CN112608268A - Method for producing chlorfenapyr intermediate pyrrole by using solvent DMF to replace acetonitrile - Google Patents
Method for producing chlorfenapyr intermediate pyrrole by using solvent DMF to replace acetonitrile Download PDFInfo
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- CN112608268A CN112608268A CN202011527298.3A CN202011527298A CN112608268A CN 112608268 A CN112608268 A CN 112608268A CN 202011527298 A CN202011527298 A CN 202011527298A CN 112608268 A CN112608268 A CN 112608268A
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- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 title claims abstract description 267
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-dimethylformamide Substances CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 title claims abstract description 144
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 title claims abstract description 78
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 55
- 239000002904 solvent Substances 0.000 title claims abstract description 45
- 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 40
- 238000006243 chemical reaction Methods 0.000 claims abstract description 56
- 238000009833 condensation Methods 0.000 claims abstract description 38
- 230000005494 condensation Effects 0.000 claims abstract description 38
- 238000004321 preservation Methods 0.000 claims abstract description 13
- 238000000605 extraction Methods 0.000 claims abstract description 9
- 238000005070 sampling Methods 0.000 claims description 22
- -1 p-chlorphenyl Chemical group 0.000 claims description 20
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 18
- 239000000463 material Substances 0.000 claims description 14
- 239000000203 mixture Substances 0.000 claims description 14
- 238000010438 heat treatment Methods 0.000 claims description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical group CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 12
- 239000002253 acid Substances 0.000 claims description 12
- 239000011230 binding agent Substances 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 11
- VEFXTGTZJOWDOF-UHFFFAOYSA-N benzene;hydrate Chemical compound O.C1=CC=CC=C1 VEFXTGTZJOWDOF-UHFFFAOYSA-N 0.000 claims description 10
- 238000004458 analytical method Methods 0.000 claims description 9
- OYUNTGBISCIYPW-UHFFFAOYSA-N 2-chloroprop-2-enenitrile Chemical compound ClC(=C)C#N OYUNTGBISCIYPW-UHFFFAOYSA-N 0.000 claims description 8
- 238000007273 lactonization reaction Methods 0.000 claims description 6
- 150000003839 salts Chemical class 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 3
- 238000007710 freezing Methods 0.000 claims description 2
- 230000008014 freezing Effects 0.000 claims description 2
- HFTPOTIPYBZVSL-UHFFFAOYSA-N 4-(4-chlorophenyl)-2-(trifluoromethyl)-2h-1,3-oxazol-5-one Chemical compound FC(F)(F)C1OC(=O)C(C=2C=CC(Cl)=CC=2)=N1 HFTPOTIPYBZVSL-UHFFFAOYSA-N 0.000 claims 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims 1
- 238000006073 displacement reaction Methods 0.000 claims 1
- 238000005086 pumping Methods 0.000 claims 1
- 239000011780 sodium chloride Substances 0.000 claims 1
- 238000007363 ring formation reaction Methods 0.000 abstract description 8
- 230000009286 beneficial effect Effects 0.000 abstract description 3
- 238000000034 method Methods 0.000 description 14
- 238000001816 cooling Methods 0.000 description 7
- 230000008569 process Effects 0.000 description 7
- 230000000694 effects Effects 0.000 description 5
- 125000003854 p-chlorophenyl group Chemical group [H]C1=C([H])C(*)=C([H])C([H])=C1Cl 0.000 description 5
- 238000011084 recovery Methods 0.000 description 5
- 239000002699 waste material Substances 0.000 description 5
- 241000238631 Hexapoda Species 0.000 description 3
- 241000607479 Yersinia pestis Species 0.000 description 3
- 238000009835 boiling Methods 0.000 description 3
- 239000012267 brine Substances 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 238000003912 environmental pollution Methods 0.000 description 3
- 230000000749 insecticidal effect Effects 0.000 description 3
- 239000002917 insecticide Substances 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000005893 bromination reaction Methods 0.000 description 2
- 210000004027 cell Anatomy 0.000 description 2
