CN100336798C - Process of preparing 2,6-difluorobenzamide by 2.6-difluorobenz nitrile non catalyzing and hydrolyzing in near critical aqueous medium - Google Patents
Process of preparing 2,6-difluorobenzamide by 2.6-difluorobenz nitrile non catalyzing and hydrolyzing in near critical aqueous medium Download PDFInfo
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- CN100336798C CN100336798C CNB2006100506269A CN200610050626A CN100336798C CN 100336798 C CN100336798 C CN 100336798C CN B2006100506269 A CNB2006100506269 A CN B2006100506269A CN 200610050626 A CN200610050626 A CN 200610050626A CN 100336798 C CN100336798 C CN 100336798C
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- difluorobenzamide
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- AVRQBXVUUXHRMY-UHFFFAOYSA-N 2,6-difluorobenzamide Chemical compound NC(=O)C1=C(F)C=CC=C1F AVRQBXVUUXHRMY-UHFFFAOYSA-N 0.000 title claims abstract description 23
- 238000000034 method Methods 0.000 title claims abstract description 20
- 239000012736 aqueous medium Substances 0.000 title claims description 9
- 230000008569 process Effects 0.000 title abstract description 7
- 230000003301 hydrolyzing effect Effects 0.000 title abstract description 3
- 150000002825 nitriles Chemical class 0.000 title 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 68
- 230000007062 hydrolysis Effects 0.000 claims abstract description 32
- 238000006460 hydrolysis reaction Methods 0.000 claims abstract description 32
- 239000000047 product Substances 0.000 claims abstract description 29
- 239000008367 deionised water Substances 0.000 claims abstract description 23
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 23
- 238000009835 boiling Methods 0.000 claims abstract description 20
- 239000000413 hydrolysate Substances 0.000 claims abstract description 20
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims abstract description 6
- 239000011780 sodium chloride Substances 0.000 claims abstract description 3
- 238000010792 warming Methods 0.000 claims description 37
- DPDMMXDBJGCCQC-UHFFFAOYSA-N [Na].[Cl] Chemical compound [Na].[Cl] DPDMMXDBJGCCQC-UHFFFAOYSA-N 0.000 claims description 20
- 238000001035 drying Methods 0.000 claims description 18
- 238000001914 filtration Methods 0.000 claims description 18
- 238000003756 stirring Methods 0.000 claims description 18
- 238000005406 washing Methods 0.000 claims description 18
- 238000006555 catalytic reaction Methods 0.000 claims description 11
- 238000002360 preparation method Methods 0.000 claims description 11
- 238000006243 chemical reaction Methods 0.000 abstract description 6
- 238000005815 base catalysis Methods 0.000 abstract description 4
- 238000003912 environmental pollution Methods 0.000 abstract description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- BNBRIFIJRKJGEI-UHFFFAOYSA-N 2,6-difluorobenzonitrile Chemical compound FC1=CC=CC(F)=C1C#N BNBRIFIJRKJGEI-UHFFFAOYSA-N 0.000 abstract 2
- 239000003054 catalyst Substances 0.000 abstract 1
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 239000005446 dissolved organic matter Substances 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 229920006395 saturated elastomer Polymers 0.000 description 3
- GKPHNZYMLJPYJJ-UHFFFAOYSA-N 2,3-difluorobenzonitrile Chemical compound FC1=CC=CC(C#N)=C1F GKPHNZYMLJPYJJ-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 2
- 241000238631 Hexapoda Species 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- HRYILSDLIGTCOP-UHFFFAOYSA-N N-benzoylurea Chemical class NC(=O)NC(=O)C1=CC=CC=C1 HRYILSDLIGTCOP-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical class [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000006386 neutralization reaction Methods 0.000 description 2
- PCKNFPQPGUWFHO-SXBRIOAWSA-N (Z)-flucycloxuron Chemical compound FC1=CC=CC(F)=C1C(=O)NC(=O)NC(C=C1)=CC=C1CO\N=C(C=1C=CC(Cl)=CC=1)\C1CC1 PCKNFPQPGUWFHO-SXBRIOAWSA-N 0.000 description 1
- JLZVIWSFUPLSOR-UHFFFAOYSA-N 2,3-difluorobenzoic acid Chemical compound OC(=O)C1=CC=CC(F)=C1F JLZVIWSFUPLSOR-UHFFFAOYSA-N 0.000 description 1
- JTHMHWAHAKLCKT-UHFFFAOYSA-N 2,6-difluoro-n-[[4-(trifluoromethyl)phenyl]carbamoyl]benzamide Chemical compound FC1=CC=CC(F)=C1C(=O)NC(=O)NC1=CC=C(C(F)(F)F)C=C1 JTHMHWAHAKLCKT-UHFFFAOYSA-N 0.000 description 1
- 239000002028 Biomass Substances 0.000 description 1
