CN104710331B - Synthetic method of benzene series overhang strand-containing difluorodiphenyl sulfone - Google Patents
Synthetic method of benzene series overhang strand-containing difluorodiphenyl sulfone Download PDFInfo
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- CN104710331B CN104710331B CN201510057582.1A CN201510057582A CN104710331B CN 104710331 B CN104710331 B CN 104710331B CN 201510057582 A CN201510057582 A CN 201510057582A CN 104710331 B CN104710331 B CN 104710331B
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- benzene series
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Abstract
The invention belongs to the field of synthesis of difluorodiphenyl sulfone compounds, and discloses a synthetic method of benzene series overhang strand-containing difluorodiphenyl sulfone, that is a water extraction and alkali addition method. The synthetic method of benzene series overhang strand-containing difluorodiphenyl sulfone comprises the following steps: brominating difluorodiphenyl sulfone to prepare difluorodiphenyl sulfone bromide, and reacting the difluorodiphenyl sulfone bromide with benzene series boric acid to synthesize the benzene series overhang strand-containing difluorodiphenyl sulfone. In the synthesis process, toluene is adopted as a water carrying agent to carry out water in a reaction system, the reaction temperature is improved, and alkalinity decreasing in the reactions system due to alkali consumption is compensated, so the reaction yield is improved. The synthetic method of benzene series overhang strand-containing difluorodiphenyl sulfone has the characteristics fo easily available raw materials, simple steps, easy product purification, high yield, short reaction time and the like. The product plays a great role in the synthesis design of polymers with related structures, and especially in the synthesis design of sulfonated polyaryl ester sulfone proton exchange membranes.
Description
Technical field
This patent belongs to difluoro aryl compound synthesis field, particularly a kind of containing benzene series pendency chain difluorodiphenyl
The synthesis of sulphones.
Background technology
Difluoro aryl compound is organic chemical industry's intermediate that a class is important, can be used for aromatic thermoplastic engineering material and gathers
The synthesis of aryl oxide；Meanwhile, also it is for medicine, dyestuff, the important intermediate of pesticide synthesis, is the important fine chemistry of a class
Product.Phenyl and substituted-phenyl are the organo-functional groups that a class is important, introduce, Ke Yiyou on the aryl skeleton main chain of polyether sulphone
Effect improves polyether sulphone nanometer middle aqueous favoring mutually and separates with hydrophobic phase, thus improves the ion exchange capacity of PEM
(IEC, Ion exchange capacity).
CN103694152 discloses a kind of synthesis method containing the difluorobenzene sulfone of methyl substituted-phenyl pendency side base:
Wherein R1For H or Br；R2ForOr。
This patent has pertained only to two kinds of substituted-phenyls, is of limited application；And the method uses silicon in purification process
Glue post, is not suitable for the purification of large-tonnage product.
It is relatively wide that the water lift that this patent proposes increases the alkaline process scope of application, can be widely applied to changing of difluorodiphenyl sulfone monomer
Property, and then polyether sulphone is modified.
Summary of the invention
In correlated response, often selecting toluene is solvent, and alkaline environment is K2CO3Or Na2CO3Aqueous solution, reaction condition
It it is 110 DEG C.According to we have discovered that, the method productivity of common backflow is relatively low.Along with reaction is carried out, alkali gradually uses up and causes alkali
Property reduce, thus prepare two benzene homologues replace, three benzene homologues replace and four benzene homologues replace time, a phenyl substituent more and
The productivity of target product is relatively low.
In order to overcome the shortcoming and defect of said method, through a large amount of and detailed research and test, the invention
Propose for benzene series pendency chain difluorodiphenyl sulfone synthesis water lift increase alkaline process.Because toluene can form good being total to water
Boiling system, its azeotropic point raises along with the reduction of water content, and azeotropic point scope is 85-110 DEG C；And such reaction generally choosing
With toluene as reaction dissolvent, then select it as water entrainer under conditions of not introducing the 3rd component.Carried out by toluene
Band water thus improve the problem that the reaction system neutral and alkali caused due to alkali consumption in reaction temperature, and compensatory reactionBu Changfanying declines, enter
And synthesize the difluorodiphenyl sulfone containing benzene series pendency chain.
