CN1666974A - Process for preparing o-trifluoromethyl aniline - Google Patents
Process for preparing o-trifluoromethyl aniline Download PDFInfo
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- CN1666974A CN1666974A CN 200410016958 CN200410016958A CN1666974A CN 1666974 A CN1666974 A CN 1666974A CN 200410016958 CN200410016958 CN 200410016958 CN 200410016958 A CN200410016958 A CN 200410016958A CN 1666974 A CN1666974 A CN 1666974A
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- trifluoromethyl aniline
- preparation
- catalytic hydrogenation
- trifluoromethyl
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- VBLXCTYLWZJBKA-UHFFFAOYSA-N 2-(trifluoromethyl)aniline Chemical compound NC1=CC=CC=C1C(F)(F)F VBLXCTYLWZJBKA-UHFFFAOYSA-N 0.000 title claims description 36
- 238000004519 manufacturing process Methods 0.000 title description 4
- 238000006298 dechlorination reaction Methods 0.000 claims abstract description 27
- 238000007327 hydrogenolysis reaction Methods 0.000 claims abstract description 23
- 238000006396 nitration reaction Methods 0.000 claims abstract description 21
- 238000002360 preparation method Methods 0.000 claims abstract description 20
- 230000003197 catalytic effect Effects 0.000 claims abstract description 14
- GETTZEONDQJALK-UHFFFAOYSA-N (trifluoromethyl)benzene Chemical compound FC(F)(F)C1=CC=CC=C1 GETTZEONDQJALK-UHFFFAOYSA-N 0.000 claims abstract description 11
- 238000000034 method Methods 0.000 claims abstract description 11
- 229910052801 chlorine Inorganic materials 0.000 claims abstract description 9
- 238000005660 chlorination reaction Methods 0.000 claims abstract description 8
- 239000000460 chlorine Substances 0.000 claims abstract description 8
- 238000006243 chemical reaction Methods 0.000 claims description 31
- 239000000203 mixture Substances 0.000 claims description 25
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 21
- SYSQUGFVNFXIIT-UHFFFAOYSA-N n-[4-(1,3-benzoxazol-2-yl)phenyl]-4-nitrobenzenesulfonamide Chemical class C1=CC([N+](=O)[O-])=CC=C1S(=O)(=O)NC1=CC=C(C=2OC3=CC=CC=C3N=2)C=C1 SYSQUGFVNFXIIT-UHFFFAOYSA-N 0.000 claims description 21
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 18
- 239000003054 catalyst Substances 0.000 claims description 12
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 11
- 239000002253 acid Substances 0.000 claims description 11
- 239000011230 binding agent Substances 0.000 claims description 9
- CFPIGEXZPWTNOR-UHFFFAOYSA-N 4-chloro-1-nitro-2-(trifluoromethyl)benzene Chemical compound [O-][N+](=O)C1=CC=C(Cl)C=C1C(F)(F)F CFPIGEXZPWTNOR-UHFFFAOYSA-N 0.000 claims description 7
- 239000002994 raw material Substances 0.000 claims description 7
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 6
- 238000004821 distillation Methods 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 6
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 5
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 5
- VIUDTWATMPPKEL-UHFFFAOYSA-N 3-(trifluoromethyl)aniline Chemical compound NC1=CC=CC(C(F)(F)F)=C1 VIUDTWATMPPKEL-UHFFFAOYSA-N 0.000 claims description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 4
- -1 catalyzer Substances 0.000 claims description 4
- 239000001257 hydrogen Substances 0.000 claims description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 3
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 2
- 238000007363 ring formation reaction Methods 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 abstract description 7
- 238000003786 synthesis reaction Methods 0.000 abstract description 2
- SLFVYFOEHHLHDW-UHFFFAOYSA-N n-(trifluoromethyl)aniline Chemical compound FC(F)(F)NC1=CC=CC=C1 SLFVYFOEHHLHDW-UHFFFAOYSA-N 0.000 abstract 3
- SLJUIFMRKYZQTI-UHFFFAOYSA-N FC(F)(F)C1=CC=CC=C1.[Cl] Chemical compound FC(F)(F)C1=CC=CC=C1.[Cl] SLJUIFMRKYZQTI-UHFFFAOYSA-N 0.000 abstract 1
- 230000015572 biosynthetic process Effects 0.000 abstract 1
- 239000000463 material Substances 0.000 abstract 1
- 238000005516 engineering process Methods 0.000 description 8
