CN112480009A - Green synthesis process of 1- (4-chlorphenyl) -3-pyrazole alcohol - Google Patents
Green synthesis process of 1- (4-chlorphenyl) -3-pyrazole alcohol Download PDFInfo
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- CN112480009A CN112480009A CN202011429574.2A CN202011429574A CN112480009A CN 112480009 A CN112480009 A CN 112480009A CN 202011429574 A CN202011429574 A CN 202011429574A CN 112480009 A CN112480009 A CN 112480009A
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- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 title claims abstract description 89
- 230000015572 biosynthetic process Effects 0.000 title claims abstract description 28
- 238000003786 synthesis reaction Methods 0.000 title claims abstract description 28
- -1 4-chlorphenyl Chemical group 0.000 title claims abstract description 24
- 238000000034 method Methods 0.000 title claims abstract description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 47
- 238000006243 chemical reaction Methods 0.000 claims abstract description 42
- 235000019441 ethanol Nutrition 0.000 claims abstract description 37
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 36
- 239000007787 solid Substances 0.000 claims abstract description 29
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 26
- 238000010992 reflux Methods 0.000 claims abstract description 22
- 238000004821 distillation Methods 0.000 claims abstract description 21
- 238000010438 heat treatment Methods 0.000 claims abstract description 17
- 238000003756 stirring Methods 0.000 claims abstract description 16
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 claims abstract description 14
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 claims abstract description 14
- YQVZREHUWCCHHX-UHFFFAOYSA-N (4-chlorophenyl)hydrazine;hydron;chloride Chemical compound Cl.NNC1=CC=C(Cl)C=C1 YQVZREHUWCCHHX-UHFFFAOYSA-N 0.000 claims abstract description 13
- 238000001035 drying Methods 0.000 claims abstract description 13
- 238000005406 washing Methods 0.000 claims abstract description 13
- QDRKDTQENPPHOJ-UHFFFAOYSA-N sodium ethoxide Chemical compound [Na+].CC[O-] QDRKDTQENPPHOJ-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000001816 cooling Methods 0.000 claims abstract description 8
- 238000010907 mechanical stirring Methods 0.000 claims abstract description 8
- QSNSCYSYFYORTR-UHFFFAOYSA-N 4-chloroaniline Chemical compound NC1=CC=C(Cl)C=C1 QSNSCYSYFYORTR-UHFFFAOYSA-N 0.000 claims abstract description 7
- DRENHOMDLNJDOG-UHFFFAOYSA-N 2-(4-chlorophenyl)-1h-pyrazol-5-one Chemical compound C1=CC(Cl)=CC=C1N1NC(=O)C=C1 DRENHOMDLNJDOG-UHFFFAOYSA-N 0.000 claims description 13
- 239000007791 liquid phase Substances 0.000 claims description 12
- 238000001514 detection method Methods 0.000 claims description 11
- 238000011084 recovery Methods 0.000 claims description 7
- 230000001105 regulatory effect Effects 0.000 claims description 6
- 239000012295 chemical reaction liquid Substances 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- 239000002994 raw material Substances 0.000 claims description 3
- 238000001308 synthesis method Methods 0.000 abstract description 3
- 238000005292 vacuum distillation Methods 0.000 description 5
- 239000005869 Pyraclostrobin Substances 0.000 description 3
- HZRSNVGNWUDEFX-UHFFFAOYSA-N pyraclostrobin Chemical compound COC(=O)N(OC)C1=CC=CC=C1COC1=NN(C=2C=CC(Cl)=CC=2)C=C1 HZRSNVGNWUDEFX-UHFFFAOYSA-N 0.000 description 3
- 230000001276 controlling effect Effects 0.000 description 2
- 230000000855 fungicidal effect Effects 0.000 description 2
- 239000000417 fungicide Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000005730 Azoxystrobin Substances 0.000 description 1
- 229930182692 Strobilurin Natural products 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- WFDXOXNFNRHQEC-GHRIWEEISA-N azoxystrobin Chemical compound CO\C=C(\C(=O)OC)C1=CC=CC=C1OC1=CC(OC=2C(=CC=CC=2)C#N)=NC=N1 WFDXOXNFNRHQEC-GHRIWEEISA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 125000003854 p-chlorophenyl group Chemical group [H]C1=C([H])C(*)=C([H])C([H])=C1Cl 0.000 description 1
