CN101250123A - Method for preparing 2,4-di(2,4-diamino phenoxy) toluene - Google Patents
Method for preparing 2,4-di(2,4-diamino phenoxy) toluene Download PDFInfo
- Publication number
- CN101250123A CN101250123A CNA2008100354848A CN200810035484A CN101250123A CN 101250123 A CN101250123 A CN 101250123A CN A2008100354848 A CNA2008100354848 A CN A2008100354848A CN 200810035484 A CN200810035484 A CN 200810035484A CN 101250123 A CN101250123 A CN 101250123A
- Authority
- CN
- China
- Prior art keywords
- toluene
- diamino phenoxy
- preparation
- palladium
- hydrazine hydrate
- 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
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to a preparation method of 2, 4-bis (2, 4-diamino phenoxy) toluene, which comprises reacting 2, 4-bis (2, 4-dinitro phenoxy) toluene in a system of palladium/charcoal, hydrazine hydrate solution and saturated fatty alcohol, at 70-85DEG C for 1-5h, filtering immediately, cooling the mother liquor, adding pure water, precipitating crystal product, filtering, drying in vacuum and obtaining 2, 4-bis (2, 4-diamino phenoxy) toluene crystal. The invention has simple operation, eliminated following refining and extraction, low time consumption, high product yield and high purity (at least 99%), which is suitable for industrial 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 2, the preparation method of two (2, the 4-diamino phenoxy) toluene of 4-.
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.
2, one of important source material that two (2, the 4-diamino phenoxy) toluene of 4-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, 2, the important raw and processed materials that two (2, the 4-diamino phenoxy) toluene of 4-also are synthetic More Malay imide resins.
Summary of the invention
The purpose of this invention is to provide a kind of 2, the preparation method of two (2, the 4-diamino phenoxy) toluene of 4-, 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 2, the preparation method of two (2, the 4-diamino phenoxy) toluene of 4-comprises the steps:
2, two (2, the 4-2,4-dinitrophenoxy base) toluene of 4-, 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 2, two (2, the 4-diamino phenoxy) the toluene crystal of 4-.
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 2, the weight ratio of two (2, the 4-2,4-dinitrophenoxy base) toluene of 4-and palladium/charcoal is 100: 1～20.
Described 2, the mol ratio of two (2,4-2,4-dinitrophenoxy base) toluene of 4-and hydrazine hydrate is 1: 20～50.
Described 2, the weightmeasurement ratio of two (2, the 4-2,4-dinitrophenoxy base) toluene of 4-and saturated fatty alcohol is 1 to restrain: 15 milliliters～100 milliliters.
Beneficial effect of the present invention
(1) the present invention is preparation 2, the commercial run of two (2, the 4-diamino phenoxy) toluene of 4-;
(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 2, the molecular structure of two (2, the 4-diamino phenoxy) toluene of 4-.
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 45.6 gram (0.1 moles) 2,4-two (2,4-2,4-dinitrophenoxy base) toluene, 0.6 gram palladium mass percent are that palladium/charcoal of 15%, 150 milliliters of ethanol and 850ml 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 4.5 hours, cold slightly, filtered while hot, the cooling mother liquor drips an amount of pure water, separate out crystallized product, filter, vacuum-drying obtains 31.9 grams 2,4-two (2, the 4-diamino phenoxy) toluene crystal, purity are 99.6%, and fusing point is 185.4 ℃～186.3 ℃.According to 2 of reality acquisition, amount of two (2, the 4-diamino phenoxy) toluene of 4-and theoretical amount (33.6 gram) calculate 2, and the yield of two (2, the 4-diamino phenoxy) toluene of 4-is 94.8%.
Embodiment 2
With 45.6 gram (0.1 moles) 2,4-two (2,4-2,4-dinitrophenoxy base) toluene, 8.9 gram palladium mass percents are that 1% palladium/charcoal, 500ml 2-methyl cellosolve and 4000ml 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, the cooling mother liquor drips an amount of pure water, separates out crystallized product, filter, vacuum-drying obtains 29.2 grams 2, two (2, the 4-diamino phenoxy) the toluene crystal of 4-, purity is 99.7%, according to 2 of reality acquisition, amount of two (2, the 4-diamino phenoxy) toluene of 4-and theoretical amount (33.6 gram), calculate 2, the yield of two (2, the 4-diamino phenoxy) toluene of 4-is 86.8%.
