CN116589393A - Process for producing chlorfenapyr by taking di-n-butylamine as acid binding agent - Google Patents
Process for producing chlorfenapyr by taking di-n-butylamine as acid binding agent Download PDFInfo
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- CN116589393A CN116589393A CN202310570312.5A CN202310570312A CN116589393A CN 116589393 A CN116589393 A CN 116589393A CN 202310570312 A CN202310570312 A CN 202310570312A CN 116589393 A CN116589393 A CN 116589393A
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- butylamine
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- JQVDAXLFBXTEQA-UHFFFAOYSA-N dibutylamine Chemical compound CCCCNCCCC JQVDAXLFBXTEQA-UHFFFAOYSA-N 0.000 title claims abstract description 236
- CWFOCCVIPCEQCK-UHFFFAOYSA-N chlorfenapyr Chemical compound BrC1=C(C(F)(F)F)N(COCC)C(C=2C=CC(Cl)=CC=2)=C1C#N CWFOCCVIPCEQCK-UHFFFAOYSA-N 0.000 title claims abstract description 88
- 238000000034 method Methods 0.000 title claims abstract description 61
- 239000002253 acid Substances 0.000 title claims abstract description 55
- 239000011230 binding agent Substances 0.000 title claims abstract description 54
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 146
- 238000003756 stirring Methods 0.000 claims abstract description 119
- 239000012071 phase Substances 0.000 claims abstract description 91
- 239000012074 organic phase Substances 0.000 claims abstract description 72
- 238000011084 recovery Methods 0.000 claims abstract description 37
- 239000011259 mixed solution Substances 0.000 claims abstract description 24
- XNFIRYXKTXAHAC-UHFFFAOYSA-N tralopyril Chemical compound BrC1=C(C(F)(F)F)NC(C=2C=CC(Cl)=CC=2)=C1C#N XNFIRYXKTXAHAC-UHFFFAOYSA-N 0.000 claims abstract description 19
- 238000010992 reflux Methods 0.000 claims abstract description 16
- HRQGCQVOJVTVLU-UHFFFAOYSA-N bis(chloromethyl) ether Chemical compound ClCOCCl HRQGCQVOJVTVLU-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000003960 organic solvent Substances 0.000 claims abstract description 4
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Natural products CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 95
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 90
- 239000000243 solution Substances 0.000 claims description 58
- 238000001816 cooling Methods 0.000 claims description 50
- 238000004821 distillation Methods 0.000 claims description 43
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 30
- NJSUFZNXBBXAAC-UHFFFAOYSA-N ethanol;toluene Chemical compound CCO.CC1=CC=CC=C1 NJSUFZNXBBXAAC-UHFFFAOYSA-N 0.000 claims description 28
- 239000012046 mixed solvent Substances 0.000 claims description 28
- 239000012535 impurity Substances 0.000 claims description 27
- 238000002156 mixing Methods 0.000 claims description 26
- 238000010438 heat treatment Methods 0.000 claims description 25
- 238000001035 drying Methods 0.000 claims description 14
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 13
- 229910052799 carbon Inorganic materials 0.000 claims description 13
- 238000001914 filtration Methods 0.000 claims description 13
- 238000004519 manufacturing process Methods 0.000 claims description 5
- DHVLDKHFGIVEIP-UHFFFAOYSA-N 2-bromo-2-(bromomethyl)pentanedinitrile Chemical compound BrCC(Br)(C#N)CCC#N DHVLDKHFGIVEIP-UHFFFAOYSA-N 0.000 claims description 3
- 239000007858 starting material Substances 0.000 claims 1
- 125000003944 tolyl group Chemical group 0.000 claims 1
- 238000007599 discharging Methods 0.000 abstract description 14
- 230000015572 biosynthetic process Effects 0.000 abstract description 3
- 238000003786 synthesis reaction Methods 0.000 abstract description 3
- 239000002994 raw material Substances 0.000 abstract 1
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 101
- 238000006243 chemical reaction Methods 0.000 description 99
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 33
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Natural products CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 24
- 230000000052 comparative effect Effects 0.000 description 23
- -1 aryl group pyrrole compound Chemical class 0.000 description 13
- 239000002699 waste material Substances 0.000 description 12
- 239000012267 brine Substances 0.000 description 11
- 159000000000 sodium salts Chemical class 0.000 description 11
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 11
- 239000002351 wastewater Substances 0.000 description 11
- 238000004064 recycling Methods 0.000 description 9
- 238000001514 detection method Methods 0.000 description 6
- 239000007789 gas Substances 0.000 description 6
- 238000009835 boiling Methods 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- XKMRRTOUMJRJIA-UHFFFAOYSA-N ammonia nh3 Chemical compound N.N XKMRRTOUMJRJIA-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000010865 sewage Substances 0.000 description 3
- 230000000895 acaricidal effect Effects 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 230000000749 insecticidal effect Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 230000001988 toxicity Effects 0.000 description 2
- 231100000419 toxicity Toxicity 0.000 description 2
- KAESVJOAVNADME-UHFFFAOYSA-N 1H-pyrrole Natural products C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 description 1
- 241000238876 Acari Species 0.000 description 1
- 244000003416 Asparagus officinalis Species 0.000 description 1
- 235000005340 Asparagus officinalis Nutrition 0.000 description 1
- 241000500437 Plutella xylostella Species 0.000 description 1
- 241000607479 Yersinia pestis Species 0.000 description 1
- 239000000642 acaricide Substances 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 239000003242 anti bacterial agent Substances 0.000 description 1
- 229940088710 antibiotic agent Drugs 0.000 description 1
- 230000001055 chewing effect Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000013505 freshwater Substances 0.000 description 1
- 230000002147 killing effect Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 210000002784 stomach Anatomy 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 230000009885 systemic effect Effects 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D207/00—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom
- C07D207/02—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D207/30—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having two double bonds between ring members or between ring members and non-ring members
- C07D207/34—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having two double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention provides a process for producing chlorfenapyr by taking di-n-butylamine as an acid-binding agent, which comprises the steps of taking 4-bromo-2- (p-chlorophenyl) -5- (trifluoromethyl) -pyrrole-3-nitrile and chloromethyl ether as starting raw materials under the condition of an organic solvent, stirring for at least 0.5 hour under the condition of normal temperature to prepare a mixed solution, then taking di-n-butylamine as the acid-binding agent, refluxing for 2 hours under the condition of 50-60 ℃, adding clear water, stirring, standing, discharging a water phase, and carrying out post-treatment on the rest organic phase to obtain the chlorfenapyr. The invention reduces the comprehensive cost of the chlorfenapyr synthesis process and the acid-binding agent recovery process, and improves the recovery rate of the acid-binding agent.
Description
Technical Field
The invention relates to the technical field of production of chlorfenapyr, in particular to a process for producing chlorfenapyr by taking di-n-butylamine as an acid binding agent.
