CN101265204A - Method for preparing 3,5-di(2,4-diaminophenoxy)benzoic acid - Google Patents
Method for preparing 3,5-di(2,4-diaminophenoxy)benzoic acid Download PDFInfo
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- CN101265204A CN101265204A CNA2008100360567A CN200810036056A CN101265204A CN 101265204 A CN101265204 A CN 101265204A CN A2008100360567 A CNA2008100360567 A CN A2008100360567A CN 200810036056 A CN200810036056 A CN 200810036056A CN 101265204 A CN101265204 A CN 101265204A
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- diamino phenoxy
- phenylformic acid
- palladium
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- hydrazine hydrate
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Abstract
The invention relates to a method of preparing 3, 5-bis(2, 4-diamino phenoxy) phenylformic acid. The method comprises the following steps: 3, 5-bis(2, 4-dinitro phenoxy) phenylformic acid reacts in palladium/carbon, hydrazine hydrate solution and the saturated fatty alcohol solvent system for 1 to 5 hours under the temperature ranging from 70 DEG C to 85 DEG C; then the hot mixed solution is filtered, mother solution is cooled, pure water is dropped in, and crystal products are precipitated; the crystal products are filtered and vacuum-dried to obtain 3, 5-bis(2, 4-diamino phenoxy) phenylformic acid crystal. The method has simple operation, subsequent refined purification technology is not needed, the time consumption is less, the obtained products have high yield rate, the purity reaches more than 99 percent, and the method is suitable for industrialized production.
Description
Technical field
The invention belongs to the preparation field of the polynary primary amine of aromatic series, particularly relate to a kind of 3, two (2, the 4-diamino phenoxy) the benzoic preparation methods of 5-.
Background technology
The heteroaromatic polymkeric substance has outstanding thermostability, anti-nuclear radiation, flame retardant resistance, organic solvent resistance and good high cryogenic mechanics performance and electric property, has obtained widespread use in space flight and aviation, electronics microelectronics, automobile boats and ships, electric contour performance field.
Along with the information electronic product towards high performance, lightweight, slimming, the development that becomes more meticulous, the insulating material of flexible copper-clad plate (FCCL) is had higher requirement, high strength heat-resisting, low-k and low-dielectric loss etc. as the needs height.Therefore, polyimide material enjoys favor in the FCCL field.
3, one of important source material that two (2, the 4-diamino phenoxy) phenylformic acid of 5-are synthetic high branched polyimide resins, therefore, it not only can be applicable to the FCCL field, strengthens advanced composite material but also can be applicable to the fire resistant polyimide carbon fiber.In addition, 3, the important raw and processed materials that two (2, the 4-diamino phenoxy) phenylformic acid of 5-also are synthetic More Malay imide resins.
Summary of the invention
The purpose of this invention is to provide a kind of 3, two (2, the 4-diamino phenoxy) the benzoic preparation methods of 5-, this method technology is simple, need not follow-up refining purifying technique, the three wastes are few, the purity of product and yield height are applicable to suitability for industrialized production.
Chemical equation of the present invention is as follows:
Of the present invention a kind of 3, two (2, the 4-diamino phenoxy) the benzoic preparation methods of 5-comprise the steps:
3, two (2, the 4-2,4-dinitrophenoxy base) phenylformic acid of 5-, in palladium/charcoal, hydrazine hydrate solution and saturated fatty alcohol solvent system in 70 ℃～85 ℃ temperature range internal reactions after 1～5 hour, filtered while hot, the cooling mother liquor drips pure water, separate out crystalline product, filter, vacuum-drying obtains 3, two (2, the 4-diamino phenoxy) the phenylformic acid crystal of 5-.
Described palladium/charcoal, its palladium mass percent is 1%～15%.
The mass percent concentration of described hydrazine hydrate solution is 60%～85%.
Described saturated fatty alcoholic solvent is selected from methyl alcohol, ethanol, Virahol, n-propyl alcohol, propyl carbinol, isopropylcarbinol, ethylene glycol, 1,2-propylene glycol, 1, ammediol, one or more mixtures in 2-methyl cellosolve, cellosolvo, 2-methyl cellosolve, 3-methoxypropanol, 2-oxyethyl group propyl alcohol, the 3-oxyethyl group propyl alcohol.
