CN112409169B - Method for preparing polyfluoroaromatic hydrocarbon - Google Patents
Method for preparing polyfluoroaromatic hydrocarbon Download PDFInfo
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- CN112409169B CN112409169B CN202011381964.7A CN202011381964A CN112409169B CN 112409169 B CN112409169 B CN 112409169B CN 202011381964 A CN202011381964 A CN 202011381964A CN 112409169 B CN112409169 B CN 112409169B
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/347—Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups
- C07C51/363—Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups by introduction of halogen; by substitution of halogen atoms by other halogen atoms
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0234—Nitrogen-, phosphorus-, arsenic- or antimony-containing compounds
- B01J31/0235—Nitrogen containing compounds
- B01J31/0239—Quaternary ammonium compounds
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/093—Preparation of halogenated hydrocarbons by replacement by halogens
- C07C17/20—Preparation of halogenated hydrocarbons by replacement by halogens of halogen atoms by other halogen atoms
- C07C17/202—Preparation of halogenated hydrocarbons by replacement by halogens of halogen atoms by other halogen atoms two or more compounds being involved in the reaction
- C07C17/208—Preparation of halogenated hydrocarbons by replacement by halogens of halogen atoms by other halogen atoms two or more compounds being involved in the reaction the other compound being MX
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C201/00—Preparation of esters of nitric or nitrous acid or of compounds containing nitro or nitroso groups bound to a carbon skeleton
- C07C201/06—Preparation of nitro compounds
- C07C201/12—Preparation of nitro compounds by reactions not involving the formation of nitro groups
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D233/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings
- C07D233/02—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having no double bonds between ring members or between ring members and non-ring members
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/40—Substitution reactions at carbon centres, e.g. C-C or C-X, i.e. carbon-hetero atom, cross-coupling, C-H activation or ring-opening reactions
- B01J2231/42—Catalytic cross-coupling, i.e. connection of previously not connected C-atoms or C- and X-atoms without rearrangement
- B01J2231/4277—C-X Cross-coupling, e.g. nucleophilic aromatic amination, alkoxylation or analogues
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
Abstract
The invention discloses a method for preparing polyfluoroaromatic hydrocarbon, which comprises the following steps:in the reactant, R 1 、R 2 、R 3 All are groups on an aromatic ring, and are hydrogen or chlorine; r is R 4 The group on the aromatic ring is hydrogen, carboxyl, nitro, cyano, acyl and other groups; in the product, R in the reactant 1 、R 2 、R 3 In the case of chlorine, R in the product 1 、R 2 、R 3 Corresponding to fluorine, R 4 Is unchanged. The catalyst is a quaternary ammonium chloride salt containing bispyrazoline. The method provides a high-efficiency method for preparing the multi-fluoro aromatic hydrocarbon compound with wide application and various structures.
Description
Technical Field
The invention belongs to the technical field of chemical production, and particularly relates to a preparation method of polyfluoroaromatic hydrocarbon.
Background
Fluorine-containing compounds often exhibit unique physicochemical properties, mainly due to the fluorine atoms having the following properties: for example, fluorine is small atoms next to hydrogen in volume, has strong electronegativity, has stronger bonding force with carbon than halogen atoms except hydrogen and fluorine, and electron cloud of fluorine element is converged, and the bond distance of carbon-fluorine bond is inflexible, has low polarization rate, has smaller dispersion force interacted with molecules of other substances, has large hydrophobicity, has high lipophilicity and the like. Therefore, the fluorine-containing compound generally has better physiological activity. The introduction of fluorine atoms, especially a plurality of fluorine atoms, on the aromatic compound can obviously improve the stability and fat solubility of the compound, change the electronic effect of compound molecules and improve the biological activity of the compound, so that the polyfluoroarene is already an important raw material and intermediate of pesticide, medicine and dye industry and liquid crystal materials, such as homotrifluoro benzene as an intermediate of medicine and liquid crystal materials, tetrafluorobenzonitrile and tetrafluorotoluene as an intermediate of synthetic pyrethroid pesticides, tetrafluorobenzonitrile and tetrafluorotoluene as an intermediate of fluoroquinolone medicines gatifloxacin, 2, 4-difluoronitrobenzene as an intermediate of medicines for treating rheumatoid arthritis and osteoarthritis, and the like.