Background
The chlorfenapyr is an arylpyrrole insecticidal acaricide, and the English common name is: chlorfenapyr, chemical name: 4-bromo-2- (p-chlorophenyl) -1-ethoxymethyl-5- (trifluoromethyl) pyrrole-3-carbonitrile. The chemical structural formula is as follows:
the basic physicochemical data are as follows:
CAS accession number: 122453-73-0; the molecular formula: c (C) 15 H 11 BrCIF 3 N 2 O; relative molecular mass: 407.62; melting point: 91-92 ℃.
The chlorfenapyr is an aryl group pyrrole compound synthesized by modifying natural antibiotics, has high efficiency and broad spectrum, and has stomach toxicity, certain contact killing effect and systemic activity. Has moderate effect on crops, has excellent control effect on boring, piercing and sucking and chewing pests and mites, has special effects on resistant plutella xylostella, asparagus caterpillar and the like, and is a high-efficiency insecticidal and acaricidal agent worthy of research and development.
In the synthetic production of the chlorfenapyr, triethylamine is widely used as an acid binding agent in domestic technology, and the triethylamine is cheap and easy to obtain and is popular. However, the boiling point of triethylamine is only 89 degrees, the triethylamine is easy to volatilize, ammonia taste is heavy, the solubility of the triethylamine in water is 170 g/L20 ℃, distillation operation is carried out in a triethylamine recovery process, a large amount of triethylamine enters tail gas emission, ammonia nitrogen value in water is high, the cost of tail gas treatment and sewage treatment is high, and the recovery rate of the acid-binding agent triethylamine is low.
Disclosure of Invention
In view of the above, the invention provides a process for producing chlorfenapyr by taking di-n-butylamine as an acid binding agent, which reduces the comprehensive cost of the chlorfenapyr synthesis process and the acid binding agent recovery process and improves the recovery rate of the acid binding agent.
In order to achieve the aim, the invention provides a process for producing chlorfenapyr by taking di-n-butylamine as an acid-binding agent, which adopts the following technical scheme:
a process for preparing bromothalonil by using di-n-butylamine as acid-binding agent includes such steps as preparing mixed solution from 4-bromo-2- (p-chlorophenyl) -5- (trifluoromethyl) -pyrrole-3-carbonitrile and chloromethyl ether by stirring at ordinary temp for 0.5 hr, reflux for 2 hr at 50-60 deg.C, adding clear water, stirring, laying aside, discharging water phase and post-treating.
Further, toluene is adopted as the organic solvent, and the molar ratio of the 4-bromo-2- (p-chlorophenyl) -5- (trifluoromethyl) -pyrrole-3-nitrile, chloromethyl ether and toluene is 1:2.5:9.
Further, after the mixed solution is prepared, the temperature is controlled to be 40-50 ℃, and the acid-binding agent di-n-butylamine is added into the mixed solution.
Further, the molar ratio of di-n-butylamine to 4-bromo-2- (p-chlorophenyl) -5- (trifluoromethyl) -pyrrole-3-carbonitrile was 2.2:1.
Further, the mass ratio of the clear water to the mixed solution is (0.65-0.75): 1.
Further, the specific operation steps of the post-treatment are as follows: controlling the temperature to be 50-60 ℃, carrying out reduced pressure distillation on the organic phase until no fraction exists, obtaining a concentrated organic phase, and cooling to 25-30 ℃; then mixing toluene-ethanol mixed solvent with the concentrated organic phase in equal volume, and uniformly stirring to obtain an organic solution; and then cooling the organic solution to 0-5 ℃, and centrifugally drying to obtain the chlorfenapyr.
Further, the temperature was kept at 50℃and the organic phase was distilled under reduced pressure until no fraction was obtained.
Further, after the concentrated organic phase was obtained, the temperature was lowered to 30 ℃.
Further, in the toluene-ethanol mixed solvent, the volume ratio of toluene to ethanol is 1:2.
Further, the recovery method of di-n-butylamine is as follows: firstly, carrying out reduced pressure distillation on the discharged water phase at the temperature of 50-60 ℃ to remove impurities, cooling to 30 ℃ after distillation till no fraction exists, dropwise adding sodium hydroxide solution, stirring simultaneously, detecting the pH value of the water phase, stopping dropwise adding the sodium hydroxide solution when the pH value of the water phase reaches 7-8, continuing stirring for 30 minutes, stopping stirring, standing for layering, separating out the water phase after 1 hour, adding active carbon, stirring and heating to 50 ℃ to adsorb impurities, and filtering to obtain di-n-butylamine.
The technical scheme of the invention at least comprises the following beneficial effects:
1. compared with triethylamine which is an acid binding agent used in the prior art, the method has the advantages that the operation is simple, the acid binding agent adopted in the method is di-n-butylamine, the di-n-butylamine is high-boiling point, not easy to volatilize and low in toxicity, compared with the maximum solubility of triethylamine in water of 170 g/L, the di-n-butylamine only has the solubility of less than 4 g/L, in actual production, the di-n-butylamine is not easy to volatilize at high boiling point, and little residue in water is left, so that the method is a safe, environment-friendly and nontoxic acid compress agent;
2. in the prior art, triethylamine is used as an acid binding agent, the boiling point is only 89 ℃, the triethylamine is volatile, the ammonia taste is heavy, distillation operation is carried out in the synthesis and triethylamine recovery processes, a large amount of triethylamine enters into the tail gas for emission, the ammonia nitrogen value in water is high, the sewage treatment and tail gas treatment costs are very high, the data of many years show that the three wastes generated by single-treatment of triethylamine are on average about 1 ten thousand yuan per ton, the recovery rate of the triethylamine is low, and only about 70 percent.
3. After the mixed solution is prepared, a large amount of heat is released when the acid-binding agent di-n-butylamine is dripped into the mixed solution, the temperature at the stage is controlled to be kept at 40-50 ℃, the temperature at the reflux stage is also controlled to be 50-60 ℃, damage to products caused by overhigh temperature due to large amount of heat release is avoided, the reaction process is prevented from being influenced due to overhigh temperature, and the yield of the chlorfenapyr product is improved;
4. the invention limits the clean water amount used for extracting the di-n-butylamine salt, the mass ratio of the clean water to the mixed solution is (0.65-0.75): 1, ensures that the di-n-butylamine salt is fully extracted, is beneficial to improving the recovery rate of the di-n-butylamine, and simultaneously avoids wasting water resources due to excessive water consumption.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention more clear, the technical solutions of the embodiments of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention. It will be apparent that the described embodiments are some, but not all, embodiments of the invention. All other embodiments, which are obtained by a person skilled in the art based on the described embodiments of the invention, fall within the scope of protection of the invention.
