CN104788341A - Method for preparing 2, 6-difluorobenzonitrile - Google Patents
Method for preparing 2, 6-difluorobenzonitrile Download PDFInfo
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- CN104788341A CN104788341A CN201410023012.6A CN201410023012A CN104788341A CN 104788341 A CN104788341 A CN 104788341A CN 201410023012 A CN201410023012 A CN 201410023012A CN 104788341 A CN104788341 A CN 104788341A
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Abstract
The invention relates to a method for preparing 2, 6-difluorobenzonitrile. The method comprises the following steps: adding an aprotic strong polar solvent, toluene, 2,6-dichlorobenzonitrile and a catalyst, controlling temperature to 110-150 DEG C, carrying out reflux and dehydration and removing methylbenzene; cooling to 90-100 DEG C and adding potassium fluoride into a reaction container; controlling reaction temperature to 150-250 DEG C, and reacting for 15-20 h; reducing temperature of the reaction container to below 50 DEG C, carrying out suction filtration to obtain a filtrate and transferring the filtrate into a rectification bottle, starting a vacuum pump with the vacuum degree being -0.1 MPa, and collecting a fraction of 105-108 DEG C so as to obtain a finished product 2, 6-difluorobenzonitrile. In comparison with the prior art, the invention has advantages as follows: reaction conditions are mild; the preparation technology is simple; and reaction yield can reach up to 98%.
Description
Technical field
The present invention relates to a kind of preparation method of agricultural chemicals, especially relate to the method that one prepares 2,6-difluorobenzonilyile.
Background technology
2,6-difluorobenzonilyile is specificity insect growth regulator(IGR): the indispensable intermediate of the benzoyl area kind such as diflubenzuron, UC 62644 agricultural chemicals, is also applicable as the synthesis of medicine, liquid crystal material simultaneously, has market outlook widely.Therefore how to synthesize 2,6-difluorobenzonilyile efficiently to get more and more people's extensive concerning, the synthetic method of 2,6-difluorobenzonilyile mainly contains following several:
1, before 1980, the synthesis of 2,6-difluorobenzonilyile mainly take chlorinated aromatic hydrocarbons and anhydrous potassium fluoride carry out in all kinds of SOLVENTS fluoridation method (see GC, Fing, et al., chem.commn, 1965, (18),
2, phase-transfer catalyst method: phase transfer catalysis process develops very fast a kind of synthetic method in organic synthesis, is widely used because it has the features such as yield is high, reaction conditions is gentle.Usual phase-transfer catalyst be quaternary ammonium salt, season phosphonium salt, polyethers, crown ether etc. (see such as family industry is beautiful, Wang Xianyi, Zeng Ying. agricultural chemicals, 1998,37 (7): 14 ~ 15 and patent CN101456827).
3, solventless method: German patent DE 3322936 reports 2,6-dichlorobenzonitrile and Potassium monofluoride reacts 3 hours in 350 DEG C under nitrogen atmosphere, and pressure remains on 1.43MPa, yield 83%, purity 99%.
4,2,3,6-trichlorobenzene nitrile synthesiss: day JP 58189151 (1983) patent mention by 2,3,6-trichlorine cyanophenyl synthesis 3-chloro-2,6-difluoro cyanophenyl, then catalytic hydrogenation and dechlorination obtains 2,6-difluorobenzonilyile.
These synthesis techniques above-mentioned, technique 1 and 2 yield is lower, and technique 3 will use high-temperature and high-pressure conditions, and technique 4 technique is loaded down with trivial details, and aftertreatment is complicated; Therefore industry member is to mild condition and the method demand efficiently preparing 2,6-difluorobenzonilyile is very urgent.
The invention provides that a kind of technique is simple, reaction time is short, react gentle, the preparation method of 2,6-difluorobenzonilyiles that yield is high.
Summary of the invention
Object of the present invention is exactly provide a kind of reaction conditions gentle to overcome defect that above-mentioned prior art exists, and preparation technology is simple, and reaction yield reaches the method for preparation 2, the 6-difluorobenzonilyile of 98%.
