CN114516780A - Preparation method of 3,4, 5-trifluorobromobenzene - Google Patents
Preparation method of 3,4, 5-trifluorobromobenzene Download PDFInfo
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- CN114516780A CN114516780A CN202111573906.9A CN202111573906A CN114516780A CN 114516780 A CN114516780 A CN 114516780A CN 202111573906 A CN202111573906 A CN 202111573906A CN 114516780 A CN114516780 A CN 114516780A
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- trifluorobromobenzene
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- trifluorobenzene
- trifluoro
- tribromomethylbenzene
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- HKJCELUUIFFSIN-UHFFFAOYSA-N 5-bromo-1,2,3-trifluorobenzene Chemical compound FC1=CC(Br)=CC(F)=C1F HKJCELUUIFFSIN-UHFFFAOYSA-N 0.000 title claims abstract description 47
- 238000002360 preparation method Methods 0.000 title claims abstract description 26
- 238000006243 chemical reaction Methods 0.000 claims abstract description 75
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 39
- AJKNNUJQFALRIK-UHFFFAOYSA-N 1,2,3-trifluorobenzene Chemical compound FC1=CC=CC(F)=C1F AJKNNUJQFALRIK-UHFFFAOYSA-N 0.000 claims abstract description 32
- AQRIWZJQUMVOAC-UHFFFAOYSA-N FC1=CC(C(Br)(Br)Br)=CC(F)=C1F Chemical compound FC1=CC(C(Br)(Br)Br)=CC(F)=C1F AQRIWZJQUMVOAC-UHFFFAOYSA-N 0.000 claims abstract description 28
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims abstract description 17
- 238000006606 decarbonylation reaction Methods 0.000 claims abstract description 17
- HJUGFYREWKUQJT-UHFFFAOYSA-N tetrabromomethane Chemical compound BrC(Br)(Br)Br HJUGFYREWKUQJT-UHFFFAOYSA-N 0.000 claims abstract description 16
- VYBVSXIVXBQRDC-UHFFFAOYSA-N O=C(C(C1F)(C=CC=C1F)F)Br Chemical compound O=C(C(C1F)(C=CC=C1F)F)Br VYBVSXIVXBQRDC-UHFFFAOYSA-N 0.000 claims abstract description 14
- 238000006460 hydrolysis reaction Methods 0.000 claims abstract description 9
- 238000006482 condensation reaction Methods 0.000 claims abstract description 7
- QBERHIJABFXGRZ-UHFFFAOYSA-M rhodium;triphenylphosphane;chloride Chemical compound [Cl-].[Rh].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 QBERHIJABFXGRZ-UHFFFAOYSA-M 0.000 claims abstract description 7
- HVPZLSGKPCMCEV-UHFFFAOYSA-N OC(C(C1F)(C=CC=C1F)F)=O Chemical compound OC(C(C1F)(C=CC=C1F)F)=O HVPZLSGKPCMCEV-UHFFFAOYSA-N 0.000 claims abstract description 6
- 238000006555 catalytic reaction Methods 0.000 claims abstract description 6
- 238000000034 method Methods 0.000 claims description 50
- 230000008569 process Effects 0.000 claims description 32
- 238000003756 stirring Methods 0.000 claims description 32
- 238000010438 heat treatment Methods 0.000 claims description 18
- 238000003682 fluorination reaction Methods 0.000 claims description 16
- JLYXXMFPNIAWKQ-GNIYUCBRSA-N gamma-hexachlorocyclohexane Chemical compound Cl[C@H]1[C@H](Cl)[C@@H](Cl)[C@@H](Cl)[C@H](Cl)[C@H]1Cl JLYXXMFPNIAWKQ-GNIYUCBRSA-N 0.000 claims description 16
- 229960002809 lindane Drugs 0.000 claims description 16
- 238000004821 distillation Methods 0.000 claims description 12
- 238000004519 manufacturing process Methods 0.000 claims description 12
- PEBWOGPSYUIOBP-UHFFFAOYSA-N 1,2,4-trifluorobenzene Chemical compound FC1=CC=C(F)C(F)=C1 PEBWOGPSYUIOBP-UHFFFAOYSA-N 0.000 claims description 11
- 239000007789 gas Substances 0.000 claims description 11
- PQJGSPVYVGXTJW-UHFFFAOYSA-N 1,2,3,4,5,6-hexafluorocyclohexane Chemical compound FC1C(F)C(F)C(F)C(F)C1F PQJGSPVYVGXTJW-UHFFFAOYSA-N 0.000 claims description 9
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 9
- 229910000040 hydrogen fluoride Inorganic materials 0.000 claims description 9
- 239000011552 falling film Substances 0.000 claims description 5
- 230000003301 hydrolyzing effect Effects 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- 238000000354 decomposition reaction Methods 0.000 claims description 4
- 238000000926 separation method Methods 0.000 claims description 2
- 230000008901 benefit Effects 0.000 abstract description 5
- 239000003054 catalyst Substances 0.000 abstract description 5
- 238000011084 recovery Methods 0.000 abstract description 2
- 238000000197 pyrolysis Methods 0.000 description 19
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 12
- 239000000463 material Substances 0.000 description 10
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 9
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 9
- 238000001816 cooling Methods 0.000 description 9
- 230000006324 decarbonylation Effects 0.000 description 9
- 229910052731 fluorine Inorganic materials 0.000 description 9
- 239000011737 fluorine Substances 0.000 description 9
- 239000000203 mixture Substances 0.000 description 9
- 239000007788 liquid Substances 0.000 description 8
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 7
- 238000003547 Friedel-Crafts alkylation reaction Methods 0.000 description 7
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 7
- 229910052794 bromium Inorganic materials 0.000 description 7
- 239000006227 byproduct Substances 0.000 description 7
- 239000012847 fine chemical Substances 0.000 description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 6
