CN114805051A - Method for preparing 2, 4-dichlorobenzoic acid from propiconazole 4-H isomer - Google Patents
Method for preparing 2, 4-dichlorobenzoic acid from propiconazole 4-H isomer Download PDFInfo
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- CN114805051A CN114805051A CN202110886275.XA CN202110886275A CN114805051A CN 114805051 A CN114805051 A CN 114805051A CN 202110886275 A CN202110886275 A CN 202110886275A CN 114805051 A CN114805051 A CN 114805051A
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Abstract
The invention relates to a method for preparing 2, 4-dichlorobenzoic acid from propiconazole 4-H isomer, which comprises the steps of hydrolysis reaction, substitution reaction and the like. The preparation method can efficiently prepare the propiconazole 4-H isomer into the 2, 4-dichlorobenzoic acid. The method can effectively reduce hazardous waste, change waste into valuable and reduce production cost. The 2, 4-dichlorobenzoic acid prepared by the method is an intermediate of bactericide, namely the pyribenzoxim, is also an intermediate of herbicides, namely the benzofenapyr and the pyrazolate, can be used for producing antimalarial drug, namely the aclepin hydrochloride and the non-mercury diuretic fast urine, can also be used as other medicine, dye and pesticide intermediates, and has wide application. The method can also provide a solution for the conversion of triazole isomers of other medicines (such as itraconazole and intermediates thereof) or pesticides (such as etaconazole and azaconazole).
Description
[ technical field ] A method for producing a semiconductor device
The invention relates to synthesis of 2, 4-dichlorobenzoic acid, in particular to a method for preparing 2, 4-dichlorobenzoic acid from propiconazole 4-H isomer.
[ background of the invention ]
Propiconazole is a systemic triazole fungicide with protection and treatment effects, can be absorbed by roots, stems and leaves, can be quickly conducted upwards in plant bodies to prevent and treat diseases caused by ascomycetes, basidiomycetes and imperfect fungi, and particularly has good prevention and treatment effects on wheat take-all, powdery mildew, rust disease, root rot, rice bakanae disease and sigatoka, and vegetables planted in greenhouses in summer have good vigorous seedling control and seedling pressing effects while the diseases are prevented and treated.
A large amount of propiconazole 4-H isomers are generated in the propiconazole condensation reaction process, after the propiconazole is extracted by conventional nitric acid salifying, the propiconazole 4-H isomers and residual liquid thereof are obtained by separation, and at present, no treatment method is available, and only dangerous waste can be treated.
2, 4-dichlorobenzoic acid is an intermediate of fungicide acetanixime, is also an intermediate of herbicides benzoxazole and pyraclostrobin, can be used as an intermediate of medicines, dyes and pesticides, and is used for producing antimalarial drug atabrine and non-mercury diuretic furosemide. The main preparation method comprises the following steps: 1. diazotizing 2, 4-diaminotoluene in the presence of sulfuric acid and sodium nitrite, replacing in the presence of cuprous chloride to obtain 2, 4-dichlorotoluene, oxidizing the 2, 4-dichlorotoluene with potassium permanganate to obtain 2, 4-potassium dichlorobenzoate, acidifying with hydrochloric acid to obtain 2, 4-dichlorobenzoic acid, crystallizing the reaction product, washing and drying to obtain the finished product. 2. 2, 4-dichlorotoluene is taken as a raw material, chlorine or phosgene is used for side chain chlorination to obtain 2, 4-alpha, alpha-pentachlorotoluene, and then hydrolysis is carried out to obtain 2, 4-dichlorobenzoyl chloride and 2, 4-dichlorobenzoic acid. 3. 2, 4-dichlorotoluene is oxidized, potassium permanganate can be used as an oxidant, and air oxidation can be carried out in the presence of a catalyst, so that 2, 4-dichlorobenzoic acid can be obtained.
However, a great deal of research work is required to convert the propiconazole 4-H isomer into 2, 4-dichlorobenzoic acid by changing the isomer into valuable substances and reducing environmental pollution.
[ summary of the invention ]
[ problem to be solved ]
The invention aims to provide a preparation method of 2, 4-dichlorobenzoic acid, which takes a propiconazole 4-H isomer as a raw material and finally obtains good yield.
