CN100556887C - 2, two [4-(3-nitro-phenoxy) phenyl]-1,1,1,3,3 of 2-, the method for purification of 3-HFC-236fa - Google Patents
2, two [4-(3-nitro-phenoxy) phenyl]-1,1,1,3,3 of 2-, the method for purification of 3-HFC-236fa Download PDFInfo
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- CN100556887C CN100556887C CN 200510023334 CN200510023334A CN100556887C CN 100556887 C CN100556887 C CN 100556887C CN 200510023334 CN200510023334 CN 200510023334 CN 200510023334 A CN200510023334 A CN 200510023334A CN 100556887 C CN100556887 C CN 100556887C
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Abstract
The invention discloses a kind of 2, two [4-(3-nitro-phenoxy) phenyl]-1,1,1,3,3 of 2-, the method for purification of 3-HFC-236fa.The present invention is dissolved in reaction solvent N with Meta-dinitrobenzene, hexafluoro bisphenol-a, in the dinethylformamide, the reaction solution that obtains with the salt of wormwood condensation after filtration, underpressure distillation, wet distillation, add high boiling solvent, molecular distillation, target product is collected in the distillate extraction from distillate.With method of purification of the present invention obtain 2, two [4-(3-nitro-phenoxy) phenyl]-1,1,1,3,3 of 2-, 3-HFC-236fa, purity reach more than 98%, productive rate is greater than 80%.The generation that method of purification cost of the present invention is low, avoided a large amount of waste water has reduced pollution, can reclaim the use reaction solvent, and resulting constant product quality is suitable for suitability for industrialized production.
Description
Technical field
The present invention relates to 2, two [4-(3-nitro-phenoxy) phenyl]-1,1,1,3,3 of 2-, the method for purification of 3-HFC-236fa.
Background technology
2, two [4-(3-nitro-phenoxy) phenyl]-1,1,1,3,3 of 2-, the 3-HFC-236fa is a kind of important industrial chemicals, especially can be used as the monomer of preparation polyimide, and application promise in clinical practice is arranged.Its structural formula is:
European patent EP 0192480 is a raw material with Meta-dinitrobenzene, hexafluoro bisphenol-a, at reaction solvent N, carries out condensation with salt of wormwood in the dinethylformamide (DMF), reaction solution pours a large amount of water, isolates to contain 2 two [4-(3-nitro-phenoxy) phenyl]-1 of 2-, 1,1,3,3, the tarry crude product of 3-HFC-236fa is dissolved in the benzene, washing, method with silica gel column chromatography is purified, and obtains the purpose product.
In above-mentioned preparation method, adopt the method purification operations difficulty of silica gel column chromatography big, the cost height has a large amount of waste water to produce in the reaction process, difficult solvent recovery, industrial prospect is undesirable.
Summary of the invention
The object of the present invention is to provide a kind of 2, two [4-(3-nitro-phenoxy) phenyl]-1,1 of 2-, 1,3,3, the method of purification of 3-HFC-236fa, available technology adopting silica gel column chromatography purification operations is loaded down with trivial details, cost is high to overcome, produce a large amount of waste water, the deficiency of difficult solvent recovery.
Method of purification of the present invention may further comprise the steps:
Meta-dinitrobenzene, hexafluoro bisphenol-a are dissolved in reaction solvent N, in the dinethylformamide (DMF), carry out condensation with salt of wormwood, with resulting reacting liquid filtering, vacuum distillation recovered solvent, wet distillation is removed low molecular weight impurities and remaining Meta-dinitrobenzene and N, dinethylformamide adds high boiling solvent, at 150～165 ℃, 0.01 target product is collected in molecular distillation under the condition of～0.2Pa from distillate.According to the present invention, adopt extraction agent from distillate, to collect target product, said extraction agent is C
1～C
3No water unit alcohol in a kind of, preferred dehydrated alcohol, the consumption of extraction agent is a hexafluoro bisphenol-a: extraction agent=1.0: 2.0～5.0, weightmeasurement ratio;
Said high boiling solvent is C
15～C
30Alkane solvent, preferred C
20～C
25Alkane solvent, the consumption of high boiling solvent is a hexafluoro bisphenol-a: high boiling solvent=1.0: 0.2～2.0, weightmeasurement ratio.
With method of purification of the present invention obtain 2, two [4-(3-nitro-phenoxy) phenyl]-1,1,1,3,3 of 2-, 3-HFC-236fa, purity reach more than 98%, productive rate is 81%.
Reaction solution used in the present invention can prepare with reference to the method for EP0192480.
