CN103420842A - Preparation method for 2,3,4-trifluoronitrobenzene - Google Patents
Preparation method for 2,3,4-trifluoronitrobenzene Download PDFInfo
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Abstract
The invention discloses a preparation method for 2,3,4-trifluoronitrobenzene. The preparation method comprises the following steps: (1), under the condition of sulfuric acid, performing nitration reaction on 2,6-dichloro fluorobenzene and nitric acid, completely reacting, and performing postprocessing to obtain a dichloro fluoronitrobenzene mixture; (2), mixing the dichloro fluoronitrobenzene mixture obtained in the step (1), potassium fluoride and a phase transfer catalyst with 3,5-dichloro-4-fluoronitrobenzene to obtain a mixed system, performing fluoro reaction, completely reacting, performing postprocessing, and separating to obtain the 3,5-dichloro-4-fluoronitrobenzene and the 2,3,4-trifluoronitrobenzene. According to the preparation method, the next fluoro-reaction is directly performed without separating a product obtained through the nitration reaction; in the fluoro-reaction, the 3,5-dichloro-4-fluoronitrobenzene serves as a solvent in a fluorination process, so that the solid-liquid ratio in the reaction is increased and the flowability in the reaction is improved.
Description
Technical field
The invention belongs to the pharmaceutical intermediate preparation field, be specifically related to a kind of 2,3, the preparation method of 4-trifluoronitrobenzene.
Background technology
2,3,4-trifluoronitrobenzene (No. CAS: 771-69-7), structure is as shown in formula I, be a kind of important pharmaceutical intermediate, be mainly used in synthetic Ofloxacine USP 23 and lomefloxacin hydrochloride, they are third generation Comprecins of HDK Pharmaceutical Co., Ltd development.
The Chinese patent application that publication number is CN1357530A discloses and a kind ofly with o-chloronitrobenzene, has prepared 2,3, the production technique of 4-trifluoronitrobenzene, o-chloronitrobenzene successively through superchlorination, fluoridize, further chlorination obtains 2, the 6-dichlor fluorbenzene, the 2,6-dichlorofluorobenzene obtained obtains 2 through nitration and fluoridation more successively, 3,4-trifluoronitrobenzene.In this production technique, 2, the 6-dichlor fluorbenzene obtains 2 after nitration reaction, the chloro-3-fluoronitrobenzene of 4-bis-and 3, the mixture of the chloro-4-fluoronitrobenzene of 5-bis-, this mixture obtains 2 after separating, the chloro-3-fluoronitrobenzene of 4-bis-is proceeded fluoridation and is obtained product 2, 3, the 4-trifluoronitrobenzene, in the end in a step fluoridation, need to use tetramethylene sulfone as reaction solvent, due to tetramethylene sulfone price comparison costliness, and this temperature of reaction is higher, tetramethylene sulfone is under high temperature and air existence condition, easily decompose polymkeric substance and the sulfurous gas that generates black, the efficiency of impact reaction.
Liu Lina has reported that take 2,6-DCA prepares 2,3 as starting raw material, the synthesis technique of 4-trifluoronitrobenzene, 2,6-DCA successively through diazotization, fluoroboric acidization then thermal degradation obtain 2, the 6-dichlor fluorbenzene, the 2,6-dichlorofluorobenzene obtained passes through nitration reaction again, separate and obtain 2, the chloro-3-fluoronitrobenzene of 4-bis-, obtain 2, the chloro-3-fluoronitrobenzene of 4-bis-obtains 2 through further fluoridation, 3,4-trifluoronitrobenzene.The fluoridation of this reaction final step solvent used is DMSO, and DMSO reclaims difficulty, causes the rising of cost, and the yield of reaction is not high, final step 2,3, and the yield of 4-trifluoronitrobenzene only has 62%.
Summary of the invention
The invention provides a kind of 2,3, the preparation method of 4-trifluoronitrobenzene, this preparation method's operation steps is simple, product yield is high, cost is lower.