[ solution ]
The invention is realized by the following technical scheme.
The invention relates to a method for preparing 2, 4-dichlorobenzoic acid from propiconazole 4-H isomer, which comprises the following steps:
(1) in the presence of acid, the propiconazole 4-H isomer of the compound shown in the formula I is subjected to ring opening reaction in water to obtain the compound shown in the formula II, namely 1- (2, 4-dichlorophenyl) -2- (4H-1,2, 4-triazol-4-yl) ethanone, wherein the reaction formula is as follows:
(2) and (2) carrying out substitution reaction on the 1- (2, 4-dichlorophenyl) -2- (4H-1,2, 4-triazole-4-yl) ethanone obtained in the step (1) and halogen or hypohalite in the presence of alkali, and acidifying to obtain 2, 4-dichlorobenzoic acid (formula III), wherein the reaction formula is as follows:
according to a preferred embodiment, the reaction temperature in step (1) is 50 to 150 ℃.
When the ring-opening reaction temperature of the step (1) is lower than 50 ℃, the reaction can also be carried out, but the reaction speed is slow, so that the reaction time is too long, and the industrial operation is not facilitated. If the reaction temperature is higher than 150 ℃, impurities generated in the reaction system may be caused, thereby affecting the reaction yield. Further preferably, the reaction temperature is 70 to 135 ℃. The person skilled in the art can also adjust the temperature appropriately, ensuring that the reaction proceeds favourably. In general, the ring-opening reaction time is controlled to be 8 to 48 hours, and too long a time results in generation of impurities in the reaction system, while too short a time easily causes partial incomplete reaction of the raw materials, and preferably 12 to 24 hours.
The ring-opening reaction of step (1) is carried out in the presence of an acid selected from the group consisting of hydrochloric acid, sulfuric acid, hydrobromic acid, phosphoric acid, p-toluenesulfonic acid, methanesulfonic acid, strong acid type resins or solid superacids or mixtures thereof.
In step (1), the reaction is facilitated by the appropriate amount of acid in the system.
Generally, hydrochloric acid with a mass concentration of 10-36%, hydrobromic acid with a mass concentration of 10-48% or sulfuric acid with a mass concentration of 10-72%, phosphoric acid, p-toluenesulfonic acid, methanesulfonic acid, strong acid type resins or solid super acids or mixtures thereof can be selected. When the concentration of the acid is less than 10%, the reaction can also be carried out, but the reaction is slow, the reaction time is long, and the industrial operation is not facilitated; when the concentration of the acid is too high, impurities are generated in the reaction system, and the reaction yield is affected. Preferably 15-25% hydrochloric or hydrobromic acid, or 15-50% sulfuric acid, phosphoric acid, p-toluenesulfonic acid, methanesulfonic acid, strong acid type resins or solid superacids or mixtures thereof are used. The amount and concentration of the acid can also be adjusted by one skilled in the art to appropriately adjust the reaction time.
In the step (1), the molar weight of the acid is 1-10 times of that of the propiconazole 4-H isomer. When the molar weight of the acid and the propiconazole 4-H isomer are less than 1, the reaction is incomplete; when the molar amount of the acid is more than 10 times that of the 4-H isomer of propiconazole, the acid is excessively excessive, preferably 2 to 8 times.
It can be seen that, the concentration and molar amount of the acid in step (1) can be properly adjusted by those skilled in the art, and the reaction is not limited to the above concentration and molar amount range, so that the reaction is smooth, and excessive impurities or waste is not generated.
After the ring-opening reaction in the step (1) is finished, cooling to 25-30 ℃, slowly adding the reaction solution into a sodium hydroxide aqueous solution, stirring for 1 hour, measuring the pH value to be alkaline, filtering, drying the obtained solid, and carrying out substitution reaction on the dried solid and a halogen or hypohalite aqueous solution at the temperature of-20-35 ℃. When the temperature is lower than-20 ℃, the substitution reaction can still be carried out, but the reaction is slow, the reaction time is long, and the industrial operation is not facilitated; if the reaction temperature is higher than 35 ℃, impurities generated in the reaction system may increase, affecting the reaction yield. Preferably, a temperature of-10 ℃ to 25 ℃ may be selected as the optimum reaction temperature. The person skilled in the art can also adjust the temperature appropriately, ensuring that the reaction proceeds favourably. The substitution reaction time is generally 1 to 8 hours, and too long a time is wasteful, while too short a time is insufficient for a part of the starting material to be completely reacted, preferably 3 to 6 hours.
