CN101456827B - Industrial production method of 2,6-difluorobenzene nitrile - Google Patents
Industrial production method of 2,6-difluorobenzene nitrile Download PDFInfo
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- CN101456827B CN101456827B CN2009100287848A CN200910028784A CN101456827B CN 101456827 B CN101456827 B CN 101456827B CN 2009100287848 A CN2009100287848 A CN 2009100287848A CN 200910028784 A CN200910028784 A CN 200910028784A CN 101456827 B CN101456827 B CN 101456827B
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- difluorobenzonilyile
- dinethylformamide
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Abstract
The invention provides a method for industrially producing 2, 6-difluorobenzonilyile, which relates to a method for industrially synthesizing a chemical raw material. The method uses 2,6-dichlorobenzonitrile as a raw material and potassium fluoride as alkali metal fluoride to synthesize the 2,6-difluorobenzonilyile in the presence of a solvent and a catalyst, wherein the solvent is absolute N,N-dimethyl formamide; the catalyst is a quaternary ammonium salt; and the synthesized 2,6-difluorobenzonilyile is rectified. The method has the advantages of high yield reaching 90 percent, stable quality, high product purity after rectification reaching 99 percent, favorability for subsequent application processing, available reaction raw materials, low cost of the raw material, environmental protection of production process, no pollution, no electric heating and low energy consumption.
Description
Technical field
The present invention relates to the industrial preparative method of industrial chemicals, particularly produce midbody 2, the synthesis technology field of the raw materials for production of 6-difluorobenzamide as agricultural chemicals, medicine, liquid crystal material.
Background technology
2, the 6-difluorobenzonilyile is the specificity insect growth regulator(IGR), is the indispensable midbody of benzamides agricultural chemicals such as diflubenzuron and UC 62644; Usually with 2, the 6-dichlorobenzonitrile is a raw material, and adopting with the polyoxyethylene glycol is catalyzer; With N, dinethylformamide, DMSO 99.8MIN. and tetramethylene sulfone are solvent, are alkaline metal fluoride cpd with the Potassium monofluoride; Carry out the fluoro Synthetic 2, the 6-difluorobenzonilyile.The temperature of reaction of this reaction process higher (need be warming up to more than 230 ℃), yield is low, and purity can only reach 98%, and the production process environmental pollution is serious.
Summary of the invention
That the object of the invention is to design is a kind of suitable suitability for industrialized production, pollution-free, low-cost, purity is high, yield is high 2, the industrialized preparing process of 6-difluorobenzonilyile.
The present invention is with 2, and the 6-dichlorobenzonitrile is a raw material, and Potassium monofluoride is an alkaline metal fluoride cpd, Synthetic 2 under the condition of solvent and catalyzer existence; The 6-difluorobenzonilyile is characterized in that said solvent is anhydrous N, dinethylformamide; Said catalyzer is a quaternary ammonium salt, synthetic 2, and the 6-difluorobenzonilyile is through rectifying.
The solvent that employing of the present invention is different with prior art adopts anhydrous N, and dinethylformamide is that solvent, quaternary ammonium salt are catalyzer, and turnout is big; Yield can reach 90%, and steady quality can reach 99% through the product purity that obtains after the rectifying, is beneficial to postorder and uses processing; Reaction raw materials is easy to get, and raw materials cost is low, the production process environmental protection; Pollution-free, need not to adopt electrically heated, it is low to consume energy.
Make bullion 2, the concrete grammar of 6-difluorobenzonilyile is: in reaction kettle, add anhydrous N, dinethylformamide earlier; Add 2 again, 6-dichlorobenzonitrile, Potassium monofluoride and quaternary ammonium salt, being steam heated to reactor temperature is 135～165 ℃; React after 5～7 hours, in the precipitation still, under the vacuum tightness of 0.08～0.1MPa; Feeding is steam heated to 110～120 ℃ and fractionates out solvent N, dinethylformamide; In the precipitation still, add entry, miscible synthetic 2,6-difluorobenzonilyile and Repone K are taken out and are expected to the steam distillation still, are heated to 110～130 ℃ and distill out bullion 2, and 6-difluorobenzonilyile and salt solution miscellany obtain 2 again after the layering of layering still, 6-difluorobenzonilyile bullion.
Present method reaction conditions is gentle, and the time is short, save energy, and less demanding to equipment is easy to produce.And, the solvent reusable edible of deviating from, the recyclable comprehensive utilization of the Repone K that obtains after the layering, the present invention can further save raw materials for production, reduces production costs.
In the above-mentioned reaction, 2,6-dichlorobenzonitrile, Potassium monofluoride, quaternary ammonium salt and anhydrous N, the mass ratio that feeds intake of dinethylformamide is 100: 70～90: 4～6: 180～220.