Example 1
The embodiment provides a process for producing chlorfenapyr by taking di-n-butylamine as an acid binding agent, which comprises the following steps:
s1, 10kg of a chlorfenapyr intermediate 4-bromo-2- (p-chlorophenyl) -5- (trifluoromethyl) -pyrrole-3-nitrile and 26kg of toluene are put into a reaction kettle, and stirred at normal temperature for 0.5 hour to be fully mixed;
s2, adding 6.77kg of chloromethyl diethyl ether into the reaction kettle, and continuously stirring for 8 minutes to obtain a mixed solution;
s3, slowly adding 9.2kg of di-n-butylamine into the reaction kettle while continuing stirring, and during the adding process, taking care of cooling the circulating water and controlling the temperature in the reaction kettle to be maintained at 45 ℃;
s4, after the addition is finished, properly heating, controlling the temperature in the reaction kettle to be 50-55 ℃, and refluxing for 2 hours;
s5, adding 30kg of clear water into the reaction kettle, stirring for 0.8 hour, extracting di-n-butylamine salt, fully dissolving the di-n-butylamine salt in the clear water, standing for 2 hours, layering an organic phase and a water phase, discharging the water phase, and leaving the organic phase in the reaction kettle;
s6, controlling the temperature in the reaction kettle to be 50-60 ℃, carrying out reduced pressure distillation on the organic phase until no fraction exists, obtaining a concentrated organic phase, and then cooling to 30 ℃;
s7, mixing toluene and ethanol according to a volume ratio of 1:2 to obtain a toluene-ethanol mixed solvent, mixing 13kg of the toluene-ethanol mixed solvent with the concentrated organic phase obtained in the S6, and uniformly stirring to obtain an organic solution;
s8, cooling the organic solution to 0-5 ℃, and centrifugally drying to obtain the chlorfenapyr, wherein the total amount of the chlorfenapyr is 11.07kg.
The recovery method of di-n-butylamine comprises the following steps: firstly, carrying out reduced pressure distillation on the discharged water phase at 50-60 ℃ to remove impurities, cooling to 30 ℃ after distillation till no fraction exists, dropwise adding sodium hydroxide solution, stirring simultaneously, detecting the pH value of the water phase, stopping dropwise adding the sodium hydroxide solution when the pH value of the water phase reaches 7-8, continuously stirring for 30 minutes, stopping stirring, standing for layering, separating out the water phase after 1 hour, adding active carbon, stirring and heating to 50 ℃ to adsorb impurities, filtering, recovering 8.56kg of di-n-butylamine, wherein the recovery rate is 93%, the detected content is 98%, and the water phase can be recycled.
And (3) adding dilute hydrochloric acid into the separated waste brine under stirring at normal temperature, and adjusting the pH value to 5-6, so that the residual di-n-butylamine and hydrochloric acid can be fully reacted to generate di-n-butylamine salt, and finally, treating the wastewater until the di-n-butylamine salt and the sodium salt are mixed together and are transported in a concentrated way.
Example 2
The embodiment provides a process for producing chlorfenapyr by taking di-n-butylamine as an acid binding agent, which comprises the following steps:
s1, 10kg of a chlorfenapyr intermediate 4-bromo-2- (p-chlorophenyl) -5- (trifluoromethyl) -pyrrole-3-nitrile and 26kg of toluene are put into a reaction kettle, and stirred at normal temperature for 0.5 hour to be fully mixed;
s2, adding 6.77kg of chloromethyl diethyl ether into the reaction kettle, and continuously stirring for 8 minutes to obtain a mixed solution;
s3, slowly adding 9.2kg of di-n-butylamine into the reaction kettle while continuing stirring, and during the adding process, taking care of cooling the circulating water and controlling the temperature in the reaction kettle to be maintained at 40 ℃;
s4, after the addition is finished, properly heating, controlling the temperature in the reaction kettle to be 50-55 ℃, and refluxing for 2 hours;
s5, adding 30kg of clear water into the reaction kettle, stirring for 0.8 hour, extracting di-n-butylamine salt, fully dissolving the di-n-butylamine salt in the clear water, standing for 2 hours, layering an organic phase and a water phase, discharging the water phase, and leaving the organic phase in the reaction kettle;
s6, controlling the temperature in the reaction kettle to be 50-60 ℃, carrying out reduced pressure distillation on the organic phase until no fraction exists, obtaining a concentrated organic phase, and then cooling to 30 ℃;
s7, mixing toluene and ethanol according to a volume ratio of 1:2 to obtain a toluene-ethanol mixed solvent, mixing 13kg of the toluene-ethanol mixed solvent with the concentrated organic phase obtained in the S6, and uniformly stirring to obtain an organic solution;
s8, cooling the organic solution to 0-5 ℃, and centrifugally drying to obtain the chlorfenapyr, wherein the total amount of the chlorfenapyr is 11.04kg.
The recovery method of di-n-butylamine comprises the following steps: firstly, carrying out reduced pressure distillation on the discharged water phase at the temperature of 50-60 ℃ to remove impurities, cooling to 30 ℃ after distillation till no fraction exists, dropwise adding sodium hydroxide solution, stirring simultaneously, detecting the pH value of the water phase, stopping dropwise adding the sodium hydroxide solution when the pH value of the water phase reaches 7-8, continuously stirring for 30 minutes, stopping stirring, standing for layering, separating out the water phase after 1 hour, adding active carbon, stirring and heating to 50 ℃ to adsorb impurities, filtering, recovering 8.52kg of di-n-butylamine, recovering 92.6%, detecting the content to be 97.8%, and recycling.
And (3) adding dilute hydrochloric acid into the separated waste brine under stirring at normal temperature, and adjusting the pH value to 5-6, so that the residual di-n-butylamine and hydrochloric acid can be fully reacted to generate di-n-butylamine salt, and finally, treating the wastewater until the di-n-butylamine salt and the sodium salt are mixed together and are transported in a concentrated way.
Example 3
The embodiment provides a process for producing chlorfenapyr by taking di-n-butylamine as an acid binding agent, which comprises the following steps:
s1, 10kg of a chlorfenapyr intermediate 4-bromo-2- (p-chlorophenyl) -5- (trifluoromethyl) -pyrrole-3-nitrile and 26kg of toluene are put into a reaction kettle, and stirred at normal temperature for 0.5 hour to be fully mixed;
s2, adding 6.77kg of chloromethyl diethyl ether into the reaction kettle, and continuously stirring for 8 minutes to obtain a mixed solution;
s3, slowly adding 9.2kg of di-n-butylamine into the reaction kettle while continuing to stir, wherein in the adding process, the circulating water is cooled, and the temperature in the reaction kettle is controlled to be maintained at 48 ℃;
s4, after the addition is finished, properly heating, controlling the temperature in the reaction kettle to be 50-55 ℃, and refluxing for 2 hours;
s5, adding 30kg of clear water into the reaction kettle, stirring for 0.8 hour, extracting di-n-butylamine salt, fully dissolving the di-n-butylamine salt in the clear water, standing for 2 hours, layering an organic phase and a water phase, discharging the water phase, and leaving the organic phase in the reaction kettle;
s6, controlling the temperature in the reaction kettle to be 50-60 ℃, carrying out reduced pressure distillation on the organic phase until no fraction exists, obtaining a concentrated organic phase, and then cooling to 30 ℃;
s7, mixing toluene and ethanol according to a volume ratio of 1:2 to obtain a toluene-ethanol mixed solvent, mixing 13kg of the toluene-ethanol mixed solvent with the concentrated organic phase obtained in the S6, and uniformly stirring to obtain an organic solution;
s8, cooling the organic solution to 0-5 ℃, and centrifugally drying to obtain the chlorfenapyr, wherein the total amount of the chlorfenapyr is 11.06kg.
