CN112608279A - Non-coplanar benzimidazole diamine and preparation method thereof - Google Patents
Non-coplanar benzimidazole diamine and preparation method thereof Download PDFInfo
- Publication number
- CN112608279A CN112608279A CN202011460689.8A CN202011460689A CN112608279A CN 112608279 A CN112608279 A CN 112608279A CN 202011460689 A CN202011460689 A CN 202011460689A CN 112608279 A CN112608279 A CN 112608279A
- Authority
- CN
- China
- Prior art keywords
- reaction
- benzimidazole
- formula
- coplanar
- preparation
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Images
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
Abstract
The invention relates to the technical field of organic synthesis, and provides non-coplanar benzimidazole diamine and a preparation method thereof. The invention provides a novel benzimidazole diamine with side groups on both a benzimidazole ring and a benzene ring, and the introduction of double side groups promotes the benzimidazole ring and the benzene ring to twist to form a non-coplanar surface, so that the conjugation effect in molecules is reduced, and the optical performance and the solubility of a polymeric material prepared by using the diamine monomer are improved; in addition, the side groups introduced into the benzimidazole ring and the benzene ring are variable in variety, so that various polymeric materials with different structures and performances can be obtained, and the preparation method has a wide application prospect. The preparation method provided by the invention can obtain the non-coplanar benzimidazole diamine through condensation reaction, ring closure reaction and catalytic hydrogenation reaction, has the advantages of cheap and easily-obtained raw materials, high process safety, simple and convenient operation, lower production cost and higher reaction yield, and is suitable for industrial production.
Description
Technical Field
The invention relates to the technical field of organic synthesis, in particular to non-coplanar benzimidazole diamine and a preparation method thereof.
Background
Diamine compounds are important chemical raw materials or intermediates, and can be used as monomers for synthesizing various polymers such as novel polyimide, polyamide, polyurea, organic silicon and the like. The introduction of aromatic heterocyclic structure in diamine can effectively improve the mechanical property, chemical corrosion resistance, high temperature resistance and flame resistance of the material, thereby expanding the application field of the material.
Benzimidazole diamine is taken as a typical rigid aromatic heterocyclic unit and is introduced into a high molecular main chain, so that the mechanical property and the heat resistance of the material can be obviously improved. The Synthesis of Benzimidazole monomers is mentioned in the documents "Synthesis and Characterization of thermal Stable, High-Module Polyimides binding Benzimidazole Moites, SHUANG WANG et al," Journal of Polymer Science: PartA: Polymer Chemistry, No. 47, No. 2024 to No. 2031, 2009 ", and it is mentioned that materials prepared using Benzimidazole monomers have excellent thermal and mechanical properties, but the optical properties of the materials are very poor due to the conjugation effect of the Benzimidazole diamine monomer itself. However, the benzimidazole diamine monomer in the prior art has a single structure, and the non-coplanar benzimidazole diamine has fewer types, so that the prepared polymeric material has a single performance, and cannot meet the requirements for synthesizing polymers with different performances, and the optical performance of the polymer is generally not high, and the construction of non-coplanar diamine monomers with different structures is a research hotspot in the field.
Disclosure of Invention
In view of the above, the present invention provides a non-coplanar benzimidazole diamine and a preparation method thereof. The non-coplanar benzimidazole diamine provided by the invention has a novel structure, the conjugation effect of molecules is small, and the polymer with good optical performance and solubility can be prepared.
In order to achieve the above object, the present invention provides the following technical solutions:
a non-coplanar benzimidazole diamine having the structure of formula I:
in formula I: x is one of the following groups:
y is one of the following groups:
preferably, the non-coplanar benzimidazole diamine has one of the following structures:
the invention provides a preparation method of the non-coplanar benzimidazole diamine, which comprises the following steps:
(1) carrying out condensation reaction on a compound with a structure shown in a formula a and a compound with a structure shown in a formula b, and carrying out ring closing reaction on the obtained condensation product to obtain a compound with a structure shown in a formula c;
the types of X and Y in the formulas a to c are the same as those in the formula I;
(2) and (3) carrying out catalytic hydrogenation reaction on the compound with the structure shown in the formula c under the hydrogen condition to obtain the non-coplanar benzimidazole diamine with the structure shown in the formula I.