- 239000010439 graphite Substances 0.000 description 6
- 229910002804 graphite Inorganic materials 0.000 description 6
- 229910000856 hastalloy Inorganic materials 0.000 description 6
- 230000007062 hydrolysis Effects 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- 239000002994 raw material Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 239000007864 aqueous solution Substances 0.000 description 4
- 230000009615 deamination Effects 0.000 description 4
- 238000006481 deamination reaction Methods 0.000 description 4
- 238000006193 diazotization reaction Methods 0.000 description 4
- 238000010992 reflux Methods 0.000 description 4
- JHJLBTNAGRQEKS-UHFFFAOYSA-M sodium bromide Chemical compound [Na+].[Br-] JHJLBTNAGRQEKS-UHFFFAOYSA-M 0.000 description 4
- WRDGNXCXTDDYBZ-UHFFFAOYSA-N 2,3,4-trifluoroaniline Chemical compound NC1=CC=C(F)C(F)=C1F WRDGNXCXTDDYBZ-UHFFFAOYSA-N 0.000 description 3
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 3
- 229910000831 Steel Inorganic materials 0.000 description 3
- 239000000460 chlorine Substances 0.000 description 3
- 229910052801 chlorine Inorganic materials 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 238000005984 hydrogenation reaction Methods 0.000 description 3
- 239000004973 liquid crystal related substance Substances 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 229910052698 phosphorus Inorganic materials 0.000 description 3
- 239000011574 phosphorus Substances 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 238000007789 sealing Methods 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 239000010959 steel Substances 0.000 description 3
- 239000002351 wastewater Substances 0.000 description 3
- HHLCSFGOTLUREE-UHFFFAOYSA-N 1,2,3-trichloro-5-nitrobenzene Chemical compound [O-][N+](=O)C1=CC(Cl)=C(Cl)C(Cl)=C1 HHLCSFGOTLUREE-UHFFFAOYSA-N 0.000 description 2
- NTBYINQTYWZXLH-UHFFFAOYSA-N 1,2-dichloro-4-nitrobenzene Chemical compound [O-][N+](=O)C1=CC=C(Cl)C(Cl)=C1 NTBYINQTYWZXLH-UHFFFAOYSA-N 0.000 description 2
- BFCFYVKQTRLZHA-UHFFFAOYSA-N 1-chloro-2-nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1Cl BFCFYVKQTRLZHA-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 239000005708 Sodium hypochlorite Substances 0.000 description 2
- 241000607479 Yersinia pestis Species 0.000 description 2
- 230000031709 bromination Effects 0.000 description 2
- 238000005893 bromination reaction Methods 0.000 description 2
- 239000000337 buffer salt Substances 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000004587 chromatography analysis Methods 0.000 description 2
- 239000012043 crude product Substances 0.000 description 2
- 238000006396 nitration reaction Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- RELMFMZEBKVZJC-UHFFFAOYSA-N 1,2,3-trichlorobenzene Chemical compound ClC1=CC=CC(Cl)=C1Cl RELMFMZEBKVZJC-UHFFFAOYSA-N 0.000 description 1
- -1 3,4, 5-trifluorobromobenzene (3,4,5-Trifluoro-1-Bromobenzene) Chemical compound 0.000 description 1
- BMYNFMYTOJXKLE-UHFFFAOYSA-N 3-azaniumyl-2-hydroxypropanoate Chemical compound NCC(O)C(O)=O BMYNFMYTOJXKLE-UHFFFAOYSA-N 0.000 description 1
- AKJNEERVRJOBPD-UHFFFAOYSA-N 6-bromo-2,3,4-trifluoroaniline Chemical compound NC1=C(Br)C=C(F)C(F)=C1F AKJNEERVRJOBPD-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 238000005646 Tsuji-Wilkinson decarbonylation reaction Methods 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 239000003899 bactericide agent Substances 0.000 description 1
- PASDCCFISLVPSO-UHFFFAOYSA-N benzoyl chloride Chemical compound ClC(=O)C1=CC=CC=C1 PASDCCFISLVPSO-UHFFFAOYSA-N 0.000 description 1
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 description 1
- XFWJKVMFIVXPKK-UHFFFAOYSA-N calcium;oxido(oxo)alumane Chemical compound [Ca+2].[O-][Al]=O.[O-][Al]=O XFWJKVMFIVXPKK-UHFFFAOYSA-N 0.000 description 1
- 238000012824 chemical production Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000001055 chewing effect Effects 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 230000002124 endocrine Effects 0.000 description 1
- 210000000750 endocrine system Anatomy 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000010436 fluorite Substances 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 238000003306 harvesting Methods 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000002917 insecticide Substances 0.000 description 1
- 210000004185 liver Anatomy 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000008267 milk Substances 0.000 description 1
- 210000004080 milk Anatomy 0.000 description 1
- 235000013336 milk Nutrition 0.000 description 1
- 229910000403 monosodium phosphate Inorganic materials 0.000 description 1
- 235000019799 monosodium phosphate Nutrition 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- ACVYVLVWPXVTIT-UHFFFAOYSA-N phosphinic acid Chemical compound O[PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-N 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- 235000011164 potassium chloride Nutrition 0.000 description 1
