CN101265205A - Method for preparing 4,4'-diamino-4''-(2,4-diaminophenoxy)triphenylmethane - Google Patents
Method for preparing 4,4'-diamino-4''-(2,4-diaminophenoxy)triphenylmethane Download PDFInfo
- Publication number
- CN101265205A CN101265205A CNA2008100360571A CN200810036057A CN101265205A CN 101265205 A CN101265205 A CN 101265205A CN A2008100360571 A CNA2008100360571 A CN A2008100360571A CN 200810036057 A CN200810036057 A CN 200810036057A CN 101265205 A CN101265205 A CN 101265205A
- Authority
- CN
- China
- Prior art keywords
- diamino
- tritane
- phenoxy
- preparation
- palladium
- 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 method of preparing 4, 4<1>-diamino-4<2>-(2, 4-diamino phenoxy) triphenylmethane. The method comprises the following steps: 4, 4<1>-diamino-4<2>-(2, 4-dinitro phenoxy) triphenylmethane reacts in palladium/carbon, hydrazine hydrate solution and the saturated fatty alcohol system for 2 to 8 hours under the temperature ranging from 70 DEG C to 85 DEG C; then the hot mixed solution is filtered, mother solution is cooled, right amount pure water is dropped in, and crystal products are precipitated; the crystal products are filtered and vacuum-dried to obtain 4, 4<1>-diamino-4<2>-(2, 4-diamino phenoxy) triphenylmethane 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 4,4 '-diamino-4 "-preparation method of (2, the 4-diamino phenoxy) tritane.
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.
4,4 '-diamino-4 "-(2, the 4-diamino phenoxy) tritane is one of important source material of synthetic high cladodification polyimide resin, 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, 4,4 '-diamino-4 "-(2, the 4-diamino phenoxy) tritane also is the important raw and processed materials of synthetic More Malay imide resin.
4,4 '-diamino-4 "-(2, the 4-diamino phenoxy) tritane is the polynary primary amine of a kind of important aromatic series, but its preparation method do not see patent is arranged, bibliographical information.
Summary of the invention
The purpose of this invention is to provide a kind of 4,4 '-diamino-4 "-preparation method of (2, the 4-diamino phenoxy) tritane, 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 4,4 '-diamino-4 "-preparation method of (2, the 4-diamino phenoxy) tritane, comprise the steps:
4,4 '-diamino-4 "-(2,4-2,4-dinitrophenoxy base) tritane; in palladium/charcoal, hydrazine hydrate solution and saturated fatty alcohol system in 70 ℃～85 ℃ temperature range internal reactions after 2～8 hours; filtered while hot, the cooling mother liquor drips an amount of pure water; separate out crystalline product; filter, vacuum-drying obtains 4; 4 '-diamino-4 "-(2, the 4-diamino phenoxy) tritane crystal.
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 4,4 '-diamino-4 "-weight ratio of (2,4-2,4-dinitrophenoxy base) tritane and palladium/charcoal is 100: 1～20.
Described 4,4 '-diamino-4 "-mol ratio of (2,4-2,4-dinitrophenoxy base) tritane and hydrazine hydrate is 1: 8～25.
Described 4,4 '-diamino-4 "-weightmeasurement ratio of (2,4-2,4-dinitrophenoxy base) tritane and saturated fatty alcohol is 1 gram: 15 milliliters～100 milliliters.
Beneficial effect of the present invention
(1) the present invention is preparation 4,4 '-diamino-4 "-commercial run of (2, the 4-diamino phenoxy) tritane;
(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) 4,4 '-diamino-4 "-(2; 4-2,4-dinitrophenoxy base) tritane raw material sources such as (Shanghai EMST Electron Material Co., Ltd stably manufactured) are convenient; and help of the present invention 4; 4 '-diamino-4 "-industrialization of (2, the 4-diamino phenoxy) tritane product and further applying;
(6) product purity reaches more than 99%, yield is high.
Description of drawings
Figure is 4,4 '-diamino-4 "-molecular structure of (2, the 4-diamino phenoxy) tritane.
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) 4,4 '-diamino-4 "-(2; 4-2,4-dinitrophenoxy base) tritane, 0.7 gram palladium mass percent are that palladium/charcoal of 15%, 200 milliliters of ethanol and 800ml 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 208.3 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 37.3 grams 4,4 '-diamino-4 "-(2, the 4-diamino phenoxy) tritane crystal, purity is 99.5%; according to reality obtain 4; 4 '-diamino-4 "-amount and the theoretical amount (39.6 gram) of (2, the 4-diamino phenoxy) tritane, calculate 4,4 '-diamino-4 "-yield of (2, the 4-diamino phenoxy) tritane is 94.2%.