In step (2), the molar ratio of 1- (2, 4-dichlorophenyl) -2- (4H-1,2, 4-triazol-4-yl) ethanone, base and halogen is 1: 4-12: 3 to 9. When the molar ratio of [ 2-chloro-4- (4-chlorophenoxy) -phenyl ] -2- [1,2,4] triazol-4-one to the base is in the above range, a part of the raw materials may not be completely reacted if the molar ratio of the halogen is less than 3, while a part of the raw materials may be excessively excessive and wasted if the molar ratio is more than 9, preferably 4 to 6. When the molar ratio of [ 2-chloro-4- (4-chlorophenoxy) -phenyl ] -2- [1,2,4] triazole-4-ethanone to halogen is within the above range, a part of the starting materials may not be completely reacted if the molar ratio of the base is less than 4, while a large excess of the starting materials may be wasted if the molar ratio is more than 12, preferably 5 to 8.
As a variant, the substitution reaction of step (2) may be carried out with hypohalite instead of halogen, when the molar ratio of 1- (2, 4-dichlorophenyl) -2- (4H-1,2, 4-triazol-4-yl) ethanone, hypohalite to base is from 1:3 to 9:0 to 9. When the molar ratio of 1- (2, 4-dichlorophenyl) -2- (4H-1,2, 4-triazol-4-yl) ethanone to hypohalite is within the range described, the reaction can proceed even if no base is present in the system, i.e., the molar ratio of the base is 0; the addition of a base accelerates the reaction, and a molar ratio of more than 9 is preferable because the base is in excess, and thus 1:1 to 5 is preferable. On the other hand, when the molar ratio of 1- (2, 4-dichlorophenyl) -2- (4H-1,2, 4-triazol-4-yl) ethanone to the base is in the above range, a proportion of the starting material is not reacted completely when the molar ratio of hypohalite is less than 3, while an excess of hypohalite is more than 9, preferably 4 to 6.
In the step (2), the alkali is lithium hydroxide, sodium hydroxide or potassium hydroxide.
In the invention, the halogen is chlorine, bromine or iodine.
The hypohalite is sodium hypochlorite, potassium hypochlorite, calcium hypochlorite, sodium hypobromite or sodium hypoiodite. The hypohalite added into the reaction system is in the form of aqueous solution of salt, the mass concentration of the hypohalite is 5-30%, although the reaction can still be carried out when the mass concentration is lower than 5%, the waste water generated by the reaction is more, and when the mass concentration is higher than 30%, the hypohalite is unstable and is easy to decompose, and the mass concentration is preferably 10-20%.
[ PROBLEMS ] A medicine for treating diabetes
The method for preparing 2, 4-dichlorobenzoic acid from the propiconazole 4-H isomer can efficiently prepare the propiconazole 4-H isomer into the 2, 4-dichlorobenzoic acid. The method can effectively reduce hazardous waste, change waste into valuable, reduce production cost and improve economic benefit. The 2, 4-dichlorobenzoic acid prepared by the method is an intermediate of bactericide, namely the pyribenzoxim, is also an intermediate of herbicides, namely the benzofenapyr and the pyrazolate, can be used for producing antimalarial drug, namely the aclepin hydrochloride and the non-mercury diuretic fast urine, can also be used as other medicine, dye and pesticide intermediates, and has wide application. The method can also provide a solution for the conversion of triazole isomers of other medicines (such as itraconazole and intermediates thereof) or pesticides (such as etaconazole and azaconazole).
