CN114516780B - Preparation method of 3,4, 5-trifluoro-bromobenzene - Google Patents
Preparation method of 3,4, 5-trifluoro-bromobenzene Download PDFInfo
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- CN114516780B CN114516780B CN202111573906.9A CN202111573906A CN114516780B CN 114516780 B CN114516780 B CN 114516780B CN 202111573906 A CN202111573906 A CN 202111573906A CN 114516780 B CN114516780 B CN 114516780B
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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 41
- 238000002360 preparation method Methods 0.000 title claims abstract description 30
- 238000006243 chemical reaction Methods 0.000 claims abstract description 73
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 44
- 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 27
- 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 16
- HJUGFYREWKUQJT-UHFFFAOYSA-N tetrabromomethane Chemical compound BrC(Br)(Br)Br HJUGFYREWKUQJT-UHFFFAOYSA-N 0.000 claims abstract description 16
- 238000006460 hydrolysis reaction Methods 0.000 claims abstract description 13
- 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 12
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000006482 condensation reaction Methods 0.000 claims abstract description 7
- 238000006555 catalytic reaction Methods 0.000 claims abstract description 6
- 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 3
- SONJTKJMTWTJCT-UHFFFAOYSA-K rhodium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Rh+3] SONJTKJMTWTJCT-UHFFFAOYSA-K 0.000 claims abstract description 3
- 238000000034 method Methods 0.000 claims description 52
- 230000008569 process Effects 0.000 claims description 39
- AJKNNUJQFALRIK-UHFFFAOYSA-N 1,2,3-trifluorobenzene Chemical compound FC1=CC=CC(F)=C1F AJKNNUJQFALRIK-UHFFFAOYSA-N 0.000 claims description 29
- 238000003756 stirring Methods 0.000 claims description 29
- 238000003682 fluorination reaction Methods 0.000 claims description 17
- 238000004821 distillation 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 15
- 229960002809 lindane Drugs 0.000 claims description 15
- 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 10
- 230000007062 hydrolysis Effects 0.000 claims description 10
- 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
- 238000010521 absorption reaction Methods 0.000 claims description 5
- 239000011552 falling film Substances 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- 238000005979 thermal decomposition reaction Methods 0.000 claims description 4
- 238000000926 separation method Methods 0.000 claims description 2
- 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 1
- 239000003054 catalyst Substances 0.000 abstract description 5
- 238000011084 recovery Methods 0.000 abstract description 3
- 238000000197 pyrolysis Methods 0.000 description 20
- 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
- 229910052731 fluorine Inorganic materials 0.000 description 9
- 239000011737 fluorine Substances 0.000 description 9
- 238000010438 heat treatment Methods 0.000 description 9
- 230000006324 decarbonylation Effects 0.000 description 8
- 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
- 239000007864 aqueous solution Substances 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
- 238000001816 cooling Methods 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
- 238000004519 manufacturing process Methods 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- 238000010992 reflux Methods 0.000 description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 5
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 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
- 239000000047 product Substances 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- JHJLBTNAGRQEKS-UHFFFAOYSA-M sodium bromide Chemical compound [Na+].[Br-] JHJLBTNAGRQEKS-UHFFFAOYSA-M 0.000 description 4
- 239000000126 substance Substances 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
- -1 3,4, 5-trifluorobromobenzene (3, 4, 5-Trifluoro-1-Bromobenzene) Chemical compound 0.000 description 3
- RKEHTSCTPDJQFR-UHFFFAOYSA-N 3,4,5-trifluorobenzoyl bromide Chemical compound Fc1cc(cc(F)c1F)C(Br)=O RKEHTSCTPDJQFR-UHFFFAOYSA-N 0.000 description 3
- 229910000831 Steel Inorganic materials 0.000 description 3
- 230000008901 benefit 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
- 238000004321 preservation Methods 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 229910052703 rhodium Inorganic materials 0.000 description 3
- 239000010948 rhodium Substances 0.000 description 3
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 3
- 238000007789 sealing Methods 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
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 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
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000004587 chromatography analysis Methods 0.000 description 2
- 239000000571 coke Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000000575 pesticide Substances 0.000 description 2
- 235000011164 potassium chloride Nutrition 0.000 description 2
- 239000001103 potassium chloride Substances 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 2
- 239000007858 starting material Substances 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