A kind of 2,3, the preparation method of 4-trifluoronitrobenzene, comprise the steps:
(1), under the condition existed at sulfuric acid, 2,6-dichlorofluorobenzene and nitric acid generation nitration reaction, after reacting completely, obtain dichloro one fluoronitrobenzene mixture through aftertreatment;
The structure of described 2,6-dichlorofluorobenzene is as shown in the formula (II):
Described dichloro one fluoronitrobenzene mixture is comprised of the chloro-3-fluoronitrobenzene of 2,4-bis-and the chloro-4-fluoronitrobenzene of 3,5-bis-;
Described 2, the structure of the chloro-3-fluoronitrobenzene of 4-bis-as shown in the formula (III):
Described 3, the structure of the chloro-4-fluoronitrobenzene of 5-bis-is suc as formula shown in (IV):
(2) dichloro one fluoronitrobenzene mixture step (1) obtained, Potassium monofluoride, phase-transfer catalyst and additional 3, the mixed system obtained after the chloro-4-fluoronitrobenzene of 5-bis-mixes carries out fluoro-reaction, after reacting completely, through aftertreatment, separate and obtain 3, the chloro-4-fluoronitrobenzene of 5-bis-and described 2,3, the 4-trifluoronitrobenzene;
Separate obtain 3, the chloro-4-fluoronitrobenzene of 5-bis-is as additional 3 after collecting, the chloro-4-fluoronitrobenzene of 5-bis-turns back in described fluoro-reaction and carries out recycle.
Reaction process is expressed as follows with chemical equation:
In step of the present invention (2), directly use dichloro one fluoronitrobenzene mixture to be reacted as reactant, avoided the step of separating, simplified operation; Moreover, also in described fluoro-reaction, further add the chloro-4-fluoronitrobenzene of 3,5-bis-, add 3, fluoro-reaction can not occur in the chloro-4-fluoronitrobenzene of 5-bis-, the role who has served as solvent, improved the solid-to-liquid ratio of reaction, increased the mobility in the reaction, and this fluoro-reaction is 3, while carrying out in the environment of the chloro-4-fluoronitrobenzene of 5-bis-, productive rate is higher, has reduced production cost; In addition, the boiling point of the chloro-4-fluoronitrobenzene of 3,5-bis-and 2,3,4-trifluoronitrobenzene differs larger, after fluoro-reaction, separates and is more prone to again.
In step (1), in step (1), described sulfuric acid is divided into two portions and adds, and a part is for dissolving 2,6-dichlorofluorobenzene, and the sulfuric acid of this part and the mol ratio of described 2,6-dichlorofluorobenzene are 1.5～2.5: 1;
Another part and nitric acid are mixed to form nitration mixture and are dripped, and the sulfuric acid of this part and the mol ratio of nitric acid are 1: 0.9～1.1;
The mol ratio of described 2,6-dichlorofluorobenzene and nitric acid is 1: 1.1～1.3.
Wherein, nitric acid generally adopts the concentrated nitric acid that concentration is 99%; Sulfuric acid generally adopts the vitriol oil that concentration is 98%.
In step (1), the temperature of described nitration reaction is 50～70 ℃, and in this temperature range, speed of reaction is higher, and side reaction is less, and can make within two components of the dichloro one fluoronitrobenzene mixture that obtains remain on suitable scope.
In step (1), in described dichloro one fluoronitrobenzene mixture 2, the massfraction of the chloro-3-fluoronitrobenzene of 4-bis-is 80～90%.
In step (1), the degree that reaction is carried out can be monitored by HPLC and TLC, and the reaction times is 2～4 hours, and reaction generally can react completely.
In step (1), described aftertreatment comprises following operation: reaction solution is cooled to room temperature, and in the impouring frozen water, stratification, get organic phase, and then alkali cleaning, be washed to neutrality, gets organic phase, obtains described dichloro one fluoronitrobenzene mixture.
