒入另一四口瓶中，升温至70℃向体系中滴加8g双乙烯酮，滴加完毕，产品5-乙酰乙酰氨基苯并咪唑酮即缓慢析出，保温1.5h，降温至45℃以下，过滤、烘干，得白色5-乙酰乙酰氨基苯并咪唑酮，收率为86.58%。Add 285g of water and 10g of 5-aminobenzimidazolone to a four-necked flask equipped with a stirrer at room temperature, start stirring, add 2.5g of sodium hydrosulfide solution with a mass concentration of 25%, and raise the temperature to about 60°C. All the solids are dissolved. Add 2.2 g of activated carbon, keep it for 1 hour, and then filter with suction to obtain the intermediate filtrate. The filtrate was poured into another four-necked flask, the temperature was raised to 70°C, and 8g of diketene was added dropwise to the system. After the dropwise addition, the product 5-acetoacetamidobenzimidazolone would slowly precipitate out. After holding for 1.5h, the temperature was lowered to 45°C. After filtering and drying, white 5-acetoacetamidobenzimidazolone was obtained with a yield of 86.58%.
对本实例得到的5-乙酰乙酰氨基苯并咪唑酮进行液相色谱检测，本发明制备的5-乙酰乙酰氨基苯并咪唑酮的纯度为99.43%，原料峰为0.015%，醋酐峰为0.181%，符合行业标准。The 5-acetoacetaminobenzimidazolone obtained in this example was detected by liquid chromatography. The purity of the 5-acetoacetaminobenzimidazolone prepared by the present invention was 99.43%, the raw material peak was 0.015%, and the acetic anhydride peak was 0.181%. , In line with industry standards.
实施例4Example 4
室温下向装有搅拌器的四口瓶中加入245g水，10g5-氨基苯并咪唑酮，开动搅拌，加入质量浓度30%的硫氢化钠溶液2.1g，升温至85℃左右，固体全部溶解，加入2g活性炭，保温0.6h后抽滤得中间体滤液。滤液倒入另一四口瓶中，85℃向体系中滴加9.5g双乙烯酮，滴加完毕，产品5-乙酰乙酰氨基苯并咪唑酮即缓慢析出，保温1.2h，降温至45℃以下，过滤、烘干，得白色5-乙酰乙酰氨基苯并咪唑酮，收率为87.14%。Add 245g of water and 10g of 5-aminobenzimidazolone to a four-necked flask equipped with a stirrer at room temperature, start stirring, add 2.1g of sodium hydrosulfide solution with a mass concentration of 30%, raise the temperature to about 85°C, and all the solids are dissolved. 2g activated carbon was added, and the intermediate filtrate was obtained by suction filtration after incubation for 0.6h. The filtrate was poured into another four-necked flask, and 9.5g of diketene was added dropwise to the system at 85°C. After the dripping was completed, the product 5-acetoacetamidobenzimidazolone would slowly precipitate out. Keep it warm for 1.2h, and cool to below 45°C. Filter , Drying to obtain white 5-acetoacetamidobenzimidazolone, the yield is 87.14%.
对本实例得到的5-乙酰乙酰氨基苯并咪唑酮进行液相色谱检测，本发明制备的5-乙酰乙酰氨基苯并咪唑酮的纯度为99.40%，原料峰为0.023%，醋酐峰为0.179%，符合行业标准。The 5-acetoacetaminobenzimidazolone obtained in this example was detected by liquid chromatography. The purity of the 5-acetoacetaminobenzimidazolone prepared by the present invention was 99.40%, the raw material peak was 0.023%, and the acetic anhydride peak was 0.179%. , In line with industry standards.
本发明不局限于上述实施方式，任何人应得知在本发明的启示下作出的结构变化，凡是与本发明具有相同或相近的技术方案，均落入本发明的保护范围之内。The present invention is not limited to the above-mentioned embodiments. Anyone should know that structural changes made under the enlightenment of the present invention, and any technical solutions that are the same or similar to those of the present invention, fall within the protection scope of the present invention.