Object of the present invention can be achieved through the following technical solutions:
One prepares the method for 2,6-difluorobenzonilyile, adopts following steps:
(1) in reaction vessel, non-proton intensive polar solvent, toluene, 2,6-dichlorobenzonitriles and catalyzer is added successively;
(2) open heating system, controlling reaction vessel temperature is 110 ~ 150 DEG C, reflux dewatering, piptonychia benzene;
(3) utilize cooling system that reaction vessel temperature is down to 90 ~ 100 DEG C, in reaction vessel, add Potassium monofluoride;
(4) open heating system, controlling reaction vessel temperature is 150 ~ 250 DEG C, reaction 15 ~ 20h;
(5) cooling system is utilized reaction vessel temperature to be down to less than 50 DEG C, suction filtration;
(6) filtrate that suction filtration obtains forwards in rectifying bottle, and open vacuum pump, vacuum tightness is-0.1MPa, collects 105 ~ 108 DEG C of cuts, obtains finished product 2,6-difluorobenzonilyile.
The molar equivalent ratio of 2,6-difluorobenzonilyile and Potassium monofluoride is 1: 2.2 ~ 5,
The consumption of catalyzer is 3% ~ 10% of 2,6-difluorobenzonilyile quality,
The mass ratio of non-proton intensive polar solvent and 2,6-difluorobenzonilyile is 1.0 ~ 5: 1.
As preferred embodiment, the molar equivalent ratio of 2,6-difluorobenzonilyile and Potassium monofluoride is 1: 2.4, and the consumption of catalyzer is 6% of 2,6-difluorobenzonilyile quality, and the mass ratio of reaction solvent and 2,6-difluorobenzonilyile is 3.
Non-proton intensive polar solvent described in step (1) is N,N-dimethylacetamide, dimethyl sulfoxide (DMSO), N-Methyl pyrrolidone, DMI or tetramethylene sulfone.
Catalyzer described in step (1) is N-alkyl pyridine quaternary ammonium salt, and structural formula is:
Wherein, the alkyl group of R to be carbon chain lengths be C1 ~ C4, X is halogen, comprises chlorine, bromine or iodine.
The preferred N-ethylpyridinium chloride of described catalyzer or chlorination N-propyIpyridine.
Temperature is risen to 110 DEG C in (2) by step, reflux dewatering 2h, then continues to be warming up to 150 DEG C and removes toluene.
Compared with prior art, the present invention adopts N-alkyl pyridine quaternary ammonium salt to be catalyzer, add Potassium monofluoride solubleness in a solvent, add the nucleophilicity of fluorion simultaneously, be conducive to fluoridation carry out and improve fluoridation yield, the fusing point of N-alkyl pyridine quaternary ammonium salt is high, catalyzer is high temperature resistant, Heat stability is good, excellent catalytic effect, yield can reach 98%, compare other quaternary ammonium salt catalyst yields and be less than 90%, thermostability is poor, and temperature of reaction can not more than 180 DEG C, improve reaction yield, reduce preparation cost; 150 ~ 250 DEG C of reactions, need not High Temperature High Pressure, reaction conditions is gentle, and preparation technology is simple, is more suitable for suitability for industrialized production; The solvent of reaction can repeat to apply mechanically, and reduces preparation cost further; The yield reacted in addition is up to 98%, and product purity is up to 99.5%, and the three wastes are little, are more suitable for industrialization.
Embodiment
Below in conjunction with specific embodiment, the present invention is described in detail.
Embodiment 1:
Be equipped with in the mechanic whirl-nett reaction bottle of condenser and water trap at 1000ml, add 1 successively, 3-dimethyl-2-imidazolinone 450g, toluene 100g, 2,6-dichlorobenzonitrile 150g (content 99.5%, 0.868mol), N-ethylpyridinium chloride 9g, stir be warmed up to 110 DEG C, reflux water-dividing 2 hours, then continue intensification piptonychia benzene, reclaim toluene 99g.
Close heating, temperature of reaction is lowered the temperature 90 DEG C, in reaction flask, adds anhydrous potassium fluoride 122g (content 99%, 2.08mol), heat and temperature of reaction is raised to 150 DEG C, insulation reaction 15 hours, close heating.
Temperature of reaction is dropped to 40 DEG C, suction filtration, filtrate forwards in rectifying bottle, opens vacuum, and vacuum tightness is-0.1MPa, collects 105 ~ 108 DEG C of cuts, obtains finished product 2,6-difluorobenzonilyile 118.8g (content 99.5%, 0.85mol), yield 98%.Distillation residual liquid recovery.