- 238000004807 desolvation Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 231100000086 high toxicity Toxicity 0.000 description 2
- LELOWRISYMNNSU-UHFFFAOYSA-N hydrogen cyanide Chemical compound N#C LELOWRISYMNNSU-UHFFFAOYSA-N 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 239000013067 intermediate product Substances 0.000 description 2
- 238000004811 liquid chromatography Methods 0.000 description 2
- 210000003470 mitochondria Anatomy 0.000 description 2
- 239000000575 pesticide Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 206010010071 Coma Diseases 0.000 description 1
- XZMCDFZZKTWFGF-UHFFFAOYSA-N Cyanamide Chemical compound NC#N XZMCDFZZKTWFGF-UHFFFAOYSA-N 0.000 description 1
- 206010067482 No adverse event Diseases 0.000 description 1
- 102000004316 Oxidoreductases Human genes 0.000 description 1
- 108090000854 Oxidoreductases Proteins 0.000 description 1
- 206010033799 Paralysis Diseases 0.000 description 1
- 206010034133 Pathogen resistance Diseases 0.000 description 1
- 230000000895 acaricidal effect Effects 0.000 description 1
- 239000000642 acaricide Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 201000010099 disease Diseases 0.000 description 1
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 230000005923 long-lasting effect Effects 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000005645 nematicide Substances 0.000 description 1
- 231100000989 no adverse effect Toxicity 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000010627 oxidative phosphorylation Effects 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 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
Abstract
The invention provides a method for producing a chlorfenapyr intermediate pyrrole by using a solvent DMF (dimethyl formamide) instead of acetonitrile. The method for producing the chlorfenapyr intermediate pyrrole by using the solvent DMF to replace acetonitrile comprises the following steps: extraction and replacement, heat preservation reaction, condensation and desolventizing. The invention has the beneficial effects that: the reaction temperature of the pyrrole cyclization reaction for preparing the intermediate is increased to 80 ℃, the yield is increased to more than 90% in a breakthrough manner, the consumed solvent amount is reduced by more than 30%, the production cost is reduced by about 86%, the production cost is greatly reduced, and the production burden of enterprises is reduced.
Description
Technical Field
The invention relates to the field of chlorfenapyr production, in particular to a method for producing chlorfenapyr intermediate pyrrole by using a solvent DMF (dimethyl formamide) to replace acetonitrile.
Background
Chlorfenapyr, english name Chlorfenapyr, chinese general name Chlorfenapyr. Is a novel heterocyclic insecticide, acaricide and nematicide developed successfully by cyanamide company in the United states. With the advent of national high-toxicity pesticide substitution policies and the improvement of environmental awareness of people, low-toxicity and high-efficiency chlorfenapyr is also receiving more and more attention as a representative of recommended pesticide varieties for controlling diseases and pests of pollution-free agricultural products.
Chlorfenapyr, which belongs to the class of arylpyrrole compounds, has no toxic effect on insects. After feeding or contacting with chlorfenapyr in the insect body, the chlorfenapyr is converted into a specific insecticidal active compound under the action of a multifunctional oxidase, and the target of the compound is mitochondria in the cells of the insect body. The cell synthesis stops the life function due to the lack of energy, and the pests become weak in activity, appear speckles, change in color, stop in activity, coma, paralysis and softness after insecticide injection, and finally die. The insecticidal mechanism is to block the oxidative phosphorylation of mitochondria.
At present, the chlorfenapyr has the characteristics of high activity, long lasting period, wide insecticidal spectrum, high activity, safety to beneficial organisms, environmental friendliness and the like, has no cross resistance with other insecticides, and has important significance for preventing and controlling resistant pests, delaying resistance generation and replacing high-toxicity varieties.