Embodiment 2
With 45.6 gram (0.1 moles) 4,4 '-diamino-4 "-(2; 4-2,4-dinitrophenoxy base) tritane, 9.0 gram palladium mass percents are that 1% palladium/charcoal and 4560ml ethanol add in the reaction flask; stir; heat temperature raising to 60 ℃; begin to drip mass concentration and be 85% hydrazine hydrate solution, totally 48.5 grams (solution weight).After hydrazine hydrate is added dropwise to complete, in 70 ℃～85 ℃ temperature range, continued stirring reaction 8 hours, cold slightly, filtered while hot, cooling mother liquor, drip an amount of pure water, separate out crystallized product, filter vacuum-drying, obtain 33.5 grams 4,4 '-diamino-4 "-(2, the 4-diamino phenoxy) tritane crystal, purity is 99.3%; according to reality obtain 4; 4 '-diamino-4 "-amount and the theoretical amount (39.6 gram) of (2, the 4-diamino phenoxy) tritane, calculate 4,4 '-diamino-4 "-yield of (2, the 4-diamino phenoxy) tritane is 84.7%.
Embodiment 3
With 45.6 gram (0.1 moles) 4,4 '-diamino-4 "-(2; 4-2,4-dinitrophenoxy base) tritane, 4.0 gram palladium mass percents are that palladium/charcoal of 5%, 100 milliliters of ethanol and 800ml 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 130.0 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 35.9 grams 4,4 '-diamino-4 "-(2, the 4-diamino phenoxy) tritane crystal, purity is 99.4%; according to reality obtain 4; 4 '-diamino-4 "-amount and the theoretical amount (39.6 gram) of (2, the 4-diamino phenoxy) tritane, calculate 4,4 '-diamino-4 "-yield of (2, the 4-diamino phenoxy) tritane is 90.7%.
Embodiment 4
With 45.6 gram (0.1 moles) 4,4 '-diamino-4 "-(2; 4-2,4-dinitrophenoxy base) tritane, 3.0 gram palladium mass percents are palladium/charcoal of 10%, 100 milliliters of ethanol and 800ml 1; the 2-propylene glycol adds in the reaction flask; stir; heat temperature raising to 60 ℃, begins to drip mass concentration and be 80% hydrazine hydrate solution, totally 55.0 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 34.8 grams 4,4 '-diamino-4 "-(2, the 4-diamino phenoxy) tritane crystal, purity is 99.2%; according to reality obtain 4; 4 '-diamino-4 "-amount and the theoretical amount (39.6 gram) of (2, the 4-diamino phenoxy) tritane, calculate 4,4 '-diamino-4 "-yield of (2, the 4-diamino phenoxy) tritane is 87.9%.
Embodiment 5
With 45.6 gram (0.1 moles) 4,4 '-diamino-4 "-(2; 4-2,4-dinitrophenoxy base) tritane, 3.5 gram palladium mass percents are that 10% palladium/charcoal, 200ml 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 140.0 grams (solution weight).After hydrazine hydrate is added dropwise to complete, in 70 ℃～85 ℃ temperature range, continued stirring reaction 8 hours, cold slightly, filtered while hot, cooling mother liquor, drip an amount of pure water, separate out crystallized product, filter vacuum-drying, obtain 35.8 grams 4,4 '-diamino-4 "-(2, the 4-diamino phenoxy) tritane crystal, purity is 99.8%; according to reality obtain 4; 4 '-diamino-4 "-amount and the theoretical amount (39.6 gram) of (2, the 4-diamino phenoxy) tritane, calculate 4,4 '-diamino-4 "-yield of (2, the 4-diamino phenoxy) tritane is 90.5%.
Embodiment 6
With 45.6 gram (0.1 moles) 4,4 '-diamino-4 "-(2; 4-2,4-dinitrophenoxy base) tritane, 1.6 gram palladium mass percents are 15% palladium/charcoal and 800ml 1; ammediol adds in the reaction flask; stir; heat temperature raising to 60 ℃, begins to drip mass concentration and be 60% hydrazine hydrate solution, totally 130.0 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 32.5 grams 4,4 '-diamino-4 "-(2, the 4-diamino phenoxy) tritane crystal, purity is 99.1%; according to reality obtain 4; 4 '-diamino-4 "-amount and the theoretical amount (39.6 gram) of (2, the 4-diamino phenoxy) tritane, calculate 4,4 '-diamino-4 "-yield of (2, the 4-diamino phenoxy) tritane is 82.1%.
Claims (7)
1. one kind 4,4 '-diamino-4 "-preparation method of (2; the 4-diamino phenoxy) tritane; comprise the steps: 4; 4 '-diamino-4 "-(2,4-2,4-dinitrophenoxy base) tritane, in palladium/charcoal, hydrazine hydrate solution and saturated fatty alcohol system in 70 ℃～85 ℃ temperature range internal reactions after 2～8 hours, filtered while hot, the cooling mother liquor, drip an amount of pure water, separate out crystalline product, filter, vacuum-drying, obtain 4,4 '-diamino-4 "-(2, the 4-diamino phenoxy) tritane.
