CN101265208A - Method for preparing 3,5-di(2,4-diaminophenoxy)trifluorotoluene - Google Patents
Method for preparing 3,5-di(2,4-diaminophenoxy)trifluorotoluene Download PDFInfo
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- CN101265208A CN101265208A CNA2008100362952A CN200810036295A CN101265208A CN 101265208 A CN101265208 A CN 101265208A CN A2008100362952 A CNA2008100362952 A CN A2008100362952A CN 200810036295 A CN200810036295 A CN 200810036295A CN 101265208 A CN101265208 A CN 101265208A
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- phenylfluoroforms
- diamino phenoxy
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Abstract
The invention relates to a method of preparing 3, 5-bis(2, 4-diamino phenoxy) benzotrifluoride. The method comprises the following steps: 3, 5-bis(2, 4-dinitro phenoxy) benzotrifluoride reacts in palladium/carbon, hydrazine hydrate solution and the saturated fatty alcohol 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 to obtain 3, 5-bis(2, 4-diamino phenoxy) benzotrifluoride 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, the preparation method of two (2, the 4-diamino phenoxy) phenylfluoroforms 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) phenylfluoroforms 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) phenylfluoroforms 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, the preparation method of two (2, the 4-diamino phenoxy) phenylfluoroforms 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, the preparation method of two (2, the 4-diamino phenoxy) phenylfluoroforms of 5-comprises the steps:
3, two (2, the 4-2,4-dinitrophenoxy base) phenylfluoroforms of 5-, in palladium/charcoal, hydrazine hydrate solution and saturated fatty alcohol 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 phenylfluoroform 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 alcohol 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) phenylfluoroforms of 5-and palladium/charcoal is 100: 1～20.
Described 3, the mol ratio of two (2,4-2,4-dinitrophenoxy base) phenylfluoroforms of 5-and hydrazine hydrate is 1: 20～50.
Described 3, the weightmeasurement ratio of two (2, the 4-2,4-dinitrophenoxy base) phenylfluoroforms of 5-and saturated fatty alcohol is 1 to restrain: 15 milliliters～100 milliliters.
Beneficial effect of the present invention
(1) the present invention is preparation 3, the commercial run of two (2, the 4-diamino phenoxy) phenylfluoroforms 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, the molecular structure of two (2, the 4-diamino phenoxy) phenylfluoroforms 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 51.0 gram (0.1 moles) 3,5-two (2,4-2,4-dinitrophenoxy base) phenylfluoroform, 0.6 gram palladium mass percent are that palladium/charcoal of 15%, 1500 milliliters of ethanol and 1600ml ethylene glycol add in the reaction flask, stir, heat temperature raising to 60 ℃, begin to drip mass concentration and be 60% hydrazine hydrate solution, totally 250.0 grams (solution weight).After hydrazine hydrate is added dropwise to complete, in 70 ℃～85 ℃ temperature range, continued stirring reaction 3.5 hours, cold slightly, filtered while hot, cooling mother liquor, drip an amount of pure water, separate out crystallized product, filter vacuum-drying, obtain 34.2 grams 3, two (2, the 4-diamino phenoxy) the phenylfluoroform crystal of 5-, purity is 99.8%, according to 3 of reality acquisition, amount of two (2, the 4-diamino phenoxy) phenylfluoroforms of 5-and theoretical amount (39.0 gram) calculate 3, the yield of two (2, the 4-diamino phenoxy) phenylfluoroforms of 5-is 87.6%.
Embodiment 2
With 51.0 gram (0.1 moles) 3,5-two (2,4-2,4-dinitrophenoxy base) phenylfluoroform, 10.0 gram palladium mass percents are that 1% palladium/charcoal, 800ml 2-methyl cellosolve and 1500ml 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 3.5 hours, cold slightly, filtered while hot, cooling mother liquor, drip an amount of pure water, separate out crystallized product, filter vacuum-drying, obtain 30.6 grams 3, two (2, the 4-diamino phenoxy) the phenylfluoroform crystal of 5-, purity is 99.2%, according to 3 of reality acquisition, amount of two (2, the 4-diamino phenoxy) phenylfluoroforms of 5-and theoretical amount (39.0 gram) calculate 3, the yield of two (2, the 4-diamino phenoxy) phenylfluoroforms of 5-is 78.5%.
Embodiment 3
With 51.0 gram (0.1 moles) 3,5-two (2,4-2,4-dinitrophenoxy base) phenylfluoroform, 8.5 gram palladium mass percents are that palladium/charcoal of 5%, 2000 milliliters of ethanol and 2000ml 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 5 hours, cold slightly, filtered while hot, cooling mother liquor, drip an amount of pure water, separate out crystallized product, filter vacuum-drying, obtain 33.0. gram 3, two (2, the 4-diamino phenoxy) the phenylfluoroform crystal of 5-, purity is 99.6%, according to 3 of reality acquisition, amount of two (2, the 4-diamino phenoxy) phenylfluoroforms of 5-and theoretical amount (39.0 gram) calculate 3, the yield of two (2, the 4-diamino phenoxy) phenylfluoroforms of 5-is 84.5%.