- 239000001103 potassium chloride Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 210000004994 reproductive system Anatomy 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical compound [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 235000013311 vegetables Nutrition 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- UTODFRQBVUVYOB-UHFFFAOYSA-P wilkinson's catalyst Chemical compound [Cl-].C1=CC=CC=C1P(C=1C=CC=CC=1)(C=1C=CC=CC=1)[Rh+](P(C=1C=CC=CC=1)(C=1C=CC=CC=1)C=1C=CC=CC=1)P(C=1C=CC=CC=1)(C=1C=CC=CC=1)C1=CC=CC=C1 UTODFRQBVUVYOB-UHFFFAOYSA-P 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/26—Preparation of halogenated hydrocarbons by reactions involving an increase in the number of carbon atoms in the skeleton
- C07C17/263—Preparation of halogenated hydrocarbons by reactions involving an increase in the number of carbon atoms in the skeleton by condensation reactions
- C07C17/269—Preparation of halogenated hydrocarbons by reactions involving an increase in the number of carbon atoms in the skeleton by condensation reactions of only halogenated hydrocarbons
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- 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
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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
- C07C51/58—Preparation of carboxylic acid halides
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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
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
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Abstract
The invention relates to a preparation method of 3,4, 5-trifluorobromobenzene, which comprises the following steps: step one, 1,2, 3-trifluorobenzene and carbon tetrabromide react to generate 1,2, 3-trifluoro-5-tribromomethylbenzene under the catalysis of anhydrous aluminum trichloride; step two, carrying out hydrolysis reaction on 1,2, 3-trifluoro-5-tribromomethylbenzene and water to generate 1,2, 3-trifluorobenzoic acid, and simultaneously carrying out condensation reaction on 1,2, 3-trifluorobenzoic acid and 1,2, 3-trifluoro-5-tribromomethylbenzene to generate 1,2, 3-trifluorobenzoyl bromide; and step three, decarbonylation reaction of the 1,2, 3-trifluorobenzoyl bromide is carried out under the catalysis of tris (triphenylphosphine) rhodium chloride to generate the 3,4, 5-trifluorobromobenzene. The preparation method of the 3,4, 5-trifluorobromobenzene has the advantages of simple and convenient operation and control, high conversion rate and easy catalyst recovery.
Description
Technical Field
The invention relates to a preparation method of 3,4, 5-trifluorobromobenzene, belonging to the technical field of chemical synthesis.
Background
Due to the special activity of fluorine element, a plurality of fluorine-containing compounds have excellent performance and extraordinary effect, and are paid more attention by chemical industry circles at home and abroad, since the middle of the 20 th century 80 s, the research on fluorine-containing fine chemicals in China is extremely active, the fluorine-containing fine chemicals are developed and become a great country for producing fluorine-containing fine chemicals by virtue of the advantages of fluorite resources, but the per-capita consumption of fluorine-containing fine chemicals and the research and innovation capability are far away from developed countries, the adjustment and transformation upgrading of industrial structures of fluorine-containing fine chemicals are at the forefront, the introduction of a high-end fluorine-containing fine chemical production technology from abroad is extremely difficult, and 3,4, 5-trifluorobromobenzene is a typical case in the fluorine-containing fine chemicals.
3,4, 5-trifluorobromobenzene (3,4,5-Trifluoro-1-Bromobenzene) is colorless transparent liquid, is mainly used for preparing bactericides and liquid crystal materials, and has the following chemical structural formula:
at present, the domestic production processes of 3,4, 5-trifluorobromobenzene are mainly divided into the following processes:
(1) chinese patent document CN103601613A discloses a production process of 3,4, 5-trifluorobromobenzene: brominating 2,3, 4-trifluoroaniline with bromine to obtain 2,3, 4-trifluoro-6-bromoaniline, diazotizing and deaminating to obtain 3,4, 5-trifluorobromobenzene, wherein the reaction equation is as follows:
bromine with strong toxic action and corrosivity is used in the process, hypophosphorous acid and a copper catalyst are also used in the diazotization deamination process, phosphorus-containing heavy metal wastewater can be generated, the environment-friendly treatment cost is high, and the occupational health protection of operators is not facilitated.
(2) Chinese patent document CN105439810A discloses a production process of 3,4, 5-trifluorobromobenzene: 2,3, 4-trifluoroaniline is used as a raw material, 1,2, 3-trifluorobenzene is obtained by diazotization deamination, and then the 1,2, 3-trifluorobenzene is reacted with bromine to obtain 3,4, 5-trifluorobromobenzene, wherein the reaction equation is as follows:
the diazotization deamination procedure of the process is similar to CN103601613A, and the only difference is that the bromine consumption is reduced by matching the bromine bromination process with the use of hydrogen peroxide, so the essential defect of the process is not changed.