In step (2), described phase-transfer catalyst is tetramethyl ammonium chloride, cetyl trimethylammonium bromide, Tetrabutyl amonium bromide, tetradecyl trimethyl ammonium chloride, benzyltriethylammoinium chloride or 4-butyl ammonium hydrogen sulfate, after using phase-transfer catalyst, can make the F of KF
-Easily participate in reaction, improve the transformation efficiency of reaction.
In step (2), in described mixed system, the mol ratio of the chloro-4-fluoronitrobenzene of 3,5-bis-and the chloro-3-fluoronitrobenzene of 2,4-bis-is 1: 2～3, now, can guarantee the solid-to-liquid ratio of reaction and the mobility in reaction, described fluoro-reaction is carried out efficiently, improve 2, the transformation efficiency of 3,4-trifluoronitrobenzene.
In step (2), the mol ratio of described dichloro one fluoronitrobenzene mixture, Potassium monofluoride, phase-transfer catalyst is 1: 2.0～2.3: 0.1～0.11.
In step (2), the temperature of described fluoro-reaction is 170～190 ℃.
In step (2), the degree that reaction is carried out can be monitored by HPLC and TLC, and the reaction times is 6～8 hours, and reaction generally can react completely.
In step (2), described aftertreatment comprises following operation: reaction solution is cooled to 100 ℃, then adds toluene, while hot suction filtration, filter cake toluene wash 2～3 times, merging filtrate, carry out rectification under vacuum, obtains 3, the chloro-4-fluoronitrobenzene of 5-bis-and described 2,3, the 4-trifluoronitrobenzene.
Compared with the existing technology, beneficial effect of the present invention is embodied in: after nitration reaction completes, the dichloro one fluoronitrobenzene mixture obtained, without separation, directly carries out next step fluoro-reaction, has simplified operation; And employing the method, can improve the productive rate of described fluoro-reaction.
Embodiment
Below in conjunction with specific embodiment, to of the present invention 2,3, the preparation method of 4-trifluoronitrobenzene does further detailed description.
Embodiment 1
(1) take 2,6-dichlor fluorbenzene 33g (0.2mol), put in the there-necked flask of 250ml, slowly add the 40g vitriol oil under stirring, then be heated to 60 ℃, start slowly to drip the ratio nitric acid of nitration mixture 38g(amount of substance: sulfuric acid=1: 1, wherein the concentration of nitric acid is 99%), control temperature of reaction 60 ℃ of left and right.After dripping end, react 2 hours, be cooled to room temperature, by in reaction solution impouring frozen water, stratification, get organic phase, then alkali cleaning, be washed to neutrality, get organic phase, obtain the chloro-3-fluoronitrobenzene of 2,4-bis-and 3, the chloro-4-fluoronitrobenzene of 5-bis-mixture 40g(HPLC detects the chloro-3-fluoronitrobenzene of 2,4-bis-and accounts for 84.5%).
(2) take the dichloro one fluoronitrobenzene mixture 21g that step (1) obtains, dry Potassium monofluoride 12.76g, phase-transfer catalyst tetramethyl ammonium chloride 1.1g(CAS:75-57-0), 3, the chloro-4-fluoronitrobenzene of 5-bis-(in former secondary responses, separation obtains) 6g, join successively in dry 100ml there-necked flask, pass into nitrogen, stir, be heated to 180 ℃, reaction 6～8h, continue logical nitrogen until temperature is down to 100 ℃, add toluene, suction filtration while hot, filter cake toluene wash 2～3 times, merging filtrate, carry out rectification under vacuum, recovery obtains 3, the chloro-4-fluoronitrobenzene of 5-bis-8.9g, obtain weak yellow liquid 2, 3, 4-trifluoronitrobenzene 12.71g(yield 85%) (HPLC detects 2, 3, 4-trifluoronitrobenzene content 99%, retention time is consistent with standard substance).In the present embodiment, the concentration of the vitriol oil is 98%, and the concentration of concentrated nitric acid is 99%, as follows.
