WO2021218073A1 - 一种水溶剂中制备苯并咪唑酮的方法 - Google Patents

一种水溶剂中制备苯并咪唑酮的方法 Download PDF

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WO2021218073A1
WO2021218073A1 PCT/CN2020/123236 CN2020123236W WO2021218073A1 WO 2021218073 A1 WO2021218073 A1 WO 2021218073A1 CN 2020123236 W CN2020123236 W CN 2020123236W WO 2021218073 A1 WO2021218073 A1 WO 2021218073A1
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auxiliary agent
reaction
water
aqueous solution
benzimidazolone
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PCT/CN2020/123236
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English (en)
French (fr)
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张国辉
姜福元
张翠翠
付德修
王磊
侯绪会
王亮亮
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山东汇海医药化工有限公司
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    • 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 field of processing by-products of biological polypeptide condensation agents, and specifically relates to a method for preparing benzimidazolones in an aqueous solvent.
  • Benzimidazolones are important organic intermediates, especially in the fields of medicine, pigments and pesticides.
  • the organic solvent used is harmful to the human body, and the process is complicated with a large amount of waste liquid;
  • the purpose of the present invention is to overcome the problems of poor safety, low yield, high production cost, etc., which are common in the prior art, and provide a method for preparing benzimidazolones in an aqueous solvent.
  • the technical solution adopted by the present invention to solve its technical problem is: a method for preparing benzimidazolone in a water solvent, including the following steps: adding an auxiliary agent aqueous solution to a reaction flask, turning on the stirring, and adding when the temperature reaches 90-140°C O-phenylenediamine and urea are incubated and reacted for 3-8h. After the reaction is completed, the auxiliary aqueous solution or mother liquor is added, filtered with suction and rinsed with water. The solid material is benzimidazolone, the mother liquor is used, and the eluent is concentrated and then used.
  • the mass ratio of the auxiliary agent to water in the auxiliary agent aqueous solution is 1-2:1-20.
  • the auxiliary agent is one or more of sodium salt, magnesium salt, aluminum salt, potassium salt, calcium salt, iron salt, copper salt, and zinc salt.
  • the mass ratio of urea to o-phenylenediamine is 1:1.3-1:1.
  • the mass ratio of the o-phenylenediamine to the water initially added to the auxiliary agent aqueous solution in the reaction flask is 1-2:1-5.
  • the temperature for adding o-phenylenediamine and urea is preferably 105-130°C.
  • the reaction route of the present invention is as follows:
  • the present invention has the following beneficial effects: the present invention selects urea and o-phenylenediamine to react to prepare benzimidazolones, uses urea as a cyclization agent, and the reproduced ammonia can be easily absorbed and utilized; the addition of auxiliary agents can effectively increase the boiling point of water and make the reaction The temperature in the process reaches the temperature of the condensation reaction of o-phenylenediamine and urea to promote the reaction.
  • the auxiliary agent selected by the invention is safe and environmentally friendly, low in price and easy to obtain.
  • the mother liquor after the reaction can also be recycled and reused without multiple addition of additives, saving material costs; the reaction materials are carried out in a homogeneous reaction system, and the reaction materials are fully mixed; the solvent water is used multiple times to achieve green synthesis and product yield Up to 99%, the purity is greater than 99.0%.
  • auxiliary agent aqueous solution Add the auxiliary agent aqueous solution to the reaction flask.
  • the auxiliary agent is sodium salt.
