CN117466823A - Preparation method of one-pot 2- (4-aminophenyl) -5-aminobenzimidazole - Google Patents
Preparation method of one-pot 2- (4-aminophenyl) -5-aminobenzimidazole Download PDFInfo
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- CN117466823A CN117466823A CN202311521819.8A CN202311521819A CN117466823A CN 117466823 A CN117466823 A CN 117466823A CN 202311521819 A CN202311521819 A CN 202311521819A CN 117466823 A CN117466823 A CN 117466823A
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- aminobenzimidazole
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- XAFOTXWPFVZQAZ-UHFFFAOYSA-N 2-(4-aminophenyl)-3h-benzimidazol-5-amine Chemical compound C1=CC(N)=CC=C1C1=NC2=CC=C(N)C=C2N1 XAFOTXWPFVZQAZ-UHFFFAOYSA-N 0.000 title claims abstract description 36
- 238000005580 one pot reaction Methods 0.000 title claims abstract description 18
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 238000000034 method Methods 0.000 claims abstract description 16
- 150000001875 compounds Chemical class 0.000 claims abstract description 12
- 239000002904 solvent Substances 0.000 claims abstract description 11
- 239000003054 catalyst Substances 0.000 claims abstract description 9
- 238000006243 chemical reaction Methods 0.000 claims abstract description 9
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 9
- 239000003929 acidic solution Substances 0.000 claims abstract description 6
- 238000006880 cross-coupling reaction Methods 0.000 claims abstract description 5
- XJIPBORERCFIIP-UHFFFAOYSA-N 6-nitro-2-(4-nitrophenyl)-1h-benzimidazole Chemical compound C1=CC([N+](=O)[O-])=CC=C1C1=NC2=CC=C([N+]([O-])=O)C=C2N1 XJIPBORERCFIIP-UHFFFAOYSA-N 0.000 claims abstract description 3
- 238000006722 reduction reaction Methods 0.000 claims abstract description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 21
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 12
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 7
- ZBRJXVVKPBZPAN-UHFFFAOYSA-L nickel(2+);triphenylphosphane;dichloride Chemical compound [Cl-].[Cl-].[Ni+2].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 ZBRJXVVKPBZPAN-UHFFFAOYSA-L 0.000 claims description 7
- 229920000642 polymer Polymers 0.000 claims description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 6
- 229910021645 metal ion Inorganic materials 0.000 claims description 6
- 239000007787 solid Substances 0.000 claims description 6
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 6
- 238000001291 vacuum drying Methods 0.000 claims description 6
- 238000006116 polymerization reaction Methods 0.000 claims description 5
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 4
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 4
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 4
- 229910052794 bromium Inorganic materials 0.000 claims description 4
- 229910052801 chlorine Inorganic materials 0.000 claims description 4
- 239000000460 chlorine Substances 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 4
- 229910052731 fluorine Inorganic materials 0.000 claims description 4
- 239000011737 fluorine Substances 0.000 claims description 4
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 claims description 4
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 claims description 3
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 3
- QQGYZOYWNCKGEK-UHFFFAOYSA-N 5-[(1,3-dioxo-2-benzofuran-5-yl)oxy]-2-benzofuran-1,3-dione Chemical compound C1=C2C(=O)OC(=O)C2=CC(OC=2C=C3C(=O)OC(C3=CC=2)=O)=C1 QQGYZOYWNCKGEK-UHFFFAOYSA-N 0.000 claims description 3
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 3
- -1 and preferably Substances 0.000 claims description 3
- YNHIGQDRGKUECZ-UHFFFAOYSA-N dichloropalladium;triphenylphosphanium Chemical compound Cl[Pd]Cl.C1=CC=CC=C1[PH+](C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1[PH+](C=1C=CC=CC=1)C1=CC=CC=C1 YNHIGQDRGKUECZ-UHFFFAOYSA-N 0.000 claims description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 2
- GTDPSWPPOUPBNX-UHFFFAOYSA-N ac1mqpva Chemical compound CC12C(=O)OC(=O)C1(C)C1(C)C2(C)C(=O)OC1=O GTDPSWPPOUPBNX-UHFFFAOYSA-N 0.000 claims description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 2