Preferably, the condensation reaction is carried out in the presence of an acid-binding agent, wherein the acid-binding agent comprises one or more of triethylamine, diisopropylethylamine, pyridine, sodium carbonate, sodium bicarbonate and potassium carbonate;
the solvent for condensation reaction comprises one or more of dichloroethane, dichloromethane, benzene, toluene, chloroform, carbon tetrachloride and tetrahydrofuran.
Preferably, the condensation reaction is carried out at the temperature of 0-25 ℃ for 5-16 h.
Preferably, the ring closing reaction is carried out in the presence of an acidic catalyst, wherein the acidic catalyst comprises one or more of acetic acid, sulfuric acid, hydrochloric acid and p-toluenesulfonic acid;
the solvent for the ring closing reaction comprises one or more of N-methyl pyrrolidone, butyrolactone, sulfolane and dichlorobenzene.
Preferably, the temperature of the ring closing reaction is 180-220 ℃, and the time is 3-6 h.
Preferably, the catalyst for catalytic hydrogenation reaction comprises one or more of palladium carbon, platinum carbon, active nickel and rhodium carbon; the solvent for catalytic hydrogenation reaction comprises one or more of tetrahydrofuran, ethanol, methanol, isopropanol, dimethylformamide, dimethylacetamide, N-methylpyrrolidone, 1, 4-dioxane, ethyl acetate, benzene, toluene and xylene.
Preferably, the temperature of the catalytic hydrogenation reaction is 40-100 ℃, the pressure is 0.5-3 MPa, and the time is 4-10 h.
The invention provides non-coplanar benzimidazole diamine which has a structure shown in a formula I. The invention provides a novel benzimidazole diamine with side groups on benzimidazole and benzene rings, wherein the introduction of double side groups promotes the benzimidazole rings and the benzene rings to twist to form a non-coplanar surface, so that the conjugation effect in molecules is reduced, and the optical performance and the solubility of a polymeric material prepared by using the diamine monomer are improved; in addition, the side groups (namely X and Y groups) introduced on the benzimidazole ring and the benzene ring are variable in types, the defect of single structure of the diamine monomer can be overcome, and the diamine monomer disclosed by the invention can be applied to synthesis of a polymeric material, so that the polymeric material with different structures and performances can be obtained, and the application prospect is wide.
The invention also provides a preparation method of the non-coplanar benzimidazole diamine, which takes a compound with a structure shown in the formula a as an initial raw material and can obtain the non-coplanar benzimidazole diamine through condensation reaction, ring closing reaction and catalytic hydrogenation reaction. The preparation method provided by the invention has the advantages of cheap and easily available raw materials, high process safety, simple and convenient operation, low production cost and high reaction yield, and is suitable for industrial production.
Drawings
FIG. 1 is a nuclear magnetic hydrogen spectrum of 5-nitro-2- (2-methyl-4-nitrobenzene) -1-phenylbenzimidazole in example 1;
FIG. 2 is a nuclear magnetic hydrogen spectrum of 5-amino-2- (2-methyl-4-aminobenzene) -1-phenylbenzimidazole in example 1;
FIG. 3 is a nuclear magnetic hydrogen spectrum of 5-nitro-2- (2-trifluoromethyl-4-nitrobenzene) -1-phenylbenzimidazole in example 2;
FIG. 4 is a nuclear magnetic hydrogen spectrum of 5-amino-2- (2-trifluoromethyl-4-aminobenzene) -1-phenylbenzimidazole in example 2;
FIG. 5 is a nuclear magnetic hydrogen spectrum of 5-nitro-2- (2-methyl-4-nitrophenyl) -1- (3-trifluoromethylbenzene) benzimidazole of example 3;
FIG. 6 is a nuclear magnetic hydrogen spectrum of 5-amino-2- (2-methyl-4-aminobenzene) -1- (3-trifluoromethylbenzene) benzimidazole of example 3;
FIG. 7 is a nuclear magnetic hydrogen spectrum of 5-nitro-2- (2-trifluoromethyl-4-nitrobenzene) -1- (3-trifluoromethylbenzene) benzimidazole of example 4;
FIG. 8 is a nuclear magnetic hydrogen spectrum of 5-amino-2- (2-trifluoromethyl-4-aminobenzene) -1- (3-trifluoromethylbenzene) benzimidazole of example 4;
FIG. 9 shows molecular simulation structures of the products of examples 1 to 2.