- 229920002101 Chitin Polymers 0.000 description 1
- 239000005893 Diflubenzuron Substances 0.000 description 1
- 108010010803 Gelatin Proteins 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- 239000005938 Teflubenzuron Substances 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 241000607479 Yersinia pestis Species 0.000 description 1
- 238000007171 acid catalysis Methods 0.000 description 1
- 238000005903 acid hydrolysis reaction Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 125000003236 benzoyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C(*)=O 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000000881 depressing effect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- QQQYTWIFVNKMRW-UHFFFAOYSA-N diflubenzuron Chemical compound FC1=CC=CC(F)=C1C(=O)NC(=O)NC1=CC=C(Cl)C=C1 QQQYTWIFVNKMRW-UHFFFAOYSA-N 0.000 description 1
- 229940019503 diflubenzuron Drugs 0.000 description 1
- RYLHNOVXKPXDIP-UHFFFAOYSA-N flufenoxuron Chemical compound C=1C=C(NC(=O)NC(=O)C=2C(=CC=CC=2F)F)C(F)=CC=1OC1=CC=C(C(F)(F)F)C=C1Cl RYLHNOVXKPXDIP-UHFFFAOYSA-N 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 229920000159 gelatin Polymers 0.000 description 1
- 239000008273 gelatin Substances 0.000 description 1
- 235000019322 gelatine Nutrition 0.000 description 1
- 235000011852 gelatine desserts Nutrition 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 230000000749 insecticidal effect Effects 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 230000001537 neural effect Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 244000144977 poultry Species 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
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- CJDWRQLODFKPEL-UHFFFAOYSA-N teflubenzuron Chemical compound FC1=CC=CC(F)=C1C(=O)NC(=O)NC1=CC(Cl)=C(F)C(Cl)=C1F CJDWRQLODFKPEL-UHFFFAOYSA-N 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
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Abstract
The present invention discloses a method for preparing 2, 6-difluorobenzamide not by catalyzing and hydrolyzing 2, 6-difluorobenz nitrile in near-critical water media. The method comprises the steps that (1) deionized water and 2, 6-difluorobenzo nitrile with the weight ratio of 1:2 to 7:1 are added into a high-pressure reaction vessel, stirred and heated at ordinary pressure until boiling and an exhaust valve is opened for 2 to 5 minutes; (2) the solution is continuously heated to 200 to 350DEGC and is hydrolyzed for 1 to 10 h; (3) the hydrolysate products are cooled to room temperature and are salted by 10 to 150 g/L of sodium chloride and the salted hydrolysate products are filtered, washed by water and dried to obtain a 2, 6-difluorobenzamide product. The present invention does not need adding any catalyst in the process of hydrolysis, solves the problem of environmental pollution by acid-base catalysis and hydrolysis, and has the advantages of simple reaction process, high product yield, good purity and green production process.
Description
Technical field
The present invention relates in a kind of near critical aqueous medium 2,6-difluorobenzonilyile non-catalysis hydrolyzation preparation 2, the method for 6-difluorobenzamide.
Background technology
Process for preparation of benzoylurea compounds is one of important kind of fluorine-containing sterilant, it has caused people's attention with synthetic this unique insecticidal mechanism that suppresses insect chitin, having overcome simultaneously is the wretched insufficiency of the conventional pesticides of action target to the toxic effect of most animal and human's class with the neural system, and can be decomposed by Institute of Micro-biology.Process for preparation of benzoylurea compounds is considered to open up new way for the chemical prevention insect pest, it has efficiently, wide spectrum, low toxicity, to advantages such as person poultry safeties, be eco-friendly sterilant new variety.In recent ten years, the benzoyl area kind agricultural chemicals has obtained developing rapidly in the world, occurred that fluorine bell urea, diflubenzuron, pyridine worm are grand, numerous products such as flufenoxuron, pyrrole worm are grand, Teflubenzuron, penfluron, flucycloxuron, and 2,6 difluorobenzamides are key intermediates of synthetic these products.