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 claims description 2
- OPRPFIIIFJLFCE-UHFFFAOYSA-L cobalt(2+);triphenylphosphane;dichloride Chemical compound Cl[Co]Cl.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 OPRPFIIIFJLFCE-UHFFFAOYSA-L 0.000 claims description 2
- 238000002425 crystallisation Methods 0.000 claims description 2
- 230000008025 crystallization Effects 0.000 claims description 2
- 238000012805 post-processing Methods 0.000 claims description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims 2
- 239000002253 acid Substances 0.000 claims 1
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical group C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 claims 1
- 230000008569 process Effects 0.000 abstract description 3
- 238000003912 environmental pollution Methods 0.000 abstract description 2
- 238000011031 large-scale manufacturing process Methods 0.000 abstract description 2
- 230000009286 beneficial effect Effects 0.000 abstract 1
- 238000001914 filtration Methods 0.000 description 8
- 239000004642 Polyimide Substances 0.000 description 6
- 229920001721 polyimide Polymers 0.000 description 6
- 239000000706 filtrate Substances 0.000 description 4
- 230000001376 precipitating effect Effects 0.000 description 4
- GWSMACGSFHRVFA-UHFFFAOYSA-N 2-chloro-6-nitro-1h-benzimidazole Chemical compound [O-][N+](=O)C1=CC=C2N=C(Cl)NC2=C1 GWSMACGSFHRVFA-UHFFFAOYSA-N 0.000 description 3
- CZGCEKJOLUNIFY-UHFFFAOYSA-N 4-Chloronitrobenzene Chemical compound [O-][N+](=O)C1=CC=C(Cl)C=C1 CZGCEKJOLUNIFY-UHFFFAOYSA-N 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 125000005462 imide group Chemical group 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 150000002828 nitro derivatives Chemical class 0.000 description 2
- ZDFBKZUDCQQKAC-UHFFFAOYSA-N 1-bromo-4-nitrobenzene Chemical compound [O-][N+](=O)C1=CC=C(Br)C=C1 ZDFBKZUDCQQKAC-UHFFFAOYSA-N 0.000 description 1
- AZDRFCMMCKMEMX-UHFFFAOYSA-N 2-bromo-6-nitro-1h-benzimidazole Chemical compound [O-][N+](=O)C1=CC=C2N=C(Br)NC2=C1 AZDRFCMMCKMEMX-UHFFFAOYSA-N 0.000 description 1
- RAUWPNXIALNKQM-UHFFFAOYSA-N 4-nitro-1,2-phenylenediamine Chemical compound NC1=CC=C([N+]([O-])=O)C=C1N RAUWPNXIALNKQM-UHFFFAOYSA-N 0.000 description 1
- BXRFQSNOROATLV-UHFFFAOYSA-N 4-nitrobenzaldehyde Chemical compound [O-][N+](=O)C1=CC=C(C=O)C=C1 BXRFQSNOROATLV-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Natural products C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 238000004128 high performance liquid chromatography Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000004377 microelectronic Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229920002120 photoresistant polymer Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 238000006798 ring closing metathesis reaction Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
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
- C07D235/18—Benzimidazoles; Hydrogenated benzimidazoles with aryl radicals directly attached in position 2
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The invention provides a preparation method of one-pot 2- (4-aminophenyl) -5-aminobenzimidazole, which comprises the steps of adding a compound (I), a compound (II), a catalyst and a reducing agent into a solvent, performing cross coupling reaction at a certain temperature to obtain 2- (4-nitrophenyl) -5-nitrobenzimidazole, dropwise adding an acidic solution into the system, performing reduction reaction, and performing post-treatment after the reaction is finished to obtain the 2- (4-aminophenyl) -5-aminobenzimidazole. The invention has the beneficial effects that: the preparation method uses a new process system, has the advantages of simple preparation, safe operation, small environmental pollution, high yield and high purity of the synthesized product, and is suitable for large-scale production.
Description
Technical Field
The invention belongs to the technical field of organic synthesis, and particularly relates to a preparation method of one-pot 2- (4-aminophenyl) -5-aminobenzimidazole.