- 125000003226 pyrazolyl group Chemical group 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D231/00—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings
- C07D231/02—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings
- C07D231/10—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
- C07D231/14—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three 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
- C07D231/18—One oxygen or sulfur atom
- C07D231/20—One oxygen atom attached in position 3 or 5
- C07D231/22—One oxygen atom attached in position 3 or 5 with aryl radicals attached to ring nitrogen atoms
Abstract
The invention discloses a green synthesis process of 1- (4-chlorphenyl) -3-pyrazole alcohol, which comprises the steps of adding p-chloroaniline, absolute ethyl alcohol and sodium ethoxide into a four-mouth bottle with a mechanical stirring and reflux condenser tube box thermometer, stirring until dissolving, then slowly adding p-chlorophenylhydrazine hydrochloride, slowly dropwise adding ethyl acrylate, heating until reflux reaction, after the reaction is finished, recovering the absolute ethyl alcohol through reduced pressure distillation, adding water into residues, stirring uniformly, adjusting the pH value to 2 with hydrochloric acid, washing precipitated solids with water, drying to obtain a product, adding water into the residues after recovering the ethanol through reduced pressure distillation for the synthesis of the 1- (4-chlorphenyl) -3-pyrazole alcohol, heating, slowly dropwise adding hydrogen peroxide, cooling to room temperature after the reaction is finished, adjusting the precipitated solids with hydrochloric acid, washing with water, drying to obtain the product, the synthesis method of the 1- (4-chlorphenyl) -3-pyrazole alcohol is reasonable, and the synthesized 1- (4-chlorphenyl) -3-pyrazole alcohol has high efficiency.
Description
Technical Field
The invention relates to the technical field of green synthesis of 1- (4-chlorphenyl) -3-pyrazole alcohol, in particular to a green synthesis process of 1- (4-chlorphenyl) -3-pyrazole alcohol.
Background
1- (4-chlorphenyl) -3-pyrazole alcohol is an important intermediate in the synthesis process of pyraclostrobin. Pyraclostrobin is a strobilurin fungicide with pyrazole structure, is discovered by Pasf Germany in 1993, is registered and marketed in 2001, and is currently used for more than 100 crops. In 2009, its sales reached $ 7.35 million, second only to azoxystrobin, becoming the second largest fungicide worldwide. The pyraclostrobin has broad spectrum, high efficiency, low toxicity, safety to non-target organisms, safety to users and environment friendliness.
The technical scheme provides a green preparation method of 1- (4-chlorphenyl) -3-pyrazole alcohol.
Disclosure of Invention
The invention aims to provide a method for preparing a reflux condenser tube thermometer, which adopts a four-mouth bottle with a mechanical stirring function, adds absolute ethyl alcohol and sodium ethoxide into the four-mouth bottle with the reflux condenser tube thermometer, stirs the mixture until the absolute ethyl alcohol and the sodium ethoxide are dissolved, then slowly adding p-chlorophenylhydrazine hydrochloride, slowly dropwise adding ethyl acrylate, heating to reflux reaction, after the reaction is finished, recovering absolute ethyl alcohol by reduced pressure distillation, adding water into residues, uniformly stirring, regulating pH to 2 by hydrochloric acid, washing precipitated solid by water, drying to obtain a product, adding water into the residues obtained after the ethanol is recovered by the reduced pressure distillation in the synthesis of 1- (4-chlorphenyl) -3-pyrazole alcohol, heating, slowly dropwise adding hydrogen peroxide, cooling to room temperature after the reaction is finished, washing and drying to obtain a green synthesis process of the 1- (4-chlorphenyl) -3-pyrazole alcohol, which is used for solving the problems in the background technology.