Detailed Description
The invention provides a non-coplanar benzimidazole diamine, which has a structure shown in a formula I:
in formula I: x is one of the following groups:
y is one of the following groups:
in the present invention, the non-coplanar benzimidazole diamine preferably has one of the following structures:
the invention provides a preparation method of the non-coplanar benzimidazole diamine, which comprises the following steps:
(1) carrying out condensation reaction on a compound with a structure shown in a formula a and a compound with a structure shown in a formula b, and carrying out ring closing reaction on the obtained condensation product to obtain a compound with a structure shown in a formula c;
the types of X and Y in the formulas a to c are the same as those in the formula I;
(2) and (3) carrying out catalytic hydrogenation reaction on the compound with the structure shown in the formula c under the hydrogen condition to obtain the non-coplanar benzimidazole diamine with the structure shown in the formula I.
The synthetic route of the non-coplanar benzimidazole diamine is shown as a formula A, and the following specific description is provided by combining the formula A:
in formula A, X and Y are the same as those in formula I.
And (2) carrying out a condensation reaction on the compound with the structure shown in the formula a and the compound with the structure shown in the formula b, and carrying out a ring closing reaction on the obtained condensation product to obtain the compound with the structure shown in the formula c. In the invention, the condensation reaction is preferably carried out in the presence of an acid-binding agent, wherein the acid-binding agent preferably comprises one or more of triethylamine, diisopropylethylamine, pyridine, sodium carbonate, sodium bicarbonate and potassium carbonate; the molar ratio of the compound with the structure shown in the formula a to the compound with the structure shown in the formula b to the acid-binding agent is preferably 1:1.2: 1.2.
In the present invention, the solvent for condensation reaction preferably includes one or more of dichloroethane, dichloromethane, benzene, toluene, chloroform, carbon tetrachloride and tetrahydrofuran. The invention has no special requirements on the dosage of the solvent, and can ensure that the reaction is carried out smoothly.
In the invention, the temperature of the condensation reaction is preferably 0-25 ℃, more preferably 15-25 ℃, and in the specific embodiment of the invention, the condensation reaction is carried out at room temperature; the time of the condensation reaction is preferably 5-16 h, and more preferably 8-15 h; in a particular embodiment of the invention, the end of the reaction is preferably monitored by TLC.
In the embodiment of the invention, the compound having the structure shown in the formula a, the solvent and the acid-binding agent are preferably mixed firstly, the mixture is cooled to 5 +/-1 ℃, then the compound having the structure shown in the formula b is dropwise added, and the reaction is carried out under the condensation reaction temperature condition after the dropwise addition is finished. The compound with the structure shown in the formula b is preferably dripped within 2-3 h.
After the condensation reaction is finished, the invention preferably mixes the obtained product feed liquid with water, then carries out solid-liquid separation, and dries the obtained solid product to obtain a crude product of the compound with the structure shown in the formula b. The method directly performs subsequent ring closing reaction on the obtained crude product, and does not need to purify the crude product.
In the invention, the ring closing reaction is preferably carried out in the presence of an acidic catalyst, and the acidic catalyst preferably comprises one or more of acetic acid, sulfuric acid, hydrochloric acid and p-toluenesulfonic acid; the invention has no special requirement on the dosage of the acid catalyst, and the dosage well known by the technicians in the field can promote the reaction to be smoothly carried out; the solvent for the ring closing reaction preferably comprises one or more of N-methyl pyrrolidone, butyrolactone, sulfolane and dichlorobenzene; the temperature of the ring closing reaction is preferably 180-220 ℃, more preferably 190-210 ℃, the time is preferably 3-6 h, more preferably 4-5 h, and in the specific embodiment of the invention, TLC is preferably used for monitoring the end of the reaction.
In a specific embodiment of the present invention, it is preferable to mix the crude product of the compound having the structure represented by formula b, the organic solvent and the catalyst, and then raise the temperature to the ring-closing reaction temperature to perform the reaction.