Embodiment 3
With 45.6 gram (0.1 moles) 2,4-two (2,4-2,4-dinitrophenoxy base) toluene, 4.3 gram palladium mass percents are that palladium/charcoal of 5%, 600 milliliters of ethanol and 1500ml 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 3.5 hours, cold slightly, filtered while hot, the cooling mother liquor drips an amount of pure water, separates out crystallized product, filter, vacuum-drying obtains 32.2 grams 2, two (2, the 4-diamino phenoxy) the toluene crystal of 4-, purity is 99.6%, according to 2 of reality acquisition, amount of two (2, the 4-diamino phenoxy) toluene of 4-and theoretical amount (33.6 gram), calculate 2, the yield of two (2, the 4-diamino phenoxy) toluene of 4-is 95.7%.
Embodiment 4
With 45.6 gram (0.1 moles) 2,4-two (2,4-2,4-dinitrophenoxy base) toluene, 3.1 gram palladium mass percents are palladium/charcoal of 10%, 300 milliliters of ethanol and 1800ml 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 4.5 hours, cold slightly, filtered while hot, the cooling mother liquor drips an amount of pure water, separates out crystallized product, filter, vacuum-drying obtains 30.3 grams 2, two (2, the 4-diamino phenoxy) the toluene crystal of 4-, purity is 99.3%, according to 2 of reality acquisition, amount of two (2, the 4-diamino phenoxy) toluene of 4-and theoretical amount (33.6 gram), calculate 2, the yield of two (2, the 4-diamino phenoxy) toluene of 4-is 90.2%.
Embodiment 5
With 45.6 gram (0.1 moles) 2,4-two (2,4-2,4-dinitrophenoxy base) toluene, 3.5 gram palladium mass percents are that 10% palladium/charcoal, 180ml methyl alcohol and 2600ml 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 3.5 hours, cold slightly, filtered while hot, the cooling mother liquor drips an amount of pure water, separates out crystallized product, filter, vacuum-drying obtains 29.4 grams 2, two (2, the 4-diamino phenoxy) the toluene crystal of 4-, purity is 99.7%, according to 2 of reality acquisition, amount of two (2, the 4-diamino phenoxy) toluene of 4-and theoretical amount (33.6 gram), calculate 2, the yield of two (2, the 4-diamino phenoxy) toluene of 4-is 87.5%.
Embodiment 6
With 45.6 gram (0.1 moles) 2,4-two (2,4-2,4-dinitrophenoxy base) toluene, 1.8 gram palladium mass percents are palladium/charcoal of 15%, 500 milliliters of ethanol and 1600ml 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, the cooling mother liquor drips an amount of pure water, separates out crystallized product, filter, vacuum-drying obtains 32.1 grams 2, two (2, the 4-diamino phenoxy) the toluene crystal of 4-, purity is 99.6%, according to 2 of reality acquisition, amount of two (2, the 4-diamino phenoxy) toluene of 4-and theoretical amount (33.6 gram), calculate 2, the yield of two (2, the 4-diamino phenoxy) toluene of 4-is 95.7%.
Claims (7)
1. one kind 2, the preparation method of two (2, the 4-diamino phenoxy) toluene of 4-, comprise the steps: 2, two (2, the 4-2,4-dinitrophenoxy base) toluene of 4-, 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 2, two (2, the 4-diamino phenoxy) toluene of 4-.
2. according to claim 12, the preparation method of two (2, the 4-diamino phenoxy) toluene of 4-, it is characterized in that: the palladium mass percent of described palladium/charcoal is 1%～15%.
3. according to claim 12, the preparation method of two (2, the 4-diamino phenoxy) toluene of 4-, it is characterized in that: the mass percent concentration of described hydrazine hydrate solution is 60%～85%.
4. according to claim 12,4-two (2, the 4-diamino phenoxy) preparation method of toluene, 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 22, the preparation method of two (2, the 4-diamino phenoxy) toluene of 4-is characterized in that: described 2, the weight ratio of two (2, the 4-2,4-dinitrophenoxy base) toluene of 4-and palladium/charcoal is 100: 1～20.
6. according to claim 1 or 3 described 2, the preparation method of two (2, the 4-diamino phenoxy) toluene of 4-is characterized in that: described 2, the mol ratio of two (2,4-2,4-dinitrophenoxy base) toluene of 4-and hydrazine hydrate is 1: 20～50.
