CN109956877B - Synthesis method of 1, 3-bis (3-aminophenoxy) benzene - Google Patents
Synthesis method of 1, 3-bis (3-aminophenoxy) benzene Download PDFInfo
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- CN109956877B CN109956877B CN201910275790.7A CN201910275790A CN109956877B CN 109956877 B CN109956877 B CN 109956877B CN 201910275790 A CN201910275790 A CN 201910275790A CN 109956877 B CN109956877 B CN 109956877B
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- C07C201/00—Preparation of esters of nitric or nitrous acid or of compounds containing nitro or nitroso groups bound to a carbon skeleton
- C07C201/06—Preparation of nitro compounds
- C07C201/12—Preparation of nitro compounds by reactions not involving the formation of nitro groups
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- C07C213/02—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton by reactions involving the formation of amino groups from compounds containing hydroxy groups or etherified or esterified hydroxy groups
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Abstract
The invention discloses a method for synthesizing 1, 3-bis (3-aminophenoxy) benzene, belonging to the field of synthesis of organic compounds. The method comprises the steps of taking m-dinitrobenzene as a raw material, adding anhydrous potassium carbonate after water separation in a mixed solvent, dropwise adding a m-diphenol solution under the protection of nitrogen to obtain an intermediate 1, 3-bis (3-nitrophenoxy) benzene, and then carrying out hydrogenation reduction to obtain a target product 1, 3-bis (3-aminophenoxy) benzene. The purity of the target product 1, 3-bis (3-aminophenoxy) benzene obtained by the method is over 99 percent, the color is white to off-white, and the total yield is over 80 percent. Compared with the existing synthesis method, the method has the advantages of easily available raw materials, no need of a catalyst, low cost, high economy and easy realization of industrial production.
Description
Technical Field
The invention relates to the field of synthesis of organic compounds, in particular to a synthesis method of 1, 3-bis (3-aminophenoxy) benzene.
Background
1, 3-bis (3-aminophenoxy) benzene belongs to polyamide and polyimide monomers and is widely applied to high polymer materials.
As early as 1985, German patent reports that 1, 3, 5-m-trichlorobenzene and m-aminophenol are used as raw materials to synthesize 1, 3-bis (3-aminophenoxy) benzene, the reaction time of the process is long, the intermediate halogenated 1, 3-bis (3-aminophenoxy) benzene can be subjected to the next dehalogenation reaction only by refining, the total yield is low, the solvent 1, 3-dimethyl-2-imidazolidinone has high boiling point, so that the post-treatment is difficult, and the process is not suitable for industrial production.
U.S. Pat. No. 4,962 reports that sodium m-aminophenol is prepared from m-aminophenol and sodium methoxide, and is reacted with m-dibromobenzene under the protection of nitrogen, and has the advantages of long reaction time, low yield, high toxicity of solvent pyridine and unsatisfactory industrial production.
Patent CN101003487A discloses that m-diphenol and m-chloronitrobenzene are used as raw materials to synthesize 1, 3-bis (3-aminophenoxy) benzene, copper and organic amine are used as catalysts in the process, and the post-treatment is complicated.
Therefore, the existing process for preparing 1, 3-bis (3-aminophenoxy) benzene generally has the problems of catalyst use, complex process, long reaction time, high toxicity, low yield, unsatisfactory industrial production and the like.
Disclosure of Invention
The invention aims to provide a method for synthesizing 1, 3-bis (3-aminophenoxy) benzene, which has the advantages of easily obtained raw materials, no need of a catalyst, simple operation, high yield, good economy and easy realization of industrial production.
