CN101134712A - Preparation method of 2,4-dichloro fluorobenzene - Google Patents
Preparation method of 2,4-dichloro fluorobenzene Download PDFInfo
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- CN101134712A CN101134712A CNA2007102019500A CN200710201950A CN101134712A CN 101134712 A CN101134712 A CN 101134712A CN A2007102019500 A CNA2007102019500 A CN A2007102019500A CN 200710201950 A CN200710201950 A CN 200710201950A CN 101134712 A CN101134712 A CN 101134712A
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Abstract
The process of preparing 2, 4-dichlor fluorobenzene includes the following steps: 1. chloridizing parachloro nitrobenzene with chlorine to produce 3, 4-dichloro nitrobenzene; 2. dissolving 3, 4-dichloro nitrobenzene in solvent, and heating to produce fluoro reaction in the presence of catalyst to produce 3-chloro-4-fluoro nitrobenzene and potassium chloride; and 3. reacting 3-chloro-4-fluoro nitrobenzene and chlorine while heating and in the presence of catalyst to eliminate nitro group and produce 2, 4-dichlor fluorobenzene and nitro acyl chloride. The present invention has reasonable reaction path, cheap facile material, low cost, high reaction selectivity, high product quality and high safety.
Description
Technical field
The present invention relates to a kind of preparation method of fluorobenzene class organic compound, especially 2,4 dichloro fluorobenzene, belong to the fluorine chemical technical field.
Background technology
2,4 dichloro fluorobenzene is water white transparency or light yellow oily liquid.Zero pour :-23 ℃; Boiling point: 172～174 ℃; Density: 1.402-1.406 (25 ℃); Refractive index: 1.523-1.525 (25 ℃).
Be mainly used in main raw material(s)s such as system antipsychotic specific medicament Triperidol, trifluperidol, penfluridol, quinolones-Ciprofloxacin, also be used for the auxiliary agent of liquid crystal, pesticide intermediate and plastics, resin simultaneously.
The preparation method of present domestic 2,4 dichloro fluorobenzene has by the initiator main route: fluorobenzene route, parachloronitrobenzene route, 2,4-dinitrochlorobenzene route, orthodichlorobenzene route etc.
Raw material fluorobenzene and 2,4 dichloro fluorobenzene market value are often hung upside down, and only are fit to the producer of self-produced aniline, by diazotization reaction self-control fluorobenzene.Diazotization reaction is polluted big, and is not suitable for scale operation.Key is that intermediate is a dinitro compound, the accident of very easily blasting in the production.
2. parachloronitrobenzene route
Use DMSO easily to produce stench in process of production, influence surrounding environment.
3.2,4-dinitrochlorobenzene route
This operational path is short, and raw materials cost is low, is present domestic main production method.But raw material and intermediate all are dinitro compounds, and the production control difficulty is very easily blasted.On July 28th, 2006, Jiangsu shining sun fluorine all chemical plant explosion hazard causes 22 people's death, and lesson is painful.
4. orthodichlorobenzene route
Orthodichlorobenzene generates the mixture of dichloronitrobenzene after with mixed acid nitrification, separates behind fluoro, can produce 2,4 dichloro fluorobenzene and 2 respectively, the 6-dichlor fluorbenzene.But this method coproduction 2, the 6-dichlor fluorbenzene acquires a certain degree of difficulty but shortcoming is a separation of intermediates fluorine chloronitrobenzene isomers, and then has influence on the purity of 2,4 dichloro fluorobenzene.
Summary of the invention
The objective of the invention is to, a kind of novel preparation method about 2,4 dichloro fluorobenzene is provided, this method cost is low, and selectivity is good, the quality product height that obtains, and production safety is reliable.
Technical scheme of the present invention: a kind of preparation method of 2,4 dichloro fluorobenzene, this method may further comprise the steps:
A, parachloronitrobenzene and chlorine generate 3 through chlorination, 4-dichloronitrobenzene and hydrogenchloride;
B, with 3 of above-mentioned gained, the 4-dichloronitrobenzene in solvent, catalyzer exist and heating condition under, carry out fluoro-reaction with fluorizating agent, generation 3-chloro-4-fluoronitrobenzene and Repone K;
C, with the 3-chloro-4-fluoronitrobenzene of above-mentioned gained catalyzer exist and heating condition under, remove nitro chlorination reaction generation 2,4 dichloro fluorobenzene and nitryl chloride with chlorine.
The preparation method of above-mentioned 2,4 dichloro fluorobenzene, in step a, used catalyzer is an Anhydrous Ferric Chloride.
