WO2023175577A1 - An industrial process for the manufacturing of crystalline polymorphic form-i of prothioconazole - Google Patents

An industrial process for the manufacturing of crystalline polymorphic form-i of prothioconazole Download PDF

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Publication number
WO2023175577A1
WO2023175577A1 PCT/IB2023/052630 IB2023052630W WO2023175577A1 WO 2023175577 A1 WO2023175577 A1 WO 2023175577A1 IB 2023052630 W IB2023052630 W IB 2023052630W WO 2023175577 A1 WO2023175577 A1 WO 2023175577A1
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Prior art keywords
prothioconazole
solvent
polymorphic form
ether
crystalline polymorphic
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PCT/IB2023/052630
Other languages
French (fr)
Inventor
Nagaprasadarao LAKONDA
Vinayak Shirishkumar LAMBATE
Dnyaneshwar Sambhajirao Nipunge
Nilesh Bhaskar WARE
Pramod Dodha SAWANT
Santosh Kumar GHOSH
Renugadevi Gurusamy
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Hikal Limited
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Publication of WO2023175577A1 publication Critical patent/WO2023175577A1/en

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    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/64—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with three nitrogen atoms as the only ring hetero atoms
    • A01N43/647—Triazoles; Hydrogenated triazoles
    • A01N43/653—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01P—BIOCIDAL, PEST REPELLANT, PEST ATTRACTANT OR PLANT GROWTH REGULATORY ACTIVITY OF CHEMICAL COMPOUNDS OR PREPARATIONS
    • A01P3/00—Fungicides
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D249/00—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms
    • C07D249/02—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms not condensed with other rings
    • C07D249/08—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles
    • C07D249/10—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles 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

