CN1515542A - Method for co-production of 3-chloro-4-fluoroaniline and 2, 6-dichlorofluorobenzene - Google Patents
Method for co-production of 3-chloro-4-fluoroaniline and 2, 6-dichlorofluorobenzene Download PDFInfo
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- CN1515542A CN1515542A CNA031506887A CN03150688A CN1515542A CN 1515542 A CN1515542 A CN 1515542A CN A031506887 A CNA031506887 A CN A031506887A CN 03150688 A CN03150688 A CN 03150688A CN 1515542 A CN1515542 A CN 1515542A
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- chloro
- fluoronitrobenzene
- fluoroaniline
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- YSEMCVGMNUUNRK-UHFFFAOYSA-N 3-chloro-4-fluoroaniline Chemical compound NC1=CC=C(F)C(Cl)=C1 YSEMCVGMNUUNRK-UHFFFAOYSA-N 0.000 title claims abstract description 28
- 238000000034 method Methods 0.000 title claims abstract description 20
- JORVCRLRRRRLFI-UHFFFAOYSA-N 1,3-dichloro-2-fluorobenzene Chemical compound FC1=C(Cl)C=CC=C1Cl JORVCRLRRRRLFI-UHFFFAOYSA-N 0.000 title claims abstract description 6
- 238000004519 manufacturing process Methods 0.000 title abstract description 8
- RFFLAFLAYFXFSW-UHFFFAOYSA-N 1,2-dichlorobenzene Chemical compound ClC1=CC=CC=C1Cl RFFLAFLAYFXFSW-UHFFFAOYSA-N 0.000 claims abstract description 28
- 239000000203 mixture Substances 0.000 claims abstract description 21
- 238000006396 nitration reaction Methods 0.000 claims abstract description 17
- RBAHXNSORRGCQA-UHFFFAOYSA-N 1-chloro-2-fluoro-3-nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC(Cl)=C1F RBAHXNSORRGCQA-UHFFFAOYSA-N 0.000 claims abstract description 15
- DPHCXXYPSYMICK-UHFFFAOYSA-N 2-chloro-1-fluoro-4-nitrobenzene Chemical compound [O-][N+](=O)C1=CC=C(F)C(Cl)=C1 DPHCXXYPSYMICK-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000002994 raw material Substances 0.000 claims abstract description 12
- 239000012074 organic phase Substances 0.000 claims abstract description 8
- 238000005660 chlorination reaction Methods 0.000 claims abstract description 7
- 238000002360 preparation method Methods 0.000 claims abstract description 5
- 238000006467 substitution reaction Methods 0.000 claims abstract description 5
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229910017604 nitric acid Inorganic materials 0.000 claims abstract description 4
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims abstract description 3
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 32
- NROKBHXJSPEDAR-UHFFFAOYSA-M potassium fluoride Chemical group [F-].[K+] NROKBHXJSPEDAR-UHFFFAOYSA-M 0.000 claims description 15
- 238000004334 fluoridation Methods 0.000 claims description 14
- 239000003444 phase transfer catalyst Substances 0.000 claims description 14
- 238000006243 chemical reaction Methods 0.000 claims description 13
- 239000000047 product Substances 0.000 claims description 13
- VLRGXXKFHVJQOL-UHFFFAOYSA-N 3-chloropentane-2,4-dione Chemical compound CC(=O)C(Cl)C(C)=O VLRGXXKFHVJQOL-UHFFFAOYSA-N 0.000 claims description 7
- 239000003795 chemical substances by application Substances 0.000 claims description 7
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 6
- OKIZCWYLBDKLSU-UHFFFAOYSA-M N,N,N-Trimethylmethanaminium chloride Chemical compound [Cl-].C[N+](C)(C)C OKIZCWYLBDKLSU-UHFFFAOYSA-M 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
- 239000000460 chlorine Substances 0.000 claims description 5
- 229910052801 chlorine Inorganic materials 0.000 claims description 5
- 239000012043 crude product Substances 0.000 claims description 5
- 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 claims description 4
- 238000000066 reactive distillation Methods 0.000 claims description 3
- 150000001555 benzenes Chemical group 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 2
- 239000002253 acid Substances 0.000 abstract description 3
- 230000008901 benefit Effects 0.000 abstract description 3
- 238000003682 fluorination reaction Methods 0.000 abstract description 3
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 abstract 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 abstract 1
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 abstract 1
- 238000005516 engineering process Methods 0.000 description 7
- XWBTZHDDWRNOQH-UHFFFAOYSA-N 3-chloro-2-fluoroaniline Chemical compound NC1=CC=CC(Cl)=C1F XWBTZHDDWRNOQH-UHFFFAOYSA-N 0.000 description 6