The purpose of the present invention is realized by following proposal:
Containing shown in benzene series pendency chain difluorodiphenyl sulphones structure such as formula ():
Formula (one)
Wherein, R be H,、 、Or；
Wherein, R1For-F ,-CH3、-NO2、-CHO、-CF3、-COOH、OrEtc. substituent group.
The above-mentioned synthesis containing benzene series pendency chain difluorodiphenyl sulphones is by bromination difluorodiphenyl sulfone and benzene series boric acid
Reaction realizes.
The difluorodiphenyl sulfone of above-mentioned bromination has a structure shown in formula (two):
Formula (two)
Wherein, R2For H or Br, and at least one is Br.
Reaction equation is shown below
Wherein, R2For H or Br, and at least one is Br； R3For H, 、Or；
Wherein, R1For-F ,-CH3、-NO2、-CHO、-CF3、-COOH、OrEtc. substituent group.
Above-mentioned synthetic method specifically comprises following two step:
Synthesis phase: bromination difluorodiphenyl sulfone and benzene series boric acid are dissolved in toluene, under an inert atmosphere add catalyst and
Alkaline aqueous solution, reacting by heating, utilize solvent toluene to carry out band water, so that temperature of reaction system raises and compensatory reactionBu Changfanying process
In due to the consumption of alkali cause alkalescence reduction, high yield generate target product；
Purification phase: decompression is distilled off solvent, after dichloromethane dissolves separated out solid, wash with water solution extremely in
Property.Organic facies rotation is evaporated off, after toluene dissolved solid recrystallization, obtains the difluorodiphenyl sulfone containing benzene series pendency chain.
Above-mentioned reaction utilizes such as the device of Fig. 1.
Described inert atmosphere is the one in nitrogen or argon.
Described catalyst is at least one in tetrakis triphenylphosphine palladium, Palladous chloride. or acid chloride.
Described alkali is at least one in sodium carbonate, potassium carbonate, sodium phosphate or potassium phosphate.
The described band water time is more than 1.5h.
Described heating condition reacts more than 5h at being 100-110 DEG C.
Described Dean-Stark device is a kind of glass apparatus conventional in chemosynthesis, its usual and reflux condenser
It is used in conjunction to ensure can be taken out of continuously by moisture present in reaction system at a reflux temperature.
Above-mentioned have multiple sulfonation site containing benzene series pendency chain difluorodiphenyl sulfone, can effectively improve the poly-virtue of sulfonation
The sulfonation group number of ether sulfone, thus improve the proton exchange capacity of PEM；Not homoatomic, the drawing of group in benzene homologues
Enter, can effectively study it to PEM performance impact；The introducing of pendency benzene homologues, can be effectively improved microcosmic knot
On structure, aqueous favoring separates with hydrophobic phase, improves proton transport speed.
The mechanism of the present invention is:
The present invention synthesizes the difluorodiphenyl sulfone containing benzene series pendency chain from the angle of MOLECULE DESIGN, is first that palladium plays catalysis work
Organic palladium compound is generated with bromination difluorodiphenyl sulfone effect.Next to that alkalescence condition activates as lewis acidic benzene series boron
Compound.With the introducing of water process, make water take out of from reaction system, on the one hand improve reaction temperature, accelerate reaction rate and effect
Rate；On the other hand the alkalescence of raising reaction environment, thus the reaction system neutral and alkali caused due to alkali consumption in compensatory reactionBu Changfanying
Decline；And due to the minimizing of moisture in reaction system, cause the Bromide generated in course of reaction to separate out, promote to react into
OK.Finally, organic palladium compound is reduced to palladium and completes C-C coupling.