2,6-difluorobenzamide outward appearance is the white, needle-shaped crystals powder, and temperature of fusion is 145～147 ℃, and the solubleness 43.1g/L in 25 ℃ of water is soluble in ethanol, acetone etc., is slightly soluble in benzene.Its synthetic method mainly contains two classes: the one, and the ammonia of difluoro-benzoic acid and derivative thereof is separated, and the 2nd, the hydrolysis of difluorobenzonitrile.The method for hydrolysis of difluorobenzonitrile is divided into two classes again: the one, and acid-catalyzed hydrolysis (sulfuric acid) as 90%, the 2nd, there is highly basic catalytic hydrolysis (as 5%～10% sodium hydroxide) down in hydrogen peroxide, these two kinds of hydrolysis process hydrolyzed product all need neutralization, not only consume a large amount of soda acids, also produce a large amount of abraum salts, environmental pollution is very serious.
Near-critical water (Near Critical Water) typically refers to the compressed liquid water of temperature between 200～350 ℃.Water has following three key properties in this zone:
1) depress at saturated vapo(u)r, the ionization constant of near-critical water has a maximum value to be about 10 near 275 ℃
-11(mol/kg)
2, its value is 1000 times of normal temperature and pressure water, and ionization constant increases the [H in the near-critical water with the increase of pressure
3O
+] and [OH
-] concentration is near weak acid or weak base, self has the function of acid catalysis and base catalysis, therefore can make some acid-base catalyzed reaction needn't add acid base catalysator, thereby avoid the neutralization of soda acid, the operations such as processing of salt;
2) depress at saturated vapo(u)r, the specific inductivity of 20 ℃ of water is 80.1, and has only 23.5 275 ℃ the time.Although the specific inductivity of near-critical water is still bigger, solubilized even ionized salts, enough little of dissolved organic matter, (275 ℃ of saturated vapo(u)rs density of depressing water is 0.76g/cm to add that the density of near-critical water is big
3, the specific inductivity of near-critical water, density and acetone are close), so near-critical water has extraordinary solubility property, has the characteristic of dissolved organic matter and inorganics simultaneously.This can carry out the building-up reactions in many near critical aqueous mediums in homogeneous phase, thereby eliminates resistance to mass transfer, improves speed of response, and the reaction back only needs simple cooling just can realize solid-liquid separation simultaneously, and water can be recycled;
3) physicochemical property such as the specific inductivity of near-critical water, ion-product constant, density, viscosity, spread coefficient, solubleness are adjustable continuously in the scope of broad with temperature, pressure, the rerum natura that is near-critical water has controllability (tuning property), therefore as reaction medium, near-critical water has different solvent properties and reactivity worth at different states.
The applied research of reacting in the near-critical water comprises that offal treatment, macromolecular material recycle, inorganic materials are synthetic, gelatin liquefaction and biomass as resources etc., to going deep into that these three characteristics are familiar with, make the Application Areas in the near-critical water constantly obtain enlarging just because of people.
Summary of the invention
The purpose of this invention is to provide a kind ofly 2, the 6-difluorobenzonilyile does not have catalysis, efficient, green hydrolysis preparation 2, the method for 6-difluorobenzamide.
The step of method is as follows:
1) in autoclave, add deionized water and 2, the 6-difluorobenzonilyile, deionized water and 2,6-difluorobenzonilyile weight ratio is 1: 2～7: 1, opens stirring, is warming up to boiling under the normal pressure, opens vent valve 2-5 minute;
2) continue to be warming up to 200～350 ℃ of hydrolysis 1～10h;
3) hydrolysate is cooled to room temperature, add 10～150g/L sodium-chlor and saltout, after filtration, after the washing, drying 2,6-difluorobenzamide product.
Described deionized water and 2,6-difluorobenzonilyile weight ratio is 1: 1～4: 1.Hydrolysis temperature is preferably 240～290 ℃.Sodium-chlor is saltoutd, and sodium chloride concentration is preferably 30～100g/L in the step.
