CN108947850B - Preparation method of 3,4, 5-trifluoroaniline - Google Patents
Preparation method of 3,4, 5-trifluoroaniline Download PDFInfo
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- CN108947850B CN108947850B CN201810810615.9A CN201810810615A CN108947850B CN 108947850 B CN108947850 B CN 108947850B CN 201810810615 A CN201810810615 A CN 201810810615A CN 108947850 B CN108947850 B CN 108947850B
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- trifluoronitrobenzene
- trifluoroaniline
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- ruthenium
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- SZRDJHHKIJHJHQ-UHFFFAOYSA-N 3,4,5-trifluoroaniline Chemical compound NC1=CC(F)=C(F)C(F)=C1 SZRDJHHKIJHJHQ-UHFFFAOYSA-N 0.000 title claims abstract description 39
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 239000012535 impurity Substances 0.000 claims abstract description 37
- FPGGTKZVZWFYPV-UHFFFAOYSA-M tetrabutylammonium fluoride Chemical compound [F-].CCCC[N+](CCCC)(CCCC)CCCC FPGGTKZVZWFYPV-UHFFFAOYSA-M 0.000 claims abstract description 36
- PTTUMBGORBMNBN-UHFFFAOYSA-N 1,2,3-trifluoro-5-nitrobenzene Chemical compound [O-][N+](=O)C1=CC(F)=C(F)C(F)=C1 PTTUMBGORBMNBN-UHFFFAOYSA-N 0.000 claims abstract description 28
- 239000003054 catalyst Substances 0.000 claims abstract description 28
- NCPHGZWGGANCAY-UHFFFAOYSA-N methane;ruthenium Chemical compound C.[Ru] NCPHGZWGGANCAY-UHFFFAOYSA-N 0.000 claims abstract description 25
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims abstract description 18
- 238000000034 method Methods 0.000 claims abstract description 16
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims abstract description 13
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000011737 fluorine Substances 0.000 claims abstract description 13
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 13
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 13
- 239000001257 hydrogen Substances 0.000 claims abstract description 13
- 238000006243 chemical reaction Methods 0.000 claims abstract description 12
- 239000012043 crude product Substances 0.000 claims abstract description 12
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000000203 mixture Substances 0.000 claims abstract description 10
- 229910052707 ruthenium Inorganic materials 0.000 claims abstract description 9
- 238000010438 heat treatment Methods 0.000 claims abstract description 8
- 239000012074 organic phase Substances 0.000 claims abstract description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 6
- 238000005292 vacuum distillation Methods 0.000 claims description 3
- 238000004817 gas chromatography Methods 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims 1
- 229910052799 carbon Inorganic materials 0.000 claims 1
- 238000001308 synthesis method Methods 0.000 abstract description 2
- KQOIBXZRCYFZSO-UHFFFAOYSA-N 3,5-difluoroaniline Chemical compound NC1=CC(F)=CC(F)=C1 KQOIBXZRCYFZSO-UHFFFAOYSA-N 0.000 description 15
- 239000006227 byproduct Substances 0.000 description 12
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 8
- 238000006722 reduction reaction Methods 0.000 description 8
- AXNUZKSSQHTNPZ-UHFFFAOYSA-N 3,4-difluoroaniline Chemical compound NC1=CC=C(F)C(F)=C1 AXNUZKSSQHTNPZ-UHFFFAOYSA-N 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 238000007792 addition Methods 0.000 description 3
- 238000006115 defluorination reaction Methods 0.000 description 3
- 239000004973 liquid crystal related substance Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 230000002401 inhibitory effect Effects 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- UHDDEIOYXFXNNJ-UHFFFAOYSA-N (3,4,5-trifluorophenyl)boronic acid Chemical compound OB(O)C1=CC(F)=C(F)C(F)=C1 UHDDEIOYXFXNNJ-UHFFFAOYSA-N 0.000 description 1
- XIQGAGQYVCBTOB-UHFFFAOYSA-N 1,5-difluorocyclohexa-2,4-dien-1-amine Chemical compound FC1(N)CC(=CC=C1)F XIQGAGQYVCBTOB-UHFFFAOYSA-N 0.000 description 1
- HHQANPWGPCTUNZ-UHFFFAOYSA-N 1,6-difluorocyclohexa-2,4-dien-1-amine Chemical compound FC1(N)C(C=CC=C1)F HHQANPWGPCTUNZ-UHFFFAOYSA-N 0.000 description 1
- KRZCOLNOCZKSDF-UHFFFAOYSA-N 4-fluoroaniline Chemical compound NC1=CC=C(F)C=C1 KRZCOLNOCZKSDF-UHFFFAOYSA-N 0.000 description 1
- 238000003747 Grignard reaction Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000005885 boration reaction Methods 0.000 description 1
- 230000031709 bromination Effects 0.000 description 1
