CN112409265A - Diamine monomer containing bisoxazole unit and preparation method thereof - Google Patents
Diamine monomer containing bisoxazole unit and preparation method thereof Download PDFInfo
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- CN112409265A CN112409265A CN202011361632.2A CN202011361632A CN112409265A CN 112409265 A CN112409265 A CN 112409265A CN 202011361632 A CN202011361632 A CN 202011361632A CN 112409265 A CN112409265 A CN 112409265A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D235/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, condensed with other rings
- C07D235/02—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, condensed with other rings condensed with carbocyclic rings or ring systems
- C07D235/04—Benzimidazoles; Hydrogenated benzimidazoles
- C07D235/20—Two benzimidazolyl-2 radicals linked together directly or via a hydrocarbon or substituted hydrocarbon radical
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D263/00—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings
- C07D263/52—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings condensed with carbocyclic rings or ring systems
- C07D263/54—Benzoxazoles; Hydrogenated benzoxazoles
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- C07D413/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms
- C07D413/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing two hetero rings
- C07D413/04—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing two hetero rings directly linked by a ring-member-to-ring-member bond
Abstract
The invention relates to the technical field of organic synthesis, and provides a diamine monomer containing a bisoxazole unit and a preparation method thereof. The diamine monomer provided by the invention contains two benzene azole units, has various molecular structures, can overcome the disadvantage of single structure of the diamine monomer in the prior art, can maintain various advantages of the original polybenzazole material by utilizing the diamine monomer to prepare the polymer, and can bring new performance to the material due to the synergistic effect of different benzene azole units. The preparation method provided by the invention introduces two benzene azole units through condensation reaction and ring closing reaction, and then obtains the diamine monomer containing the bis-benzene azole units through 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.
Description
Technical Field
The invention relates to the technical field of organic synthesis, in particular to a diamine monomer containing a bisoxazole unit.
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 and different side groups in diamine can effectively improve the mechanical property, chemical corrosion resistance, high temperature resistance and solubility of the material, thereby expanding the application field of the material.
Diamine containing benzene azole units such as benzimidazole and benzoxazole is introduced into a high molecular main chain as a typical rigid aromatic heterocyclic unit, so that the mechanical property and the heat resistance of the material can be obviously improved. However, the types of the diamine monomer containing the phenylpropanimidazole unit and the diamine monomer containing the benzoxazole unit in the prior art are few, the structure is single, and the construction of the diamine monomer with different structures is a research hotspot in the art.
Disclosure of Invention
In view of the above, the present invention provides a novel diamine monomer containing a bisbenzoxazole unit and a preparation method thereof. The diamine monomer provided by the invention contains two benzene azole units, has diversified molecules, can solve the disadvantage of single structure of the diamine monomer in the prior art, and brings new performance and functions to materials.
In order to achieve the above object, the present invention provides the following technical solutions:
a diamine monomer containing a bisbenzoxazole unit has a structure shown in formula I:
in formula I: a is-NH-or O, B is-NH-or O.
Preferably, one of the following structures:
preferably, one of the following structures:
the invention provides a preparation method of a diamine monomer containing a bisoxazole unit in the scheme, which comprises the following steps:
(1) carrying out condensation reaction on a compound with a structure shown in a formula a and 2,2, 2-trichloroacetimido methyl ester to obtain a compound with a structure shown in a formula b;
(2) carrying out a ring closing reaction on a compound with a structure shown in a formula b and a compound with a structure shown in a formula a to obtain a compound with a structure shown in a formula c;
(3) carrying out catalytic hydrogenation reaction on a compound with a structure shown in a formula c under the condition of hydrogen to obtain a diamine monomer containing a bisoxazole unit with a structure shown in a formula I;
wherein X in the formula a is-NH2or-OH; the A, B categories in formulas b and c are identical to those in formula I.
Preferably, the condensation reaction is carried out under the condition of an acidic reagent, and the acidic reagent comprises one or more of acetic acid, hydrochloric acid and sulfuric acid.
Preferably, the condensation reaction is carried out at the temperature of 5-30 ℃ for 10-12 h.
Preferably, the ring closing 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 ring closing reaction comprises one or more of ethanol, methanol, dichloroethane, dichloromethane, benzene, toluene, carbon tetrachloride and tetrahydrofuran.
Preferably, the temperature of the ring closing reaction is 50-100 ℃, and the time is 22-98 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 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 reaction time is 4-6 h.