- BFCFYVKQTRLZHA-UHFFFAOYSA-N 1-chloro-2-nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1Cl BFCFYVKQTRLZHA-UHFFFAOYSA-N 0.000 description 1
- CZGCEKJOLUNIFY-UHFFFAOYSA-N 4-Chloronitrobenzene Chemical compound [O-][N+](=O)C1=CC=C(Cl)C=C1 CZGCEKJOLUNIFY-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
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-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
- 239000007983 Tris buffer Substances 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
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000001055 chewing effect Effects 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 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
- 239000012043 crude product Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 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
- 210000004709 eyebrow Anatomy 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
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 210000004185 liver Anatomy 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
- 238000006396 nitration reaction Methods 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 238000012946 outsourcing Methods 0.000 description 1
- 230000001590 oxidative effect Effects 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
- 239000000843 powder Substances 0.000 description 1
- 210000004994 reproductive system Anatomy 0.000 description 1
- FCQRKDSALKMOGU-UHFFFAOYSA-K rhodium(3+);triphenylphosphane;trichloride Chemical compound Cl[Rh](Cl)Cl.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 FCQRKDSALKMOGU-UHFFFAOYSA-K 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical compound [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 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
Classifications
-
- 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
-
- 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
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/58—Preparation of carboxylic acid halides
-
- 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
- Y02W10/00—Technologies for wastewater treatment
- Y02W10/30—Wastewater or sewage treatment systems using renewable energies
- Y02W10/37—Wastewater or sewage treatment systems using renewable energies using solar energy
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to a preparation method of 3,4, 5-trifluoro-bromobenzene, which comprises the following steps: step one, reacting 1,2, 3-trifluoro-5-tribromomethyl benzene with carbon tetrabromide under the catalysis of anhydrous aluminum trichloride to generate 1,2, 3-trifluoro-5-tribromomethyl benzene; step two, carrying out hydrolysis reaction on 1,2, 3-trifluoro-5-tribromomethylbenzene and water to generate 1,2, 3-trifluoro-benzoic acid, and simultaneously carrying out condensation reaction on 1,2, 3-trifluoro-5-tribromomethylbenzene and 1,2, 3-trifluoro-benzoyl bromide; step three, carrying out decarbonylation reaction on 1,2, 3-trifluoro-benzoyl bromide under the catalysis of rhodium chloride of tri (triphenylphosphine) to generate 3,4, 5-trifluoro-bromobenzene. The preparation method of the 3,4,5-trifluoro bromobenzene has 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-trifluoro-bromobenzene, belonging to the technical field of chemical synthesis.
Background
Because of the special activity of fluorine elements, a plurality of fluorine-containing compounds have excellent performance and supernormal effects, which are valued by domestic and foreign chemical industry, the research on fluorine-containing fine chemicals in China is extremely active in the middle of the 80 th century, the fluorine-containing fine chemicals are developed in the field of fluorine-containing fine chemicals by virtue of the advantages of fluorite resources, but the average consumption and scientific research innovation capability of the fluorine-containing fine chemicals are greatly different from those of developed countries, the industrial structure adjustment and transformation upgrading of the fluorine-containing fine chemicals are forced to be carried out in the eyebrows, and the introduction of high-end fluorine-containing fine chemicals from abroad is extremely difficult, and 3,4, 5-trifluoro-bromobenzene is a typical case in fluorine-containing fine chemicals.
3,4, 5-trifluorobromobenzene (3, 4, 5-Trifluoro-1-Bromobenzene) is colorless transparent liquid, and is mainly used for preparing bactericides and liquid crystal materials, and has the following chemical structural formula:
at present, the domestic production process of 3,4, 5-trifluoro-bromobenzene mainly comprises the following steps:
(1) Chinese patent document CN103601613a discloses a process for producing 3,4, 5-trifluorobromobenzene: 2,3, 4-trifluoroaniline is firstly brominated by bromine to obtain 2,3, 4-trifluoro-6-bromoaniline, and then diazotized and deaminated to obtain 3,4, 5-trifluorobromobenzene, wherein the reaction equation is as follows:
the process uses bromine with strong toxic action and corrosiveness, hypophosphorous acid and a copper catalyst are also needed in the diazotization deamination process, phosphorus-containing heavy metal wastewater can be generated, the environmental protection and disposal cost is high, and the professional health protection of operators is also not facilitated.