The purpose that " is warming up to boiling under the normal pressure, opened vent valve 2-5 minute " in the step 1) of the present invention is to utilize water vapour to take away the interior oxygen of still, to reduce the generation of side reaction, improves the yield of product.
Step 2) the system reaction pressure is a water saturation vapour pressure under this temperature in.
The sodium-chlor of the water in the step 3) can reclaim through concentrated, crystallization.
2, the 6-difluorobenzamide is further hydrolysis generation 2 in near-critical water, the 6-difluoro-benzoic acid, thereby need strict control reaction time, so that improve product 2, the yield of 6-difluorobenzamide.
The present invention need not add any catalyzer in hydrolytic process, self acid-base catalysis characteristic of utilizing near-critical water makes 2 with characteristic that can dissolved organic matter, the hydrolysis in near-critical water of 6-difluorobenzonilyile generates 2, the 6-difluorobenzamide, solved an acid-base catalysis hydrolysis pollution on the environment difficult problem, reaction process is simple, the product yield height, purity is better, has realized the greenization of production process.
Description of drawings
Accompanying drawing is in the near critical aqueous medium 2,6-difluorobenzonilyile non-catalysis hydrolyzation preparation 2, the process flow diagram of 6-difluorobenzamide.
Embodiment
The present invention is applied in 2 with the characteristic of near-critical water, in the hydrolysis of 6-difluorobenzonilyile, provides in a kind of near critical aqueous medium 2,6-difluorobenzonilyile non-catalysis hydrolyzation preparation 2, the method of 6-difluorobenzamide, thus realize 2, the no catalysis of 6-difluorobenzonilyile, efficient, green hydrolysis.
Embodiment 1
Add 350g deionized water and 50g 2 in 500mL intermittent type autoclave, the 6-difluorobenzonilyile is opened stirring, is warming up to boiling under the normal pressure, opens vent valve 5 minutes, utilizes water vapour to get rid of the interior air of still; Continue to be warming up to 200 ℃ of hydrolysis 10h; Hydrolysate is cooled to room temperature, add 150g/L sodium-chlor and saltout, after filtration, after the washing, drying 2,6-difluorobenzamide product 15.2g, content be 11.2% (wt%, liquid phase chromatography, down with).
Embodiment 2
Add 330g deionized water and 55g 2 in 500mL intermittent type autoclave, the 6-difluorobenzonilyile is opened stirring, is warming up to boiling under the normal pressure, opens vent valve 4 minutes, utilizes water vapour to get rid of the interior air of still; Continue to be warming up to 220 ℃ of hydrolysis 8h; Hydrolysate is cooled to room temperature, add 125g/L sodium-chlor and saltout, after filtration, after the washing, drying 2,6-difluorobenzamide product 27.1g, content are 26.7% (wt%).
Embodiment 3
Add 300g deionized water and 60g 2 in 500mL intermittent type autoclave, the 6-difluorobenzonilyile is opened stirring, is warming up to boiling under the normal pressure, opens vent valve 3 minutes, utilizes water vapour to get rid of the interior air of still; Continue to be warming up to 240 ℃ of hydrolysis 6h; Hydrolysate is cooled to room temperature, add 100g/L sodium-chlor and saltout, after filtration, after the washing, drying 2,6-difluorobenzamide product 39.5g, content are 51.2% (wt%).
Embodiment 4
Add 300g deionized water and 75g 2 in 500mL intermittent type autoclave, the 6-difluorobenzonilyile is opened stirring, is warming up to boiling under the normal pressure, opens vent valve 2 minutes, utilizes water vapour to get rid of the interior air of still; Continue to be warming up to 260 ℃ of hydrolysis 5h; Hydrolysate is cooled to room temperature, add 80g/L sodium-chlor and saltout, after filtration, after the washing, drying 2,6-difluorobenzamide product 56.4g, content are 92.4% (wt%).
Embodiment 5
Add 270g deionized water and 90g 2 in 500mL intermittent type autoclave, the 6-difluorobenzonilyile is opened stirring, is warming up to boiling under the normal pressure, opens vent valve 5 minutes, utilizes water vapour to get rid of the interior air of still; Continue to be warming up to 280 ℃ of hydrolysis 4h; Hydrolysate is cooled to room temperature, add 60g/L sodium-chlor and saltout, after filtration, after the washing, drying 2,6-difluorobenzamide product 71.6g, content are 96.8% (wt%).
