CN112898205A - Method for synthesizing benzimidazole by using carbon dioxide and o-phenylenediamine compound - Google Patents
Method for synthesizing benzimidazole by using carbon dioxide and o-phenylenediamine compound Download PDFInfo
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- CN112898205A CN112898205A CN202110038267.XA CN202110038267A CN112898205A CN 112898205 A CN112898205 A CN 112898205A CN 202110038267 A CN202110038267 A CN 202110038267A CN 112898205 A CN112898205 A CN 112898205A
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- 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
- C07D235/06—Benzimidazoles; Hydrogenated benzimidazoles with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached in position 2
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Abstract
The invention discloses a method for synthesizing benzimidazole by carbon dioxide and o-phenylenediamine compounds, which is characterized in that an amino-containing functionalized ordered mesoporous polymer is used as a catalyst, o-phenylenediamine and carbon dioxide are used as raw materials, dimethylamino borane is used as a hydrogen reduction reagent, the reaction of the carbon dioxide and the o-phenylenediamine compounds is catalyzed in an NMP solvent to generate the benzimidazole compounds, and the dosage of the catalyst is 0.01-1 mol% of the nitrogen content of the o-phenylenediamine compounds; the carbon dioxide charging pressure is 0.1-2 MPa; the reaction temperature is 60-180 ℃; the molar ratio of the catalyst to NMP was 1: 50 to 100. Compared with the prior art, the method has the advantages of simple catalyst preparation, high catalytic activity, capability of catalyzing the reaction of carbon dioxide and o-phenylenediamine compounds to generate benzimidazole and derivatives thereof under mild conditions, and the like.
Description
Technical Field
The invention relates to organic synthetic chemistry, in particular to a method for synthesizing benzimidazole by carbon dioxide and o-phenylenediamine compounds.
Background
Benzimidazole is a nitrogen-containing aromatic heterocyclic compound, is formed by fusing a benzene ring and an imidazole ring, and is an important pharmacodynamic group. The benzimidazole and the derivative thereof have good biological activity and reactivity, are widely applied to the aspects of antibiosis, cancer resistance, diabetes resistance, ulcer resistance, hypertension resistance and the like, and have profound significance in synthesis research. Recent research shows that the benzimidazole and the derivatives thereof have good anticoagulant activity, and the dabigatran etexilate serving as a novel thrombin inhibitor has the characteristics of predictable anticoagulant effect, oral administration, no need of clinical detection, less drug interaction and the like, and has a wide application prospect. Therefore, the benzimidazole compound has important research value in the field of medicinal chemistry. In recent years, the synthesis of such heterocyclic compounds and the research on their biological activity have increasingly become hot spots in the research on heterocyclic chemistry. The traditional benzimidazole synthesis method is to take o-phenylenediamine as a raw material to carry out cyclization and dehydration reaction with carboxylic acid and derivatives thereof, and the preparation method needs strong acidic conditions and is complicated to operate (Chemistry select.2019,4, 7968-7975); another type of process is obtained by reacting o-phenylenediamine with an aldehyde in the presence of an oxidizing agent, but this process has a large number of by-products and relatively difficult separation and purification of the desired product (RSC adv.,2016,6, 86982). Therefore, a method for synthesizing the benzimidazole derivative simply and efficiently is sought, and the method has important significance for enriching the synthetic method of the compound and researching the bioactivity more widely in the future.
Recently, there have been reports of ionic liquids, organic bases, metal complexes, etc., which catalyze the reaction of carbon dioxide and o-phenylenediamine to benzimidazole, and great progress has been made (ACS Catal.2015,5, 6648-6652; Green chem.,2019,21, 1695-1701). However, the homogeneous catalyst is limited in further use due to problems such as difficulty in recovery, trouble in separation, or metal contamination. Some heterogeneous catalysts have been reported for the reaction of carbon dioxide with o-phenylenediamine, but further applications of these catalysts are limited due to low catalytic yield, severe reaction conditions, or complicated catalyst support preparation process (chemcat chem 2017,9, 3632-. The ordered mesoporous phenolic resin polymer material has the characteristics of simple preparation, large specific surface area, uniform pore channel arrangement and the like, is an ordered two-dimensional hexagonal structure, and is widely used as a carrier in a heterogeneous catalytic system. Therefore, the development of a reaction research of the mesoporous material with simple preparation, good stability and good catalytic performance for catalyzing carbon dioxide and o-phenylenediamine is of great significance.
