CN102351713A - Industrialized production method of 2,6-difluoroaniline - Google Patents
Industrialized production method of 2,6-difluoroaniline Download PDFInfo
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- CN102351713A CN102351713A CN2011102296124A CN201110229612A CN102351713A CN 102351713 A CN102351713 A CN 102351713A CN 2011102296124 A CN2011102296124 A CN 2011102296124A CN 201110229612 A CN201110229612 A CN 201110229612A CN 102351713 A CN102351713 A CN 102351713A
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Abstract
The invention discloses an industrialized production method of 2,6-difluoroaniline, and relates to the technical field of 2,6-difluoroaniline industrialized production. The industrialized production method of 2,6-difluoroaniline comprises the following steps that 2,6-difluorobenzamide, a sodium hydroxide aqueous solution and a sodium hypochlorite aqueous solution undergo a degradation reaction to produce 2,6-difluoroaniline, sodium carbonate, common salt and water; a mass of salts and impurities produced by the degradation reaction are removed in distillation; and a 2,6-difluoroaniline finished product with high 2,6-difluoroaniline content is obtained by rectification in the presence of sulfolane under a vacuum condition. Through the industrialized production method of 2,6-difluoroaniline, a product yield reaches 90%; product purity reaches 99.9%; and water content reaches 0.2%. The industrialized production method of 2,6-difluoroaniline does not produce pollution in production processes, is environmentally friendly, realizes a high yield, is beneficial for reduction of a production cost, and is beneficial for later application because of realization of high product purity.
Description
Technical field
The present invention relates to suitability for industrialized production 2, the method and technology field of 6--difluoroaniline.
Background technology
2, the 6-difluoroaniline is a kind of key intermediate of synthetic benzoyl area kind novel agrochemical, can be made into multiple Insecticides (tech) & Herbicides (tech)s such as fluorine bell urea, flufenoxuron, UC 62644, Teflubenzuron.This series pesticide has can not be casted off a skin larva to grow up to the effect of adult, thereby makes their consumption few, and low, the no resistance of toxicity is a novel agrochemical efficient, low toxicity.This fluoro-containing pesticide has active height, consumption is very low, minimum to environmental influence, is novel agrochemical efficient, low toxicity.2, the 6-difluoroaniline also can be used for producing flumetsulam.Flumetsulam is a kind of broad spectrum weeding agent, can prevent annual and perennial broadleaf weed, and children gramineous weeds in age is also had restraining effect.This product also can be used for the synthetic of fluorine-containing fine chemicals such as medicine, also is widely used in the industries such as liquid crystal material of medicine, agricultural chemicals, dyestuff, electron trade.
Existing various 2, the synthesis method of 6--difluoroaniline all exists the water content of the insecurity of production process and product yield is low, water content is high problem, particularly premium grads to be controlled at less than 0.2%.
Summary of the invention
The object of the invention is to propose a kind ofly to improve 2,6--difluoroaniline yield, reduces 2 of water ratio, the synthesis method of 6--difluoroaniline.
The present invention includes DeR, distillation and rectification process step; Said DeR is with 2, and 6-difluorobenzamide and aqueous sodium hydroxide solution, aqueous sodium hypochlorite solution carry out DeR; Said distillation is the material with said DeR Cheng Sheng, be warming up to 100～120 ℃ method evaporation through water vapor after, the cooling layering obtains 2,6--difluoroaniline crude product; Said rectifying is: 2, add tetramethylene sulfone in the 6--difluoroaniline crude product, rectifying gets 2 under the vacuum condition, the pure article of 6--difluoroaniline.
The present invention is with 2; 6-difluorobenzamide, aqueous sodium hydroxide solution and aqueous sodium hypochlorite solution carry out DeR; Generate 2; 6--difluoroaniline, yellow soda ash, sodium-chlor and water; Reaction generates more than when distillation, removing a large amount of salt and impurity when rectifying, are the rectifying protective material with the tetramethylene sulfone; Under the vacuum condition rectifying get high-load 2,6--difluoroaniline finished product.
Through the product yield of above explained hereafter>90%, purity 99.9%, water-content < 0.2%.Production process of the present invention is pollution-free, is the green production process, and yield is high, is beneficial to reduce production costs, and the purity usury was used in the later stage.