  • the mass ratio of auxiliary agent to water in the auxiliary agent aqueous solution is 1:8.
  • the mass ratio of phenylenediamine is 1:1.1, the mass ratio of o-phenylenediamine to the water initially added to the auxiliary agent aqueous solution in the reaction flask is 2:5, and the reaction is kept at 130°C for 5 hours.
  • auxiliary agent aqueous solution 14 After the reaction is completed, add auxiliary agent aqueous solution 14 , Suction filtration and rinsing with water, the filter cake is dried into benzimidazolone, the filtrate is the mother liquor after being concentrated, the benzimidazolone yield is 99.04%, and the purity is 99.32%.
  • auxiliary agent aqueous solution Add the auxiliary agent aqueous solution to the reaction flask.
  • the auxiliary agent is magnesium salt.
  • the mass ratio of auxiliary agent to water in the auxiliary agent aqueous solution is 2:15.
  • the mass ratio of phenylenediamine is 1:1, the mass ratio of o-phenylenediamine to the water initially added to the auxiliary agent aqueous solution in the reaction flask is 1:3, and the reaction is kept at 105°C for 3 hours.
  • the auxiliary agent aqueous solution is added. Suction filtration and rinsing with water, the filter cake is dried into benzimidazolone, the filtrate is the mother liquor after being concentrated, the yield of benzimidazolone is 99.19%, and the purity is 99.61%.
  • the auxiliary agent is a mixture of aluminum salt and zinc salt
  • the mass ratio of auxiliary agent to water in the auxiliary agent aqueous solution is 1.1:20
  • turn on the stirring and add o-phenylenediamine
  • the mass ratio of urea, urea and o-phenylenediamine is 1:1.2
  • the mass ratio of o-phenylenediamine to the water initially added to the auxiliary agent aqueous solution in the reaction flask is 1:4.
  • the reaction is kept at 90°C for 7 hours.
  • auxiliary agent aqueous solution Add the auxiliary agent aqueous solution to the reaction flask.
  • the auxiliary agent is potassium salt.
  • the mass ratio of auxiliary agent to water in the auxiliary agent aqueous solution is 1:1.
  • the mass ratio of phenylenediamine is 1:1.3, the mass ratio of o-phenylenediamine to the water initially added to the auxiliary agent aqueous solution in the reaction flask is 1.8:3.5, and the reaction is kept at 120°C for 6 hours.
  • the mother liquor is added and filtered with suction. It is rinsed with water, the filter cake is dried into benzimidazolone, and the filtrate, which is the mother liquor, is concentrated and used.
  • the yield of benzimidazolone is 99.53% and the purity is 99.05%.
  • the auxiliary agent is a mixture of iron salt and copper salt
  • the mass ratio of auxiliary agent to water in the auxiliary agent aqueous solution is 1.5:13, turn on the stirring, and add o-phenylenediamine and
  • the mass ratio of urea, urea and o-phenylenediamine is 1:1.2, and the mass ratio of o-phenylenediamine to the water initially added to the auxiliary aqueous solution in the reaction flask is 1.3:2.
  • the reaction is kept at 140°C for 4 hours.
  • auxiliary agent aqueous solution Add the auxiliary agent aqueous solution to the reaction flask.
  • the auxiliary agent is calcium salt.
  • the mass ratio of auxiliary agent to water in the auxiliary agent aqueous solution is 1.7:10.
  • the mass ratio of phenylenediamine is 1:1.3, the mass ratio of o-phenylenediamine to the water initially added to the auxiliary agent aqueous solution in the reaction flask is 1:1, and the reaction is kept at 110°C for 8 hours.
  • the mother liquor is added and filtered with suction. It is rinsed with water, the filter cake is dried into benzimidazolone, and the filtrate is the mother liquor after being concentrated.
  • the yield of benzimidazolone is 99.18% and the purity is 99.45%.
  • the present invention is not limited to the above-mentioned embodiments.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Nitrogen Condensed Heterocyclic Rings (AREA)