The invention provides a diamine monomer containing a bisbenzoxazole unit, which has a structure shown in a formula I. The diamine monomer provided by the invention contains two benzoxazole units, and specifically contains two benzimidazole units, two benzoxazole units or one benzimidazole unit and one benzoxazole unit. The diamine monomer provided by the invention has various molecular structures, can solve the disadvantage of single structure of the diamine monomer in the prior art, and the diamine monomer provided by the invention can be used for preparing polymers, so that various advantages of the original polybenzazole material can be maintained, and new properties can be brought to the material due to the synergistic effect of different benzoxazole units. The diamine monomer provided by the invention has wide application prospect in the field of synthesis of functional polymers.
The invention provides a preparation method of a diamine monomer containing a bisoxazole unit in the scheme, which takes a compound with a structure shown in a formula a as a starting material, introduces two benzoxazole units through condensation reaction and ring closure reaction, and then obtains the diamine monomer containing the bisoxazole unit with the structure shown in the formula I through 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(5 '), 6(6 ') -diamino-2, 2 ' -bibenzimidazole prepared in example 1;
FIG. 2 is a nuclear magnetic hydrogen spectrum of 5,5 '-diamino-2, 2' -bisbenzoxazole prepared in example 2;
FIG. 3 is a nuclear magnetic spectrum of 5,5 ' (6 ') -diamino-2-benzoxazole-2 ' -benzimidazole prepared in example 3.
Detailed Description
The invention provides a diamine monomer containing a bisbenzoxazole unit, which has a structure shown in a formula I:
in formula I: a is-NH-or O, B is-NH-or O, and A and B are preferably not simultaneously-NH-.
In the present invention, the two amino groups in formula I are preferably located at the 5-or 6-position of the benzoxazole unit and the 5 '-or 6' -position of the p-benzoxazole unit, respectively.
In the present invention, the diamine monomer containing a bisbenzoxazole unit preferably has one of the following structures:
in the present invention, the diamine monomer containing a bisbenzoxazole unit preferably has one of the following structures:
the invention also provides a preparation method of the diamine monomer containing the bisoxazole unit, which comprises the following steps:
(1) carrying out condensation reaction on a compound with a structure shown in a formula a and 2,2, 2-trichloroacetimido methyl ester to obtain a compound with a structure shown in a formula b;
(2) carrying out a ring closing reaction on a compound with a structure shown in a formula b and a compound with a structure shown in a formula a to obtain a compound with a structure shown in a formula c;
(3) carrying out catalytic hydrogenation reaction on a compound with a structure shown in a formula c under the condition of hydrogen to obtain a diamine monomer containing a bisoxazole unit with a structure shown in a formula I;
wherein X in the formula a is-NH2or-OH; the A, B categories in formulas b and c are identical to those in formula I.
The synthetic route of the diamine monomer containing the bisoxazole unit is shown as a formula e, and the following formula e is specifically explained:
in formula e: x is-NH2or-OH, the type of A and B being the same as in formula I.
The invention carries out condensation reaction on the compound 2,2, 2-trichloroacetimidate methyl ester with the structure shown in the formula a to obtain the compound with the structure shown in the formula b. In the present invention, the compound having the structure represented by formula a is specifically 4-nitro-1, 2-diamine, 2-hydroxy-4-nitroaniline or 2-hydroxy-5-nitroaniline according to the nitro position and the kind of X group, and the correspondingly obtained compound having the structure represented by formula b is 2-trichloromethyl-5 (6) -nitrobenzimidazole or 2-trichloromethyl-5-nitrobenzoxazole or 2-trichloromethyl-6-nitrobenzoxazole.
In the invention, the molar ratio of the compound having the structure shown in the formula a to methyl 2,2, 2-trichloroacetimidate is preferably 1.0-1.2: 1, and more preferably 1.1: 1.
In the invention, the condensation reaction is preferably carried out under the condition of an acidic reagent, and the acidic reagent preferably comprises one or more of acetic acid, hydrochloric acid and sulfuric acid; the compound having the structure shown in formula a and the acidic reagent are preferably used in an amount ratio of 1 g: 10-11 mL, more preferably 1 g: 10 mL.
In the invention, the temperature of the condensation reaction is preferably 5-30 ℃, more preferably 10-25 ℃, and in the specific embodiment of the invention, the condensation reaction is preferably performed at room temperature; the time of the condensation reaction is preferably 10-12 h, and more preferably 11 h; in a particular embodiment of the invention, the end of the reaction is preferably monitored by TLC.
