CN110577495A - amide-containing N-substituted benzimidazole diamine and preparation method thereof - Google Patents
amide-containing N-substituted benzimidazole diamine and preparation method thereof Download PDFInfo
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- 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
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Abstract
the invention provides amide-containing N-substituted benzimidazole diamine and a preparation method thereof, belonging to the technical field of organic synthesis. The amide-containing N-substituted benzimidazole diamine has a structure shown in a formula I. According to the invention, amide-containing N-substituted benzimidazole diamine with a new structure and new performance is obtained by introducing two groups, namely amide and N-substituted benzimidazole, into diamine molecules. The N-substituted benzimidazole diamine containing amide provided by the invention is prepared by a condensation, ring closing and reduction three-step method, the synthetic route is short, the raw materials are cheap and easy to obtain, the process safety is high, the operation is simple and convenient, the production cost is low, the reaction yield is high, and the N-substituted benzimidazole diamine containing amide is suitable for industrial production.
Description
Technical Field
The invention relates to the technical field of organic synthesis, in particular to amide-containing N-substituted benzimidazole diamine and a preparation method thereof.
Background
Diamine compounds are important chemical raw materials or intermediates, and can also be used as monomers for synthesizing various polymers such as novel polyimide, polyamide, polyurea, organic silicon and the like. By introducing special substituent groups into the diamine structure, the mechanical property, chemical corrosion resistance, high temperature resistance and flame resistance of the material can be effectively improved, so that the application field of diamine compounds is expanded.
benzimidazole is a typical rigid aromatic heterocyclic unit, and the mechanical property and the heat resistance of the material can be obviously improved by introducing the benzimidazole into a high-molecular main chain; the introduction of amido bond can greatly enhance the mechanical property of the material and improve the dimensional stability of the material. Currently, both benzimidazolediamines and diamine containing amides have been successfully synthesized, for example, "Synthesis and catalysis of thermal Stable, High-Module polymers conjugation benzimidazole Moeties" (Shuang Wang et al, Journal of Polymer Science: Part A: Polymer Chemistry, 47, 2024. sup. 2031, 2009) which discloses the cyclization of polyphosphoric acid to benzimidazolediamine at 195 ℃; "preparation and Performance characterization of polyimide films containing Hydrogen bonds" (Shenhua et al, science and engineering of Polymer materials, 5 th, pp. 125-128, 2012) disclose the preparation of diamine monomers containing amides by condensation reaction.
however, the mechanical properties and dimensional stability of diamine compounds containing only benzimidazole or amide are still to be improved.
disclosure of Invention
the invention aims to provide an amide-containing N-substituted benzimidazole diamine and a preparation method thereof. The material prepared by using the amide-containing N-substituted benzimidazole diamine as the raw material has excellent dimensional stability, thermal stability and mechanical property.
the preparation method provided by the invention is simple to operate and suitable for industrial production.
in order to achieve the above object, the present invention provides the following technical solutions:
the invention provides amide-containing N-substituted benzimidazole diamine, which has a structure shown in a formula I:
in formula I, X includes any one of the following substituents:
the invention provides a preparation method of amide-containing N-substituted benzimidazole diamine, which comprises the following steps:
Mixing paranitrobenzoyl chloride, cyanamide, an acid-binding agent and a first solvent, and carrying out condensation reaction to obtain N-cyano paranitrobenzamide;
Mixing the N-cyano-p-nitrobenzamide, the aniline derivative, the acid catalyst and a second solvent, and carrying out a ring closure reaction to obtain amide-containing N-substituted benzimidazole dinitro;
Under the condition of protective atmosphere, mixing the amide-containing N-substituted benzimidazole dinitro, a hydrogenation catalyst and a third solvent, and filling hydrogen to perform a reduction reaction to obtain amide-containing N-substituted benzimidazole diamine with the structure shown in the formula I;
The aniline derivative has a structure shown as a formula A:
in the formula A, X comprises any one of the following substituents:
Preferably, the acid-binding agent comprises one or more of triethylamine, diisopropylethylamine, pyridine, sodium carbonate, sodium bicarbonate, potassium carbonate and sodium hydroxide.