(3) Chinese patent document CN108947763A discloses a production process of 3,4, 5-trifluorobromobenzene: 1,2, 3-trifluorobenzene is taken as an initial raw material, is firstly dispersed in an organic solvent and then is mixed with a sodium bromide aqueous solution containing buffer salt, a sodium hypochlorite aqueous solution is dripped to obtain a 3,4, 5-trifluorobromobenzene crude product, and the 3,4, 5-trifluorobromobenzene finished product is obtained by melting and crystallizing, wherein the chemical reaction equation is as follows:
the process is improved based on CN103601613A and CN105439810A, the use of bromine is successfully avoided, the mode of oxidizing sodium bromide by sodium hypochlorite is used for replacing the bromine, the occupational hazard is reduced, the unit consumption of buffer salt sodium dihydrogen phosphate is as high as 0.6, and the treatment cost of high-phosphorus wastewater is still high.
(4) Chinese patent document CN112010733A discloses a production process of 3,4, 5-trifluorobromobenzene: the 2,3, 4-trifluoroaniline is prepared by taking 3,4, 5-trichloronitrobenzene which is a byproduct generated in the process of preparing 3, 4-dichloronitrobenzene from chloronitrobenzene through chlorine as a raw material through six procedures of fluorination, hydrogenation reduction, diazotization deamination, nitration, fluorination and hydrogenation reduction, the subsequent process is similar to CN103601613A, and the reaction equation is as follows:
the process relates to two procedures of nitration and hydrogenation reduction with great dangerousness, has high safety risk and certain limitation, is only suitable for treating 3,4, 5-trichloronitrobenzene which is a byproduct generated in the process of preparing the 3, 4-dichloronitrobenzene by introducing chlorine into the chloronitrobenzene, and has high comprehensive cost and no industrial value.
(5) In 2020, ykeky optimizes the above process, and in world pesticide 2020, volume 42, phase 4, pages 54 to 56, a paper entitled "new process for synthesizing 3,4, 5-trifluorobromobenzene" is published, and the paper reports that 3,4, 5-trifluorobromobenzene can be synthesized from 1,2, 3-trichlorobenzene as a starting material by two steps of fluorination and bromination, wherein the reaction equation is as follows:
the process only changes the initial raw materials, the reaction essence is not changed, high-phosphorus wastewater is still generated, in addition, the purity of by-products, namely potassium chloride and sodium chloride, generated by the process is low, and the by-products need to be treated as waste salt, so the process has the advantages of high environmental protection cost, low market competitiveness and low industrial feasibility.
Disclosure of Invention
The invention aims to solve the technical problem of providing a preparation method of 3,4, 5-trifluorobromobenzene, which has the advantages of simple and convenient operation control, high conversion rate and easy catalyst recovery.
The invention provides a technical scheme for solving the technical problems, which comprises the following steps: a preparation method of 3,4, 5-trifluorobromobenzene comprises the following steps:
step one, reacting 1,2, 3-trifluorobenzene with carbon tetrabromide under the catalysis of anhydrous aluminum trichloride to generate 1,2, 3-trifluoro-5-tribromomethylbenzene, wherein the reaction formula is as follows:
step two, carrying out hydrolysis reaction on 1,2, 3-trifluoro-5-tribromomethylbenzene and water to generate 1,2, 3-trifluorobenzoic acid, and simultaneously carrying out condensation reaction on 1,2, 3-trifluorobenzoic acid and 1,2, 3-trifluoro-5-tribromomethylbenzene to generate 1,2, 3-trifluorobenzoyl bromide, wherein the reaction formula is as follows:
and step three, decarbonylation reaction of the 1,2, 3-trifluorobenzoyl bromide is carried out under the catalysis of tris (triphenylphosphine) rhodium chloride to generate 3,4, 5-trifluorobromobenzene, and the reaction formula is as follows:
the 1,2, 3-trifluorobenzene is prepared by the fluorination reaction of hexachlorocyclohexane and anhydrous hydrogen fluoride to prepare hexafluorocyclohexane, and the reaction formula is as follows:
heating and decomposing the obtained hexafluorocyclohexane to obtain 1,2, 3-trifluorobenzene and 1,2, 4-trifluorobenzene, wherein the reaction formula is as follows:
then, 1,2, 3-trifluorobenzene and 1,2, 4-trifluorobenzene were separated by distillation.
In the first step, 1,2, 3-trifluorobenzene and carbon tetrabromide are added, stirred and heated to 45-55 ℃ for uniform mixing, anhydrous aluminum trichloride is added for continuous stirring, generated gas is absorbed by a water falling film, then the temperature is heated to 140-150 ℃ for reaction, water is added after the reaction is finished, and 1,2, 3-trifluoro-5-tribromomethylbenzene distilled out along with steam is collected.
The temperature of the hydrolytic condensation reaction in the second step is 120-125 ℃, and the pressure of the hydrolytic condensation reaction is normal pressure.
The decarbonylation reaction temperature in the third step is 200-250 ℃.
The temperature of the fluorination reaction is 180-190 ℃, and the pressure of the fluorination reaction is normal pressure.
The temperature of the heating decomposition is 250-260 ℃, and the pressure of the heating decomposition is 0.3-0.4 Mpa.
The distillation separation is carried out under the pressure of-0.095 Mpa, the fraction obtained at 45-55 ℃ is 1,2, 4-trifluorobenzene, and the fraction obtained at 55-85 ℃ is 1,2, 3-trifluorobenzene.
The mass of the anhydrous aluminum trichloride added is 1 to 1.5 times of that of 1,2, 3-trifluorobenzene.
The above tris (triphenylphosphine) rhodium chloride was added in an amount of 0.8 to 1.2 times by mass as much as 1,2, 3-trifluorobenzene.