Embodiment 6
Add 240g deionized water and 120g 2 in 500mL intermittent type autoclave, the 6-difluorobenzonilyile is opened stirring, is warming up to boiling under the normal pressure, opens vent valve 4 minutes, utilizes water vapour to get rid of the interior air of still; Continue to be warming up to 300 ℃ of hydrolysis 3h; Hydrolysate is cooled to room temperature, add 40g/L sodium-chlor and saltout, after filtration, after the washing, drying 2,6-difluorobenzamide product 92.5g, content are 89.4% (wt%).
Embodiment 7
Add 200g deionized water and 200g 2 in 500mL intermittent type autoclave, the 6-difluorobenzonilyile is opened stirring, is warming up to boiling under the normal pressure, opens vent valve 3 minutes, utilizes water vapour to get rid of the interior air of still; Continue to be warming up to 320 ℃ of hydrolysis 2h; Hydrolysate is cooled to room temperature, add 20g/L sodium-chlor and saltout, after filtration, after the washing, drying 2,6-difluorobenzamide product 160.6g, content are 79.2% (wt%).
Embodiment 8
Add 120g deionized water and 240g 2 in 500mL intermittent type autoclave, the 6-difluorobenzonilyile is opened stirring, is warming up to boiling under the normal pressure, opens vent valve 2 minutes, utilizes water vapour to get rid of the interior air of still; Continue to be warming up to 350 ℃ of hydrolysis 1h; Hydrolysate is cooled to room temperature, add 10g/L sodium-chlor and saltout, after filtration, after the washing, drying 2,6-difluorobenzamide product 182.7g, content are 57.3% (wt%).
Embodiment 9
Add 300g deionized water and 75g 2 in 500mL intermittent type autoclave, the 6-difluorobenzonilyile is opened stirring, is warming up to boiling under the normal pressure, opens vent valve 5 minutes, utilizes water vapour to get rid of the interior air of still; Continue to be warming up to 240 ℃ of hydrolysis 8h; Hydrolysate is cooled to room temperature, add 100g/L sodium-chlor and saltout, after filtration, after the washing, drying 2,6-difluorobenzamide product 58.7g, content are 79.5% (wt%).
Embodiment 10
Add 270g deionized water and 90g 2 in 500mL intermittent type autoclave, the 6-difluorobenzonilyile is opened stirring, is warming up to boiling under the normal pressure, opens vent valve 4 minutes, utilizes water vapour to get rid of the interior air of still; Continue to be warming up to 260 ℃ of hydrolysis 6h; Hydrolysate is cooled to room temperature, add 80g/L sodium-chlor and saltout, after filtration, after the washing, drying 2,6-difluorobenzamide product 73.2g, content are 95.9% (wt%).
Embodiment 11
Add 240g deionized water and 120g 2 in 500mL intermittent type autoclave, the 6-difluorobenzonilyile is opened stirring, is warming up to boiling under the normal pressure, opens vent valve 3 minutes, utilizes water vapour to get rid of the interior air of still; Continue to be warming up to 275 ℃ of hydrolysis 5h; Hydrolysate is cooled to room temperature, add 60g/L sodium-chlor and saltout, after filtration, after the washing, drying 2,6-difluorobenzamide product 94.7g, content are 97.1% (wt%).
Embodiment 12
Add 200g deionized water and 200g 2 in 500mL intermittent type autoclave, the 6-difluorobenzonilyile is opened stirring, is warming up to boiling under the normal pressure, opens vent valve 2 minutes, utilizes water vapour to get rid of the interior air of still; Continue to be warming up to 290 ℃ of hydrolysis 4h; Hydrolysate is cooled to room temperature, add 40g/L sodium-chlor and saltout, after filtration, after the washing, drying 2,6-difluorobenzamide product 155.3g, content are 94.6% (wt%).