The synthesis process of the chlorfenapyr mainly comprises the following reaction processes: 1. the lactonization reaction is used for preparing 4- (p-chlorphenyl) -2-trifluoromethyl-3-oxazoline-5-ketone, and the chemical reaction equation is as follows:
2. pyrrole (cyclization) reaction for preparing intermediate 2- (4-chlorphenyl) -5-trifluoromethyl-3-nitrile has the following chemical reaction equation:
the applicant finds that the solvent adopted in the pyrrole (cyclization) reaction for preparing the intermediate is acetonitrile with a low boiling point, so that the reaction temperature cannot be raised to 80 ℃, the conversion is not complete and incomplete in the later stage of the reaction, the yield of the intermediate product is always lower than 85%, and the product cannot be effectively raised, so that the problem of restricting the production of the chlorfenapyr is solved. Furthermore, due to the defect of low boiling point of the acetonitrile, the recovery loss is large in the later recovery process; not only causes the waste of resources, but also increases the production cost of production enterprises. Meanwhile, the acetonitrile is flammable, harmful and unstable, so that the danger coefficient is high; in addition, in the desolventizing process, if the operation is not proper, the highly toxic hydrogen cyanide is easily decomposed and generated, and great potential safety hazards are caused to production workers.
Disclosure of Invention
In order to solve the technical problems in the prior art, the invention provides a method for producing a chlorfenapyr intermediate pyrrole by using a solvent DMF to replace acetonitrile, which aims to realize the following purposes:
(1) the method solves the problems that the reaction temperature cannot be raised to 80 ℃ due to the self-characteristic limitation of acetonitrile, so that the conversion in the later stage of the reaction is incomplete, the yield of intermediate products is always lower than 85%, and the yield cannot be effectively improved.
(2) The problems of large recovery loss, resource waste and increased production cost of acetonitrile in the later recovery process are solved.
(3) The problem that acetonitrile is flammable, harmful and easy to decompose in the production and application process, and causes great potential safety hazard to production workers is solved.
In order to solve the technical problems, the technical scheme adopted by the invention is as follows:
a method for producing a chlorfenapyr intermediate pyrrole by using a solvent DMF to replace acetonitrile adopts DMF to replace acetonitrile as the solvent.
The method for producing the chlorfenapyr intermediate pyrrole by using the solvent DMF to replace acetonitrile comprises the following steps: extraction and replacement, heat preservation reaction, condensation and desolventizing.
After the extraction replacement and the lactonization reaction are finished, removing acetonitrile;
removing acetonitrile, keeping the vacuum degree at-0.1 MPa, heating to 65 ℃, and removing acetonitrile;
and removing acetonitrile, sampling and detecting the acetonitrile content when the temperature is raised to 65 ℃, and carrying out the following treatment according to the acetonitrile content:
a. if the acetonitrile content is less than 1%, removing the acetonitrile;
b. and if the acetonitrile content is more than or equal to 1 percent, continuously preserving the heat and removing for 10-20min, sampling again to detect the acetonitrile content, and carrying out a or b treatment according to the acetonitrile content.
The extraction and replacement further comprises: after removing acetonitrile, adding a benzene-water mixture, heating to 40 ℃, and extracting to obtain 4- (p-chlorphenyl) -2-trifluoromethyl-3-oxazoline-5-ketone; then adding 2 times of DMF (dimethyl formamide) by weight, stirring, and fully and uniformly mixing to obtain a mixed material;
the benzene-water mixture is a mixture of toluene and water.
Performing the heat preservation reaction, namely cooling the mixed material prepared by the extraction and replacement to below 20 ℃ by adopting frozen brine;
then adding a certain amount of 2-chloroacrylonitrile, and stirring;
keeping the temperature of the mixed material below 20 ℃, dropwise adding an alkaline acid-binding agent, and stirring after dropwise adding;
then heating to 30-35 ℃, and reacting for 1 hour under the condition of heat preservation;
the temperature is continuously increased to 80 ℃, and the reaction is kept for 2 hours.