7. according to claim 1 or 4 described 2, the preparation method of two (2, the 4-diamino phenoxy) toluene of 4-is characterized in that: described 2, the weightmeasurement ratio of two (2, the 4-2,4-dinitrophenoxy base) toluene of 4-and saturated fatty alcohol is 1 to restrain: 15 milliliters～100 milliliters.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2008100354848A CN101250123A (en) | 2008-04-02 | 2008-04-02 | Method for preparing 2,4-di(2,4-diamino phenoxy) toluene |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2008100354848A CN101250123A (en) | 2008-04-02 | 2008-04-02 | Method for preparing 2,4-di(2,4-diamino phenoxy) toluene |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN101250123A true CN101250123A (en) | 2008-08-27 |
Family
ID=39953740
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNA2008100354848A Pending CN101250123A (en) | 2008-04-02 | 2008-04-02 | Method for preparing 2,4-di(2,4-diamino phenoxy) toluene |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101250123A (en) |
-
2008
- 2008-04-02 CN CNA2008100354848A patent/CN101250123A/en active Pending
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101245026A (en) | Process for producing 1,4-(2,4-diaminophenyloxy)-2,5-di-t-butyl benzene | |
| CN101245024A (en) | Process for producing 1,3-bis(2,4-diaminophenyloxy)benzene | |
| CN101284793B (en) | Preparation method of 2,2-di[4-(2,4-diamino phenoxy) phenyl group] propane | |
| CN101250124A (en) | Method for preparing 2,5-di(2,4-diamino phenoxy) toluene | |
| CN101245023A (en) | Process for producing 2,2-bis[2,4-diaminophenyloxy)phenyl]hexafluoropropane | |
| CN101250120B (en) | Method for preparing 4,4-di(2,4-diamino phenoxy) diphenylmethane | |
| CN101245041B (en) | Process for producing 4,4'-bis(2,4-diaminophenyloxy)diphenyl sulfone | |
| CN101293842B (en) | Method for preparing 4,4'-di(2,4-diaminophenyloxy)biphenyl | |
| CN101215241A (en) | Method for preparing 1,4-di(2,4-diaminophenoxy)benzene | |
| CN101260052A (en) | Method for preparing 2,6-di(2,4-diaminophenoxy)toluene | |
| CN101250128A (en) | Method for preparing 1,4-di(2,4-diamino phenoxy) naphthalene | |
| CN101245030B (en) | Process for producing 1,2-bis(2,4-diaminophenyloxy)benzene | |
| CN101260053A (en) | Method for preparing 2,2-di[3-amino-4-(2,4-diaminophenoxy)phenyl]hexafluoropropane | |
| CN101250123A (en) | Method for preparing 2,4-di(2,4-diamino phenoxy) toluene | |
| CN101260057A (en) | Method for preparing 1,3,5-tri(2,4-diaminophenoxy)benzene | |
| CN101250142A (en) | Method for preparing 4,4'-di(2,4-diamino phenoxy)-3,3',5,5'-tetramethyl diphenyl sulfone | |
| CN101260058A (en) | Method for preparing 4,4'-di(2,4-diaminophenoxy)diphenyl ether | |
| CN101289406A (en) | Method for preparing 1,4-di(2,4- diaminophenyloxy)-2-tert-butyl benzene | |
| CN101250127A (en) | Method for preparing 1,4-di(2,4-diamino phenoxy)-2-naphthoic acid | |
| CN101260059A (en) | Method for preparing 2,6-dimethyl-1,4-di(2,4-diaminophenoxy)benzene | |
| CN101265207A (en) | Method for preparing 2,2-di[4-(2,4-diaminophenoxy)-3,5-dimethylphenyl]hexafluoropropane | |
| CN101245022A (en) | Process for producing 3,5-bis(2,4-diaminophenyloxy)-2-naphthoic acid | |
| CN101250126A (en) | Method for preparing 1,7-di(2,4-diamino phenoxy) naphthalene | |
| CN101250122A (en) | Method for preparing 2,3-di(2,4-diamino phenoxy) naphthalene | |
| CN101250121A (en) | Method for preparing 2,6-di(2,4-diamino phenoxy) benzotrifluoride |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Open date: 20080827 |