CN114436762A - Safe and green production method of pentafluorobenzene - Google Patents
Safe and green production method of pentafluorobenzene Download PDFInfo
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- CN114436762A CN114436762A CN202111592972.0A CN202111592972A CN114436762A CN 114436762 A CN114436762 A CN 114436762A CN 202111592972 A CN202111592972 A CN 202111592972A CN 114436762 A CN114436762 A CN 114436762A
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- WACNXHCZHTVBJM-UHFFFAOYSA-N 1,2,3,4,5-pentafluorobenzene Chemical compound FC1=CC(F)=C(F)C(F)=C1F WACNXHCZHTVBJM-UHFFFAOYSA-N 0.000 title claims abstract description 72
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 18
- 238000006243 chemical reaction Methods 0.000 claims abstract description 32
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 28
- 239000000047 product Substances 0.000 claims abstract description 23
- MEXUTNIFSHFQRG-UHFFFAOYSA-N 6,7,12,13-tetrahydro-5h-indolo[2,3-a]pyrrolo[3,4-c]carbazol-5-one Chemical compound C12=C3C=CC=C[C]3NC2=C2NC3=CC=C[CH]C3=C2C2=C1C(=O)NC2 MEXUTNIFSHFQRG-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000012043 crude product Substances 0.000 claims abstract description 13
- 239000012267 brine Substances 0.000 claims abstract description 12
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 claims abstract description 12
- -1 alkyl tertiary amine Chemical class 0.000 claims abstract description 11
- 238000010992 reflux Methods 0.000 claims abstract description 11
- 238000000926 separation method Methods 0.000 claims abstract description 4
- 239000002994 raw material Substances 0.000 claims abstract description 3
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical group [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 7
- 239000012295 chemical reaction liquid Substances 0.000 claims description 7
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical group [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 6
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 6
- 235000011152 sodium sulphate Nutrition 0.000 claims description 6
- NHLUVTZJQOJKCC-UHFFFAOYSA-N n,n-dimethylhexadecan-1-amine Chemical group CCCCCCCCCCCCCCCCN(C)C NHLUVTZJQOJKCC-UHFFFAOYSA-N 0.000 claims description 5
- 239000000243 solution Substances 0.000 claims description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 4
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 4
- 238000009835 boiling Methods 0.000 claims description 4
- YWFWDNVOPHGWMX-UHFFFAOYSA-N n,n-dimethyldodecan-1-amine Chemical compound CCCCCCCCCCCCN(C)C YWFWDNVOPHGWMX-UHFFFAOYSA-N 0.000 claims description 4
- 239000011780 sodium chloride Substances 0.000 claims description 4
- 239000007864 aqueous solution Substances 0.000 claims description 3
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 2
- 235000011164 potassium chloride Nutrition 0.000 claims description 2
- 239000001103 potassium chloride Substances 0.000 claims description 2
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 claims description 2
- 229910052939 potassium sulfate Inorganic materials 0.000 claims description 2
- 235000011151 potassium sulphates Nutrition 0.000 claims description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 abstract description 22
- 238000000034 method Methods 0.000 abstract description 13
- 229910052757 nitrogen Inorganic materials 0.000 abstract description 11
- 230000008569 process Effects 0.000 abstract description 3
- 238000003889 chemical engineering Methods 0.000 abstract description 2
- 239000012847 fine chemical Substances 0.000 abstract description 2
- 239000002351 wastewater Substances 0.000 abstract description 2
- 238000006114 decarboxylation reaction Methods 0.000 description 18
- 239000012071 phase Substances 0.000 description 10
- JLTDJTHDQAWBAV-UHFFFAOYSA-N N,N-dimethylaniline Chemical compound CN(C)C1=CC=CC=C1 JLTDJTHDQAWBAV-UHFFFAOYSA-N 0.000 description 6
- 238000001816 cooling Methods 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- 238000011084 recovery Methods 0.000 description 6
- 238000003756 stirring Methods 0.000 description 5
- 239000002904 solvent Substances 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000012429 reaction media Substances 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- FQRURPFZTFUXEZ-MRVPVSSYSA-N (2s)-2,3,3,3-tetrafluoro-2-(n-fluoroanilino)propanoic acid Chemical compound OC(=O)[C@](F)(C(F)(F)F)N(F)C1=CC=CC=C1 FQRURPFZTFUXEZ-MRVPVSSYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000010933 acylation Effects 0.000 description 1
- 238000005917 acylation reaction Methods 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 230000029936 alkylation Effects 0.000 description 1