Beneficial effect
The present invention has the generation that constant product quality, cost are low, avoided a large amount of waste water compared with prior art, has reduced pollution, and reaction solvent can reclaim use, is suitable for the advantage of 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 reflux condensing tube, agitator, thermometer are housed, add Meta-dinitrobenzene 24g (0.14mol) respectively, hexafluoro bisphenol-a 20g (0.059mol), N, dinethylformamide (DMF) 100ml stirs adding salt of wormwood 19.4g (0.14mol) down, be heated to backflow gradually, reacted 7 hours, the reaction solution cooling is filtered, the filtrate decompression distillation is steamed and is removed DMF solvent (recovery set is used).Steam surplus liquid wet distillation, steam and remove low-molecular-weight fraction, cooling adds C
20～C
25Alkane solvent 10ml, 160 ± 2 ℃ of controlled temperature, pressure 0.1Pa carries out molecular distillation, adds dehydrated alcohol 50ml in the cut of collection and extracts, and stirs 10min, leaves standstill the back and divides oil-yielding stratum, the C that obtains
20～C
25Alkane solvent recovery set usefulness desolventizes ethanol with alcohol layer underpressure distillation steaming, obtains light yellow oily 2, two [4-(3-nitro-phenoxy) phenyl]-1,1,1,3,3 of 2-, 3-HFC-236fa product 27.6g, productive rate 81%, purity 98.6% (HPLC).
Comparative example 1
The reaction solution that obtains with example 1 same procedure filters, and the filtrate decompression distillation adds C after the wet distillation
20～C
25Alkane solvent 20ml, 190 ± 2 ℃ of controlled temperature, pressure 0.1～0.2Pa carries out molecular distillation, has decomposing phenomenon to produce in the fraction collection process, extracts adding dehydrated alcohol 50ml in the cut of collecting, and stirs, leaves standstill the back and divide oil-yielding stratum, the C that obtains
20～C
25Alkane solvent recovery set usefulness desolventizes ethanol with alcohol layer underpressure distillation steaming, obtains light yellow oily 2, two [4-(3-nitro-phenoxy) phenyl]-1,1,1,3,3 of 2-, 3-HFC-236fa product 23.1g, productive rate 68%, purity 98.2% (HPLC).
As can be seen, too high from comparative example 1 when the temperature of molecular distillation, can cause in the fraction collection process and to produce decomposing phenomenon and then reduction productive rate because of temperature is high.
Comparative example 2
The reaction solution that obtains with example 1 same procedure filters, and underpressure distillation is after the wet distillation, 160 ± 2 ℃ of controlled temperature, pressure 0.1Pa carries out molecular distillation, obtains light yellow oily 2, two [4-(3-nitro-phenoxy) phenyl]-1 of 2-, 1,1,3,3,3-HFC-236fa product 25.6g, productive rate 75%, purity 98.1% (HPLC).
As can be seen, the use of high boiling solvent if the cancellation high boiling solvent can cause productive rate to descend, therefore must be used high boiling solvent for guaranteeing that good productive rate is very important from comparative example 2.
Claims (5)
1. one kind 2, two [4-(3-nitro-phenoxy) phenyl]-1,1,1,3,3 of 2-, the method for purification of 3-HFC-236fa is characterized in that comprising the steps:
Meta-dinitrobenzene, hexafluoro bisphenol-a are dissolved in reaction solvent N, in the dinethylformamide, carry out condensation with salt of wormwood, with resulting reacting liquid filtering, vacuum distillation recovered solvent, wet distillation is removed low molecular weight impurities and remaining Meta-dinitrobenzene and N, and dinethylformamide adds high boiling solvent, at 150-165 ℃, 0.01-0.2Pa condition under molecular distillation, adopt extraction agent from distillate, to collect target product, described high boiling solvent is C
15～C
30Alkane solvent; Said extraction agent is C
1～C
3No water unit alcohol in a kind of.
2. method according to claim 1 is characterized in that high boiling solvent is C
20～C
25Alkane solvent.
3. method according to claim 1 is characterized in that extraction agent is a dehydrated alcohol.
4. method according to claim 1, the consumption that it is characterized in that high boiling solvent is a hexafluoro bisphenol-a: high boiling solvent=1.0: 0.2～2.0, weightmeasurement ratio.
5. method according to claim 1, the consumption that it is characterized in that extraction agent is a hexafluoro bisphenol-a: extraction agent=1.0: 2.0～5.0, weightmeasurement ratio.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200510023334 CN100556887C (en) | 2005-01-14 | 2005-01-14 | 2, two [4-(3-nitro-phenoxy) phenyl]-1,1,1,3,3 of 2-, the method for purification of 3-HFC-236fa |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200510023334 CN100556887C (en) | 2005-01-14 | 2005-01-14 | 2, two [4-(3-nitro-phenoxy) phenyl]-1,1,1,3,3 of 2-, the method for purification of 3-HFC-236fa |
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|---|---|
| CN1803759A CN1803759A (en) | 2006-07-19 |
| CN100556887C true CN100556887C (en) | 2009-11-04 |
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| CN 200510023334 Expired - Fee Related CN100556887C (en) | 2005-01-14 | 2005-01-14 | 2, two [4-(3-nitro-phenoxy) phenyl]-1,1,1,3,3 of 2-, the method for purification of 3-HFC-236fa |
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