The molar ratio of the 2-chloroacrylonitrile to the 4- (p-chlorophenyl) -2-trifluoromethyl-3-oxazoline-5-ketone is 1.1-1.3: 1;
the molar ratio of the alkaline acid-binding agent to the 4- (p-chlorphenyl) -2-trifluoromethyl-3-oxazoline-5-ketone is 1.05-1.5: 1.
The alkaline acid-binding agent is triethylamine, and the dropping speed is 100 kg/h.
And (3) performing condensation and desolventization, sampling and analyzing, detecting the content of the 2- (4-chlorphenyl) -5-trifluoromethyl-3-nitrile, calculating the conversion rate, and performing the following operations according to the content and the conversion rate:
c. if the content of the 2- (4-chlorphenyl) -5-trifluoromethyl-3-nitrile is less than or equal to 80 percent or the conversion rate is less than or equal to 90 percent, continuing the heat preservation reaction for 1 hour, and then sampling and analyzing again;
d. if the content of the 2- (4-chlorphenyl) -5-trifluoromethyl-3-nitrile is more than 80 percent and the conversion rate is more than 90 percent, carrying out condensation desolventizing treatment.
Carrying out condensation desolventizing treatment, heating, simultaneously starting two stages of condensing devices, and then vacuumizing;
when the vacuum degree is more than or equal to 0.098MPa, carrying out condensation desolventizing treatment;
sampling to detect the DMF content when the temperature is raised to 100 ℃, and carrying out the following operations according to the DMF content:
e. if the content of DMF is more than 1%, keeping the temperature at 100 ℃ and continuing desolventizing for 20min, and then sampling again for analysis;
f. if the content of DMF is less than or equal to 1 percent, completing the condensation and desolventizing treatment to prepare the intermediate pyrrole.
The two-stage condensation is carried out, wherein the first-stage condensation is circulating water condensation, and the condensation temperature is less than 20 ℃; the secondary condensation is freezing salt water condensation, and the condensation temperature is-10 ℃.
Compared with the prior art, the invention has the beneficial effects that:
(1) according to the method for producing the chlorfenapyr intermediate pyrrole by replacing acetonitrile with the solvent DMF, the reaction temperature of the pyrrole (cyclization) reaction for preparing the intermediate is raised to 80 ℃, so that the conversion at the later stage of the reaction is more thorough and complete, the yield is raised to more than 90% from less than 85%, and the technical problem is effectively solved, the production efficiency is improved, the industrial structure is optimized, and the production cost is reduced.
(2) The method for producing the chlorfenapyr intermediate pyrrole by using the solvent DMF to replace acetonitrile adopts a novel solvent which can be used for replacing acetonitrile in the reaction process, and has strong polarity and high dissolving capacity; compared with acetonitrile, the method has no adverse effect on reaction yield; meanwhile, the method does not need to add new equipment and facilities, can fully utilize all facilities of the original acetonitrile process, and effectively realizes zero-cost technology upgrading and reconstruction.
(3) According to the method for producing the chlorfenapyr intermediate pyrrole by using the solvent DMF to replace acetonitrile, the consumed solvent amount is reduced by more than 30%, the unit weight price of the solvent DMF is only 20% of the price of the acetonitrile, the production cost is reduced by about 86% under comprehensive measurement, the production cost is greatly reduced, and the production burden of enterprises is reduced; and because its boiling point is 153 ℃, in the recovery process, it is low to reclaim energy consumption; not only effectively saving resources, but also greatly reducing the total production cost.
(4) The method for producing the chlorfenapyr intermediate pyrrole by using the solvent DMF instead of acetonitrile effectively solves the problems that the traditional acetonitrile solvent is flammable, harmful and easy to decompose in the production and application process and causes great potential safety hazards to production workers, and effectively avoids production safety accidents.