- 238000000926 separation method Methods 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 238000009835 boiling Methods 0.000 description 4
- 238000006193 diazotization reaction Methods 0.000 description 4
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- 239000003905 agrochemical Substances 0.000 description 2
- 229960005081 diclofenamide Drugs 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000001149 thermolysis Methods 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- CMVQZRLQEOAYSW-UHFFFAOYSA-N 1,2-dichloro-3-nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC(Cl)=C1Cl CMVQZRLQEOAYSW-UHFFFAOYSA-N 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 230000000802 nitrating effect Effects 0.000 description 1
- 239000012044 organic layer Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 150000007660 quinolones Chemical class 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 238000005057 refrigeration Methods 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- 239000002912 waste gas Substances 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a method for co-producing 3-chloro-4-fluoroaniline and 2, 6-dichlorofluorobenzene, which takes ortho-dichlorobenzene as a raw material and comprises the following preparation steps: a. carrying out nitration reaction on ortho-dichlorobenzene and mixed acid consisting of concentrated sulfuric acid and concentrated nitric acid, and deacidifying and dewatering after the nitration reaction to obtain an organic phase in the ortho-dichlorobenzene; b. carrying out fluorination reaction on the organic phase, and separating to obtain a mixture of 3-chloro-2-fluoronitrobenzene and 3-chloro-4-fluoronitrobenzene after the fluorination reaction is finished; c. performing reduced pressure rectification on the mixture to obtain 3-chloro-2-fluoronitrobenzene and 3-chloro-4-fluoronitrobenzene; d. reducing the 3-chloro-4-fluoronitrobenzene to obtain 3-chloro-4-fluoroaniline; and the 3-chloro-2-fluoronitrobenzene and chlorine gas are subjected to chlorination substitution reaction to substitute nitro on a benzene ring, so as to obtain 2, 6-dichlorofluorobenzene. Has the advantages of reasonable process, easily obtained raw materials, less pollution and greatly reduced production cost.
Description
Technical field
The present invention relates to 3-chloro-4-fluoroaniline and 2, the preparation method of 6-dichlor fluorbenzene is to be raw material with the orthodichlorobenzene specifically, coproduction 3-chloro-4-fluoroaniline and 2, the method for 6-dichlor fluorbenzene.
Background technology
3-chloro-4-fluoroaniline and 2,6-dichlor fluorbenzene are the important intermediate of synthetic quinolones and agricultural chemicals.
At present, no matter from the angle of production security, the still angle from reducing cost is that to produce the said products all are comparatively rational operational paths to starting raw material with the orthodichlorobenzene.
In the prior art, producing 3-chloro-4-fluoroaniline generally is to be starting raw material with the orthodichlorobenzene, through mixed acid nitrification, fluoridize, behind the nitroreduction, obtain the mixture of 3-chloro-4-fluoroaniline and 3-chloro-2-fluoroaniline, wherein contain about 70% 3-chloro-4-fluoroaniline, take recrystallization method then, obtain the pure product of 3-chloro-4-fluoroaniline and, contain 60% 3-chloro-4-fluoroaniline in this secondary mixture approximately as the 3-chloro-4-fluoroaniline of waste treatment and the secondary mixture of 3-chloro-2-fluoroaniline.This method not only energy consumption is big, and the yield of target product is very low, directly causes the price of 3-chloro-4-fluoroaniline very expensive, seriously restricts the production and the popularization of its follow-up medicine or agricultural chemicals.Also have employing will obtain 3-chloro-4-fluoroaniline and 3-chloro-2-fluoroaniline the direct rectifying separation of mixture method and obtain 3-chloro-4-fluoroaniline and 3-chloro-2-fluoroaniline respectively, but, because aminated compounds chemical stability at high temperature is relatively poor, thereby very harsh to the conditional request of rectifying, facility investment is big, maintenance of the equipment is difficult and technological operation is complicated.