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 239000007789 gas Substances 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 239000000706 filtrate Substances 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- DGRVQOKCSKDWIH-UHFFFAOYSA-N 1-chloro-2-(trifluoromethyl)benzene Chemical compound FC(F)(F)C1=CC=CC=C1Cl DGRVQOKCSKDWIH-UHFFFAOYSA-N 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 3
- 239000007868 Raney catalyst Substances 0.000 description 3
- 229910000564 Raney nickel Inorganic materials 0.000 description 3
- NPXOKRUENSOPAO-UHFFFAOYSA-N Raney nickel Chemical compound [Al].[Ni] NPXOKRUENSOPAO-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000004587 chromatography analysis Methods 0.000 description 3
- 239000000975 dye Substances 0.000 description 3
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 3
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- IBEDHQUPZORDNY-UHFFFAOYSA-N (1-chloro-2,2,2-trifluoro-1-nitroethyl)benzene Chemical compound ClC(C1=CC=CC=C1)(C(F)(F)F)[N+](=O)[O-] IBEDHQUPZORDNY-UHFFFAOYSA-N 0.000 description 2
- ODGIMMLDVSWADK-UHFFFAOYSA-N 4-trifluoromethylaniline Chemical class NC1=CC=C(C(F)(F)F)C=C1 ODGIMMLDVSWADK-UHFFFAOYSA-N 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 2
- GNHQSAUHXKRQMC-UHFFFAOYSA-N benzene;chlorine Chemical compound [Cl].C1=CC=CC=C1 GNHQSAUHXKRQMC-UHFFFAOYSA-N 0.000 description 2
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 238000005984 hydrogenation reaction Methods 0.000 description 2
- 238000006386 neutralization reaction Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 238000006722 reduction reaction Methods 0.000 description 2
- 125000006413 ring segment Chemical group 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- 235000017550 sodium carbonate Nutrition 0.000 description 2
- GQYYVDLUKVSOBL-UHFFFAOYSA-N (2,2,2-trifluoro-1-nitroethyl)benzene Chemical group [O-][N+](=O)C(C(F)(F)F)C1=CC=CC=C1 GQYYVDLUKVSOBL-UHFFFAOYSA-N 0.000 description 1
- GZWGTVZRRFPVAS-UHFFFAOYSA-N 1-isocyanato-2-(trifluoromethyl)benzene Chemical compound FC(F)(F)C1=CC=CC=C1N=C=O GZWGTVZRRFPVAS-UHFFFAOYSA-N 0.000 description 1
- CVINWVPRKDIGLL-UHFFFAOYSA-N 4-chloro-2-(trifluoromethyl)aniline Chemical compound NC1=CC=C(Cl)C=C1C(F)(F)F CVINWVPRKDIGLL-UHFFFAOYSA-N 0.000 description 1
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000010933 acylation Effects 0.000 description 1
- 238000005917 acylation reaction Methods 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- NNBZCPXTIHJBJL-UHFFFAOYSA-N decalin Chemical compound C1CCCC2CCCCC21 NNBZCPXTIHJBJL-UHFFFAOYSA-N 0.000 description 1
- 125000000664 diazo group Chemical group [N-]=[N+]=[*] 0.000 description 1
- 238000006193 diazotization reaction Methods 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910001629 magnesium chloride Inorganic materials 0.000 description 1
- WALYXZANOBBHCI-UHFFFAOYSA-K magnesium sodium trichloride hydrate Chemical compound O.[Cl-].[Na+].[Mg+2].[Cl-].[Cl-] WALYXZANOBBHCI-UHFFFAOYSA-K 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- MWAVGMOUEMRXSM-UHFFFAOYSA-N n-[2-(trifluoromethyl)phenyl]carbamoyl fluoride Chemical compound FC(=O)NC1=CC=CC=C1C(F)(F)F MWAVGMOUEMRXSM-UHFFFAOYSA-N 0.000 description 1
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 1
- 239000002574 poison Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 239000001632 sodium acetate Substances 0.000 description 1
- 229960004249 sodium acetate Drugs 0.000 description 1
- 235000017281 sodium acetate Nutrition 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
This invention is a preparation method of near trifluoromethyl aniline, the material is benzotrifluoride, and it is generated into compound of between chlorine benzotrifluoride and its isomer through circle chlorination reaction. Then the got compound is generated into compound of 2-nitryl-5-chlorine benzotrifluoride and its isomer through nitration. Finally the compound after nitration is proceeded by catalytic hydrogenation-hydrogenolysis dechlorination reaction to generate three isomers compound which is mainly near trifluoromethyl aniline, then pure near trifluoromethyl aniline is got after rectification. The synthesis line is short, technique is advanced, and result is good and easy to be industrial generated.