Preferably, the acidic catalyst comprises one or more of acetic acid, sulfuric acid and hydrochloric acid;
the hydrogenation catalyst comprises one or more of palladium carbon, platinum carbon, active nickel and rhodium carbon.
Preferably, the molar ratio of the cyanamide to the paranitrobenzoyl chloride to the acid-binding agent is 1 (0.15-0.25) to 0.5-0.55;
The dosage ratio of the N-cyano-paranitrobenzamide to the aniline derivative to the acid catalyst is 1mol (1.0-2) mol (120-130) mL;
the molar ratio of the N-substituted benzimidazole dinitro containing amide to the hydrogenation catalyst is 1 (0.005-0.02).
Preferably, the condensation reaction is carried out at the temperature of 0-25 ℃ for 10-20 h.
Preferably, the temperature of the ring closing reaction is 60-100 ℃, and the time is 10-20 h.
Preferably, the temperature of the reduction reaction is 40-100 ℃, and the time is 3-8 h.
preferably, the pressure of the hydrogen is 0.5-3.0 MPa.
the invention provides amide-containing N-substituted benzimidazole diamine which has a structure shown in a formula I. The amide-containing N-substituted benzimidazole diamine provided by the invention contains both benzimidazole groups and amide groups, and ensures the rigidity of the amide-containing N-substituted benzimidazole diamine molecule, so that the amide-containing N-substituted benzimidazole diamine has excellent dimensional stability, thermal stability and mechanical properties.
The preparation method of the amide-containing N-substituted benzimidazole diamine provided by the invention comprises the three steps of condensation, ring closing and reduction, and is short in synthetic route, low in price and easy to obtain raw materials, high in process safety, simple and convenient to operate, low in production cost, high in reaction yield and suitable for industrial production.
drawings
FIG. 1 is a schematic diagram of a synthesis scheme for amide-containing N-substituted benzimidazolediamines;
FIG. 2 is a hydrogen spectrum of 4-nitro-N- (5-nitrobenzimidazol-2-yl) -benzamide prepared in example 1;
FIG. 3 is a hydrogen spectrum of 4-amino-N- (5-aminobenzimidazol-2-yl) -benzamide prepared in example 1;
FIG. 4 is a hydrogen spectrum of-nitro-N- (5-nitro-1-methylbenzimidazol-2-yl) -benzamide prepared in example 2;
FIG. 5 is a hydrogen spectrum of 4-amino-N- (5-amino-1-methylbenzimidazol-2-yl) -benzamide prepared in example 2;
FIG. 6 is a hydrogen spectrum of 4-nitro-N- (5-nitro-1-phenylbenzimidazol-2-yl) -benzamide prepared in example 3;
FIG. 7 is a hydrogen spectrum of 4-amino-N- (5-amino-1-phenylbenzimidazol-2-yl) -benzamide prepared in example 3.
Detailed Description
the invention provides amide-containing N-substituted benzimidazole diamine, which has a structure shown in a formula I:
In formula I, X includes any one of the following substituents:
In the present invention, the amide-containing N-substituted benzimidazole diamine preferably has a structure represented by formulas I-1 to I-3:
the invention provides a preparation method of amide-containing N-substituted benzimidazole diamine, which comprises the following steps:
Mixing paranitrobenzoyl chloride, cyanamide, an acid-binding agent and a first solvent, and carrying out condensation reaction to obtain N-cyano paranitrobenzamide;
Mixing the N-cyano-p-nitrobenzamide, the aniline derivative, the acid catalyst and a second solvent, and carrying out a ring closure reaction to obtain amide-containing N-substituted benzimidazole dinitro;
Under the condition of protective atmosphere, mixing the amide-containing N-substituted benzimidazole dinitro, a hydrogenation catalyst and a third solvent, and filling hydrogen to perform a reduction reaction to obtain amide-containing N-substituted benzimidazole diamine with the structure shown in the formula I;
The aniline derivative has a structure shown as a formula A:
In the formula A, X comprises any one of the following substituents:
In the present invention, the synthesis route of amide-containing N-substituted benzimidazole diamine with the structure shown in formula I is shown in FIG. 1.