The preparation method of aforesaid 2,4 dichloro fluorobenzene, in step b, described solvent is a dimethyl formamide, and described catalyzer is a quaternary ammonium salt with the mixture of quaternary alkylphosphonium salt, and described fluoro agent is active Potassium monofluoride, reacts under 175～185 ℃.
The preparation method of aforesaid 2,4 dichloro fluorobenzene, described quaternary ammonium salt is with in the mixture of quaternary alkylphosphonium salt, quaternary ammonium salt is that tetramethyl ammonium chloride ， quaternary alkylphosphonium salt is a 4-phenyl phosphonium bromide, wherein, tetramethyl ammonium chloride 70%～90%, 4-phenyl phosphonium bromide 10%～30%.
The preparation method of aforesaid 2,4 dichloro fluorobenzene, described step b carries out in closed reactor.
The preparation method of aforesaid 2,4 dichloro fluorobenzene, in step c, described catalyzer is a Diisopropyl azodicarboxylate, the described nitro chlorination reaction of going is to react under 195～210 ℃.
The preparation method of aforesaid 2,4 dichloro fluorobenzene, among the described step c, 3-chloro-4-fluoronitrobenzene mixes in material-compound tank in advance with the catalyzer Diisopropyl azodicarboxylate and is incubated at 95 ℃～100 ℃.
The preparation method of aforesaid 2,4 dichloro fluorobenzene, among the described step c, the quality consumption of catalyzer Diisopropyl azodicarboxylate accounts for 0.1%～1% of 3-chloro-4-fluoronitrobenzene quality.
The preparation method of aforesaid 2,4 dichloro fluorobenzene is among the described step c, constantly draw along with generating product from the cat head of chlorination reactor, from material-compound tank postreaction raw material to chlorination tank, the liquid level in the control chlorination tank is constant constantly, reaches the purpose of successive reaction.
Compared with prior art, because the present invention has adopted rational reaction scheme, raw material cheaply is easy to get, and cost is low; Good reaction selectivity, the quality product height; Safe and reliable, avoided picture 2, the explosion hazard of 4-dinitrochlorobenzene route.Quaternary ammonium salt selected for use by catalyzer in the fluoro-reaction of step b with the mixture of quaternary alkylphosphonium salt, and adopts suitable proportioning, good reaction selectivity, yield height, and drop to 175～185 ℃ by original about 190～230 ℃ temperature of reaction.Solvent in the fluoro-reaction of step b is selected dimethyl formamide (DMF) for use in addition, substitutes the tetramethylene sulfone (TMSO of common usefulness
2), dimethyl sulfoxide (DMSO) (DMSO), not only cost descends, boiling point is low, easily reclaims, but also the stench of having avoided DMSO to produce in using operating process.Its boiling point of 153 ℃ is well below TMSO in addition
2The boiling point of (289 ℃) and DMSO (189 ℃), and be lower than temperature of reaction, adopt withstand voltage reactor, under air-tight state, carry out the fluoro-reaction of step b, make energy consumption low, good operational environment.
Description of drawings
Accompanying drawing 1 is a process flow sheet of the present invention;
Accompanying drawing 2 is device schemas in the nitroxyl chloride metallization processes of going of step c of the present invention.
Embodiment
Embodiments of the invention: reaction process of the present invention is as follows:
Entire reaction is starting raw material with the parachloronitrobenzene.Undertaken by following step:
A, be catalyzer, feed chlorine in the reactor, generate 3,4-dichloronitrobenzene and hydrogenchloride with the parachloronitrobenzene reaction with the Anhydrous Ferric Chloride.Hydrogenchloride absorbs through water, gets by-product hydrochloric acid.3, the rectifying after washing of 4-dichloronitrobenzene is used for the fluoro-reaction of step b.
B, with 3, the 4-dichloronitrobenzene is in solvent DMF, with quaternary ammonium salt content is that 70%～90% He quaternary alkylphosphonium salt content is that 10%～30% mixture is as catalyzer, under 175～185 ℃ of temperature, generate 3-chloro-4-fluoronitrobenzene and Repone K with Potassium monofluoride (FK), remove by filter Repone K, solvent DMF is reclaimed in fractionation, obtains 3-chloro-4-fluoronitrobenzene.