(5) Compared with the prior acetonitrile solvent consumption, the novel solvent consumption of the method for producing the chlorfenapyr intermediate pyrrole by using the solvent DMF instead of acetonitrile is reduced by more than 30 percent, thereby effectively reducing the environmental pollution and reducing the three-waste treatment cost.
Detailed Description
In order to more clearly understand the technical features, objects, and effects of the present invention, specific embodiments of the present invention will now be described.
Example 1
A method for producing a chlorfenapyr intermediate pyrrole by using a solvent DMF to replace acetonitrile adopts DMF to replace acetonitrile as the solvent.
The method for producing the chlorfenapyr intermediate pyrrole by using the solvent DMF instead of acetonitrile comprises the following steps:
(1) after the lactonization reaction is finished, removing acetonitrile; then adding a benzene-water mixture, heating to 40 ℃, and extracting to obtain 4- (p-chlorphenyl) -2-trifluoromethyl-3-oxazoline-5-ketone with the content being more than 90%; then 2 times of DMF (dimethyl formamide) in parts by weight is added, stirred for 30 minutes at 85RPM, and fully and uniformly mixed to prepare a mixed material.
In the process of removing the acetonitrile, the vacuum degree is kept at-0.1 MPa, the temperature is slowly increased to 65 ℃, and the temperature increase rate is 0.1-1 ℃/min.
And removing acetonitrile, when the temperature is raised to 65 ℃, sampling and detecting the acetonitrile content, and carrying out the following treatment according to the acetonitrile content:
a. if the acetonitrile content is less than 1%, removing the acetonitrile;
b. and if the acetonitrile content is more than or equal to 1 percent, continuously preserving the heat and removing for 10-20min, sampling again to detect the acetonitrile content, and carrying out a or b treatment according to the acetonitrile content.
The weight ratio of the material after acetonitrile removal to the benzene-water mixture is 1: 4.
The benzene-water mixture is a mixture of toluene and water; the toluene: the weight ratio of water is 1: 1.
(2) Transferring the mixed material into a cyclization reaction kettle, and cooling to below 20 ℃ by adopting frozen brine; then adding quantitative 2-chloroacrylonitrile, and stirring for 30 minutes at 85 RPM; keeping the temperature below 20 ℃, slowly dripping an alkaline acid-binding agent, and stirring for 30 minutes at 85RPM after finishing dripping; then slowly starting steam, heating to 30-35 ℃, and reacting for 1 hour under the condition of heat preservation; the temperature is continuously increased to 80 ℃, and the reaction is continuously kept for 2 hours.
The molar ratio of the 2-chloroacrylonitrile to the 4- (p-chlorophenyl) -2-trifluoromethyl-3-oxazoline-5-ketone is 1.15: 1.
The molar ratio of the alkaline acid-binding agent to the 4- (p-chlorphenyl) -2-trifluoromethyl-3-oxazoline-5-ketone is 1.05: 1.
The alkaline acid-binding agent is triethylamine, and the dropping speed is 100 kg/h.
(3) Sampling is carried out, the content of 2- (4-chlorphenyl) -5-trifluoromethyl-3-nitrile is detected by adopting liquid chromatography analysis, the conversion rate is calculated, and the following operations are carried out according to the content and the conversion rate:
c. if the content of the 2- (4-chlorphenyl) -5-trifluoromethyl-3-nitrile is less than or equal to 80 percent or the conversion rate is less than or equal to 90 percent, continuing the heat preservation reaction for 1 hour, and then sampling again for analysis.
d. If the content of 2- (4-chlorophenyl) -5-trifluoromethyl-3-carbonitrile is > 80% and the conversion is > 90%, a desolvation treatment is carried out.