The invention has the positive effects that:
(1) in the preparation method of the 3,4, 5-trifluorobromobenzene, the process of preparing the 1,2, 3-trifluoro-5-tribromomethylbenzene from the 1,2, 3-trifluorobenzene is a Friedel-crafts alkylation reaction which is convenient to operate and control, the byproduct hydrobromic acid water solution is a material which is in high demand in the market, and the byproduct aluminum trichloride water solution can be prepared into the polyaluminum chloride which is used for the water treatment process in the environmental protection field. The process for preparing the 1,2, 3-trifluorobenzoyl bromide by hydrolyzing the 1,2, 3-trifluoro-5-tribromomethylbenzene adopts an industrial process for preparing benzoyl chloride, and has more advanced complete equipment and less difficulty in equipment model selection. The decarbonylation of the 1,2, 3-trifluorobenzoyl bromide is a Tsuji-Wilkinson decarbonylation reaction invented by J.Tsuji and K.Ono in 1965, the conversion rate is high, the catalyst is easy to recover, and the decarbonylation comprehensive cost is low.
(2) The raw material for synthesizing 1,2, 3-trifluorobenzene by the preparation method of 3,4, 5-trifluorobromobenzene adopts hexachlorocyclohexane (hexachlorocyclohexane). Hexachlorocyclohexane is an organic insecticide which is used earliest and most in China, and is widely used for preventing and treating various piercing-sucking and chewing mouthparts pests on crops, fruit trees, vegetables and forest trees, so that the harvest of the crops is ensured, and the pests are reduced. However, because of its long residual period in the environment (up to 50 years), hexachlorocyclohexane remained in the environment and on crops can be transferred to liver, fat and milk after being taken into human body, and is accumulated in human body, and has certain damage effect on endocrine and reproductive system. Therefore, china stopped production since 1983. Because the production of hexachlorocyclohexane is stopped, some pure benzene with poor quality in the coal chemical industry is less and a more economic way is taken, and the effective implementation of the invention can improve an environment-friendly and economic way for the pure benzene with poor quality: adding low-quality pure benzene and chlorine to obtain hexachlorocyclohexane, fluorinating to obtain hexafluorocyclohexane, and estimating according to the national production scale of 20000 tons of 3,4, 5-trifluorobromobenzene per year, and can create economic benefit of billions yuan each year. The hydrogen fluoride generated in the pyrolysis process of the hexachlorocyclohexane can be used for the fluorination of the hexachlorocyclohexane, the utilization rate of fluorine atoms can be improved to the maximum extent, and the method is economical and environment-friendly. In addition, 1,2, 4-trifluorobenzene, a by-product generated in the pyrolysis process of hexafluorocyclohexane, is a precious electronic chemical applied to the field of liquid crystal materials, and 1,2, 4-trifluorobenzene can be separated from 1,2, 3-trifluorobenzene by simple rectification.
Drawings
FIG. 1 is a chromatogram of a finished product of 3,4, 5-trifluorobromobenzene of example 1 of the present invention.
Detailed Description
The present invention is described in detail below by way of examples, it should be noted that the following examples are only for illustrating the present invention and should not be construed as limiting the scope of the present invention, and those skilled in the art can make some insubstantial modifications and adaptations of the present invention based on the above-described disclosure. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs.
The chemical reagents used in the invention are all purchased reagents without special description, and the concentration is chemical purity.
Example 1
The preparation method of 3,4, 5-trifluorobromobenzene of the embodiment comprises the following steps:
1. fluorination: and (3) preparing hexafluorocyclohexane.
Putting hexachlorocyclohexane (2500.00kg, 8.60kmol) into a 3000L Hastelloy reaction kettle, stirring and heating to 190 ℃, stirring until the reaction materials are molten, continuously introducing anhydrous hydrogen fluoride gas (the flow is 20.00L/min) into the reaction kettle until the conversion rate of hexachlorocyclohexane reaches above 90%, wherein the reaction system is viscous brown liquid, and stopping introducing the anhydrous hydrogen fluoride gas for pyrolysis.
2. Pyrolysis: preparation of 1,2, 3-trifluorobenzene.
And (3) sealing the Hastelloy reaction kettle used in the fluorination procedure in the previous step, continuously heating to 260 ℃, increasing the pressure in the reaction kettle to about 0.2MPa, and continuously introducing dry nitrogen into the reaction kettle until the pyrolysis pressure reaches 0.4 MPa. The pressure in the reaction kettle continuously rises along with the pyrolysis, and the maximum pressure can reach 0.5 MPa. And after the stirring time at 260 ℃ reaches 10h, the pyrolysis is basically finished.
After pyrolysis, pressure is relieved to normal pressure (normal-temperature dry nitrogen is introduced for cooling in the pressure relief process), negative pressure distillation is started to be carried out (the pressure is reduced to minus 0.095MPa, 45-85 ℃), and the fraction before 55 ℃ under the negative pressure is 1,2, 4-trifluorobenzene which is sold and applied to the field of liquid crystal materials after refining. The fraction at 55-85 ℃ under negative pressure was 803.56kg of 1,2, 3-trifluorobenzene as a colorless liquid.