Background
Polyimide (PI) is a polymer with an imide structure in the main chain, and has excellent comprehensive performance due to the unique molecular structure, and is positioned at the front end of a high polymer material. PI has been widely used in flexible display, aerospace, electrical insulation, microelectronics, batteries, photoresists, and the like.
The aromatic polyimide has excellent heat stability, mechanical performance and chemical stability because of its rigid imide ring and benzene ring. The 2- (4-aminophenyl) -5-aminobenzimidazole is an important polyimide monomer, and polyimide synthesized by using the monomer has wide application prospect.
At present, the common synthesis method mainly uses 4-nitroo-phenylenediamine and p-nitrobenzaldehyde as starting materials, and the final product is prepared by synthesizing nitro compounds through ring closure and then reducing. The coupling reaction process has low general yield, and the yield can reach 95 percent (DOI: 10.1039/d2ra03491 c) after microwave reaction, but industrialization is difficult to realize. And the nitro compound needs post-treatment and refining, and then is reduced to prepare the 2- (4-aminophenyl) -5-aminobenzimidazole, which has long period, high production cost and difficult industrial production.
Disclosure of Invention
In view of the above, the present invention aims to provide a one-pot method for preparing 2- (4-aminophenyl) -5-aminobenzimidazole.
In order to achieve the above purpose, the technical scheme of the invention is realized as follows:
a preparation method of one-pot 2- (4-aminophenyl) -5-aminobenzimidazole comprises the following steps:
adding a compound (I), a compound (II), a catalyst and a reducing agent into a solvent, performing cross coupling reaction at a certain temperature to obtain 2- (4-nitrophenyl) -5-nitrobenzimidazole, dropwise adding an acidic solution into the system, performing reduction reaction, and performing treatment after the reaction is finished to obtain 2- (4-aminophenyl) -5-aminobenzimidazole;
the X is 1 Comprising one of fluorine, chlorine, bromine or iodine, said X 2 Comprising one of fluorine, chlorine, bromine or iodine, X 1 And X 2 The same or different.
Further, the catalyst comprises one or more of bis (triphenylphosphine) nickel chloride, bis (triphenylphosphine) palladium chloride and bis (triphenylphosphine) cobalt chloride, and preferably the catalyst is bis (triphenylphosphine) nickel chloride.
Further, the reducing agent comprises one or more of zinc powder, magnesium powder and iron powder, and preferably, the reducing agent is zinc powder.
Further, the mol ratio of the solvent, the catalyst, the reducing agent, the compound (II) and the compound (I) is (30-80): (0.001-0.007): (7-12): (1-1.5): 1.
Further, the solvent comprises one or more of tetrahydrofuran, 1, 4-dioxane, 1, 2-dichloroethane and dimethylformamide, and preferably, the solvent is tetrahydrofuran.
Further, the acidic solution is one or more of sulfuric acid, hydrochloric acid, phosphoric acid and acetic acid, and preferably, the acidic solution is acetic acid.
Further, the cross-coupling reaction is carried out at a temperature of 30-60 ℃.
Further, the molar ratio of the acidic solvent to the compound (I) is 10- (30:1);
and/or, the post-processing includes: after the reaction is finished, cooling to separate out white solid, vacuum drying to obtain 2- (4-aminophenyl) -5-aminobenzimidazole,
preferably, the crystallization temperature of the cooling is 0-10 ℃.
Further, the metal ion of the prepared 2- (4-aminophenyl) -5-aminobenzimidazole is less than 100ppb.
The 2- (4-aminophenyl) -5-aminobenzimidazole prepared by the preparation method of the one-pot method is applied to the polymerization reaction of the 2- (4-aminophenyl) -5-aminobenzimidazole, hexafluorodianhydride (6 FDA), 3', 4' -Benzophenone Tetracarboxylic Dianhydride (BTDA) and 4,4' -diphenyl ether dianhydride (ODPA), and the molecular weight of the obtained polymer is 50-90 ten thousand.
Compared with the prior art, the preparation method of the one-pot 2- (4-aminophenyl) -5-aminobenzimidazole has the following advantages:
the preparation method uses a new process system, has the advantages of simple preparation, safe operation, small environmental pollution, high yield and high purity of the synthesized product, and is suitable for large-scale production.