本发明未详细描述的技术部分均为公知技术。The technical parts not described in detail in the present invention are all well-known technologies.
Claims (7)
- 一种5-乙酰乙酰氨基苯并咪唑酮的制备方法，其特征在于，包括以下步骤：A preparation method of 5-acetoacetamidobenzimidazolone, which is characterized in that it comprises the following steps:1）以水为溶剂，加入5-氨基苯并咪唑酮、硫氢化钠溶液、活性炭混合并在一定温度反应一定时间，过滤得中间体滤液；1) Using water as the solvent, add 5-aminobenzimidazolone, sodium hydrosulfide solution, activated carbon and mix and react at a certain temperature for a certain time, and filter to obtain the intermediate filtrate;2）在一定温度下向步骤1）中间体滤液中滴加双乙烯酮，保温一定时间后，降温过滤、烘干，得到5-乙酰乙酰氨基苯并咪唑酮。2) Add diketene dropwise to the intermediate filtrate of step 1) at a certain temperature, after keeping it for a certain period of time, cooling, filtering, and drying to obtain 5-acetoacetamidobenzimidazolone.
- 如权利要求1所述的5-乙酰乙酰氨基苯并咪唑酮的制备方法，其特征在于，所述步骤1）中硫氢化钠溶液的质量浓度为15-30%。The method for preparing 5-acetoacetamidobenzimidazolone according to claim 1, wherein the mass concentration of the sodium hydrosulfide solution in the step 1) is 15-30%.
- 如权利要求1所述的5-乙酰乙酰氨基苯并咪唑酮的制备方法，其特征在于，所述步骤1）中溶剂水、5-氨基苯并咪唑酮、硫氢化钠溶液以及活性炭的质量比为：（21.4-28.5）：1：（0.21-0.36）：（0.1-0.22）。The method for preparing 5-acetoacetamidobenzimidazolone according to claim 1, wherein the mass ratio of solvent water, 5-aminobenzimidazolone, sodium hydrosulfide solution and activated carbon in said step 1) For: (21.4-28.5): 1: (0.21-0.36): (0.1-0.22).
- 如权利要求1所述的5-乙酰乙酰氨基苯并咪唑酮的制备方法，其特征在于，所述步骤1）中的温度为60-85℃，时间为0.5-1h。The method for preparing 5-acetoacetamidobenzimidazolone according to claim 1, wherein the temperature in step 1) is 60-85°C and the time is 0.5-1h.
- 如权利要求1所述的5-乙酰乙酰氨基苯并咪唑酮的制备方法，其特征在于，所述步骤2）中的双乙烯酮与5-氨基苯并咪唑酮的质量比为（0.7-0.95）：1。The method for preparing 5-acetoacetaminobenzimidazolone according to claim 1, wherein the mass ratio of diketene to 5-aminobenzimidazolone in step 2) is (0.7-0.95): 1.
- 如权利要求1所述的5-乙酰乙酰氨基苯并咪唑酮的制备方法，其特征在于，所述步骤2）中保温温度为60-85℃，保温时间为0.5-1.5h。The method for preparing 5-acetoacetamidobenzimidazolone according to claim 1, wherein the holding temperature in step 2) is 60-85°C, and the holding time is 0.5-1.5h.