Abstract

本发明公开了一种水溶剂中制备苯并咪唑酮的方法，向反应瓶中加入助剂水溶液，开启搅拌，升温至90-140℃时加入邻苯二胺和尿素，保温反应3-8h，反应完成后，加入助剂水溶液或母液，抽滤并用水淋洗，固体料为苯并咪唑酮，母液套用，淋洗液提浓后套用。实现了常压条件下水为溶剂合成苯并咪唑酮的工艺方案，苯并咪唑酮收率大于99%，纯度大于99%。本工艺以水为溶剂，母液实现循环套用，绿色环保，安全可行，生产成本低，适合工业化生产。

Description

一种水溶剂中制备苯并咪唑酮的方法 技术领域
本发明属于生物多肽缩合剂副产物处理领域，具体涉及一种水溶剂中制备苯并咪唑酮的方法。
 背景技术
苯并咪唑酮是重要的有机中间体，尤其是应用于医药、颜料和农药等领域。
J.Am.Chem.Soc.80,1657(1958)公开的文献中，提供了一种用邻苯二胺和光气反应制备苯并咪唑酮的方法。但此方法所使用的光气有高度的危险性，另外反应生成的副产物氯化氢对设备有很强的腐蚀性。
US-4138568中，邻苯二胺类化合物与尿素及尿素衍生物在水不溶性有机溶剂中反应，其中温度在100℃至200℃，得到苯并咪唑酮，然后要经过复杂的提纯过程，溶剂消耗大， 产生大量废液。
DE2052026中，采用水作为反应介质，邻苯二胺与尿素缩合，在加压条件下收率可达到96%。
US-4269989和中国期刊《化学与生物工程》2003年增刊5-乙酰乙酰基氨基苯并咪唑酮的合成新方法中，公开了一种在水中邻苯二胺和尿素反应合成苯并咪唑酮的方法。此方法温度在90℃至120℃，利用酸调节控制pH在4至9，制备苯并咪唑酮，由于反应不稳定，导致收率、产品质量不稳定，且大量的废水导致污染环境。
总结来讲，现有制备苯并咪唑酮的方法通常存在以下缺点：
1、光气有高度的危险性，反应副产物氯化氢腐蚀设备严重，不宜工业化生产；
2、使用的有机溶剂对人体伤害大，并且过程复杂伴有大量废液；
3、以水为溶剂的则是加压或调酸，加压工艺危险性大，收率略低，调酸产生大量无机盐，并且反应不稳定，产品收率、质量不稳定。
 技术问题
本发明的目的在于克服现有技术中普遍存在的安全性差、收率低、生产成本高等问题而提供一种水溶剂中制备苯并咪唑酮的方法。
 技术解决方案
本发明解决其技术问题所采用的技术方案是：一种水溶剂中制备苯并咪唑酮的方法，包括以下步骤：向反应瓶中加入助剂水溶液，开启搅拌，升温至90-140℃时加入邻苯二胺和尿素，保温反应3-8h，反应完成后，加入助剂水溶液或母液，抽滤并用水淋洗，固体料为苯并咪唑酮，母液套用，淋洗液提浓后套用。
具体地，所述助剂水溶液中助剂与水的质量比为1-2：1-20。
具体地，所述助剂为钠盐、镁盐、铝盐、钾盐、钙盐、铁盐、铜盐、锌盐中的一种或几种。
具体地，所述尿素与邻苯二胺的质量比为1:1.3 - 1:1。
具体地，所述邻苯二胺与起始加入反应瓶内助剂水溶液中的水的质量比为1-2:1-5。
进一步的，加入邻苯二胺和尿素的温度优选为105-130℃。
本发明反应路线如下：
Figure dest_path_image001
。
 有益效果
本发明具有以下有益效果：本发明选用尿素与邻苯二胺反应制备苯并咪唑酮，使用尿素做环合剂，复产的氨气易于吸收利用；加入助剂能够有效提高水的沸点，使反应过程中的温度达到邻苯二胺和尿素缩合反应的温度，促进反应发生。本发明选用的助剂安全环保，价格低廉，容易获取。反应后的母液还可以循环套用，无需多次添加助剂，节约物料成本；实现反应物料在均相反应体系中进行，反应物料充分混合；溶剂水多次套用，实现了绿色合成，产品收率达99%，纯度大于99.0%。
 本发明的最佳实施方式
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。
实施例1