The recovery method of di-n-butylamine comprises the following steps: firstly, carrying out reduced pressure distillation on the discharged water phase at the temperature of 50-60 ℃ to remove impurities, cooling to 30 ℃ after distillation till no fraction exists, dropwise adding sodium hydroxide solution, stirring simultaneously, detecting the pH value of the water phase, stopping dropwise adding the sodium hydroxide solution when the pH value of the water phase reaches 7-8, continuously stirring for 30 minutes, stopping stirring, standing for layering, separating out the water phase after 1 hour, adding active carbon, stirring and heating to 50 ℃ to adsorb impurities, filtering, recovering 8.5kg of di-n-butylamine, and recycling the water phase with the detection content of 97.5%.
And (3) adding dilute hydrochloric acid into the separated waste brine under stirring at normal temperature, and adjusting the pH value to 5-6, so that the residual di-n-butylamine and hydrochloric acid can be fully reacted to generate di-n-butylamine salt, and finally, treating the wastewater until the di-n-butylamine salt and the sodium salt are mixed together and are transported in a concentrated way.
Example 4
The embodiment provides a process for producing chlorfenapyr by taking di-n-butylamine as an acid binding agent, which comprises the following steps:
s1, 10kg of a chlorfenapyr intermediate 4-bromo-2- (p-chlorophenyl) -5- (trifluoromethyl) -pyrrole-3-nitrile and 26kg of toluene are put into a reaction kettle, and stirred at normal temperature for 0.5 hour to be fully mixed;
s2, adding 6.77kg of chloromethyl diethyl ether into the reaction kettle, and continuously stirring for 8 minutes to obtain a mixed solution;
s3, slowly adding 9.2kg of di-n-butylamine into the reaction kettle while continuing stirring, and controlling the temperature in the reaction kettle to be 50 ℃ by taking care of cooling the circulating water in the adding process;
s4, after the addition is finished, properly heating, controlling the temperature in the reaction kettle to be 50-55 ℃, and refluxing for 2 hours;
s5, adding 30kg of clear water into the reaction kettle, stirring for 0.8 hour, extracting di-n-butylamine salt, fully dissolving the di-n-butylamine salt in the clear water, standing for 2 hours, layering an organic phase and a water phase, discharging the water phase, and leaving the organic phase in the reaction kettle;
s6, controlling the temperature in the reaction kettle to be 50-60 ℃, carrying out reduced pressure distillation on the organic phase until no fraction exists, obtaining a concentrated organic phase, and then cooling to 30 ℃;
s7, mixing toluene and ethanol according to a volume ratio of 1:2 to obtain a toluene-ethanol mixed solvent, mixing 13kg of the toluene-ethanol mixed solvent with the concentrated organic phase obtained in the S6, and uniformly stirring to obtain an organic solution;
s8, cooling the organic solution to 0-5 ℃, and centrifugally drying to obtain the chlorfenapyr, wherein the total amount of the chlorfenapyr is 11.06kg.
The recovery method of di-n-butylamine comprises the following steps: firstly, carrying out reduced pressure distillation on the discharged water phase at the temperature of 50-60 ℃ to remove impurities, cooling to 30 ℃ after distillation till no fraction exists, dropwise adding sodium hydroxide solution, stirring simultaneously, detecting the pH value of the water phase, stopping dropwise adding the sodium hydroxide solution when the pH value of the water phase reaches 7-8, continuously stirring for 30 minutes, stopping stirring, standing for layering, separating out the water phase after 1 hour, adding active carbon, stirring and heating to 50 ℃ to adsorb impurities, filtering, recovering 8.55kg of di-n-butylamine, wherein the recovery rate is 92.9%, and the detected content is 97.1%, so that the water phase can be recycled.
And (3) adding dilute hydrochloric acid into the separated waste brine under stirring at normal temperature, and adjusting the pH value to 5-6, so that the residual di-n-butylamine and hydrochloric acid can be fully reacted to generate di-n-butylamine salt, and finally, treating the wastewater until the di-n-butylamine salt and the sodium salt are mixed together and are transported in a concentrated way.
Example 5
The embodiment provides a process for producing chlorfenapyr by taking di-n-butylamine as an acid binding agent, which comprises the following steps:
s1, 10kg of a chlorfenapyr intermediate 4-bromo-2- (p-chlorophenyl) -5- (trifluoromethyl) -pyrrole-3-nitrile and 26kg of toluene are put into a reaction kettle, and stirred at normal temperature for 0.5 hour to be fully mixed;
s2, adding 6.77kg of chloromethyl diethyl ether into the reaction kettle, and continuously stirring for 8 minutes to obtain a mixed solution;
s3, slowly adding 9.2kg of di-n-butylamine into the reaction kettle while continuing stirring, and controlling the temperature in the reaction kettle to be maintained between 45 ℃ by taking care of cooling of circulating water in the adding process;
s4, after the addition is finished, properly heating, controlling the temperature in the reaction kettle to be 55-60 ℃, and refluxing for 2 hours;
s5, adding 30kg of clear water into the reaction kettle, stirring for 0.8 hour, extracting di-n-butylamine salt, fully dissolving the di-n-butylamine salt in the clear water, standing for 2 hours, layering an organic phase and a water phase, discharging the water phase, and leaving the organic phase in the reaction kettle;
s6, controlling the temperature in the reaction kettle to be 50-60 ℃, carrying out reduced pressure distillation on the organic phase until no fraction exists, obtaining a concentrated organic phase, and then cooling to 30 ℃;
s7, mixing toluene and ethanol according to a volume ratio of 1:2 to obtain a toluene-ethanol mixed solvent, mixing 13kg of the toluene-ethanol mixed solvent with the concentrated organic phase obtained in the S6, and uniformly stirring to obtain an organic solution;
s8, cooling the organic solution to 0-5 ℃, and centrifugally drying to obtain the chlorfenapyr, wherein the total amount of the chlorfenapyr is 11.03kg.
The recovery method of di-n-butylamine comprises the following steps: firstly, carrying out reduced pressure distillation on the discharged water phase at the temperature of 50-60 ℃ to remove impurities, cooling to 30 ℃ after distillation till no fraction exists, dropwise adding sodium hydroxide solution, stirring simultaneously, detecting the pH value of the water phase, stopping dropwise adding the sodium hydroxide solution when the pH value of the water phase reaches 7-8, continuously stirring for 30 minutes, stopping stirring, standing for layering, separating out the water phase after 1 hour, adding active carbon, stirring and heating to 50 ℃ to adsorb impurities, filtering, recovering 8.42kg of di-n-butylamine, and recycling the water phase with the detection content of 98%.
