CN105152937B - A kind of low temperature quickly prepares 2,2 two（4‑（4 amino-benzene oxygens) phenyl）The method of HFC-236fa and its intermediate - Google Patents
A kind of low temperature quickly prepares 2,2 two（4‑（4 amino-benzene oxygens) phenyl）The method of HFC-236fa and its intermediate Download PDFInfo
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- CN105152937B CN105152937B CN201510391850.3A CN201510391850A CN105152937B CN 105152937 B CN105152937 B CN 105152937B CN 201510391850 A CN201510391850 A CN 201510391850A CN 105152937 B CN105152937 B CN 105152937B
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Abstract
The present invention provides a kind of low temperature and quickly prepares 2,2 two（4‑（4 amino-benzene oxygens) phenyl）The method of HFC-236fa intermediate, described 2,2 two（4‑（4 amino-benzene oxygens) phenyl）HFC-236fa intermediate is 2,2 two（4‑（4 nitro-phenoxies) phenyl）HFC-236fa, by 2,2 two（4 hydroxy phenyls）HFC-236fa and para-halo nitrobenzene are reacted in the presence of solvent, catalyst A and alkali, obtain 2,2 two（4‑（4 nitro-phenoxies) phenyl）HFC-236fa.The present invention also provides low temperature and quickly prepares 2,2 two（4‑（4 amino-benzene oxygens) phenyl）The method of HFC-236fa.The present invention uses reaction at low-temperature operation, 65~80 DEG C just to complete the preparation of intermediate in 8 hours；The method of the present invention can improve product yield, and yield is more than 78%；Production cost can be reduced simultaneously.
Description
Technical field
The invention belongs to compound technical, and in particular to a kind of low temperature quickly prepares (4- (the 4- aminobenzene oxygen of 2,2- bis-
Base) phenyl) HFC-236fa and its intermediate method.
Background technology
2,2- bis- (4- (4- amino-benzene oxygens) phenyl) HFC-236fas (abbreviation 4-BDAF), English name 2,2-bis (4-
(4-aminophenoxy (- phenyl)-hexa-fluoropropane, molecular formula：C27H20F6N2O2, structural formula such as formula (I)
It is shown：
4-BDAF be prepare Thin Film Transistor-LCD (TFT-LCD) with the primary raw material of liquid crystal aligning material it
One, and be widely used in and produce fluorine-containing vulcanization accelerator and thermoplastic resin, in WO02100949, WO2004011528,
Related in US5504128.
Existing 4-BDAF preparation method mainly has following several：
Method one：Reaction equation is as follows
In US4111906, first by (4- hydroxy phenyls) HFC-236fas of 2,2- bis- and sodium hydroxide in N, N- dimethyl second
Acid amides and reflux in toluene point water, prepare the double sodium salt of 2,2- bis- (4- hydroxy phenyls) HFC-236fa, then again and to chlorine nitro
Benzene is reacted 48 hours in 150 DEG C, and reaction solution is poured into water, and separates out 2,2- bis- (4- (4-nitrophenoxy) phenyl) hexafluoro third
Alkane, after 2,2- bis- (4- (4-nitrophenoxy) phenyl) HFC-236fa is purified by ethyl alcohol recrystallization, with iron powder/hydrochloric acid system
Reduction, obtains target product 4-BDAF.
In such a method, reaction temperature is up to 150 DEG C, and the double sodium salt of 2,2- bis- (4- hydroxy phenyls) HFC-236fa and
The parachloronitrobenzene reaction time is up to 48 hours.And during the separation of 2,2- bis- (4- (4-nitrophenoxy) phenyl) HFC-236fa, need
It is poured into water and filters out solid, produces a large amount of waste water containing DMA, be extremely not suitable for industrial production.
Method two：Reaction equation is as follows
In US5043478, and method one is comparatively, the system of the double sodium salt of 2,2- bis- (4- hydroxy phenyls) HFC-236fas
During standby, nitrogen protection is employed, sodium hydroxide is added portionwise in addition, then again with parachloronitrobenzene in 150 DEG C of reactions, and
Reaction time has narrowed down to 4 hours.But the post processing of 2,2- bis- (4- (4-nitrophenoxy) phenyl) HFC-236fas, or will
Reaction solution is poured into the mixed liquor of first alcohol and water, 2,2- bis- (4- (4-nitrophenoxy) phenyl) HFC-236fa is separated out, by 2,2-
After two (4- (4-nitrophenoxy) phenyl) HFC-236fas are by ethyl acetate and methanol mixed solvent recrystallization purification, Pd/C is urged
Under change, hydrogen reducing obtains target product 4-BDAF.