3. Friedel-crafts alkylation: preparation of 1,2, 3-trifluoro-5-tribromomethylbenzene.
1,2, 3-trifluorobenzene (1500.00kg, 11.36kmol) and carbon tetrabromide (3950.00kg, 11.91kmol) are put into a 8000L steel lining graphite reaction kettle, stirred and heated to 55 ℃, and after uniform mixing, anhydrous aluminum trichloride (1600.00kg, 12.05kmol) is added in one step.
After adding anhydrous aluminum trichloride, controlling the temperature to be 55 ℃ and continuing stirring for 2 hours, wherein a large amount of gas is generated in the stirring process and is absorbed by a water falling film.
Controlling the temperature to be 55 ℃ and stirring, slowly heating until the reaction system is slightly refluxed, the temperature is about 95 ℃, keeping the reaction system in a slightly refluxed state and stirring for 1h, then continuously heating to 150 ℃, and then keeping the temperature and stirring for 5 h.
After the temperature is controlled to 150 ℃, the mixture is kept and stirred, water is directly added into the reaction system without cooling, 1,2, 3-trifluoro-5-tribromomethylbenzene is distilled out along with water vapor and is received by another 5000L steel-lined graphite reaction kettle with circulating water cooling. When no 1,2, 3-trifluoro-5-tribromomethylbenzene is distilled out along with the steam, the water is stopped to be added, the water layer is the water solution of aluminum trichloride, and the calcium aluminate powder is added to prepare the polyaluminium chloride which is sold as a water treatment agent in the environmental protection field. The mixture of water and 1,2, 3-trifluoro-5-tribromomethylbenzene is directly fed into the next step without treatment.
4. Hydrolysis: preparation of 1,2, 3-trifluorobenzoyl bromide.
And (2) distilling the mixture of the 1,2, 3-trifluoro-5-tribromomethylbenzene obtained in the Friedel-crafts alkylation procedure and water under negative pressure to 115 ℃, wherein the water content of a reaction system is about 4% (determined by a Karl Fischer method), closing a vacuum system, changing to normal pressure distillation, controlling the temperature to 125 ℃, and stirring for 3 hours.
After the temperature control stirring is finished, the material is transferred to decarbonylation equipment without treatment and directly enters the next decarbonylation reaction procedure.
5. Decarbonylation: preparation of 3,4, 5-trifluorobromobenzene.
The crude 1,2, 3-trifluorobenzoyl bromide obtained in the previous hydrolysis step is pumped into a reaction tower filled with tris (triphenyl phosphine) rhodium chloride (15000.00kg, 16.21kmol) under negative pressure, the temperature of the reaction tower is maintained at 250 ℃, and 2109.12kg of 3,4, 5-trifluorobromobenzene can be obtained and is colorless liquid, and the content of gas chromatography is 99.85%. The chromatogram of the finished 3,4, 5-trifluorobromobenzene is shown in FIG. 1, and the chromatographic analysis results of the finished 3,4, 5-trifluorobromobenzene are shown in Table 1. After the reaction tower is used for a period of time, tar impurities are deposited in a catalyst filling area and the bottom of the tower, 500 ℃ air needs to be introduced for burning, and the circulating decarbonylation can be continuously carried out after burning.
TABLE 1 chromatographic analysis results Table
Example 2
The preparation method of 3,4, 5-trifluorobromobenzene of the embodiment comprises the following steps:
1. fluorination: and (3) preparing hexafluorocyclohexane.
Putting hexachlorocyclohexane (2500.00kg, 8.60kmol) into a 3000L Hastelloy reaction kettle, stirring and heating to 180 ℃, stirring until the reaction material is molten, continuously introducing anhydrous hydrogen fluoride gas (flow is 20.00L/min) into the reaction kettle until the conversion rate of hexachlorocyclohexane reaches over 90%, wherein the reaction system is viscous brown liquid, and stopping introducing the anhydrous hydrogen fluoride gas to be pyrolyzed.
2. Pyrolysis: preparation of 1,2, 3-trifluorobenzene.
And (3) sealing the Hastelloy reaction kettle used in the fluorination procedure in the previous step, continuously heating to 250 ℃, increasing the pressure in the reaction kettle to about 0.2MPa, and continuously introducing dry nitrogen into the reaction kettle until the pyrolysis pressure reaches 0.3 MPa. The pressure in the reaction kettle continuously rises along with the pyrolysis, and the maximum pressure can reach 0.5 MPa. And after the stirring time at 255 ℃ reaches 10h, the pyrolysis is basically finished.
After pyrolysis, pressure is released to normal pressure (normal temperature dry nitrogen is introduced for cooling in the pressure release process), negative pressure distillation is started (at-0.095 MPa, 45-85 ℃), and the fraction before 55 ℃ under negative pressure is 1,2, 4-trifluorobenzene. The fraction at 55-85 ℃ under negative pressure was 802.35kg of 1,2, 3-trifluorobenzene as a colorless liquid.
3. Friedel-crafts alkylation: preparation of 1,2, 3-trifluoro-5-tribromomethylbenzene.
1,2, 3-trifluorobenzene (1500.00kg, 11.36kmol) and carbon tetrabromide (3950.00kg, 11.91kmol) are put into a 8000L steel lining graphite reaction kettle, stirred and heated to 45 ℃, and after uniform mixing, anhydrous aluminum trichloride (1600.00kg, 12.05kmol) is added in one step.
After adding anhydrous aluminum trichloride, controlling the temperature to be 45 ℃ and continuing stirring for 2 hours, wherein a large amount of gas is generated in the stirring process and is absorbed by a water falling film.