And (3) adding dilute hydrochloric acid into the separated waste brine under stirring at normal temperature, and adjusting the pH value to 5-6, so that the residual di-n-butylamine and hydrochloric acid can be fully reacted to generate di-n-butylamine salt, and finally, treating the wastewater until the di-n-butylamine salt and the sodium salt are mixed together and are transported in a concentrated way.
Example 6
The embodiment provides a process for producing chlorfenapyr by taking di-n-butylamine as an acid binding agent, which comprises the following steps:
s1, 10kg of a chlorfenapyr intermediate 4-bromo-2- (p-chlorophenyl) -5- (trifluoromethyl) -pyrrole-3-nitrile and 26kg of toluene are put into a reaction kettle, and stirred at normal temperature for 0.5 hour to be fully mixed;
s2, adding 6.77kg of chloromethyl diethyl ether into the reaction kettle, and continuously stirring for 8 minutes to obtain a mixed solution;
s3, slowly adding 9.2kg of di-n-butylamine into the reaction kettle while continuing stirring, and during the adding process, paying attention to cooling the circulating water and controlling the temperature in the reaction kettle to be maintained between 42 ℃;
s4, after the addition is finished, properly heating, controlling the temperature in the reaction kettle to be 55-60 ℃, and refluxing for 2 hours;
s5, adding 30kg of clear water into the reaction kettle, stirring for 0.8 hour, extracting di-n-butylamine salt, fully dissolving the di-n-butylamine salt in the clear water, standing for 2 hours, layering an organic phase and a water phase, discharging the water phase, and leaving the organic phase in the reaction kettle;
s6, controlling the temperature in the reaction kettle to be 50-60 ℃, carrying out reduced pressure distillation on the organic phase until no fraction exists, obtaining a concentrated organic phase, and then cooling to 30 ℃;
s7, mixing toluene and ethanol according to a volume ratio of 1:2 to obtain a toluene-ethanol mixed solvent, mixing 13kg of the toluene-ethanol mixed solvent with the concentrated organic phase obtained in the S6, and uniformly stirring to obtain an organic solution;
s8, cooling the organic solution to 0-5 ℃, and centrifugally drying to obtain the chlorfenapyr, wherein the total amount of the chlorfenapyr is 11.02kg.
The recovery method of di-n-butylamine comprises the following steps: firstly, carrying out reduced pressure distillation on the discharged water phase at the temperature of 50-60 ℃ to remove impurities, cooling to 30 ℃ after distillation till no fraction exists, dropwise adding sodium hydroxide solution, stirring simultaneously, detecting the pH value of the water phase, stopping dropwise adding the sodium hydroxide solution when the pH value of the water phase reaches 7-8, continuously stirring for 30 minutes, stopping stirring, standing for layering, separating out the water phase after 1 hour, adding active carbon, stirring and heating to 50 ℃ to adsorb impurities, filtering, recovering 8.51kg of di-n-butylamine, recovering 92.5%, detecting the content to 97.7%, and recycling.
And (3) adding dilute hydrochloric acid into the separated waste brine under stirring at normal temperature, and adjusting the pH value to 5-6, so that the residual di-n-butylamine and hydrochloric acid can be fully reacted to generate di-n-butylamine salt, and finally, treating the wastewater until the di-n-butylamine salt and the sodium salt are mixed together and are transported in a concentrated way.
Example 7
The embodiment provides a process for producing chlorfenapyr by taking di-n-butylamine as an acid binding agent, which comprises the following steps:
s1, 10kg of a chlorfenapyr intermediate 4-bromo-2- (p-chlorophenyl) -5- (trifluoromethyl) -pyrrole-3-nitrile and 26kg of toluene are put into a reaction kettle, and stirred at normal temperature for 0.5 hour to be fully mixed;
s2, adding 6.77kg of chloromethyl diethyl ether into the reaction kettle, and continuously stirring for 8 minutes to obtain a mixed solution;
s3, slowly adding 9.2kg of di-n-butylamine into the reaction kettle while continuing stirring, and controlling the temperature in the reaction kettle to be maintained between 48 ℃ by taking care of cooling of circulating water in the adding process;
s4, after the addition is finished, properly heating, controlling the temperature in the reaction kettle to be 55-60 ℃, and refluxing for 2 hours;
s5, adding 30kg of clear water into the reaction kettle, stirring for 0.8 hour, extracting di-n-butylamine salt, fully dissolving the di-n-butylamine salt in the clear water, standing for 2 hours, layering an organic phase and a water phase, discharging the water phase, and leaving the organic phase in the reaction kettle;
s6, controlling the temperature in the reaction kettle to be 50-60 ℃, carrying out reduced pressure distillation on the organic phase until no fraction exists, obtaining a concentrated organic phase, and then cooling to 30 ℃;
s7, mixing toluene and ethanol according to a volume ratio of 1:2 to obtain a toluene-ethanol mixed solvent, mixing 13kg of the toluene-ethanol mixed solvent with the concentrated organic phase obtained in the S6, and uniformly stirring to obtain an organic solution;
s8, cooling the organic solution to 0-5 ℃, and centrifugally drying to obtain the chlorfenapyr, wherein the total amount of the chlorfenapyr is 11.05kg.
The recovery method of di-n-butylamine comprises the following steps: firstly, carrying out reduced pressure distillation on the discharged water phase at the temperature of 50-60 ℃ to remove impurities, cooling to 30 ℃ after distillation till no fraction exists, dropwise adding sodium hydroxide solution, stirring simultaneously, detecting the pH value of the water phase, stopping dropwise adding the sodium hydroxide solution when the pH value of the water phase reaches 7-8, continuously stirring for 30 minutes, stopping stirring, standing for layering, separating out the water phase after 1 hour, adding active carbon, stirring and heating to 50 ℃ to adsorb impurities, filtering, recovering 8.44kg of di-n-butylamine, and recycling the water phase with the detection content of 97.8%.
And (3) adding dilute hydrochloric acid into the separated waste brine under stirring at normal temperature, and adjusting the pH value to 5-6, so that the residual di-n-butylamine and hydrochloric acid can be fully reacted to generate di-n-butylamine salt, and finally, treating the wastewater until the di-n-butylamine salt and the sodium salt are mixed together and are transported in a concentrated way.