In order to achieve the purpose, the technical scheme of the invention is as follows:
a method for synthesizing 1, 3-bis (3-aminophenoxy) benzene comprises the following steps:
(1) weighing m-dinitrobenzene, adding the m-dinitrobenzene into a mixed azeotropic solvent, heating until reflux water diversion occurs, evaporating the azeotropic solvent after no water is separated out, cooling to 80-100 ℃ under the protection of nitrogen, adding anhydrous carbonate, weighing m-diphenol, dissolving the m-dinitrobenzene into a reaction solvent, dropwise adding the m-dinitrobenzene solution into a m-dinitrobenzene solution system under the protection of nitrogen and in a reflux state, continuing reflux reaction for 5-9 hours after dropwise adding, filtering to remove inorganic salt while hot after the reaction is finished, concentrating filtrate, recovering the solvent, cooling to 20-30 ℃, adding alcohol, pulping, filtering, and rinsing to obtain an intermediate 1, 3-bis (3-nitrophenoxy) benzene;
(2) weighing intermediate 1, 3-bis (3-nitrophenoxy) benzene, palladium carbon and ethanol, adding into a hydrogenation kettle, replacing with nitrogen for 3 times, then replacing with hydrogen for 3 times, pressurizing to 0.5-3MPa, reacting for 4-10h, and collecting the target product 1, 3-bis (3-aminophenoxy) benzene after the reaction is finished.
Preferably, in step (1), the reaction solvent in the mixed azeotropic solvent is N, N-dimethylformamide or N, N-dimethylacetamide, and the azeotropic solvent is toluene or xylene.
Further, the proportion (mass ratio) of the azeotropic solvent mixture is: the ratio of the reaction solvent to the azeotropic solvent is 4: 1-1: 1.
Preferably, the raw materials used for synthesizing the intermediate 1, 3-bis (3-nitrophenoxy) benzene in the step (1) comprise m-dinitrobenzene and m-diphenol.
Furthermore, the molar ratio of the reactant ingredients used for synthesizing the intermediate 1, 3-bis (3-nitrophenoxy) benzene is as follows: m-diphenol, M-dinitrobenzene, carbonate (1M), (2-4) M and (1-2) M.
Preferably, the carbonate used for synthesizing the intermediate 1, 3-bis (3-nitrophenoxy) benzene in step (1) is sodium carbonate, potassium carbonate, cesium carbonate or lithium carbonate.
Preferably, the alcohol used for pulping in the step (1) for synthesizing the intermediate 1, 3-bis (3-nitrophenoxy) benzene is: methanol, ethanol, propanol or isopropanol.
Preferably, the step of collecting the target product 1, 3-bis (3-aminophenoxy) benzene in the step (2) is: after the reaction is finished, filtering to remove Pd carbon, concentrating the filtrate, cooling to 10-30 ℃ for crystallization, performing suction filtration, rinsing with cold water, and performing vacuum drying to obtain a white crystal target product 1, 3-bis (3-aminophenoxy) benzene.
The technical route of the invention is as follows:
the method comprises the steps of taking m-dinitrobenzene as a raw material, adding anhydrous potassium carbonate after water separation in a mixed solvent, dropwise adding a m-diphenol solution under the protection of nitrogen to obtain an intermediate 1, 3-bis (3-nitrophenoxy) benzene, and then carrying out hydrogenation reduction to obtain a target product 1, 3-bis (3-aminophenoxy) benzene. Compared with the prior art, the method has the following advantages:
1. the reaction raw materials adopted by the invention are different from the raw materials of the prior art, and the raw materials of m-dinitrobenzene and m-diphenol are easy to obtain;
2. the synthesis method does not need to use a catalyst, has very simple operation steps and high yield;
3. the method for collecting the target product is simple, the Pd carbon can be removed only by simple filtration, the 1, 3-bis (3-aminophenoxy) benzene is easy to collect, and the purity of the target product is high and can reach more than 99%.
4. The invention adopts specific raw materials, the specific raw materials are matched with a specific method and reaction parameters, and the method does not need to use a catalyst in the reaction process, has simple operation and good effect, thereby facilitating the industrial production, easily controlling the production process and having high economic benefit.