[ description of the drawings ]
FIG. 1 is a liquid chromatogram of propiconazole 4-H isomer as a raw material of ring-opening reaction in the first step of the preparation method;
FIG. 2 is a liquid chromatogram of a ring-opening reaction product [ 2-chloro-4- (4-chlorophenoxy) -phenyl ] -2- [1,2,4] triazole-4-ethanone in the first step of the preparation method;
FIG. 3 is a liquid chromatogram of a disubstituted reaction product, 2, 4-dichlorobenzoic acid, obtained in the steps of the preparation method of the present invention;
FIG. 4 is a liquid chromatogram of a 2, 4-dichlorobenzoic acid standard.
[ detailed description ] embodiments
The invention will be better understood from the following examples.
In the present invention, "%" used for specifying concentrations is mass percent and ": all "are molar ratios.
In the invention, the raw materials and products of each step are analyzed and confirmed by liquid chromatography, and the analysis conditions are as follows: tnatural C185 micron, 4.6 × 150mm chromatographic column, methanol-water 75:25(1 ‰ phosphoric acid) as mobile phase, flow rate of 1ml/min, and wavelength of 230 nm.
Example 1: synthesis of [ 2-chloro-4- (4-chlorophenoxy) -phenyl ] -2- [1,2,4] triazole-4-ethanone
100 g (0.29mol) of propiconazole 4-H isomer and 112 g (0.58mol) of 19% hydrochloric acid are put into a reaction bottle, the temperature is raised to 95 ℃, and the reaction is kept for 18 hours.
To confirm the reaction product in this step, after the reaction was completed, the temperature was reduced to 25 to 30 ℃, the reaction mixture was slowly added to a 15% aqueous solution of sodium hydroxide, stirred for 1 hour, and the pH was measured to be 11, followed by filtration, and the obtained solid was dried to obtain 72.1 g of a product having a content of 96.3% by liquid phase analysis and a yield of 92.8%, which was confirmed to be 1- (2, 4-dichlorophenyl) -2- (4H-1,2, 4-triazol-4-yl) ethanone by liquid chromatography, as shown in FIG. 2.
Example 2: synthesis of [ 2-chloro-4- (4-chlorophenoxy) -phenyl ] -2- [1,2,4] triazole-4-ethanone
The same as in example 1, except that the 19% hydrochloric acid was replaced by 72% sulfuric acid, the temperature was raised to 140 ℃ and other conditions and process operations were unchanged.
As a result, 70.1 g of 1- (2, 4-dichlorophenyl) -2- (4H-1,2, 4-triazol-4-yl) ethanone was obtained. The liquid phase analysis and detection confirm that the product content is 96.8 percent, and the calculated yield is 90.7 percent.
Example 3: synthesis of [ 2-chloro-4- (4-chlorophenoxy) -phenyl ] -2- [1,2,4] triazole-4-ethanone
The same as example 1, except that the 19% hydrochloric acid was replaced by 50% methanesulfonic acid (molar weight was unchanged), and other conditions and process operations were unchanged.
As a result, 71.3 g of 1- (2, 4-dichlorophenyl) -2- (4H-1,2, 4-triazol-4-yl) ethanone was obtained. The liquid phase analysis and detection confirm that the product content is 96.5 percent, and the yield is calculated to be 92 percent.
Example 4: synthesis of [ 2-chloro-4- (4-chlorophenoxy) -phenyl ] -2- [1,2,4] triazole-4-ethanone
The same as example 1, except that the temperature was controlled at 50 ℃ and the 19% hydrochloric acid amount was adjusted to 2.9mol, and other conditions and process operations were not changed.
As a result, 72.7 g of 1- (2, 4-dichlorophenyl) -2- (4H-1,2, 4-triazol-4-yl) ethanone was obtained. The liquid phase analysis and detection confirm that the product content is 96.7 percent, and the yield is calculated to be 94 percent.
Example 5: synthesis of 2, 4-Dichlorobenzoic acid (reaction with hypohalite)
838 g (1.1mol) of 10% sodium hypochlorite solution and 11.3 g (0.28mol) of sodium hydroxide are put into a reaction bottle, 72.1 g (0.28mol) of 1- (2, 4-dichlorophenyl) -2- (4H-1,2, 4-triazol-4-yl) ethanone is slowly put into the reaction bottle, the temperature is controlled to be 25-35 ℃, and after all the addition is finished, the stirring is continued for 1 hour. After the reaction is finished, 210 g of 31% industrial hydrochloric acid is dripped to carry out acidification treatment until the pH value is 3, the obtained solid is filtered, the obtained solid is dried to obtain 51.2 g of a product, the content of the product is 98.1% by liquid phase analysis, the yield is 93.4%, and the product is proved to be 2, 4-dichlorobenzoic acid by liquid phase chromatography detection, as shown in figure 3.