Controlling the temperature to be 45 ℃ and stirring, slowly heating to the reaction system for a little reflux, keeping the reaction system at the temperature of about 90 ℃ in a little reflux state, stirring for 1h, then continuously heating to 140 ℃, preserving the temperature and stirring for 5 h.
After the temperature is controlled to 140 ℃, the mixture is kept and stirred, water is directly added into the reaction system without cooling, 1,2, 3-trifluoro-5-tribromomethylbenzene is distilled out along with water vapor and is received by another 5000L steel-lined graphite reaction kettle with circulating water cooling. When no 1,2, 3-trifluoro-5-tribromomethylbenzene is distilled out along with the steam, the water addition is stopped, and the water layer is the aqueous solution of aluminum trichloride. The mixture of water and 1,2, 3-trifluoro-5-tribromomethylbenzene was carried on to the next step without treatment.
4. Hydrolysis: preparation of 1,2, 3-trifluorobenzoyl bromide.
And (3) carrying out negative pressure distillation on the mixture of the 1,2, 3-trifluoro-5-tribromomethylbenzene obtained in the last friedel-crafts alkylation procedure and water to 115 ℃, wherein the water content of a reaction system is about 4 percent (determined by a Karl Fischer method), closing a vacuum system, changing to normal pressure distillation, and controlling the temperature to be 120 ℃ and stirring for 3 hours.
After the temperature control stirring is finished, the material is transferred to decarbonylation equipment without treatment and directly enters the next decarbonylation reaction procedure.
5. Decarbonylation: preparation of 3,4, 5-trifluorobromobenzene.
The crude product of the 1,2, 3-trifluorobenzoyl bromide obtained in the previous hydrolysis step is pumped into a reaction tower filled with tris (triphenyl phosphine) rhodium chloride (15000.00kg, 16.21kmol) under negative pressure, and the temperature of the reaction tower is maintained at 230 ℃ to obtain 2107.83kg of 3,4, 5-trifluorobromobenzene.
Example 3
The preparation method of 3,4, 5-trifluorobromobenzene of the embodiment comprises the following steps:
1. fluorination: and (3) preparing hexafluorocyclohexane.
Putting hexachlorocyclohexane (2500.00kg, 8.60kmol) into a 3000L Hastelloy reaction kettle, stirring and heating to 185 ℃, stirring until the reaction materials are molten, continuously introducing anhydrous hydrogen fluoride gas (the flow is 20.00L/min) into the reaction kettle until the conversion rate of hexachlorocyclohexane reaches above 90%, wherein the reaction system is viscous brown liquid, and stopping introducing the anhydrous hydrogen fluoride gas for pyrolysis.
2. Pyrolysis: preparation of 1,2, 3-trifluorobenzene.
And (3) sealing the Hastelloy reaction kettle used in the fluorination procedure in the previous step, continuously heating to 255 ℃, increasing the pressure in the reaction kettle to about 0.2MPa, and continuously introducing dry nitrogen into the reaction kettle until the pyrolysis pressure reaches 0.35 MPa. The pressure in the reaction kettle continuously rises along with the pyrolysis, and the maximum pressure can reach 0.5 MPa. And after the heat preservation and stirring time at 250 ℃ reaches 10 hours, basically completing pyrolysis.
After pyrolysis, pressure is released to normal pressure (normal temperature dry nitrogen is introduced for cooling in the pressure release process), negative pressure distillation is started (at-0.095 MPa, 45-85 ℃), and the fraction before 55 ℃ under negative pressure is 1,2, 4-trifluorobenzene. The fraction at 55-85 ℃ under negative pressure was 801.89kg of 1,2, 3-trifluorobenzene as a colorless liquid.
3. Friedel-crafts alkylation: preparation of 1,2, 3-trifluoro-5-tribromomethylbenzene.
1,2, 3-trifluorobenzene (1500.00kg, 11.36kmol) and carbon tetrabromide (3950.00kg, 11.91kmol) are put into a 8000L steel lining graphite reaction kettle, stirred and heated to 50 ℃, and after uniform mixing, anhydrous aluminum trichloride (1600.00kg, 12.05kmol) is added in one step.
After adding anhydrous aluminum trichloride, controlling the temperature to be 50 ℃ and continuing stirring for 2 hours, wherein a large amount of gas is generated in the stirring process and is absorbed by a water falling film.
Controlling the temperature to be 50 ℃ and stirring, slowly heating to the reaction system for a little reflux, keeping the reaction system at the temperature of about 93 ℃ in a little reflux state, stirring for 1h, then continuously heating to 145 ℃, preserving the temperature and stirring for 5 h.
After the temperature is controlled to 145 ℃, the mixture is kept and stirred, water is directly added into the reaction system without cooling, 1,2, 3-trifluoro-5-tribromomethylbenzene is distilled out along with water vapor and is received by another 5000L steel-lined graphite reaction kettle with circulating water cooling. When no 1,2, 3-trifluoro-5-tribromomethylbenzene is distilled out along with the steam, the water addition is stopped, and the water layer is the aqueous solution of aluminum trichloride. The mixture of water and 1,2, 3-trifluoro-5-tribromomethylbenzene was carried on directly to the next step without treatment.
