CN107973707A - The method that one kettle way prepares high-purity 4,4 '-difluorodiphenyl base ketone - Google Patents
The method that one kettle way prepares high-purity 4,4 '-difluorodiphenyl base ketone Download PDFInfo
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- CN107973707A CN107973707A CN201610921705.6A CN201610921705A CN107973707A CN 107973707 A CN107973707 A CN 107973707A CN 201610921705 A CN201610921705 A CN 201610921705A CN 107973707 A CN107973707 A CN 107973707A
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- C07—ORGANIC CHEMISTRY
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- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/45—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by condensation
- C07C45/46—Friedel-Crafts reactions
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- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/16—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation
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- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/58—Preparation of carboxylic acid halides
- C07C51/60—Preparation of carboxylic acid halides by conversion of carboxylic acids or their anhydrides or esters, lactones, salts into halides with the same carboxylic acid part
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Abstract
The method of 4, the 4 ' difluoro benzophenones prepared the invention discloses one kettle way, using 4 toluene fluorides as starting material; oxidized, F C are acylated condensation; multistage cooling fractional crystallization finally obtains 4,4 ' difluoro benzophenone of target product, and the fusing point of the product is 107 DEG C 109 DEG C; purity >=99.9%; present invention process is simple, and raw material is cheap and easy to get, and catalyst is easily recycled; the purity of product is high, is worthy to be popularized.
Description
Technical field
The present invention relates to the preparation field of fluoro-containing intermediate, and in particular to a kind of one kettle way prepares high-purity 4,4 '-difluoro
The method of diphenylketone.
Background technology
Polyether-ether-ketone has extremely outstanding physical and mechanical properties, is protruded mitigating quality, improving aspect of performance contribution,
With high temperature resistant, self-lubricating, wear-resistant and antifatigue characteristic, the trend of big substituted traditional metal materials, becomes now most
One of popular high performance engineering plastics.But polyether-ether-ketone is since developing, just always by as a kind of important strategic
Defence and military material, therefore many country's limitation outlets.
4,4 '-difluoro benzophenone (DFBP) is new hemicrystalline thermoplastic aromatic Engineering Plastics Polyetheretherketone
(PEEK) important synthesis precursor.Pharmaceutically, available for the potent cerebral vasodilators medicine of synthesizing new and treatment senile dementia
The medicine of class, is alternatively arranged as the preparation and charge control agent of optical recording and electrographic recording material, can also be used as some polymerisations
Initiator.
Aromatic fluoride market development at present is rapid, as PEEK is in military project, aerospace, machinery, oil, chemical industry, core
Electricity, track traffic, the field of electronic information and medicine are widely used, and the market development of related drugs.Its demand
Increase year by year, therefore the research and development of DFBP new technique for synthesizing and scale industrial production have extremely vast potential for future development.
The synthetic route of the DFBP of existing report is more, mainly has：Heavy nitrogen, F-C alkylation process, halogen exchange method, urge
Change carbonyl process, catalytie esterification method, dichloroethylene oxidizing process etc..
Diazotising method：With 4,4 '-diaminodiphenylmethane and NaNO3Diazo-reaction is carried out under low temperature in HF acid,
Diazonium compound is made under low temperature with nitric acid oxidation.Raw material syntheti c route is long, pollution is big.
F-C alkylation process：Using 4- fluorobenzene and carbon tetrachloride as raw material, raw 4, the 4 ' difluorobenzenes under Catalyzed by Anhydrous Aluminium Chloride
Base dichloromethane, recycles unreacted carbon tetrachloride and 4- fluorobenzene, hydrolysis obtains crude product at low temperature, then passes through with steam distillation
Cross and distill, be recrystallized to give finished product.The method corrosivity is serious, and carbon tetrachloride is disabled.
Halogen exchange method：With 4,4 '-dichloro benzophenone and KF for raw material, DFBP, yield 65- are prepared with F substitutions Cl
85%.The method synthesis technique is fairly simple, but raw material sources are more difficult with synthesizing.
Catalyzed carbonylation method：By 4- fluorobenzene and CO in atmosphere, using palladium bichloride and iron chloride as catalyst is reacted and
Obtain DFBP.The reaction is high-temperature high-voltage reaction, and technical difficulty is bigger, and the preparation of wherein effective catalyst is crucial.The technology
Still it is in laboratory stage.
