CN106045828A - Preparation method of 4,4'-difluorobenzophenone - Google Patents
Preparation method of 4,4'-difluorobenzophenone Download PDFInfo
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- CN106045828A CN106045828A CN201610513756.5A CN201610513756A CN106045828A CN 106045828 A CN106045828 A CN 106045828A CN 201610513756 A CN201610513756 A CN 201610513756A CN 106045828 A CN106045828 A CN 106045828A
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- difluoro benzophenone
- difluorophenyl
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- DXQVFHQUHOFROC-UHFFFAOYSA-N Fc1ccc(Cc(cc2)ccc2F)cc1 Chemical compound Fc1ccc(Cc(cc2)ccc2F)cc1 DXQVFHQUHOFROC-UHFFFAOYSA-N 0.000 description 1
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/42—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by hydrolysis
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Abstract
The invention relates to a preparation method of 4,4'-difluorobenzophenone, belonging to the field of chemical synthesis. The preparation method comprises the steps of carrying out acylation reaction on fluorine benzotrichloride and fluorobenzene under the catalysis of aluminum trichloride, and carrying out hydrolysis reaction, so as to obtain 4,4'-difluorobenzophenone. The preparation method of 4,4'-difluorobenzophenone has the beneficial effects of simple process, high yield, good selectivity and low cost.
Description
Technical field
The present invention relates to one 4, the preparation method of 4 '-difluoro benzophenone, belong to the field of chemical synthesis.
Background technology
4,4 '-difluoro benzophenone is the main intermediate of preparation engineering plastics polyether-ether-ketone (PEEK).Polyether-ether-ketone
(PEEK) be a kind of semi-crystalline state aromatic series plastic engineering plastics, have temperature classification height, radiation hardness, corrosion-resistant, impact strength is high,
Wearability and fatigue durability is good, fire-retardant and the feature such as excellent electrical property, with the Physical and mechanical properties that it is outstanding, in many fields
Can substitute for the material such as metal, pottery, be one of current popular high performance engineering plastics, Aero-Space, electric, doctor
The every field such as treatment, the energy, electric power, machinery, automobile and coating obtain a wide range of applications, and become indispensable crucial material
Material.
And the preparation cost appreciable impact process warp of the key intermediate 4,4 '-difluoro benzophenone of polyether-ether-ketone (PEEK)
Ji property, the synthesising process research to this compound gives attention greatly both at home and abroad.There is following technique road
Report from a liner road:
JP 57-169441 have employed fluorine chlorine exchange process synthesis 4, and 4 '-difluoro benzophenone, it is by 4,4 '-dichloro
Benzophenone and potassium fluoride react and prepare, and document yield is at 65-85%:
Owing to this course of reaction is that balance is reversible, its conversion ratio can not completely and be difficult to purify, its preparation cost height.
Eur 4710 (1979) have employed overlapization, oxidizing process synthesis 4, and 4 '-difluoro benzophenone, two-step reaction yield divides
Not being 69.6% and 89.3%, total recovery only has 62.1%:
This raw materials technology cost is high, and technical process is the most complicated, is not possess competitiveness.
Japanization association will 1982 (2) 310-312 reports and pays a gram acylation method synthesis 4,4 '-difluoro benzophenone, it
Need strong acid and lewis acidic nitration mixture catalytic action:
Due to the acylation reaction relative difficult of carboxyl Yu aromatic hydrocarbons, and raw material is more expensive, does not possess cost advantage.
JP 58-126829 uses carbon monoxide addition process synthesis 4, and 4 '-difluoro benzophenone, it is by fluorobromobenzene
Half amount make Grignard reagent after add carbon monoxide and prepare:
Owing to the condensation reaction between Grignard reagent and bromobenzene is easier, therefore the side reaction generating biphenyl is inevitable
, it is difficult to obtain higher yield.
Medical industry (8) 34-35 (1985) reports olefin oxidation method synthesis technique:
It is the technical process of special material, higher cost, does not has actual application value.
Organic fluoride industry 2015 (1) 3-6 reports and pays gram alkylation, is the industrial method of current domestic employing:
The process employs and having a strong impact on the carbon tetrachloride of environmental quality is raw material, and the isomer generated is higher, because of
And yield can only achieve 68%.
Chinese patent CN102531872 be use 4-fluorine benzotrichloride be raw material, through Light chlorimation, hydrolyze, pay gram be acylated
Reaction preparation 4,4 '-difluoro benzophenone:
Three-step reaction total recovery reaches 84.5%, but, this process steps is more, and process is wayward, and yield
Unsatisfactory.
Summary of the invention
The present invention passes through new 4,4 '-difluoro benzophenone synthetic route, solves the problems referred to above.