Disclosure of Invention
The invention aims to provide a method for synthesizing benzimidazole by carbon dioxide and o-phenylenediamine compounds, aiming at the defects of the prior art, the method adopts an amino-containing functionalized ordered mesoporous polymer as a catalyst, o-phenylenediamine and carbon dioxide as raw materials, and dimethylamino borane as a hydrogen reduction reagent, and synthesizes the benzimidazole compound in an NMP solvent in a catalytic manner.
The specific technical scheme for realizing the aim of the invention is as follows: a method for synthesizing benzimidazole by carbon dioxide and o-phenylenediamine compounds is characterized in that an amino functionalized ordered mesoporous phenolic resin polymer is used as a catalyst, dimethylamino borane is used as a hydrogen reduction reagent, the reaction of the carbon dioxide and the o-phenylenediamine compounds is catalyzed in an NMP solvent to generate the benzimidazole compounds, and the reaction equation is as follows:
wherein: R-H, CH3、CH3O、Br、Cl、NO2；
The dosage of the catalyst is 0.01-1 mol% based on the nitrogen content of the o-phenylenediamine compound; the carbon dioxide charging pressure is 0.1-2 MPa; the reaction temperature is 60-180 ℃, and the reaction time is 6-48 hours; the mol ratio of the NMP to the catalyst is 50-100: 1.
the amino functionalized ordered mesoporous phenolic resin polymer is prepared by the following specific steps:
preparation of (I) dimethylamino functionalized precursor
Mixing and melting dimethylamino phenol and phenol at the temperature of 45 ℃, adding 10 wt% NaOH solution after 5-10 minutes, uniformly stirring, adding 38 wt% formaldehyde solution after 25-30 minutes, heating to 70 ℃, stirring and refluxing for 1-2 hours, cooling to room temperature after the reaction is finished, adjusting the pH of the reaction solution to 7 by using hydrochloric acid, and performing rotary evaporation to obtain a product, namely a dimethylamino functionalized precursor, wherein the molar ratio of the dimethylamino phenol to the formaldehyde to the sodium hydroxide is 1: 8-10: 14-18: 2 to 4.
Preparation of (di) dimethylamino functionalized ordered mesoporous polymer
Mixing the prepared dimethylamino functionalized precursor, polyether (F127) and ethanol according to the weight ratio of 1: 1: mixing the materials according to a molar ratio of 18-25, stirring the materials for 20-50 minutes, then flatly paving the materials on a glass plate, volatilizing the materials for 8-12 hours at room temperature, placing the materials in an oven at 100-120 ℃, drying the materials for 18-24 hours, and then calcining the cured film in a tubular furnace at 350 ℃ for 3 hours under the protection of nitrogen to remove a template agent to prepare the dimethylamino functionalized ordered mesoporous phenolic resin polymer.
Compared with the prior art, the method has the advantages of mild reaction conditions, simple operation, easy recovery of the heterogeneous catalyst, reusability, no pollution to the environment and the like, and is an environment-friendly, simple operation, convenient raw materials and high-efficiency method for preparing the o-phenylenediamine compound.
Detailed Description
The present invention is further illustrated by the following specific examples.
Example 1
Preparation of (I) dimethylamino functionalized precursor
At the temperature of 45 ℃, reducing 0.74g of p-xylenol and 2.02g of phenol, heating, mixing and melting, adding 2.3g of NaOH solution with the concentration of 10 wt% after 10 minutes, fully and uniformly stirring, adding 5.8g of formaldehyde solution with the concentration of 38 wt% after 30 minutes, heating to 70 ℃, stirring and refluxing for 2 hours, cooling to room temperature after the reaction is finished, adjusting the pH of the reaction liquid to 7 by using 1mol/L hydrochloric acid, and performing rotary evaporation to remove water in the system to obtain 4g of dimethylamino functionalized precursor.