In such a method, compare and improve to some extent with method one, also there is larger shortening in the reaction time, but reaction temperature is still
Up to 150 DEG C.And, it is necessary to be poured into the mixing of first alcohol and water during the separation of 2,2- bis- (4- (4-nitrophenoxy) phenyl) HFC-236fa
In liquid, solid is filtered out, a large amount of waste water containing DMA and methanol is produced, is still not suitable for industrial production.
Method three：Reaction equation is as follows
In the method that Zhang Jianli etc. (liquid crystal and display, 2009,3,345-349) is used, 2,2- bis- (4- hydroxy phenyls)
HFC-236fa and sodium hydroxide are in DMA, first in 70~80 DEG C of reaction generation 2,2- bis- (4- hydroxy phenyls)
The double sodium salt of HFC-236fa, is then added dropwise parachloronitrobenzene, in 5 hours reaction time, reaction is finished in 140 DEG C, and vacuum distillation is returned
Most DMA is received, leftover materials are poured into water, separate out 2,2- bis- (4- (4-nitrophenoxy) phenyl)
HFC-236fa, the mixed solvent of (4- (4-nitrophenoxy) phenyl) the HFC-236fa ethanol of 2,2- bis- and toluene is recrystallized
Afterwards, under Pd/C catalysis, hydrogen reducing obtains target product 4-BDAF.
Such a method, although reclaimed most of DMA, still, the DMA of recovery
In contain moisture, it is impossible to recovery.And reaction temperature is up to 140 DEG C.And a large amount of waste water generations are still had, be not suitable for
Industrial production.
The content of the invention
The main object of the present invention is to solve above-mentioned a variety of drawbacks of the 4-BDAF in preparation process to receive there is provided a kind of height
The method that rate, easy to operate and environmentally friendly low temperature quickly prepare 4-BDAF and its intermediate.
By the unremitting effort of inventor, the preparation in 2,2- bis- (4- (4-nitrophenoxy) phenyl) HFC-236fa is found
During, from suitable solvent, in the presence of catalyst A and alkali, can very easily it be reacted, reaction temperature is low
And the time is short；Reaction can be carried out in less expensive solvent, easy to operate control, and product yield and product content are equal
Compare high.2,2- bis- (4- (4-nitrophenoxy) phenyl) HFC-236fa of this step operation preparation, can very easily be reduced into
2,2- bis- (4- (4- amino-benzene oxygens) phenyl) HFC-236fas.
Reaction scheme is as follows：
The present invention provides a kind of low temperature and quickly prepares 2,2- bis- (4- (4- amino-benzene oxygens) phenyl) HFC-236fa intermediate
Method, 2,2- bis- (4- (4- amino-benzene oxygens) phenyl) the HFC-236fa intermediate be (4- (the 4- nitrobenzene oxygen of 2,2- bis-
Base) phenyl) HFC-236fa is in solvent, catalyst A by (4- hydroxy phenyls) HFC-236fas of 2,2- bis- and para-halo nitrobenzene
And reacted in the presence of alkali, obtain 2,2- bis- (4- (4-nitrophenoxy) phenyl) HFC-236fa；Wherein：
Described para-halo nitrobenzene, preferably is selected from parachloronitrobenzene, p-fluoronitrobenzene；Both are commonly used, and are easy to get, just
Preferably.Activity is higher；And bromo nitryl benzene activity is not high, reaction yield is bad.
Described alkali, preferably is selected from potassium carbonate, sodium carbonate, potassium hydroxide, sodium hydroxide；From this several conventional alkali, easily
, cheaply.
Described solvent, one kind in following (1) or (2)：
(1) water；
(2) one or more kinds of mixtures in water and ethanol, methanol, acetone；
Described catalyst A, the mixture of the one or two kinds of in following C-1 and C-2 structures：
C-1 is:Double [di-t-butyl-(4- dimethylaminophenyls) phosphine] palladium chlorides (II), C-2 is:Double [two tertiary fourths
Base-(4- diethylaminos phenyl) phosphine] palladium chloride (II).