- 238000005893 bromination reaction Methods 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000006193 diazotization reaction Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- UKVIEHSSVKSQBA-UHFFFAOYSA-N methane;palladium Chemical compound C.[Pd] UKVIEHSSVKSQBA-UHFFFAOYSA-N 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 238000011946 reduction process Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
- C07C209/30—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds
- C07C209/32—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds by reduction of nitro groups
- C07C209/36—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds by reduction of nitro groups by reduction of nitro groups bound to carbon atoms of six-membered aromatic rings in presence of hydrogen-containing gases and a catalyst
- C07C209/365—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds by reduction of nitro groups by reduction of nitro groups bound to carbon atoms of six-membered aromatic rings in presence of hydrogen-containing gases and a catalyst by reduction with preservation of halogen-atoms in compounds containing nitro groups and halogen atoms bound to the same carbon skeleton
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
- C07C209/82—Purification; Separation; Stabilisation; Use of additives
- C07C209/84—Purification
Abstract
The invention relates to a preparation method of 3,4, 5-trifluoroaniline, which comprises the following steps: (1) dispersing 3,4, 5-trifluoronitrobenzene in water, adding a catalyst, and heating for reaction in a hydrogen atmosphere to obtain a crude product; the catalyst is a mixture of ruthenium carbon and tetrabutylammonium fluoride in a mass ratio of 1.8-2.2: 1, wherein the ruthenium carbon is calculated by 5% of carbon-supported ruthenium; (2) and (3) extracting the crude product by using dichloromethane, and carrying out primary vacuum rectification on an organic phase to obtain the 3,4, 5-trifluoroaniline. According to the synthesis method provided by the invention, the specific catalyst is selected, so that the generation of fluorine impurities in the process of preparing 3,4, 5-trifluoroaniline from 3,4, 5-trifluoronitrobenzene can be reduced, and the purity of the 3,4, 5-trifluoroaniline can be improved; particularly, when the catalyst selects a mixture of ruthenium carbon and tetrabutylammonium fluoride with the mass ratio of 2:1, and the number of rectification tower plates is 1000-2000 per 50g of 3,4, 5-trifluoronitrobenzene, the purity of the 3,4, 5-trifluoroaniline is more than 99.
Description
Technical Field
The invention belongs to the field of intermediate synthesis, and particularly relates to a preparation method of 3,4, 5-trifluoroaniline.
Background
3,4, 5-trifluoroaniline is an important raw material for preparing liquid crystal materials, and 3,4, 5-trifluoroaniline can be used for preparing 3,4, 5-trifluorophenylboronic acid through a series of reactions such as diazotization, bromination, Grignard reaction, boration and the like. Raw materials for liquid crystal materials have strict requirements on homologues in order to ensure the purity of the liquid crystal materials, and generally the homologue impurities are required to be less than 50ppm, so that the homologue impurities need to be controlled from the raw materials used in each step.
3,4, 5-trifluoronitrobenzene is subjected to nitro reduction to prepare 3,4, 5-trifluoroaniline, the method is various, iron powder reduction (the method has too much waste water and the nation prohibits the nitro reduction by using iron powder), palladium carbon reduction, nickel reduction, ruthenium reduction, platinum reduction and the like can be carried out, but the method cannot effectively control defluorination byproducts (such as m-difluoroaniline, o-difluoroaniline, monofluoroaniline and the like).
In the prior art, no effective means is available for inhibiting the generation of fluorine-removing by-products. Generally, by controlling the reaction conditions appropriately, the reduction reaction only has a side reaction of one fluorine, and does not have a side reaction of two or three fluorine, so that the fluorine removal by-products in the prior art are mostly 3, 4-difluoroaniline and/or 3, 5-difluoroaniline.
The field needs to develop a preparation method of 3,4, 5-trifluoroaniline capable of inhibiting the defluorination by-product, wherein the defluorination by-product of the 3,4, 5-trifluoroaniline is less than or equal to 50ppm, and the purity of the 3,4, 5-trifluoroaniline can be more than or equal to 99% only by once rectification.