Preparation of (di) dimethylamino functionalized ordered mesoporous polymer
Dissolving 4g F127 in 100mL of solution with the mass concentration of 99%, adding 3.2g of the prepared dimethylamino functionalized precursor, mixing and stirring for 40 minutes, spreading the mixture on a glass plate, volatilizing for 8 hours at room temperature, placing the mixture in an oven at 120 ℃ for drying for 24 hours, calcining the cured film in a tube furnace at 350 ℃ for 3 hours under the protection of nitrogen to remove a template agent, and preparing 3g of dimethylamino functionalized ordered mesoporous phenolic resin polymer.
Preparation of (tri) benzimidazole compounds
50mg (0.1 mol%) of the prepared dimethylamino functionalized ordered mesoporous phenolic resin polymer serving as a catalyst and 0.108g (1mmol) of o-phenylenediamine are weighed and placed in a stainless steel reaction kettle lined with polytetrafluoroethylene, 0.177g of DMAB (3eq) and 5ml of NMP solution are weighed and added into a device, the temperature is raised to 120 ℃, and then carbon dioxide with the pressure of 1MPa is introduced to carry out the synthesis reaction with the following reaction structural formula:
after 24 hours of reaction, the mixture was naturally cooled to room temperature, and the mixture was filtered with suction and washed with 20ml of saturated brine, and the catalyst was separated. Adding 60ml of ethyl acetate into the filtrate for extraction for three times, taking a water layer, taking an organic layer, adding anhydrous sodium sulfate for drying for half an hour, carrying out spin drying on the organic layer, and carrying out column chromatography on the residual liquid to obtain a pure product, namely the benzimidazole compound, wherein the yield is 90%. The filtered catalyst can be recycled by drying after being washed by deionized water and acetone.
Example 2
50mg (0.1 mol%) of the prepared nitrogen-containing ordered mesoporous polymer catalyst and 0.122g (1mmol) of o-phenylenediamine are weighed and placed in a stainless steel reaction kettle with a polytetrafluoroethylene lining, 0.177g of DMAB (3eq) and 5ml of NMP solution are weighed and added into a device, the temperature is raised to 120 ℃, and then carbon dioxide with the pressure of 1MPa is introduced to carry out the synthesis reaction with the following reaction structural formula:
after 24 hours of reaction, the mixture was naturally cooled to room temperature, and the mixture was filtered with suction and washed with 20ml of saturated brine, and the catalyst was separated. Adding 60ml of ethyl acetate into the filtrate for extraction for three times, taking a water layer, taking an organic layer, adding anhydrous sodium sulfate for drying for half an hour, carrying out spin drying on the organic layer, and carrying out column chromatography on the residual liquid to obtain a pure product, namely the benzimidazole compound, wherein the yield is 85%. The filtered catalyst can be recycled after being washed by deionized water and acetone and dried.
Example 3
50mg (0.1 mol%) of the ordered mesoporous polymer catalyst containing nitrogen prepared in example 1 and 0.142g (1mmol) of o-phenylenediamine were weighed into a stainless steel reaction kettle lined with polytetrafluoroethylene, 0.177g of DMAB (3eq) and 5ml of NMP solution were weighed into a device, heated to 120 ℃, and then carbon dioxide at a pressure of 1MPa was introduced to carry out the synthesis reaction of the following reaction formula:
after 24h of reaction, the mixture is naturally cooled to room temperature, and the mixed solution is filtered by suction and washed by 20ml of saturated saline solution to separate the catalyst. The filtrate was extracted three times with 60ml of ethyl acetate to obtain a water layer. And (3) taking the organic layer, adding anhydrous sodium sulfate, drying for half an hour, spin-drying the organic phase, and performing column chromatography on the residual liquid to obtain a pure product, namely the benzimidazole compound, wherein the yield is 88%. The filtered catalyst can be recycled after being washed by deionized water and acetone and dried.