(2) Chinese patent document CN105439810a discloses a process for producing 3,4, 5-trifluorobromobenzene: 2,3, 4-trifluoroaniline is taken as a raw material, 1,2, 3-trifluorobenzene is obtained through diazotization deamination, and then the 1,2, 3-trifluorobenzene reacts with bromine to obtain 3,4, 5-trifluorobromobenzene, wherein the reaction equation is as follows:
the diazotization deamination process of the process is the same as that of CN103601613A, and the only difference is that the bromine bromination process is matched with the use of hydrogen peroxide to reduce the use amount of bromine, so that the essential defect of the process is not changed.
(3) Chinese patent document CN108947763a discloses a process for producing 3,4, 5-trifluorobromobenzene: 1,2, 3-trifluorobenzene is taken as a starting material, dispersed in an organic solvent, then mixed with sodium bromide aqueous solution containing buffer salt, and dropwise added with sodium hypochlorite aqueous solution to obtain a 3,4, 5-trifluorobromobenzene crude product, and the 3,4, 5-trifluorobromobenzene finished product is obtained through melt crystallization, wherein the chemical reaction equation is as follows:
the technology is improved based on CN103601613A and CN105439810A, the use of bromine is successfully avoided, sodium hypochlorite is used for oxidizing sodium bromide instead of bromine, the occupational hazard is reduced, the unit consumption of buffer salt sodium dihydrogen phosphate is up to 0.6, and the disposal cost of high-phosphorus wastewater is still high.
(4) Chinese patent document CN112010733a discloses a process for producing 3,4, 5-trifluorobromobenzene: the 2,3, 4-trifluoroaniline is prepared by using 3,4, 5-trichloronitrobenzene which is a byproduct generated in the process of preparing 3, 4-dichloronitrobenzene by using chloronitrobenzene as a raw material through six procedures of fluorination, hydrogenation reduction, diazotization deamination, nitration, fluorination and hydrogenation reduction, and the subsequent process is similar to CN103601613A, and the reaction equation is as follows:
the process relates to two procedures of nitrification and hydrogenation reduction with extremely high risk, has certain limitation, is only suitable for treating byproduct 3,4, 5-trichloronitrobenzene generated in the process of preparing 3, 4-dichloronitrobenzene by passing p-chloronitrobenzene through chlorine, has high comprehensive cost and has no industrial value.
(5) In 2020, yin Kaiji optimizes the process, and in the paper entitled "new process for synthesizing 3,4, 5-trifluorobromobenzene" published on pages 54-56 of the 42 th phase of the volume of the "pesticide in the world", the paper reports that 3,4, 5-trifluorobromobenzene can be synthesized from 1,2, 3-trichlorobenzene as a starting material through two steps of fluorination and bromination, and the reaction equation is as follows:
the process only changes the initial raw materials, the reaction nature is unchanged, high-phosphorus wastewater is still produced, and in addition, the purity of the byproducts of potassium chloride and sodium chloride produced by the process is lower and the byproducts of potassium chloride and sodium chloride are required to be treated as waste salt, so the process has extremely 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 operation control, high conversion rate and easy catalyst recovery.
The invention provides a technical scheme for solving the technical problems, which is as follows: a preparation method of 3,4, 5-trifluoro-bromobenzene comprises the following steps:
step one, reacting 1,2, 3-trifluoro-5-tribromomethyl benzene with carbon tetrabromide under the catalysis of anhydrous aluminum trichloride, 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-trifluoro-benzoic acid, and simultaneously carrying out condensation reaction on 1,2, 3-trifluoro-5-tribromomethylbenzene and 1,2, 3-trifluoro-benzoyl bromide, wherein the reaction formula is as follows:
step three, carrying out decarbonylation reaction on 1,2, 3-trifluoro benzoyl bromide under the catalysis of rhodium chloride of tri (triphenylphosphine) to generate 3,4,5-trifluoro bromobenzene, wherein the reaction formula is as follows:
the preparation of the 1,2, 3-trifluoro benzene is that hexachlorocyclohexane and anhydrous hydrogen fluoride are subjected to fluorination reaction to prepare the hexafluorocyclohexane, and the reaction formula is as follows:
the obtained hexafluorocyclohexane is heated and decomposed to prepare 1,2, 3-trifluoro benzene and 1,2, 4-trifluoro benzene, and the reaction formula is as follows:
the 1,2, 3-trifluorobenzene and 1,2, 4-trifluorobenzene are then separated by distillation.