- 如权利要求1所述的5-乙酰乙酰氨基苯并咪唑酮的制备方法，其特征在于，所述步骤2）中降温至45℃以下过滤。The method for preparing 5-acetoacetamidobenzimidazolone according to claim 1, characterized in that, in step 2), the temperature is lowered to 45° C. and filtered.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911264329.8 | 2019-12-11 | ||
| CN201911264329.8A CN110845424B (en) | 2019-12-11 | 2019-12-11 | Preparation method of 5-acetoacetylaminobenzimidazolone |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| WO2021114893A1 true WO2021114893A1 (en) | 2021-06-17 |
Family
ID=69608676
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PCT/CN2020/123240 WO2021114893A1 (en) | 2019-12-11 | 2020-10-23 | Method for preparing 5-acetyl acetylaminobenzimidazolone |
Country Status (2)
| Country | Link |
|---|---|
| CN (1) | CN110845424B (en) |
| WO (1) | WO2021114893A1 (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110845424B (en) * | 2019-12-11 | 2021-03-26 | 山东汇海医药化工有限公司 | Preparation method of 5-acetoacetylaminobenzimidazolone |
| CN111763174B (en) * | 2020-08-03 | 2023-06-09 | 山东汇海医药化工有限公司 | Method for reducing distillation residues of 5-acetoacetyl amino benzimidazolone mother liquor |
| CN113979948B (en) * | 2021-12-15 | 2024-02-06 | 山东汇海医药化工有限公司 | Method for recovering AABI from AABI reduction process mother liquor |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1541970A (en) * | 1976-03-24 | 1979-03-14 | Hoechst Ag | Process for the manufacture of 5-acetoacetylamino-benzimidazolone |
| JPH05213896A (en) * | 1992-02-07 | 1993-08-24 | Honsyu Kagaku Kogyo Kk | Production of 5-acetoacetylaminobenzimidazolone |
| CN1106391A (en) * | 1993-10-19 | 1995-08-09 | 赫彻斯特股份公司 | Preparation of 5-acetoactylaminobenzimidazolon-2 |
| CN1745056A (en) * | 2003-01-30 | 2006-03-08 | 科莱恩有限公司 | Acetoacetylation of alcohols, thiols and amines in a microreactor |
| CN109232435A (en) * | 2018-11-01 | 2019-01-18 | 山东汇海医药化工有限公司 | A kind of preparation method of high-purity 5-acetoacetamido benzimidazolone |
| CN109748877A (en) * | 2019-03-21 | 2019-05-14 | 济南大学 | A kind of preparation method of 5-acetoacetamido benzimidazolone |
| CN110128350A (en) * | 2019-07-01 | 2019-08-16 | 山东汇海医药化工有限公司 | A method of improving 5-acetoacetamido benzimidazolone quality |
| CN110845424A (en) * | 2019-12-11 | 2020-02-28 | 山东汇海医药化工有限公司 | Preparation method of 5-acetoacetylaminobenzimidazolone |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2518922C2 (en) * | 1975-04-29 | 1982-08-19 | Hoechst Ag, 6000 Frankfurt | Process for the preparation of 5-acetoacetylaminobenzimidazolone- (2) |
| CN101223247B (en) * | 2005-07-14 | 2015-04-29 | 爱克发印艺公司 | Pigment dispersions with polymeric dispersants having pending chromophore groups |
| PL1790696T3 (en) * | 2005-11-28 | 2013-09-30 | Agfa Nv | Non-aqueous pigment dispersions containing specific dispersion synergists |
| CN103664794B (en) * | 2013-12-30 | 2016-03-30 | 青岛双桃精细化工（集团）有限公司 | A kind of preparation method of 5-acetoacetylaminobenzimidazolone |
| CN108101850B (en) * | 2017-12-21 | 2021-12-07 | 山东汇海医药化工有限公司 | Method for improving quality of 5-acetoacetylaminobenzimidazolone |
| CN110183385A (en) * | 2019-07-01 | 2019-08-30 | 山东汇海医药化工有限公司 | A method of improving 5-acetoacetamido benzimidazolone purity |
-
2019
- 2019-12-11 CN CN201911264329.8A patent/CN110845424B/en active Active
-
2020
- 2020-10-23 WO PCT/CN2020/123240 patent/WO2021114893A1/en active Application Filing
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1541970A (en) * | 1976-03-24 | 1979-03-14 | Hoechst Ag | Process for the manufacture of 5-acetoacetylamino-benzimidazolone |
| JPH05213896A (en) * | 1992-02-07 | 1993-08-24 | Honsyu Kagaku Kogyo Kk | Production of 5-acetoacetylaminobenzimidazolone |