- 238000005804 alkylation reaction Methods 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 230000031709 bromination Effects 0.000 description 1
- 238000005893 bromination reaction Methods 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 230000003031 feeding effect Effects 0.000 description 1
- 231100000086 high toxicity Toxicity 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000006396 nitration reaction Methods 0.000 description 1
- OGJPXUAPXNRGGI-UHFFFAOYSA-N norfloxacin Chemical compound C1=C2N(CC)C=C(C(O)=O)C(=O)C2=CC(F)=C1N1CCNCC1 OGJPXUAPXNRGGI-UHFFFAOYSA-N 0.000 description 1
- 229960001180 norfloxacin Drugs 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/361—Preparation of halogenated hydrocarbons by reactions involving a decrease in the number of carbon atoms
- C07C17/363—Preparation of halogenated hydrocarbons by reactions involving a decrease in the number of carbon atoms by elimination of carboxyl groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/38—Separation; Purification; Stabilisation; Use of additives
- C07C17/383—Separation; Purification; Stabilisation; Use of additives by distillation
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a safe and green production method of pentafluorobenzene, belonging to the field of fine chemical engineering. Under the protection of nitrogen, taking pentafluorobenzoic acid as a raw material, carrying out reflux reaction under the conditions of long-chain alkyl tertiary amine and high-concentration brine, continuously distilling out a product during the reaction, carrying out oil-water separation on a distillate to obtain a pentafluorobenzene crude product, and rectifying to obtain a pentafluorobenzene finished product. The purity of the pentafluorobenzene obtained by the method is more than 99.5 percent, and the moisture content is less than 0.10 percent. After the reaction is finished, the kettle residue containing the long-carbon chain alkyl tertiary amine can be directly applied under the protection of nitrogen, and the application frequency can reach more than three times, so that the wastewater discharge is greatly reduced, the green production of the pentafluorobenzene is realized, the pollution in the whole operation process is small, and the production process is safe and reliable.
Description
Technical Field
The invention relates to a safe and green production method of pentafluorobenzene, belonging to the technical field of fine chemical engineering.
Background
Pentafluorobenzene is an important organofluoro compound, CAS: 363-72-4, colorless liquid, density of 1.514, melting point of-48 ℃, boiling point of 85 ℃, refractive index of 1.39 and flash point of 10 ℃. Can be mixed with solvents such as ethanol, diethyl ether, acetone, carbon tetrachloride and the like, and is insoluble in water; the structural formula is as follows:
pentafluorobenzene is an important aromatic fluoride, and can be used for synthesizing various intermediates of medicines, pesticides, dyes and high polymer plastics, such as norfloxacin, pentafluorophenothrin, pentafluorophenylalanine and the like, through chemical reactions such as nitration, chlorination, bromination, alkylation, acylation and the like. At present, the industrial method for synthesizing pentafluorobenzene mainly comprises two methods:
the first one is pentafluorobenzene is decarboxylated at 170 ℃ under the action of N, N-dimethylaniline reaction medium and catalysis to obtain pentafluorobenzene. The process is mature and has high yield, but the reagent N, N-dimethylaniline used in the process has high toxicity and is not environment-friendly.
And the other is to prepare pentafluorobenzene by decarboxylation under the condition of taking high-temperature liquid water as a solvent, namely pentafluorobenzoic acid, without a catalyst. High temperature liquid water generally refers to compressed liquid water at temperatures between 150 ℃ and 350 ℃. The high-temperature liquid water as a reaction medium has different solvent properties and reaction performances in different states. However, high-temperature liquid water needs high-pressure equipment, which is not safe; meanwhile, the product cannot be separated from the reaction system, and byproducts are easily generated.
Disclosure of Invention
In order to solve the technical problems, the invention aims to provide a safe and effective green preparation method of pentafluorobenzene. The method comprises the process steps of decarboxylation reaction, distillation, rectification, kettle residue use and the like.