In the first step, 1,2, 3-trifluoro benzene and carbon tetrabromide are added, stirred and heated to 45-55 ℃ for uniform mixing, anhydrous aluminum trichloride is added for continuous stirring, gas is generated for water falling film absorption, then the temperature is raised to 140-150 ℃ for reaction, water is added after the reaction is finished, and 1,2, 3-trifluoro-5-tribromomethyl benzene distilled along with water vapor is collected.
The hydrolysis condensation reaction temperature in the second step is 120-125 ℃, and the hydrolysis condensation reaction pressure is normal pressure.
The decarbonylation reaction temperature in the step III 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 thermal decomposition is 250-260 ℃, and the pressure of the thermal decomposition is 0.3-0.4 Mpa.
The distillation separation is carried out under the pressure of-0.095 Mpa, the fraction 1,2, 4-trifluorobenzene is obtained at 45-55 ℃, and the fraction 1,2, 3-trifluorobenzene is obtained at 55-85 ℃.
The mass of the anhydrous aluminum trichloride added is 1 to 1.5 times of the mass of the 1,2, 3-trifluorobenzene.
The mass of the added rhodium chloride tris (triphenylphosphine) is 0.8 to 1.2 times that of 1,2, 3-trifluorobenzene.
The invention has the positive effects that:
(1) In the preparation method of 3,4, 5-trifluoro-bromobenzene, the process of preparing 1,2, 3-trifluoro-5-tribromomethyl benzene from 1,2, 3-trifluoro-bromobenzene is Friedel-crafts alkylation reaction, the operation and the control are convenient, the byproduct hydrobromoacid aqueous solution is a material with a pretty market, and the byproduct aluminum trichloride aqueous solution can be prepared into polyaluminum chloride for water treatment procedures in the field of environmental protection. The process for preparing the 1,2, 3-trifluoro-5-tribromomethyl benzene by hydrolyzing adopts the industrial process for preparing benzoyl chloride, so that the advanced complete equipment is more, and the difficulty in selecting the type of the equipment is small. The 1,2, 3-trifluoro benzoyl bromodecarbonylation adopts the Tsuji-Wilkinson decarbonylation reaction invented by J.Tsuji and K.Ono in 1965, the conversion rate is high, the catalyst recovery is easy, and the decarbonylation comprehensive cost is low.
(2) The preparation method of 3,4, 5-trifluoro-bromobenzene adopts hexachlorocyclohexane (hexahexakis) as raw material for synthesizing 1,2, 3-trifluoro-benzene. Hexachlorocyclohexane is the earliest organic pesticide used in China and has the greatest dosage, and is widely used for preventing and controlling various piercing-sucking and chewing pests on crops, fruit trees, vegetables and forests, thereby playing a great role in ensuring crop harvest and alleviating pests. However, since the hexachlorocyclohexane has a long residual period in the environment (the residual period is as long as 50 years), after being ingested into human body, hexachlorocyclohexane remained in the environment and on crops can be transferred into liver, fat and milk and accumulated in human body, and has certain damage to endocrine and reproductive systems. Thus, production was stopped in China since 1983. Because of the production stopping of hexachlorocyclohexane, some pure benzene with poor quality in the coal chemical industry is less and more economic, the effective implementation of the invention can improve an environment-friendly and economic way for the pure benzene with poor quality: the addition of low-quality pure benzene and chlorine gas can obtain hexachlorocyclohexane, and the fluorination can obtain the hexafluorocyclohexane, and the economic benefit can be created by billions yuan each year according to the production scale estimation of 20000 tons per year of 3,4, 5-trifluorobromobenzene in China. The hydrogen fluoride generated in the pyrolysis process of the hexafluorocyclohexane can be sleeved in the fluorination of the hexachlorocyclohexane, so that the utilization rate of fluorine atoms can be improved to the maximum extent, and the method is economical and environment-friendly. In addition, the byproduct 1,2, 4-trifluorobenzene generated in the pyrolysis process of hexafluorocyclohexane is a precious electronic chemical applied to the field of liquid crystal materials, and the 1,2, 4-trifluorobenzene can be separated from the 1,2, 3-trifluorobenzene by simple rectification.