Example 6: synthesis of 2, 4-Dichlorobenzoic acid (reaction with hypohalite)
The same as example 5, except that the concentration of sodium hypochlorite of 10% was adjusted to 30% and other conditions and process operations were not changed. As a result, 50.3 g of 2, 4-dichlorobenzoic acid was obtained, which was 98.3% in liquid phase analysis and 91.9% in yield.
Example 7: synthesis of 2, 4-Dichlorobenzoic acid (reaction with hypohalite)
The process was carried out under the same conditions and with the same process as in example 5 except that the 10% sodium hypochlorite was adjusted to potassium hypochlorite. As a result, 51.8 g of 2, 4-dichlorobenzoic acid was obtained, which was 98.5% in liquid phase analysis and was found to have a yield of 94.9%.
Example 8: synthesis of 2, 4-Dichlorobenzoic acid (reaction with hypohalite)
The same as in example 5, except that the temperature was controlled to be-10 to-5 ℃ and other conditions and process operations were not changed. As a result, 50.9 g of 2, 4-dichlorobenzoic acid was obtained, which was 98.3% in liquid phase analysis and was found to be in a yield of 93%.
Example 9: synthesis of 2, 4-Dichlorobenzoic acid (reaction with halogen)
Adding 72.1 g (0.28mol) of 1- (2, 4-dichlorophenyl) -2- (4H-1,2, 4-triazole-4-yl) ethanone, 192 g of water and 48 g (1.2mol) of sodium hydroxide into a reaction bottle, controlling the temperature to be 0-5 ℃, slowly introducing 60 g (0.85mol) of chlorine, continuing stirring for 1 hour after the dropwise addition is finished, dropwise adding 65 g of 20% industrial hydrochloric acid after the reaction is finished, acidifying until the pH is 3, filtering, drying the obtained solid to obtain 50.6 g of 2, 4-dichlorobenzoic acid, wherein the content of the obtained solid is 98.4% by liquid phase analysis, and the yield is 92.6%.
Example 10: synthesis of 2, 4-Dichlorobenzoic acid (reaction with halogen)
The same as in example 9, except that liquid bromine was used in place of chlorine, the other conditions and process operation were not changed. As a result, 51.3 g of 2, 4-dichlorobenzoic acid was obtained, which was 98.0% in liquid phase analysis and was found to have a yield of 93.5%.
Example 11: synthesis of 2, 4-dichlorobenzoic acid
The same as in example 9, except that the molar amount of sodium hydroxide was adjusted to 3.36mol and the molar amount of chlorine was adjusted to 2.52mol, and other conditions and process operations were not changed. As a result, 51.0 g of 2, 4-dichlorobenzoic acid was obtained, which was 98.2% in liquid phase analysis and was found to have a yield of 93.1%.
Therefore, the method for preparing the 2, 4-dichlorobenzoic acid from the propiconazole 4-H isomer can efficiently prepare the 2, 4-dichlorobenzoic acid from the propiconazole 4-H isomer, has good yield, higher product content and low production cost, and can effectively improve the economic benefit.
Claims (10)
1. A method for preparing 2, 4-dichlorobenzoic acid from propiconazole 4-H isomer, characterized in that the method comprises the following steps:
(1) in the presence of acid, the propiconazole 4-H isomer of the compound shown in the formula I is subjected to ring opening reaction in water to obtain the compound shown in the formula II, namely 1- (2, 4-dichlorophenyl) -2- (4H-1,2, 4-triazol-4-yl) ethanone, wherein the reaction formula is as follows:
(2) and (2) carrying out substitution reaction on the 1- (2, 4-dichlorophenyl) -2- (4H-1,2, 4-triazole-4-yl) ethanone obtained in the step (1) and an aqueous solution of halogen or hypohalite in the presence of alkali, and acidifying to obtain 2, 4-dichlorobenzoic acid (formula III), wherein the reaction formula is as follows:
2. the method according to claim 1, wherein the reaction temperature in the step (1) is 50 to 150 ℃.