in the present invention, all the raw material components are commercially available products well known to those skilled in the art unless otherwise specified.
Mixing p-nitrobenzoyl chloride, cyanamide, an acid-binding agent and a first solvent, and carrying out condensation reaction to obtain N-cyano-p-nitrobenzamide;
the aniline derivative has a structure shown as a formula A:
In the formula A, X comprises any one of the following substituents:
In the present invention, the cyanamide is preferably used in the form of an aqueous solution of cyanamide in the present invention. In the present invention, the mass concentration of the cyanamide aqueous solution is preferably 45 to 55%, and more preferably 50%.
In the invention, the acid-binding agent preferably comprises one or more of triethylamine, diisopropylethylamine, pyridine, sodium carbonate, sodium bicarbonate, potassium carbonate and sodium hydroxide, and more preferably comprises triethylamine, diisopropylethylamine, pyridine, sodium carbonate, sodium bicarbonate, potassium carbonate or sodium hydroxide.
in the present invention, the first solvent preferably includes one or more of dichloroethane, dichloromethane, benzene, toluene, chloroform, carbon tetrachloride, water and tetrahydrofuran. The amount of the first solvent used in the present invention is not particularly limited, and any solvent known in the art may be used, and specifically, the molar ratio of the paranitrobenzoyl chloride to the first solvent is 1: 10.
in the invention, the molar ratio of the cyanamide to the paranitrobenzoyl chloride to the acid-binding agent is 1 (0.15-0.25): 0.5-0.55), more preferably 1 (0.16-0.24): 0.51-0.54), and most preferably 1 (0.18-0.23): 0.52-0.53.
In the invention, the mixing mode of the paranitrobenzoyl chloride, the cyanamide, the acid-binding agent and the first solvent is preferably that the cyanamide, the acid-binding agent and the first solvent are mixed and then cooled, the paranitrobenzoyl chloride and the first solvent are mixed, and the obtained paranitrobenzoyl chloride solution is added into the mixed system. In the invention, the temperature after temperature reduction is preferably 4-6 ℃. In the invention, the p-nitrobenzoyl chloride solution is preferably added dropwise in a manner of dripping for 2-3 h.
In the invention, the condensation reaction temperature is preferably 0-25 ℃, and more preferably 20-25 ℃; the time of the condensation reaction is preferably 10-20 hours, and more preferably 15-17 hours.
After the condensation reaction is finished, the obtained system is preferably concentrated and then subjected to solid-liquid separation in the invention, and the obtained solid material is dried to obtain the N-cyano-p-nitrobenzamide. The concentration method of the present invention is not particularly limited, and a concentration method known in the art may be used, specifically, distillation under reduced pressure. The solid-liquid separation mode is not particularly limited in the invention, and a solid-liquid separation mode well known in the field can be adopted, such as reduced pressure suction filtration. In the invention, the drying temperature is preferably 60-150 ℃, and more preferably 60-120 ℃; the drying time is preferably 6-24 hours, and more preferably 6-12 hours.
after the N-cyano-p-nitrobenzamide is obtained, the N-cyano-p-nitrobenzamide, the aniline derivative, the acid catalyst and the second solvent are mixed for a ring closing reaction to obtain the N-substituted benzimidazole dinitro containing the amide.
in the present invention, the acidic catalyst preferably comprises one or more of acetic acid, sulfuric acid and hydrochloric acid, and more preferably comprises acetic acid, sulfuric acid or hydrochloric acid.
in the present invention, the second solvent is preferably one or more of methanol, ethanol, isopropanol and dioxane. The amount of the second solvent used in the present invention is not particularly limited, and any solvent known in the art may be used, and for example, the molar ratio of N-cyano-p-nitrobenzamide to the second solvent is preferably 1: 10.