2, the production of 6-dichlor fluorbenzene mainly is with 3-chloro-2-fluoroaniline or 2, and the 6-dichlorphenamide bulk powder is a raw material, makes through diazotization posthydrolysis or thermolysis.But one side 3-chloro-2-fluoroaniline and 2, the 6-dichlorphenamide bulk powder itself is not easy to obtain, on the high side, moreover, the wastewater discharge of diazotization posthydrolysis technology is big, and owing to need to use strong carcinogen---nitrite, be unfavorable for environmental protection, sewage load is big and processing cost is high, in addition, diazotization reaction needs to carry out at low temperature, needs special refrigeration equipment, running cost is higher, after the diazotization thermal decomposition process then exist waste gas BF3 to the pollution of air, thermolysis control difficulty, be difficult to problem such as production in enormous quantities.In addition, also have with 2, the 3-dichloronitrobenzene is a raw material, through fluoridizing, the production technique that chlorination replaces, because in the nitration product of orthodichlorobenzene 2, the 3-dichloronitrobenzene generally only accounts for 10～20%, 3 of nitration product gross weight, and the 4-dichloronitrobenzene generally accounts for 80～90%, the former boiling point is 257～258 ℃, fusing point is 61～62 ℃, the latter's boiling point is 255～256 ℃, fusing point is 41～44 ℃, and boiling-point difference of the two and physical properties difference are very little, and it separates quite difficulty, separation costs is very high, thereby directly cause holding at high price of subsequent product, so there is raw material 2 equally in this technology, 3-dichloronitrobenzene itself is difficult for the problem of acquisition.
Summary of the invention
Technical problem to be solved by this invention is that the coproduction 3-chloro-4-fluoroaniline and 2 that a kind of technology is reasonable, raw material is easy to get, pollutes less, production cost significantly reduces, the method for 6-dichlor fluorbenzene are provided at above-mentioned prior art present situation.
The present invention solves the problems of the technologies described above the technical scheme that is adopted: this kind coproduction 3-chloro-4-fluoroaniline and 2, and the method for 6-dichlor fluorbenzene, it is a raw material with the orthodichlorobenzene, preparation process is as follows:
A, orthodichlorobenzene and carry out nitration reaction by the nitration mixture that the vitriol oil and concentrated nitric acid are formed, nitration reaction is after depickling, remove water treatment and obtain wherein organic phase;
B, above-mentioned organic phase is carried out fluoridation, fluoridation is finished after separate the mixture that obtains 3-chloro-2-fluoronitrobenzene and 3-chloro-4-fluoronitrobenzene;
C, with the said mixture rectification under vacuum, obtain 3-chloro-2-fluoronitrobenzene and 3-chloro-4-fluoronitrobenzene;
D, 3-chloro-4-fluoronitrobenzene obtain 3-chloro-4-fluoroaniline through reduction; 3-chloro-2-fluoronitrobenzene then with chlorine generation chlorination substitution reaction, the nitro on the substituted benzene ring obtains 2, the 6-dichlor fluorbenzene.
Described fluoridation is carried out with having under the phase-transfer catalyst existence condition solvent-free, fluorizating agent is a Potassium monofluoride, temperature of reaction is 140～190 ℃, and 3,4-dichloronitrobenzene and 2, the miscellany of 3-dichloronitrobenzene, Potassium monofluoride and phase-transfer catalyst three's mol ratio is 1: 1.05～1.2: 0.01～0.04.
Described fluoridation is solvent with the dimethyl sulfoxide (DMSO), with the Potassium monofluoride is fluorizating agent, under the phase-transfer catalyst existence condition, carry out in 140～170 ℃, and 3,4-dichloronitrobenzene and 2, the mol ratio of the miscellany of 3-dichloronitrobenzene, Potassium monofluoride, dimethyl sulfoxide (DMSO) and phase-transfer catalyst are 1: 1.05～1.2: 2.0～5.0: 0.01～0.04.