After the ring-closing reaction is finished, the invention preferably carries out post-treatment on the obtained product feed liquid, wherein the post-treatment comprises the following steps: mixing the product liquid obtained by the ring closing reaction with water, then carrying out solid-liquid separation, drying the solid product, then recrystallizing by using a mixed solvent of N-methylformamide and water, and sequentially filtering and drying the obtained crystal liquid to obtain a compound with a structure shown in a formula c; the volume ratio of N-methylformamide to water in the mixed solvent is preferably 5: 1.
After the compound with the structure shown in the formula c is obtained, the compound with the structure shown in the formula c is subjected to catalytic hydrogenation reaction under the hydrogen condition to obtain the non-coplanar benzimidazole diamine with the structure shown in the formula I. In the invention, the catalyst for catalytic hydrogenation reaction preferably comprises one or more of palladium carbon, platinum carbon, active nickel and rhodium carbon; the amount of the catalyst is preferably 9-10% of the amount of the compound having the structure represented by formula c.
In the present invention, the solvent for hydrogenation reaction preferably includes one or more of tetrahydrofuran, ethanol, methanol, isopropanol, dimethylformamide, dimethylacetamide, N-methylpyrrolidone, 1, 4-dioxane, ethyl acetate, benzene, toluene, and xylene. The method has no special requirement on the dosage of the solvent, and can ensure the smooth proceeding of the catalytic hydrogenation reaction.
In the invention, the temperature of the catalytic hydrogenation reaction is preferably 40-100 ℃, more preferably 60-80 ℃, the pressure is preferably 0.5-3 MPa, more preferably 1-2 MPa, the reaction time is preferably 4-10 h, more preferably 5-6 h, and in a specific embodiment of the invention, TLC is preferably used for monitoring the reaction completion; the catalytic hydrogenation reaction is preferably carried out in an autoclave.
In the embodiment of the present invention, it is preferable that the compound having the structure represented by formula c, the solvent and the catalyst are first charged into an autoclave, then the air in the autoclave is replaced with nitrogen three times, and then hydrogen is charged to perform the reaction.
After the catalytic hydrogenation reaction is finished, the invention preferably carries out post-treatment on the obtained product feed liquid, and the post-treatment preferably comprises the following steps: and (2) filtering a product liquid obtained by catalytic hydrogenation reaction, recovering the catalyst, and sequentially cooling, crystallizing, filtering and drying the obtained filtrate to obtain the N-substituted bis-benzimidazole diamine with the structure shown in the formula I. In the present invention, the temperature of the cooling crystallization is preferably 0 ℃.
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
In this example, the specific structure of the non-coplanar benzimidazole diamine is as follows, with the name 5-amino-2- (2-methyl-4-aminophenyl) -1-phenylbenzimidazole:
the preparation method of the 5-amino-2- (2-methyl-4-aminobenzene) -1-phenylbenzimidazole comprises the following steps:
(1) adding 50.0g N-phenyl-4-nitrobenzene-1, 2-diamine, 33.1g of triethylamine and 500.0g of dichloromethane into a reaction bottle, cooling to 5 +/-1 ℃, dropwise adding 52.1g of 3-methyl-4-nitrobenzoyl chloride, completing dropwise adding within 2-3 h, reacting for 16h at room temperature, and determining that the reaction is finished by TLC. Adding 1000.0g of water into a reaction system, carrying out vacuum filtration to obtain 85.6g of a crude product, drying, adding 800.0g of butyrolactone and 45.0g of p-toluenesulfonic acid, reacting for 4 hours at 200 ℃, reducing the temperature to 0-5 ℃ after TLC (thin layer chromatography) determines that the reaction is finished, adding 1400.0g of water into the reaction system, carrying out vacuum filtration, drying, recrystallizing N-methylformamide and water, filtering, drying to obtain 44.7g of 5-nitro-2- (2-methyl-4-nitrobenzene) -1-phenylbenzimidazole, wherein the yield is 89.5%, and the nuclear magnetic resonance is confirmed, and the nuclear magnetic hydrogen spectrum is shown in figure 1, and the melting point is: 207.5 ℃.