The invention relates to a safe and green production method of pentafluorobenzene, which comprises the following steps: using pentafluorobenzoic acid as a raw material, carrying out reflux reaction under the conditions of long-chain alkyl tertiary amine and high-concentration brine, continuously distilling out a product during the reaction, carrying out oil-water separation on a distillate to obtain a crude pentafluorobenzene product, and rectifying to obtain a finished pentafluorobenzene product.
Further, in the above technical solution, the high-concentration brine is an inorganic brine solution, and includes a sulfate or hydrochloride aqueous solution, the sulfate is sodium sulfate or potassium sulfate, and the hydrochloride is sodium chloride or potassium chloride. The inorganic salt solution with a certain concentration can increase the boiling point of the aqueous solution. Generally, the reaction rate can be increased by 2 to 4 times every 10 ℃ increase of the reaction temperature; increasing the reaction temperature facilitates decarboxylation.
Further, in the above technical solution, the high concentration brine means a brine having a salt concentration of 30% or more, preferably 40% or more. The dosage is 2-10 parts (parts refer to mass ratio, the same below).
Further, in the above technical scheme, the decarboxylation reaction is to perform reflux decarboxylation on pentafluorobenzoic acid and long-chain alkyl tertiary amine in saline water to generate pentafluorobenzene.
Further, in the above-described embodiments, the long-chain alkyl tertiary amine refers to a tertiary amine having a long carbon chain such as hexadecyldimethylamine or dodecyldimethylamine. The long-chain alkyl tertiary amine substance is selected by salifying amino in a molecular structure and carboxyl in a pentafluorobenzoic acid molecular structure and simultaneously improving decarboxylation activity by utilizing the hydrophobic effect of long-chain alkyl.
Further, in the technical scheme, the dosage of the long-chain alkyl tertiary amine is 0.005-0.5 part, and the preferred dosage is 0.01-0.05 part.
Further, in the above technical scheme, the product is continuously distilled out while the reaction is carried out as follows: pentafluorobenzene is gradually generated after the temperature is increased and the reflux is carried out for a period of time, and the boiling point is reduced, so that the pentafluorobenzene needs to be distilled off to increase the reaction temperature. When pentafluorobenzene is evaporated, part of water is carried out, and the lower layer is an organic phase.
Further, in the above technical scheme, after the reaction is completed, the reaction liquid kettle residue after the pentafluorobenzene is evaporated is directly used for the next batch of feeding materials, and the reaction liquid kettle residue is circularly used for more than three times.
The residue can be used for decarboxylation in the next batch under the protection of nitrogen, which means that the reaction liquid after distilling pentafluorobenzene still has decarboxylation activity under the protection of nitrogen. The three times of the application mean that the reaction liquid after the pentafluorobenzene is evaporated is used for decarboxylation reaction to carry out three batches of feeding activities without obvious reduction.
Further, in the above technical solution, the rectification operation is: and (3) rectifying the crude pentafluorobenzene product at the oil bath temperature of below 120 ℃ by a rectifying column to obtain a refined pentafluorobenzene product. The purity of the obtained pentafluorobenzene pure product is more than 99.5 percent, the maximum single impurity content is less than 0.10 percent, and the water content is less than 0.10 percent.
Further, in the above technical scheme, the reaction is performed under a nitrogen atmosphere.
The technical scheme of the application is typically operated as follows: under the protection of nitrogen, 2-10 parts of high-concentration brine is taken as a solvent, pentafluorobenzoic acid is subjected to decarboxylation reaction under the catalysis of 0.005-1.0 part of long-chain alkyl tertiary amine, and a product is generated and is distilled to obtain a pentafluorobenzene crude product. Cooling, and using the residual nitrogen protection of the kettle for decarboxylation of the next batch; thus, the application can be carried out for three times. And rectifying the crude pentafluorobenzene product to obtain a pure pentafluorobenzene product.
Advantageous effects of the invention
The method effectively overcomes the defect that a highly toxic reagent N, N-dimethylaniline is adopted for decarboxylation in the preparation of the pentafluorobenzene, and also avoids the potential safety hazard of decarboxylation under the high-pressure condition by adopting high-pressure equipment. By applying the reaction liquid, the wastewater discharge amount is effectively reduced, so that the green production of the pentafluorobenzene is realized.