Described phase-transfer catalyst is at least a in cetyl trimethylammonium bromide, the tetramethyl ammonium chloride.
Described rectification under vacuum is carried out under 10mmHg, and collects the cut of 90～92 ℃ and 99～101 ℃ respectively.
The reactive distillation mode is adopted in described chlorination substitution reaction, and control reaction temperature is 180～210 ℃, constantly steams product 2 when feeding chlorine in the reactor, 6-dichlor fluorbenzene crude product, and 2,6-dichlor fluorbenzene crude product is through refining and get finished product.
Compared with prior art, the invention has the advantages that: 1, rectifying separation step of the present invention is after fluorination reaction step, the boiling point of 3-chloro-2-fluoronitrobenzene is 226～228 ℃, the boiling point of 3-chloro-4-fluoronitrobenzene is 240～242 ℃, the boiling-point difference of the two reaches more than 12 ℃, and the two chemical property under hot conditions is more stable, thereby rectifying separation is easy to realize and control, thereby technology is more reasonable, and has reduced the rectifying separation cost in producing; 2, the orthodichlorobenzene raw material is easy to get among the present invention, and its two kinds of nitration products all are fully utilized, and has changed into two kinds of high value-added products respectively, has reduced unnecessary waste, thereby has significantly reduced cost, has realized comprehensive benefit; 3, discharge of wastewater significantly reduces, and does not contain the material that is difficult to handle, thereby it handles easily, helps environment protection and processing cost is low.
Embodiment
Below in conjunction with embodiment the present invention is described in further detail.
Embodiment
One, nitrated
In the nitration reaction still, drop into deployed nitration mixture in advance earlier, the weight ratio of the concentrated nitric acid and the vitriol oil is 1: 1.2 in the nitration mixture, be warming up to 45～50 ℃, open and stir, in nitrating pot, drip the orthodichlorobenzene that measures then, the dropping total amount of orthodichlorobenzene is half of nitration mixture gross weight, and the nitrated temperature of control is 65～70 ℃ in the dropping process, dropwises the reaction of follow-up continuation of insurance temperature and finishes reaction in 2 hours.Telling spent acid layer recovery set after the cooling uses.Organic layer gets 2 after alkali lye neutralization, washing, drying, 3-dichloronitrobenzene and 3, and the mixture of 4-dichloronitrobenzene is used for next step fluoridation.
Two, fluoridize
The fluorizating agent of fluoridation generally uses Potassium monofluoride, reaction can be carried out in the presence of solvent, also can in the presence of solvent-free, carry out, solvent commonly used has dimethyl sulfoxide (DMSO), dimethyl formamide etc., outside desolventizing, general also phase-transfer catalyst such as adding quaternary ammonium salts in the reaction system, quaternary ammonium salts phase-transfer catalyst commonly used has cetyl trimethylammonium bromide, tetramethyl ammonium chloride etc., and temperature of reaction is generally at 140～200 ℃.Adopt dual mode to carry out fluoridation below respectively:
1, the solvent situation is arranged
Be fluorizating agent with the Potassium monofluoride in this example, be solvent, be phase-transfer catalyst with the cetyl trimethylammonium bromide with the dimethyl sulfoxide (DMSO).The mol ratio of nitration reaction gained organic phase, Potassium monofluoride, dimethyl sulfoxide (DMSO) and cetyl trimethylammonium bromide can be 1: 1.05～1.2: 2.0～5.0: 0.01～0.04, and four mol ratio is 1: 1.1: 3.5 in this example: 0.02.Dimethyl sulfoxide (DMSO) and cetyl trimethylammonium bromide are dropped in the fluoridation still, drop into Potassium monofluoride, stirring and dissolving, add 2 again, 3-dichloronitrobenzene and 3, the mixture of 4-dichloronitrobenzene, stir, heat up, control reaction temperature is about 165 ℃, stopped reaction after 6 hours.After the cooling, after filtration, washing, dry, distillation desolventize, 3-chloro-2-fluoronitrobenzene and 3-chloro-4-fluoronitrobenzene mixture;
2, solvent-free situation
Be fluorizating agent with the Potassium monofluoride in this example, be phase-transfer catalyst with the tetramethyl ammonium chloride.Nitration reaction gained organic phase, Potassium monofluoride and tetramethyl ammonium chloride three's mol ratio can be 1: 1.05～1.2: 0.01～0.04, and three's mol ratio is 1: 1.2: 0.04 in this example.With 2,3-dichloronitrobenzene and 3, the mixture of 4-dichloronitrobenzene drop in the fluoridation still, add Potassium monofluoride and tetramethyl ammonium chloride in the time of stirring, stir, heat up, and control reaction temperature is about 180 ℃, stopped reaction after 8 hours.After the cooling, after filtration, washing, drying, 3-chloro-2-fluoronitrobenzene and 3-chloro-4-fluoronitrobenzene mixture.