Description
Technical field
The present invention relates to a kind of preparation method of product, the hydrogenolysis dechlorination technology of chlorine atom on especially a kind of preparation method of o-trifluoromethyl aniline and the aromatic ring.
Background technology
O-trifluoromethyl aniline is a kind of important organic synthesis intermediate, is mainly used in the synthetic of dyestuff and agricultural chemicals.For example o-trifluoromethyl aniline can be used for synthesizing acyl dihydroxy-benzene azoic dyestuff, and this dyestuff is used for polyolefine, and the particularly dyeing of polypropylene fabric can produce strong vivid tone, and fast colours, and is colour-fast.O-trifluoromethyl aniline can be used for synthetic N-alkyl diphenyl aminated compounds for another example, and this compound can be used for making and belong to agent and sterilant extremely.
Preparation about o-trifluoromethyl aniline; people such as Forbes are raw material with m-trifluoromethyl aniline; through acylations, nitrated, hydrolysis, diazotization, take off five steps reaction such as diazo and make adjacent nitro-trifluoromethyl toluene, in the presence of the Raney nickel catalyzer, carry out catalytic hydrogenation then and then obtain o-trifluoromethyl aniline.People such as Maginnity P.M. have also made o-trifluoromethyl aniline with same synthetic route, and just the final step reduction reaction adopts the method for chemical reduction.In addition, disclosed patent had announced once also that with Raney nickel or palladium/charcoal be catalyzer, with yellow soda ash, triethylamine etc. is acid binding agent, and 2-trifluoromethyl-4-chloroaniline is carried out the hydrogenolysis dechlorination or 2-nitro-5-chlorobenzotrifluoride is carried out catalytic hydrogenation preparing o-trifluoromethyl aniline.People such as Henry C.L. were raw material with the o-trifluoromethyl phenyl isocyanate once, prepared o-trifluoromethyl aniline with the hydrofluoric acid reaction via o-trifluoromethyl phenyl amino formyl fluoride.But the above method for preparing o-trifluoromethyl aniline, the synthetic route that has is oversize, and the raw material that has is difficult to obtain, and the Technology that has is not good enough, all is not a kind of ideal production method.
Summary of the invention
It is longer to the invention solves the existing in prior technology synthetic route, and raw material is not easy to obtain, the technical problem of grade that Technology is not good enough, provide a kind of convenience, economy, can be for the preparation method of the o-trifluoromethyl aniline of suitability for industrialized production.
Above-mentioned technical purpose of the present invention solves by the following technical programs: a kind of preparation method of o-trifluoromethyl aniline is a raw material with the phenylfluoroform, comprises three-step reaction and corresponding technological process:
1. in the presence of iron powder or ferric chloride catalyst, phenylfluoroform and chlorine initial ring chlorination reaction, obtain with meta-chlorobenzotrifluoride be main content the neighbour,, to three kinds of mixture of isomers;
2. with the meta-chlorobenzotrifluoride and the mixture of isomers thereof of the first step cyclization gained, in the presence of the vitriol oil, with nitrosonitric acid generation nitration reaction, obtaining with 2-nitro-5 chlorobenzotrifluoride is the multiple mixture of isomers of main content;
3. 2-nitro-5-chlorine three that the second step nitration reaction is obtained is tied up the multiple mixture of isomers that toluene is main content, in the presence of solvent, catalyzer, acid binding agent, with hydrogen generation catalytic hydrogenation-hydrogenolysis dechlorination reaction, generation with o-trifluoromethyl aniline be main content the neighbour,, to three kinds of mixture of isomers, through distillation, obtain pure o-trifluoromethyl aniline, simultaneously, can also obtain the m-trifluoromethyl aniline of a part.