The invention provides a kind of 4, the preparation method of 4 '-difluoro benzophenone, described preparation method is first will be to fluorine three
Chlorotoluene reacts with fluorobenzene acylization under Aluminium Trichloride as Catalyst effect, then hydrolysis obtains 4,4 '-difluoro benzophenone.
100:200-1000 that fluorine benzotrichloride, fluorobenzene, the weight ratio of aluminum chloride and water are preferably of the present invention:
65-195:600-1800.
Acylation reaction of the present invention is preferably and is mixed with aluminum chloride by fluorobenzene, is cooled to 0-25 DEG C, adds fluorine
Benzotrichloride reaction 10-30min, obtains 4,4 '-difluorophenyl dichloromethane.
Hydrolysis of the present invention is preferably and is mixed with water by 4,4 '-difluorophenyl dichloromethane, is heated to azeotropic temperature
Degree, reacts 4-6h, is cooled to room temperature, filters, and is dried, recrystallization, filters, and washing is dried, obtains 4,4 '-difluoro benzophenone.
Fluorine benzotrichloride preferably will be mixed by acylation reaction of the present invention with fluorobenzene, be cooled to 0-25 DEG C, add
Aluminum chloride reaction 10-30min, obtains 4,4 '-difluorophenyl dichloromethane.
Hydrolysis of the present invention is preferably and is mixed with water by 4,4 '-difluorophenyl dichloromethane, is heated to azeotropic temperature
Degree, reacts 4-6h, is cooled to room temperature, filters, and is dried, recrystallization, filters, and washing is dried, obtains 4,4 '-difluoro benzophenone.
The preparation method technique that present invention have the beneficial effect that 4,4 '-difluoro benzophenone of the present invention is simple, yield
Height, selectivity are good, low cost.
Detailed description of the invention
Following limiting examples can make those of ordinary skill in the art that the present invention is more fully understood, but not to appoint
Where formula limits the present invention.
Embodiment 1
A kind of 4, the preparation method of 4 '-difluoro benzophenone, described preparation method comprises the steps:
1. being mixed with 65g aluminum trichloride (anhydrous) by 200g fluorobenzene, be cooled to 0-5 DEG C, 100g is anti-to fluorine benzotrichloride in dropping
Answer 20min, obtain 4,4 '-difluorophenyl dichloromethane；
2. 4,4 '-difluorophenyl dichloromethane is joined in 600g water and mix, be heated to azeotropic temperature and reclaim fluorine simultaneously
Benzene 140g, reacts 5h, is cooled to room temperature, filters, and is dried to obtain faint yellow solid crude product 102g, uses 200g recrystallizing methanol,
Filter, washing, be dried, obtain the white crystals 92g that fusing point is 107-108 DEG C, reach 99.9% through gas chromatographic analysis purity, receive
Rate is 90%.Warp1H-NMR detects: δ 7.28 (4H, t, the hydrogen at fluorine ortho position on phenyl ring)；(4H, m, on phenyl ring, carbonyl faces position to δ 7.81
Hydrogen), meet 4,4 '-difluoro benzophenone structure.
Embodiment 2
A kind of 4, the preparation method of 4 '-difluoro benzophenone, described preparation method comprises the steps:
1. fluorine benzotrichloride is mixed with the anhydrous fluorobenzene of 200g by 100g, be cooled to 0-5 DEG C, be dividedly in some parts 70g anhydrous three
Aluminium reaction 20min, obtains 4,4 '-difluorophenyl dichloromethane；
2. 4,4 '-difluorophenyl dichloromethane is joined in 600g water and mix, be heated to azeotropic temperature and reclaim fluorine simultaneously
Benzene 139.2g, reacts 5h, is cooled to room temperature, filters, and is dried to obtain faint yellow solid crude product 102.8g, uses 200g methanol heavily to tie
Crystalline substance, filters, and washing is dried, obtains the white crystals 93g that fusing point is 107-108 DEG C, reach through gas chromatographic analysis purity
99.9%, yield is 91%.Warp1H-NMR detects:, δ 7.28 (4H, t, the hydrogen at fluorine ortho position on phenyl ring)；δ 7.81 (4H, m, phenyl ring
Upper carbonyl faces the hydrogen of position), meet 4,4 '-difluoro benzophenone structure.
Claims (6)
1. one kind 4, the preparation method of 4 '-difluoro benzophenone, it is characterised in that: described preparation method is first will be to fluorine three chloromethane
Benzene reacts with fluorobenzene acylization under Aluminium Trichloride as Catalyst effect, then hydrolysis obtains 4,4 '-difluoro benzophenone.