Three, rectification under vacuum
To under 10mmHg, carry out rectification under vacuum through 3-chloro-2-fluoronitrobenzene and the 3-chloro-4-fluoronitrobenzene mixture that fluoridation makes, collect the cut of 90～92 ℃ and 99～101 ℃, obtain 3-chloro-2-fluoronitrobenzene and 3-chloro-4-fluoronitrobenzene respectively.
Four, preparation 3-chloro-4-fluoroaniline and 2, the 6-dichlor fluorbenzene
It is mature technology that 3-chloro-4-fluoronitrobenzene is reduced to 3-chloro-4-fluoroaniline, can adopt the method for shortening or iron powder reducing.
3-chloro-2-fluoronitrobenzene is dropped in the chlorination tank, feed the chlorine of drying, control still temperature adopts the reactive distillation mode at 190～200 ℃, reacted about 10 hours, and collected distillate, be washed to neutrality, get crude product 2, the 6-dichlor fluorbenzene, underpressure distillation promptly makes 2, the pure product of 6-dichlor fluorbenzene.
Claims (6)
1, a kind of coproduction 3-chloro-4-fluoroaniline and 2, the method for 6-dichlor fluorbenzene, it is raw material with the orthodichlorobenzene, preparation process is as follows:
A, orthodichlorobenzene and carry out nitration reaction by the nitration mixture that the vitriol oil and concentrated nitric acid are formed, nitration reaction is after depickling, remove water treatment and obtain wherein organic phase;
B, above-mentioned organic phase is carried out fluoridation, fluoridation is finished after separate the mixture that obtains 3-chloro-2-fluoronitrobenzene and 3-chloro-4-fluoronitrobenzene;
C, with the said mixture rectification under vacuum, obtain 3-chloro-2-fluoronitrobenzene and 3-chloro-4-fluoronitrobenzene;
D, 3-chloro-4-fluoronitrobenzene obtain 3-chloro-4-fluoroaniline through reduction; 3-chloro-2-fluoronitrobenzene then with chlorine generation chlorination substitution reaction, the nitro on the substituted benzene ring obtains 2, the 6-dichlor fluorbenzene.
2, coproduction 3-chloro-4-fluoroaniline according to claim 1 and 2, the method of 6-dichlor fluorbenzene, it is characterized in that described fluoridation is solvent-free and have under the phase-transfer catalyst existence condition and carry out, fluorizating agent is a Potassium monofluoride, temperature of reaction is 140～190 ℃, and 3,4-dichloronitrobenzene and 2, the miscellany of 3-dichloronitrobenzene, Potassium monofluoride and phase-transfer catalyst three's mol ratio is 1: 1.05～1.2: 0.01～0.04.
3, coproduction 3-chloro-4-fluoroaniline according to claim 1 and 2, the method of 6-dichlor fluorbenzene, it is characterized in that described fluoridation is solvent with the dimethyl sulfoxide (DMSO), with the Potassium monofluoride is fluorizating agent, under the phase-transfer catalyst existence condition, carry out in 140～170 ℃, and 3,4-dichloronitrobenzene and 2, the mol ratio of the miscellany of 3-dichloronitrobenzene, Potassium monofluoride, dimethyl sulfoxide (DMSO) and phase-transfer catalyst is 1: 1.05～1.2: 2.0～5.0: 0.01～0.04.