In the specific embodiment of the invention, preferably, the 2-amino-4-nitroaniline and the acidic reagent are mixed, the mixture is cooled to 10 +/-1 ℃, then the methyl 2,2, 2-trichloroacetimidate is dripped, and after the dripping is finished, the temperature is raised to the condensation reaction temperature for reaction. The invention preferably finishes dripping the 2,2, 2-trichloroacetimidate methyl ester within 0.5-1 h.
After the condensation reaction is completed, the invention preferably carries out post-treatment on the obtained product feed liquid, and the post-treatment preferably comprises the following steps:
mixing the product liquid obtained by the condensation reaction with water, and then carrying out solid-liquid separation to obtain a crude product; and (3) recrystallizing the crude product by using ethanol, and then sequentially carrying out solid-liquid separation and drying to obtain the compound with the structure shown in the formula b.
The invention has no special requirements on the dosage of water, the specific conditions of recrystallization, solid-liquid separation and drying, and the conditions which are well known by the technicians in the field can be adopted.
After the compound with the structure shown in the formula b is obtained, the compound with the structure shown in the formula b and the compound with the structure shown in the formula a are subjected to ring closing reaction to obtain the compound with the structure shown in the formula c. In the present invention, the X group in the compound having the structure represented by formula a used in the above-mentioned step (1) and step (2) may be the same or different, and may be determined depending on the kind of A, B group in the target product.
In the invention, the ring closing 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;
in the invention, the molar ratio of the compound with the structure shown in the formula b to the compound with the structure shown in the formula a is preferably 1: 2.0-2.5, and more preferably 1: 2.2; the molar ratio of the compound having the structure represented by the formula b to the acid-binding agent is preferably 1: 1.0-1.5, and more preferably 1: 1.2.
In the present invention, the solvent for the ring closure reaction preferably includes one or more of ethanol, methanol, dichloroethane, dichloromethane, benzene, toluene, 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 ring closing reaction is preferably 50-100 ℃, more preferably 60-80 ℃, and the time of the ring closing reaction is preferably 22-98 h, more preferably 22-24 h; in a particular embodiment of the invention, the end of the reaction is preferably detected by TLC.
In the specific embodiment of the invention, the compound having the structure shown in the formula b, the compound having the structure shown in the formula a and the solvent are preferably mixed, the mixture is heated to 80 +/-1 ℃, then the acid-binding agent is dropwise added, and the mixture is heated to the ring-closing reaction temperature after the dropwise addition is finished to carry out the reaction. The acid-binding agent is preferably added dropwise within 1-2 h.
After the ring-closing reaction is finished, the obtained product feed liquid is preferably subjected to post-treatment, the post-treatment method is preferably consistent with the post-treatment method of the condensation reaction product feed liquid, and only the recrystallization reagent is replaced by N, N-dimethylacetamide.
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 diamine monomer containing the bisoxazole unit 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 mass ratio of the catalyst to the compound having the structure shown in the formula c is preferably 0.1-0.15: 1, and more preferably 0.1: 1.
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 operation of the hydrogenation reaction.
In the invention, the temperature of the catalytic hydrogenation reaction is preferably 40-100 ℃, more preferably 65-88 ℃, the pressure is preferably 0.5-3 MPa, more preferably 1.5-2.5 MPa, the reaction time is preferably 4-6 h, more preferably 5h, 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 diamine monomer containing the bisoxazole unit with the structure shown in the formula I. In the invention, the cooling crystallization temperature is preferably 20-25 ℃.
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 diamine monomer containing a bisbenzoxazole unit has the following specific structure, which is referred to as 5(5 '), 6(6 ') -diamino-2, 2 ' -bibenzimidazole:
the preparation method of the 5(5 '), 6(6 ') -diamino-2, 2 ' -bibenzimidazole comprises the following steps:
(1) adding 50.0g of 4-nitrodiphenylamine and 500.0g of acetic acid into a reaction bottle, cooling to 10 +/-1 ℃, dropwise adding 69.1g of 2,2, 2-trichloroacetimido methyl ester, completing dropwise adding within 0.5-1 h, reacting at room temperature for 12h, and determining the reaction to be finished by TLC. Adding 1500.0g of water into a reaction system, carrying out vacuum filtration to obtain 85g of a crude product, recrystallizing with ethanol, filtering, and drying to obtain 60.2g of 2-trichloromethyl-5 (6) -nitrobenzimidazole, wherein the yield is as follows: 73.6 percent.