The present invention, relative to prior art, has the advantage that and beneficial effect:
Gained of the present invention have containing pendency benzene homologues difluorodiphenyl sulphones that raw material is easy to get, step is simple, product
It is prone to purification, productivity relatively high.Gained contains pendency benzene homologues difluorodiphenyl sulfone, has multiple sulfonation site, Ke Yiyou
Effect ground improves the sulfonation group number of sulfonated polyether sulphone, thus improves the proton exchange capacity of PEM；In benzene homologues not
Homoatomic, the introducing of group, can study it effectively to PEM performance impact；The introducing of pendency benzene homologues, permissible
It is effectively improved aqueous favoring in microstructure to separate with hydrophobic phase, improves proton transport speed.Such difluorodiphenyl sulfone derives
Thing is the Polymer Synthesizing intermediate that a class is important, is with a wide range of applications.
Accompanying drawing explanation
Fig. 1 is the reaction unit figure that water lift increases alkaline process, wherein 1-condensing tube, 2-water knockout drum, the thermometer wrap of 3-band arm
Pipe, 4-thermometer, 5-mechanical agitator, 6-oil bath device.
Fig. 2 is the reaction unit figure of comparative example 1,2, wherein 1-condensing tube, the thermometer boss of 2-band arm, 3-temperature
Meter, 4-mechanical agitator, 5-oil bath device.
Detailed description of the invention
Below in conjunction with embodiment, the present invention will be further described.
Embodiment 1:3,3 ' synthesis of-diphenyl 4,4 '-difluorodiphenyl sulfone
250mL with Dean-Stark device, mechanical agitation, thermometer boss there-necked flask in add 1.65g
(4mmol) 3,3 '-two bromo-4,4 '-difluorodiphenyl sulfone and 30mL toluene, treat 3,3 '-two bromo-4, after 4 '-difluorodiphenyl sulfone dissolves
Adding 1.07g (8.8mmol) phenylboric acid, oil bath is heated to 50 DEG C and opens nitrogen protection.After being passed through nitrogen 30min, to instead
Answer and bottle adds 20mL 10wt.% aqueous sodium carbonate and 0.1g tetrakis triphenylphosphine palladium.Oil bath temperature is increased to 100 DEG C,
Utilizing solvent to carry out band water reaction, after a period of time, be warming up to 110 DEG C, in question response system, moisture is taken out of completely, is taken
Between maintain 1.5-2h.After reaction, rotation is steamed solvent and is obtained solid, utilizes dichloromethane dissolved solid, and water washing dichloromethane is molten
Liquid, to neutral, take organic facies and carries out rotation dichloromethane solvent is evaporated off, then utilize re crystallization from toluene to obtain white solid twice
3,3 '-diphenyl 4,4 '-difluorodiphenyl sulfone, productivity is 85.4%.
1H NMR (400Hz, DMSO-d6; ppm): 8.2(2H); 7.5(14H)。
Reaction equation is as follows:
Reaction unit is as shown in Figure 1.
Comparative example 1:
250mL with condensing tube, mechanical agitation, thermometer boss there-necked flask in add 1.65g (4mmol) 3,3 '-
Two bromo-4,4 '-difluorodiphenyl sulfone and 30mL toluene, treat 3,3 '-dibromo 4,4 '-difluorodiphenyl sulfone adds 1.07g after dissolving
(8.8mmol) phenylboric acid, oil bath is heated to 50 DEG C and opens nitrogen protection.After being passed through nitrogen 30min, add in reaction bulb
20mL 10wt.% aqueous sodium carbonate and 0.1g tetrakis triphenylphosphine palladium.Oil bath temperature is increased to 110 DEG C, now reacts temperature
Degree is increased to 92 DEG C, and after this system back flow reaction 5h, rotation is steamed solvent and obtained solid, uses dichloromethane dissolved solid, distillation washing
Wash dichloromethane solution the most neutral, take organic facies and carry out rotation steaming, utilize re crystallization from toluene to obtain white solid 3,3 '-hexichol for twice
Base-4,4 '-difluorodiphenyl sulfone, productivity is 15.4%.
Reaction equation is as follows:
1H NMR (400Hz, DMSO-d6; ppm): 8.2(2H); 7.5(14H)。
Reaction unit is illustrated in fig. 2 shown below.