Catalytie esterification method：DFBP is condensed to yield by the directly acylation of 4- fluorobenzene and phosgene.The reaction yield is low.And phosgene is acute
Poison, constrains the development of the method.
Dichloroethylene oxidizing process：With 4,4 '-difluorophenyl dichloroethylene for raw material, HNO is used in methylene chloride3In 30-
Aoxidized at 40 DEG C and DFBP is made.The method high income, good product quality, but raw material sources are difficult, and equipment corrosion is than more serious.
In conclusion the 4 of existing report, the synthetic method of 4 '-difluoro benzophenone is there are complex process, time-consuming, urges
Agent recycling is difficult, it is difficult to industrialized production.
The content of the invention
For overcome the deficiencies in the prior art, the present invention provides prepared by one kettle way 4, the side of 4 '-difluoro benzophenone
Method, technique is simple, and pollution is small, and catalyst easily recycles, and product purity is high.
Present invention employs the goal of the invention that following technical scheme realizes the above：
Using 4- toluene fluorides as starting material, oxidized, F-C acylations-condensation, multistage cooling fractional crystallization finally obtains target
Product 4,4 '-difluoro benzophenone.
Specifically, including following synthesis step：
(1), oxidation reaction：Under room temperature, 4- toluene fluorides are added in liquor potassic permanganate, react 1-2h, acidifying filtering, dries
Do to obtain 4- fluobenzoic acids, yield 97.3% or so；
The potassium permanganate solution is neutral or acid；
The amount ratio of the material of 4- toluene fluorides and potassium permanganate is 1:2.05-2.2；
(2), F-C is acylated and condensation one pot process：Obtained 4- fluobenzoic acids are dissolved in 1.2 equivalent thionyl chlorides,
Generation acyl chloride reaction, 80 DEG C of reflux 2-3h, persistently takes HCl and SO away2, and absorbed and recycled with film, 4- fluorobenzoyl chlorides are obtained, are
Solid；
Dichloroethanes dissolving 4- fluorobenzoyl chlorides are added, add catalyst, and 4- fluorobenzene is added dropwise into system, 65 DEG C -75
DEG C, reaction time 3h-5h, after reaction, is recovered by filtration catalyst, frozen water agitation and filtration, filtrate recycling, obtain 4,4 '-
Difluoro benzophenone crude product, yield is 96% or so；
4- fluorobenzene, 4- fluorobenzoyl chlorides, the molar ratio of catalyst are 1:0.85-0.95:1.
The catalyst is load H3PO4Molecular sieve (by molecular sieve be added to commercial concentration be 85% phosphoric acid dilute
In liquid, in reaction kettle after heating crystallization, cool down, filter, drying).
(3) refine:Obtained 4,4 '-difluoro benzophenone crude product is dissolved in the multistage cooling substep of saturation ethanol solution to tie
Crystalline substance, filtrate purifying recycling, dries to obtain sterling DFBP (fusing point is 107 DEG C -109 DEG C).
The raw material of the present invention is cheap and easy to get, and catalyst is easily recycled, and the purity of product is high (purity >=99.9%), technique letter
Single, environmental protection, is worthy to be popularized.
Brief description of the drawings
Fig. 1 is the nuclear magnetic resonance spectroscopy of 1 products therefrom of embodiment；Parsing：1H NMR δ=7.796-7.839 (m, 4H), δ
=7.231-7.277 (m, 4H), it can be seen that, numbers of hydrogen atoms and position can determine that on phenyl ring, the molecular weight with reference to obtained by mass spectrum
Can be determined that product is 4,4 '-difluoro benzophenone.
Fig. 2 is the high performance liquid chromatography of 1 products therefrom of embodiment；Parsing：There is simple spike in 9.991min, content 100%,
It can be seen from the above that 4,4 '-difluoro benzophenone purity is more than 99.9%.