In order to achieve the purpose, the invention provides the following technical scheme: a green synthesis process of 1- (4-chlorphenyl) -3-pyrazole alcohol comprises the following steps:
A. adding p-chloroaniline, absolute ethyl alcohol and sodium ethoxide which are used as raw materials into a four-mouth bottle with a mechanical stirring reflux condenser tube box thermometer, and stirring until the p-chloroaniline, the absolute ethyl alcohol and the sodium ethoxide are dissolved;
B. then slowly adding p-chlorophenylhydrazine hydrochloride, slowly dropwise adding ethyl acrylate, and heating to reflux reaction;
C. after the reaction is finished, recovering anhydrous ethanol by reduced pressure distillation, adding water into residues, uniformly stirring, and adjusting the pH value;
D. washing the precipitated solid with water, drying to obtain a product, adding water into the residue obtained after the ethanol is recovered through reduced pressure distillation in the synthesis of 1- (4-chlorphenyl) -3-pyrazole alcohol, heating, slowly dropwise adding hydrogen peroxide, and cooling to room temperature after the reaction is finished;
E. regulating the separated solid with hydrochloric acid, washing with water and drying to obtain the product.
Preferably, 200mL of absolute ethanol and 340g of 5mol sodium ethoxide are added into a 500mL four-mouth bottle with a mechanical stirring and reflux condenser box thermometer according to the step A and stirred until the solution is dissolved.
Preferably, according to the step B, 35.8g of 02mol of p-chlorophenylhydrazine hydrochloride is slowly added, 240g of 0.24mol of ethyl acrylate is slowly added dropwise, the temperature is increased to reflux, the reaction is carried out for 6 hours, and the reaction liquid gradually turns green and a large amount of green solid is separated out.
Preferably, said step C is carried out
a. After the reaction is finished, recovering 75 percent of anhydrous ethanol by reduced pressure distillation;
b. the residue was added to 150mL of water, stirred well and the pH adjusted to 2 with hydrochloric acid.
Preferably, said step D
a. The precipitated solid is washed by water and dried to obtain 334g of product, the content is 97.5 percent through liquid phase detection, and the yield is 85 percent. 3 percent;
b. synthesis of 1- (4-chlorophenyl) -3-pyrazolol to the residue after ethanol recovery by reduced pressure distillation was added 200mL of water, the temperature was raised to 85 ℃, then hydrogen peroxide was slowly added dropwise, the temperature was controlled at about 85 ℃ for 1 hour, and then the reaction was continued for 1.5 hours.
Preferably, after the reaction according to the step E is finished, the reaction is cooled to room temperature, the pH value is adjusted to 2 by hydrochloric acid, the precipitated solid is washed by water and dried to obtain 31.0g of a product, the content of the product is 97.1% by liquid phase detection, and the total yield of the two steps is 79.8%.
Compared with the prior art, the invention has the beneficial effects that:
the synthesis method of the 1- (4-chlorphenyl) -3-pyrazole alcohol is reasonable, and the synthesized 1- (4-chlorphenyl) -3-pyrazole alcohol has high efficiency.
Drawings
FIG. 1 is a flow chart of the green synthesis process of 1- (4-chlorophenyl) -3-pyrazolol of the present invention.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Referring to fig. 1, the present invention provides a technical solution: a green synthesis process of 1- (4-chlorphenyl) -3-pyrazole alcohol comprises the following steps:
A. adding p-chloroaniline, absolute ethyl alcohol and sodium ethoxide which are used as raw materials into a four-mouth bottle with a mechanical stirring reflux condenser tube box thermometer, and stirring until the p-chloroaniline, the absolute ethyl alcohol and the sodium ethoxide are dissolved;
B. then slowly adding p-chlorophenylhydrazine hydrochloride, slowly dropwise adding ethyl acrylate, and heating to reflux reaction;
C. after the reaction is finished, recovering anhydrous ethanol by reduced pressure distillation, adding water into residues, uniformly stirring, and adjusting the pH value;
D. washing the precipitated solid with water, drying to obtain a product, adding water into the residue obtained after the ethanol is recovered through reduced pressure distillation in the synthesis of 1- (4-chlorphenyl) -3-pyrazole alcohol, heating, slowly dropwise adding hydrogen peroxide, and cooling to room temperature after the reaction is finished;
E. regulating the separated solid with hydrochloric acid, washing with water and drying to obtain the product.
200mL of absolute ethanol and 340go5mol of sodium ethoxide are added into a 500mL four-mouth bottle with a mechanical stirring and reflux condenser tube box thermometer and stirred until the mixture is dissolved.