From the results contrast of embodiment 1 with 1 two kinds of methods of comparative example, use the productivity increase of water lift increase and decrease method about
70%。
Comparative example 2:
250mL with condensing tube, mechanical agitation, thermometer boss there-necked flask in add 1.65g (4mmol) 3,3 '-
Two bromo-4,4 '-difluorodiphenyl sulfone and 30mL toluene, treat 3,3 '-dibromo 4,4 '-difluorodiphenyl sulfone adds 1.07g after dissolving
(8.8mmol) phenylboric acid, oil bath is heated to 50 DEG C and opens nitrogen protection.After being passed through nitrogen 30min, add in reaction bulb
2.2g sodium carbonate and 0.1g tetrakis triphenylphosphine palladium.Oil bath temperature is increased to 110 DEG C, and now reaction temperature is 110 DEG C, maintains
This thermotonus 5h.Rotation steam solvent obtain solid, use dichloromethane dissolved solid, distilled water wash dichloromethane solution in
Property, taking organic facies carries out rotation steaming, then utilizes re crystallization from toluene twice, carries out nmr analysis, does not finds product.
From the results contrast of embodiment 1 with 2 two kinds of methods of comparative example, when reaction system does not contains moisture, by
Being aprotic solvent in solvent, so sodium carbonate cannot play the effect providing alkalescence, reaction cannot be carried out, so this reaction needs
Aquo System is carried out.
The synthesis of embodiment 2:3,3 ', 5,5 '-tetraphenyl-4,4 '-difluorodiphenyl sulfone
250mL with Dean-Stark device, mechanical agitation, thermometer boss there-necked flask in add 2.28g
(4mmol) 3,5,3 ', 5 '-four bromo-4,4 '-difluorodiphenyl sulfone and 30mL toluene, treat 3,3 '-dibromo 4,4 '-difluorodiphenyl sulfone is molten
Adding 2.05g (16.8mmol) phenylboric acid after solution, oil bath is heated to 50 DEG C and opens nitrogen protection.It is being passed through nitrogen 30min
After, in reaction bulb, add 10wt.% wet chemical 40mL and 0.2g tetrakis triphenylphosphine palladium.Oil bath temperature is increased to
100 DEG C, utilizing solvent to carry out band water reaction, after a period of time, be warming up to 110 DEG C, in question response system, moisture is taken out of completely,
Required time maintains 1.5-2h.After reaction, rotation is steamed solvent and is obtained solid, utilizes dichloromethane dissolved solid, water washing dichloro
Dichloromethane, to neutral, take organic facies and carries out rotation and steam, and then utilizes re crystallization from toluene to obtain white solid 3 for twice, 3 ', 5,5 '-
Tetraphenyl-4,4 '-difluorodiphenyl sulfone, productivity is 82.3%.
Reaction equation is as follows:
1H NMR(400Hz, DMSO-d6; ppm) : 7.45-7.55(12H), 7.46-7.58 (8H), 8.02-
8.04 (4H)。
Embodiment 3:3,3 '-two (4-methylbenzene)-4,4 ' synthesis of-difluorodiphenyl sulfone
250mL with Dean-Stark device, mechanical agitation, thermometer boss there-necked flask in add 1.65g
(4mmol) 3,3 '-two bromo-4,4 '-difluorodiphenyl sulfone and 30mL toluene, treat 3,3 '-two bromo-4, after 4 '-difluorodiphenyl sulfone dissolves
Addition 1.32g (8.8mmol) is to methylphenylboronic acid, and oil bath is heated to 50 DEG C and opens nitrogen protection.It is being passed through nitrogen 30min
After, in reaction bulb, add 20% aqueous potassium phosphate solution 20mL and 0.1g palladium.Oil bath temperature is increased to 100 DEG C, utilizes molten
Agent carries out band water reaction, after a period of time, is warming up to 110 DEG C, and in question response system, moisture is taken out of completely, and required time maintains
At 1.5-2h.After reaction, rotation is steamed solvent and is obtained solid, utilizes dichloromethane dissolved solid, water washing dichloromethane solution in
Property, taking organic facies carries out rotation steaming, then utilizes re crystallization from toluene to obtain white solid for twice, 3,3 '-two (4-methylbenzene)-4,
4 '-difluorodiphenyl sulfone, productivity is 79.5%.
