CN1199941C - Method for preparing 2,6-difluorobenzonitrile by using 2,6-dichlorobenzonitrile fluoro - Google Patents
Method for preparing 2,6-difluorobenzonitrile by using 2,6-dichlorobenzonitrile fluoro Download PDFInfo
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- CN1199941C CN1199941C CN 02111009 CN02111009A CN1199941C CN 1199941 C CN1199941 C CN 1199941C CN 02111009 CN02111009 CN 02111009 CN 02111009 A CN02111009 A CN 02111009A CN 1199941 C CN1199941 C CN 1199941C
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- difluorobenzonitrile
- dichlorobenzonitrile
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- fluoro
- ether compound
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Abstract
The present invention relates to a method for preparing 2, 6-difluorobenzonitrile from 2, 6-dichlorobenzonitrile fluoro, which mainly solves the problems of only high-content pure product used for raw materials, large solvent consumption in the reaction process, complicated reaction operation and long reaction period existing in the previous art. The present invention nicely solves the problems by the technical scheme that the 2, 6-difluorobenzonitrile as a crude product is used as a raw material, sulfolane is used as a solvent, a low grade polyaliphatic alcohol ether compound is used as a catalyst, and the 2, 6-difluorobenzonitrile, the sulfolane and the low grade polyaliphatic alcohol ether compound react with each other for 2 to 5 hours under the conditions that the reaction temperature is from 170 to 250DEG C and the reaction pressure is the normal pressure. The present invention can be used for the industrial production of the 2, 6-difluorobenzonitrile.
Description
Technical field
The present invention relates to 2,6-dichlorobenzonitrile fluoro preparation 2, the method for 6-difluorobenzonitrile.
Background technology
2, (2,6-Difluorobenzonitrile is called for short 2 to the 6-difluorobenzonitrile, 6-DFBN) is the important intermediate of synthetic process for preparation of benzoylurea compounds.Benzoyl urea compound has unique insecticidal action mechanism, and strong by its selectivity, usage quantity is little, environmentally friendly, be described as the environment friendly agricultural of 21st century, be subjected to the synthetic plant worker's of reaching of agricultural chemicals attention, the production technology of developing this type of intermediate seems more and more important.
Both at home and abroad the method for the synthesizing fluoro cyanobenzene of report mainly contains following several: (1) with 2, and the 6-dichlorobenzonitrile (2,6-DCBN) fluoridize Synthetic 2,6-DFBN for raw material; (2) with 2,3,6-trichlorobenzene formonitrile HCN be raw material through fluoridize, the synthetic DFBN of hydrogenating reduction.Relatively Chang Yong method is (1).
Introduced a kind of production 2 in the document German patent DE 3422936, the method for 6-difluorobenzonitrile.It is with 2, and 6-DCBN mixes with anhydrous potassium fluoride, need not solvent, and pressure is 1.40MPa, and 350 ℃ of temperature were reacted yield 83% 3 hours.This method is simple to operate, but the temperature of reaction height, the conversion unit complexity, unsuitable industry is used.
Introduced a kind of preparation method of fluoro benzonitrile among the document Chinese patent CN85100467.It is with 2, and 6-DCBN and anhydrous potassium fluoride are raw material, and tetramethylene sulfone is a solvent, is catalyzer with perfluoroalkyl oxa-carboxylic acid derivative, in 210～230 ℃ of reactions 8～10 hours, yield 86%.The catalyzer that this method is used is more difficult to get, and the reaction times is longer.
Introduced a kind of method of benzene halide formonitrile HCN among the document Japanese Patent JP6072851, it is with 2, and 6-DCBN and anhydrous potassium fluoride are in sulfolane solvent, heat temperature raising, 170 ℃ kept 0.5 hour, and 175 ℃ kept 2.0 hours, 210～230 ℃ kept yield 95.6% 4.0 hours.This method mild condition, the reaction yield height.But the inventor finds through test, and the purpose product yield that this method obtains only 82.7% is lower.
The super beginning raw material 2 that uses in the above document, the 6-dichlorobenzonitrile is high-load pure product, and easily distils during raw material drying, and the solvent usage quantity is big in the reaction process, and operation is also more loaded down with trivial details, and reaction time is also longer.
Summary of the invention
Technical problem to be solved by this invention is to overcome in the past to exist raw material can only use high-load 2 in the document, 6-DCBN, the solvent usage quantity is big in the reaction process, operation is loaded down with trivial details, the problem that reaction time is long, provide a kind of new 2,6-dichlorobenzonitrile fluoro preparation 2, the method for 6-difluorobenzonitrile.This method has raw material can use 2,6-dichlorobenzonitrile crude product, and the solvent usage quantity is little in the reaction process, and is easy and simple to handle, and the reaction times is short, and product 2,6-difluorobenzonitrile yield advantage of higher.