Described 3, the weight ratio of two (2, the 4-2,4-dinitrophenoxy base) phenylformic acid of 5-and palladium/charcoal is 100: 1～20.
Described 3, the mol ratio of two (2,4-2,4-dinitrophenoxy base) phenylformic acid of 5-and hydrazine hydrate is 1: 20～50.
Described 3, the weightmeasurement ratio of two (2, the 4-2,4-dinitrophenoxy base) phenylformic acid of 5-and saturated fatty alcoholic solvent is 1 to restrain: 15 milliliters～100 milliliters.
Beneficial effect of the present invention
(1) the present invention is preparation 3, two (2, the 4-diamino phenoxy) the benzoic commercial runs of 5-;
(2) three wastes are few, and are environmentally friendly;
(3) consuming time few, obviously energy-saving and cost-reducing;
(4) simple to operate, related industrial chemicals is few;
(5) raw material sources are convenient;
(6) product purity reaches more than 99%, yield is high.
Description of drawings
Figure is 3, two (2, the 4-diamino phenoxy) the benzoic molecular structures of 5-.
Embodiment
Below in conjunction with specific embodiment, further set forth the present invention.Should be understood that these embodiment only to be used to the present invention is described and be not used in and limit the scope of the invention.Should be understood that in addition those skilled in the art can make various changes or modifications the present invention after the content of having read the present invention's instruction, these equivalent form of values fall within the application's appended claims institute restricted portion equally.
Embodiment 1
With 48.6 gram (0.1 moles) 3,5-two (2,4-2,4-dinitrophenoxy base) phenylformic acid, 0.50 gram palladium mass percent are that palladium/charcoal of 15%, 80 milliliters of ethanol and 700ml ethylene glycol add in the reaction flask, stir, heat temperature raising to 60 ℃, begin to drip mass concentration and be 60% hydrazine hydrate solution (the hydrazine hydrate molecular weight is 50.06), totally 250.0 grams (solution weight).After hydrazine hydrate is added dropwise to complete, in 70 ℃～85 ℃ temperature range, continued stirring reaction 1 hour, cold slightly, filtered while hot, cooling mother liquor, drip an amount of pure water, separate out crystallized product, filter vacuum-drying, obtain 34.7 grams 3, two (2, the 4-diamino phenoxy) the phenylformic acid crystal of 5-, purity is 99.6%, according to 3 of reality acquisition, two (2, the 4-diamino phenoxy) benzoic amounts of 5-and theoretical amount (36.6 gram) calculate 3, two (2, the 4-diamino phenoxy) the benzoic yields of 5-are 94.7%.
Embodiment 2
With 48.6 gram (0.1 moles) 3,5-two (2,4-2,4-dinitrophenoxy base) phenylformic acid, 8.8 gram palladium mass percents are that 1% palladium/charcoal and 4860ml ethanol add in the reaction flask, stir, heat temperature raising to 60 ℃, begin to drip mass concentration and be 85% hydrazine hydrate solution, totally 294.1 grams (solution weight).After hydrazine hydrate is added dropwise to complete, in 70 ℃～85 ℃ temperature range, continued stirring reaction 5 hours, cold slightly, filtered while hot, cooling mother liquor, drip an amount of pure water, separate out crystallized product, filter vacuum-drying, obtain 34.9 grams 3, two (2, the 4-diamino phenoxy) the phenylformic acid crystal of 5-, purity is 99.8%, according to 3 of reality acquisition, two (2, the 4-diamino phenoxy) benzoic amounts of 5-and theoretical amount (36.6 gram) calculate 3, two (2, the 4-diamino phenoxy) the benzoic yields of 5-are 95.3%.