Two kinds of catalyst can be mixed with arbitrary proportion, can reach preferable catalytic effect.
Preferably, the consumption of the catalyst A is the amount of the material of 2,2- bis- (4- hydroxy phenyls) HFC-236fa
0.01%~1%；Preferably, the consumption of the catalyst A is the amount of the material of 2,2- bis- (4- hydroxy phenyls) HFC-236fa
0.02%~0.2%.Catalyst has preferable yield and a quality within this range, improve catalyst usage amount to product quality and
Yield influence is not particularly significant.Therefore, from low catalyst levels, (catalyst A consumption is (the 4- hydroxyls of 2,2- bis- in the reaction
Phenyl) HFC-236fa material amount 0.02%~0.2%).
Preferably, when preparing 2,2- bis- (4- (4-nitrophenoxy) phenyl) HFC-236fa, reaction temperature is 65~80
℃.Product content and total yield of products are high in this range of reaction temperature.
Preferably, the solvent is water.
Preferably, the solvent is the mixture of water and acetone；Or the mixture that the solvent is water and ethanol；Or it is described
Solvent is the mixture of water and methanol；Or the mixture that the solvent is water and ethanol and acetone.
Further, the mass content of the water in a solvent is 40-99%.
It is highly preferred that the mass content of the water in a solvent is 80-99%.Low sweetening agent gets up with water content,
The high solvent yield of water content and product quality are without clear superiority, but water, as solvent, inexpensively, environmental protection, cost is low, with equivalent
Really, how more economical water is.
Preferably, by 2,2- bis- (4- hydroxy phenyls) HFC-236fa, para-halo nitrobenzene, solvent, catalyst A, once
Property add in reaction vessel, reacted in 65~80 DEG C 8 hours, after completion of the reaction, be cooled to 1 DEG C, filtering obtains the (4- of 2,2- bis-
(4-nitrophenoxy) phenyl) HFC-236fa crude product；By crude product through recrystallization, (4- (4-nitrophenoxy) benzene of 2,2- bis- is obtained
Base) HFC-236fa fine work.
The present invention also provides the side that a kind of low temperature quickly prepares 2,2- bis- (4- (4- amino-benzene oxygens) phenyl) HFC-236fa
Method, step is as follows：
(1) 2,2- bis- (4- (4- amino-benzene oxygens) phenyl) hexafluoro is prepared according to any described methods of claim 1-7
Propane intermediate, i.e. 2,2- bis- (4- (4-nitrophenoxy) phenyl) HFC-236fa；
(2) 2,2- bis- (4- (4-nitrophenoxy) phenyl) HFC-236fa for preparing step (1) is added in ethyl acetate,
In the presence of Pd/C, 2,2- bis- (4- (4- amino-benzene oxygens) phenyl) HFC-236fa is prepared with hydrogen reducing.
Preferably, the pressure of reduction reaction is 0.05MPa in step (2), and reaction temperature is 20-40 DEG C.
The method of the present invention uses reaction at low-temperature operation, 65-80 DEG C just to complete within 8 hours the preparation of intermediate, this
The method of invention can improve product yield, and yield reduces production cost more than 78%.
Brief description of the drawings
Accompanying drawing is used for providing a further understanding of the present invention, and constitutes a part for specification, the reality with the present invention
Applying example is used to explain the present invention together, is not construed as limiting the invention.In the accompanying drawings：
Fig. 1 is the HPLC collection of illustrative plates of the final product of the embodiment of the present invention 1.
Embodiment
Following embodiment facilitates a better understanding of the present invention, but does not limit the present invention.Experiment in following embodiments
Method, is conventional method unless otherwise specified.Test material used, is city unless otherwise specified in following embodiments
Sell.
