CN103420842B - 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 pharmaceutical intermediate preparation field, be specifically related to a kind of preparation method of 2,3,4-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 synthesis Ofloxacine USP 23 and lomefloxacin hydrochloride, they are third generation Comprecins of HDK Pharmaceutical Co., Ltd development.
Publication number is that the Chinese patent application of CN1357530A discloses one o-chloronitrobenzene and prepares 2,3, the production technique of 4-trifluoronitrobenzene, o-chloronitrobenzene successively through superchlorination, fluoridize, further chlorination obtain 2,6-dichlor fluorbenzene, the 2,6-dichlorofluorobenzene obtained obtains 2 through nitration and fluoridation more successively, 3,4-trifluoronitrobenzene.In this production technique, 2, 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 being separated, the chloro-3-fluoronitrobenzene of 4-bis-proceeds fluoridation and obtains product 2, 3, 4-trifluoronitrobenzene, in the end in a step fluoridation, need to use tetramethylene sulfone as reaction solvent, because tetramethylene sulfone price comparison is expensive, and this temperature of reaction is higher, tetramethylene sulfone is under high temperature and air existence condition, easy polymkeric substance and the sulfurous gas decomposing generation black, the efficiency of impact reaction.
It is that starting raw material prepares 2,3 that Liu Lina reports with 2,6-DCA, the synthesis technique of 4-trifluoronitrobenzene, 2,6-DCA successively through diazotization, fluoroboric acidization then thermal degradation obtain 2,6-dichlor fluorbenzene, the 2,6-dichlorofluorobenzene obtained is again through nitration reaction, separation obtains 2, the chloro-3-fluoronitrobenzene of 4-bis-, obtain 2,4-bis-chloro-3-fluoronitrobenzenes obtain 2 through further fluoridation, 3,4-trifluoronitrobenzene.The solvent that the fluoridation of this reaction final step is used is that DMSO, DMSO reclaim difficulty, and cause the rising of cost, and the yield of reaction is not high, the yield of final step 2,3,4-trifluoronitrobenzene only has 62%.
Summary of the invention
The invention provides a kind of preparation method of 2,3,4-trifluoronitrobenzene, this preparation method's operation steps is simple, and product yield is high, and cost is lower.
A kind of preparation method of 2,3,4-trifluoronitrobenzene, comprises the steps:
(1) under sulfuric acid existent condition, 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 made up of 2,4-bis-chloro-3-fluoronitrobenzene and the chloro-4-fluoronitrobenzene of 3,5-bis-;
The structure of described 2,4-bis-chloro-3-fluoronitrobenzenes is as shown in the formula (III):
The structure of described 3,5-bis-chloro-4-fluoronitrobenzenes is such as formula shown in (IV):
(2) the dichloro one fluoronitrobenzene mixture, Potassium monofluoride, the phase-transfer catalyst and additional 3 that step (1) are obtained, the mixed system obtained after the chloro-4-fluoronitrobenzene mixing of 5-bis-carries out fluoro-reaction, after reacting completely, through aftertreatment, separation obtains 3,5-bis-chloro-4-fluoronitrobenzene and 2,3,4-described trifluoronitrobenzenes;
3, the 5-bis-chloro-4-fluoronitrobenzenes that separation obtains turn back in described fluoro-reaction as additional 3,5-bis-chloro-4-fluoronitrobenzenes and carry out recycle after collecting.
Reaction process chemical equation is expressed as follows:
In step of the present invention (2), directly use dichloro one fluoronitrobenzene mixture to react as reactant, avoid the step of separation, simplify operation; Moreover, in described fluoro-reaction, also add the chloro-4-fluoronitrobenzene of 3,5-bis-further, add 3, can not fluoro-reaction be there is in the chloro-4-fluoronitrobenzene of 5-bis-, act as the role of solvent, improve the solid-to-liquid ratio of reaction, add the mobility in reaction, and this fluoro-reaction is 3, when carrying out in the environment of the chloro-4-fluoronitrobenzene of 5-bis-, productive rate is higher, reduces production cost; In addition, the boiling point of the chloro-4-fluoronitrobenzene of 3,5-bis-and 2,3,4-trifluoronitrobenzene differs comparatively large, is separated again and is more prone to after fluoro-reaction.