There are various methods for introducing fluorine atoms into aromatic compounds, among which the Balz-Schiemann method, the HF-diazotization method and the halogen exchange method are relatively mature and sophisticated. However, the two methods need to be subjected to a preparation process of diazotization and then fluorination, toxic reagents are needed in the preparation, diazonium salts are easy to explode, the process is unsafe, the route is long, the yield is low, the cost is high, and the industrialized use is less. The halogen exchange fluorination method has the advantages of easily available raw materials, simple process and safety, and becomes a main industrial method for synthesizing fluorine-containing aromatic compounds in recent years.
The preparation method of the polyfluoroaromatic hydrocarbon has been reported in the literature at home and abroad, generally, a halogen exchange method is adopted, namely, monochloroaromatic hydrocarbon is used as a substrate, KF is used as a fluoro reagent, monofluoro reaction is carried out under the action of a phase transfer catalyst, for example, 3, 5-difluorochlorobenzene which is more expensive is used as a raw material, the raw material is expensive and not easy to obtain, and industrialization is difficult to implement at low cost; there is also reported a method for realizing multiple chlorine atom fluoro-substituted by one step using polychlorinated aromatic hydrocarbon as substrate, which has low cost and easy availability of raw materials, but because of insufficient catalytic performance of the catalyst, it is difficult to realize that multiple chlorine atoms are simultaneously substituted by fluorine atoms, thereby generating byproducts such as monofluoro aromatic hydrocarbon, difluoro aromatic hydrocarbon, etc., which are difficult to separate from the product polyfluoro aromatic hydrocarbon, and complicated post-treatment such as rectification is required, resulting in complex process, low product purity, and being not suitable for industrial production.
Disclosure of Invention
The invention aims to overcome the defects that raw materials are not easy to obtain, expensive, easy to produce impurities, low in yield, complex in operation, poor in process safety and the like in the existing technology for preparing the polyfluoroaromatic hydrocarbon shown in the formula (I), and the like, which are unfavorable for industrial production, and provides an effective method for synthesizing the polyfluoroaromatic hydrocarbon shown in the formula (I).
The technical scheme of the invention is summarized as follows:
adding a 1, 3-dichloro aromatic compound shown in the formula (II), potassium fluoride and a solvent into a reaction kettle, adding toluene, installing a water dividing device, heating and refluxing to divide a small amount of water in the system, adding PEG 6000 and a catalyst, reacting for a certain time at a certain temperature, and performing post-treatment to obtain the polyfluoroaromatic compound shown in the formula (I).
The synthetic route is as follows:
in the reactant, R 1 、R 2 、R 3 Is hydrogen or chlorine; r is R 4 Hydrogen, carboxyl, nitro, cyano, formyl, acetyl and the like; in the product, R in the reactant 1 、R 2 、R 3 In the case of chlorine, R in the product 1 、R 2 、R 3 Corresponding to fluorine, R 4 Is unchanged.
The catalyst is a quaternary ammonium chloride salt containing bispyrazoline, and the structure of the catalyst is as follows:
wherein R is 5 And R is 6 Is C 1 ～C 4 Is a hydrocarbon group.
The catalyst is relatively simple to prepare, 1, 3-dimethyl-2-imidazolinone reacts with triphosgene to obtain N, N-dimethyl imidazolidine chloride, metformin reacts with halohydrocarbon to obtain alkylated metformin, the two obtained compounds are mixed to generate condensation reaction, and the condensation product reacts with sodium methoxide to obtain the quaternary ammonium salt containing the bispyrazoline.
The catalyst has high catalytic efficiency, and the dosage of the catalyst is only 2-8% of the dosage of the compound shown in the formula (II), so that a plurality of chlorine atoms can be fluorinated at the same time.
The catalyst is directly recycled without recovery, the utilization rate is high, the catalyst is recycled for 4 times, and the yield is reduced by 3-5%.
The heating temperature is 140-250 ℃.
The solvent is aprotic polar solvents such as sulfolane, 1, 3-dimethyl-2-imidazolone, DMF, DMSO, DMAC, N-methylpyrrolidone and the like, and most of the solvents can be used repeatedly.
The method can convert the polychlorinated aromatic hydrocarbon substrate which is cheap and easy to obtain into the polyfluorinated aromatic hydrocarbon in one step, and provides a high-efficiency method for preparing the polyfluorinated aromatic hydrocarbon compound with various structures and wide application.
Detailed Description
The invention will be further illustrated with reference to specific examples; it is to be understood that these examples are illustrative of the present invention and are not intended to limit the scope of the present invention.