Slowly adding 35.8g of 02mol of p-chlorophenylhydrazine hydrochloride, slowly dropwise adding 240g of 0.24mol of ethyl acrylate, heating to reflux, reacting for 6 hours, gradually turning the reaction solution to green and separating out a large amount of green solid, recovering 75% of anhydrous ethanol by reduced pressure distillation after the reaction is finished, adding 150mL of water into the residue, uniformly stirring, and adjusting the pH to 2 by hydrochloric acid.
The precipitated solid is washed by water and dried to obtain 334g of product, the content is 97.5 percent through liquid phase detection, and the yield is 85 percent. 3% synthesis of 1- (4-chlorophenyl) -3-pyrazolol 200mL of water was added to the residue obtained after ethanol recovery by vacuum distillation, the temperature was raised to 85 ℃, hydrogen peroxide was slowly added dropwise, the temperature was controlled to about 85 ℃ for 1 hour, and then the reaction was continued for 1.5 hours.
In the case of the example 1, the following examples are given,
slowly adding 40g of 02mol of p-chlorophenylhydrazine hydrochloride, slowly dropwise adding 250g of 0.24mol of ethyl acrylate, heating to reflux, reacting for 6h, gradually turning the reaction solution to green and separating out a large amount of green solid, recovering 75% of anhydrous ethanol by reduced pressure distillation after the reaction is finished, adding 150mL of water into the residue, stirring uniformly, and adjusting the pH to 2 by hydrochloric acid.
The precipitated solid is washed by water and dried to obtain 340g of product, the content is 97.5 percent through liquid phase detection, and the yield is 85 percent. 3% synthesis of 1- (4-chlorophenyl) -3-pyrazolol 200mL of water was added to the residue obtained after ethanol recovery by vacuum distillation, the temperature was raised to 85 ℃, hydrogen peroxide was slowly added dropwise, the temperature was controlled to about 85 ℃ for 1 hour, and then the reaction was continued for 1.5 hours.
In the case of the example 2, the following examples are given,
slowly adding 30g of 02mol of p-chlorophenylhydrazine hydrochloride, slowly dropwise adding 220g of 0.24mol of ethyl acrylate, heating to reflux, reacting for 6 hours, gradually turning the reaction solution to green and separating out a large amount of green solid, recovering 75% of anhydrous ethanol by reduced pressure distillation after the reaction is finished, adding 150mL of water into the residue, uniformly stirring, and adjusting the pH to 2 by hydrochloric acid.
The precipitated solid is washed by water and dried to obtain 310g of product, the content is 97.5 percent through liquid phase detection, and the yield is 85 percent. 3% synthesis of 1- (4-chlorophenyl) -3-pyrazolol 200mL of water was added to the residue obtained after ethanol recovery by vacuum distillation, the temperature was raised to 85 ℃, hydrogen peroxide was slowly added dropwise, the temperature was controlled to about 85 ℃ for 1 hour, and then the reaction was continued for 1.5 hours.
In the case of the example 3, the following examples are given,
slowly adding 45g of 02mol of p-chlorophenylhydrazine hydrochloride, slowly dropwise adding 260g of 0.24mol of ethyl acrylate, heating to reflux, reacting for 6h, gradually turning the reaction solution to green and separating out a large amount of green solid, recovering 75% of anhydrous ethanol by reduced pressure distillation after the reaction is finished, adding 150mL of water into the residue, uniformly stirring, and adjusting the pH to 2 by hydrochloric acid.
The precipitated solid is washed by water and dried to obtain 360g of product, the content is 97.5 percent through liquid phase detection, and the yield is 85 percent. 3% synthesis of 1- (4-chlorophenyl) -3-pyrazolol 200mL of water was added to the residue obtained after ethanol recovery by vacuum distillation, the temperature was raised to 85 ℃, hydrogen peroxide was slowly added dropwise, the temperature was controlled to about 85 ℃ for 1 hour, and then the reaction was continued for 1.5 hours.
After the reaction is finished, cooling to room temperature, regulating the pH value to 2 by hydrochloric acid, washing precipitated solid by water, and drying to obtain 31.0g of product, wherein the content of the product is 97.1% by liquid phase detection, and the total yield of the two steps is 79.8%.