Embodiment 3
With 48.6 gram (0.1 moles) 3,5-two (2,4-2,4-dinitrophenoxy base) phenylformic acid, 4.0 gram palladium mass percents are that 5% palladium/charcoal, 280 ml methanol and 1000ml 2-methyl cellosolve add in the reaction flask, stir, heat temperature raising to 60 ℃, begin to drip mass concentration and be 80% hydrazine hydrate solution, totally 260.0 grams (solution weight).After hydrazine hydrate is added dropwise to complete, in 70 ℃～85 ℃ temperature range, continued stirring reaction 4 hours, cold slightly, filtered while hot, cooling mother liquor, drip an amount of pure water, separate out crystallized product, filter vacuum-drying, obtain 35.2 grams 3, two (2, the 4-diamino phenoxy) the phenylformic acid crystal of 5-, purity is 99.4%, according to 3 of reality acquisition, two (2, the 4-diamino phenoxy) benzoic amounts of 5-and theoretical amount (36.6 gram) calculate 3, two (2, the 4-diamino phenoxy) the benzoic yields of 5-are 96.2%.
Embodiment 4
With 48.6 gram (0.1 moles) 3,5-two (2,4-2,4-dinitrophenoxy base) phenylformic acid, 3.0 gram palladium mass percents are 10% palladium/charcoal and 800ml 1, the 2-propylene glycol adds in the reaction flask, stir, heat temperature raising to 60 ℃ begins to drip mass concentration and is 80% hydrazine hydrate solution, totally 300.0 grams (solution weight).After hydrazine hydrate is added dropwise to complete, in 70 ℃～85 ℃ temperature range, continued stirring reaction 3 hours, cold slightly, filtered while hot, cooling mother liquor, drip an amount of pure water, separate out crystallized product, filter vacuum-drying, obtain 33.9 grams 3, two (2, the 4-diamino phenoxy) the phenylformic acid crystal of 5-, purity is 99.7%, according to 3 of reality acquisition, two (2, the 4-diamino phenoxy) benzoic amounts of 5-and theoretical amount (36.6 gram) calculate 3, two (2, the 4-diamino phenoxy) the benzoic yields of 5-are 92.5%.
Embodiment 5
With 48.6 gram (0.1 moles) 3,5-two (2,4-2,4-dinitrophenoxy base) phenylformic acid, 3.5 gram palladium mass percents are that 10% palladium/charcoal, 120ml methyl alcohol and 1000ml cellosolvo add in the reaction flask, stir, heat temperature raising to 60 ℃, begin to drip mass concentration and be 85% hydrazine hydrate solution, totally 280.0 grams (solution weight).After hydrazine hydrate is added dropwise to complete, in 70 ℃～85 ℃ temperature range, continued stirring reaction 2 hours, cold slightly, filtered while hot, cooling mother liquor, drip an amount of pure water, separate out crystallized product, filter vacuum-drying, obtain 33.6 grams 3, two (2, the 4-diamino phenoxy) the phenylformic acid crystal of 5-, purity is 99.4%, according to 3 of reality acquisition, two (2, the 4-diamino phenoxy) benzoic amounts of 5-and theoretical amount (36.6 gram) calculate 3, two (2, the 4-diamino phenoxy) the benzoic yields of 5-are 91.7%.
Embodiment 6
With 48.6 gram (0.1 moles) 3,5-two (2,4-2,4-dinitrophenoxy base) phenylformic acid, 1.6 gram palladium mass percents are palladium/charcoal of 15%, 100 ml methanol, 100 milliliters of ethanol and 800ml 1, ammediol adds in the reaction flask, stir, heat temperature raising to 60 ℃ begins to drip mass concentration and is 60% hydrazine hydrate solution, totally 260.0 grams (solution weight).After hydrazine hydrate is added dropwise to complete, in 70 ℃～85 ℃ temperature range, continued stirring reaction 5 hours, cold slightly, filtered while hot, cooling mother liquor, drip an amount of pure water, separate out crystallized product, filter vacuum-drying, obtain 34.4 grams 3, two (2, the 4-diamino phenoxy) the phenylformic acid crystal of 5-, purity is 99.4%, according to 3 of reality acquisition, two (2, the 4-diamino phenoxy) benzoic amounts of 5-and theoretical amount (36.6 gram) calculate 3, two (2, the 4-diamino phenoxy) the benzoic yields of 5-are 94.1%.