In the invention, the dosage ratio of the N-cyano-paranitrobenzamide to the aniline derivative to the acid catalyst is 1mol (1.0-2) mol (120-130) mL, more preferably 1mol (1.0-1.5) mol (124-126) mL, and most preferably 1mol (1.0-1.2) mol (125 mL).
in the invention, the temperature of the ring closing reaction is preferably 60-100 ℃, more preferably 75-90 ℃, and most preferably 80 ℃; the time of the ring closing reaction is 10-20 h, more preferably 15-17 h, and most preferably 16 h.
After the ring closing reaction is completed, the reaction system is preferably cooled to 0-5 ℃, then water is added and the reaction system is kept stand for solid-liquid separation, the obtained solid is dried and recrystallized, then the solid-liquid separation is carried out, and the obtained solid is dried to obtain the N-substituted benzimidazole dinitrogen containing the amide. The solid-liquid separation mode is not particularly limited in the invention, and a solid-liquid separation mode well known in the field can be adopted, such as reduced pressure suction filtration or filtration. In the invention, the drying temperature is preferably 60-150 ℃, and more preferably 60-120 ℃; the drying time is preferably 6-24 hours, and more preferably 6-12 hours. In the invention, the solvent used for crystallization is preferably a mixed solvent of dimethylformamide and water, and the volume ratio of the dimethylformamide to the water is preferably 1 (0.1-0.5).
after the amide-containing N-substituted benzimidazole dinitro is obtained, the amide-containing N-substituted benzimidazole dinitro, a hydrogenation catalyst and a third solvent are mixed under the protective atmosphere condition, and hydrogen is filled into the mixture to carry out reduction reaction, so that the amide-containing N-substituted benzimidazole diamine with the structure shown in the formula I is obtained.
the protective atmosphere used in the present invention is not particularly limited, and any protective atmosphere known in the art may be used, specifically, nitrogen or argon.
In the present invention, the hydrogenation catalyst preferably includes one or more of palladium carbon, platinum carbon, active nickel and rhodium carbon, and more preferably includes palladium carbon, platinum carbon, active nickel or rhodium carbon.
In the present invention, the third solvent preferably includes one or more of tetrahydrofuran, ethanol, methanol, isopropanol, dimethylformamide, dimethylacetamide, N-methyl pyrrolidone, 1, 4-dioxane, ethyl acetate, benzene, toluene, and xylene. The amount of the second solvent used in the present invention is not particularly limited, and any solvent known in the art may be used, and for example, the molar ratio of N-cyano-p-nitrobenzamide to the second solvent is preferably 1: 10.
in the invention, the molar ratio of the N-substituted benzimidazole dinitro containing amide to the hydrogenation catalyst is preferably 1 (0.005-0.02), more preferably 1 (0.008-0.015), and most preferably 1: 0.01.
in the present invention, before the filling of hydrogen gas, it is preferable to include discharging air in the reaction vessel with a protective atmosphere. In the present invention, the pressure of the hydrogen gas is preferably 0.5 to 3.0MPa, more preferably 0.6 to 2MPa, and most preferably 0.7 to 1 MPa.