The desolventizing treatment is carried out by heating with steam, starting a two-stage condenser and vacuumizing; when the vacuum degree is more than or equal to 0.098MPa, carrying out desolventizing treatment; when the temperature is raised to 100 ℃, the desolventizing treatment is stopped, a sample is taken to detect the DMF content in the material, and the following operations are carried out according to the DMF content:
e. if the DMF content is more than 1 percent, keeping the temperature at 100 ℃ and continuing desolventizing for 20min, and then sampling again for analysis.
f. If the content of DMF is less than or equal to 1 percent, completing desolventizing treatment to prepare intermediate pyrrole, and transferring to the next procedure for bromination reaction.
The second-stage condensation is carried out, the first-stage condensation is water cooling, and the condensation temperature is less than 20 ℃; the secondary condensation is salt cooling, and the condensation temperature is-10 ℃.
The DMF solvent can be recycled by the desolventizing treatment.
In the method for producing the chlorfenapyr intermediate pyrrole by using the solvent DMF instead of acetonitrile, the reaction temperature of the pyrrole (cyclization) reaction for preparing the intermediate is up to 80 ℃, so that the conversion at the later stage of the reaction is more thorough and complete, and the yield is increased to 92.4%; meanwhile, by the method, the consumed solvent amount is reduced by more than 30%, the production cost is reduced by about 86% under comprehensive measurement, the production cost is greatly reduced, and the production burden of enterprises is reduced; compared with the prior acetonitrile solvent, the consumption of the adopted novel solvent is reduced by 33.7 percent, thereby effectively reducing the environmental pollution and reducing the three-waste treatment cost.
Example 2
A method for producing a chlorfenapyr intermediate pyrrole by using a solvent DMF to replace acetonitrile adopts DMF to replace acetonitrile as the solvent.
The method for producing the chlorfenapyr intermediate pyrrole by using the solvent DMF instead of acetonitrile comprises the following steps:
(1) after the lactonization reaction is finished, removing acetonitrile; then adding a benzene-water mixture, heating to 40 ℃, and extracting to obtain 4- (p-chlorphenyl) -2-trifluoromethyl-3-oxazoline-5-ketone with the content being more than 90%; then adding 1.8 times of DMF by weight, stirring at 75RPM for 20 minutes, and fully mixing to obtain a mixed material.
In the process of removing the acetonitrile, the vacuum degree is kept at-0.1 MPa, the temperature is slowly increased to 65 ℃, and the temperature increase rate is 1 ℃/min.
And removing acetonitrile, when the temperature is raised to 65 ℃, sampling and detecting the acetonitrile content, and carrying out the following treatment according to the acetonitrile content:
a. if the acetonitrile content is less than 1%, removing the acetonitrile;
b. and if the acetonitrile content is more than or equal to 1 percent, continuously preserving the heat and removing for 10min, sampling again to detect the acetonitrile content, and carrying out a or b treatment according to the acetonitrile content.
The weight ratio of the material after acetonitrile removal to the benzene-water mixture is 1: 4.
The benzene-water mixture is a mixture of toluene and water; the toluene: the weight ratio of water is 1: 1.
(2) Transferring the mixed material into a cyclization reaction kettle, and cooling to below 20 ℃ by adopting frozen brine; then adding quantitative 2-chloroacrylonitrile, and stirring for 20 minutes at 75 RPM; keeping the temperature below 20 ℃, slowly dripping an alkaline acid-binding agent, and stirring at 75RPM for 20 minutes after finishing dripping; then slowly starting steam, heating to 30 ℃, and carrying out heat preservation reaction for 1 hour; the temperature is continuously increased to 80 ℃, and the reaction is continuously kept for 2 hours.
The molar ratio of the 2-chloroacrylonitrile to the 4- (p-chlorophenyl) -2-trifluoromethyl-3-oxazoline-5-ketone is 1.3: 1.
The molar ratio of the alkaline acid-binding agent to the 4- (p-chlorphenyl) -2-trifluoromethyl-3-oxazoline-5-ketone is 1.5: 1.