Method of the present invention is to be raw material with the phenylfluoroform, in the presence of iron powder or iron trichloride, generates meta-chlorobenzotrifluoride and mixture of isomers thereof through the ring chlorination reaction.Then this mixture is carried out nitration reaction and generate 2-nitro-5-chlorobenzotrifluoride and mixture of isomers thereof.At last, the resulting mixture of nitration reaction is carried out catalytic hydrogenation-hydrogenolysis dechlorination reaction in the presence of Pd/carbon catalyst and magnesium powder, generate with o-trifluoromethyl aniline be main content the neighbour,, to three kinds of mixture of isomers.This mixture is carried out rectifying just can obtain pure o-trifluoromethyl aniline.Be expressed as down with chemical equation:
The gordian technique that the present invention prepares o-trifluoromethyl aniline is to slough benzene chlorine in ring atom by hydrogenolysis, i.e. hydrogenolysis dechlorination technology.Disclosed dechlorination method has multiple, and for example, people such as Bryce-Smith slough benzene chlorine in ring atom with magnesium powder and Virahol and chlorobenzene reaction in the presence of naphthane.But be to use more dechlorination method still to adopt the method for catalyzer hydrogenolysis, and the hydrogenolysis dechlorination all is to be catalyzer (making catalyzer with Raney nickel poisons easily) with palladium/charcoal usually, with sodium hydroxide, yellow soda ash, sodium-acetate, triethylamine etc. is acid binding agent, need to use relatively large Pd/carbon catalyst in this way yet make, dechlorination sometimes is also incomplete.Our the hydrogenolysis dechlorination technology of invention is solvent with the aqueous methanol, carries out the hydrogenolysis dechlorination in the presence of Pd/carbon catalyst and magnesium powder, and the hydrogenolysis dechlorination only need use the Pd/carbon catalyst of minute quantity just can reach good dechlorination effect in this way.Among the present invention, the magnesium powder is not only acid binding agent, is used for the hydrogenchloride that generates in the absorption reaction, also participates in dechlorination reaction simultaneously.
As preferably, the preparation method of described o-trifluoromethyl aniline, the temperature of reaction of ring chlorination reaction is 0 ℃～40 ℃, reaction times is 7～12 hours, used catalyzer is iron powder or iron trichloride in the reaction, and catalyst consumption is 1～3% (in phenylfluoroform, mol ratio).Whether reaction is finished, and can determine by the gas chromatographic analysis to reaction solution.After the reaction, rush to remain in chlorine and hydrogen chloride gas in the reaction solution, remove by filter catalyzer, filtrate rectifying with pressurized air.Collect meta-chlorobenzotrifluoride and mixture of isomers cut thereof.
As preferably, the preparation method of described o-trifluoromethyl aniline, the temperature of reaction of nitration reaction are 10 ℃～50 ℃, and the reaction times is 2～5 hours.The consumption of 95% nitrosonitric acid is 1～1.2mol (in a 1mol chloro phenylfluoroform), the consumption of 98% the vitriol oil is 1.5～4mol (in a 1mol chloro phenylfluoroform), after the nitration reaction, tell lower floor's spent acid, the upper strata nitration product washs with suitable quantity of water, and it is the multiple mixture of isomers of main content that neutralization is with 2-nitro-5-chlorobenzotrifluoride.
As preferably, the preparation method of described o-trifluoromethyl aniline, in catalytic hydrogenation-hydrogenolysis dechlorination reaction, solvent for use is an aqueous methanol; Catalyst system therefor is 5%Pd/C, and consumption is 0.8～2g (in a 1mol chloro nitro-trifluoromethyl toluene); Used acid binding agent is the magnesium powder, and its consumption is 0.5～0.502mol (in a 1mol chloro nitro-trifluoromethyl toluene); Temperature of reaction is 40 ℃～80 ℃, and reaction pressure is 0.5～1.0Mpa, 2～4 hours reaction times.After reaction finished, cooling removed by filter catalyzer and remaining magnesium powder, and methyl alcohol is reclaimed in the filtrate distillation, and cooling distillation residual solution is told lower floor's magnesium chloride brine, carries out rectifying after the upper strata hydrogenation products washes with water, then can obtain pure o-trifluoromethyl aniline.
Therefore, the present invention have that synthetic route is short, technology is advanced, yield is high, effective, characteristics such as suitability for industrialized production is simple and easy to do.
Embodiment
Below by specific embodiment, and in conjunction with the accompanying drawings, technical scheme of the present invention is described in further detail.