(2) Adding 44.0g of 5-nitro-2- (2-methyl-4-nitrobenzene) -1-phenylbenzimidazole, 400.0g of methanol and 4.0g of palladium carbon into an autoclave, replacing with nitrogen for three times, then filling hydrogen to the pressure of 0.7-0.8 MPa, controlling the temperature to be 50-60 ℃, keeping the temperature and maintaining the pressure for 5 hours, confirming the reaction by TLC, filtering to recover the catalyst, cooling and crystallizing the filtrate, filtering, drying to obtain 58.2g of 5-amino-2- (2-methyl-4-aminobenzene) -1-phenylbenzimidazole, wherein the yield is 96.4%, and the nuclear magnetic resonance is confirmed, and the nuclear magnetic resonance is shown in figure 2, and the melting point: 216.0 deg.C.
Example 2
In this example, the specific structure of the non-coplanar benzimidazole diamine is as follows, with the generic name 5-amino-2- (2-trifluoromethyl-4-aminophenyl) -1-phenylbenzimidazole:
the preparation method of the 5-amino-2- (2-trifluoromethyl-4-aminobenzene) -1-phenylbenzimidazole comprises the following steps:
(1) adding 50.0g N-phenyl-4-nitrobenzene-1, 2-diamine, 25.9g of pyridine and 500.0g of dichloromethane into a reaction bottle, cooling to 5 +/-1 ℃, dropwise adding 66.3g of 3-trifluoromethyl-4-nitrobenzoyl chloride, completing dropwise adding within 2-3 h, reacting for 16h at room temperature, and determining the reaction to be finished by TLC. Adding 1000.0g of water into a reaction system, carrying out reduced pressure filtration to obtain 97.0g of a crude product, drying, adding 1000.0g of sulfolane and 21.8mL of concentrated hydrochloric acid, reacting at 200 ℃ for 4 hours, determining that the reaction is finished by TLC, cooling to 0-5 ℃, adding 1400.0g of water into the reaction system, carrying out reduced pressure filtration, drying, recrystallizing N-methylformamide and water, filtering, drying to obtain 76.9g of 5-nitro-2- (2-trifluoromethyl-4-nitrobenzene) -1-phenylbenzimidazole, wherein the yield is 82.3%, carrying out nuclear magnetic resonance confirmation on a product structure, and obtaining a nuclear magnetic hydrogen spectrum as shown in figure 3, wherein the melting point is: 230.9 deg.C.
(2) Adding 76.0g of 5-nitro-2- (2-trifluoromethyl-4-nitrobenzene) -1-phenylbenzimidazole, 700.0g of ethanol and 7.0g of platinum carbon into an autoclave, replacing the mixture with nitrogen for three times, then filling hydrogen into the autoclave until the pressure is 0.7-0.8 MPa, controlling the temperature to be 50-60 ℃, keeping the temperature and maintaining the pressure for 5 hours, confirming the reaction by TLC, filtering and recovering the catalyst, cooling and crystallizing the filtrate, filtering and drying the filtrate to obtain 61.4g of 5-amino-2- (2-trifluoromethyl-4-aminobenzene) -1-phenylbenzimidazole, wherein the yield is 93.9%, confirming the structure of the product by nuclear magnetic resonance, and the nuclear magnetic resonance spectrum is shown in figure 4, and the melting point: 100.1 ℃.
Example 3
In this example, the specific structure of the non-coplanar benzimidazole diamine is as follows, with the generic name 5-amino-2- (2-methyl-4-aminophenyl) -1- (3-trifluoromethylphenyl) benzimidazole:
the preparation method of the 5-amino-2- (2-methyl-4-aminobenzene) -1- (3-trifluoromethylbenzene) benzimidazole comprises the following steps:
(1) adding 50.0g N- (3-trifluoromethylbenzene) -4-nitrobenzene-1, 2-diamine, 34.8g of potassium carbonate and 500.0g of chloroform into a reaction bottle, cooling to 5 +/-1 ℃, dropwise adding 40.2g of 3-methyl-4-nitrobenzoyl chloride, completing dropwise adding within 2-3 h, reacting for 16h at room temperature, and determining the reaction to be finished by TLC. Adding 1000.0g of water into a reaction system, carrying out reduced pressure filtration to obtain 77.0g of a crude product, drying, adding 700.0g of dichlorobenzene and 19.8g of concentrated sulfuric acid, reacting at 200 ℃ for 4 hours, determining that the reaction is finished by TLC, cooling to 0-5 ℃, adding 1000.0g of water into the reaction system, carrying out reduced pressure filtration, drying, recrystallizing N-methylformamide and water, filtering, and drying to obtain 64.9g of 5-nitro-2- (2-methyl-4-nitrobenzene) -1- (3-trifluoromethylbenzene) benzimidazole, wherein the yield is 87.2%, the nuclear magnetic resonance of the product structure is determined, and the nuclear magnetic hydrogen spectrum is shown in figure 5, and the melting point is: 178.5 ℃.