In the case of the example 4, the following examples are given,
slowly adding 55g of 02mol of p-chlorophenylhydrazine hydrochloride, slowly dropwise adding 280g of ethyl acrylate, heating to reflux, reacting for 6h, gradually changing the reaction liquid into green and separating out a large amount of green solid, recovering 75% of anhydrous ethanol by reduced pressure distillation after the reaction is finished, adding 150mL of water into the residue, stirring uniformly, and adjusting the pH to 2 by hydrochloric acid.
The precipitated solid is washed by water and dried to obtain 370g of product, the content is 97.5 percent through liquid phase detection, and the yield is 85 percent. 3% synthesis of 1- (4-chlorophenyl) -3-pyrazolol 200mL of water was added to the residue obtained after ethanol recovery by vacuum distillation, the temperature was raised to 85 ℃, hydrogen peroxide was slowly added dropwise, the temperature was controlled to about 85 ℃ for 1 hour, and then the reaction was continued for 1.5 hours.
After the reaction is finished, cooling to room temperature, regulating the pH value to 2 by hydrochloric acid, washing precipitated solid by water, and drying to obtain 31.0g of product, wherein the content of the product is 97.1% by liquid phase detection, and the total yield of the two steps is 79.8%.
1- (4-chlorophenyl) -3-pyrazole alcohol is prepared according to the actual proportion, 35.8g of 02mol of p-chlorophenylhydrazine hydrochloride is slowly added, 240g of 0.24mol of ethyl acrylate is slowly added dropwise, the temperature is raised to reflux, the reaction is carried out for 6h, the reaction liquid gradually turns green during the reaction and a large amount of green solid is separated out, after the reaction is finished, 75 percent of anhydrous ethanol is recovered by reduced pressure distillation, 150mL of water is added into the residue, the mixture is uniformly stirred, and the pH value is adjusted to 2 by hydrochloric acid.
The precipitated solid is washed by water and dried to obtain 334g of product, the content is 97.5 percent through liquid phase detection, and the yield is 85 percent. 3 percent of 1- (4-chlorphenyl) -3-pyrazole alcohol is synthesized by adding 200mL of water into the residue obtained after ethanol is recovered by reduced pressure distillation, heating to 85 ℃, slowly dropwise adding hydrogen peroxide, controlling the temperature to be about 85 ℃, and controlling the dropwise adding time to be 1h, wherein the 1- (4-chlorphenyl) -3-pyrazole alcohol prepared by continuing to react for 1.5h has the best product quality and the highest preparation efficiency.
The synthesis method of the 1- (4-chlorphenyl) -3-pyrazole alcohol is reasonable, and the synthesized 1- (4-chlorphenyl) -3-pyrazole alcohol has high efficiency.
Although embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that changes, modifications, substitutions and alterations can be made in these embodiments without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.
Claims (6)
1. A green synthesis process of 1- (4-chlorphenyl) -3-pyrazole alcohol is characterized in that: the method comprises the following steps:
A. adding p-chloroaniline, absolute ethyl alcohol and sodium ethoxide which are used as raw materials into a four-mouth bottle with a mechanical stirring reflux condenser tube box thermometer, and stirring until the p-chloroaniline, the absolute ethyl alcohol and the sodium ethoxide are dissolved;
B. then slowly adding p-chlorophenylhydrazine hydrochloride, slowly dropwise adding ethyl acrylate, and heating to reflux reaction;
C. after the reaction is finished, recovering anhydrous ethanol by reduced pressure distillation, adding water into residues, uniformly stirring, and adjusting the pH value;
D. washing the precipitated solid with water, drying to obtain a product, adding water into the residue obtained after the ethanol is recovered through reduced pressure distillation in the synthesis of 1- (4-chlorphenyl) -3-pyrazole alcohol, heating, slowly dropwise adding hydrogen peroxide, and cooling to room temperature after the reaction is finished;
E. regulating the separated solid with hydrochloric acid, washing with water and drying to obtain the product.
2. The green synthesis process of 1- (4-chlorophenyl) -3-pyrazolol according to claim 1, characterized in that: and B, adding 200mL of absolute ethyl alcohol into a 500mL four-mouth bottle with a mechanical stirring and reflux condenser tube box thermometer according to the step A, adding 340go5mol of sodium ethoxide, and stirring until the mixture is dissolved.