Disclosure of Invention
The invention aims to provide a preparation method of 3,4, 5-trifluoroaniline, wherein the fluorine removal by-product is less than or equal to 50ppm, and the method comprises the following steps:
(1) dispersing 3,4, 5-trifluoronitrobenzene in water, adding a catalyst, and heating for reaction in a hydrogen atmosphere to obtain a crude product; the catalyst is a mixture of 1.8-2.2: 1 (such as 1.9:1, 2.0:1, 2.1:1 and the like) of ruthenium carbon and tetrabutylammonium fluoride in a mass ratio, wherein the ruthenium carbon is calculated by 5% of carbon-supported ruthenium;
(2) and (3) extracting the crude product by using dichloromethane, and carrying out primary vacuum rectification on an organic phase to obtain the 3,4, 5-trifluoroaniline.
The 5% carbon-supported ruthenium means that the ruthenium content in the ruthenium carbon is 5 wt%.
According to the method provided by the invention, 3,4, 5-trifluoronitrobenzene is subjected to composite catalysis by ruthenium carbon and tetrabutylammonium fluoride in a mass ratio of 1.8-2.2: 1, so that the loss of fluorine atoms in the reduction process can be inhibited, the generation of fluorine-removing byproducts is reduced, and the content of the fluorine-removing byproducts is controlled.
Preferably, the mass ratio of the ruthenium carbon to the tetrabutylammonium fluoride in the catalyst is 2:1, and the ruthenium carbon is calculated by 5% of carbon-supported ruthenium.
Preferably, the amount of the ruthenium carbon added is 0.18 to 0.22 times (e.g., 0.19 times, 0.20 times, 0.21 times) the mass of the 3,4, 5-trifluoronitrobenzene, and preferably 0.20 times.
The proper addition of the catalyst can ensure that more 3,4, 5-trifluoronitrobenzene is reduced into 3,4, 5-trifluoroaniline, and the fluorine byproduct is less generated.
Preferably, the dispersion concentration of the 3,4, 5-trifluoronitrobenzene in the reaction system of the step (1) is 8-12 wt% (e.g. 9 wt%, 10 wt%, 11 wt%, etc.), preferably 10 wt%.
Preferably, the gas chromatography purity of the 3,4, 5-trifluoronitrobenzene is more than or equal to 99 wt%, the maximum single impurity content is less than or equal to 0.04%, and the fluorine-removed impurity content is less than or equal to 50 ppm.
When the purity of the 3,4, 5-trifluoronitrobenzene is higher, the purity of the obtained 3,4, 5-trifluoroaniline is also higher.
Preferably, in the hydrogen atmosphere in the step (1), the hydrogen pressure is 4.0 to 5.0MPa (e.g., 4.2MPa, 4.5MPa, 4.8MPa, etc.).
Preferably, the heating reaction temperature in step (1) is 145-155 ℃ (e.g. 146 ℃, 147 ℃, 148 ℃, 149 ℃, 150 ℃, 151 ℃, 152 ℃, 153 ℃, 154 ℃, etc.), and the reaction time is 11-13 h (e.g. 11.5h, 12.0h, 12.5h, etc.).
Preferably, in the vacuum distillation process, the number of plates per 50g of 3,4, 5-trifluoronitrobenzene is 1000 to 2000 (e.g., 1200, 1500, 1800, etc.).
As a preferred technical scheme, the preparation method of the 3,4, 5-trifluoroaniline of which the fluorine removal by-product is less than or equal to 50ppm comprises the following steps:
(1) dispersing 3,4, 5-trifluoronitrobenzene with the purity of more than or equal to 99 wt%, the maximum single impurity content of less than or equal to 0.04% and the fluorine impurity content of less than or equal to 50ppm in water according to the concentration of 8-12 wt%, adding ruthenium carbon and tetrabutylammonium fluoride as catalysts in the mass ratio of 1.8-2.2: 1, and heating to 145-155 ℃ under the hydrogen atmosphere with the hydrogen pressure of 4.0-5.0 MPa for reaction for 11-13 h to obtain a crude product; the addition amount of the ruthenium-carbon is 0.18-0.22 time of the mass of the 3,4, 5-trifluoronitrobenzene;
(2) and (3) extracting the crude product by using dichloromethane, and carrying out once reduced pressure rectification on an organic phase according to the condition that the number of tower plates of each 50g of 3,4, 5-trifluoronitrobenzene is 1000-2000 to obtain the 3,4, 5-trifluoroaniline.