Embodiment 1
Prepare 1000 milliliters of there-necked flasks, be equipped with mechanical agitation and distilling apparatus, add 2,2- bis- (4- hydroxy phenyls) hexafluoro
Propane 33.6g (0.1mol), water 400g, C-10.007g (0.00001mol) potassium carbonate 27.6g (0.2mol), parachloronitrobenzene
34.66g (0.22mol), under nitrogen protection, is warming up to 70 DEG C, reacts 8 hours, be cooled to 1 DEG C, filter, dry, resulting
Solid is recrystallized with 800 milliliters of ethanol and 200 milliliters of ethyl acetate mixed solvents, obtains (the 4- (4-nitrophenoxy) of 2,2- bis-
Phenyl) HFC-236fa 54.9g.HPLC 99.6%, mp159.7 DEG C；Yield 95%.
2,2- bis- (4- (4-nitrophenoxy) phenyl) HFC-236fa 54.9g, ethyl acetate is added in stainless steel hydrogenation kettle
600 milliliters, 5% palladium carbon 8g after nitrogen displacement, in 30 DEG C, after control 0.05MPa hydrogen reducings react 6 hours, has reacted
Finish.Stop after reaction, nitrogen displacement, taking-up material, Filtration of catalyst, be concentrated under reduced pressure removing ethyl acetate, and what is obtained consolidates
Body obtains white crystal (being 2,2- bis- (4- (4- aminophenoxy phenyls)) HFC-236fa) with 5 times of ethyl alcohol recrystallizations
43.6g, HPLC 99.8%, mp162.7 DEG C of yield 88.6%, product HPLC spectrograms are shown in Fig. 1.Content is calculated using the spectrogram
Method is referring to table 1.
Table 12, the calculating of 2- bis- (4- (4- amino-benzene oxygens) phenyl) HFC-236fa content
Two-step reaction total recovery 84.2%.
Embodiment 2 is to embodiment 33
In embodiment 2- embodiments 33, the difference is that preparing 2,2- bis- (4- (4-nitrophenoxy) phenyl) hexafluoro third
During alkane, the species of halogenated nitrobenzene, the species and ratio of solvent, the species and consumption of catalyst, the species of alkali, reaction temperature
The one or more spent in differing, remaining design parameter and consumption and preparation method are same as Example 1, actual conditions
As shown in table 2A and table 2B：
Table 2A embodiment 2- embodiments 20
Table 2B embodiment 21- embodiments 33
Finally it should be noted that：The preferred embodiments of the present invention are the foregoing is only, are not intended to limit the invention,
Although the present invention is described in detail with reference to the foregoing embodiments, for those skilled in the art, it still may be used
To be modified to the technical scheme described in foregoing embodiments, or equivalent substitution is carried out to which part technical characteristic.
Within the spirit and principles of the invention, any modification, equivalent substitution and improvements made etc., should be included in the present invention's
Within protection domain.
Claims (10)
1. a kind of low temperature quickly prepares 2,2- bis-（4-（4- amino-benzene oxygens) phenyl）The method of HFC-236fa intermediate, described 2,
2- bis-（4-（4- amino-benzene oxygens) phenyl）HFC-236fa intermediate is 2,2- bis-（4-（4-nitrophenoxy) phenyl）Hexafluoro third
Alkane, it is characterised in that：By 2,2- bis-（4- hydroxy phenyls）HFC-236fa and para-halo nitrobenzene are in solvent, catalyst A and alkali
In the presence of reacted, reaction temperature be 65~80 DEG C, the reaction time be 8 hours, obtain 2,2- bis-（4-（4- nitros
Phenoxy group) phenyl）HFC-236fa；Wherein：
Described para-halo nitrobenzene, selected from parachloronitrobenzene or p-fluoronitrobenzene；
Described alkali, selected from potassium carbonate, sodium carbonate, one kind in potassium hydroxide or sodium hydroxide；
Described solvent, selected from following（1）Or（2）In one kind：
（1）Water；
（2）It is more than the one or two kinds of in ethanol, methanol, acetone and water mixture, the quality of the water in a solvent contains
Measure as 40-99%；
Described catalyst A, the mixture of the one or two kinds of in following C-1 and C-2 structures：
C-1 is:Double [di-t-butyl-(4- dimethylaminophenyls) phosphine] palladium chlorides (II), C-2 is:Double [di-t-butyls-(4-
Diethylamino phenyl) phosphine] palladium chloride (II).
2. according to the method described in claim 1, it is characterised in that：The consumption of the catalyst A is 2,2- bis-（4- hydroxy benzenes
Base）The 0.01%~1% of the amount of the material of HFC-236fa.