Embodiment 4
With 51.0 gram (0.1 moles) 3,5-two (2,4-2,4-dinitrophenoxy base) phenylfluoroform, 3.5 gram palladium mass percents are palladium/charcoal of 10%, 200 milliliters of ethanol and 1000ml 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 2.5 hours, cold slightly, filtered while hot, cooling mother liquor, drip an amount of pure water, separate out crystallized product, filter vacuum-drying, obtain 35.3 grams 3, two (2, the 4-diamino phenoxy) the phenylfluoroform crystal of 5-, purity is 99.6%, according to 3 of reality acquisition, amount of two (2, the 4-diamino phenoxy) phenylfluoroforms of 5-and theoretical amount (39.0 gram) calculate 3, the yield of two (2, the 4-diamino phenoxy) phenylfluoroforms of 5-is 90.4%.
Embodiment 5
With 51.0 gram (0.1 moles) 3,5-two (2,4-2,4-dinitrophenoxy base) phenylfluoroform, 4.5 gram palladium mass percents are that 10% palladium/charcoal, 200ml methyl alcohol and 2500ml 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 4.5 hours, cold slightly, filtered while hot, cooling mother liquor, drip an amount of pure water, separate out crystallized product, filter vacuum-drying, obtain 36.3 grams 3, two (2, the 4-diamino phenoxy) the phenylfluoroform crystal of 5-, purity is 99.6%, according to 3 of reality acquisition, amount of two (2, the 4-diamino phenoxy) phenylfluoroforms of 5-and theoretical amount (39.0 gram) calculate 3, the yield of two (2, the 4-diamino phenoxy) phenylfluoroforms of 5-is 93.0%.
Embodiment 6
With 51.0 gram (0.1 moles) 3,5-two (2,4-2,4-dinitrophenoxy base) phenylfluoroform, 2.5 gram palladium mass percents are palladium/charcoal of 15%, 1600 milliliters of ethanol and 1200ml 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 3.5 hours, cold slightly, filtered while hot, cooling mother liquor, drip an amount of pure water, separate out crystallized product, filter vacuum-drying, obtain 36.1 grams 3, two (2, the 4-diamino phenoxy) the phenylfluoroform crystal of 5-, purity is 99.8%, according to 3 of reality acquisition, amount of two (2, the 4-diamino phenoxy) phenylfluoroforms of 5-and theoretical amount (39.0 gram) calculate 3, the yield of two (2, the 4-diamino phenoxy) phenylfluoroforms of 5-is 92.6%.
Embodiment 7
With 51.0 gram (0.1 moles) 3,5-) two (2,4-2,4-dinitrophenoxy base) phenylfluoroform, 3.5 gram palladium mass percents are that palladium/charcoal of 15%, 5100 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, totally 260.0 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 36.7 grams 3, two (2, the 4-diamino phenoxy) the phenylfluoroform crystal of 5-, purity is 99.8%, according to 3 of reality acquisition, amount of two (2, the 4-diamino phenoxy) phenylfluoroforms of 5-and theoretical amount (39.0 gram) calculate 3, the yield of two (2, the 4-diamino phenoxy) phenylfluoroforms of 5-is 94.0%.
Claims (7)
1. one kind 3, the preparation method of two (2, the 4-diamino phenoxy) phenylfluoroforms of 5-, comprise the steps: 3, two (2, the 4-2,4-dinitrophenoxy base) phenylfluoroforms of 5-, in palladium/charcoal, hydrazine hydrate solution and saturated fatty alcohol 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) phenylfluoroforms of 5-.
2. according to claim 13, the preparation method of two (2, the 4-diamino phenoxy) phenylfluoroforms of 5-, it is characterized in that: the palladium mass percent of described palladium/charcoal is 1%～15%.
3. according to claim 13, the preparation method of two (2, the 4-diamino phenoxy) phenylfluoroforms 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) preparation method of phenylfluoroform, it is characterized in that: described saturated fatty alcohol 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, the preparation method of two (2, the 4-diamino phenoxy) phenylfluoroforms of 5-is characterized in that: described 3, the weight ratio of two (2, the 4-2,4-dinitrophenoxy base) phenylfluoroforms of 5-and palladium/charcoal is 100: 1～20.
6. according to claim 1 or 3 described 3, the preparation method of two (2, the 4-diamino phenoxy) phenylfluoroforms of 5-is characterized in that: described 3, the mol ratio of two (2,4-2,4-dinitrophenoxy base) phenylfluoroforms of 5-and hydrazine hydrate is 1: 20～50.
7. according to claim 1 or 4 described 3, the preparation method of two (2, the 4-diamino phenoxy) phenylfluoroforms of 5-is characterized in that: described 3, the weightmeasurement ratio of two (2,4-2,4-dinitrophenoxy base) phenylfluoroforms of 5-and saturated fatty alcohol is 1 gram: 15 milliliters～100 milliliters.
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| CNA2008100362952A CN101265208A (en) | 2008-04-18 | 2008-04-18 | Method for preparing 3,5-di(2,4-diaminophenoxy)trifluorotoluene |
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| CNA2008100362952A CN101265208A (en) | 2008-04-18 | 2008-04-18 | Method for preparing 3,5-di(2,4-diaminophenoxy)trifluorotoluene |
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| CNA2008100362952A Pending CN101265208A (en) | 2008-04-18 | 2008-04-18 | Method for preparing 3,5-di(2,4-diaminophenoxy)trifluorotoluene |
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Open date: 20080917 |