Detailed Description
Example 1
To a 5L four-necked flask, 1800 g of water and 1200 g of sodium sulfate were added. With stirring, 750 g of pentafluorobenzoic acid (3.536mol) are introduced. Under nitrogen, 9.44 g of hexadecyldimethylamine (0.035mol) were added. The temperature was raised to reflux and pentafluorobenzene began to be produced after 5 hours. And (4) distilling the pentafluorobenzene out, and returning water to the reaction kettle. The reaction was continued for about 20 hours, and stopped when no oil phase was distilled off. Cooling, and using the residue in decarboxylation of the next batch; thus, the method can be applied for three times.
Separating a pentafluorobenzene crude product from the distilled oil-water phase, and rectifying the pentafluorobenzene crude product to obtain a pentafluorobenzene pure product, wherein the yield is 96 percent, and the purity is more than 99.9 percent.
The first recovery rate is 96 percent and the purity is 99.9 percent. The secondary yield is 95 percent and the purity is 99.8 percent.
Example 2
To a 5L four-necked flask, 1800 g of water and 1200 g of sodium sulfate were added. With stirring, 750 g of pentafluorobenzoic acid (3.536mol) are introduced. Under nitrogen, 18.87 g of hexadecyldimethylamine (0.07mol) were added. The temperature was raised to reflux and pentafluorobenzene began to be produced after 4 hours. And (4) distilling the pentafluorobenzene out, and returning water to the reaction kettle. The reaction was carried out for about 15 hours, and the reaction was stopped when no oil phase was distilled off. Cooling, and using the residue in decarboxylation of the next batch; thus, the method can be applied for three times.
Separating a pentafluorobenzene crude product from the distilled oil-water phase, and rectifying the pentafluorobenzene crude product to obtain a pentafluorobenzene pure product, wherein the yield is 98 percent, and the purity is more than 99.9 percent.
The first recovery rate is 98 percent and the purity is 99.9 percent. The second recovery rate is 97 percent and the purity is 99.9 percent.
Example 3
To a 5L four-necked flask, 1800 g of water and 1200 g of sodium sulfate were added. With stirring, 750 g of pentafluorobenzoic acid (3.536mol) are introduced. Under nitrogen, 7.45 g of dodecyldimethylamine (0.035mol) were added. The temperature was raised to reflux and pentafluorobenzene began to be produced after 6 hours. And (4) distilling the pentafluorobenzene out, and returning water to the reaction kettle. The reaction was continued for about 20 hours, and stopped when no oil phase was distilled off. Cooling, and using the residue in decarboxylation of the next batch; thus, the method can be applied for three times.
Separating a pentafluorobenzene crude product from the distilled oil-water phase, and rectifying the pentafluorobenzene crude product to obtain a pentafluorobenzene pure product, wherein the yield is 95%, and the purity is more than 99.9%.
The first recovery rate is 95 percent and the purity is 99.9 percent. The secondary yield is 93 percent and the purity is 99.8 percent.
Example 4
To a 5L four-necked flask, 1800 g of water and 1200 g of sodium sulfate were added. With stirring, 750 g of pentafluorobenzoic acid (3.536mol) are introduced. Under nitrogen, 14.9 g of dodecyldimethylamine (0.07mol) were added. The temperature was raised to reflux and pentafluorobenzene began to be produced after 5 hours. And (4) distilling the pentafluorobenzene out, and returning water to the reaction kettle. The reaction was continued for about 24 hours, and stopped when no oil phase was distilled off. Cooling, and using the residue in decarboxylation of the next batch; thus, the method can be applied for three times.
Separating a pentafluorobenzene crude product from the distilled oil-water phase, and rectifying the pentafluorobenzene crude product to obtain a pentafluorobenzene pure product, wherein the yield is 96 percent, and the purity is more than 99.9 percent.
The first recovery rate is 96 percent and the purity is 99.9 percent. The secondary yield is 95 percent and the purity is 99.8 percent.