(2) Adding 65.0g of 2-trichloromethyl-5 (6) -nitrobenzimidazole, 35.5g of 4-nitrodiphenylamine and 650.0g of ethanol into a reaction bottle provided with a reflux condensing device, heating to 80 +/-1 ℃, dropwise adding 35.1g of triethylamine, completing dropwise adding within 1-2 h, reacting at 80-85 ℃ for 24h, and determining the reaction to be finished by TLC. Adding 2000.0g of water into the reaction system, carrying out vacuum filtration to obtain 76g of a crude product, recrystallizing by DMAc, filtering, and drying to obtain 62.8g of 5(5 '), 6(6 ') -diamino-2, 2 ' -bibenzimidazole, yield: 83.6 percent.
(3) Adding 60.0g of 5(5 '), 6 (6') -diamino-2, 2 '-bibenzimidazole, 600.0g of 1,4 dioxane and 6.0g of palladium carbon into an autoclave, replacing three times by nitrogen, 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 and recovering the catalyst, cooling and crystallizing the filtrate, filtering and drying to obtain 45.1g of 1-methyl-6, 5' (6 ') -diamino-2, 2' -bibenzimidazole, wherein the yield is 92.3%, and the nuclear magnetic hydrogen spectrum is confirmed by nuclear magnetism of the product structure and is shown in figure 1.
Example 2
In this example, the diamine monomer containing a bisbenzoxazole unit has the following specific structure, which is named as 5,5 '-diamino-2, 2' -bisbenzoxazole:
the preparation method of the 5,5 '-diamino-2, 2' -bisbenzoxazole comprises the following steps:
(1) adding 50.0g of 2-hydroxy-5-nitroaniline and 500.0g of acetic acid into a reaction bottle, cooling to 10 +/-1 ℃, dropwise adding 68.7g of methyl 2,2, 2-trichloroacetimidate, completing dropwise adding within 0.5-1 h, reacting for 12h at room temperature, and determining the reaction to be finished by TLC. Adding 1500.0g of water into the reaction system, carrying out vacuum suction filtration to obtain 74g of a crude product, recrystallizing by using ethanol, filtering, and drying to obtain 64.2g of 2-trichloromethyl-5-nitrobenzoxazole with the yield: 70.3 percent.
(2) Adding 60g of 2-trichloromethyl-5-nitrobenzoxazole, 32.8g of 2-hydroxy-5-nitroaniline and 600.0g of ethanol into a reaction bottle provided with a reflux condensing device, heating to 80 +/-1 ℃, dropwise adding 32.4g of triethylamine, completing dropwise adding within 1-2 h, reacting at 80-85 ℃ for 98h, and determining the reaction to be finished by TLC. 2000.0g of water was added to the reaction system, and 58g of crude product was obtained by vacuum filtration, recrystallized from DMAc, filtered and dried to obtain 47.9g of 5,5 '-dinitro-2, 2' -bisbenzoxazole, yield: 68.9 percent.
(3) Adding 45.0g of 5,5 '-dinitro-2, 2' -bisbenzoxazole, 450.0g of 1, 4-dioxane and 4.5g of palladium carbon into an autoclave, replacing the mixture by 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 and recovering the catalyst, cooling and crystallizing the filtrate, filtering and drying to obtain 33.3g of 5,5 '-diamino-2, 2' -bisbenzoxazole, wherein the yield is 90.8%, and the nuclear magnetic hydrogen spectrum of the product is confirmed by nuclear magnetic resonance, and is shown in figure 2.
Example 3
In this example, the specific structure of the diamine monomer containing a bisbenzoxazole unit is as follows, and the name of the monomer is 5,5 ' (6 ') -diamino-2-benzoxazole-2 ' -benzimidazole:
the preparation method of the 5,5 ' (6 ') -diamino-2-benzoxazole-2 ' -benzimidazole comprises the following steps:
(1) adding 50.0g of 4-nitrodiphenylamine and 500.0g of acetic acid into a reaction bottle, cooling to 10 +/-1 ℃, dropwise adding 69.1g of 2,2, 2-trichloroacetimido methyl ester, completing dropwise adding within 0.5-1 h, reacting at room temperature for 12h, and determining the reaction to be finished by TLC. Adding 1500.0g of water into a reaction system, carrying out vacuum filtration to obtain 85g of a crude product, recrystallizing with ethanol, filtering, and drying to obtain 68.9g of 2-trichloromethyl-5 (6) -nitrobenzimidazole, wherein the yield is as follows: 84.3 percent.