Drawings
FIG. 1 is a chromatogram of the finished 3,4, 5-trifluorobromobenzene product of example 1 of the present invention.
Detailed Description
The present invention is described in detail below by way of examples, which are necessary to be pointed out herein for further illustration of the invention and are not to be construed as limiting the scope of the invention, since numerous insubstantial modifications and adaptations of the invention will be to those skilled in the art in light of the foregoing 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.
The chemical reagents used in the invention are outsourcing reagents unless specified, and the concentration is chemically pure.
Example 1
The preparation method of the 3,4, 5-trifluoro-bromobenzene comprises the following specific steps:
1. fluorination: preparation of hexafluorocyclohexane.
Hexachlorocyclohexane (2500.00 kg,8.60 kmol) is put into a 3000L hastelloy reaction kettle, stirred and heated to 190 ℃, anhydrous hydrogen fluoride gas (the flow rate is 20.00L/min) is continuously introduced into the reaction kettle after the reaction materials are melted, the conversion rate of hexachlorocyclohexane is more than 90%, at the moment, the reaction system is a viscous brown liquid, the introduction of the anhydrous hydrogen fluoride gas is stopped, and pyrolysis is carried out.
2. And (3) pyrolysis: preparation of 1,2, 3-trifluorobenzene.
And sealing the hastelloy reaction kettle used in the previous step of fluorination process, 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 0.4MPa. Along with the pyrolysis, the pressure in the reaction kettle continuously rises to be up to 0.5MPa. And after the heat preservation and stirring time of 260 ℃ reaches 10 hours, the pyrolysis is basically completed.
After pyrolysis, the pressure is released to normal pressure (normal temperature dry nitrogen is introduced for cooling in the pressure release process), negative pressure distillation (-0.095 MPa, 45-85 ℃) is started, the fraction before the negative pressure reaches 55 ℃ is 1,2, 4-trifluorobenzene, and the refined fraction is sold in the field of liquid crystal materials. The fraction at the negative pressure of 55-85 ℃ is 1,2, 3-trifluoro benzene, which is 803.56kg and is colorless liquid.
3. Friedel-crafts alkylation: preparation of 1,2, 3-trifluoro-5-tribromomethylbenzene.
1,2, 3-trifluorobenzene (1500.00 kg,11.36 kmol) and carbon tetrabromide (3950.00 kg, 11.91 kmol) were charged into a 8000L steel-lined graphite reactor, stirred and heated to 55 ℃, and after mixing uniformly, anhydrous aluminum trichloride (1600.00 kg,12.05 kmol) was added at one time.
After the anhydrous aluminum trichloride is added, the stirring is continued for 2 hours at the temperature of 55 ℃, a large amount of gas is generated during the stirring process, and the water is used for falling film absorption.
After stirring at the temperature of 55 ℃, slowly heating to a small amount of reflux of the reaction system, keeping the reflux state of the reaction system at about 95 ℃, stirring for 1h, continuously heating to 150 ℃, and keeping the temperature and stirring for 5h.
After the temperature is controlled to be 150 ℃, the stirring is completed, water is directly added into the reaction system without reducing the temperature, 1,2, 3-trifluoro-5-tribromomethyl benzene is distilled out along with water vapor, and is received by another 5000L steel lining graphite reaction kettle with circulating water cooling. Stopping adding water when 1,2, 3-trifluoro-5-tribromomethyl benzene is not distilled out along with water vapor, wherein the water layer is an aqueous solution of aluminum trichloride, and adding calcium aluminate powder to prepare polyaluminum chloride which is used as a water treatment agent in the environment-friendly field for sale. The mixture of water and 1,2, 3-trifluoro-5-tribromomethylbenzene is directly carried into the next procedure 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 and water obtained in the previous Friedel-crafts alkylation process until the water content of the reaction system reaches 115, wherein the water content of the reaction system is about 4 percent (measured by a Karl Fischer method), closing a vacuum system, changing the normal pressure distillation into normal pressure distillation, and stirring for 3 hours at the temperature of 125 ℃.