3. The method according to claim 1, wherein in the step (1), the acid is selected from the group consisting of hydrochloric acid, sulfuric acid, hydrobromic acid, phosphoric acid, p-toluenesulfonic acid, methanesulfonic acid, a strong acid type resin, a solid super acid, and a mixture thereof.
4. The method according to claim 1, wherein in the step (2), the reaction temperature is-20 to 35 ℃.
5. The process according to claim 1, wherein in step (2), the molar ratio of 1- (2, 4-dichlorophenyl) -2- (4H-1,2, 4-triazol-4-yl) ethanone, base and halogen is 1: 4-12: 3 to 9.
6. The process according to claim 1, wherein in the step (2), the molar ratio of 1- (2, 4-dichlorophenyl) -2- (4H-1,2, 4-triazol-4-yl) ethanone, hypohalite to base is 1:3-9: 0-9.
7. The method according to claim 5 or 6, wherein the base is lithium hydroxide, sodium hydroxide or potassium hydroxide.
8. The method according to claim 5 or 6, wherein the halogen is chlorine, bromine or iodine.
9. The method according to claim 5, wherein the hypohalite is sodium hypochlorite, potassium hypochlorite, calcium hypochlorite, sodium hypobromite or sodium hypoiodate, and the aqueous solution of the hypohalite has a mass concentration of 5% to 30%.
10. The process according to claim 1, wherein after the completion of the step (2), the reaction system is adjusted to pH 2 to 3 with hydrochloric acid, stirred for 1 hour, then filtered to obtain a crude product, and dried to obtain 2, 4-dichlorobenzoic acid.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115594668A (en) * | 2022-12-16 | 2023-01-13 | 江苏七洲绿色化工股份有限公司（Cn） | Purification method of propiconazole 4-H isomer |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4161611A (en) * | 1976-02-23 | 1979-07-17 | Veesicol Chemical Corporation | Process for the production of 2-methoxy-3,6-dichlorobenzoic acid |
| US5886218A (en) * | 1996-05-02 | 1999-03-23 | Hoechst Aktiengesellschaft | Process for preparing 4, 5-dichloro-2-methylbenzoic acid |
| CN103224451A (en) * | 2013-05-20 | 2013-07-31 | 山东潍坊润丰化工有限公司 | Method for synthesizing 3,5-dichlorobenzoic acid |
| CN105837432A (en) * | 2016-05-03 | 2016-08-10 | 山东润博生物科技有限公司 | Novel preparation method of 3,5-dichlorobenzoyl chloride |
| CN105906502A (en) * | 2016-05-03 | 2016-08-31 | 山东润博生物科技有限公司 | Preparation method of 3,5-dichlorobenzoyl chloride |
-
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4161611A (en) * | 1976-02-23 | 1979-07-17 | Veesicol Chemical Corporation | Process for the production of 2-methoxy-3,6-dichlorobenzoic acid |
| US5886218A (en) * | 1996-05-02 | 1999-03-23 | Hoechst Aktiengesellschaft | Process for preparing 4, 5-dichloro-2-methylbenzoic acid |
| CN103224451A (en) * | 2013-05-20 | 2013-07-31 | 山东潍坊润丰化工有限公司 | Method for synthesizing 3,5-dichlorobenzoic acid |
| CN105837432A (en) * | 2016-05-03 | 2016-08-10 | 山东润博生物科技有限公司 | Novel preparation method of 3,5-dichlorobenzoyl chloride |
| CN105906502A (en) * | 2016-05-03 | 2016-08-31 | 山东润博生物科技有限公司 | Preparation method of 3,5-dichlorobenzoyl chloride |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115594668A (en) * | 2022-12-16 | 2023-01-13 | 江苏七洲绿色化工股份有限公司（Cn） | Purification method of propiconazole 4-H isomer |
| CN115594668B (en) * | 2022-12-16 | 2023-03-14 | 江苏七洲绿色化工股份有限公司 | Purification method of propiconazole 4-H isomer |
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