The concrete DeR of the present invention is: aqueous sodium hydroxide solution and clorox are dropped into earlier in the reaction kettle, when the temperature of control aqueous sodium hydroxide solution and clorox is reduced to below 0 ℃, drop into 2 to reaction kettle, the 6-difluorobenzamide reacts.
The mass concentration of aqueous sodium hydroxide solution according to the invention is 28～32%; The mass concentration of said aqueous sodium hypochlorite solution is 12～13%; Said 2, the mass ratio that feeds intake of 6-difluorobenzamide, aqueous sodium hydroxide solution and aqueous sodium hypochlorite solution is 5 ︰, 20 ︰ 9.
Drop into 2, behind the 6-difluorobenzamide, when reactor temperature rises to 70～75 ℃ fast; When dropping to 30 ℃～50 ℃ then, get material sample analysis in the reaction kettle, in the material sample 2; 6-difluorobenzamide mass concentration is less than at 0.5% o'clock, then termination reaction.
The employing refrigerated water is that the reaction kettle of said DeR is lowered the temperature outward, and control drops into 2, and the refrigerated water leaving water temperature(LWT) before the 6-difluorobenzamide is-10 ℃～-25 ℃.Because DeR is a strong exothermal reaction, at high temperature side reaction can take place, impurity increases, and yield descends.After the present invention's temperature reduction in advance, drop into 2 again, the 6-difluorobenzamide helps temperature of reaction control.
Because aqueous sodium hypochlorite solution is unstable at normal temperatures, is prone to decompose.The content of clorox plays conclusive effect in DeR.Otherwise DeR is incomplete, and impurity increases, and yield descends, so the content that needs to analyze clorox before the present invention feeds intake is controlled at 12～13%.
Concrete distillation is: the material that will react good is evacuated to the still kettle with chuck; The steam that in chuck, feeds temperature and be 100 ℃～120 ℃ distills; When overhead product does not have the oil droplet phenomenon; In chuck, feeding water coolant will distill the reception still and reduce to normal temperature; To distill the interior material reception of reception still then leaves standstill; Take off layer, be 2,6--difluoroaniline crude product.
Because 2, the 6--difluoroaniline is water insoluble, when a small amount of, state is " oil droplet " shape in water, and it is heavier than water, with water obvious layering is arranged.So steam distillation endpoint of the present invention is when overhead product does not have the oil droplet phenomenon, to be considered as distillation and to finish.
Concrete rectifying is: with 2; 6--difluoroaniline crude product and tetramethylene sulfone place rectifying still with the mass ratio of 75 ︰ 1, open vacuum system and condenser cooling water, when the condensator outlet vacustat greater than 0.098MPa the time; Open rectifying still steam, control pressure 0.1 ± 0.001 MPa; In rectifying still 2, when 6--difluoroaniline crude product came to life, steam regulation control rectifying temperature in the kettle was 80～95 ℃, when the stable back of the tower top temperature maintenance total reflux of rectifying still one hour, then with the per hour slowly discharging of speed of 10 ± 1kg; When not having overhead product, product is received to the reception still; In the rectifying, the maintenance condensator outlet is a normal temperature.
The above rectification process of the present invention adopts rectification under vacuum, makes the material boiling point lowering, reduces energy consumption.Different according to the material boiling point, can remove impurity, improve 2, the purity of 6--difluoroaniline.In addition, in the rectifying of the present invention, the maintenance condensator outlet is normal temperature, and is too high like temperature, causes the material evaporation, taken away by vacuum, and product yield is descended.
Rectifying finishes back semi-closure steam, opens cooling water temperature, closes vacuum system when the rectifying still temperature is grand to time below 50 ℃.
Embodiment
One, feed ratio:
Material name content quantity (unit: Kg)
2,6-difluorobenzamide 99% 500
Clorox 12.5% 2000
Liquid caustic soda 30% 890
Two, technology:
1, DeR:
The liquid caustic soda and the clorox that measure are dropped into reaction kettle.