In step (1), in step (1), described sulfuric acid is divided into two portions to add, 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 drip, and the sulfuric acid of this part and the mol ratio of nitric acid are 1: 0.9 ~ 1.1;
Described 2,6-dichlorofluorobenzene and the mol ratio of nitric acid are 1: 1.1 ~ 1.3.
Wherein, nitric acid generally adopt concentration be 99% concentrated nitric acid; Sulfuric acid generally adopt concentration be 98% the vitriol oil.
In step (1), the temperature of described nitration reaction is 50 ~ 70 DEG C, and in this temperature range, speed of reaction is higher, and side reaction is less, and two components of the dichloro one fluoronitrobenzene mixture obtained can be made to remain within suitable scope.
In step (1), in described dichloro one fluoronitrobenzene mixture, the massfraction of 2,4-bis-chloro-3-fluoronitrobenzenes is 80 ~ 90%.
In step (1), reacting the degree of carrying 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 impouring frozen water, stratification, gets organic phase, then alkali cleaning, is 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, the F of KF can be made
-easily participate in reaction, improve the transformation efficiency of reaction.
In step (2), in described mixed system, the mol ratio of 3,5-bis-chloro-4-fluoronitrobenzene and the chloro-3-fluoronitrobenzene of 2,4-bis-is 1: 2 ~ 3, now, the solid-to-liquid ratio of reaction and the mobility in reacting can be ensured, described fluoro-reaction is carried out efficiently, improves 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 DEG C.
In step (2), reacting the degree of carrying 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 DEG C, then adds toluene, while hot suction filtration, filter cake toluene wash 2 ~ 3 times, merging filtrate, carries out rectification under vacuum, obtains 3,5-bis-chloro-4-fluoronitrobenzene and 2,3,4-described trifluoronitrobenzenes.
Compared with the existing technology, beneficial effect of the present invention is embodied in: after nitration reaction completes, and the dichloro one fluoronitrobenzene mixture obtained, without separation, directly carries out next step fluoro-reaction, simplifies operation; And employing the method, the productive rate of described fluoro-reaction can be improved.
Embodiment
Below in conjunction with specific embodiment, the preparation method to 2,3,4-trifluoronitrobenzenes of the present invention does further detailed description.
Embodiment 1
(1) 2 are taken, 6-dichlor fluorbenzene 33g (0.2mol), put in the there-necked flask of 250ml, the 40g vitriol oil is slowly added under stirring, then 60 DEG C are heated to, start the ratio nitric acid slowly dripping nitration mixture 38g(amount of substance: sulfuric acid=1: 1, wherein the concentration of nitric acid is 99%), control temperature of reaction at about 60 DEG C.After dropping terminates, react 2 hours, be cooled to room temperature, by in reaction solution impouring frozen water, stratification, gets organic phase, then alkali cleaning, be washed to neutrality, get organic phase, obtain the chloro-3-fluoronitrobenzene of 2,4-bis-and 3,5-bis-chloro-4-fluoronitrobenzene mixture 40g(HPLC detects the chloro-3-fluoronitrobenzene of 2,4-bis-and accounts for 84.5%).
(2) the dichloro one fluoronitrobenzene mixture 21g that step (1) obtains is taken, dry Potassium monofluoride 12.76g, phase-transfer catalyst tetramethyl ammonium chloride 1.1g(CAS:75-57-0), 3, 5-bis-chloro-4-fluoronitrobenzene (in former secondary response, separation obtains) 6g, join in dry 100ml there-necked flask successively, pass into nitrogen, stir, be heated to 180 DEG C, reaction 6 ~ 8h, continue logical nitrogen until temperature is down to 100 DEG C, add toluene, suction filtration while hot, filter cake toluene wash 2 ~ 3 times, merging filtrate, carry out rectification under vacuum, recovery obtains 3, 5-bis-chloro-4-fluoronitrobenzene 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) 2 are taken, 6-dichlor fluorbenzene 33g (0.2mol), put in the there-necked flask of 250ml, the 40g vitriol oil is slowly added under stirring, then 60 DEG C are heated to, start the ratio concentrated nitric acid slowly dripping nitration mixture 38g(amount of substance: the vitriol oil=1: 1), control temperature of reaction at about 60 DEG C.After dropping terminates, react 2 hours, be cooled to room temperature, by in reaction solution impouring frozen water, stratification, gets organic phase, then alkali cleaning, be washed to neutrality, get organic phase, obtain the chloro-3-fluoronitrobenzene of 2,4-bis-and 3,5-bis-chloro-4-fluoronitrobenzene mixture 40g(2, the chloro-3-fluoronitrobenzene of 4-bis-accounts for 84.5%).