(2) Adding 64.0g of 5-nitro-2- (2-methyl-4-nitrobenzene) -1- (3-trifluoromethylbenzene) benzimidazole, 600.0g of 1, 4-dioxane and 6.0g of active nickel into an autoclave, replacing three times by nitrogen, then filling hydrogen to the pressure of 0.7-0.8 MPa, controlling the temperature at 50-60 ℃, keeping the temperature and pressure for 5 hours, confirming the end of the reaction by TLC, filtering and recovering the catalyst, cooling and crystallizing the filtrate, filtering and drying to obtain 50.5g of 5-amino-2- (2-methyl-4-aminobenzene) -1- (3-trifluoromethylbenzene) benzimidazole, wherein the yield is 91.2%, and the nuclear magnetic resonance of the product structure is confirmed, and the nuclear magnetic hydrogen spectrum is shown in figure 6, and the melting point is: 103.0 ℃.
Example 4
In this example, the specific structure of the non-coplanar benzimidazole diamine is as follows, with the generic name 5-amino-2- (2-trifluoromethyl-4-aminophenyl) -1- (3-trifluoromethylphenyl) benzimidazole:
the preparation method of the 5-amino-2- (2-trifluoromethyl-4-aminobenzene) -1- (3-trifluoromethylbenzene) benzimidazole comprises the following steps:
(1) adding 50.0g N- (3-trifluoromethylbenzene) -4-nitrobenzene-1, 2-diamine, 26.7g of sodium carbonate and 500.0g of dichloroethane into a reaction bottle, cooling to 5 +/-1 ℃, dropwise adding 51.0g of 3-trifluoromethyl-4-nitrobenzoyl chloride, finishing dropwise adding for 2-3 h, reacting for 16h at room temperature, and determining the reaction to be finished by TLC. Adding 1000.0g of water into a reaction system, carrying out reduced pressure filtration to obtain 86.5g of a crude product, drying, adding 700.0g of N-methylpyrrolidone and 34.8g of p-toluenesulfonic acid, reacting at 200 ℃ for 4 hours, determining that the reaction is finished by TLC, cooling to 0-5 ℃, adding 1000.0g of water into the reaction system, carrying out reduced pressure filtration, drying, recrystallizing N-methylformamide and water, filtering, and drying to obtain 67.8g of 5-nitro-2- (2-trifluoromethyl-4-nitrobenzene) -1- (3-trifluoromethylbenzene) benzimidazole, wherein the yield is 81.2%, the nuclear magnetic resonance of the product structure is determined, the nuclear magnetic hydrogen spectrum is shown in figure 7, and the melting point: 205.2 ℃.
(2) Adding 67.0g of 5-nitro-2- (2-methyl-4-nitrobenzene) -1- (3-trifluoromethyl benzene) benzimidazole, 600.0g of 1, 4-isopropanol and 6.0g of rhodium carbon into an autoclave, replacing three times by nitrogen, then filling hydrogen to the pressure of 0.7-0.8 MPa, controlling the temperature at 50-60 ℃, keeping the temperature and pressure for 5 hours, confirming the reaction by TLC, filtering and recovering a catalyst, cooling and crystallizing a filtrate, filtering and drying to obtain 54.3g of 5-amino-2- (2-trifluoromethyl-4-aminobenzene) -1- (3-trifluoromethyl benzene) benzimidazole, wherein the yield is 92.1%, and the nuclear magnetic resonance of the product structure is confirmed, and the nuclear magnetic hydrogen spectrum is shown in a figure 8, and the melting point: 313.6 ℃.