Compared with the prior art, the invention has the following beneficial effects:
according to the synthesis method provided by the invention, the specific catalyst is selected, so that the generation of fluorine impurities in the process of preparing 3,4, 5-trifluoroaniline from 3,4, 5-trifluoronitrobenzene can be reduced, and the purity of the 3,4, 5-trifluoroaniline can be improved; particularly, when the catalyst selects a mixture of ruthenium carbon and tetrabutylammonium fluoride with the mass ratio of 2:1, and the number of rectification tower plates is 1000-2000 per 50g of 3,4, 5-trifluoronitrobenzene, the purity of the 3,4, 5-trifluoroaniline is more than 99%.
Detailed Description
The technical solution of the present invention is further explained by the following embodiments.
It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitations of the present invention.
Example 1
The preparation method of the 3,4, 5-trifluoroaniline comprises the following steps:
(1) dispersing 50g of 3,4, 5-trifluoronitrobenzene with the purity of 99.2 wt%, the maximum single impurity content of 0.03% and the fluorine impurity content of 40ppm in 500g of pure water by using a gas chromatograph, adding 10g of ruthenium-carbon (5 wt% of carbon-supported ruthenium) and 5g of tetrabutylammonium fluoride as catalysts, and heating to 150 ℃ in a hydrogen atmosphere with the hydrogen pressure of 4.5MPa for reaction for 12 hours to obtain a crude product;
(2) the crude product is extracted 2 times with 200g of dichloromethane, the organic phase is distilled under normal pressure to remove the solvent, and then the 3,4, 5-trifluoroaniline is obtained by one-time vacuum rectification according to the tower plate number of 1500.
3,4, 5-trifluoroaniline (the peak-out time is 45.5min, and the standard ratio is confirmed) obtained by carrying out gas chromatography-mass spectrometry on the obtained 3,4, 5-trifluoroaniline (the conditions are that the peak-out time is 45.5min from 80 ℃ to 150 ℃ and the temperature is 20 ℃/min to 280 ℃), wherein the purity of [ M ] 147.03 is 99.91%; the impurity was 3, 5-difluoroaniline (peak time 45.1min, confirmed by comparison with the impurity of 3, 5-difluoroaniline standard), [ M ] 129.04, at a content of 35 ppm.
Comparative example 1
The difference from example 1 is that in step (1), tetrabutylammonium fluoride was not added, and only 10g of ruthenium carbon was used as a catalyst.
3,4, 5-trifluoroaniline (the peak-out time is 45.5min), the purity is 98.19 percent, and the impurity is 3, 5-difluoroaniline (the peak-out time is 45.1min, and is confirmed by impurity comparison of a 3, 5-difluoroaniline standard product) is obtained by carrying out gas chromatography-mass spectrometry on the obtained 3,4, 5-trifluoroaniline (the conditions are that the peak-out time is 1 ℃/min to 150 ℃ from 80 ℃ and 20 ℃/min to 280 ℃), wherein [ M ] is 129.04, and the content is 200 ppm; the impurity was 3, 4-difluoroaniline (peak time 45.3min, confirmed by comparison with the impurity of 3, 4-difluoroaniline standard), [ M ] 129.04, at a content of 150 ppm.
Comparative example 2
The difference from example 1 is that the catalyst of step (1) is a mixture of 10g of 5% palladium on carbon and 5g of tetrabutylammonium fluoride as catalyst.
3,4, 5-trifluoroaniline (the peak-off time is 45.5min), the purity is 97.61%, the impurity is 3, 5-difluoroaniline (the peak-off time is 45.1min, and the impurity is confirmed by comparing 3, 5-difluoroaniline standard substance impurities) obtained by a gas chromatography-mass spectrometry combined test (the conditions are that the peak-off time is 1 ℃/min to 150 ℃ from 80 ℃, and 20 ℃/min to 280 ℃), and the content of [ M ]:129.04 is 290 ppm. The impurity was 3, 4-difluoroaniline (peak time 45.3min, confirmed by 3, 4-difluoroaniline, standard impurity comparison), [ M ] 129.04, content 180 ppm.
Comparative example 3
The difference from example 1 is that the catalyst of step (1) is a mixture of 5g of ruthenium on carbon and 5g of tetrabutylammonium fluoride as catalyst.