The method of rectifying of the present invention is: with bullion 2, the 6-difluorobenzonilyile is in the rectifying still of 0.08～0.10MPa as for vacuum tightness, after stablizing 0.5～2 hour under the condition of tower top temperature≤120 ℃; Begin to receive foreshot, receive the flow≤50L/hr of foreshot, in foreshot 2; 6-difluorobenzonilyile mass percentage content>=98% o'clock; Begin to receive main fraction, receive the flow≤100L/hr of main fraction, in main fraction 2; 6-difluorobenzonilyile mass percentage content＜98% or 2-chloro-6-fluorobenzonitrile mass percentage content＞0.2% o'clock, stop to receive main fraction.
In order to obtain anhydrous N, dinethylformamide, the present invention is with benzene and N, and dinethylformamide drops into earlier in the reaction kettle, and feeding steam, to be warming up to reactor temperature be 135～150 ℃, and moisture is sloughed in layering; Again reactor temperature is upgraded to 135～165 ℃, slough benzene after, reactor temperature drops to when negative pressure occurring in the still, adopts nitrogen protection, is cooled to 35～50 ℃, waits for fluoridizing feeding intake.
Wherein, benzene and N, the mass ratio that feeds intake of dinethylformamide is (3～4): (18～22).
Quaternary ammonium salt according to the invention can be a Tetrabutyl amonium bromide, also can be tetramethyl ammonium chloride.
Embodiment
Production stage:
One, solvent dehydration takes off benzene
With benzene 300～400kg and N, dinethylformamide 1800～2200kg drops into earlier in the reaction kettle, and it is 130～150 ℃ that feeding steam is warming up to reactor temperature, and moisture is sloughed in layering.In the reaction kettle when moisture content≤0.20%, the dehydration procedure end.
Again reactor temperature is upgraded to 135～165 ℃, slough benzene after, reactor temperature drops to when negative pressure occurring in the still, in reaction kettle, feeds nitrogen, protects, and is cooled to 45～50 ℃, waits for fluoridizing feeding intake.
Two, fluoridation
Confirm anhydrous N in the above reaction kettle, when dinethylformamide is 1800～2200kg, add 2; 6-dichlorobenzonitrile 1000kg, Potassium monofluoride 700～900kg, Tetrabutyl amonium bromide or tetramethyl ammonium chloride 40～60kg; Being steam heated to reactor temperature is 135～165 ℃, reacts 5～7 hours, when 2; 6-difluorobenzonilyile content＞85% o'clock, fluoridation finishes.
Three, deviate from solvent
In the precipitation still, under the vacuum tightness of 0.08～0.1MPa, feed steam and be warming up to 110～120 ℃, fractionate out solvent N, dinethylformamide.
Four, steam distillation
In the precipitation still, add 2000～4000L water; Be stirred to synthetic 2, the complete mixed dissolution of 6-difluorobenzonilyile and Repone K is taken out and is expected to the steam distillation still; Water steam steams bullion 2; 6-difluorobenzonilyile and saline mixture, vapor temperature are controlled at 110～130 ℃, make the gas-vapor mix cooling no material layering in back in the steam distillation still.
Five, material layering
In the layering still, leave standstill and carry out material layering, with 2,6-difluorobenzonilyile bullion branches away and supplies rectifying to use, and upper strata salt solution is collected the back and supplied precipitation to add water jacket usefulness, and Repone K can fully utilize after collecting.
Six, bullion rectifying
With bullion 2, the 6-difluorobenzonilyile is in the rectifying still of 0.08～0.10MPa as for vacuum tightness, after stablizing 0.5～2 hour under the condition of tower top temperature≤120 ℃, begins to receive foreshot, and control receives the flow≤50L/hr of foreshot.In foreshot 2,6-difluorobenzonilyile mass percentage content>=98% o'clock begins to receive main fraction, receives the reception flow≤100L/hr of main fraction.When tower top temperature changes, sampling analysis, in main fraction 2,6-difluorobenzonilyile mass percentage content＜98% or 2-chloro-6-fluorobenzonitrile mass percentage content＞0.2% o'clock, rectifying finishes.
Specification product packing warehouse-in, foreshot is put into down batch rectifying, and workshop section carries out fluoridation again before the heals input of rectifying still.
The finished product 2,6-difluorobenzonilyile content >=99%.
Claims (6)
1.2 the industrialized preparing process of 6-difluorobenzonilyile is with 2; The 6-dichlorobenzonitrile is a raw material, and Potassium monofluoride is an alkaline metal fluoride cpd, Synthetic 2 under the condition of solvent and catalyzer existence; 6-difluorobenzonilyile, said solvent are anhydrous N, dinethylformamide; Said catalyzer is a quaternary ammonium salt, synthetic 2, and the 6-difluorobenzonilyile is through rectifying; It is characterized in that in reaction kettle, adding anhydrous N earlier, dinethylformamide adds 2 again; 6-dichlorobenzonitrile, Potassium monofluoride and quaternary ammonium salt, being steam heated to reactor temperature is 135～165 ℃, reacts after 5～7 hours; In the precipitation still; Under the vacuum tightness of 0.08～0.1MPa, feeding is steam heated to 110～120 ℃ and fractionates out solvent N, dinethylformamide; In the precipitation still, add entry, miscible synthetic 2,6-difluorobenzonilyile and Repone K are taken out and are expected to the steam distillation still, are heated to 110～130 ℃ and distill out bullion 2, and 6-difluorobenzonilyile and salt solution miscellany obtain 2 again after the layering of layering still, 6-difluorobenzonilyile bullion.