In the present invention, the reduction reaction is preferably carried out in an autoclave. In the invention, the temperature of the reduction reaction is preferably 40-100 ℃, more preferably 45-80 ℃, and most preferably 50-60 ℃; the time of the reduction reaction is preferably 3-8 h, more preferably 4-7 h, and most preferably 5-6 h.
after the reduction reaction is completed, the invention preferably further comprises the steps of carrying out solid-liquid separation on the obtained reaction system, cooling the obtained filtrate to room temperature, crystallizing, carrying out solid-liquid separation, and drying the obtained solid to obtain the amide-containing N-substituted benzimidazole diamine. The solid-liquid separation mode is not particularly limited in the invention, and a solid-liquid separation mode well known in the field can be adopted, such as reduced pressure suction filtration or filtration. In the invention, the drying temperature is preferably 60-150 ℃, and more preferably 60-120 ℃; the drying time is preferably 6-24 hours, and more preferably 6-12 hours. In the invention, the solvent used for crystallization is preferably a mixed solvent of ethanol and water, and the volume ratio of the ethanol to the water is preferably 1 (0.1-0.5).
the amide-containing N-substituted benzimidazole diamine film prepared by taking dianhydride and diamine containing benzimidazole and amide structures as raw materials has high glass transition temperature (T)g) The ultra-low coefficient of linear expansion (CTE) and excellent mechanical properties can meet the requirements of the OLED flexible substrate on high glass transition temperature and low coefficient of linear expansion.
The technical solution of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. It is to be understood that the described embodiments are merely exemplary of the invention, and not restrictive of the full scope of the invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
(1) Mixing 50.0g of cyanamide (50 wt% aqueous solution), 25.0g of sodium hydroxide, 200.0mL of water and 100.0mL of tetrahydrofuran, cooling to 4 ℃, dissolving 50.0g of paranitrobenzoyl chloride in 100.0mL of tetrahydrofuran, dropwise adding the paranitrobenzoyl chloride solution into the mixed system within 2-3 h, starting timing after dropwise adding, reacting for 16h at room temperature, after confirming that the reaction is finished by TLC, removing the organic solvent in the reaction system by rotary removal under reduced pressure, filtering under reduced pressure, and drying for 16h at 80 ℃ to obtain 50.0g of N-cyano paranitrobenzamide (the yield is 82%);
(2) Mixing 11.0g of N-cyano-p-nitrobenzamide, 8.8g of 4-nitrobenzene-1, 2-diamine, 7.2mL of concentrated hydrochloric acid and 100.0mL of ethanol, reacting for 16h at 80 ℃, cooling a reaction system to 0 ℃ after confirming the reaction by TLC, adding 200.0mL of water into the reaction system, performing vacuum filtration, drying for 12h at 100 ℃, and adopting a volume ratio of 1: 0.2 of dimethylformamide and water, filtration, drying at 100 ℃ for 100h to give 4-nitro-N- (5-nitrobenzimidazol-2-yl) -benzamide (15.4g, 82.1% yield, 98.2% purity, 333.2 ℃ melting point); the structural nuclear magnetic number is shown in fig. 2.
(3) Adding 15.0g of 4-nitro-N- (5-nitrobenzimidazole-2-yl) -benzamide, 150.0g of methanol and 1.5g of palladium carbon into an autoclave, filling nitrogen for three times, then filling hydrogen to the pressure of 0.7-0.8 MPa, reacting for 5 hours at 50-60 ℃, after confirming the reaction is finished by TLC, filtering the obtained reaction system to recover a hydrogenation catalyst, cooling the filtrate to room temperature, crystallizing by using ethanol and water with the volume ratio of 1:0.5, drying the filtered solid for 12 hours at 80 ℃ to obtain 4-amino-2- (4-aminobenzene) -1-methylbenzimidazole (11.2g, the yield is 91.4%, the purity is 98.1%, and the melting point is 302.5 ℃); the structural nuclear magnetic number is shown in fig. 3.