The raw materials or reagents used in the examples were commercially available unless otherwise specified.
Example 1
Preparation of 2,3,5, 6-tetrafluorobenzoic acid
The reaction formula is:
6mol of potassium fluoride, 1mol of 2,3,5, 6-tetrachlorobenzoic acid, 500mL of sulfolane and 60mL of toluene were sequentially charged into a reaction flask equipped with a water separator. Heating, stirring, refluxing and water diversion, opening a water diversion device switch when water diversion is finished, and completely evaporating toluene by increasing the temperature, wherein the evaporated toluene can be recycled. Slightly cooling, transferring the reaction mixture into a 1.5L reaction kettle, adding 5g of PEG 6000 and 0.06mol of catalyst, heating to 230 ℃ for reaction for 18h, starting a rectifying column to receive a crude 2,3,5, 6-tetrafluorobenzoic acid product after reaction for 5h, and rectifying the obtained crude product twice to obtain a product with the purity of 99%, wherein the yield is: 86%.
After the reaction is finished, cooling and filtering, eluting a filter cake by sulfolane, and collecting filtrate containing the catalyst to directly apply to the next batch of material; the white potassium chloride product can be recovered after the filter cake is treated.
Example 2
Preparation of 2,3,5, 6-tetrafluorobenzoic acid
Into a 1.5L reactor, 0.9mol of 2,3,5, 6-tetrachlorobenzoic acid, 450mL of sulfolane recovered in example 1, 0.01mol of catalyst, 4g of PEG 6000 and 5.5mol of potassium fluoride were added in sequence, and the temperature was raised to 230 ℃ to react for 18 hours. Meanwhile, the rectifying column receives the crude 2,3,5, 6-tetrafluorobenzoic acid, and the obtained crude product is subjected to secondary rectification to obtain a product with the purity of 99 percent, and the yield is: 85%.
After the reaction is finished, cooling and filtering, eluting a filter cake by sulfolane, and collecting filtrate containing the catalyst and directly applying the filtrate to the next batch of material; the white potassium chloride product can be recovered after the filter cake is treated.
Example 3
Preparation of homotrifluorobenzene
The reaction formula is:
into a reaction flask equipped with a water separator, 4.5mol of potassium fluoride, 1mol of tricyclobenzene, 500mL of 1, 3-dimethyl-2-imidazolidinone, and 60mL of toluene were sequentially added. Heating, stirring, refluxing and distributing water, opening a water distributor switch when water distribution is finished, raising the temperature to completely evaporate toluene, slightly cooling, transferring the reaction mixture into a 1.5L reaction kettle, adding 5g of PEG 6000 and 0.06mol of catalyst, and heating to 220 ℃ for reaction for 24 hours. After the reaction is finished, distilling at normal pressure, collecting fractions at 50-120 ℃ to obtain crude products of the benzotrifluoride, and rectifying the obtained crude products at normal pressure for the second time to obtain products with the purity of 99%, wherein the yield is as follows: 79%.
Combining the rectified residue with the residue after the first distillation, filtering, eluting a filter cake by using 1, 3-dimethyl-2-imidazolidinone, and collecting a filtrate containing the catalyst to directly apply to the next batch of feeding; the white potassium chloride product can be recovered after the filter cake is treated.
Example 4
Preparation of homotrifluorobenzene
The filtrate recovered from example 3, containing the catalyst, was directly used in the preparation of the homotrifluorobenzene, and the experimental procedure of example 2 and example 3 was followed to obtain a product with a purity of 99%, yield: 78.2%.
Mixing the residues after rectification and distillation, and filtering to obtain a filtrate containing the catalyst, wherein the filtrate can be reused for the next batch of feeding; the white potassium chloride product can be recovered after the filter cake is treated.
Example 5
Preparation of 2, 4-difluoronitrobenzene
The reaction formula is:
into a reaction flask equipped with a water separator, 2.8mol of potassium fluoride, 1mol of 2, 4-dichloronitrobenzene, 400mL of 1, 3-dimethyl-2-imidazolidinone, and 60mL of toluene were successively added. Heating, stirring, refluxing and dividing water, opening a water divider switch when water division is finished, raising the temperature to completely evaporate toluene, slightly cooling, transferring a reaction mixture into a 1.5L reaction kettle, adding 4.8g of PEG 6000 and 0.02mol of catalyst, heating to 140 ℃ for reaction for 3 hours, starting a rectifying column to receive a 2, 4-difluoronitrobenzene crude product after reaction for 1.5 hours, and rectifying the obtained crude product secondarily to obtain a product with the purity of 99 percent, wherein the yield is as follows: 93%.