Example 4
50mg (0.1 mol%) of the ordered mesoporous polymer catalyst containing nitrogen prepared in example 1 and 0.187g (1mmol) of o-phenylenediamine were weighed into a stainless steel reaction kettle lined with polytetrafluoroethylene, 0.177g of DMAB (3eq) and 5ml of NMP solution were weighed into a device, heated to 120 ℃, and then carbon dioxide at a pressure of 1MPa was introduced to carry out the synthesis reaction of the following reaction formula:
after 24 hours of reaction, the mixture was naturally cooled to room temperature, and the mixture was filtered with suction and washed with 20ml of saturated brine, and the catalyst was separated. Adding 60ml of ethyl acetate into the filtrate for extraction for three times, taking a water layer, taking an organic layer, adding anhydrous sodium sulfate for drying for half an hour, carrying out spin drying on the organic layer, and carrying out column chromatography on the residual liquid to obtain a pure product, namely the benzimidazole compound, wherein the yield is 91%. The filtered catalyst can be recycled after being washed by deionized water and acetone and dried.
Example 5
50mg (0.1 mol%) of the ordered mesoporous polymer catalyst containing nitrogen prepared in example 1 and 0.138g (1mmol) of o-phenylenediamine were weighed into a stainless steel reaction kettle lined with polytetrafluoroethylene, 0.177g of DMAB (3eq) and 5ml of NMP solution were weighed into a device, heated to 120 ℃, and then carbon dioxide with a pressure of 1MPa was introduced to carry out the synthesis reaction of the following reaction formula:
after 24 hours of reaction, the mixture was naturally cooled to room temperature, and the mixture was filtered with suction and washed with 20ml of saturated brine, and the catalyst was separated. The filtrate was extracted three times with 60ml of ethyl acetate to obtain a water layer. And (3) taking the organic layer, adding anhydrous sodium sulfate, drying for half an hour, carrying out spin drying on the organic phase, and carrying out column chromatography on the residual liquid to obtain a pure product, namely the benzimidazole compound, wherein the yield is 83%. The filtered catalyst can be recycled after being washed by deionized water and acetone and dried.
Example 6
50mg (0.1 mol%) of the ordered mesoporous polymer catalyst containing nitrogen prepared in example 1 and 0.153g (1mmol) of o-phenylenediamine were weighed into a stainless steel reaction kettle lined with polytetrafluoroethylene, 0.177g of DMAB (3eq) and 5ml of NMP solution were weighed into a device, heated to 120 ℃, and then carbon dioxide at a pressure of 1MPa was introduced to carry out the synthesis reaction of the following reaction formula:
after 24h of reaction, the mixture is naturally cooled to room temperature, and the mixed solution is filtered by suction and washed by 20ml of saturated saline solution to separate the catalyst. The filtrate was extracted three times with 60ml of ethyl acetate to obtain a water layer. And (3) taking the organic layer, adding anhydrous sodium sulfate, drying for half an hour, spin-drying the organic phase, and performing column chromatography on the residual liquid to obtain a pure product, namely the benzimidazole compound, wherein the yield is 79%. The filtered catalyst can be recycled after being washed by deionized water and acetone and dried.
The invention has been described in further detail in order to avoid limiting the scope of the invention, and it is intended that all such equivalent embodiments be included within the scope of the following claims.
Claims (3)
1. A method for synthesizing benzimidazole by carbon dioxide and o-phenylenediamine compounds is characterized in that an amino functionalized ordered mesoporous phenolic resin polymer is used as a catalyst, dimethylamino borane is used as a hydrogen reduction reagent, the reaction of the carbon dioxide and the o-phenylenediamine compounds is catalyzed in an NMP solvent to generate the benzimidazole compounds, and the reaction equation is as follows:
wherein: R-H, CH3、CH3O、Br、Cl、NO2；
The dosage of the catalyst is 0.01-1 mol% based on the nitrogen content of the o-phenylenediamine compound; the carbon dioxide charging pressure is 0.1-2 MPa; the reaction temperature is 60-180 ℃, and the reaction time is 6-48 hours; the mol ratio of the NMP to the catalyst is 50-100: 1.
2. the method for synthesizing benzimidazole by carbon dioxide and o-phenylenediamine compound according to claim 1, wherein the amino-functionalized ordered mesoporous phenolic resin polymer is dimethylamino-functionalized ordered mesoporous polymer, amino-functionalized ordered mesoporous polymer or methylamino-functionalized ordered polymer, preferably dimethylamino-functionalized ordered mesoporous polymer.
3. The method for synthesizing benzimidazole from carbon dioxide and o-phenylenediamine compounds according to claim 1, wherein the o-phenylenediamine compounds are o-phenylenediamine and its derivatives.
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