Example 2
(1) mixing 50.0g of cyanamide (50 wt% aqueous solution), 85.0g of potassium carbonate, 200.0mL of water and 100.0mL of tetrahydrofuran, cooling to 5 ℃, dissolving 50.0g of paranitrobenzoyl chloride in 100.0mL of tetrahydrofuran, dropwise adding the paranitrobenzoyl chloride solution into the mixed system within 2-3 h, starting timing after dropwise adding, reacting for 16h at room temperature, after confirming that the reaction is finished by TLC, removing the organic solvent in the reaction system under reduced pressure, filtering under reduced pressure, and drying for 10h at 100 ℃ to obtain 41.0g of N-cyano paranitrobenzamide (the yield is 86.0%);
(2) Mixing 11.0g N-cyano-paranitrobenzamide, 9.6g N-methyl-4-nitrobenzene-1, 2-diamine, 7.2mL acetic acid and 100.0mL ethanol, reacting for 16h at 80 ℃, cooling a reaction system to 3 ℃ after confirming the reaction by TLC, adding 200.0mL water into the reaction system, decompressing, filtering, drying for 12h at 100 ℃, and adopting a volume ratio of 1: 0.2 of dimethylformamide and water, filtration, drying at 100 ℃ for 12h to give 4-nitro-N- (5-nitro-1-methylbenzimidazol-2-yl) -benzamide (14.7g, 75.1% yield, 98.5% purity, melting point 324.1 ℃); the structural nuclear magnetic number is shown in fig. 4.
(3) Adding 15.0g of 4-nitro-N- (5-nitrobenzimidazole-2-yl) -benzamide, 100.0g of methanol and 1.0g of rhodium carbon into an autoclave, filling nitrogen for three times, then filling hydrogen to the pressure of 0.7-0.8 MPa, reacting for 5 hours at 50-60 ℃, after confirming the reaction is finished by TLC, filtering the obtained reaction system to recover a hydrogenation catalyst, cooling the filtrate to room temperature, crystallizing by using ethanol and water with the volume ratio of 1:0.3, drying the filtered solid for 16 hours at 90 ℃ to obtain 4-amino-N- (5-amino-1-methylbenzimidazole-2-yl) -benzamide (7.6g, the yield is 92.7%, the purity is 98.2%, and the melting point is 297.1 ℃); the structural nuclear magnetic number is shown in fig. 5.
example 3
(1) Mixing 50.0g of cyanamide (50 wt% aqueous solution), 62.7g of triethylamine, 200.0mL of water and 100.0mL of dichloromethane, cooling to 6 ℃, dissolving 50.0g of paranitrobenzoyl chloride in 100.0mL of dichloromethane, dropwise adding the paranitrobenzoyl chloride solution into the mixed system within 2-3 h, starting timing after dropwise adding, reacting for 16h at room temperature, after confirming that the reaction is finished by TLC, removing the organic solvent in the reaction system by rotary removal under reduced pressure, filtering under reduced pressure, and drying for 12h at 100 ℃ to obtain N-cyano paranitrobenzamide (44.0g, the yield is 89.5%);
(2) Mixing 11.0g N-cyano-paranitrobenzamide, 13.2g N-phenyl-4-nitrobenzene-1, 2-diamine, 7.2mL of concentrated sulfuric acid and 100.0mL of ethanol, reacting for 16h at 80 ℃, cooling a reaction system to 3 ℃ after confirming the reaction by TLC, adding 200.0mL of water into the reaction system, performing vacuum filtration, drying for 15h at 100 ℃, and adopting a volume ratio of 1: 0.4 of dimethylformamide and water, filtering and drying for 16h at 100 ℃ to obtain 4-nitro-N- (5-nitro-1-phenylbenzimidazol-2-yl) -benzamide (18.1g, yield 78.2%, purity 98.9%, melting point 308.5 ℃); the structural nuclear magnetic number is shown in fig. 6.