Fig. 9 shows the molecular simulation structure of the products of examples 1 to 2, and table 1 shows specific values of α angle and β angle obtained by molecular simulation, and it can be seen from the results in fig. 9 and table 1 that the product structures obtained in examples 1 to 2 have large dihedral angles and obvious twisted structures.
TABLE 1 specific values of alpha and beta angles obtained by molecular simulation
The molecular simulation of the products obtained in examples 3-4 shows that the product structures all have obvious twisted structures, and the products are all non-coplanar benzimidazole diamines.
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. A non-coplanar benzimidazole diamine having the structure of formula I:
in formula I: x is one of the following groups:
-CH3 -C2H5 
y is one of the following groups:
-CH3 -CF3 -F -Cl -Br
2. the non-coplanar benzimidazole diamine of claim 1, wherein the non-coplanar benzimidazole diamine has one of the following structures:
3. a process for preparing a non-coplanar benzimidazole diamine according to claim 1 or 2, comprising the steps of:
(1) carrying out condensation reaction on a compound with a structure shown in a formula a and a compound with a structure shown in a formula b, and carrying out ring closing reaction on the obtained condensation product to obtain a compound with a structure shown in a formula c;
the types of X and Y in the formulas a to c are the same as those in the formula I;
(2) and (3) carrying out catalytic hydrogenation reaction on the compound with the structure shown in the formula c under the hydrogen condition to obtain the non-coplanar benzimidazole diamine with the structure shown in the formula I.
4. The preparation method of claim 3, wherein the condensation reaction is carried out in the presence of an acid-binding agent, wherein the acid-binding agent comprises one or more of triethylamine, diisopropylethylamine, pyridine, sodium carbonate, sodium bicarbonate and potassium carbonate;
the solvent for condensation reaction comprises one or more of dichloroethane, dichloromethane, benzene, toluene, chloroform, carbon tetrachloride and tetrahydrofuran.
5. The preparation method according to claim 3 or 4, wherein the condensation reaction is carried out at a temperature of 0-25 ℃ for 5-16 h.
6. The preparation method of claim 3, wherein the ring closing reaction is carried out in the presence of an acidic catalyst, wherein the acidic catalyst comprises one or more of acetic acid, sulfuric acid, hydrochloric acid and p-toluenesulfonic acid;
the solvent for the ring closing reaction comprises one or more of N-methyl pyrrolidone, butyrolactone, sulfolane and dichlorobenzene.
7. The preparation method according to claim 3 or 6, wherein the temperature of the ring closing reaction is 180-220 ℃ and the time is 3-6 h.
8. The preparation method according to claim 3, wherein the catalyst for catalytic hydrogenation reaction comprises one or more of palladium carbon, platinum carbon, active nickel and rhodium carbon; the solvent for catalytic hydrogenation reaction comprises one or more of tetrahydrofuran, ethanol, methanol, isopropanol, dimethylformamide, dimethylacetamide, N-methylpyrrolidone, 1, 4-dioxane, ethyl acetate, benzene, toluene and xylene.