2. said 2 according to claim 1, the industrialized preparing process of 6-difluorobenzonilyile is characterized in that 2,6-dichlorobenzonitrile, Potassium monofluoride, quaternary ammonium salt and anhydrous N, and the mass ratio that feeds intake of dinethylformamide is 100: 70～90: 4～6: 180～220.
3. said 2 according to claim 1, the industrialized preparing process of 6-difluorobenzonilyile is characterized in that the method for rectifying is: with bullion 2; The 6-difluorobenzonilyile is in the rectifying still of 0.08～0.10MPa as for vacuum tightness, after stablizing 0.5～2 hour under the condition of tower top temperature≤120 ℃, begins to receive foreshot; Receive the flow≤50L/hr of foreshot, in foreshot 2,6-difluorobenzonilyile mass percentage content>=98% o'clock; Begin to receive main fraction, receive the flow≤100L/hr of main fraction, in main fraction 2; 6-difluorobenzonilyile mass percentage content＜98% or 2-chloro-6-fluorobenzonitrile mass percentage content＞0.2% o'clock, stop to receive main fraction.
4. according to claim 1 said 2; The industrialized preparing process of 6-difluorobenzonilyile; It is characterized in that anhydrous N, the preparation method of dinethylformamide is: with benzene and N, dinethylformamide drops in the reaction kettle earlier; It is 135～150 ℃ that feeding steam is warming up to reactor temperature, and moisture is sloughed in layering; Again reactor temperature is upgraded to 135～165 ℃, slough benzene after, reactor temperature drops to when negative pressure occurring in the still, adopts nitrogen protection, is cooled to 35～50 ℃, waits for fluoridizing feeding intake.
5. said 2 according to claim 4, the industrialized preparing process of 6-difluorobenzonilyile is characterized in that benzene and N, and the mass ratio that feeds intake of dinethylformamide is (3～4): (18～22).
6. said 2 according to claim 1, the industrialized preparing process of 6-difluorobenzonilyile is characterized in that said quaternary amine is Tetrabutyl amonium bromide or tetramethyl ammonium chloride.
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| CN2009100287848A CN101456827B (en) | 2009-01-05 | 2009-01-05 | Industrial production method of 2,6-difluorobenzene nitrile |
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| CN2009100287848A CN101456827B (en) | 2009-01-05 | 2009-01-05 | Industrial production method of 2,6-difluorobenzene nitrile |
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| CN101456827B true CN101456827B (en) | 2012-07-04 |
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Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104788341B (en) * | 2014-01-17 | 2017-01-04 | 上海泰禾国际贸易有限公司 | A kind of method preparing 2,6-difluorobenzonilyile |
| CN104387289B (en) * | 2014-10-30 | 2017-09-01 | 天津河清化学工业有限公司 | The method of catalyst amount is reduced in difluorobenzonilyile production |
| CN111187180A (en) * | 2018-11-15 | 2020-05-22 | 江苏优士化学有限公司 | Method for recycling tetrafluoroterephthalonitrile synthetic wastewater |
| CN111454174A (en) * | 2019-01-18 | 2020-07-28 | 南通泰禾化工股份有限公司 | Method for preparing fluorobenzonitrile |
| CN113620841A (en) * | 2021-08-03 | 2021-11-09 | 南京硕达生物科技有限公司 | Method for preparing 2, 6-difluorobenzonitrile |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1443753A (en) * | 2002-03-13 | 2003-09-24 | 中国石油化工股份有限公司 | Method for preparing 2,6-difluorobenzonitrile by using 2,6-dichlorobenzonitrile fluoro |
| CN1580042A (en) * | 2003-08-15 | 2005-02-16 | 中国科学院动物研究所 | Substituted benzoyl urea insect growth regulator synthesizing method |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1443753A (en) * | 2002-03-13 | 2003-09-24 | 中国石油化工股份有限公司 | Method for preparing 2,6-difluorobenzonitrile by using 2,6-dichlorobenzonitrile fluoro |
| CN1580042A (en) * | 2003-08-15 | 2005-02-16 | 中国科学院动物研究所 | Substituted benzoyl urea insect growth regulator synthesizing method |
Non-Patent Citations (4)
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| 冉高泽等.2，6-二氟苯甲酰胺的合成.《农药》.1996,第35卷(第3期),第12页. * |
| 李忠民等.2,6-二氟苯腈的合成及其在农药合成中的应用.《浙江化工》.2001,第32卷(第3期),第51-53页. * |
| 邱滔等.2，6-二氟苯腈的合成.《精细化工》.2000,第17卷(第1期),第52-54页. * |
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