C, at first in material-compound tank with the 3-chloro-4-fluoronitrobenzene of step b gained and 5 ‰ (w/w) catalyzer Diisopropyl azodicarboxylate (promptly when 3-chloro-4-fluoronitrobenzene is 100g, adding Diisopropyl azodicarboxylate 0.5g) mixes in material-compound tank 1 in advance and insulation at 95 ℃～100 ℃; In chlorination reaction still 4, add compound then to the liquid level of setting (in reaction process after this, remaining the constant of liquid level), begin heating.After temperature rises to 185 ℃, at the bottom of the still of reactor 4, feed chlorine and dominant discharge by Chlorination tube 2, optimum temperature range generates 2,4 dichloro fluorobenzene and nitryl chloride (NO at 195 ℃～210 ℃
2Cl), promptly go the nitro chlorination reaction.Wherein, chlorination reactor 3 is made up of reactor 4 and reaction tower 5, and reactor 4 connects into an integral body with reaction tower 5, and reaction tower 5 is positioned at the top of reactor 4.Chlorination reaction is mainly carried out in reactor 4; The effect of reaction tower 5 is that chlorination is proceeded in the gas phase of utilizing after the internal space of body of the tower makes product gasify, and regulates, controls the amount that raw material is overflowed with resultant.Temperature is gaseous state in the reactor 4 because of boiling point is lower than, and 2,4 dichloro fluorobenzene is drawn from the top of reaction tower 5 with nitryl chloride, realizes gas-liquid separation through condenser 6 condensations.Constantly draw along with generating product from the cat head of chlorination reaction tower 5, to the charging opening of chlorination reaction still 4, replenish the miscellany of 3-chloro-4-fluoronitrobenzene and catalyzer Diisopropyl azodicarboxylate constantly from material-compound tank 1, add chlorine from Chlorination tube 2, liquid level in the control chlorination tank is constant, reaches the purpose of successive reaction.Gas phase is the tail gas nitryl chloride, absorbs through multi-stage spray, generates the mixing solutions of hydrochloric acid and nitric acid, with liquid caustic soda or unslaked lime neutralization, qualified discharge.Arrive crude product jar 7 behind the liquid phase condensate, be the 2,4 dichloro fluorobenzene crude product, wherein contain 3-chloro-4-fluoronitrobenzene and dissolving nitryl chloride wherein.Crude product is in washing still 8, through washing the flush away nitryl chloride, washing lotion and above-mentioned spray absorption liquid and 3,4-dichloronitrobenzene water lotion merging processing.Crude product after the washing is again through rectifying still 9 rectifying, and 10 pairs of rectifying products of condenser carry out condensation, and condensed product enters receiving tank 11, obtains finished product to product jar 12 again, and purity is more than 99.5%.
Claims (9)
1. the preparation method of a 2,4 dichloro fluorobenzene, it is characterized in that: this method may further comprise the steps:
A, parachloronitrobenzene and chlorine generate 3 through chlorination in the presence of catalyzer, 4-dichloronitrobenzene and hydrogenchloride;
B, with 3 of above-mentioned gained, the 4-dichloronitrobenzene in solvent, catalyzer exist and heating condition under, carry out fluoro-reaction with the fluoro agent, generate 3 chlorine, 4 fluoronitrobenzenes and Repone K;
C, with the 3-chloro-4-fluoronitrobenzene of above-mentioned gained catalyzer exist and heating condition under, remove nitro chlorination reaction generation 2,4 dichloro fluorobenzene and nitryl chloride with chlorine.
2. the preparation method of 2,4 dichloro fluorobenzene according to claim 1, it is characterized in that: in step a, used catalyzer is an Anhydrous Ferric Chloride.
3. the preparation method of 2,4 dichloro fluorobenzene according to claim 1, it is characterized in that: in step b, described solvent is a dimethyl formamide; Described catalyzer is that quaternary ammonium salt is with the mixture of quaternary alkylphosphonium salt; Described fluoro agent is a Potassium monofluoride; Described fluoro-reaction is to react under 175～185 ℃.
4. according to claim 32, the preparation method of 4-dichlor fluorbenzene, it is characterized in that: described quaternary ammonium salt is with in the mixture of quaternary alkylphosphonium salt, quaternary ammonium salt is that tetramethyl ammonium chloride quaternary alkylphosphonium salt is a 4-phenyl phosphonium bromide, wherein, tetramethyl ammonium chloride 70%～90%, 4-phenyl phosphonium bromide 10%～30%.
5. the preparation method of 2,4 dichloro fluorobenzene according to claim 1, it is characterized in that: described step b carries out in closed reactor.
6. the preparation method of 2,4 dichloro fluorobenzene according to claim 1, it is characterized in that: in step c, described catalyzer is a Diisopropyl azodicarboxylate, the described nitro chlorination reaction of going is to react under 195～210 ℃.
7. the preparation method of 2,4 dichloro fluorobenzene according to claim 6, it is characterized in that: among the described step c, 3-chloro-4-fluoronitrobenzene mixes in material-compound tank in advance with the catalyzer Diisopropyl azodicarboxylate and is incubated at 95 ℃～100 ℃.