(2) the dichloro one fluoronitrobenzene mixture 21g that step (1) obtains is taken, dry Potassium monofluoride 12.76g, phase-transfer catalyst tetramethyl ammonium chloride 1.1g, 3, 5-bis-chloro-4-fluoronitrobenzene (in former secondary response, separation obtains) 3g, join in dry 100ml there-necked flask successively, pass into nitrogen, stir, be heated to 180 DEG C, reaction 6 ~ 8h, continue logical nitrogen until temperature is down to 100 DEG C, 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, 5-bis-chloro-4-fluoronitrobenzene 5.9g.
Embodiment 3
(1) 2 are taken, 6-dichlor fluorbenzene 33g (0.2mol), put in the there-necked flask of 250ml, the 40g vitriol oil is slowly added under stirring, then 60 DEG C are heated to, start the ratio concentrated nitric acid slowly dripping nitration mixture 38g(amount of substance: the vitriol oil=1:1), control temperature of reaction at about 60 DEG C.After dropping terminates, react 2 hours, be cooled to room temperature, by in reaction solution impouring frozen water, stratification, gets organic phase, then alkali cleaning, be washed to neutrality, get organic phase, obtain the chloro-3-fluoronitrobenzene of 2,4-bis-and 3,5-bis-chloro-4-fluoronitrobenzene mixture 40g(2, the chloro-3-fluoronitrobenzene of 4-bis-accounts for 84.5%).
(2) the dichloro one fluoronitrobenzene mixture 21g that step (1) obtains is taken, dry Potassium monofluoride 12.76g, phase-transfer catalyst tetramethyl ammonium chloride 2.2g, 3, 5-bis-chloro-4-fluoronitrobenzene (in former secondary response, separation obtains) 6g, join in dry 100ml there-necked flask successively, pass into nitrogen, stir, be heated to 180 DEG C, reaction 6 ~ 8h, continue logical nitrogen until temperature is down to 100 DEG C, 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, 5-bis-chloro-4-fluoronitrobenzene 8.9g.
Comparative example 1
(1) 2 are taken, 6-dichlor fluorbenzene 33g (0.2mol), put in the there-necked flask of 250ml, the 40g vitriol oil is slowly added under stirring, then 60 DEG C are heated to, start the ratio concentrated nitric acid slowly dripping nitration mixture 38g(amount of substance: the vitriol oil=1: 1), control temperature of reaction at about 60 DEG C.After dropping terminates, react 2 hours, be cooled to room temperature, by in reaction solution impouring frozen water, stratification, gets organic phase, then alkali cleaning, be washed to neutrality, get organic phase, obtain the chloro-3-fluoronitrobenzene of 2,4-bis-and 3,5-bis-chloro-4-fluoronitrobenzene mixture 40g(2, the chloro-3-fluoronitrobenzene of 4-bis-accounts for 84.5%).
(2) the dichloro one fluoronitrobenzene mixture 21g obtained in step (1) is taken, dry Potassium monofluoride 12.76g, phase-transfer catalyst tetramethyl ammonium chloride 1.1g, tetramethylene sulfone 40g, join in dry 100ml there-necked flask successively, be heated to 180 DEG C, reaction 6 ~ 8h, room temperature is cooled to after reaction terminates, suction filtration, filtrate carries out underpressure distillation, steam tetramethylene sulfone, 90 ~ 93 DEG C 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 example 2
(1) 2 are taken, 6-dichlor fluorbenzene 33g (0.2mol), put in the there-necked flask of 250ml, the 40g vitriol oil is slowly added under stirring, then 60 DEG C are heated to, start the ratio concentrated nitric acid slowly dripping nitration mixture 38g(amount of substance: the vitriol oil=1: 1), control temperature of reaction at about 60 DEG C.After dropping terminates, react 2 hours, be cooled to room temperature, by in reaction solution impouring frozen water, stratification, gets organic phase, then alkali cleaning, is washed to neutrality, gets organic phase, obtain 2,4-bis-chloro-3-fluoronitrobenzene and 3,5-bis-chloro-4-fluoronitrobenzene mixture 40g(2, the chloro-3-fluoronitrobenzene of 4-bis-accounts for 84.5%), be separated through underpressure distillation and obtain 2,4-bis-chloro-3-fluoronitrobenzene 33g.