2. according to claim 14,4 '-diamino-4 "-preparation method of (2, the 4-diamino phenoxy) tritane, it is characterized in that: the palladium mass percent of described palladium/charcoal is 1%～15%.
3. according to claim 14,4 '-diamino-4 "-preparation method of (2, the 4-diamino phenoxy) tritane, it is characterized in that: the mass percent concentration of described hydrazine hydrate solution is 60%～85%.
4. according to claim 14,4 '-diamino-4 "-preparation method of (2; the 4-diamino phenoxy) tritane; 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 24,4 '-diamino-4 "-preparation method of (2, the 4-diamino phenoxy) tritane, it is characterized in that: described 4; 4 '-diamino-4 "-weight ratio of (2,4-2,4-dinitrophenoxy base) tritane and palladium/charcoal is 100: 1～20.
6. according to claim 1 or 3 described 4,4 '-diamino-4 "-preparation method of (2, the 4-diamino phenoxy) tritane, it is characterized in that: described 4; 4 '-diamino-4 "-mol ratio of (2,4-2,4-dinitrophenoxy base) tritane and hydrazine hydrate is 1: 8～25.
7. according to claim 1 or 4 described 4,4 '-diamino-4 "-preparation method of (2; the 4-diamino phenoxy) tritane; it is characterized in that: described 4; 4 '-diamino-4 "-weightmeasurement ratio of (2,4-2,4-dinitrophenoxy base) tritane and saturated fatty alcohol is 1 gram: 15 milliliters～100 milliliters.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2008100360571A CN101265205A (en) | 2008-04-15 | 2008-04-15 | Method for preparing 4,4'-diamino-4''-(2,4-diaminophenoxy)triphenylmethane |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2008100360571A CN101265205A (en) | 2008-04-15 | 2008-04-15 | Method for preparing 4,4'-diamino-4''-(2,4-diaminophenoxy)triphenylmethane |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN101265205A true CN101265205A (en) | 2008-09-17 |
Family
ID=39987924
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNA2008100360571A Pending CN101265205A (en) | 2008-04-15 | 2008-04-15 | Method for preparing 4,4'-diamino-4''-(2,4-diaminophenoxy)triphenylmethane |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101265205A (en) |
-
2008
- 2008-04-15 CN CNA2008100360571A patent/CN101265205A/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 | |
| CN101284793B (en) | Preparation method of 2,2-di[4-(2,4-diamino phenoxy) phenyl group] propane | |
| CN101245024A (en) | Process for producing 1,3-bis(2,4-diaminophenyloxy)benzene | |
| CN101245023A (en) | Process for producing 2,2-bis[2,4-diaminophenyloxy)phenyl]hexafluoropropane | |
| CN101250124A (en) | Method for preparing 2,5-di(2,4-diamino phenoxy) toluene | |
| CN101245041B (en) | Process for producing 4,4'-bis(2,4-diaminophenyloxy)diphenyl sulfone | |
| CN101250120B (en) | Method for preparing 4,4-di(2,4-diamino phenoxy) diphenylmethane | |
| 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 | |
| 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 | |
| CN101250128A (en) | Method for preparing 1,4-di(2,4-diamino phenoxy) naphthalene | |
| CN101265205A (en) | Method for preparing 4,4'-diamino-4''-(2,4-diaminophenoxy)triphenylmethane | |
| CN101260058A (en) | Method for preparing 4,4'-di(2,4-diaminophenoxy)diphenyl ether | |
| CN101265207A (en) | Method for preparing 2,2-di[4-(2,4-diaminophenoxy)-3,5-dimethylphenyl]hexafluoropropane | |
| CN101260057A (en) | Method for preparing 1,3,5-tri(2,4-diaminophenoxy)benzene | |
| CN101245028A (en) | Process for producing 2,2-bis[3-amido-4-(4-aminophenoxy)phenyl] hexafluoropropane | |
| CN101289407A (en) | Method for preparing 4,4'-di(2,4- diaminophenyloxy)-3,3',5,5'-tetramethylbiphenyl | |
| CN101265203A (en) | Method for preparing 3,3'-diamino-4,4'-di(2,4-diaminophenoxy)diphenyl | |
| CN101250142A (en) | Method for preparing 4,4'-di(2,4-diamino phenoxy)-3,3',5,5'-tetramethyl diphenyl sulfone | |
| CN101265208A (en) | Method for preparing 3,5-di(2,4-diaminophenoxy)trifluorotoluene | |
| CN101245031A (en) | Process for producing 1,2-bis(2,4-diaminophenyloxy)naphthalin | |
| CN101293843A (en) | Method for preparing 3,3'-diamino--4,4'-di(4-aminophenoxy)biphenyl | |
| CN101265202A (en) | Method for preparing 2,7-di(2,4-diaminophenoxy)naphthalene |
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: 20080917 |