(2) Adding 65.0g of 2-trichloromethyl-5 (6) -nitrobenzimidazole, 35.7g of 2-hydroxy-5-nitroaniline and 650.0g of ethanol into a reaction bottle provided with a reflux condensing device, heating to 80 +/-1 ℃, dropwise adding 35.1g of triethylamine, finishing dropwise adding within 1-2 h, reacting at 80-85 ℃ for 24h, and determining that the reaction is finished by TLC. 2000.0g of water was added to the reaction system, and 77g of crude product was obtained by vacuum filtration, and then recrystallized from DMAc, filtered and dried to obtain 59.6g of 5,5 ' (6 ') -dinitro-2-benzoxazole-2 ' -benzimidazole, yield: 79.3 percent.
(3) Adding 55.0g of 5,5 '(6') -dinitro-2-benzoxazole-2 '-benzimidazole, 550.0g of dioxane and 5.5g of palladium carbon into an autoclave, replacing the mixture by 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 reaction 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 41.2g of 5, 5' (6 ') -dinitro-2-benzoxazole-2' -benzimidazole, wherein the yield is 91.7 percent, and the nuclear magnetic spectrum is confirmed as shown in figure 3.
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 (10)
1. A diamine monomer containing a bisbenzoxazole unit is characterized by having a structure shown in formula I:
in formula I: a is-NH-or O, B is-NH-or O.
2. A diamine monomer containing a bisoxazole unit as set forth in claim 1 having one of the following structures:
3. a diamine monomer containing a bisoxazole unit as set forth in claim 1 having one of the following structures:
4. a process for producing a bisazole unit-containing diamine monomer according to any one of claims 1 to 3, comprising the steps of:
(1) carrying out condensation reaction on a compound with a structure shown in a formula a and 2,2, 2-trichloroacetimido methyl ester to obtain a compound with a structure shown in a formula b;
(2) carrying out a ring closing reaction on a compound with a structure shown in a formula b and a compound with a structure shown in a formula a to obtain a compound with a structure shown in a formula c;
(3) carrying out catalytic hydrogenation reaction on a compound with a structure shown in a formula c under the condition of hydrogen to obtain a diamine monomer containing a bisoxazole unit with a structure shown in a formula I;
wherein X in the formula a is-NH2or-OH; the A, B categories in formulas b and c are identical to those in formula I.
5. The method according to claim 4, wherein the condensation reaction is carried out under an acidic reagent comprising one or more of acetic acid, hydrochloric acid and sulfuric acid.
6. The preparation method according to claim 4 or 5, wherein the condensation reaction is carried out at a temperature of 5-30 ℃ for 10-12 hours.
7. The preparation method of claim 4, wherein the ring closing 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 ring closing reaction comprises one or more of ethanol, methanol, dichloroethane, dichloromethane, benzene, toluene, carbon tetrachloride and tetrahydrofuran.
8. The preparation method according to claim 4 or 7, wherein the temperature of the ring closing reaction is 50-100 ℃ and the time is 22-98 h.
9. The preparation method according to claim 4, wherein the catalyst for catalytic hydrogenation reaction comprises one or more of palladium carbon, platinum carbon, active nickel and rhodium carbon;
the solvent for hydrogenation reaction comprises one or more of tetrahydrofuran, ethanol, methanol, isopropanol, dimethylformamide, dimethylacetamide, N-methylpyrrolidone, 1, 4-dioxane, ethyl acetate, benzene, toluene and xylene.
10. The preparation method according to claim 4 or 9, wherein the temperature of the catalytic hydrogenation reaction is 40-100 ℃, the pressure is 0.5-3 MPa, and the reaction time is 4-6 h.
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| CN113265048A (en) * | 2021-04-11 | 2021-08-17 | 常州市尚科新材料有限公司 | Polyimide superfine powder for mould pressing and preparation method thereof |
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| CN113265048B (en) * | 2021-04-11 | 2023-03-10 | 常州市尚科新材料有限公司 | Polyimide superfine powder for mould pressing and preparation method thereof |
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