After the reaction is finished, cooling and filtering, eluting a filter cake by using 1, 3-dimethyl-2-imidazolone, and collecting filtrate containing the catalyst to directly apply to the next batch of material; the white potassium chloride product can be recovered after the filter cake is treated.
Claims (4)
1. A method for preparing polyfluoroaromatic hydrocarbon is characterized in that the reaction formula of the preparation method is as follows:
in the reactant, R 1 、R 2 、R 3 Is hydrogen or chlorine; r is R 4 Hydrogen, carboxyl, nitro, cyano, formyl and acetyl; in the product, R in the reactant 1 、R 2 、R 3 In the case of chlorine, R in the product 1 、R 2 、R 3 Corresponding to fluorine, R 4 Hydrogen, carboxyl, nitro, cyano, formyl and acetyl;
the preparation method comprises the following steps: adding potassium fluoride, a polychloroaromatic compound of the formula (II) and a solvent into a reaction kettle, adding toluene, installing a water diversion device, heating, refluxing, separating out a small amount of water in the system, steaming out toluene, transferring the toluene into the reaction kettle, adding PEG 6000 and a catalyst, reacting for a certain time at a certain temperature, and performing post-treatment to obtain the polyfluoroaromatic compound of the formula (I);
the catalyst in the step is a quaternary ammonium chloride salt containing bispyrazoline, and the structure of the catalyst is as follows:
wherein R is 5 And R is 6 Is C 1 ～C 4 Is a hydrocarbon group.
2. A process for preparing polyfluoroaromatic hydrocarbon according to claim 1, wherein: the catalyst in the step has high catalytic efficiency, and the dosage of the catalyst is 2-8% of the dosage of the compound in the formula (II).
3. A process for preparing polyfluoroaromatic hydrocarbon according to claim 1, wherein: the reaction temperature in the step is 140-250 ℃.
4. A process for preparing polyfluoroaromatic hydrocarbon according to claim 1, wherein: the solvent in the step is aprotic polar solvent sulfolane, 1, 3-dimethyl-2-imidazolone and DMF, DMSO, DMAC, N-methylpyrrolidone.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001058965A (en) * | 1999-08-20 | 2001-03-06 | Nippon Shokubai Co Ltd | Production of fluorinated aromatic compound |
| US6265627B1 (en) * | 1999-11-23 | 2001-07-24 | Sergei Mikhailovich Igumnov | Process for preparing polyfluoroaromatic compounds |
| CN105315142A (en) * | 2015-11-20 | 2016-02-10 | 扬州天辰精细化工有限公司 | Industrial production method for 2, 6-difluorobenzaldehyde |
| CN107141192A (en) * | 2017-05-09 | 2017-09-08 | 大连奇凯医药科技有限公司 | A kind of preparation method of equal trifluoro-benzene |
| CN111153779A (en) * | 2019-12-31 | 2020-05-15 | 浙江解氏新材料股份有限公司 | Efficient synthesis method of m-fluoroanisole |
-
2020
- 2020-12-01 CN CN202011381964.7A patent/CN112409169B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001058965A (en) * | 1999-08-20 | 2001-03-06 | Nippon Shokubai Co Ltd | Production of fluorinated aromatic compound |
| US6265627B1 (en) * | 1999-11-23 | 2001-07-24 | Sergei Mikhailovich Igumnov | Process for preparing polyfluoroaromatic compounds |
| CN105315142A (en) * | 2015-11-20 | 2016-02-10 | 扬州天辰精细化工有限公司 | Industrial production method for 2, 6-difluorobenzaldehyde |
| CN107141192A (en) * | 2017-05-09 | 2017-09-08 | 大连奇凯医药科技有限公司 | A kind of preparation method of equal trifluoro-benzene |
| CN111153779A (en) * | 2019-12-31 | 2020-05-15 | 浙江解氏新材料股份有限公司 | Efficient synthesis method of m-fluoroanisole |
Non-Patent Citations (1)
| Title |
|---|
| 药物中间体2，4-二氟苯甲酸的合成研究;梁飞;《中国优秀硕士学位论文全文数据库》;20111215(第S1期);第B016-47页 * |
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