Preparation method the most according to claim 1, it is characterised in that: described to fluorine benzotrichloride, fluorobenzene, aluminum chloride with
The weight ratio of water is 100:200-1000:65-195:600-1800.
Preparation method the most according to claim 1, it is characterised in that: described acylation reaction is by fluorobenzene and aluminum chloride
Mixing, is cooled to 0-25 DEG C, adds and fluorine benzotrichloride is reacted 10-30min, obtain 4,4 '-difluorophenyl dichloromethane.
Preparation method the most according to claim 3, it is characterised in that: described hydrolysis is by 4,4 '-difluorophenyl two
Chloromethanes mixes with water, is heated to azeotropic temperature, reacts 4-6h, is cooled to room temperature, filters, and is dried, recrystallization, filters, washing,
It is dried, obtains 4,4 '-difluoro benzophenone.
Preparation method the most according to claim 1, it is characterised in that: described acylation reaction be will to fluorine benzotrichloride with
Fluorobenzene mixes, and is cooled to 0-25 DEG C, adds aluminum chloride reaction 10-30min, obtains 4,4 '-difluorophenyl dichloromethane.
Preparation method the most according to claim 5, it is characterised in that: described hydrolysis is by 4,4 '-difluorophenyl two
Chloromethanes mixes with water, is heated to azeotropic temperature, reacts 4-6h, is cooled to room temperature, filters, and is dried, recrystallization, filters, washing,
It is dried, obtains 4,4 '-difluoro benzophenone.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108610245A (en) * | 2018-05-22 | 2018-10-02 | 江苏万隆化学有限公司 | A kind of preparation method of high-purity difluoro benzophenone |
| CN109574863A (en) * | 2017-09-28 | 2019-04-05 | 安徽省庆云医药股份有限公司 | A kind of synthetic method of -4 ' of 2- amino-fluoro- benzophenone |
| CN110776406A (en) * | 2019-02-15 | 2020-02-11 | 福建永晶科技股份有限公司 | Novel Friedel-Crafts reaction method and catalyst thereof |
| WO2020164291A1 (en) | 2019-02-15 | 2020-08-20 | Fujian Yongjing Technology Co., Ltd | New process for manufacture of fluorinated benzenes and fluorinated benzophenones, and derivatives thereof |
| CN113321574A (en) * | 2021-06-03 | 2021-08-31 | 陕西延长石油（集团）有限责任公司 | Preparation method of 4, 4' -difluorobenzophenone and intermediate thereof |
| 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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Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109574863B (en) * | 2017-09-28 | 2021-09-14 | 安徽省庆云医药股份有限公司 | Synthesis method of 2-amino-4' -fluoro-benzophenone |
| CN109574863A (en) * | 2017-09-28 | 2019-04-05 | 安徽省庆云医药股份有限公司 | A kind of synthetic method of -4 ' of 2- amino-fluoro- benzophenone |
| CN108610245A (en) * | 2018-05-22 | 2018-10-02 | 江苏万隆化学有限公司 | A kind of preparation method of high-purity difluoro benzophenone |
| US11465958B2 (en) | 2019-02-15 | 2022-10-11 | Fujian Yongjing Technology Co., Ltd. | Process for Friedel-Crafts reaction, and catalyst therefore |
| EP3713907A4 (en) * | 2019-02-15 | 2020-11-25 | Fujian Yongjing Technology Co., Ltd | New process for manufacture of fluorinated benzenes and fluorinated benzophenones, and derivatives thereof |
| US11008273B2 (en) | 2019-02-15 | 2021-05-18 | Fujian Yongjing Technology Co., Ltd | Process for the manufacture of fluorinated benzenes and fluorinated benzophenones, and derivatives thereof |
| WO2020164291A1 (en) | 2019-02-15 | 2020-08-20 | Fujian Yongjing Technology Co., Ltd | New process for manufacture of fluorinated benzenes and fluorinated benzophenones, and derivatives thereof |
| CN110776406A (en) * | 2019-02-15 | 2020-02-11 | 福建永晶科技股份有限公司 | Novel Friedel-Crafts reaction method and catalyst thereof |
| CN110776406B (en) * | 2019-02-15 | 2022-11-04 | 福建永晶科技股份有限公司 | Novel Friedel-Crafts reaction method and catalyst thereof |
| CN113321574A (en) * | 2021-06-03 | 2021-08-31 | 陕西延长石油（集团）有限责任公司 | Preparation method of 4, 4' -difluorobenzophenone and intermediate thereof |
| CN113321574B (en) * | 2021-06-03 | 2023-09-19 | 陕西延长石油（集团）有限责任公司 | Preparation method of 4,4' -difluorobenzophenone and intermediate thereof |
| 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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