For solving the problems of the technologies described above, the technical solution used in the present invention is as follows: a kind of 2,6-dichlorobenzonitrile fluoro preparation 2, the method of 6-difluorobenzonitrile, with weight percentage be 75～96% 2,6-dichlorobenzonitrile crude product and alkaline metal fluoride cpd are raw material, with the tetramethylene sulfone is solvent, with rudimentary polyester fat alcohol ether compound is catalyzer, with molar ratio computing 2,6-dichlorobenzonitrile: alkaline metal fluoride cpd: tetramethylene sulfone: rudimentary polyester fat alcohol ether compound is 1: 2.1～5.0: 3.0～9.0: 0.001～0.05, in temperature of reaction is 170～250 ℃, reaction pressure is to react under the condition of normal pressure to get product 2 in 2～5 hours, the 6-difluorobenzonitrile, and it is C that described rudimentary polyester fat alcohol ether compound is selected from molecular formula
mH
2m+1O (C
nH
2n+1O)
xC
mH
2m+1, its molecular-weight average is 200～2000, and wherein n is 2～5 positive integer, and m is 1～4 positive integer, and x is the number that satisfies the molecular weight requirement.
The preferred version of alkaline metal fluoride cpd is a Potassium monofluoride in the technique scheme.The preferable range of rudimentary polyester fat alcohol ether compound is 300～1200.The preferred value of m is m=1; The preferred value of n is 2 or 3, and more preferably value is n=2.
Because fluoridation is a solid-liquid inhomogeneous reaction, the nucleophilicity that increases fluorion helps the carrying out of fluoridation and improves reaction yield among the present invention.The present invention makes raw material 2 owing to adopt rudimentary polyester fat alcohol ether compound as catalyst, and the 6-dichlorobenzonitrile can adopt the raw material of thick content.Thick in addition 2, the 6-dichlorobenzonitrile has saved the trouble of purifying, purification as raw material, makes operation become easier, adopts less quantity of solvent and suitable reaction temperature and short reaction times simultaneously, make the yield of purpose product be up to 91.5%, obtained better technical effect.
The invention will be further elaborated below by embodiment.
Embodiment
[embodiment 1]
In 250 milliliters the there-necked flask that has agitator, prolong, thermometer, add 2,6-dichlorobenzonitrile crude product 24.1 grams (massfraction is 85.1%), toluene 50.0 grams, reflux, change air distillation when not having the obvious globule into and remove toluene (recording its water yield is 3.9 grams), boil off 2 in 130 ℃/13kPa again, 6-toluene dichloride (this is preparation 2, the starting raw material of 6-dichlorobenzonitrile).Cooling adds 60.0 milliliters of tetramethylene sulfone, anhydrous potassium fluoride 13.3 gram (0.23 mole) and C
mH
2m+1O (C
nH
2n+1O)
xC
mH
2m+1(n=2, m=1, molecular-weight average M:300) 0.9 gram is warming up to 220 ℃ under stirring fast, and keeps this temperature reaction 4.0 hours.After reaction 3 hours, the sampling and measuring conversion of raw material gets final product stopped reaction greater than 95%.After reaction finishes, rectification under vacuum, the product 12.5 of collecting 92～98 ℃/2.5kPa restrains, and 2,6-DFBN yield 89.9%, massfraction 99.0%.Tetramethylene sulfone is after further underpressure distillation, and recovery set is used.
[comparative example 1]
In 250 milliliters the there-necked flask that has agitator, prolong, thermometer, add exsiccant 2,6-dichlorobenzonitrile (massfraction＞99.0%) 17.2 gram (0.1 mole), 60.0 milliliters of tetramethylene sulfone, anhydrous potassium fluoride 13.3 gram (0.23 mole) and C
mH
2m+1O (C
nH
2n+1O)
xC
mH
2m+1(n=2, m=1, molecular-weight average M:600) 0.9 gram.Operation gets product 12.6 grams with embodiment 1, and 2,6-DFBN yield 90.6%, massfraction 98.9%.Tetramethylene sulfone is after further underpressure distillation, and recovery set is used.
[comparative example 2]
In 250 milliliters the there-necked flask that has agitator, prolong, thermometer, add exsiccant 2,6-dichlorobenzonitrile (massfraction＞99.0%) 17.2 gram (0.1 mole), 60.0 milliliters of tetramethylene sulfone, anhydrous potassium fluoride 13.3 grams (0.23 mole).Heat temperature raising, 170 ℃ were reacted 0.5 hour, and 175 ℃ were reacted 2.0 hours, and 220 ℃ were reacted 4.0 hours.All the other operations get product 11.5 grams with embodiment 1, and 2,6-DFBN yield 82.7%, massfraction 98.8%.Tetramethylene sulfone is after further underpressure distillation, and recovery set is used.