Embodiment 2
(1) take 2,6-dichlor fluorbenzene 33g (0.2mol), put in the there-necked flask of 250ml, slowly add the 40g vitriol oil under stirring, then be heated to 60 ℃, start slowly to drip the ratio concentrated nitric acid of nitration mixture 38g(amount of substance: the vitriol oil=1: 1), control temperature of reaction 60 ℃ of left and right.After dripping end, react 2 hours, be cooled to room temperature, by in reaction solution impouring frozen water, stratification, get organic phase, then alkali cleaning, be washed to neutrality, get organic phase, obtain the chloro-3-fluoronitrobenzene of 2,4-bis-and 3, the chloro-4-fluoronitrobenzene of 5-bis-mixture 40g(2, the chloro-3-fluoronitrobenzene of 4-bis-accounts for 84.5%).
(2) take the dichloro one fluoronitrobenzene mixture 21g that step (1) obtains, dry Potassium monofluoride 12.76g, phase-transfer catalyst tetramethyl ammonium chloride 1.1g, 3, the chloro-4-fluoronitrobenzene of 5-bis-(in former secondary responses, separation obtains) 3g, join successively in dry 100ml there-necked flask, pass into nitrogen, stir, be heated to 180 ℃, reaction 6～8h, continue logical nitrogen until temperature is down to 100 ℃, add toluene, suction filtration while hot, filter cake toluene wash 2～3 times, merging filtrate, carry out rectification under vacuum, obtain weak yellow liquid 2, 3, 4-trifluoronitrobenzene 11.96g(yield 80%) (HPLC detects 2, 3, 4-trifluoronitrobenzene content 99%, retention time is consistent with standard substance) and 3, the chloro-4-fluoronitrobenzene of 5-bis-5.9g.
Embodiment 3
(1) take 2,6-dichlorofluorobenzene 33g (0.2mol), put in the there-necked flask of 250ml, slowly add the 40g vitriol oil under stirring, then be heated to 60 ℃, start slowly to drip the ratio concentrated nitric acid of nitration mixture 38g(amount of substance: the vitriol oil=1:1), control temperature of reaction 60 ℃ of left and right.After dripping end, react 2 hours, be cooled to room temperature, by in reaction solution impouring frozen water, stratification, get organic phase, then alkali cleaning, be washed to neutrality, get organic phase, obtain the chloro-3-fluoronitrobenzene of 2,4-bis-and 3, the chloro-4-fluoronitrobenzene of 5-bis-mixture 40g(2, the chloro-3-fluoronitrobenzene of 4-bis-accounts for 84.5%).
(2) take the dichloro one fluoronitrobenzene mixture 21g that step (1) obtains, dry Potassium monofluoride 12.76g, phase-transfer catalyst tetramethyl ammonium chloride 2.2g, 3, the chloro-4-fluoronitrobenzene of 5-bis-(in former secondary responses, separation obtains) 6g, join successively in dry 100ml there-necked flask, pass into nitrogen, stir, be heated to 180 ℃, reaction 6～8h, continue logical nitrogen until temperature is down to 100 ℃, add toluene, suction filtration while hot, filter cake toluene wash 2～3 times, merging filtrate, carry out rectification under vacuum, obtain weak yellow liquid 2, 3, 4-trifluoronitrobenzene 12.86g(yield 86%) (HPLC detects 2, 3, 4-trifluoronitrobenzene content 99%, retention time is consistent with standard substance) and 3, the chloro-4-fluoronitrobenzene of 5-bis-8.9g.
