CN100460381C - Preparation method of 2,2-bi (3-amino-4-hydroxyphenyl) hexafluoro propane - Google Patents
Preparation method of 2,2-bi (3-amino-4-hydroxyphenyl) hexafluoro propane Download PDFInfo
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- CN100460381C CN100460381C CNB2005100303880A CN200510030388A CN100460381C CN 100460381 C CN100460381 C CN 100460381C CN B2005100303880 A CNB2005100303880 A CN B2005100303880A CN 200510030388 A CN200510030388 A CN 200510030388A CN 100460381 C CN100460381 C CN 100460381C
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- hydroxy phenyl
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Abstract
The present invention discloses a preparation method of 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane. Said invention uses 2,2-bis (3-nitro-4-hydroxyphernyl) hexafluoropropane as raw material, uses anhydrous ammonium formate as reducing agent, and makes them produce reaction in the presence of catalyst so as to prepare the described 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane at room temperature. Its purity can be up to above 99%, yield is up to above 85% and its melting point is 216-218 deg.C.
Description
Technical field
The present invention relates to a kind of 2, the preparation method of two (the 3-amino-4-hydroxy phenyl) HFC-236fa of 2-.
Background technology
2, two (the 3-amino-4-hydroxy phenyl) HFC-236fa of 2-are a kind of polyimide monomers, can be used as the monomer of preparation polyimide speciality polymer functional materials especially, are widely used in making electric wire flame-resistant high-temperature-resistant material, and its structural formula is as follows:
The flat 11-100356 of Japanese Patent Application Laid-Open, European patent application EP 0895985 discloses respectively and has utilized 2, two (3-nitro-4-hydroxy phenyl) HFC-236fa of 2-are reacted with hydrazine hydrate under the effect of catalyzer, reduzate carries out purifying with a large amount of solvent recrystallization, obtain 2, the method of two (the 3-amino-4-hydroxy phenyl) HFC-236fa of 2-, yield only is 50～60%.
In above-mentioned method of reducing, be catalyzer with palladium charcoal or Reynolds nickel, hydrazine hydrate is that reductive agent reduces, and yield is low, and the cost height pollutes greatly, is unfavorable for environment protection.
Summary of the invention
The object of the present invention is to provide a kind of 2, the preparation method of two (the 3-amino-4-hydroxy phenyl) HFC-236fa of 2-, low to overcome available technology adopting hydrazine hydrate reduction method yield, cost height, heavy-polluted defective.
Technical conceive of the present invention is such:
The present invention is with 2, and two (3-nitro-4-hydroxy phenyl) HFC-236fa of 2-are raw material, are reductive agent with the anhydrous formic acid ammonium, carry out reduction reaction in the presence of catalyzer, thus can at room temperature prepare said 2, two (the 3-amino-4-hydroxy phenyl) HFC-236fa of 2-
Technical scheme of the present invention:
With 2, two (3-nitro-4-hydroxy phenyl) HFC-236fa of 2-, reductive agent anhydrous formic acid ammonium, catalyzer adds in the alcoholic solvent respectively, 15-25 ℃ was reacted 2-3 hour, collected target product 2 then from reaction product, two (the 3-amino-4-hydroxy phenyl) HFC-236fa of 2-.
According to the present invention, the palladium charcoal that uses 2-10% is as catalyzer, and the palladium charcoal of preferred 5-10% is as catalyzer.
Alcoholic solvent used in the present invention is C
1-C
3Alcoholic solvent, a kind of in particular methanol, ethanol, propyl alcohol or the Virahol wherein, special particular methanol.
According to the present invention, the mol ratio of reactant and reductive agent anhydrous formic acid ammonium is 1:8-12, and the mass ratio of reactant and catalyzer is 20-10:1, and the weightmeasurement ratio of reactant and alcoholic solvent is 1:4-10.
From reaction product, collect target product 2, two (the 3-amino-4-hydroxy phenyl) HFC-236fa of 2-can comprise the steps: reacting liquid filtering, in water, separate out crude product, use activated carbon decolorizing, in toluene solvant, separate out the white crystal product and be target product of the present invention.
Reaction formula of the present invention is as follows:
With preparation method of the present invention obtain 2, two (the 3-amino-4-hydroxy phenyl) HFC-236fa of 2-, purity reaches more than 99%, productive rate reaches more than 85%, fusing point is 216-218 ℃
Used in the present invention 2, two (3-nitro-4-hydroxy phenyl) HFC-236fa of 2-can prepare by the flat 6-211752 disclosed method of Japanese Patent Application Laid-Open.
The present invention has the room temperature of being reflected at and carries out compared with prior art, and mild condition is easy and simple to handle, and pollute and lack, the yield height, the advantage that product purity is high is suitable for suitability for industrialized production.
Embodiment
The invention will be further described below by embodiment, but embodiment does not limit protection scope of the present invention.
Embodiment 1
In the reactor that has stirring, thermometer, add 21.3g (0.05mol) 2 respectively, two (3-nitro-4-hydroxy phenyl) HFC-236fa of 2-, 29.0g (0.46mol) anhydrous formic acid ammonium, 100ml methyl alcohol, stir and add the 2.0g5%Pd/C catalyzer down, 15-25 ℃ was reacted 3 hours, and determined reaction end with thin-layer chromatographic analysis.
Filtering reacting liquid in the filtrate impouring 500ml water, is separated out reduzate, filters, and dry back adds the 0.5g gac and decolours with 20ml dehydrated alcohol heating for dissolving, and filtered while hot in the filtrate impouring 60ml toluene, is separated out white crystal, is cooled to room temperature.Filter, drying obtains 2, two (3-amino-4-hydroxy phenyl) the HFC-236fa 15.9g of 2-, yield 87.1%, purity 99.6% (HPLC).