Reaction equation is as follows:
1H NMR(400Hz, DMSO-d6;Ppm): 2.37 (6H), 7.32-7.34 (4H), 7.48-7.50 (4H),
7.59-7.61(2H), 8.13-8.15(4H)。
The above, only presently preferred embodiments of the present invention, it is not limited to the present invention, all essences in the present invention
Any amendment, equivalent or the improvement etc. made within god and principle, should be included within the scope of the present invention.
Claims (7)
1. the synthetic method containing benzene series pendency chain difluorodiphenyl sulfone, for by suzuki reaction mechanism, with bromination difluoro two
Benzene sulfone and benzene series boric acid raw material, by the preparation of water lift increase and decrease method containing benzene series pendency chain difluorodiphenyl sulphones, i.e. in system
Middle utilize water entrainer that the water byproduct of reaction takes out of reaction system, improve in reaction temperature compensatory reactionBu Changfanying owing to alkali consumption is led
The decline of the reaction system neutral and alkali caused, thus preparation is containing benzene series pendency chain difluorodiphenyl sulphones；Its concrete side of synthesis
Method is as follows:
Synthesis phase: bromination difluorodiphenyl sulfone and benzene series boric acid are dissolved in toluene, adds catalyst and alkalescence under an inert atmosphere
Aqueous solution, reacting by heating, utilize solvent toluene to carry out band water so that temperature of reaction system raise and compensatory reactionBu Changfanying during by
The alkalescence reduction that consumption in alkali causes, high yield generates target product；
Purification phase: decompression is distilled off solvent, is washed with water to neutrality after dichloromethane solution modeling solid, revolves organic facies
Steam, after re crystallization from toluene, obtain the difluorodiphenyl sulfone containing benzene series pendency chain；
Shown in the architectural feature of its target product such as formula ():
Formula (one)
Wherein, R be H,、、Or；
Wherein, R1For-F ,-CH3、-NO2、-CHO、-CF3、-COOH、OrSubstituent group.
Preparation method containing benzene series pendency chain difluorodiphenyl sulphones the most according to claim 1, it is characterised in that:
Reaction unit introduces Dean-Stark device.
Preparation method containing benzene series pendency chain difluorodiphenyl sulfone the most according to claim 1, it is characterised in that: indifferent gas
Atmosphere is at least one in nitrogen or argon.
Preparation method containing benzene series pendency chain difluorodiphenyl sulfone the most according to claim 1, it is characterised in that: described
Catalyst is at least one in tetrakis triphenylphosphine palladium, Palladous chloride. or acid chloride.
Preparation method containing benzene series pendency chain difluorodiphenyl sulfone the most according to claim 1, it is characterised in that: described alkali
For at least one in sodium carbonate, potassium carbonate, sodium phosphate or potassium phosphate.
Preparation method containing benzene series pendency chain difluorodiphenyl sulfone the most according to claim 1, it is characterised in that: during band water
Between be more than 1.5h.
Preparation method containing benzene series pendency chain difluorodiphenyl sulfone the most according to claim 1, it is characterised in that: described
Reacting by heating condition reacts more than 5h at being 100-110 DEG C.
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| US5072049A (en) * | 1989-02-01 | 1991-12-10 | Basf Aktiengesellschaft | Process for the preparation of bis(4-hydroxyphenyl) sulfone |
| CN102757300B (en) * | 2012-05-31 | 2015-04-15 | 吉林奥来德光电材料股份有限公司 | Benzophenanthrene derivative, preparation method and light emitting device made thereof |
| CN103420878B (en) * | 2013-07-16 | 2014-12-17 | 常州大学 | Aromatic diamine monomer containing multi-trifluoromethyl structure and preparation method of aromatic diamine monomer |
| CN103694152A (en) * | 2013-12-20 | 2014-04-02 | 华南理工大学 | Difluorodiphenyl sulphone compound with pendent polymethyl-substituted-phenyl groups and synthesis method |
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