The alkaline acid-binding agent is triethylamine, and the dropping speed is 100 kg/h.
(3) Sampling is carried out, the content of 2- (4-chlorphenyl) -5-trifluoromethyl-3-nitrile is detected by adopting liquid chromatography analysis, the conversion rate is calculated, and the following operations are carried out according to the content and the conversion rate:
c. if the content of the 2- (4-chlorphenyl) -5-trifluoromethyl-3-nitrile is less than or equal to 80 percent or the conversion rate is less than or equal to 90 percent, continuing the heat preservation reaction for 1 hour, and then sampling again for analysis.
d. If the content of 2- (4-chlorophenyl) -5-trifluoromethyl-3-carbonitrile is > 80% and the conversion is > 90%, a desolvation treatment is carried out.
The desolventizing treatment is carried out by heating with steam, starting a two-stage condenser and vacuumizing; when the vacuum degree is more than or equal to 0.098MPa, carrying out desolventizing treatment; when the temperature is raised to 100 ℃, the desolventizing treatment is stopped, a sample is taken to detect the DMF content in the material, and the following operations are carried out according to the DMF content:
e. if the DMF content is more than 1 percent, keeping the temperature at 100 ℃ and continuing desolventizing for 20min, and then sampling again for analysis.
f. If the content of DMF is less than or equal to 1 percent, completing desolventizing treatment to prepare intermediate pyrrole, and transferring to the next procedure for bromination reaction.
The second-stage condensation is carried out, the first-stage condensation is water cooling, and the condensation temperature is less than 20 ℃; the secondary condensation is salt cooling, and the condensation temperature is-10 ℃.
The DMF solvent can be recycled by the desolventizing treatment.
In the method for producing the chlorfenapyr intermediate pyrrole by using the solvent DMF instead of acetonitrile, the reaction temperature of the pyrrole (cyclization) reaction for preparing the intermediate is up to 80 ℃, so that the conversion at the later stage of the reaction is more thorough and complete, and the yield is improved to 90.7%; meanwhile, by the method, the consumed solvent amount is reduced by more than 30%, the production cost is reduced by about 86% under comprehensive measurement, the production cost is greatly reduced, and the production burden of enterprises is reduced; compared with the prior acetonitrile solvent, the consumption of the adopted novel solvent is reduced by 31.5 percent, thereby effectively reducing the environmental pollution and reducing the three-waste treatment cost.
All percentages used in the present invention are mass percentages unless otherwise indicated.
Finally, it should be noted that: although the present invention has been described in detail with reference to the foregoing embodiments, it will be apparent to those skilled in the art that changes may be made in the embodiments and/or equivalents thereof without departing from the spirit and scope of the invention. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. A method for producing a chlorfenapyr intermediate pyrrole by using a solvent DMF to replace acetonitrile is characterized in that DMF is used as the solvent to replace acetonitrile.
2. The method for producing the chlorfenapyr intermediate pyrrole according to claim 1 by replacing acetonitrile with a solvent DMF, which is characterized by comprising the following steps: extraction and replacement, heat preservation reaction, condensation and desolventizing.
3. The method for producing the chlorfenapyr intermediate pyrrole by replacing acetonitrile with the solvent DMF as claimed in claim 2, wherein the acetonitrile is removed after the lactonization reaction of the extraction displacement and the lactonization reaction is finished;
removing acetonitrile, keeping the vacuum degree at-0.1 MPa, heating to 65 ℃, and removing acetonitrile;
and removing acetonitrile, sampling and detecting the acetonitrile content when the temperature is raised to 65 ℃, and carrying out the following treatment according to the acetonitrile content:
a. if the acetonitrile content is less than 1%, removing the acetonitrile;
b. and if the acetonitrile content is more than or equal to 1 percent, continuously preserving the heat and removing for 10-20min, sampling again to detect the acetonitrile content, and carrying out a or b treatment according to the acetonitrile content.