Embodiment 2:
Be equipped with in the mechanic whirl-nett reaction bottle of condenser and water trap at 1000ml, add 1 successively, 3-dimethyl-2-imidazolinone 450g, toluene 100g, 2,6-dichlorobenzonitrile 150g (content 99.5%, 0.868mol), chlorination N-propyIpyridine 9g, stir be warmed up to 110 DEG C, reflux water-dividing 2 hours, then continue intensification piptonychia benzene, reclaim toluene 99g.
Close heating, temperature of reaction is lowered the temperature 90 DEG C, in reaction flask, adds anhydrous potassium fluoride 122g (content 99%, 2.08mol), heat and temperature of reaction is raised to 150 DEG C, insulation reaction 15 hours, close heating.
Temperature of reaction is dropped to 40 DEG C, suction filtration, filtrate forwards in rectifying bottle, opens vacuum, and vacuum tightness is-0.1MPa, collects 105 ~ 108 DEG C of cuts, obtains finished product 2,6-difluorobenzonilyile 119g (content 99.5%, 0.852mol), yield 98.17%.Distillation residual liquid recovery.
Embodiment 3:
Be equipped with in the mechanic whirl-nett reaction bottle of condenser and water trap at 1000ml, add dimethyl sulfoxide (DMSO), toluene 100g, 2 successively, 6-dichlorobenzonitrile 150g (content 99.5%, 0.868mol), N-ethylpyridinium chloride 9g, stirring is warmed up to 110 DEG C, reflux water-dividing 2 hours, then continues intensification piptonychia benzene, reclaims toluene 99g.
Close heating, temperature of reaction is lowered the temperature 90 DEG C, in reaction flask, adds anhydrous potassium fluoride 122g (content 99%, 2.08mol), heat and temperature of reaction is raised to 150 DEG C, insulation reaction 15 hours, close heating.
Temperature of reaction is dropped to 40 DEG C, suction filtration, filtrate forwards in rectifying bottle, opens vacuum, and vacuum tightness is-0.1MPa, collects 105 ~ 108 DEG C of cuts, obtains finished product 2,6-difluorobenzonilyile 119.2g (content 99.5%, 0.853mol), yield 98.34%.Distillation residual liquid recovery.
Embodiment 4:
Be equipped with in the mechanic whirl-nett reaction bottle of condenser and water trap at 1000ml, add tetramethylene sulfone 450g, toluene 100g, 2 successively, 6-dichlorobenzonitrile 150g (content 99.5%, 0.868mol), N-ethylpyridinium chloride 9g, stirring is warmed up to 110 DEG C, reflux water-dividing 2 hours, then continues intensification piptonychia benzene, reclaims toluene 99g.
Close heating, temperature of reaction is lowered the temperature 90 DEG C, in reaction flask, adds anhydrous potassium fluoride 122g (content 99%, 2.08mol), heat and temperature of reaction is raised to 190 DEG C, insulation reaction 15 hours, close heating.
Temperature of reaction is dropped to 40 DEG C, suction filtration, filtrate forwards in rectifying bottle, opens vacuum, and vacuum tightness is-0.1MPa, collects 105 ~ 108 DEG C of cuts, obtains finished product 2,6-difluorobenzonilyile 118.8g (content 99.5%, 0.85mol), yield 98%.Distillation residual liquid recovery.
Embodiment 6
One prepares the method for 2,6-difluorobenzonilyile, adopts following steps:
(1) in reaction vessel, 1 is added successively, 3-dimethyl-2-imidazolinone, toluene, 2,6-dichlorobenzonitrile and catalyzer bromination N-ethylpyridine, wherein, the consumption of catalyzer is 3%, 1 of 2,6-difluorobenzonilyile quality, the mass ratio of 3-dimethyl-2-imidazolinone and 2,6-difluorobenzonilyile is 1: 1;
(2) open heating system, controlling reaction vessel temperature is 110 DEG C, and reflux dewatering 2h, then continues to be warming up to 150 DEG C and remove toluene;
(3) utilize cooling system that reaction vessel temperature is down to 90 DEG C, in reaction vessel, add Potassium monofluoride, the molar equivalent ratio of 2,6-difluorobenzonilyile and Potassium monofluoride is 1: 2.2;
(4) open heating system, controlling reaction vessel temperature is 150 DEG C, reaction 20h;
(5) cooling system is utilized reaction vessel temperature to be down to less than 50 DEG C, suction filtration;
(6) filtrate that suction filtration obtains forwards in rectifying bottle, and open vacuum pump, vacuum tightness is-0.1MPa, collects 105 ~ 108 DEG C of cuts, obtains finished product 2,6-difluorobenzonilyile.