Embodiment
Technical scheme is illustrated below with reference to embodiment：
Embodiment 1:
The method that one kettle way prepares 4,4 '-difluoro benzophenone, step are as follows：
The first step：220.2g 4- toluene fluorides (being 2mol through conversion, molal weight 110.1), 648g (2.05 equivalent) is high
Potassium manganate, which is added in 2L water, stirs 2h, after hydrochloric acid acidifying, separates out white solid, filtering, filter cake dries to obtain 4- fluorobenzene at 65 DEG C
Formic acid 266.4g, disposing mother liquor utilize.
Second step：Equipped with stirring, thermometer, in the 500mL there-necked flasks of reflux condensing tube, adds 140.1g (1mol) 4- fluorine
Benzoic acid, adds 143g thionyl chlorides, 80 DEG C of reflux, take HCl and SO away2, and absorbed and recycled with film, 4- fluorobenzoyl chlorides are obtained,
For solid；
Load H is added into there-necked flask3PO4Molecular sieve, dichloroethanes 200mL, by 90g 4- fluorobenzene in constant pressure addition leak
In bucket, at 65-75 DEG C 40min is added dropwise, the reaction was continued, and 2h terminates in temperature control.It is recovered by filtration catalyst, adds frozen water, agitation and filtration,
Solid 209.3g, yield is up to 96%.
3rd step：By obtained 4,4 '-difluoro benzophenone crude product is dissolved in the multistage cooling fractional crystallization of saturation ethanol solution,
Filtrate purifying recycling, dries to obtain DFBP, and purity is up to more than 99.9%.The qualitative and purity of product structure passes through nuclear magnetic resonance spectroscopy
And efficient liquid phase is identified.
Embodiment 2
The method of 4,4 '-difluoro benzophenone prepared by one kettle way, step are as follows：
The first step：Under room temperature, 110.1g 4- toluene fluorides (1mol), 348g (2.2 equivalent) potassium permanganate are added to 1L water
In, 2h is stirred, is separated out after hydrochloric acid acidifying for white solid, filters filter cake, 65 DEG C dry to obtain 4- fluobenzoic acid 136.4g, and mother liquor returns
Receipts are used again.
Second step：Equipped with stirring, thermometer, in the 250mL there-necked flasks of reflux condensing tube, adds 70g (1mol) 4- fluorobenzene
Formic acid, adds 71.5g thionyl chlorides, 80 DEG C of reflux, take HCl and SO away2, appropriate load H is added into there-necked flask3PO4Molecule
Sieve, dichloroethanes 100mL, by 64g4- fluorobenzene in constant pressure funnel, at 65-75 DEG C 40min is added dropwise, the reaction was continued in temperature control
3h terminates.It is recovered by filtration catalyst, adds frozen water, agitation and filtration obtains solid 105g, and yield is up to 96.3%.
3rd step：By obtained 4,4 '-difluoro benzophenone crude product is dissolved in the multistage cooling fractional crystallization of ethanol, filtrate purifying
Recycling, dries to obtain DFBP, and purity is up to more than 99.9%.
Embodiment 3
Content different from embodiment 1 is：
The first step：Reaction time is 1h；
Second step：Equipped with stirring, thermometer, in the 500mL there-necked flasks of reflux condensing tube, adds 140.1g (1mol) 4- fluorine
Benzoic acid, adds 143g thionyl chlorides, 80 DEG C of reflux, take HCl and SO away2, appropriate load H is added into there-necked flask3PO4Molecule
Sieve, dichloroethanes 200mL, by 90g4- fluorobenzene in constant pressure funnel, at 65-75 DEG C 40min is added dropwise, the reaction was continued in temperature control
3h terminates.It is recovered by filtration molecular sieve, adds frozen water, agitation and filtration obtains solid 209.3g, and yield is up to 96%.
3rd step：By obtained 4,4 '-difluoro benzophenone crude product is dissolved in the multistage cooling fractional crystallization of ethanol, filtrate purifying
Recycling, dries to obtain DFBP, and purity is up to more than 99.9%.