Embodiment 13
Add 300g deionized water and 75g 2 in 500mL intermittent type autoclave, the 6-difluorobenzonilyile is opened stirring, is warming up to boiling under the normal pressure, opens vent valve 5 minutes, utilizes water vapour to get rid of the interior air of still; Continue to be warming up to 280 ℃ of hydrolysis 5h; Hydrolysate is cooled to room temperature, add 120g/L sodium-chlor and saltout, after filtration, after the washing, drying 2,6-difluorobenzamide product 67.4g, content are 94.7% (wt%).
Embodiment 14
Add 270g deionized water and 90g 2 in 500mL intermittent type autoclave, the 6-difluorobenzonilyile is opened stirring, is warming up to boiling under the normal pressure, opens vent valve 4 minutes, utilizes water vapour to get rid of the interior air of still; Continue to be warming up to 270 ℃ of hydrolysis 6h; Hydrolysate is cooled to room temperature, add 100g/L sodium-chlor and saltout, after filtration, after the washing, drying 2,6-difluorobenzamide product 82.3g, content are 95.8% (wt%).
Embodiment 15
Add 240g deionized water and 120g 2 in 500mL intermittent type autoclave, the 6-difluorobenzonilyile is opened stirring, is warming up to boiling under the normal pressure, opens vent valve 3 minutes, utilizes water vapour to get rid of the interior air of still; Continue to be warming up to 260 ℃ of hydrolysis 7h; Hydrolysate is cooled to room temperature, add 80g/L sodium-chlor and saltout, after filtration, after the washing, drying 2,6-difluorobenzamide product 96.0g, content are 96.2% (wt%).
Embodiment 16
Add 200g deionized water and 200g 2 in 500mL intermittent type autoclave, the 6-difluorobenzonilyile is opened stirring, is warming up to boiling under the normal pressure, opens vent valve 2 minutes, utilizes water vapour to get rid of the interior air of still; Continue to be warming up to 250 ℃ of hydrolysis 8h; Hydrolysate is cooled to room temperature, add 60g/L sodium-chlor and saltout, after filtration, after the washing, drying 2,6-difluorobenzamide product 162.4g, content are 87.9% (wt%).
Claims (4)
1. in the near critical aqueous medium 2,6-difluorobenzonilyile non-catalysis hydrolyzation preparation 2, the method for 6-difluorobenzamide is characterized in that, the step of method is as follows:
1) in autoclave, add deionized water and 2, the 6-difluorobenzonilyile, deionized water and 2,6-difluorobenzonilyile weight ratio is 1: 2～7: 1, opens stirring, is warming up to boiling under the normal pressure, opens vent valve 2-5 minute;
2) continue to be warming up to 200～350 ℃ of hydrolysis 1～10h;
3) hydrolysate is cooled to room temperature, add 10～150g/L sodium-chlor and saltout, after filtration, after the washing, drying 2,6-difluorobenzamide product.
2. in a kind of near critical aqueous medium according to claim 12,6-difluorobenzonilyile non-catalysis hydrolyzation preparation 2, the method for 6-difluorobenzamide is characterized in that described deionized water and 2,6-difluorobenzonilyile weight ratio is 1: 1～4: 1.
3. in a kind of near critical aqueous medium according to claim 12,6-difluorobenzonilyile non-catalysis hydrolyzation preparation 2, the method for 6-difluorobenzamide is characterized in that described hydrolysis temperature is 240～290 ℃.
4. in a kind of near critical aqueous medium according to claim 12,6-difluorobenzonilyile non-catalysis hydrolyzation preparation 2, the method for 6-difluorobenzamide, sodium chloride concentration is 30～100g/L in the step to it is characterized in that saltouing described sodium-chlor.
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| CN113651711A (en) * | 2021-07-28 | 2021-11-16 | 南京硕达生物科技有限公司 | Preparation method of 2, 6-difluorobenzamide |
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| CN87104545A (en) * | 1986-07-02 | 1988-04-27 | 国际壳牌研究公司 | Preparation method of difluorobenzamide |
| CN1277637A (en) * | 1997-10-24 | 2000-12-20 | 罗狄亚化学公司 | Method for preparing a substituted benzamide |
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| CN87104545A (en) * | 1986-07-02 | 1988-04-27 | 国际壳牌研究公司 | Preparation method of difluorobenzamide |
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| CN103232359A (en) * | 2013-05-09 | 2013-08-07 | 温州大学 | Environmental-friendly nitrile hydrolysis method |
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