The ring chlorination reaction:
Embodiment 1: in 1000 ml flasks, drop into the 400g phenylfluoroform, the 10g iron trichloride, keeping temperature of reaction is 10～15 ℃, stirs down and feeds chlorine 9 hours, and reaction is finished, catch up with chlorine residual in the reaction flask and hydrogen chloride gas with pressurized air, remove by filter catalyzer, filtrate is through gas chromatographic analysis, and the content of each component is: 4.8% phenylfluoroform, 72.8% meta-chlorobenzotrifluoride, 4.2% chlorobenzotrifluoride, 6.2% p-chloro benzo trifluoride-99,12% is polychloride.Rectification process liquid is collected 120～130 ℃/0.04Mpa (vacuum tightness) cut, be with meta-chlorobenzotrifluoride be main content the neighbour,, to three kinds of mixture of isomers.
Embodiment 2-5 is with embodiment 1.
The principal reaction condition is to the quantized data table of reaction influence in the table 1 ring chlorination reaction
The nitration reaction of meta-chlorobenzotrifluoride and mixture of isomers thereof:
Embodiment 1: in the 1000ml flask, drop into the vitriol oil of 210g, under the cold water cooling, drip the 104.4g nitrosonitric acid, under 10～15 ℃ of maintenance temperature of reaction, drip 270.7g meta-chlorobenzotrifluoride and mixture of isomers thereof, about 1 hour of dropping time.Drip and finish, reacted 2 hours down at 45～50 ℃, after having reacted, tell lower floor's spent acid, the upper strata nitration product is after water washing, neutralization, and being with 2-nitro-5-chlorobenzotrifluoride is the multiple mixture of isomers of main content, and content is 79.6%.
Embodiment 2-5 is with embodiment 1.
The principal reaction condition is to the quantized data table of reaction influence in table 2 nitration reaction
Catalytic hydrogenation-hydrogenolysis dechlorination reaction:
Embodiment 1: in one liter autoclave, drop into 225g 2-nitro-5-chlorobenzotrifluoride and mixture of isomers thereof, 600ml methyl alcohol, 1g Pd/C catalyzer, 12g magnesium powder.Build kettle cover, catch up with in the autoclave air three times with nitrogen, use hydrogen exchange nitrogen again three times, pour hydrogen then, pressure is 0.5～1.0MPa.Under 40～50 ℃ of temperature of reaction, reacted 40～60 minutes, reacted 15～2 hours down at 65～75 ℃ then.Reaction is finished, cooling, and reaction solution is taken out in release, removes by filter Pd/C catalyzer and small portion of residual magnesium powder.Methyl alcohol is reclaimed in the filtrate distillation, after the distillation residuum cools off slightly, tells the aqueous solution of lower floor's magnesium chloride.Distill after the upper strata hydrogenation products washes with water, collect 80～100 ℃.The cut of (0.098MPa vacuum tightness), be the neighbour,, three kinds of mixture of isomers of p-trifluoromethylaniline.Mixture is through gas chromatographic analysis, and the content of each isomer is: 92% o-trifluoromethyl aniline, and 5.5% m-trifluoromethyl aniline, 0.7% is p-trifluoromethylaniline, 0.9% is dechlorination product not.
Embodiment 2-9 is with embodiment 1.
The principal reaction condition is to the quantized data table of reaction influence in table 3 catalytic hydrogenation-hydrogenolysis dechlorination reaction
Claims (10)
1, a kind of preparation method of o-trifluoromethyl aniline is a raw material with the phenylfluoroform, comprises three-step reaction and corresponding technological process:
1. in the presence of iron powder or ferric chloride catalyst, phenylfluoroform and chlorine initial ring chlorination reaction, obtain with meta-chlorobenzotrifluoride be main content the neighbour,, to three kinds of mixture of isomers;
2. with the meta-chlorobenzotrifluoride and the mixture of isomers thereof of the first step cyclization gained, in the presence of the vitriol oil, with nitrosonitric acid generation nitration reaction, obtaining with 2-nitro-5 chlorobenzotrifluoride is the multiple mixture of isomers of main content;
3. 2-nitro-5-chlorine three that the second step nitration reaction is obtained is tied up the multiple mixture of isomers that toluene is main content, in the presence of solvent, catalyzer, acid binding agent, with hydrogen generation catalytic hydrogenation-hydrogenolysis dechlorination reaction, generation with o-trifluoromethyl aniline be main content the neighbour,, to three kinds of mixture of isomers, through distillation, obtain pure o-trifluoromethyl aniline, simultaneously, can also obtain the m-trifluoromethyl aniline of a part.
2, the preparation method of o-trifluoromethyl aniline according to claim 1, the catalyst consumption that it is characterized in that encircling chlorination reaction is 1～5% (in phenylfluoroform, mol ratio), temperature of reaction is 0 ℃～40 ℃.