Comparative Examples 1
(1) take 2,6-dichlor fluorbenzene 33g (0.2mol), put in the there-necked flask of 250ml, slowly add the 40g vitriol oil under stirring, then be heated to 60 ℃, start slowly to drip the ratio concentrated nitric acid of nitration mixture 38g(amount of substance: the vitriol oil=1: 1), control temperature of reaction 60 ℃ of left and right.After dripping end, react 2 hours, be cooled to room temperature, by in reaction solution impouring frozen water, stratification, get organic phase, then alkali cleaning, be washed to neutrality, get organic phase, obtain the chloro-3-fluoronitrobenzene of 2,4-bis-and 3, the chloro-4-fluoronitrobenzene of 5-bis-mixture 40g(2, the chloro-3-fluoronitrobenzene of 4-bis-accounts for 84.5%).
(2) take the dichloro one fluoronitrobenzene mixture 21g obtained in step (1), dry Potassium monofluoride 12.76g, phase-transfer catalyst tetramethyl ammonium chloride 1.1g, tetramethylene sulfone 40g, join successively in dry 100ml there-necked flask, be heated to 180 ℃, reaction 6～8h, reaction is cooled to room temperature after finishing, suction filtration, filtrate is carried out underpressure distillation, steam tetramethylene sulfone, 90～93 ℃ of cuts are collected in rectification under vacuum, obtain weak yellow liquid 2, 3, 4-trifluoronitrobenzene 11.65g(yield 78%) (HPLC detects 2, 3, 4-trifluoronitrobenzene content 99%, retention time is consistent with standard substance).
Comparative Examples 2
(1) take 2,6-dichlor fluorbenzene 33g (0.2mol), put in the there-necked flask of 250ml, slowly add the 40g vitriol oil under stirring, then be heated to 60 ℃, start slowly to drip the ratio concentrated nitric acid of nitration mixture 38g(amount of substance: the vitriol oil=1: 1), control temperature of reaction 60 ℃ of left and right.After dripping end, react 2 hours, be cooled to room temperature, by in reaction solution impouring frozen water, stratification, get organic phase, then alkali cleaning, be washed to neutrality, gets organic phase, obtain 2, the chloro-3-fluoronitrobenzene of 4-bis-and the chloro-4-fluoronitrobenzene of 3,5-bis-mixture 40g(2, the chloro-3-fluoronitrobenzene of 4-bis-accounts for 84.5%), separate and obtain the chloro-3-fluoronitrobenzene of 2,4-bis-33g through underpressure distillation.
(2) take in step (1), obtain 2, the chloro-3-fluoronitrobenzene of 4-bis-18g, dry Potassium monofluoride 12.76g, phase-transfer catalyst tetramethyl ammonium chloride 1.1g, tetramethylene sulfone 40g, join successively in dry 100ml there-necked flask, be heated to 180 ℃, reaction 6～8h, reaction is cooled to room temperature after finishing, suction filtration, filtrate is carried out underpressure distillation, steam tetramethylene sulfone, 90～93 ℃ of cuts are collected in rectification under vacuum, obtain weak yellow liquid 2, 3, 4-trifluoronitrobenzene 10.97g(yield 72%) (HPLC detects 2, 3, 4-trifluoronitrobenzene content 99%, retention time is consistent with standard substance).
Claims (8)
1. one kind 2,3, the preparation method of 4-trifluoronitrobenzene, is characterized in that, comprises the steps:
(1), under the condition existed at sulfuric acid, 2,6-dichlorofluorobenzene and nitric acid generation nitration reaction, after reacting completely, obtain dichloro one fluoronitrobenzene mixture through aftertreatment;
The structure of described 2,6-dichlorofluorobenzene is as shown in the formula (II):
Described dichloro one fluoronitrobenzene mixture is comprised of the chloro-3-fluoronitrobenzene of 2,4-bis-and the chloro-4-fluoronitrobenzene of 3,5-bis-;
Described 2, the structure of the chloro-3-fluoronitrobenzene of 4-bis-as shown in the formula (III):
Described 3, the structure of the chloro-4-fluoronitrobenzene of 5-bis-is suc as formula shown in (IV):
(2) dichloro one fluoronitrobenzene mixture step (1) obtained, Potassium monofluoride, phase-transfer catalyst and additional 3, the mixed system obtained after the chloro-4-fluoronitrobenzene of 5-bis-mixes carries out fluoro-reaction, after reacting completely, through aftertreatment, separate and obtain 3, the chloro-4-fluoronitrobenzene of 5-bis-and described 2,3, the 4-trifluoronitrobenzene;
Separate obtain 3, the chloro-4-fluoronitrobenzene of 5-bis-is as additional 3 after collecting, the chloro-4-fluoronitrobenzene of 5-bis-turns back in described fluoro-reaction and carries out recycle.