Claims (5)
1. the 4 of one kettle way preparation, the method for 4 '-difluoro benzophenone, it is characterised in that comprise the following steps：
(1), oxidation reaction：Under room temperature, 4- toluene fluorides are added in liquor potassic permanganate, react 1-2h, acidifying filtering, is dried
4- fluobenzoic acids；
(2), F-C is acylated and condensation one pot process：4- fluobenzoic acids are dissolved in 1.2 equivalent thionyl chlorides, chloride occurs
Reaction, 80 DEG C of reflux 2-3h, persistently takes HCl and SO away2, and absorbed and recycled with film, obtain 4- fluorobenzoyl chlorides；
Dichloroethanes dissolving 4- fluorobenzoyl chlorides are added, add catalyst, and 4- fluorobenzene is added dropwise into system, 65 DEG C -75 DEG C anti-
3h-5h is answered, after reaction, catalyst is recovered by filtration, frozen water agitation and filtration, filtrate recycling, obtains 4,4 '-difluoro benzophenone
Crude product；
(3) refine:By obtained 4,4 '-difluoro benzophenone crude product is dissolved in the multistage cooling fractional crystallization of saturation ethanol solution, filter
Liquid purifying recycling, dries to obtain sterling.
2. the 4 of one kettle way preparation according to claim 1, the method for 4 '-difluoro benzophenone, it is characterised in that step
(1) in, the potassium permanganate solution is neutral or acid.
3. the 4 of one kettle way preparation according to claim 1, the method for 4 '-difluoro benzophenone, it is characterised in that step
(1) in, the molar ratio of 4- toluene fluorides and potassium permanganate is 1:2.05-2.2.
4. the 4 of one kettle way preparation according to claim 1, the method for 4 '-difluoro benzophenone, it is characterised in that step
(2) 4- fluorobenzene, 4- fluorobenzoyl chlorides, the molar ratio of catalyst are 1 in:0.85-0.95:1.
5. the 4 of one kettle way preparation according to claim 1, the method for 4 '-difluoro benzophenone, it is characterised in that step
(2) molecular sieve that the catalyst described in is load H3PO4.
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| CN201610921705.6A CN107973707A (en) | 2016-10-21 | 2016-10-21 | The method that one kettle way prepares high-purity 4,4 '-difluorodiphenyl base ketone |
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| CN201610921705.6A CN107973707A (en) | 2016-10-21 | 2016-10-21 | The method that one kettle way prepares high-purity 4,4 '-difluorodiphenyl base ketone |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111440058A (en) * | 2020-03-29 | 2020-07-24 | 吉林省中研高分子材料股份有限公司 | Preparation method of high-purity 4, 4' -difluorobenzophenone |
| CN114292169A (en) * | 2022-01-04 | 2022-04-08 | 浙江三美化工股份有限公司 | Method for synthesizing 4,4' -difluorobenzophenone by fluorobenzene |
| CN115108898A (en) * | 2022-07-02 | 2022-09-27 | 浙江三美化工股份有限公司 | Preparation method and reaction device for synthesizing 4,4' -difluorobenzophenone by fluorobenzene |
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|---|---|---|---|---|
| US2475564A (en) * | 1946-06-12 | 1949-07-05 | Socony Vacuum Oil Co Inc | Catalytic acylation of phenyl alkyl ethers |
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2016
- 2016-10-21 CN CN201610921705.6A patent/CN107973707A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2475564A (en) * | 1946-06-12 | 1949-07-05 | Socony Vacuum Oil Co Inc | Catalytic acylation of phenyl alkyl ethers |
Non-Patent Citations (2)
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| 孙宏元等: "苯甲酸制备方法的绿色化改进研究", 《河南科技》 * |
| 宋夏辉等: "4,4’-二氟二苯甲酮的合成研究", 《江西化工》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111440058A (en) * | 2020-03-29 | 2020-07-24 | 吉林省中研高分子材料股份有限公司 | Preparation method of high-purity 4, 4' -difluorobenzophenone |
| CN114292169A (en) * | 2022-01-04 | 2022-04-08 | 浙江三美化工股份有限公司 | Method for synthesizing 4,4' -difluorobenzophenone by fluorobenzene |
| CN115108898A (en) * | 2022-07-02 | 2022-09-27 | 浙江三美化工股份有限公司 | Preparation method and reaction device for synthesizing 4,4' -difluorobenzophenone by fluorobenzene |
| CN115108898B (en) * | 2022-07-02 | 2023-10-10 | 浙江三美化工股份有限公司 | Preparation method of fluorobenzene synthesized 4,4' -difluorobenzophenone and reaction device thereof |
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Application publication date: 20180501 |