| CN1106391A (en) * | 1993-10-19 | 1995-08-09 | 赫彻斯特股份公司 | Preparation of 5-acetoactylaminobenzimidazolon-2 |
| CN1745056A (en) * | 2003-01-30 | 2006-03-08 | 科莱恩有限公司 | Acetoacetylation of alcohols, thiols and amines in a microreactor |
| CN109232435A (en) * | 2018-11-01 | 2019-01-18 | 山东汇海医药化工有限公司 | A kind of preparation method of high-purity 5-acetoacetamido benzimidazolone |
| CN109748877A (en) * | 2019-03-21 | 2019-05-14 | 济南大学 | A kind of preparation method of 5-acetoacetamido benzimidazolone |
| CN110128350A (en) * | 2019-07-01 | 2019-08-16 | 山东汇海医药化工有限公司 | A method of improving 5-acetoacetamido benzimidazolone quality |
| CN110845424A (en) * | 2019-12-11 | 2020-02-28 | 山东汇海医药化工有限公司 | Preparation method of 5-acetoacetylaminobenzimidazolone |
Non-Patent Citations (1)
| Title |
|---|
| 1 June 2007, article TAN, CHUANJIANG: "Synthesis and Improvement on Process of 5-Aminobenzimidazolone-2", pages: 1 - 53, XP055820621 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN110845424B (en) | 2021-03-26 |
| CN110845424A (en) | 2020-02-28 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| WO2021114893A1 (en) | Method for preparing 5-acetyl acetylaminobenzimidazolone | |
| CN111763174B (en) | Method for reducing distillation residues of 5-acetoacetyl amino benzimidazolone mother liquor | |
| CN104693009A (en) | Method for cooperatively producing 1-naphthol and 2-naphthol from naphthalene sulfonation product by virtue of direct alkali fusion | |
| CN109553550B (en) | Method for synthesizing dihydrooat alkaloid | |
| CN104292122A (en) | Method for reducing generation of by-product ethyl 3-(phenylamino)but-2-enoate in production of N-acetoacetanilide | |
| CN109748877A (en) | A kind of preparation method of 5-acetoacetamido benzimidazolone | |
| CN103254073B (en) | Preparation method of high-purity (bi)pentaerythritol crylic acid non-complete esterification product | |
| WO2021218073A1 (en) | Method for preparing benzimidazolone in aqueous solvent | |
| CN114507240A (en) | Preparation method of cyclobutane tetracarboxylic dianhydride | |
| CN106478422B (en) | A kind of preparation method of paranitrophenylacetic acid | |
| CN110590702B (en) | Novel method for preparing 2-mercaptobenzothiazole | |
| CN108752218B (en) | Route for preparing dolutegravir key intermediate 2, 4-difluorobenzylamine | |
| CN107827821B (en) | Continuous flow clean production process of pyrazolone series products | |
| CN107778160B (en) | Preparation method of 3,4,5, 6-tetrafluorophthalic acid | |
| CN109456172B (en) | Method for purifying dodecanedioic acid in water phase | |
| CN102924961B (en) | Preparation method for disperse red | |
| CN112574007B (en) | Novel cyclohexylimine ionic liquid and method for catalyzing synthesis of butyl citrate and bisphenol F | |
| CN111574387A (en) | P-aminomethyl benzoic acid and preparation method thereof | |
| CN112457170B (en) | Preparation method of 2,2,4, 4-tetramethyl-1, 3-cyclobutanediol | |
| CN104230747B (en) | A kind of preparation method of asymmetry aromatic azo-compound | |
| CN109734645B (en) | Synthetic process of isatin | |
| CN110330443B (en) | Synthetic process of p-chlorophenylhydrazine hydrochloride | |
| CN108191753A (en) | A kind of preparation method of 5- chloro-8-hydroxyquinolines | |
| CN117567249B (en) | Preparation method of 2, 6-dihydroxytoluene | |
| CN115677523B (en) | Preparation method of 2, 6-difluorobenzamide |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| 121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 20898533 Country of ref document: EP Kind code of ref document: A1 |
|
| NENP | Non-entry into the national phase |
Ref country code: DE |
|
| 122 | Ep: pct application non-entry in european phase |
Ref document number: 20898533 Country of ref document: EP Kind code of ref document: A1 |