2. according to claim 12,3, the preparation method of 4-trifluoronitrobenzene, is characterized in that, in step (1), described sulfuric acid is divided into two portions and adds, and a part is for dissolving 2, the 6-dichlor fluorbenzene, the sulfuric acid of this part and the mol ratio of described 2,6-dichlorofluorobenzene are 1.5～2.5: 1;
Another part and nitric acid are mixed to form nitration mixture and are dripped, and the sulfuric acid of this part and the mol ratio of nitric acid are 1: 0.9～1.1;
The mol ratio of described 2,6-dichlorofluorobenzene and nitric acid is 1: 1.1～1.3.
3. according to claim 12,3, the preparation method of 4-trifluoronitrobenzene, is characterized in that, in step (1), the temperature of described nitration reaction is 50～70 ℃.
4. according to claim 12,3, the preparation method of 4-trifluoronitrobenzene, is characterized in that, in step (1), in described dichloro one fluoronitrobenzene mixture 2, the massfraction of the chloro-3-fluoronitrobenzene of 4-bis-is 80～90%.
5. according to claim 12,3, the preparation method of 4-trifluoronitrobenzene, is characterized in that, in step (2), in described mixed system, the mol ratio of the chloro-4-fluoronitrobenzene of 3,5-bis-and the chloro-3-fluoronitrobenzene of 2,4-bis-is 1: 2～3.
6. according to claim 12,3, the preparation method of 4-trifluoronitrobenzene, it is characterized in that, in step (2), described phase-transfer catalyst is tetramethyl ammonium chloride, cetyl trimethylammonium bromide, Tetrabutyl amonium bromide, tetradecyl trimethyl ammonium chloride, benzyltriethylammoinium chloride or 4-butyl ammonium hydrogen sulfate.
7. described 2,3 according to claim 1 or 6, the preparation method of 4-trifluoronitrobenzene, is characterized in that, in step (2), the mol ratio of described dichloro one fluoronitrobenzene mixture, Potassium monofluoride, phase-transfer catalyst is 1: 2.0～2.3: 0.1～0.11.
8. according to claim 12,3, the preparation method of 4-trifluoronitrobenzene, is characterized in that, in step (2), the temperature of described fluoro-reaction is 170～190 ℃, and the reaction times is 6～8h.
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| CN104478731A (en) * | 2014-12-31 | 2015-04-01 | 浙江永太科技股份有限公司 | Method for synthesizing 2, 4-dichloro-3-fluoronitrobenzene by means of micro-channel reactors |
| CN105646140A (en) * | 2016-03-28 | 2016-06-08 | 浙江工业大学 | Preparation method of 1,2,4,5-tetrafluorobenzene |
| CN109438248A (en) * | 2018-10-18 | 2019-03-08 | 信阳师范学院 | A kind of preparation method of the fluoro- 1,5- dinitrobenzene of castexplosive 2,3,4- tri- |
| CN115850085A (en) * | 2022-12-29 | 2023-03-28 | 中国科学技术大学苏州高等研究院 | Method for preparing fluoronitrobenzene from chloronitrobenzene |
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| CN103420842B (en) | 2015-01-07 |
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