4. Hydrolysis: preparation of 1,2, 3-trifluorobenzoyl bromide.
And (3) carrying out negative pressure distillation on the mixture of the 1,2, 3-trifluoro-5-tribromomethylbenzene obtained in the last friedel-crafts alkylation procedure and water to 118 ℃, wherein the water content of a reaction system is about 4 percent (determined by a Karl Fischer method), closing a vacuum system, changing to normal pressure distillation, and controlling the temperature to be 123 ℃ and stirring for 3 hours.
After the temperature control stirring is finished, the material is transferred to decarbonylation equipment without treatment and directly enters the next decarbonylation reaction procedure.
5. Decarbonylation: preparation of 3,4, 5-trifluorobromobenzene.
The crude 1,2, 3-trifluorobenzoyl bromide obtained in the previous hydrolysis step was pumped into a reaction tower filled with tris (triphenylphosphino) rhodium chloride (15000.00kg, 16.21kmol) under negative pressure, and the temperature of the reaction tower was maintained at 240 ℃ to obtain 2106.88kg of 3,4, 5-trifluorobromobenzene.
It should be understood that the above examples are only for clearly illustrating the present invention and are not intended to limit the embodiments of the present invention. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. And such obvious variations or modifications which fall within the spirit of the invention are intended to be covered by the scope of the present invention.
Claims (10)
1. A preparation method of 3,4, 5-trifluorobromobenzene is characterized by comprising the following steps: the method comprises the following steps:
step one, reacting 1,2, 3-trifluorobenzene with carbon tetrabromide under the catalysis of anhydrous aluminum trichloride to generate 1,2, 3-trifluoro-5-tribromomethylbenzene, wherein the reaction formula is as follows:
step two, carrying out hydrolysis reaction on 1,2, 3-trifluoro-5-tribromomethylbenzene and water to generate 1,2, 3-trifluorobenzoic acid, and simultaneously carrying out condensation reaction on the 1,2, 3-trifluorobenzoic acid and the 1,2, 3-trifluoro-5-tribromomethylbenzene to generate 1,2, 3-trifluorobenzoyl bromide, wherein the reaction formula is as follows:
and step three, decarbonylation reaction of the 1,2, 3-trifluorobenzoyl bromide is carried out under the catalysis of tris (triphenylphosphine) rhodium chloride to generate 3,4, 5-trifluorobromobenzene, and the reaction formula is as follows:
2. the process for producing 3,4, 5-trifluorobromobenzene as claimed in claim 1, wherein: the preparation method of the 1,2, 3-trifluorobenzene comprises the following steps of carrying out fluorination reaction on hexachlorocyclohexane and anhydrous hydrogen fluoride to prepare hexafluorocyclohexane, wherein the reaction formula is as follows:
heating and decomposing the obtained hexafluorocyclohexane to obtain 1,2, 3-trifluorobenzene and 1,2, 4-trifluorobenzene, wherein the reaction formula is as follows:
then, 1,2, 3-trifluorobenzene and 1,2, 4-trifluorobenzene were separated by distillation.
3. The process for producing 3,4, 5-trifluorobromobenzene as claimed in claim 1, wherein: in the first step, 1,2, 3-trifluorobenzene and carbon tetrabromide are added, stirred and heated to 45-55 ℃ for uniform mixing, anhydrous aluminum trichloride is added for continuous stirring, generated gas is absorbed by a water falling film, then the temperature is heated to 140-150 ℃ for reaction, water is added after the reaction is finished, and 1,2, 3-trifluoro-5-tribromomethylbenzene distilled out along with steam is collected.
4. The process for producing 3,4, 5-trifluorobromobenzene as claimed in claim 1, wherein: the temperature of the hydrolytic condensation reaction in the second step is 120-125 ℃, and the pressure of the hydrolytic condensation reaction is normal pressure.
5. The process for producing 3,4, 5-trifluorobromobenzene as claimed in claim 1, wherein: the decarbonylation reaction temperature in the third step is 200-250 ℃.
6. The method for preparing 3,4, 5-trifluorobromobenzene according to claim 2, characterized in that: the temperature of the fluorination reaction is 180-190 ℃, and the pressure of the fluorination reaction is normal pressure.
7. The process for producing 3,4, 5-trifluorobromobenzene as claimed in claim 2, characterized in that: the temperature of the heating decomposition is 250-260 ℃, and the pressure of the heating decomposition is 0.3-0.4 Mpa.
8. The process for producing 3,4, 5-trifluorobromobenzene as claimed in claim 2, characterized in that: the distillation separation is carried out under the pressure of-0.095 Mpa, the fraction obtained at 45-55 ℃ is 1,2, 4-trifluorobenzene, and the fraction obtained at 55-85 ℃ is 1,2, 3-trifluorobenzene.
9. The method for producing 3,4, 5-trifluorobromobenzene according to any one of claims 1 to 8, characterized in that: the mass of the added anhydrous aluminum trichloride is 1 to 1.5 times of that of 1,2, 3-trifluorobenzene.
10. The method for producing 3,4, 5-trifluorobromobenzene according to any one of claims 1 to 8, characterized in that: the mass of the added tris (triphenylphosphine) rhodium chloride is 0.8 to 1.2 times of that of 1,2, 3-trifluorobenzene.
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| CN116553997B (en) * | 2023-07-10 | 2023-09-26 | 山东国邦药业有限公司 | Synthesis method of intermediate 1,2, 3-trifluoro-benzene for synthesizing 3,4, 5-trifluoro-bromobenzene |
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