Drawings
The accompanying drawings, which are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description serve to explain the invention. In the drawings:
FIG. 1 is a synthetic scheme of 2- (4-aminophenyl) -5-aminobenzimidazole of the present invention;
FIG. 2 is an HPLC chart of 2- (4-aminophenyl) -5-aminobenzimidazole obtained in example 1 of the present invention.
Detailed Description
It should be noted that, without conflict, the embodiments of the present invention and features of the embodiments may be combined with each other.
The invention will be described in detail below with reference to the drawings in connection with embodiments.
Example 1
50g of p-chloronitrobenzene, 65.84g of 2-chloro-5-nitro-1H-1, 3-benzimidazole, 0.62g of bis (triphenylphosphine) nickel chloride and 248.94g of zinc powder were added to 915g of tetrahydrofuran, and the mixture was heated to 50℃and reacted for 10 hours. Reducing to room temperature, slowly dropwise adding 280g of acetic acid, reacting for 5 hours, filtering, reducing the filtrate to 5 ℃, precipitating white solid, filtering, and vacuum drying at 80 ℃ for 10 hours to obtain 68.07g of 2- (4-aminophenyl) -5-aminobenzimidazole with the molar yield of 95.64%, the purity of 99.91% and the metal ion content of 40ppb. And polymerizing with 6FDA to obtain the polymer with the molecular weight of 99.8 ten thousand.
Example 2
50g of p-chloronitrobenzene, 65.84g of 2-chloro-5-nitro-1H-1, 3-benzimidazole, 1.03g of bis (triphenylphosphine) nickel chloride and 207.45g of zinc powder were added to 840g of 1, 4-dioxane, and the mixture was heated to 40℃to react for 10 hours. And (3) reducing the reaction temperature to room temperature, slowly dropwise adding 290g of acetic acid, reacting for 5 hours, filtering, reducing the filtrate to 0 ℃, precipitating white solid, filtering, and vacuum drying at 90 ℃ for 10 hours to obtain 67.42g of 2- (4-aminophenyl) -5-aminobenzimidazole, wherein the molar yield is 94.72%, the purity is 99.89%, and the total content of metal ions is 50ppb. Polymerization with BTDA gave a polymer having a molecular weight of 70.4 ten thousand.
Example 3
50g of p-chloronitrobenzene, 68.96g of 2-chloro-5-nitro-1H-1, 3-benzimidazole, 0.23g of bis (triphenylphosphine) palladium dichloride and 207.45g of magnesium powder are added into 90g of tetrahydrofuran, and the temperature is raised to 50 ℃ for reaction for 10 hours. Reducing to room temperature, slowly dropwise adding 300g of hydrochloric acid, reacting for 5 hours, filtering, reducing the filtrate to 0 ℃, precipitating white solid, filtering, and vacuum drying at 90 ℃ for 10 hours to obtain 67.32g of 2- (4-aminophenyl) -5-aminobenzimidazole, wherein the molar yield is 94.59%, the purity is 99.83%, and the total content of metal ions is 45ppb. Polymerization with 6FDA gave a polymer having a molecular weight of 88.4 tens of thousands.
Example 4
50g of p-bromonitrobenzene, 65.89g of 2-bromo-6-nitro-1H-benzimidazole, 1.45g of bis (triphenylphosphine) nickel chloride, 161.82g of zinc powder were added to 1400g of 1, 2-dichloroethane, and the mixture was heated to 60℃and reacted for 10 hours. And (3) reducing the temperature to room temperature, slowly dropwise adding 300g of acetic acid, reacting for 5 hours, filtering, reducing the filtrate to 0 ℃, precipitating white solid, filtering, and vacuum drying at 90 ℃ for 10 hours to obtain 52.17g of 2- (4-aminophenyl) -5-aminobenzimidazole, wherein the molar yield is 93.99%, the purity is 99.79%, and the total metal ion content is 53ppb. Polymerization with ODPA gave a polymer of 58.9 ten thousand molecular weight.