Definitions

  • the present invention relates to an industrial scale process for the preparation of crystallization of polymorphic form-I of Prothioconazole formula (I) in high yield and greater chemical purity.
  • Prothioconazole 2- [2-(l -Chlorocyclopropyl) -3-(2-chlorophenyl) -2-hydroxypropyl] -2, 4-dihydro-3H-l, 2, 4-triazole-3-thione (I) is a broad spectrum anti-fungal agent of triazo linthione family and is used as a fungicide to treat infected crops, especially in cereals.
  • Prothioconazole was exist into two different crystalline polymorphic forms, Crystal form-1 and Crystal form-II.
  • PCT publication WO1996/16048A1 discloses the preparation of form-1 of Prothioconazole by reacting 2-(l-chloro-cyclopropyl)-l-(2-chlorophenyl)-3- (1,2,4- triazol-l-yl)-propan-2-ol with n-butyl lithium in presence of tetrahydro furan, n-hexane, sulfur powder, water, sulfuric acid, and ethyl acetate.
  • US patent no. 7,176,226 discloses the Crystal modification II (form- II) of Prothioconazole by reacting Crystal form-1 in presence of water, and/or aliphatic alcohol, and/or dialkyl ketones, and/or alkyl alkylcarboxylates.
  • US patent no. 9,290,461 discloses the crystalline DMSO solvate of Prothioconazole; amorphous Prothioconazole and process for their preparation.
  • form-1 as metastable at room temperature and form-II is thermodynamically stable at room temperature.
  • Different crystalline forms, amorphous form, crystalline solvate forms were commercially important as they possess different physico-chemical properties, which may be useful in different contexts. For example, crystalline forms are more stable than amorphous forms, which makes them useful for long-term storage of the solid material, whereas amorphous forms are often more readily soluble than crystalline forms and may thus be more useful for administration than crystalline forms for certain purposes.
  • Crystalline forms of Prothioconazole affects its physico-chemical properties, such as melting point, solubility, or dissolution rate.
  • crystalline form may contain contamination or mixture of other polymorphic forms having different physico-chemical properties which may affect formulation or in final treatment. Therefore, there is a need for a process which prepare polymorphic form-1 of Prothioconazole with absence of other polymorphic forms, especially form-II and any other impurities. There is also a need for a robust process which result in crystalline form-1 with industrial friendly and economically viable manner. Thus, the inventors of instant application motivated to develop an industrial, robust process for polymorphic form-1 of Prothioconazole.
  • the present invention involves a single isolation step using economical reagents, solvents; and results in high chemical yield and purity of polymorphic form-1 of Prothioconazole.
  • the present invention provides a process for the preparation of crystalline polymorphic form-I of Prothioconazole of formula (I).
  • the present invention provides an industrial process for the preparation of crystalline polymorphic form-1 of Prothioconazole of formula (I) comprising the step of: a) obtaining a prothioconazole of formula (I) by reacting compound of formula (II) with oxidizing agent in solvent(s) and filtering the reaction mixture; b) providing a condition for crystallization of polymorphic form-1 of Prothioconazole; and c) isolating crystalline polymorphic form-1 of Prothioconazole.
  • condition for crystallization comprising steps of: i) distilling filtrate od step (a) to minimum reaction volume; ii) cooling the reaction volume; iii) optionally seeding; and iv) cooling the mixture.
  • the present invention provides an industrial process for the preparation of crystalline polymorphic form-1 of Prothioconazole of formula (I) comprising the step of: a) reacting compound of formula (II) with oxidizing agent in solvent(s) to obtain suspension of compound of formula (I); b) crystallizing compound (I) obtained in step (a) by steps of: i) filtering; ii) distillation of solvent to minimum reaction volume, at suitable temperature; iii) cooling; iv) seeding; v) cooling; and vi) filtering to obtain crystalline polymorphic form-I.
  • solvent used herein refers to the single solvent or mixture of solvents.
  • the present invention provides the preparation of crystalline Prothioconazole form-1 in one step, starting from compound of formula (II), thus the process is economical and industrially viable.
  • the present invention provides a process for preparation of crystalline Prothioconazole form-1 which involve minimum reagent, solvents, avoiding critical and/or multiple purification processes and resulting into less effluent generation, thus makes process environment friendly, safer, and commercially viable.
  • the present invention provides a process for the preparation of crystalline polymorphic form-1 of Prothioconazole with purity greater than 98%, preferably greater than 99%.
  • the oxidizing agent is selected from the group consisting of iron (III) chloride hexahydrate (FeCh.bEhO) with or without hydrochloric acid (HC1), hydrogen peroxide (H2O2), p-toluene sulfonic acid (p- TSA), acetic acid (AcOH), hydrochloric acid (HC1) and the like; or by using air along with solvent.
  • solvent(s) used is selected from water, aliphatic, alicyclic and aromatic hydrocarbons solvent which is selected from toluene, cyclohexane, methylcyclohexane, xylene, benzene, 2-methyltetrahydrofuran, methyl tert-butyl ether, isopropyl ether, dimethoxyethane, dimethoxymethane, 1,3- dioxane, 1,4-dioxane, ethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dibutyl ether, polyethylene glycol dimethyl ether, cyclic and acyclic ethers of one, several or a mixture in any proportions; in this embodiment hydrocarbon solvent is used in 6 to 10 volume; and lower alkyl alcohols, preferably C1-C4 alcohols which is selected from methanol, ethanol, iso
  • solvent used are in combination of alcoholic solvent and hydrocarbon solvent; in this embodiment the combination of solvent is in ratio of 1:8 to 1:20 respectively.
  • the oxidation step is performed at a temperature between 20°C to 40°C.
  • condition for crystallization of compound (I) is performed by simple step such as filtration, distillation, cooling, seeding, and finally isolation by filtration to obtain crystalline polymorphic form-I.
  • minimum reaction volume after distillation is 2-6 volume of total reaction volume.
  • temperature for distillation of solvent is 70°C to 100°C temperature.
  • minimum reaction volume is a volume which contains compound of formula (I) in a solution in an organic solvent.
  • the minimum reaction volume is ‘essentially free’ from alcoholic solvent.
  • essentially free means that the concentration of alcoholic solvent in the solution of compound of formula (I) does not exceed lwt.%, often 0.5wt.%.
  • seeding is performed at 50°C to 70°C temperature; in this embodiment the seeding is performed using crystalline form-I.
  • cooling temperature is 0°C to 70°C.
  • the organic layer was distilled to obtain minimum reaction volume at 70°C to 100°C and stirred at for Ih.
  • the resulting solution was cooled to 50°C to 70°C and seeded with crystalline polymorphic form-I.
  • the precipitated polymorphic crystals were further cooled to 0°C to 10°C and filtered.
  • the crystalline polymorphic form-1 were washed with toluene, dried to obtain pure crystalline polymorphic form-1 of Prothioconazole as an off-white to white solid (79.09% yield, HPLC purity >99.9%).
  • the resulting solution was cooled to 50°C to 70°C and seeded with crystalline polymorphic form-1.
  • the precipitated polymorphic crystals were further cooled to 0°C to 10°C and filtered.
  • the crystalline polymorphic form-1 was washed with toluene, dried to obtain pure crystalline polymorphic form-1 of Prothioconazole as an off-white to white solid (35.5 Kg, 78% yield, HPLC purity >99.9%).