3, the preparation method of o-trifluoromethyl aniline according to claim 1 and 2, the temperature that it is characterized in that nitration reaction are 10 ℃～50 ℃.
4, the preparation method of o-trifluoromethyl aniline according to claim 1 and 2 is characterized in that in catalytic hydrogenation-hydrogenolysis dechlorination reaction, solvent for use is an aqueous methanol.
5, the preparation method of o-trifluoromethyl aniline according to claim 3 is characterized in that in catalytic hydrogenation-hydrogenolysis dechlorination reaction, solvent for use is an aqueous methanol.
6, according to the preparation method of claim 1 or 2 or 5 described o-trifluoromethyl anilines, it is characterized in that in catalytic hydrogenation-hydrogenolysis dechlorination reaction, catalyst system therefor is 5%Pd/C, consumption is 0.8～2g (in the 1mol nitration product); Used acid binding agent is the magnesium powder, and its consumption is 0.5～0.502mol (in the 1mol nitration product).
7, the preparation method of o-trifluoromethyl aniline according to claim 3 is characterized in that in catalytic hydrogenation-hydrogenolysis dechlorination reaction, catalyst system therefor is 5% Pd/C, and consumption is 0.8～2g (in the 1mol nitration product); Used acid binding agent is the magnesium powder, and its consumption is 0.5～0.502mol (in the 1mol nitration product).
8, the preparation method of o-trifluoromethyl aniline according to claim 4 is characterized in that in catalytic hydrogenation-hydrogenolysis dechlorination reaction, catalyst system therefor is 5% Pd/C, and consumption is 0.8～2g (in the 1mol nitration product); Used acid binding agent is the magnesium powder, and its consumption is 0.5～0.502mol (in the 1mol nitration product).
9, according to the preparation method of claim 1 or 2 or 5 or 7 or 8 described o-trifluoromethyl anilines, it is characterized in that catalytic hydrogenation-hydrogenolysis dechlorination reaction temperature is 40 ℃～80 ℃, reaction pressure is 0.5～1.0MPa.
10, the preparation method of o-trifluoromethyl aniline according to claim 3 is characterized in that catalytic hydrogenation-hydrogenolysis dechlorination reaction temperature is 40 ℃～80 ℃, and reaction pressure is 0.5～1.0MPa.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100368378C (en) * | 2006-05-15 | 2008-02-13 | 南通市东昌化工有限公司 | Production process of o-trifluoromethyl aniline |
| CN101182295B (en) * | 2007-12-14 | 2010-09-01 | 浙江工业大学 | Method for synthesizing 2-amido-5-chlorobenzotrifluoride |
| CN101538206B (en) * | 2009-04-27 | 2012-07-25 | 浙江工业大学 | Method for processing and utilizing trifluoromethyl aniline distillation still residue |
| CN103880686A (en) * | 2014-02-21 | 2014-06-25 | 江苏丰华化学工业有限公司 | Method for recycling wastes of trifluoromethyl phenylamine kettle residue |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2496098A1 (en) * | 1980-12-12 | 1982-06-18 | Rhone Poulenc Ind | PROCESS FOR THE PREPARATION OF ORTHOTRIFLUOROMETHYLANILINE |
| US4469890A (en) * | 1983-09-07 | 1984-09-04 | Monsanto Company | Preparation of ortho-aminobenzotrifluoride |
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- 2004-03-12 CN CNB2004100169586A patent/CN100371313C/en not_active Expired - Lifetime
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100368378C (en) * | 2006-05-15 | 2008-02-13 | 南通市东昌化工有限公司 | Production process of o-trifluoromethyl aniline |
| CN101182295B (en) * | 2007-12-14 | 2010-09-01 | 浙江工业大学 | Method for synthesizing 2-amido-5-chlorobenzotrifluoride |
| CN101538206B (en) * | 2009-04-27 | 2012-07-25 | 浙江工业大学 | Method for processing and utilizing trifluoromethyl aniline distillation still residue |
| CN103880686A (en) * | 2014-02-21 | 2014-06-25 | 江苏丰华化学工业有限公司 | Method for recycling wastes of trifluoromethyl phenylamine kettle residue |
| CN103880686B (en) * | 2014-02-21 | 2015-03-25 | 江苏丰华化学工业有限公司 | Method for recycling trifluoromethyl aniline kettle residue waste |
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| CN100371313C (en) | 2008-02-27 |
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