Example 8
The embodiment provides a process for producing chlorfenapyr by taking di-n-butylamine as an acid binding agent, which comprises the following steps:
s1, 10kg of a chlorfenapyr intermediate 4-bromo-2- (p-chlorophenyl) -5- (trifluoromethyl) -pyrrole-3-nitrile and 26kg of toluene are put into a reaction kettle, and stirred at normal temperature for 0.5 hour to be fully mixed;
s2, adding 6.77kg of chloromethyl diethyl ether into the reaction kettle, and continuously stirring for 8 minutes to obtain a mixed solution;
s3, slowly adding 9.2kg of di-n-butylamine into the reaction kettle while continuing stirring, and during the adding process, taking care of cooling the circulating water and controlling the temperature in the reaction kettle to be maintained at 45 ℃;
s4, after the addition is finished, properly heating, controlling the temperature in the reaction kettle to be 50-55 ℃, and refluxing for 2 hours;
s5, adding 28kg of clear water into the reaction kettle, stirring for 0.8 hour, extracting di-n-butylamine salt, fully dissolving the di-n-butylamine salt in the clear water, standing for 2 hours, layering an organic phase and a water phase, discharging the water phase, and leaving the organic phase in the reaction kettle;
s6, controlling the temperature in the reaction kettle to be 50-60 ℃, carrying out reduced pressure distillation on the organic phase until no fraction exists, obtaining a concentrated organic phase, and then cooling to 30 ℃;
s7, mixing toluene and ethanol according to a volume ratio of 1:2 to obtain a toluene-ethanol mixed solvent, mixing 13kg of the toluene-ethanol mixed solvent with the concentrated organic phase obtained in the S6, and uniformly stirring to obtain an organic solution;
s8, cooling the organic solution to 0-5 ℃, and centrifugally drying to obtain the chlorfenapyr, wherein the total amount of the chlorfenapyr is 11.06kg.
The recovery method of di-n-butylamine comprises the following steps: firstly, carrying out reduced pressure distillation on the discharged water phase at the temperature of 50-60 ℃ to remove impurities, cooling to 30 ℃ after distillation till no fraction exists, dropwise adding sodium hydroxide solution, stirring simultaneously, detecting the pH value of the water phase, stopping dropwise adding the sodium hydroxide solution when the pH value of the water phase reaches 7-8, continuously stirring for 30 minutes, stopping stirring, standing for layering, separating out the water phase after 1 hour, adding active carbon, stirring and heating to 50 ℃ to adsorb impurities, filtering, recovering 8.51kg of di-n-butylamine, recovering 92.5%, detecting the content to 97.7%, and recycling.
And (3) adding dilute hydrochloric acid into the separated waste brine under stirring at normal temperature, and adjusting the pH value to 5-6, so that the residual di-n-butylamine and hydrochloric acid can be fully reacted to generate di-n-butylamine salt, and finally, treating the wastewater until the di-n-butylamine salt and the sodium salt are mixed together and are transported in a concentrated way.
Comparative example 1
The comparative example provides a process for producing chlorfenapyr by using triethylamine as an acid binding agent, which comprises the following steps:
s1, 10kg of a chlorfenapyr intermediate 4-bromo-2- (p-chlorophenyl) -5- (trifluoromethyl) -pyrrole-3-nitrile, 7.44kg of chloromethyl diethyl ether and 26kg of toluene are put into a reaction kettle;
s2, heating the temperature in the reaction kettle to 50 ℃, and stirring for 0.5 hour to enable the substrate to be fully dissolved in toluene as a solvent to obtain a mixed solution;
s3, slowly dripping 7.22kg of triethylamine into the reaction kettle, wherein in the process, the temperature of circulating water is reduced, and the temperature in the reaction kettle is controlled to be preferably 50 ℃;
s4, controlling the temperature in the reaction kettle to be 50-55 ℃, and refluxing for 2 hours;
s5, adding 30kg of clear water into the reaction kettle, stirring for 0.5 hour, extracting triethylamine salt, fully transferring and dissolving the triethylamine salt in the water, standing for 2 hours, layering an organic phase and a water phase, discharging the water phase, and leaving the organic phase in the reaction kettle;
s6, controlling the temperature in the reaction kettle to be kept at 50 ℃, carrying out reduced pressure distillation on the organic phase until no fraction exists, obtaining a concentrated organic phase, and cooling to room temperature of 25 ℃;
s7, mixing toluene and ethanol according to a volume ratio of 1:2 to obtain a toluene-ethanol mixed solvent, mixing the toluene-ethanol mixed solvent with the concentrated organic phase in equal volume, and uniformly stirring to obtain an organic solution;
s8, cooling the organic solution to 0-5 ℃, and centrifugally drying to obtain the chlorfenapyr, wherein the total amount of the chlorfenapyr is 11.05kg.
The method for recovering triethylamine comprises the following steps: and S5, distilling the water phase discharged by about 50 ℃ under reduced pressure until no obvious distillate is distilled, wherein the distillate mainly comprises water, toluene, ethanol and other organic volatile impurities, then dropwise adding sodium hydroxide solution into the water phase, stirring at the same time, detecting the pH value of the water phase, stopping dropwise adding the sodium hydroxide solution when the pH value of the water phase reaches 7-8, standing at room temperature for 1 hour, distilling at normal pressure until the triethylamine and the water are separated, stirring at the same time until no distillate is obtained, distilling the distillate, namely crude triethylamine, circulating the crude triethylamine through a sodium hydroxide bed, absorbing the water by using sodium hydroxide, continuously and circularly washing for 1 hour, obtaining 5.05 kg of triethylamine, and repeatedly applying the triethylamine with the recovery rate of 69.9 percent and the detected triethylamine content of about 95 percent.
This comparative example differs from example 1 only in that: the acid-binding agent in this comparative example was triethylamine, and the acid-binding agent in example 1 was di-n-butylamine.
Comparison results: the yield of chlorfenapyr in this comparative example was 11.05kg, and the yield of chlorfenapyr in example 1 was 11.07kg, which revealed that the yield of chlorfenapyr in this comparative example was slightly lower than that in example 1;
the recovery rate of the acid-binding agent triethylamine in this comparative example was 5.05 kg, the recovery rate was 69.9%, and the recovery rate of the acid-binding agent di-n-butylamine in example 1 was 8.56kg, and the recovery rate was 93%, whereby the recovery rate of the acid-binding agent triethylamine in this comparative example was significantly lower than that of the acid-binding agent di-n-butylamine in example 1. The method is mainly characterized in that the boiling point of triethylamine is only 89 degrees, the triethylamine is easy to volatilize, distillation operation is carried out in both the process of organically synthesizing the chlorfenapyr and the process of recovering the acid binding agent, a large amount of triethylamine enters into tail gas emission, the triethylamine is wasted, and the recovery rate of the triethylamine is low. Meanwhile, the ammonia nitrogen value in water is high, and the cost of tail gas treatment and sewage treatment is high.