Open freezing water for cooling, require the refrigerated water leaving water temperature(LWT) to be-10 ℃～-25 ℃ after, drop into again measure 2; The 6-difluorobenzamide; Keep refrigerated water often to open, this moment, temperature can constantly slowly rise, and rose to 20～25 ℃ in about 1.5 hours; Descend gradually after can rising to 70～75 ℃ fast then; When temperature is reduced to 30 ℃～50 ℃, get material sample analysis in the reaction kettle, in the material sample 2; 6-difluorobenzamide mass concentration is less than at 0.5% o'clock, then termination reaction.
2, distillation:
The material that reaction is good is evacuated to the steam distillation still.
Open jacket steam and heat up, steam valve feeding steam carries out steam distillation at the bottom of the unlatching still when being raised to 100 ℃～120 ℃.
When overhead product does not have oil droplet, be considered as distillation and finish, to open water coolant and will distill and receive still and reduce to normal temperature, process water goes to handle the back and discharges in the still.
To receive the crude product layering barrelling of still, rectifying is treated in metering.Lower floor is a material, promptly 2, and 6--difluoroaniline crude product, the upper strata is a water.
3, rectifying:
To the rectifying still input measure 2,6--difluoroaniline crude product, about 1500kg adds the 20kg tetramethylene sulfone simultaneously.
The open vacuum system, condenser cooling water, after vacuum was stable, this moment, condensator outlet vacuum tightness should be opened rectifying still steam, about control pressure 0.1 MPa greater than 0.098MPa.
When 85 ℃ of left and right sides of still temperature, material comes to life, 80～95 ℃ of steam regulation control this moment still temperature, and tower top temperature can constantly raise, and the maintenance total reflux is one hour after tower top temperature is stable, then slowly discharging per hour about 10Kg.When not having overhead product, receive product entirely to receiving still, in still below the material 60kg.Must keep condenser to produce therebetween and be normal temperature.As find that temperature has the rising phenomenon should turn down steam and while immediately and close condensation and exports vacuum valve, treat to recover after temperature is normally.
Rectifying finishes back semi-closure steam, opens cooling water temperature, closes vacuum system when the rectifying still temperature is grand to time below 50 ℃.
4, will receive still product accurate measurement packing, foreshot and still be residual to be incorporated into next batch rectifying.
5, finished product detection:
Outward appearance: colourless transparent liquid.
Sample through gas-chromatography separate, fid detector detects, the peak area normalization method is quantitative, the result:
2,6--difluoroaniline content: 99.91%, moisture (comprising water and tetramethylene sulfone) content: 0.07%.
Claims (8)
1.2 the industrialized preparing process of 6-difluoroaniline is characterized in that comprising DeR, distillation and rectification process step; Said DeR is with 2, and 6-difluorobenzamide and aqueous sodium hydroxide solution, aqueous sodium hypochlorite solution carry out DeR; Said distillation is the material with said DeR Cheng Sheng, be warming up to 100～120 ℃ method evaporation through water vapor after, the cooling layering obtains 2,6--difluoroaniline crude product; Said rectifying is: 2, add tetramethylene sulfone in the 6--difluoroaniline crude product, rectifying gets 2 under the vacuum condition, the pure article of 6--difluoroaniline.
2. according to claim 1 said 2; The industrialized preparing process of 6--difluoroaniline; It is characterized in that said DeR is: drop into aqueous sodium hydroxide solution and clorox in the reaction kettle earlier; When the temperature of control aqueous sodium hydroxide solution and clorox is reduced to below 0 ℃; Drop into 2 to reaction kettle, the 6-difluorobenzamide reacts.
3. according to claim 2 said 2; The industrialized preparing process of 6--difluoroaniline; The mass concentration that it is characterized in that said aqueous sodium hydroxide solution is 28～32%; The mass concentration of said aqueous sodium hypochlorite solution is 12～13%; Said 2, the mass ratio that feeds intake of 6-difluorobenzamide, aqueous sodium hydroxide solution and aqueous sodium hypochlorite solution is 5 ︰, 20 ︰ 9.
4. according to claim 2 or 3 said 2; The industrialized preparing process of 6--difluoroaniline; It is characterized in that dropping into 2; Behind the 6-difluorobenzamide, when reactor temperature rises to 70～75 ℃ fast, when dropping to 30～50 ℃ then; Get material sample analysis in the reaction kettle; In the material sample 2,6-difluorobenzamide mass concentration is less than at 0.5% o'clock, then termination reaction.