3,4, 5-trifluoroaniline (the peak-out time is 45.5min), the purity is 98.45%, the impurity is 3, 5-difluoroaniline (the peak-out time is 45.1min, and the comparison of the 3, 5-difluoroaniline and the standard impurity confirms) obtained by a gas chromatography-mass spectrometry combined test (the conditions are that the peak-out time is 1 ℃/min to 150 ℃ from 80 ℃, and 20 ℃/min to 280 ℃), and the content of [ M ] 129.04 is 40 ppm.
Comparative example 4
The difference from example 1 is that the catalyst of step (1) is a mixture of 5g of nickel and 5g of tetrabutylammonium fluoride as catalyst.
3,4, 5-trifluoroaniline (the peak-out time is 45.5min), the purity is 95.55%, the impurity 1 is 3, 5-difluoroaniline (the peak-out time is 45.1min, and the comparison of the 3, 5-difluoroaniline and the standard impurity confirms) obtained by a gas chromatography-mass spectrometry combined test (the conditions are that the peak-out time is 1 ℃/min to 150 ℃ from 80 ℃, and 20 ℃/min to 280 ℃), and the content of [ M ] is 129.04, and is 500 ppm; impurity 2 was 3, 4-difluoroaniline (peak time 45.3min, confirmed by 3, 4-difluoroaniline, standard impurity comparison), [ M ] 129.04, at a content of 380 ppm.
Comparative example 5
The difference from example 1 is that the catalyst of step (1) was 5g of ruthenium-carbon and 2.5g of tetrabutylammonium fluoride as a catalyst.
3,4, 5-trifluoroaniline (the peak-out time is 45.5min), the purity is 98.66%, the impurity is 3, 5-difluoroaniline (the peak-out time is 45.1min, and the comparison of the impurity of the standard product is confirmed by 3, 5-difluoroaniline) obtained by a gas chromatography-mass spectrometry combined test (the conditions are that the peak-out time is 1 ℃/min to 150 ℃ from 80 ℃), the content of [ M ] 129.04 is 40 ppm.
Example 2
The only difference from example 1 is that 3,4, 5-trifluoronitrobenzene had a gas chromatographic purity of 99.1 wt%, a maximum single impurity content of 0.06%, and a fluorine rejection impurity content of 65 ppm.
3,4, 5-trifluoroaniline (the peak-out time is 45.5min), the purity is 99.25 percent, the impurity is 3, 5-difluoroaniline (the peak-out time is 45.1min, and the comparison of the impurity of the standard product and the 3, 5-difluoroaniline is confirmed) obtained by a gas chromatography-mass spectrometry combined test (the conditions are that the peak-out time is 1 ℃/min to 150 ℃ from 80 ℃, and the 20 ℃/min to 280 ℃), and the content of [ M ] 129.04 is 55 ppm.
Examples 3 to 6
The only difference from example 1 is that the theoretical plate numbers of the vacuum distillation in step (2) are 1000 (example 3), 2000 (example 4), 800 (example 5) and 2200 (example 6).
The purity of the 3,4, 5-trifluoroaniline obtained by gas chromatography-mass spectrometry (conditions: 80 ℃ C. at 1 ℃/min to 150 ℃ C., 20 ℃/min to 280 ℃) was 99.08% (example 3), 99.91% (example 4), 98.95% (example 5), 99.92% (example 6), respectively.
From the results of the examples and the comparative examples, the mixture of ruthenium carbon and tetrabutylammonium fluoride with the mass ratio of 1.8-2.2: 1 is used as a catalyst to catalytically reduce 3,4, 5-trifluoronitrobenzene, the content of fluorine-removing byproducts is less than or equal to 50ppm, and the purity of the 3,4, 5-trifluoroaniline can be more than or equal to 99% only by one-time rectification.
As can be seen from the comparative example, when the catalyst does not adopt the mixture of ruthenium carbon and tetrabutylammonium fluoride with the mass ratio of 1.8-2.2: 1 as the catalyst, the fluorine removal by-product is obviously increased, and the purity of the product is obviously reduced.
The applicant states that the present invention is illustrated by the above examples of the process of the present invention, but the present invention is not limited to the above process steps, i.e. it is not meant that the present invention must rely on the above process steps to be carried out. It will be apparent to those skilled in the art that any modification of the present invention, equivalent substitutions of selected materials and additions of auxiliary components, selection of specific modes and the like, which are within the scope and disclosure of the present invention, are contemplated by the present invention.