8. the preparation method of 2,4 dichloro fluorobenzene according to claim 7, it is characterized in that: among the described step c, the quality consumption of catalyzer Diisopropyl azodicarboxylate accounts for 0.1%～1% of 3-chloro-4-fluoronitrobenzene quality.
9. according to claim 1,6 or 7 described 2, the preparation method of 4-dichlor fluorbenzene is characterized in that: among the described step c, constantly draw from the cat head of chlorination reactor along with generating product, from material-compound tank postreaction raw material to chlorination tank, the liquid level in the control chlorination tank is constant constantly.
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102617353A (en) * | 2012-03-12 | 2012-08-01 | 苏州市罗森助剂有限公司 | Preparation method of 3, 4-dichloronitrobenzene |
| CN110642720A (en) * | 2019-10-12 | 2020-01-03 | 浙江林江化工股份有限公司 | Preparation method of 2, 4-difluoro-3, 5-dichloronitrobenzene |
| WO2021036060A1 (en) * | 2019-08-29 | 2021-03-04 | Fujian Yongjing Technology Co., Ltd | Process for preparing fluorobenzene and catalyst therefore |
| CN113429254A (en) * | 2021-07-22 | 2021-09-24 | 浙江解氏新材料股份有限公司 | Efficient synthesis method of 2, 4-dichlorofluorobenzene based on ceramic packed tower |
| CN113582804A (en) * | 2020-04-30 | 2021-11-02 | 浙江省常山长盛化工有限公司 | Production process for producing high-purity 2, 4-dichlorofluorobenzene from p-nitrochlorobenzene |
| CN113929553A (en) * | 2021-12-16 | 2022-01-14 | 山东国邦药业有限公司 | Synthetic method of 2, 4-dichlorofluorobenzene |
| 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 |
| CN116063143A (en) * | 2023-01-28 | 2023-05-05 | 山东国邦药业有限公司 | Preparation method of 2, 4-dichloro fluorobenzene |
| CN116553997A (en) * | 2023-07-10 | 2023-08-08 | 山东国邦药业有限公司 | Synthesis method of intermediate 1,2, 3-trifluoro-benzene for synthesizing 3,4, 5-trifluoro-bromobenzene |
-
2007
- 2007-10-08 CN CNA2007102019500A patent/CN101134712A/en active Pending
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102617353A (en) * | 2012-03-12 | 2012-08-01 | 苏州市罗森助剂有限公司 | Preparation method of 3, 4-dichloronitrobenzene |
| CN114805011A (en) * | 2019-08-29 | 2022-07-29 | 福建永晶科技股份有限公司 | Process for preparing fluorobenzene and its catalyst |
| WO2021036060A1 (en) * | 2019-08-29 | 2021-03-04 | Fujian Yongjing Technology Co., Ltd | Process for preparing fluorobenzene and catalyst therefore |
| CN110642720A (en) * | 2019-10-12 | 2020-01-03 | 浙江林江化工股份有限公司 | Preparation method of 2, 4-difluoro-3, 5-dichloronitrobenzene |
| CN110642720B (en) * | 2019-10-12 | 2022-09-27 | 浙江吉泰新材料股份有限公司 | Preparation method of 2, 4-difluoro-3, 5-dichloronitrobenzene |
| CN113582804A (en) * | 2020-04-30 | 2021-11-02 | 浙江省常山长盛化工有限公司 | Production process for producing high-purity 2, 4-dichlorofluorobenzene from p-nitrochlorobenzene |
| CN113429254A (en) * | 2021-07-22 | 2021-09-24 | 浙江解氏新材料股份有限公司 | Efficient synthesis method of 2, 4-dichlorofluorobenzene based on ceramic packed tower |
| CN113929553A (en) * | 2021-12-16 | 2022-01-14 | 山东国邦药业有限公司 | Synthetic method of 2, 4-dichlorofluorobenzene |
| 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 |
| CN116063143A (en) * | 2023-01-28 | 2023-05-05 | 山东国邦药业有限公司 | Preparation method of 2, 4-dichloro fluorobenzene |
| CN116063143B (en) * | 2023-01-28 | 2023-06-09 | 山东国邦药业有限公司 | Preparation method of 2, 4-dichloro fluorobenzene |
| CN116553997A (en) * | 2023-07-10 | 2023-08-08 | 山东国邦药业有限公司 | Synthesis method of intermediate 1,2, 3-trifluoro-benzene for synthesizing 3,4, 5-trifluoro-bromobenzene |
| CN116553997B (en) * | 2023-07-10 | 2023-09-26 | 山东国邦药业有限公司 | Synthesis method of intermediate 1,2, 3-trifluoro-benzene for synthesizing 3,4, 5-trifluoro-bromobenzene |
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