Embodiment 7
One prepares the method for 2,6-difluorobenzonilyile, adopts following steps:
(1) in reaction vessel, add tetramethylene sulfone, toluene, 2,6-dichlorobenzonitriles and catalyzer bromination N-isobutyl pyridine successively, wherein, the consumption of catalyzer is 6% of 2,6-difluorobenzonilyile quality, and the mass ratio of tetramethylene sulfone and 2,6-difluorobenzonilyile is 3: 1;
(2) open heating system, controlling reaction vessel temperature is 110 DEG C, and reflux dewatering 2h, then continues to be warming up to 150 DEG C and remove toluene;
(3) utilize cooling system that reaction vessel temperature is down to 90 DEG C, in reaction vessel, add Potassium monofluoride, the molar equivalent ratio of 2,6-difluorobenzonilyile and Potassium monofluoride is 1: 2.4;
(4) open heating system, controlling reaction vessel temperature is 200 DEG C, reaction 18h;
(5) cooling system is utilized reaction vessel temperature to be down to less than 50 DEG C, suction filtration;
(6) filtrate that suction filtration obtains forwards in rectifying bottle, and open vacuum pump, vacuum tightness is-0.1MPa, collects 105 ~ 108 DEG C of cuts, obtains finished product 2,6-difluorobenzonilyile.
Embodiment 8
One prepares the method for 2,6-difluorobenzonilyile, adopts following steps:
(1) in reaction vessel, add tetramethylene sulfone, toluene, 2,6-dichlorobenzonitriles and catalyzer iodate N-propyIpyridine successively, wherein, the consumption of catalyzer is 10% of 2,6-difluorobenzonilyile quality, and the mass ratio of tetramethylene sulfone and 2,6-difluorobenzonilyile is 5: 1;
(2) open heating system, controlling reaction vessel temperature is 110 DEG C, and reflux dewatering 2h, then continues to be warming up to 150 DEG C and remove toluene;
(3) utilize cooling system that reaction vessel temperature is down to 100 DEG C, in reaction vessel, add Potassium monofluoride, the molar equivalent ratio of 2,6-difluorobenzonilyile and Potassium monofluoride is 1: 5;
(4) open heating system, controlling reaction vessel temperature is 250 DEG C, reaction 15h;
(5) cooling system is utilized reaction vessel temperature to be down to less than 50 DEG C, suction filtration;
(6) filtrate that suction filtration obtains forwards in rectifying bottle, and open vacuum pump, vacuum tightness is-0.1MPa, collects 105 ~ 108 DEG C of cuts, obtains finished product 2,6-difluorobenzonilyile.
Claims (7)
1. prepare the method for 2,6-difluorobenzonilyile for one kind, it is characterized in that, the method adopts following steps:
(1) in reaction vessel, non-proton intensive polar solvent, toluene, 2,6-dichlorobenzonitriles and catalyzer is added successively;
(2) open heating system, controlling reaction vessel temperature is 110 ~ 150 DEG C, reflux dewatering, piptonychia benzene;
(3) utilize cooling system that reaction vessel temperature is down to 90 ~ 100 DEG C, in reaction vessel, add Potassium monofluoride;
(4) open heating system, controlling reaction vessel temperature is 150 ~ 250 DEG C, reaction 15 ~ 20h;
(5) cooling system is utilized reaction vessel temperature to be down to less than 50 DEG C, suction filtration;
(6) filtrate that suction filtration obtains forwards in rectifying bottle, and open vacuum pump, vacuum tightness is-0.1MPa, collects 105 ~ 108 DEG C of cuts, obtains finished product 2,6-difluorobenzonilyile.