(3) Adding 15.0g of 4-nitro-N- (5-nitro-1-phenylbenzimidazol-2-yl) -benzamide and 100.0g of tetrahydrofuran and 1.0g of platinum carbon into an autoclave, charging nitrogen for three times, then charging hydrogen until the pressure is 0.7-0.8 MPa, reacting for 5 hours at 50-60 ℃, after TLC is adopted to determine that the reaction is finished, filtering the obtained reaction system to recover a hydrogenation catalyst, cooling the filtrate to room temperature, crystallizing by adopting ethanol and water with the volume ratio of 1:0.5, and drying the solid obtained by filtering at 80 ℃ for 10 hours to obtain 4-amino-N- (5-amino-1-phenylbenzimidazol-2-yl) -benzamide (7.7g, the yield is 90.1%, the purity is 99.2%, and the melting point is 260.1 ℃); the structural nuclear magnetic numbers are shown in FIG. 7.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (9)
1. an amide-containing N-substituted benzimidazole diamine, characterized by having the structure shown in formula I:
In formula I, X includes any one of the following substituents:
2. the method of preparing an amide-containing N-substituted benzimidazole diamine according to claim 1, comprising the steps of:
Mixing paranitrobenzoyl chloride, cyanamide, an acid-binding agent and a first solvent, and carrying out condensation reaction to obtain N-cyano paranitrobenzamide;
Mixing the N-cyano-p-nitrobenzamide, the aniline derivative, the acid catalyst and a second solvent, and carrying out a ring closure reaction to obtain amide-containing N-substituted benzimidazole dinitro;
under the condition of protective atmosphere, mixing the amide-containing N-substituted benzimidazole dinitro, a hydrogenation catalyst and a third solvent, and filling hydrogen to perform a reduction reaction to obtain amide-containing N-substituted benzimidazole diamine with the structure shown in the formula I;
The aniline derivative has a structure shown as a formula A:
In the formula A, X comprises any one of the following substituents:
3. The preparation method of claim 2, wherein the acid-binding agent comprises one or more of triethylamine, diisopropylethylamine, pyridine, sodium carbonate, sodium bicarbonate, potassium carbonate and sodium hydroxide.
4. The preparation method according to claim 2, wherein the acidic catalyst comprises one or more of acetic acid, sulfuric acid and hydrochloric acid;
the hydrogenation catalyst comprises one or more of palladium carbon, platinum carbon, active nickel and rhodium carbon.
5. The method according to any one of claims 2 to 4, wherein the molar ratio of the cyanamide to the paranitrobenzoyl chloride to the acid-binding agent is 1 (0.15 to 0.25) to (0.5 to 0.55);
The dosage ratio of the N-cyano-paranitrobenzamide to the aniline derivative to the acid catalyst is 1mol (1.0-2) mol (120-130) mL;
The molar ratio of the N-substituted benzimidazole dinitro containing amide to the hydrogenation catalyst is 1 (0.005-0.02).
6. The preparation method according to claim 2, wherein the condensation reaction is carried out at a temperature of 0-25 ℃ for 10-20 h.
7. The preparation method according to claim 2, wherein the temperature of the ring closing reaction is 60-100 ℃ and the time is 10-20 h.
8. the preparation method according to claim 2, wherein the temperature of the reduction reaction is 40-100 ℃ and the time is 3-8 h.
9. The production method according to claim 2, wherein the pressure of the hydrogen gas is 0.5 to 3.0 MPa.
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| CN112625239A (en) * | 2020-12-11 | 2021-04-09 | 东华大学 | Polyimide containing non-coplanar benzimidazole and preparation method thereof, and transparent polyimide film and preparation method and application thereof |
| CN115322156A (en) * | 2022-09-06 | 2022-11-11 | 东华大学 | Non-coplanar benzimidazole diamine and preparation method and application thereof |
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| CN115322156A (en) * | 2022-09-06 | 2022-11-11 | 东华大学 | Non-coplanar benzimidazole diamine and preparation method and application thereof |
| CN115322156B (en) * | 2022-09-06 | 2024-05-28 | 东华大学 | Non-coplanar benzimidazole diamine and preparation method and application thereof |
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