4, according to claim 2 or 3 described coproduction 3-chloro-4-fluoroanilines and 2, the method for 6-dichlor fluorbenzene is characterized in that described phase-transfer catalyst is at least a in cetyl trimethylammonium bromide, the tetramethyl ammonium chloride.
5, coproduction 3-chloro-4-fluoroaniline according to claim 1 and 2, the method for 6-dichlor fluorbenzene is characterized in that described rectification under vacuum carries out under 10mmHg, and collects the cut of 90～92 ℃ and 99～101 ℃ respectively.
6, coproduction 3-chloro-4-fluoroaniline according to claim 1 and 2, the method of 6-dichlor fluorbenzene, it is characterized in that described chlorination substitution reaction employing reactive distillation mode, control reaction temperature is 180～210 ℃, constantly steam product 2 when feeding chlorine in the reactor, 6-dichlor fluorbenzene crude product, 2,6-dichlor fluorbenzene crude product gets finished product through making with extra care.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 03150688 CN1258519C (en) | 2003-08-28 | 2003-08-28 | Method for co-production of 3-chloro-4-fluoroaniline and 2, 6-dichlorofluorobenzene |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 03150688 CN1258519C (en) | 2003-08-28 | 2003-08-28 | Method for co-production of 3-chloro-4-fluoroaniline and 2, 6-dichlorofluorobenzene |
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| CN1515542A true CN1515542A (en) | 2004-07-28 |
| CN1258519C CN1258519C (en) | 2006-06-07 |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103709044A (en) * | 2013-12-12 | 2014-04-09 | 江苏集贤绿色化学科技研究院有限公司 | Preparation method of 3-chloro-4-fluoroaniline hydrochloride |
| CN104496824A (en) * | 2011-05-09 | 2015-04-08 | 滨海永太医化有限公司 | Method for combined production of quinolone medicine key intermediate by taking o-dichlorobenzene as raw material |
| CN105418439A (en) * | 2015-11-17 | 2016-03-23 | 山东沾化天九化工有限公司 | Method and device for producing 3-chlorine-4-fluoroaniline |
| CN109400459A (en) * | 2018-12-17 | 2019-03-01 | 浙江工业大学上虞研究院有限公司 | The preparation method of 2,4,5- trifluoro benzene acetic acid |
| CN115611745A (en) * | 2022-09-26 | 2023-01-17 | 浙江闰土股份有限公司 | Method for continuously producing 3, 4-dichloronitrobenzene |
-
2003
- 2003-08-28 CN CN 03150688 patent/CN1258519C/en not_active Expired - Lifetime
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104496824A (en) * | 2011-05-09 | 2015-04-08 | 滨海永太医化有限公司 | Method for combined production of quinolone medicine key intermediate by taking o-dichlorobenzene as raw material |
| CN104496824B (en) * | 2011-05-09 | 2017-09-29 | 滨海永太医化有限公司 | A kind of method using o-dichlorohenzene as raw material coproduction QNS key intermediate |
| CN103709044A (en) * | 2013-12-12 | 2014-04-09 | 江苏集贤绿色化学科技研究院有限公司 | Preparation method of 3-chloro-4-fluoroaniline hydrochloride |
| CN105418439A (en) * | 2015-11-17 | 2016-03-23 | 山东沾化天九化工有限公司 | Method and device for producing 3-chlorine-4-fluoroaniline |
| CN109400459A (en) * | 2018-12-17 | 2019-03-01 | 浙江工业大学上虞研究院有限公司 | The preparation method of 2,4,5- trifluoro benzene acetic acid |
| CN109400459B (en) * | 2018-12-17 | 2021-07-23 | 浙江工业大学上虞研究院有限公司 | Preparation method of 2,4, 5-trifluoro-phenylacetic acid |
| CN115611745A (en) * | 2022-09-26 | 2023-01-17 | 浙江闰土股份有限公司 | Method for continuously producing 3, 4-dichloronitrobenzene |
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| Publication number | Publication date |
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| CN1258519C (en) | 2006-06-07 |
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