Example 5
To a 5L four-necked flask, 1800 grams of water and 1000 grams of sodium chloride were added. With stirring, 750 g of pentafluorobenzoic acid (3.536mol) are introduced. Under nitrogen, 9.44 g of hexadecyldimethylamine (0.035mol) were added. The temperature was raised to reflux and pentafluorobenzene began to be produced after 7 hours. And (4) distilling the pentafluorobenzene out, and returning water to the reaction kettle. The reaction was continued for about 25 hours, and stopped when no oil phase was distilled off. Cooling, and using the residue in decarboxylation of the next batch; thus, the method can be applied for three times.
Separating a pentafluorobenzene crude product from the distilled oil-water phase, and rectifying the pentafluorobenzene crude product to obtain a pentafluorobenzene pure product, wherein the yield is 93%, and the purity is more than 99.9%.
The first recovery rate is 93 percent and the purity is 99.9 percent. The secondary yield is 92 percent and the purity is 99.8 percent.
The foregoing embodiments have described the general principles, principal features and advantages of the invention. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, which are merely illustrative of the principles of the present invention, and that various changes and modifications may be made without departing from the scope of the principles of the present invention, and the invention is intended to be covered by the appended claims.
Claims (9)
1. The safe and green production method of pentafluorobenzene is characterized by comprising the following steps of: using pentafluorobenzoic acid as a raw material, carrying out reflux reaction under the conditions of long-chain alkyl tertiary amine and high-concentration brine, continuously distilling out a product during the reaction, carrying out oil-water separation on a distillate to obtain a crude pentafluorobenzene product, and rectifying to obtain a finished pentafluorobenzene product.
2. The safe green production method of pentafluorobenzene according to claim 1, characterized in that: the high-concentration brine is an inorganic brine solution, including a sulfate or hydrochloride aqueous solution, and has a concentration of more than 30%, preferably 40%.
3. The safe green production method of pentafluorobenzene according to claim 2, characterized in that: the sulfate is sodium sulfate or potassium sulfate, and the hydrochloride is sodium chloride or potassium chloride.
4. The safe and green production method of pentafluorobenzene as claimed in claim 1, characterized in that: the long-chain alkyl tertiary amine is hexadecyl dimethylamine or dodecyl dimethylamine with long carbon chain tertiary amine.
5. The safe green production method of pentafluorobenzene according to claim 1, characterized in that: the mass ratio of the pentafluorobenzoic acid to the high-concentration brine to the long-chain alkyl tertiary amine is 1: 2-10: 0.005-0.5.
6. The safe green production method of pentafluorobenzene according to claim 1, characterized in that: the reaction temperature is the boiling point of high-concentration brine, a product is continuously generated in the reflux reaction process, and the distillate is slowly evaporated to obtain.
7. The safe green production method of pentafluorobenzene according to claim 1, characterized in that: and rectifying the pentafluorobenzene crude product after water separation to obtain a pure product with the purity of more than 99.5 percent.
8. The safe green production method of pentafluorobenzene according to claim 1, characterized in that: after the reaction is finished, the reaction liquid kettle residue after the pentafluorobenzene is evaporated is directly used for feeding the next batch, and the reaction liquid kettle residue is circularly used for more than three times.
9. The safe and green production method of pentafluorobenzene according to any of claims 1 to 8, characterized in that: the reaction was carried out under a nitrogen atmosphere.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5329054A (en) * | 1993-07-19 | 1994-07-12 | Albemarle Corporation | Decarboxylation process |
| JP2566976B2 (en) * | 1987-04-08 | 1996-12-25 | 日本カーバイド工業株式会社 | Method for decarboxylation of halogen-substituted benzenecarboxylic acid |
| CN101225016A (en) * | 2008-01-14 | 2008-07-23 | 浙江大学 | Method for preparing entafluorobenzene by non-catalytic decarboxylation of entafluorobenzoic acid in high-temperature liquid water |
-
2021
- 2021-12-23 CN CN202111592972.0A patent/CN114436762A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2566976B2 (en) * | 1987-04-08 | 1996-12-25 | 日本カーバイド工業株式会社 | Method for decarboxylation of halogen-substituted benzenecarboxylic acid |
| US5329054A (en) * | 1993-07-19 | 1994-07-12 | Albemarle Corporation | Decarboxylation process |
| CN101225016A (en) * | 2008-01-14 | 2008-07-23 | 浙江大学 | Method for preparing entafluorobenzene by non-catalytic decarboxylation of entafluorobenzoic acid in high-temperature liquid water |
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