Detailed Description
Example 1
Weighing 37g of m-dinitrobenzene, adding 112g of N, N-dimethylformamide and 56g of toluene, heating until reflux is divided into water, evaporating the toluene after no water is separated out, cooling to 85 ℃ under the protection of nitrogen, adding 16.6g of anhydrous potassium carbonate, weighing 11g of m-diphenol, dissolving in 50g of N, N-dimethylformamide, dropwise adding the m-diphenol solution into a reflux system under the protection of nitrogen and in a reflux state, continuously carrying out reflux reaction for 6 hours after dropwise adding is finished, filtering to remove inorganic salts when the reaction is hot, concentrating filtrate, recovering N, N-dimethylformamide, cooling the residual liquid to 20 ℃, adding 150g of methanol, pulping, filtering, and rinsing to obtain 32.1g of intermediate 1, 3-bis (3-nitrophenoxy) benzene, wherein the yield is 91.2%;
example 2
Weighing 50.4g of m-dinitrobenzene, adding 168g of N, N-dimethylformamide and 84g of toluene, heating until reflux is divided into water, evaporating the toluene after no water is divided out, cooling to 85 ℃ under the protection of nitrogen, adding 16.6g of anhydrous potassium carbonate, weighing 11g of m-diphenol, dissolving in 50g of N, N-dimethylformamide, dropwise adding the m-diphenol solution into a reflux system under the protection of nitrogen and in a reflux state, continuously carrying out reflux reaction for 6 hours after dropwise adding is finished, filtering to remove inorganic salts when the reaction is hot, concentrating filtrate, recovering the N, N-dimethylformamide, cooling the residual liquid to 20 ℃, adding 150g of methanol, pulping, filtering, rinsing to obtain 31.9g of intermediate 1, 3-bis (3-nitrophenoxy) benzene, wherein the yield is 90.8%;
example 3
Weighing 92.4g of m-dinitrobenzene, adding 310g of N, N-dimethylacetamide and 154g of toluene, heating until reflux is divided into water, evaporating out the toluene after no water is divided, cooling to 85 ℃ under the protection of nitrogen, adding 82.8g of anhydrous potassium carbonate, weighing 55g of m-diphenol, dissolving in 150g of N, N-dimethylacetamide, dropwise adding the m-diphenol solution into a reflux system under the protection of nitrogen and in a reflux state, continuously carrying out reflux reaction for 6 hours after dropwise adding is finished, filtering to remove inorganic salts when the reaction is hot, concentrating the filtrate, recovering the N, N-dimethylacetamide, cooling the residual solution to 20 ℃, adding 450g of methanol, pulping, filtering, and rinsing to obtain 149.9g of intermediate 1, 3-bis (3-nitrophenoxy) benzene, wherein the yield is 85.1%;
example 4
Weighing 106g of intermediate 1, 3-bis (3-nitrophenoxy) benzene and 1.4g of 5% palladium carbon (containing 50% of water), adding 750g of ethanol into a 2L hydrogenation kettle, replacing with nitrogen for 3 times, then replacing with hydrogen for 3 times, pressurizing to 2MPa, reacting for 8 hours, filtering to remove Pd carbon after the reaction is finished, concentrating the filtrate, desolventizing to remove 80% of ethanol, cooling to 20 ℃, stirring, crystallizing for 30 minutes, performing suction filtration, rinsing with cold water for 2-3 times, and performing vacuum drying at 60 ℃ to obtain 82.7g of white crystal target product 1, 3-bis (3-aminophenoxy) benzene, wherein the yield is 94%, and the HPLC is 99.2%.
Claims (5)
1. A method for synthesizing 1, 3-bis (3-aminophenoxy) benzene is characterized in that: the method comprises the following steps:
(1) weighing m-dinitrobenzene, adding the m-dinitrobenzene into a mixed azeotropic solvent, heating until reflux water diversion occurs, evaporating the azeotropic solvent after no water is separated out, cooling to 80-100 ℃ under the protection of nitrogen, adding anhydrous carbonate, weighing m-diphenol, dissolving the m-dinitrobenzene into a reaction solvent, dropwise adding the m-dinitrobenzene solution into a m-dinitrobenzene solution system under the protection of nitrogen and in a reflux state, continuing reflux reaction for 5-9 hours after dropwise adding, filtering to remove inorganic salt while hot after the reaction is finished, concentrating filtrate, recovering the solvent, cooling to 20-30 ℃, adding alcohol, pulping, filtering, and rinsing to obtain an intermediate 1, 3-bis (3-nitrophenoxy) benzene;
(2) weighing intermediate 1, 3-bis (3-nitrophenoxy) benzene, palladium carbon and ethanol, adding into a hydrogenation kettle, replacing with nitrogen for 3 times, then replacing with hydrogen for 3 times, pressurizing to 0.5-3MPa, reacting for 4-10h, and collecting a target product 1, 3-bis (3-aminophenoxy) benzene after the reaction is finished; wherein, in the step (1), the reaction solvent in the mixed azeotropic solvent is N, N-dimethylformamide or N, N-dimethylacetamide, and the azeotropic solvent is toluene or xylene; the molar ratio of reactant ingredients used for synthesizing the intermediate 1, 3-bis (3-nitrophenoxy) benzene is as follows: m-diphenol, M-dinitrobenzene, carbonate (1M), (2-4) M and (1-2) M.