9. The preparation method according to claim 3 or 8, wherein the temperature of the catalytic hydrogenation reaction is 40-100 ℃, the pressure is 0.5-3 MPa, and the time is 4-10 h.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011460689.8A CN112608279A (en) | 2020-12-11 | 2020-12-11 | Non-coplanar benzimidazole diamine and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011460689.8A CN112608279A (en) | 2020-12-11 | 2020-12-11 | Non-coplanar benzimidazole diamine and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN112608279A true CN112608279A (en) | 2021-04-06 |
Family
ID=75233557
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202011460689.8A Pending CN112608279A (en) | 2020-12-11 | 2020-12-11 | Non-coplanar benzimidazole diamine and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112608279A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115322156A (en) * | 2022-09-06 | 2022-11-11 | 东华大学 | Non-coplanar benzimidazole diamine and preparation method and application thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20120140603A (en) * | 2011-06-21 | 2012-12-31 | 주식회사 알파켐 | New material for transporting electron and organic electroluminescent device using the same |
| CN105348201A (en) * | 2015-11-17 | 2016-02-24 | 中国科学院长春应用化学研究所 | Hydroxyl-containing benzimidazole diamines and preparation method thereof |
| CN109400536A (en) * | 2018-12-21 | 2019-03-01 | 东华大学 | A kind of N substituted benzimidazole diamines and preparation method thereof |
| CN110204719A (en) * | 2019-06-25 | 2019-09-06 | 东华大学 | A kind of polyimides that benzimidazole replaces and the Kapton that preparation method, benzimidazole replace and preparation method and application |
-
2020
- 2020-12-11 CN CN202011460689.8A patent/CN112608279A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20120140603A (en) * | 2011-06-21 | 2012-12-31 | 주식회사 알파켐 | New material for transporting electron and organic electroluminescent device using the same |
| CN105348201A (en) * | 2015-11-17 | 2016-02-24 | 中国科学院长春应用化学研究所 | Hydroxyl-containing benzimidazole diamines and preparation method thereof |
| CN109400536A (en) * | 2018-12-21 | 2019-03-01 | 东华大学 | A kind of N substituted benzimidazole diamines and preparation method thereof |
| CN110204719A (en) * | 2019-06-25 | 2019-09-06 | 东华大学 | A kind of polyimides that benzimidazole replaces and the Kapton that preparation method, benzimidazole replace and preparation method and application |
Non-Patent Citations (2)
| Title |
|---|
| HYUNGSAM CHOI ET AL.: "Soluble polyimides from unsymmetrical diamine containing benzimidazole ring and trifluoromethyl pendent group", 《POLYMER》 * |
| WU9233: "高分子材料的光学性能", 《豆丁网HTTPS://WWW.DOCIN.COM/P-842954609.HTML》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115322156A (en) * | 2022-09-06 | 2022-11-11 | 东华大学 | Non-coplanar benzimidazole diamine and preparation method and application thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109400536A (en) | A kind of N substituted benzimidazole diamines and preparation method thereof | |
| CN112608279A (en) | Non-coplanar benzimidazole diamine and preparation method thereof | |
| CN114573569B (en) | Preparation method of isoquinoline compound | |
| CN110577495A (en) | amide-containing N-substituted benzimidazole diamine and preparation method thereof | |
| CN107021930B (en) | Synthesize 1H, 1`H-(2,2`- bisbenzimidazole) -5,5`- diamines method | |
| CN112409265A (en) | Diamine monomer containing bisoxazole unit and preparation method thereof | |
| CN114031557B (en) | Synthesis method of 2- (4-aminophenyl) -5-aminobenzimidazole | |
| WO2006085493A1 (en) | Aromatic diamine and process for producing the same | |
| CN114516817B (en) | Chemical intermediate and preparation method thereof | |
| CN112500352A (en) | N-substituted bis-benzimidazole diamine and preparation method thereof | |
| CN112194585B (en) | Synthetic method of bromhexine hydrochloride | |
| CN110372564B (en) | 2-amino-4-acyl pyrrole compound and preparation method thereof | |
| CN112778211A (en) | Diamine containing double N-substituted benzimidazole and preparation method and application thereof | |
| CN107382898B (en) | Energetic material based on ANPZ energetic parent structure and synthetic method thereof | |
| Lohr et al. | Polyimidines, 7. Synthesis and the polymerization of 3‐(p‐Aminophenyl)‐3‐phenylphthalide | |
| Ueda et al. | Synthesis of polyamides by ring‐opening polyaddition: Reaction of 4, 4′‐disubstituted bisazlactones with diamines | |
| CN111393373A (en) | Benzimidazole diamine monomer and preparation method thereof | |
| CN113943256B (en) | Synthesis method of 2- (4-aminophenyl) -5-aminobenzimidazole | |
| CN111362877A (en) | Diamine monomer containing benzimidazole group and preparation method thereof | |
| JP7094545B2 (en) | Polybenzimidazole | |
| CN112300013B (en) | Preparation method of asymmetric aromatic diamine containing double bonds | |
| CN109575275B (en) | High-solubility polyaramid containing di-tert-butyl benzene and dimethyl structure simultaneously and preparation method and application thereof | |
| CN101168532B (en) | Method for synthesizing N-methylpiperazine substituted anilin | |
| JP4016301B2 (en) | Novel azo group-containing aromatic compound and process for producing the same | |
| CN115322156A (en) | Non-coplanar benzimidazole diamine and preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20210406 |