5. said 2 according to claim 2, the industrialized preparing process of 6--difluoroaniline, it is characterized in that adopting refrigerated water is that the reaction kettle of said DeR is lowered the temperature outward, and control drops into 2, and the refrigerated water leaving water temperature(LWT) before the 6-difluorobenzamide is-10 ℃～-25 ℃.
6. according to claim 1 said 2; The industrialized preparing process of 6--difluoroaniline; It is characterized in that said distillation is: the material that will react good is evacuated to the still kettle with chuck; The steam that in chuck, feeds temperature and be 100 ℃～120 ℃ distills, and when overhead product does not have the oil droplet phenomenon, in chuck, feeds water coolant and will distill the reception still and reduce to normal temperature; To distill the interior material reception of reception still then leaves standstill; Take off layer, be 2,6--difluoroaniline crude product.
7. according to claim 1 said 2; The industrialized preparing process of 6--difluoroaniline; It is characterized in that said rectifying is: with 2; 6--difluoroaniline crude product and tetramethylene sulfone place rectifying still with the mass ratio of 75 ︰ 1; Open vacuum system and condenser cooling water; When the condensator outlet vacustat greater than 0.098MPa the time, open rectifying still steam, control pressure 0.1 ± 0.001 MPa; In rectifying still 2, when 6--difluoroaniline crude product came to life, steam regulation control rectifying temperature in the kettle was 80～95 ℃, when the stable back of the tower top temperature maintenance total reflux of rectifying still one hour, then with the per hour slowly discharging of speed of 10 ± 1kg; When not having overhead product, product is received to the reception still; In the rectifying, the maintenance condensator outlet is a normal temperature.
8. said 2 according to claim 7, the industrialized preparing process of 6--difluoroaniline is characterized in that rectifying finishes back semi-closure steam, opens cooling water temperature, closes vacuum system when the rectifying still temperature is grand to time below 50 ℃.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108558674A (en) * | 2018-05-31 | 2018-09-21 | 张金河 | The production method of one kind 2,4- difluoroanilines |
| CN109456224A (en) * | 2018-12-17 | 2019-03-12 | 鲁东大学 | A method of preparing 2,6- difluoro indophenols acetic acid esters |
| CN111777515A (en) * | 2020-07-27 | 2020-10-16 | 恒劲生物技术(大连)有限公司 | Safe and green production method of high-quality 2, 6-difluoroaniline |
| CN113501762A (en) * | 2021-07-27 | 2021-10-15 | 南京硕达生物科技有限公司 | Industrial production method of 2, 6-difluoroaniline |
| CN115141101A (en) * | 2022-06-15 | 2022-10-04 | 江苏省农用激素工程技术研究中心有限公司 | Synthesis method of 2, 6-difluoroaniline |
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| US5410082A (en) * | 1993-05-11 | 1995-04-25 | Pfirmann; Ralf | Process for preparing amines |
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| US5410082A (en) * | 1993-05-11 | 1995-04-25 | Pfirmann; Ralf | Process for preparing amines |
| CN1608047A (en) * | 2001-12-19 | 2005-04-20 | 拜尔化学品股份公司 | Method for producing amines |
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| 祝鸿，黄山: "2,6-二氟苯胺和2,6-二氟苯酚的合成", 《化工时刊》, no. 12, 15 December 1999 (1999-12-15) * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108558674A (en) * | 2018-05-31 | 2018-09-21 | 张金河 | The production method of one kind 2,4- difluoroanilines |
| CN109456224A (en) * | 2018-12-17 | 2019-03-12 | 鲁东大学 | A method of preparing 2,6- difluoro indophenols acetic acid esters |
| CN111777515A (en) * | 2020-07-27 | 2020-10-16 | 恒劲生物技术(大连)有限公司 | Safe and green production method of high-quality 2, 6-difluoroaniline |
| CN113501762A (en) * | 2021-07-27 | 2021-10-15 | 南京硕达生物科技有限公司 | Industrial production method of 2, 6-difluoroaniline |
| CN115141101A (en) * | 2022-06-15 | 2022-10-04 | 江苏省农用激素工程技术研究中心有限公司 | Synthesis method of 2, 6-difluoroaniline |
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