After temperature control and stirring, the materials are transferred to decarbonylation equipment without treatment and directly enter the next decarbonylation reaction process.
5. Decarbonylation: preparation of 3,4, 5-trifluorobromobenzene.
The crude 1,2, 3-trifluoro-benzoyl bromide obtained in the previous hydrolysis step is pumped into a reaction tower filled with rhodium (15000.00 kg,16.21 kmol) chloride of tris (triphenylphosphine), the temperature of the reaction tower is maintained at 250 ℃, 2109.12kg of 3,4, 5-trifluoro-benzoyl bromide can be obtained as colorless liquid, and the gas chromatography content is 99.85%. The chromatogram of the 3,4, 5-trifluorobromobenzene finished product is shown in figure 1, and the chromatographic analysis result of the 3,4, 5-trifluorobromobenzene finished product is 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, and the coke is burnt by introducing 500 ℃ of air, so that the cycle decarbonylation can be continued after the coke is burnt.
TABLE 1 chromatographic analysis results Table
Example 2
The preparation method of the 3,4, 5-trifluoro-bromobenzene comprises the following specific steps:
1. fluorination: preparation of hexafluorocyclohexane.
Hexachlorocyclohexane (2500.00 kg,8.60 kmol) is put into a 3000L hastelloy reaction kettle, stirred and heated to 180 ℃, anhydrous hydrogen fluoride gas (the flow rate is 20.00L/min) is continuously introduced into the reaction kettle after the reaction materials are melted, the conversion rate of hexachlorocyclohexane is more than 90%, at the moment, the reaction system is a viscous brown liquid, the introduction of the anhydrous hydrogen fluoride gas is stopped, and pyrolysis is carried out.
2. And (3) pyrolysis: preparation of 1,2, 3-trifluorobenzene.
And sealing the hastelloy reaction kettle used in the previous step of fluorination process, 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 0.3MPa. Along with the pyrolysis, the pressure in the reaction kettle continuously rises to be up to 0.5MPa. And after the heat preservation and stirring time of 255 ℃ reaches 10 hours, the pyrolysis is basically completed.
After pyrolysis, the pressure is released to normal pressure (normal temperature dry nitrogen is introduced for cooling in the pressure release process), negative pressure distillation (-0.095 MPa, 45-85 ℃) is started, and the fraction before the negative pressure reaches 55 ℃ is 1,2, 4-trifluorobenzene. The fraction at the negative pressure of 55-85 ℃ is 1,2, 3-trifluoro benzene, which is 802.35kg and is colorless liquid.
3. Friedel-crafts alkylation: preparation of 1,2, 3-trifluoro-5-tribromomethylbenzene.
1,2, 3-trifluorobenzene (1500.00 kg,11.36 kmol) and carbon tetrabromide (3950.00 kg, 11.91 kmol) were charged into a 8000L steel-lined graphite reactor, stirred and heated to 45℃and, after mixing well, anhydrous aluminum trichloride (1600.00 kg,12.05 kmol) was added at once.
After the anhydrous aluminum trichloride is added, the stirring is continued for 2 hours at the temperature of 45 ℃, a large amount of gas is generated during the stirring process, and the water is used for falling film absorption.
After stirring at 45 ℃ is completed, slowly heating to a small amount of reflux of the reaction system, keeping the reflux state of the reaction system at about 90 ℃, stirring for 1h, continuously heating to 140 ℃, and keeping the temperature and stirring for 5h.
After the temperature is controlled to 140 ℃, the stirring is completed, water is directly added into the reaction system without reducing the temperature, 1,2, 3-trifluoro-5-tribromomethyl benzene is distilled out along with water vapor, and is received by another 5000L steel lining graphite reaction kettle with circulating water cooling. When the added water is no longer distilled out along with the water vapor, the added water is stopped, and the water layer is an aqueous solution of aluminum trichloride. The mixture of water and 1,2, 3-trifluoro-5-tribromomethylbenzene was directly taken 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-tribromomethyl benzene and water obtained in the previous Friedel-crafts alkylation process to 115 ℃, at the moment, the water content of the reaction system is about 4 percent (measured by a Karl Fischer method), closing a vacuum system, changing the normal pressure distillation into normal pressure distillation, and stirring for 3 hours at the temperature of 120 ℃.