(2) obtain in step (1) 2 are taken, 4-bis-chloro-3-fluoronitrobenzene 18g, dry Potassium monofluoride 12.76g, phase-transfer catalyst tetramethyl ammonium chloride 1.1g, tetramethylene sulfone 40g, join in dry 100ml there-necked flask successively, be heated to 180 DEG C, reaction 6 ~ 8h, room temperature is cooled to after reaction terminates, suction filtration, filtrate carries out underpressure distillation, steam tetramethylene sulfone, 90 ~ 93 DEG C 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 (7)
1. the preparation method of a trifluoronitrobenzene, is characterized in that, comprises the steps:
(1) under sulfuric acid existent condition, 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 formula II:
Described dichloro one fluoronitrobenzene mixture is made up of 2,4-bis-chloro-3-fluoronitrobenzene and the chloro-4-fluoronitrobenzene of 3,5-bis-;
The structure of described 2,4-bis-chloro-3-fluoronitrobenzenes is as shown in formula III:
The structure of described 3,5-bis-chloro-4-fluoronitrobenzenes is as shown in formula IV:
(2) the dichloro one fluoronitrobenzene mixture, Potassium monofluoride, the phase-transfer catalyst and additional 3 that step (1) are obtained, the mixed system obtained after the chloro-4-fluoronitrobenzene mixing of 5-bis-carries out fluoro-reaction, after reacting completely, through aftertreatment, separation obtains 3,5-bis-chloro-4-fluoronitrobenzene and 2,3,4-described trifluoronitrobenzenes;
3, the 5-bis-chloro-4-fluoronitrobenzenes that separation obtains turn back in described fluoro-reaction as additional 3,5-bis-chloro-4-fluoronitrobenzenes and carry out recycle after collecting;
In step (2), in described mixed system, the mol ratio of 3,5-bis-chloro-4-fluoronitrobenzene and the chloro-3-fluoronitrobenzene of 2,4-bis-is 1:2 ~ 3.
2. according to claim 12,3, the preparation method of 4-trifluoronitrobenzene, it is characterized in that, in step (1), described sulfuric acid is divided into two portions to add, a part is for dissolving 2,6-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 drip, and the sulfuric acid of this part and the mol ratio of nitric acid are 1:0.9 ~ 1.1;
Described 2,6-dichlorofluorobenzene and the mol ratio of nitric acid are 1:1.1 ~ 1.3.
3. the preparation method of 2,3,4-trifluoronitrobenzenes according to claim 1, is characterized in that, in step (1), the temperature of described nitration reaction is 50 ~ 70 DEG C.
4. the preparation method of 2,3,4-trifluoronitrobenzenes according to claim 1, is characterized in that, in step (1), in described dichloro one fluoronitrobenzene mixture, the massfraction of 2,4-bis-chloro-3-fluoronitrobenzenes is 80 ~ 90%.
5. 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.
6. according to claim 1 or 52, the preparation method of 3,4-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.
7. the preparation method of 2,3,4-trifluoronitrobenzenes according to claim 1, is characterized in that, in step (2), the temperature of described fluoro-reaction is 170 ~ 190 DEG C, and the reaction times is 6 ~ 8h.
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| 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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| CP03 | Change of name, title or address |
Address after: 312369 Shangyu, Shaoxing, Hangzhou Bay Economic and Technological Development Zone, No. three weft Road No. 8, No. Patentee after: ZHEJIANG LINJIANG CHEMICAL CO., LTD. Address before: 312369, No. three, No. 8, Shangyu Industrial Park, Hangzhou Bay, Zhejiang, Shaoxing Patentee before: Shangyu Linjiang Chemical Co., Ltd. |
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| CP01 | Change in the name or title of a patent holder | ||
| CP01 | Change in the name or title of a patent holder |
Address after: 312369, No. three, No. 8, Shangyu economic and Technological Development Zone, Hangzhou Bay, Zhejiang, Shaoxing, China Patentee after: Zhejiang Jitai New Material Co., Ltd Address before: 312369, No. three, No. 8, Shangyu economic and Technological Development Zone, Hangzhou Bay, Zhejiang, Shaoxing, China Patentee before: ZHEJIANG LINJIANG CHEMICAL Co.,Ltd. |