Embodiment 2
In the reactor that has stirring, thermometer, add 21.3g (0.05mol) 2 respectively, two (3-nitro-4-hydroxy phenyl) HFC-236fa of 2-, 25.24g (0.40mol) anhydrous formic acid ammonium, 100ml ethanol, stir and add the 2.0g5%Pd/C catalyzer down, 15-25 ℃ was reacted 3 hours, and determined reaction end with thin-layer chromatographic analysis.
Filtering reacting liquid in the filtrate impouring 500ml water, is separated out reduzate, filters, and dry back adds the 0.5g gac and decolours with 20ml dehydrated alcohol heating for dissolving, and filtered while hot in the filtrate impouring 60ml toluene, is separated out white crystal, is cooled to room temperature.Filter, drying obtains 2, two (3-amino-4-hydroxy phenyl) the HFC-236fa 15.6g of 2-, yield 85.0%, purity 99.2% (HPLC).
Embodiment 3
In the reactor that has stirring, thermometer, add 42.6g (0.1mol) 2 respectively, two (3-nitro-4-hydroxy phenyl) HFC-236fa of 2-, 63.0g (1.0mol) anhydrous formic acid ammonium, 250ml methyl alcohol, stir and add the 3.0g10%Pd/C catalyzer down, 15-25 ℃ was reacted 2 hours, and determined reaction end with thin-layer chromatographic analysis.
Filtering reacting liquid in the filtrate impouring 1000ml water, is separated out reduzate.Filter, dry back adds the 1.0g gac and decolours with 40ml Virahol heating for dissolving, and filtered while hot among the filtrate impouring 120ml toluene 60ml, is separated out white crystal, is cooled to room temperature.Filter, drying obtains 2, two (3-amino-4-hydroxy phenyl) the HFC-236fa 32.0g of 2-, yield 87.4%, purity 99.7% (HPLC).
Claims (10)
1. one kind 2, the preparation method of two (the 3-amino-4-hydroxy phenyl) HFC-236fa of 2-is characterized in that comprising the steps:
With reactant 2, two (3-nitro-4-hydroxy phenyl) HFC-236fa of 2-, reductive agent anhydrous formic acid ammonium, catalyzer adds in the alcoholic solvent respectively, 15-25 ℃ was reacted 2-3 hour, collected target product 2 then from reaction product, two (the 3-amino-4-hydroxy phenyl) HFC-236fa of 2-.
2. method according to claim 1 is characterized in that, said catalyzer is the palladium charcoal of 2-10%.
3. method according to claim 2 is characterized in that, said catalyzer is the palladium charcoal of 5-10%.
4. method according to claim 1 is characterized in that, said alcoholic solvent is C
1-C
3Alcoholic solvent.
5. method according to claim 4 is characterized in that, said alcoholic solvent is methyl alcohol or ethanol or propyl alcohol or Virahol.
6. method according to claim 4 is characterized in that, said alcoholic solvent is a methyl alcohol.
7. according to each described method of claim 1-6, it is characterized in that the mol ratio of reactant and reductive agent anhydrous formic acid ammonium is 1:8-12.
8. according to each described method of claim 1-6, it is characterized in that the mass ratio of reactant and catalyzer is 20-10:1.
9. according to each described method of claim 1-6, it is characterized in that the weightmeasurement ratio of reactant and alcoholic solvent is 1:4-10.
10. method according to claim 1, it is characterized in that, from reaction product, collect target product 2, two (the 3-amino-4-hydroxy phenyl) HFC-236fa of 2-comprise the steps: reacting liquid filtering, in water, separate out crude product, use activated carbon decolorizing, in toluene solvant, separate out the white crystal product and be target product of the present invention.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005100303880A CN100460381C (en) | 2005-10-11 | 2005-10-11 | Preparation method of 2,2-bi (3-amino-4-hydroxyphenyl) hexafluoro propane |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005100303880A CN100460381C (en) | 2005-10-11 | 2005-10-11 | Preparation method of 2,2-bi (3-amino-4-hydroxyphenyl) hexafluoro propane |
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| CN1948273A CN1948273A (en) | 2007-04-18 |
| CN100460381C true CN100460381C (en) | 2009-02-11 |
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| CNB2005100303880A Expired - Fee Related CN100460381C (en) | 2005-10-11 | 2005-10-11 | Preparation method of 2,2-bi (3-amino-4-hydroxyphenyl) hexafluoro propane |
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Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101481318B (en) * | 2009-03-02 | 2012-10-03 | 常州市阳光药业有限公司 | Method for preparing electronic grade 2,2-bis[(3-amino-4-hydroxy)phenyl]- hexafluoropropane |
| CN105218387B (en) * | 2015-09-30 | 2017-07-11 | 衡水均凯化工有限公司 | The preparation method of 2,2 pairs of (hydroxy phenyl of 3 amino 4) HFC-236fas |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5977413A (en) * | 1997-08-04 | 1999-11-02 | Nippon Kayaku Kabushiki Kaisha | Method for producing bis(3-amino-4-hydroxyphenyl) compounds |
| US20040220229A1 (en) * | 2003-04-30 | 2004-11-04 | Pfizer Inc | Anti-diabetic agents |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5977413A (en) * | 1997-08-04 | 1999-11-02 | Nippon Kayaku Kabushiki Kaisha | Method for producing bis(3-amino-4-hydroxyphenyl) compounds |
| US20040220229A1 (en) * | 2003-04-30 | 2004-11-04 | Pfizer Inc | Anti-diabetic agents |
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Granted publication date: 20090211 Termination date: 20121011 |