Comparative example 2
The comparative example provides a process for producing chlorfenapyr by taking di-n-butylamine as an acid binding agent, which comprises the following steps:
s1, 10kg of a chlorfenapyr intermediate 4-bromo-2- (p-chlorophenyl) -5- (trifluoromethyl) -pyrrole-3-nitrile and 26kg of toluene are put into a reaction kettle, and stirred at normal temperature for 0.5 hour to be fully mixed;
s2, adding 6.77kg of chloromethyl diethyl ether into the reaction kettle, and continuously stirring for 8 minutes to obtain a mixed solution;
s3, slowly adding 9.2kg of di-n-butylamine into the reaction kettle while continuing to stir, wherein in the adding process, the temperature of circulating water is controlled to be reduced, and the temperature in the reaction kettle is controlled to be maintained at 55 ℃;
s4, after the addition is finished, properly heating, controlling the temperature in the reaction kettle to be 60-65 ℃, and refluxing for 2 hours;
s5, adding 30kg of clear water into the reaction kettle, stirring for 0.8 hour, extracting di-n-butylamine salt, fully dissolving the di-n-butylamine salt in the clear water, standing for 2 hours, layering an organic phase and a water phase, discharging the water phase, and leaving the organic phase in the reaction kettle;
s6, controlling the temperature in the reaction kettle to be 50-60 ℃, carrying out reduced pressure distillation on the organic phase until no fraction exists, obtaining a concentrated organic phase, and then cooling to 30 ℃;
s7, mixing toluene and ethanol according to a volume ratio of 1:2 to obtain a toluene-ethanol mixed solvent, mixing 13kg of the toluene-ethanol mixed solvent with the concentrated organic phase obtained in the S6, and uniformly stirring to obtain an organic solution;
s8, cooling the organic solution to 0-5 ℃, and centrifugally drying to obtain the chlorfenapyr, wherein the total amount of the chlorfenapyr is 10.37kg.
The recovery method of di-n-butylamine comprises the following steps: firstly, carrying out reduced pressure distillation on the discharged water phase at the temperature of 50-60 ℃ to remove impurities, cooling to 30 ℃ after distillation till no fraction exists, dropwise adding sodium hydroxide solution, stirring simultaneously, detecting the pH value of the water phase, stopping dropwise adding the sodium hydroxide solution when the pH value of the water phase reaches 7-8, continuously stirring for 30 minutes, stopping stirring, standing for layering, separating out the water phase after 1 hour, adding active carbon, stirring and heating to 50 ℃ to adsorb impurities, filtering, recovering 8.49kg of di-n-butylamine, and recycling the water phase with the detection content of 97.9%.
And (3) adding dilute hydrochloric acid into the separated waste brine under stirring at normal temperature, and adjusting the pH value to 5-6, so that the residual di-n-butylamine and hydrochloric acid can be fully reacted to generate di-n-butylamine salt, and finally, treating the wastewater until the di-n-butylamine salt and the sodium salt are mixed together and are transported in a concentrated way.
This comparative example differs from example 1 only in that: the control temperatures during both S3 and S4 are outside the protective (limiting) range of the present invention.
Comparison results: the yield of chlorfenapyr in this comparative example was 10.37kg, and the yield of chlorfenapyr in example 1 was 11.07kg, whereby it was found that the yield of chlorfenapyr in this comparative example was significantly lower than that in example 1. Indicating that too high a reaction temperature would decrease the yield of chlorfenapyr.
Comparative example 3
The comparative example provides a process for producing chlorfenapyr by taking di-n-butylamine as an acid binding agent, which comprises the following steps:
s1, 10kg of a chlorfenapyr intermediate 4-bromo-2- (p-chlorophenyl) -5- (trifluoromethyl) -pyrrole-3-nitrile and 26kg of toluene are put into a reaction kettle, and stirred at normal temperature for 0.5 hour to be fully mixed;
s2, adding 6.77kg of chloromethyl diethyl ether into the reaction kettle, and continuously stirring for 8 minutes to obtain a mixed solution;
s3, slowly adding 9.2kg of di-n-butylamine into the reaction kettle while continuing stirring, and during the adding process, taking care of cooling the circulating water and controlling the temperature in the reaction kettle to be maintained at 35 ℃;
s4, after the addition is finished, properly heating, controlling the temperature in the reaction kettle to be 40-45 ℃, and refluxing for 2 hours;
s5, adding 30kg of clear water into the reaction kettle, stirring for 0.8 hour, extracting di-n-butylamine salt, fully dissolving the di-n-butylamine salt in the clear water, standing for 2 hours, layering an organic phase and a water phase, discharging the water phase, and leaving the organic phase in the reaction kettle;
s6, controlling the temperature in the reaction kettle to be 50-60 ℃, carrying out reduced pressure distillation on the organic phase until no fraction exists, obtaining a concentrated organic phase, and then cooling to 30 ℃;
s7, mixing toluene and ethanol according to a volume ratio of 1:2 to obtain a toluene-ethanol mixed solvent, mixing 13kg of the toluene-ethanol mixed solvent with the concentrated organic phase obtained in the S6, and uniformly stirring to obtain an organic solution;
s8, cooling the organic solution to 0-5 ℃, and centrifugally drying to obtain the chlorfenapyr, wherein the total amount of the chlorfenapyr is 10.31kg.
The recovery method of di-n-butylamine comprises the following steps: firstly, carrying out reduced pressure distillation on the discharged water phase at the temperature of 50-60 ℃ to remove impurities, cooling to 30 ℃ after distillation till no fraction exists, dropwise adding sodium hydroxide solution, stirring simultaneously, detecting the pH value of the water phase, stopping dropwise adding the sodium hydroxide solution when the pH value of the water phase reaches 7-8, continuously stirring for 30 minutes, stopping stirring, standing for layering, separating out the water phase after 1 hour, adding active carbon, stirring and heating to 50 ℃ to adsorb impurities, filtering, recovering 8.44kg of di-n-butylamine, and recycling the water phase with the detection content of 97.9%.
And (3) adding dilute hydrochloric acid into the separated waste brine under stirring at normal temperature, and adjusting the pH value to 5-6, so that the residual di-n-butylamine and hydrochloric acid can be fully reacted to generate di-n-butylamine salt, and finally, treating the wastewater until the di-n-butylamine salt and the sodium salt are mixed together and are transported in a concentrated way.
This comparative example differs from example 1 only in that: the control temperatures during both S3 and S4 are below the protection (limit) range of the present invention.
Comparison results: the yield of chlorfenapyr in this comparative example was 10.31kg, and the yield of chlorfenapyr in example 1 was 11.07kg, whereby it was found that the yield of chlorfenapyr in this comparative example was significantly lower than that in example 1. Indicating that too low a reaction temperature would decrease the yield of chlorfenapyr.