3. method according to claim 2, it is characterised in that：The consumption of the catalyst A is 2,2- bis-（4- hydroxy benzenes
Base）The 0.01%~0.2% of the amount of the material of HFC-236fa.
4. according to the method described in claim 1, it is characterised in that：The solvent is water.
5. according to the method described in claim 1, it is characterised in that：The solvent is the mixture of water and acetone；Or it is described molten
Agent is the mixture of water and ethanol；Or the mixture that the solvent is water and methanol；Or the solvent is water and ethanol and acetone
Mixture.
6. according to the method described in claim 1, it is characterised in that：The mass content of the water in a solvent is 80-99%.
7. according to any described methods of claim 1-6, it is characterised in that：By 2,2- bis-（4- hydroxy phenyls）HFC-236fa,
Para-halo nitrobenzene, solvent, catalyst A is disposable to add in reaction vessel, is reacted 8 hours in 65~80 DEG C, reaction is finished
Afterwards, 1 DEG C is cooled to, filtering obtains 2,2- bis-（4-（4-nitrophenoxy) phenyl）HFC-236fa crude product；By crude product through tying again
Crystalline substance, obtains 2,2- bis-（4-（4-nitrophenoxy) phenyl）HFC-236fa fine work.
8. according to the method described in claim 1, it is characterised in that：By 2,2- bis-（4- hydroxy phenyls）HFC-236fa, water, C-1,
Potassium carbonate, parachloronitrobenzene are disposably added in reaction vessel, under nitrogen protection, are warming up to 70 DEG C, are reacted 8 hours, cooling
To 1 DEG C, filter, dry, resulting solid ethanol and ethyl acetate mixed solvent recrystallization obtain 2,2- bis-（4-（4- nitre
Phenoxyl) phenyl）HFC-236fa；
Wherein, 2, the 2- bis-（4- hydroxy phenyls）The amount ratio of the material of HFC-236fa and parachloronitrobenzene is 10:22；
The consumption of the C-1 is 2,2- bis-（4- hydroxy phenyls）The 0.01% of the amount of the material of HFC-236fa；
The volume ratio of the ethanol and ethyl acetate is 4:1.
9. a kind of low temperature quickly prepares 2,2- bis-（4-（4- amino-benzene oxygens) phenyl）The method of HFC-236fa, it is characterised in that：
Step is as follows：（1）2,2- bis- is prepared according to any described methods of claim 1-8（4-（4- amino-benzene oxygens) phenyl）Six
Fluoro-propane intermediate, i.e. 2,2- bis-（4-（4-nitrophenoxy) phenyl）HFC-236fa；
（2）By step（1）2, the 2- bis- prepared（4-（4-nitrophenoxy) phenyl）HFC-236fa is added in ethyl acetate,
In the presence of Pd/C, 2,2- bis- is prepared with hydrogen reducing（4-（4- amino-benzene oxygens) phenyl）HFC-236fa.
10. method according to claim 9, it is characterised in that：Step（2）The pressure of middle reduction reaction is 0.05MPa, instead
It is 20-40 DEG C to answer temperature.
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| CN201510391850.3A CN105152937B (en) | 2015-07-06 | 2015-07-06 | A kind of low temperature quickly prepares 2,2 two（4‑（4 amino-benzene oxygens) phenyl）The method of HFC-236fa and its intermediate |
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Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4111906A (en) * | 1976-07-19 | 1978-09-05 | Trw Inc. | Polyimides prepared from perfluoroisopropylidene diamine |
| US5043478A (en) * | 1989-04-18 | 1991-08-27 | Ethyl Corporation | Process for the preparation of fluorinate aromatic diamine |
| CN1907952A (en) * | 2006-08-11 | 2007-02-07 | 上海市合成树脂研究所 | Preparation method of 2,2-di[4-(4-amidophenoxy)phenyl]hexafluoropropane |
| CN101239919B (en) * | 2008-01-11 | 2011-01-12 | 南京工业大学 | Synthetic method of aromatic diamine monomer |
| CN103788020B (en) * | 2014-01-22 | 2015-11-04 | 苏州明锐医药科技有限公司 | The fertile preparation method for Xi Ting |
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