As can be seen from examples 1-4, the molar yield of the 2- (4-aminophenyl) -5-aminobenzimidazole prepared by the method is more than 93.5%, the molar yield can reach 95.6%, and the purity can reach 99.7%, even 99.9%.
The foregoing description of the preferred embodiments of the invention is not intended to be limiting, but rather is intended to cover all modifications, equivalents, alternatives, and improvements that fall within the spirit and scope of the invention.
Claims (10)
1. A preparation method of one-pot 2- (4-aminophenyl) -5-aminobenzimidazole is characterized by comprising the following steps: the method comprises the following steps:
adding a compound (I), a compound (II), a catalyst and a reducing agent into a solvent, performing cross coupling reaction at a certain temperature to obtain 2- (4-nitrophenyl) -5-nitrobenzimidazole, dropwise adding an acidic solution into the system, performing reduction reaction, and performing treatment after the reaction is finished to obtain 2- (4-aminophenyl) -5-aminobenzimidazole;
the X is 1 Comprising one of fluorine, chlorine, bromine or iodine, said X 2 Comprising one of fluorine, chlorine, bromine or iodine, X 1 And X 2 The same or different.
2. The method for preparing the one-pot 2- (4-aminophenyl) -5-aminobenzimidazole according to claim 1, which is characterized by comprising the following steps of: the catalyst comprises one or more of bis (triphenylphosphine) nickel chloride, bis (triphenylphosphine) palladium chloride and bis (triphenylphosphine) cobalt chloride, and preferably the catalyst is bis (triphenylphosphine) nickel chloride.
3. The method for preparing the one-pot 2- (4-aminophenyl) -5-aminobenzimidazole according to claim 1, which is characterized by comprising the following steps of: the reducing agent comprises one or more of zinc powder, magnesium powder and iron powder, and preferably the reducing agent is zinc powder.
4. The method for preparing the one-pot 2- (4-aminophenyl) -5-aminobenzimidazole according to claim 1, which is characterized by comprising the following steps of: the mol ratio of the solvent, the catalyst, the reducing agent, the compound (II) and the compound (I) is (30-80): 0.001-0.007): 7-12): 1-1.5): 1.
5. The method for preparing the one-pot 2- (4-aminophenyl) -5-aminobenzimidazole according to claim 1, which is characterized by comprising the following steps of: the solvent comprises one or more of tetrahydrofuran, 1, 4-dioxane, 1, 2-dichloroethane and dimethylformamide, and preferably, the solvent is tetrahydrofuran.
6. The method for preparing the one-pot 2- (4-aminophenyl) -5-aminobenzimidazole according to claim 1, which is characterized by comprising the following steps of: the acidic solution is one or more of sulfuric acid, hydrochloric acid, phosphoric acid and acetic acid, preferably acetic acid.
7. The method for preparing the one-pot 2- (4-aminophenyl) -5-aminobenzimidazole according to claim 1, which is characterized by comprising the following steps of: the temperature at which the cross-coupling reaction is carried out is 30-60 ℃.
8. The method for preparing the one-pot 2- (4-aminophenyl) -5-aminobenzimidazole according to claim 1, which is characterized by comprising the following steps of: the molar ratio of the acid solvent to the compound (I) is 10- (30:1);
and/or, the post-processing includes: after the reaction is finished, cooling to separate out white solid, vacuum drying to obtain 2- (4-aminophenyl) -5-aminobenzimidazole,
preferably, the crystallization temperature of the cooling is 0-10 ℃.
9. The method for preparing the one-pot 2- (4-aminophenyl) -5-aminobenzimidazole according to claim 1, which is characterized by comprising the following steps of: the metal ions of the prepared 2- (4-aminophenyl) -5-aminobenzimidazole are less than 100ppb.
10. The application of 2- (4-aminophenyl) -5-aminobenzimidazole prepared by the one-pot method 2- (4-aminophenyl) -5-aminobenzimidazole preparation method according to any one of claims 1 to 9 to polymerization with hexafluorodianhydride (6 FDA), 3', 4' -Benzophenone Tetracarboxylic Dianhydride (BTDA) and 4,4' -biphenyl ether dianhydride (ODPA), which is characterized in that: the molecular weight of the polymer obtained by the reaction is 50-90 ten thousand.
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