Comparative example 4
The comparative example provides a process for producing chlorfenapyr by taking di-n-butylamine as an acid binding agent, which comprises the following steps:
s1, 10kg of a chlorfenapyr intermediate 4-bromo-2- (p-chlorophenyl) -5- (trifluoromethyl) -pyrrole-3-nitrile and 26kg of toluene are put into a reaction kettle, and stirred at normal temperature for 0.5 hour to be fully mixed;
s2, adding 6.77kg of chloromethyl diethyl ether into the reaction kettle, and continuously stirring for 8 minutes to obtain a mixed solution;
s3, slowly adding 9.2kg of di-n-butylamine into the reaction kettle while continuing stirring, and during the adding process, taking care of cooling the circulating water and controlling the temperature in the reaction kettle to be maintained at 45 ℃;
s4, after the addition is finished, properly heating, controlling the temperature in the reaction kettle to be 50-55 ℃, and refluxing for 2 hours;
s5, adding 20kg of clear water into the reaction kettle, stirring for 0.8 hour, extracting di-n-butylamine salt, fully dissolving the di-n-butylamine salt in the clear water, standing for 2 hours, layering an organic phase and a water phase, discharging the water phase, and leaving the organic phase in the reaction kettle;
s6, controlling the temperature in the reaction kettle to be 50-60 ℃, carrying out reduced pressure distillation on the organic phase until no fraction exists, obtaining a concentrated organic phase, and then cooling to 30 ℃;
s7, mixing toluene and ethanol according to a volume ratio of 1:2 to obtain a toluene-ethanol mixed solvent, mixing 13kg of the toluene-ethanol mixed solvent with the concentrated organic phase obtained in the S6, and uniformly stirring to obtain an organic solution;
s8, cooling the organic solution to 0-5 ℃, and centrifugally drying to obtain the chlorfenapyr, wherein the total amount of the chlorfenapyr is 11.06kg.
The recovery method of di-n-butylamine comprises the following steps: firstly, carrying out reduced pressure distillation on the discharged water phase at the temperature of 50-60 ℃ to remove impurities, cooling to 30 ℃ after distillation till no fraction exists, dropwise adding sodium hydroxide solution, stirring simultaneously, detecting the pH value of the water phase, stopping dropwise adding the sodium hydroxide solution when the pH value of the water phase reaches 7-8, continuing stirring for 30 minutes, stopping stirring, standing for layering, separating out the water phase after 1 hour, adding active carbon, stirring and heating to 50 ℃ to adsorb impurities, filtering, recovering 7.98kg of di-n-butylamine, and recycling the water phase with the detection content of 97.1 percent.
And (3) adding dilute hydrochloric acid into the separated waste brine under stirring at normal temperature, and adjusting the pH value to 5-6, so that the residual di-n-butylamine and hydrochloric acid can be fully reacted to generate di-n-butylamine salt, and finally, treating the wastewater until the di-n-butylamine salt and the sodium salt are mixed together and are transported in a concentrated way.
This comparative example differs from example 1 only in that: the amount of fresh water added in S5 is below the protection (limit) range of the invention.
Comparison results: the recovery rate of the acid-binding agent di-n-butylamine in this comparative example was 7.98kg, the recovery rate was 86.7%, and the recovery rate of the acid-binding agent di-n-butylamine in example 1 was 8.56kg, and the recovery rate was 93%, whereby the recovery rate of the acid-binding agent di-n-butylamine in this comparative example was significantly lower than that in example 1. The result shows that the recovery rate of the acid-binding agent di-n-butylamine is reduced due to the too small amount of clear water used for extraction.
The foregoing is a preferred embodiment of the present invention and it should be noted that modifications and adaptations to those skilled in the art may be made without departing from the principles of the present invention and are intended to be comprehended within the scope of the present invention.
Claims (10)
1. A process for preparing chlorfenapyr by taking di-n-butylamine as an acid-binding agent is characterized in that 4-bromo-2- (p-chlorophenyl) -5- (trifluoromethyl) -pyrrole-3-nitrile and chloromethyl ether are taken as starting materials under the condition of an organic solvent, at least stirred for 0.5 hour under the condition of normal temperature to prepare a mixed solution, then the di-n-butylamine is taken as the acid-binding agent, reflux is carried out for 2 hours under the condition of 50-60 ℃, clear water is added, stirring is carried out, water phase is discharged after standing, and the rest organic phase is subjected to post treatment to obtain the chlorfenapyr.
2. The process for producing the chlorfenapyr by taking di-n-butylamine as an acid-binding agent according to claim 1, wherein the organic solvent is toluene, and the molar ratio of the 4-bromo-2- (p-chlorophenyl) -5- (trifluoromethyl) -pyrrole-3-nitrile, chloromethyl ether and toluene is 1:2.5:9.
3. The process for producing chlorfenapyr using di-n-butylamine as an acid-binding agent according to claim 1, wherein after preparing the mixed solution, the temperature is controlled to be 40-50 ℃, and the acid-binding agent di-n-butylamine is added into the mixed solution.
4. The process for producing a bromothalonil using di-n-butylamine as an acid-binding agent according to claim 1, wherein the molar ratio of di-n-butylamine to 4-bromo-2- (p-chlorophenyl) -5- (trifluoromethyl) -pyrrole-3-carbonitrile is 2.2:1.
5. The process for producing the chlorfenapyr by taking di-n-butylamine as an acid-binding agent according to claim 1, wherein the mass ratio of the clear water to the mixed solution is (0.65-0.75): 1.
6. The process for producing the chlorfenapyr by taking di-n-butylamine as an acid-binding agent according to claim 1, wherein the specific operation steps of the post-treatment are as follows: controlling the temperature to be 50-60 ℃, carrying out reduced pressure distillation on the organic phase until no fraction exists, obtaining a concentrated organic phase, and cooling to 25-30 ℃; then mixing toluene-ethanol mixed solvent with the concentrated organic phase in equal volume, and uniformly stirring to obtain an organic solution; and then cooling the organic solution to 0-5 ℃, and centrifugally drying to obtain the chlorfenapyr.
7. The process for producing a bromothalonil by using di-n-butylamine as an acid-binding agent according to claim 6, wherein the temperature is controlled to be 50 ℃, and the organic phase is distilled under reduced pressure until no fraction is obtained.
8. The process for producing chlorfenapyr using di-n-butylamine as an acid-binding agent according to claim 6, wherein the concentrated organic phase is obtained and cooled to 30 ℃.
9. The process for producing the chlorfenapyr by taking di-n-butylamine as an acid-binding agent according to claim 6, wherein the volume ratio of toluene to ethanol in the toluene-ethanol mixed solvent is 1:2.
10. The process for producing chlorfenapyr by using di-n-butylamine as an acid-binding agent according to any one of claims 1 to 9, wherein the recovery method of di-n-butylamine is as follows: firstly, carrying out reduced pressure distillation on the discharged water phase at the temperature of 50-60 ℃ to remove impurities, cooling to 30 ℃ after distillation till no fraction exists, dropwise adding sodium hydroxide solution, stirring simultaneously, detecting the pH value of the water phase, stopping dropwise adding the sodium hydroxide solution when the pH value of the water phase reaches 7-8, continuing stirring for 30 minutes, stopping stirring, standing for layering, separating out the water phase after 1 hour, adding active carbon, stirring and heating to 50 ℃ to adsorb impurities, and filtering to obtain di-n-butylamine.
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