After temperature control and stirring, the materials are transferred to decarbonylation equipment without treatment and directly enter the next decarbonylation reaction process.
5. Decarbonylation: preparation of 3,4, 5-trifluorobromobenzene.
The crude 1,2, 3-trifluoro-benzoyl bromide obtained in the previous hydrolysis step is pumped into a reaction tower filled with rhodium (15000.00 kg,16.21 kmol) chloride of tri (triphenylphosphine), and the temperature of the reaction tower is maintained at 230 ℃, thus obtaining 2107.83kg of 3,4, 5-trifluoro-benzoyl bromide.
Example 3
The preparation method of the 3,4, 5-trifluoro-bromobenzene comprises the following specific steps:
1. fluorination: preparation of hexafluorocyclohexane.
Hexachlorocyclohexane (2500.00 kg,8.60 kmol) is put into a 3000L hastelloy reaction kettle, stirred and heated to 185 ℃, anhydrous hydrogen fluoride gas (the flow rate is 20.00L/min) is continuously introduced into the reaction kettle after the reaction materials are melted, the conversion rate of hexachlorocyclohexane is more than 90%, at the moment, the reaction system is a viscous brown liquid, the introduction of the anhydrous hydrogen fluoride gas is stopped, and pyrolysis is carried out.
2. And (3) pyrolysis: preparation of 1,2, 3-trifluorobenzene.
And sealing the hastelloy reaction kettle used in the previous step of fluorination process, 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 0.35MPa. Along with the pyrolysis, the pressure in the reaction kettle continuously rises to be up to 0.5MPa. And after the heat preservation and stirring time reaches 10 hours at 250 ℃, the pyrolysis is basically completed.
After pyrolysis, the pressure is released to normal pressure (normal temperature dry nitrogen is introduced for cooling in the pressure release process), negative pressure distillation (-0.095 MPa, 45-85 ℃) is started, and the fraction before the negative pressure reaches 55 ℃ is 1,2, 4-trifluorobenzene. The fraction at the negative pressure of 55-85 ℃ is 1,2, 3-trifluoro benzene, which is 801.89kg and is colorless liquid.
3. Friedel-crafts alkylation: preparation of 1,2, 3-trifluoro-5-tribromomethylbenzene.
1,2, 3-trifluorobenzene (1500.00 kg,11.36 kmol) and carbon tetrabromide (3950.00 kg, 11.91 kmol) were charged into a 8000L steel-lined graphite reactor, stirred and heated to 50 ℃, and after mixing uniformly, anhydrous aluminum trichloride (1600.00 kg,12.05 kmol) was added at one time.
After the anhydrous aluminum trichloride is added, the stirring is continued for 2 hours at the temperature of 50 ℃, a large amount of gas is generated during the stirring process, and the water is used for falling film absorption.
After stirring at the temperature of 50 ℃, slowly heating to a small amount of reflux of the reaction system, keeping the reflux state of the reaction system at about 93 ℃, stirring for 1h, continuously heating to 145 ℃, and keeping the temperature and stirring for 5h.
After the temperature is controlled to 145 ℃, the stirring is completed, water is directly added into the reaction system without reducing the temperature, 1,2, 3-trifluoro-5-tribromomethyl benzene is distilled out along with water vapor, and is received by another 5000L steel lining graphite reaction kettle with circulating water cooling. When the added water is no longer distilled out along with the water vapor, the added water is stopped, and the water layer is an aqueous solution of aluminum trichloride. The mixture of water and 1,2, 3-trifluoro-5-tribromomethylbenzene was directly taken 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 and water obtained in the previous Friedel-crafts alkylation process to 118 ℃, at the moment, the water content of a reaction system is about 4 percent (measured by a Karl Fischer method), closing a vacuum system, changing the normal pressure distillation into normal pressure distillation, and stirring for 3 hours at the temperature of 123 ℃.
After temperature control and stirring, the materials are transferred to decarbonylation equipment without treatment and directly enter the next decarbonylation reaction process.