Embodiment 7
With 48.6 gram (0.1 moles) 3,5-two (2,4-2,4-dinitrophenoxy base) phenylformic acid, 0.50 gram palladium mass percent are that palladium/charcoal of 15%, 4860 milliliters of ethanol add in the reaction flask, stir, heat temperature raising to 60 ℃, begin to drip mass concentration and be 60% hydrazine hydrate solution (the hydrazine hydrate molecular weight is 50.06), totally 250.0 grams (solution weight).After hydrazine hydrate is added dropwise to complete, in 70 ℃～85 ℃ temperature range, continued stirring reaction 1 hour, cold slightly, filtered while hot, cooling mother liquor, drip an amount of pure water, separate out crystallized product, filter vacuum-drying, obtain 32.8 grams 3, two (2, the 4-diamino phenoxy) the phenylformic acid crystal of 5-, purity is 99.8%, according to 3 of reality acquisition, two (2, the 4-diamino phenoxy) benzoic amounts of 5-and theoretical amount (36.6 gram) calculate 3, two (2, the 4-diamino phenoxy) the benzoic yields of 5-are 89.7%.
Claims (7)
1. one kind 3, two (2, the 4-diamino phenoxy) the benzoic preparation methods of 5-, comprise the steps: 3, two (2, the 4-2,4-dinitrophenoxy base) phenylformic acid of 5-, in palladium/charcoal, hydrazine hydrate solution and saturated fatty alcohol solvent system in 70 ℃～85 ℃ temperature range internal reactions after 1～5 hour, filtered while hot, cooling mother liquor, drip pure water, separate out crystalline product, filter, vacuum-drying, obtain 3, two (2, the 4-diamino phenoxy) phenylformic acid of 5-.
2. according to claim 13, two (2, the 4-diamino phenoxy) the benzoic preparation methods of 5-, it is characterized in that: the palladium mass percent of described palladium/charcoal is 1%～15%.
3. according to claim 13, two (2, the 4-diamino phenoxy) the benzoic preparation methods of 5-, it is characterized in that: the mass percent concentration of described hydrazine hydrate solution is 60%～85%.
4. according to claim 13,5-two (2, the 4-diamino phenoxy) benzoic preparation method, it is characterized in that: described saturated fatty alcoholic solvent is selected from methyl alcohol, ethanol, Virahol, n-propyl alcohol, propyl carbinol, isopropylcarbinol, ethylene glycol, 1,2-propylene glycol, 1, ammediol, one or more mixtures in 2-methyl cellosolve, cellosolvo, 2-methyl cellosolve, 3-methoxypropanol, 2-oxyethyl group propyl alcohol, the 3-oxyethyl group propyl alcohol.
5. according to claim 1 and 23, two (2, the 4-diamino phenoxy) the benzoic preparation methods of 5-is characterized in that: described 3, the weight ratio of two (2, the 4-2,4-dinitrophenoxy base) phenylformic acid of 5-and palladium/charcoal is 100: 1～20.
6. according to claim 1 or 3 described 3, two (2, the 4-diamino phenoxy) the benzoic preparation methods of 5-is characterized in that: described 3, the mol ratio of two (2,4-2,4-dinitrophenoxy base) phenylformic acid of 5-and hydrazine hydrate is 1: 20～50.
7. according to claim 1 or 4 described 3, two (2, the 4-diamino phenoxy) the benzoic preparation methods of 5-is characterized in that: described 3, the weightmeasurement ratio of two (2,4-2,4-dinitrophenoxy base) phenylformic acid of 5-and saturated fatty alcoholic solvent is 1 gram: 15 milliliters～100 milliliters.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2008100360567A CN101265204A (en) | 2008-04-15 | 2008-04-15 | Method for preparing 3,5-di(2,4-diaminophenoxy)benzoic acid |
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| CNA2008100360567A CN101265204A (en) | 2008-04-15 | 2008-04-15 | Method for preparing 3,5-di(2,4-diaminophenoxy)benzoic acid |
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| CN101265204A true CN101265204A (en) | 2008-09-17 |
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| CNA2008100360567A Pending CN101265204A (en) | 2008-04-15 | 2008-04-15 | Method for preparing 3,5-di(2,4-diaminophenoxy)benzoic acid |
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Open date: 20080917 |