向反应瓶中加入助剂水溶液，助剂为钠盐，助剂水溶液中助剂与水的质量比为1：8，开启搅拌，升温至130℃时加入邻苯二胺和尿素，尿素与邻苯二胺的质量比为1：1.1，邻苯二胺与起始加入反应瓶内助剂水溶液中的水的质量比为2: 5，130℃保温反应5h，反应完成后，加入助剂水溶液 14，抽滤并用水淋洗，滤饼烘干为苯并咪唑酮，滤液即母液提浓后套用，苯并咪唑酮收率99.04%，纯度99.32%。
 本发明的实施方式
实施例2
向反应瓶中加入助剂水溶液，助剂为镁盐，助剂水溶液中助剂与水的质量比为2：15，开启搅拌，升温至105℃时加入邻苯二胺和尿素，尿素与邻苯二胺的质量比为1：1，邻苯二胺与起始加入反应瓶内助剂水溶液中的水的质量比为1:3，105℃保温反应3h，反应完成后，加入助剂水溶液，抽滤并用水淋洗，滤饼烘干为苯并咪唑酮，滤液即母液提浓后套用，苯并咪唑酮收率99.19%，纯度99.61%。
实施例3
向反应瓶中加入助剂水溶液，助剂为铝盐和锌盐的混合物，助剂水溶液中助剂与水的质量比为1.1：20，开启搅拌，升温至90℃时加入邻苯二胺和尿素，尿素与邻苯二胺的质量比为1：1.2，邻苯二胺与起始加入反应瓶内助剂水溶液中的水的质量比为1:4，90℃保温反应7h，反应完成后，加入助剂水溶液，抽滤并用水淋洗，滤饼烘干为苯并咪唑酮，滤液即母液提浓后套用，苯并咪唑酮收率99.53%，纯度99.78%。
实施例4
向反应瓶中加入助剂水溶液，助剂为钾盐，助剂水溶液中助剂与水的质量比为1：1，开启搅拌，升温至120℃时加入邻苯二胺和尿素，尿素与邻苯二胺的质量比为1：1.3，邻苯二胺与起始加入反应瓶内助剂水溶液中的水的质量比为1.8:3.5，120℃保温反应6h，反应完成后，加入母液，抽滤并用水淋洗，滤饼烘干为苯并咪唑酮，滤液即母液提浓后套用，苯并咪唑酮收率99.53%，纯度99.05%。
实施例5
向反应瓶中加入助剂水溶液，助剂为铁盐和铜盐的混合物，助剂水溶液中助剂与水的质量比为1.5：13，开启搅拌，升温至140℃时加入邻苯二胺和尿素，尿素与邻苯二胺的质量比为1：1.2，邻苯二胺与起始加入反应瓶内助剂水溶液中的水的质量比为1.3:2，140℃保温反应4h，反应完成后，加入母液，抽滤并用水淋洗，滤饼烘干为苯并咪唑酮，滤液即母液提浓后套用，苯并咪唑酮收率99.43%，纯度99.55%。
实施例6
向反应瓶中加入助剂水溶液，助剂为钙盐，助剂水溶液中助剂与水的质量比为1.7：10，开启搅拌，升温至110℃时加入邻苯二胺和尿素，尿素与邻苯二胺的质量比为1：1.3，邻苯二胺与起始加入反应瓶内助剂水溶液中的水的质量比为1:1，110℃保温反应8h，反应完成后，加入母液，抽滤并用水淋洗，滤饼烘干为苯并咪唑酮，滤液即母液提浓后套用，苯并咪唑酮收率99.18%，纯度99.45%。
 序列表自由内容
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。
本发明未详细描述的技术、形状、构造部分均为公知技术。

Claims (5)

  1. 一种水溶剂中制备苯并咪唑酮的方法，其特征在于，包括以下步骤：向反应瓶中加入助剂水溶液，开启搅拌，升温至90-140℃时加入邻苯二胺和尿素，保温反应3-8h，反应完成后，加入助剂水溶液或母液，抽滤并用水淋洗，固体料为苯并咪唑酮，母液套用，淋洗液提浓后套用。
  2. 如权利要求1所述的水溶剂中制备苯并咪唑酮的方法，其特征在于，所述助剂水溶液中助剂与水的质量比为1-2：1-20。
  3. 如权利要求1或2所述的水溶剂中制备苯并咪唑酮的方法，其特征在于，所述助剂为钠盐、镁盐、铝盐、钾盐、钙盐、铁盐、铜盐、锌盐中的一种或几种。
  4. 如权利要求1所述的水溶剂中制备苯并咪唑酮的方法，其特征在于，所述尿素与邻苯二胺的质量比为1:1.3 - 1:1。
  5. 如权利要求1所述的水溶剂中制备苯并咪唑酮的方法，其特征在于，所述邻苯二胺与起始加入反应瓶内助剂水溶液中的水的质量比为1-2:1-5。
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