5. Decarbonylation: preparation of 3,4, 5-trifluorobromobenzene.
The crude 1,2, 3-trifluoro-benzoyl bromide obtained in the previous hydrolysis step is pumped into a reaction tower filled with rhodium (15000.00 kg,16.21 kmol) chloride of tri (triphenylphosphine), and the temperature of the reaction tower is maintained at 240 ℃, thus obtaining 2106.88kg of 3,4, 5-trifluoro-benzoyl bromide.
It is apparent that the above examples are merely illustrative of the present invention and are not limiting of the embodiments of the present invention. Other variations or modifications of the above teachings will be apparent to those of ordinary skill in the art. It is not necessary here nor is it exhaustive of all embodiments. While remaining within the scope of the invention, obvious variations or modifications are incorporated by reference herein.
Claims (7)
1. A preparation method of 3,4, 5-trifluoro-bromobenzene is characterized in that: the method comprises the following steps:
step one, reacting 1,2, 3-trifluoro benzene and carbon tetrabromide under the catalysis of anhydrous aluminum trichloride to generate 1,2, 3-trifluoro-5-tribromomethyl benzene, wherein in the step one, the 1,2, 3-trifluoro benzene and the carbon tetrabromide are added, then stirred and heated to 45-55 ℃ for uniform mixing, the anhydrous aluminum trichloride is added for continuous stirring, gas is generated for water falling film absorption, then the temperature is heated to 140-150 ℃ for reaction, water is added after the reaction is finished, and the 1,2, 3-trifluoro-5-tribromomethyl benzene distilled along with water vapor is collected, 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-trifluoro-benzoic acid, and simultaneously carrying out condensation reaction on 1,2, 3-trifluoro-5-tribromomethylbenzene and 1,2, 3-trifluoro-benzoyl bromide, wherein the hydrolysis condensation reaction temperature is 120-125 ℃, the hydrolysis condensation reaction pressure is normal pressure, and the reaction formula is as follows:
；
step three, carrying out decarbonylation reaction on 1,2, 3-trifluoro benzoyl bromide under the catalysis of rhodium chloride of tri (triphenylphosphine) to generate 3,4,5-trifluoro bromobenzene, wherein the decarbonylation reaction temperature in the step three is 200-250 ℃, and the reaction formula is as follows:
。
2. the method for preparing 3,4, 5-trifluorobromobenzene according to claim 1, wherein: the preparation method of the 1,2, 3-trifluoro-benzene is characterized in that hexachlorocyclohexane and anhydrous hydrogen fluoride are subjected to fluorination reaction to prepare the hexafluorocyclohexane, and the reaction formula is as follows:
；
the obtained hexafluorocyclohexane is heated and decomposed to prepare 1,2, 3-trifluoro benzene and 1,2, 4-trifluoro benzene, and the reaction formula is as follows:
，
the 1,2, 3-trifluorobenzene and 1,2, 4-trifluorobenzene are then separated by distillation.
3. The method for preparing 3,4, 5-trifluorobromobenzene according to claim 2, wherein: the temperature of the fluorination reaction is 180-190 ℃, and the pressure of the fluorination reaction is normal pressure.
4. The method for preparing 3,4, 5-trifluorobromobenzene according to claim 2, wherein: the temperature of the thermal decomposition is 250-260 ℃, and the pressure of the thermal decomposition is 0.3-0.4 Mpa.
5. The method for preparing 3,4, 5-trifluorobromobenzene according to claim 2, wherein: the distillation separation is carried out under the pressure of-0.095 Mpa, the fraction 1,2, 4-trifluorobenzene is obtained at 45-55 ℃, and the fraction 1,2, 3-trifluorobenzene is obtained at 55-85 ℃.
6. The process for producing 3,4, 5-trifluorobromobenzene as claimed in any one of claims 1 to 5, wherein: the mass of the anhydrous aluminum trichloride added is 1 to 1.5 times of the mass of the 1,2, 3-trifluorobenzene.
7. The process for producing 3,4, 5-trifluorobromobenzene as claimed in any one of claims 1 to 5, wherein: the added mass of the tris (triphenylphosphine) rhodium chloride is 0.8 to 1.2 times of the mass of the 1,2, 3-trifluorobenzene.
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