4. The method for producing the chlorfenapyr intermediate pyrrole according to claim 2, wherein the extraction and replacement further comprises the following steps: after removing acetonitrile, adding a benzene-water mixture, heating to 40 ℃, and extracting to obtain 4- (p-chlorphenyl) -2-trifluoromethyl-3-oxazoline-5-ketone; then adding 2 times of DMF (dimethyl formamide) by weight, stirring, and fully and uniformly mixing to obtain a mixed material;
the benzene-water mixture is a mixture of toluene and water.
5. The method for producing the chlorfenapyr intermediate pyrrole according to claim 2, wherein the solvent DMF replaces acetonitrile, and the temperature of the mixed material obtained by the extraction and replacement is reduced to below 20 ℃ by adopting frozen saline water through the heat preservation reaction;
then adding a certain amount of 2-chloroacrylonitrile, and stirring;
keeping the temperature of the mixed material below 20 ℃, dropwise adding an alkaline acid-binding agent, and stirring after dropwise adding;
then heating to 30-35 ℃, and reacting for 1 hour under the condition of heat preservation;
the temperature is continuously increased to 80 ℃, and the reaction is kept for 2 hours.
6. The method for producing the chlorfenapyr intermediate pyrrole according to claim 5, wherein the molar ratio of the 2-chloroacrylonitrile to the 4- (p-chlorophenyl) -2-trifluoromethyl-3-oxazoline-5-one is 1.1-1.3: 1;
the molar ratio of the alkaline acid-binding agent to the 4- (p-chlorphenyl) -2-trifluoromethyl-3-oxazoline-5-ketone is 1.05-1.5: 1.
7. The method for producing the chlorfenapyr intermediate pyrrole according to claim 2, wherein the solvent DMF replaces acetonitrile, and the condensation desolventizing is carried out, sampling analysis is carried out firstly, the content of 2- (4-chlorphenyl) -5-trifluoromethyl-3-nitrile is detected, the conversion rate is calculated, and the following operations are carried out according to the content and the conversion rate:
c. if the content of the 2- (4-chlorphenyl) -5-trifluoromethyl-3-nitrile is less than or equal to 80 percent or the conversion rate is less than or equal to 90 percent, continuing the heat preservation reaction for 1 hour, and then sampling and analyzing again;
d. if the content of the 2- (4-chlorphenyl) -5-trifluoromethyl-3-nitrile is more than 80 percent and the conversion rate is more than 90 percent, carrying out condensation desolventizing treatment.
8. The method for producing the chlorfenapyr intermediate pyrrole by using the solvent DMF to replace acetonitrile according to claim 7, wherein the condensation desolventizing treatment is carried out, the temperature is increased, a two-stage condensation device is started simultaneously, and then the vacuum pumping is carried out;
when the vacuum degree is more than or equal to 0.098MPa, carrying out condensation desolventizing treatment;
sampling to detect the DMF content when the temperature is raised to 100 ℃, and carrying out the following operations according to the DMF content:
e. if the content of DMF is more than 1%, keeping the temperature at 100 ℃ and continuing desolventizing for 20min, and then sampling again for analysis;
f. if the content of DMF is less than or equal to 1 percent, completing the condensation and desolventizing treatment to prepare the intermediate pyrrole.
9. The method for producing the chlorfenapyr intermediate pyrrole according to claim 8, wherein the two-stage condensation is carried out, the first-stage condensation is circulating water condensation, and the condensation temperature is less than 20 ℃; the secondary condensation is freezing salt water condensation, and the condensation temperature is-10 ℃.
10. The method for producing the chlorfenapyr intermediate pyrrole according to claim 5, wherein the basic acid-binding agent is triethylamine, and the dropping rate is 100 kg/h.
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| CN114524758A (en) * | 2022-01-12 | 2022-05-24 | 山东潍坊双星农药有限公司 | Novel synthesis process of chlorfenapyr |
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