Claims (7)
1. A preparation method of 3,4, 5-trifluoroaniline is characterized by comprising the following steps:
(1) dispersing 3,4, 5-trifluoronitrobenzene in water, adding a catalyst, and heating for reaction in a hydrogen atmosphere to obtain a crude product; the catalyst is a mixture of ruthenium carbon and tetrabutylammonium fluoride in a mass ratio of 1.8-2.2: 1, wherein the ruthenium carbon is calculated by 5% of carbon-supported ruthenium;
(2) extracting the crude product by dichloromethane, and carrying out primary vacuum rectification on an organic phase to obtain 3,4, 5-trifluoroaniline;
the addition amount of the ruthenium carbon is 0.18-0.22 time of the mass of the 3,4, 5-trifluoronitrobenzene;
the gas chromatography purity of the 3,4, 5-trifluoronitrobenzene is more than or equal to 99 wt%, the maximum single impurity content is less than or equal to 0.04%, and the fluorine-removed impurity content is less than or equal to 50 ppm.
2. The method according to claim 1, wherein the catalyst comprises ruthenium carbon and tetrabutylammonium fluoride in a mass ratio of 2: 1; the ruthenium carbon was calculated as 5% carbon supported ruthenium.
3. The method according to claim 1, wherein the 3,4, 5-trifluoronitrobenzene is dispersed in the reaction system of the step (1) at a concentration of 8 to 12 wt%.
4. The method according to claim 1, wherein the hydrogen pressure in the hydrogen atmosphere in the step (1) is 4.0 to 5.0 MPa.
5. The preparation method according to claim 1, wherein the heating reaction temperature in the step (1) is 145-155 ℃ and the reaction time is 11-13 h.
6. The method according to claim 1, wherein the number of plates per 50g of 3,4, 5-trifluoronitrobenzene in the vacuum distillation is 1000 to 2000.
7. The method of claim 1, comprising the steps of:
(1) dispersing 3,4, 5-trifluoronitrobenzene with the purity of more than or equal to 99 wt%, the maximum single impurity content of less than or equal to 0.04% and the fluorine impurity content of less than or equal to 50ppm in water according to the concentration of 8-12 wt%, adding ruthenium carbon and tetrabutylammonium fluoride as catalysts in the mass ratio of 1.8-2.2: 1, and heating to 145-155 ℃ under the hydrogen atmosphere with the hydrogen pressure of 4.0-5.0 MPa for reaction for 11-13 h to obtain a crude product; the addition amount of the ruthenium-carbon is 0.18-0.22 time of the mass of the 3,4, 5-trifluoronitrobenzene;
(2) and (3) extracting the crude product by using dichloromethane, and carrying out once reduced pressure rectification on an organic phase according to the condition that the number of tower plates of each 50g of 3,4, 5-trifluoronitrobenzene is 1000-2000 to obtain the 3,4, 5-trifluoroaniline.
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| CN201810810615.9A CN108947850B (en) | 2018-07-23 | 2018-07-23 | Preparation method of 3,4, 5-trifluoroaniline |
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| CN201810810615.9A CN108947850B (en) | 2018-07-23 | 2018-07-23 | Preparation method of 3,4, 5-trifluoroaniline |
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| AU2002346724B2 (en) * | 2001-12-14 | 2009-04-30 | Exelixis, Inc. | Human ADAM-10 inhibitors |
| EP2436676A1 (en) * | 2002-06-12 | 2012-04-04 | Symphony Evolution, Inc. | Human adam-10 inhibitors |
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| WO2003062225A1 (en) * | 2002-01-23 | 2003-07-31 | Bayer Pharmaceuticals Corporation | Pyrimidine derivatives as rho-kinase inhibitors |
| CN102639134A (en) * | 2009-10-01 | 2012-08-15 | 和谐进化股份有限公司 | Methods of treating aneurysmal dilatation, blood vessel wall weakness and specifically abdominal aortic and thoracic aneurysm using matrix metalloprotease-2 inhibitors |
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| CN103140465A (en) * | 2010-09-29 | 2013-06-05 | 宝洁公司 | Methods of synthesizing 2-methoxymethyl-1,4-benzenediamine |
| CN102285891A (en) * | 2011-06-30 | 2011-12-21 | 浙江工业大学 | Method for preparing arylamine by catalytic hydrogenation of aromatic nitro compound |
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| CN104710316A (en) * | 2015-03-23 | 2015-06-17 | 西安凯立化工有限公司 | Method for preparing fluoroaniline through continuous catalytic hydrogenation of fluoronitrobenzene |
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