2. one according to claim 1 prepares the method for 2,6-difluorobenzonilyile, it is characterized in that,
The molar equivalent ratio of 2,6-difluorobenzonilyile and Potassium monofluoride is 1: 2.2 ~ 5,
The consumption of catalyzer is 3% ~ 10% of 2,6-difluorobenzonilyile quality,
The mass ratio of non-proton intensive polar solvent and 2,6-difluorobenzonilyile is 1.0 ~ 5: 1.
3. one according to claim 1 prepares the method for 2,6-difluorobenzonilyile, it is characterized in that,
The molar equivalent ratio of 2,6-difluorobenzonilyile and Potassium monofluoride is 1: 2.4,
The consumption of catalyzer is 6% of 2,6-difluorobenzonilyile quality,
The mass ratio of reaction solvent and 2,6-difluorobenzonilyile is 3.
4. one according to claim 1 prepares 2, the method of 6-difluorobenzonilyile, is characterized in that, the non-proton intensive polar solvent described in step (1) is N, N-N,N-DIMETHYLACETAMIDE, dimethyl sulfoxide (DMSO), N-Methyl pyrrolidone, DMI or tetramethylene sulfone.
5. one according to claim 1 prepares the method for 2,6-difluorobenzonilyile, it is characterized in that, the catalyzer described in step (1) is N-alkyl pyridine quaternary ammonium salt, and structural formula is:
Wherein, the alkyl group of R to be carbon chain lengths be C1 ~ C4, X is halogen, comprises chlorine, bromine or iodine.
6. one according to claim 4 prepares the method for 2,6-difluorobenzonilyile, it is characterized in that, the preferred N-ethylpyridinium chloride of described catalyzer or chlorination N-propyIpyridine.
7. one according to claim 1 prepares the method for 2,6-difluorobenzonilyile, it is characterized in that, temperature is risen to 110 DEG C in (2) by step, reflux dewatering 2h, then continues to be warming up to 150 DEG C and removes toluene.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN111454174A (en) * | 2019-01-18 | 2020-07-28 | 南通泰禾化工股份有限公司 | Method for preparing fluorobenzonitrile |
| CN113024414A (en) * | 2021-03-23 | 2021-06-25 | 江苏合泰新材料科技有限公司 | Method for efficiently synthesizing fluorine-containing compound |
| 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 |
| CN113929595A (en) * | 2021-11-12 | 2022-01-14 | 江苏新河农用化工有限公司 | Preparation method of 2, 6-difluorobenzonitrile |
| CN114755332A (en) * | 2022-04-07 | 2022-07-15 | 连云港杰瑞药业有限公司 | Method for detecting isomer impurities in para-fluorobenzonitrile by gas chromatography |
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| FR2808268B1 (en) * | 2000-04-26 | 2002-08-30 | Atofina | IONIC LIQUIDS DERIVED FROM TITANIUM, NIOBIUM, TANTALUM, TIN OR ANTIMONY LEWIS ACIDS AND THEIR APPLICATIONS |
| CN1218935C (en) * | 2003-08-15 | 2005-09-14 | 中国科学院动物研究所 | Substituted benzoyl urea insect growth regulator synthesizing method |
| 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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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN111454174A (en) * | 2019-01-18 | 2020-07-28 | 南通泰禾化工股份有限公司 | Method for preparing fluorobenzonitrile |
| CN113024414A (en) * | 2021-03-23 | 2021-06-25 | 江苏合泰新材料科技有限公司 | Method for efficiently synthesizing fluorine-containing compound |
| 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 |
| CN113929595A (en) * | 2021-11-12 | 2022-01-14 | 江苏新河农用化工有限公司 | Preparation method of 2, 6-difluorobenzonitrile |
| CN114755332A (en) * | 2022-04-07 | 2022-07-15 | 连云港杰瑞药业有限公司 | Method for detecting isomer impurities in para-fluorobenzonitrile by gas chromatography |
| CN114755332B (en) * | 2022-04-07 | 2024-04-02 | 连云港杰瑞药业有限公司 | Method for detecting isomer impurities in p-fluorobenzonitrile by gas chromatography |
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Inventor after: Yang Binglian Inventor after: Zhou Qingjiang Inventor after: Wu Yong Inventor after: Xie Simian Inventor after: Tian Xiaohong Inventor before: Zhou Qingjiang Inventor before: Wu Yong Inventor before: Xie Simian Inventor before: Tian Xiaohong |