3. The green synthesis process of 1- (4-chlorophenyl) -3-pyrazolol according to claim 1, characterized in that: and B, slowly adding 35.8g of 02mol of p-chlorophenylhydrazine hydrochloride according to the step B, slowly dropwise adding 240g of ethyl acrylate and 0.24mol of ethyl acrylate, heating to reflux, reacting for 6 hours, wherein the reaction liquid gradually becomes green and a large amount of green solids are separated out.
4. The green synthesis process of 1- (4-chlorophenyl) -3-pyrazolol according to claim 1, characterized in that: according to step C
a. After the reaction is finished, recovering 75 percent of anhydrous ethanol by reduced pressure distillation;
b. the residue was added to 150mL of water, stirred well and the pH adjusted to 2 with hydrochloric acid.
5. The green synthesis process of 1- (4-chlorophenyl) -3-pyrazolol according to claim 1, characterized in that: said according to step D
a. The precipitated solid is washed by water and dried to obtain 334g of product, the content is 97.5 percent through liquid phase detection, and the yield is 85 percent. 3 percent;
b. synthesis of 1- (4-chlorophenyl) -3-pyrazolol to the residue after ethanol recovery by reduced pressure distillation was added 200mL of water, the temperature was raised to 85 ℃, then hydrogen peroxide was slowly added dropwise, the temperature was controlled at about 85 ℃ for 1 hour, and then the reaction was continued for 1.5 hours.
6. The green synthesis process of 1- (4-chlorophenyl) -3-pyrazolol according to claim 1, characterized in that: and E, cooling to room temperature after the reaction is finished according to the step E, adjusting the pH to 2 by using hydrochloric acid, washing precipitated solid by water, and drying to obtain 31.0g of a product, wherein the content of the product is detected by a liquid phase is 97.1%, and the total yield of the two steps is 79.8%.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103588708A (en) * | 2013-11-12 | 2014-02-19 | 京博农化科技股份有限公司 | Preparation method of 1-(4-chlorophenyl)-3-hydroxypyrazole |
| CN105968048A (en) * | 2016-06-07 | 2016-09-28 | 四川福思达生物技术开发有限责任公司 | Method for synthesizing pyraclostrobin intermediate 1-(4-chlorophenyl)-3-hydroxy-1-h-pyrazole |
| CN106008348A (en) * | 2016-06-07 | 2016-10-12 | 四川福思达生物技术开发有限责任公司 | Method for synthesizing pyraclostrobin intermediate |
| CN106061950A (en) * | 2014-02-28 | 2016-10-26 | 住友化学株式会社 | Method for producing pyrazole compound |
-
2020
- 2020-12-07 CN CN202011429574.2A patent/CN112480009A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103588708A (en) * | 2013-11-12 | 2014-02-19 | 京博农化科技股份有限公司 | Preparation method of 1-(4-chlorophenyl)-3-hydroxypyrazole |
| CN106061950A (en) * | 2014-02-28 | 2016-10-26 | 住友化学株式会社 | Method for producing pyrazole compound |
| CN105968048A (en) * | 2016-06-07 | 2016-09-28 | 四川福思达生物技术开发有限责任公司 | Method for synthesizing pyraclostrobin intermediate 1-(4-chlorophenyl)-3-hydroxy-1-h-pyrazole |
| CN106008348A (en) * | 2016-06-07 | 2016-10-12 | 四川福思达生物技术开发有限责任公司 | Method for synthesizing pyraclostrobin intermediate |
Non-Patent Citations (1)
| Title |
|---|
| YUANYUAN LIU等: "Synthesis, fungicidal activity,structure-activity relationships (SARs) and density functional theory (DFT) studies of novel strobilurin analogues containing arylpyrazole rings", 《SCIENTIFIC REPORTS》, vol. 8, no. 1, 18 May 2018 (2018-05-18), pages 1 - 14 * |
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Application publication date: 20210312 |