[embodiment 2]
In 250 milliliters the there-necked flask that has agitator, prolong, thermometer, add dichlorobenzonitrile crude product 27.3 grams (massfraction is 75.1%), toluene 50.0 grams, reflux, change air distillation when not having the obvious globule into and remove toluene (recording its water yield is 4.4 grams), boil off 2 in 130 ℃/13kPa again, 6-toluene dichloride (this is preparation 2, the starting raw material of 6-dichlorobenzonitrile).Cooling adds 70.0 milliliters of tetramethylene sulfone, anhydrous potassium fluoride 17.4 gram (0.30 mole) and C
mH
2m+1O (C
nH
2n+1O)
xC
mH
2m+1(n=2, m=1, molecular-weight average M:600) 0.5 gram is warming up to 250 ℃ under stirring fast, and keeps this temperature reaction 3.5 hours.After reaction finishes, rectification under vacuum, the product 12.7 of collecting 92～98 ℃/2.5kPa restrains, and 2,6-DFBN yield 91.5%, massfraction 99.2%.Tetramethylene sulfone is after further underpressure distillation, and recovery set is used.
[embodiment 3]
In 250 milliliters the there-necked flask that has agitator, prolong, thermometer, add dichlorobenzonitrile crude product 21.3 grams (massfraction is 96.0%), toluene 50.0 grams, reflux, change air distillation when not having the obvious globule into and remove toluene (recording its water yield is 3.4 grams), boil off 2 in 130 ℃/13kPa again, 6-toluene dichloride (this is preparation 2, the starting raw material of 6-dichlorobenzonitrile).Cooling adds 85.7 milliliters of tetramethylene sulfone, anhydrous potassium fluoride 29.0 gram (0.50 mole) and C
mH
2m+1O (C
nH
2n+1O)
xC
mH
2m+1(n=3, m=2, molecular-weight average M:1200) 1.2 grams are warming up to 230 ℃ under stirring fast, and keep this temperature reaction 5.0 hours.After reaction finishes, rectification under vacuum, the product 12.2 of collecting 92～98 ℃/2.5kPa restrains, and 2,6-DFBN yield 87.7%, massfraction 99.1%.Tetramethylene sulfone is after further underpressure distillation, and recovery set is used.
Claims (6)
1, a kind of 2,6-dichlorobenzonitrile fluoro preparation 2, the method of 6-difluorobenzonitrile, with weight percentage be 75～96% 2,6-dichlorobenzonitrile crude product and alkaline metal fluoride cpd are raw material, with the tetramethylene sulfone is solvent, with rudimentary polyester fat alcohol ether compound is catalyzer, with molar ratio computing 2,6-dichlorobenzonitrile: alkaline metal fluoride cpd: tetramethylene sulfone: rudimentary polyester fat alcohol ether compound is 1: 2.1～5.0: 3.0～9.0: 0.001～0.05, is 170～250 ℃ in temperature of reaction, and reaction pressure is to react under the condition of normal pressure to get product 2 in 2～5 hours, the 6-difluorobenzonitrile, it is C that described rudimentary polyester fat alcohol ether compound is selected from molecular formula
nH
2m+1O (C
nH
2n+1O)
xC
mH
2m+1, its molecular-weight average is 200～2000, and wherein n is 2～5 positive integer, and m is 1～4 positive integer, and x is the number that satisfies the molecular weight requirement.
2, described 2 according to claim 1,6-dichlorobenzonitrile fluoro preparation 2, the method for 6-difluorobenzonitrile is characterized in that alkaline metal fluoride cpd is a Potassium monofluoride.
3, described 2 according to claim 1,6-dichlorobenzonitrile fluoro preparation 2, the method for 6-difluorobenzonitrile is characterized in that molecular-weight average is 300～1200.
4, described 2 according to claim 1,6-dichlorobenzonitrile fluoro preparation 2, the method for 6-difluorobenzonitrile, the value that it is characterized in that m is 1.
5, described 2 according to claim 1,6-dichlorobenzonitrile fluoro preparation 2, the method for 6-difluorobenzonitrile, the value that it is characterized in that n is 2 or 3.
6, described 2 according to claim 5,6-dichlorobenzonitrile fluoro preparation 2, the method for 6-difluorobenzonitrile, the value that it is characterized in that n is 2.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 02111009 CN1199941C (en) | 2002-03-13 | 2002-03-13 | Method for preparing 2,6-difluorobenzonitrile by using 2,6-dichlorobenzonitrile fluoro |
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|---|---|---|---|
| CN 02111009 CN1199941C (en) | 2002-03-13 | 2002-03-13 | Method for preparing 2,6-difluorobenzonitrile by using 2,6-dichlorobenzonitrile fluoro |
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| CN1199941C true CN1199941C (en) | 2005-05-04 |
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| CN101456827B (en) * | 2009-01-05 | 2012-07-04 | 扬州天辰精细化工有限公司 | Industrial production method of 2,6-difluorobenzene nitrile |
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