2. The method of synthesis according to claim 1, characterized in that: the mass ratio of the mixed azeotropic solvent is as follows: the ratio of the reaction solvent to the azeotropic solvent is 4: 1-1: 1.
3. The method of synthesis according to claim 1, characterized in that: the carbonate used for synthesizing the intermediate 1, 3-bis (3-nitrophenoxy) benzene in the step (1) is sodium carbonate, potassium carbonate, cesium carbonate or lithium carbonate.
4. The method of synthesis according to claim 1, characterized in that: the alcohol used for pulping in the step (1) for synthesizing the intermediate 1, 3-bis (3-nitrophenoxy) benzene is: methanol, ethanol, propanol or isopropanol.
5. The method of synthesis according to claim 1, characterized in that: the step of collecting the target product 1, 3-bis (3-aminophenoxy) benzene in the step (2) is as follows: after the reaction is finished, filtering to remove Pd carbon, concentrating the filtrate, cooling to 10-30 ℃ for crystallization, performing suction filtration, rinsing with cold water, and performing vacuum drying to obtain a white crystal target product 1, 3-bis (3-aminophenoxy) benzene.
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Citations (6)
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| US3845018A (en) * | 1973-04-03 | 1974-10-29 | Hughes Aircraft Co | Acetylene substituted polyamide oligomers |
| US4222962A (en) * | 1978-12-11 | 1980-09-16 | Gulf Research & Development Company | Process for preparing a substituted diphenoxybenzene |
| US6124503A (en) * | 1998-12-31 | 2000-09-26 | Eastman Kodak Company | Processes for making and using alkylaminoarylcarbonyl compounds |
| JP2005060333A (en) * | 2003-08-19 | 2005-03-10 | Air Water Chemical Inc | Method for production of 1,3-bis(3-aminophenoxy)benzene |
| JP2005179223A (en) * | 2003-12-18 | 2005-07-07 | Air Water Chemical Inc | Method for isolating 1,3-bis(3-aminophenoxy)benzene |
| CN101157623A (en) * | 2007-05-29 | 2008-04-09 | 东华大学 | Method for preparing 1,4-di(4-amino-benzene oxygen) benzene |
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| US3845018A (en) * | 1973-04-03 | 1974-10-29 | Hughes Aircraft Co | Acetylene substituted polyamide oligomers |
| US4222962A (en) * | 1978-12-11 | 1980-09-16 | Gulf Research & Development Company | Process for preparing a substituted diphenoxybenzene |
| US6124503A (en) * | 1998-12-31 | 2000-09-26 | Eastman Kodak Company | Processes for making and using alkylaminoarylcarbonyl compounds |
| JP2005060333A (en) * | 2003-08-19 | 2005-03-10 | Air Water Chemical Inc | Method for production of 1,3-bis(3-aminophenoxy)benzene |
| JP2005179223A (en) * | 2003-12-18 | 2005-07-07 | Air Water Chemical Inc | Method for isolating 1,3-bis(3-aminophenoxy)benzene |
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| Reaction of 1,3,5-trinitrobenzene with phenols: synthesis of 3,5-dinitrophenyl aryl ethers;Shevelev, Svyatoslv A.等;《Mendeleev Communications》;19950428(第4期);第158页表1序号17 * |
| Synthesis of 1,4-Bis(3-amino-5-trifluoromethylphenoxy)benzene and Properties of the Polyimide Film Therefrom;YunHua Lu等;《Advanced Materials Research Vols》;20121231;第581-582卷;第297-300页 * |
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