Abstract

The present invention relates to an industrial scale process for the preparation and crystallization of polymorphic form-I of Prothioconazole formula (I) in high yield and greater chemical purity.

Description

“AN INDUSTRIAL PROCESS FOR THE MANUFACTURING OF CRYSTALLINE POLYMORPHIC FORM - OF PROTHIOCONAZOLE”
Figure imgf000002_0001
RELATED APPLICATION
This application claims the benefit of Indian Provisional Application No. IN202221014978 filed on March 18, 2022, the contents of which are incorporated by reference herein.
FIELD OF THE INVENTION
The present invention relates to an industrial scale process for the preparation of crystallization of polymorphic form-I of Prothioconazole formula (I) in high yield and greater chemical purity.
Figure imgf000002_0002
I
BACKGROUND OF THE INVENTION
Prothioconazole, 2- [2-(l -Chlorocyclopropyl) -3-(2-chlorophenyl) -2-hydroxypropyl] -2, 4-dihydro-3H-l, 2, 4-triazole-3-thione (I) is a broad spectrum anti-fungal agent of triazo linthione family and is used as a fungicide to treat infected crops, especially in cereals. Prothioconazole was exist into two different crystalline polymorphic forms, Crystal form-1 and Crystal form-II.
The PCT publication WO1996/16048A1 discloses the preparation of form-1 of Prothioconazole by reacting 2-(l-chloro-cyclopropyl)-l-(2-chlorophenyl)-3- (1,2,4- triazol-l-yl)-propan-2-ol with n-butyl lithium in presence of tetrahydro furan, n-hexane, sulfur powder, water, sulfuric acid, and ethyl acetate.
US patent no. 7,176,226 (henceforth '226) discloses the Crystal modification II (form- II) of Prothioconazole by reacting Crystal form-1 in presence of water, and/or aliphatic alcohol, and/or dialkyl ketones, and/or alkyl alkylcarboxylates. US patent no. 9,290,461 (henceforth '461) discloses the crystalline DMSO solvate of Prothioconazole; amorphous Prothioconazole and process for their preparation.
The PCT publication WO2021/074739A1 discloses a process for preparation Prothioconazole, but it may result into mixture of crystalline form-I and form- II.
The prior publications disclose form-1 as metastable at room temperature and form-II is thermodynamically stable at room temperature. Different crystalline forms, amorphous form, crystalline solvate forms were commercially important as they possess different physico-chemical properties, which may be useful in different contexts. For example, crystalline forms are more stable than amorphous forms, which makes them useful for long-term storage of the solid material, whereas amorphous forms are often more readily soluble than crystalline forms and may thus be more useful for administration than crystalline forms for certain purposes.
Crystalline forms of Prothioconazole affects its physico-chemical properties, such as melting point, solubility, or dissolution rate. Thus, it is advantages to prepare crystalline forms (form-1 or form-II) having different range of lattice energies, which facilitate the effectiveness in treatment [e.g., agricultural (such as plant treatment), veterinary or medicinal treatment]. Thus, it will be an advantage to prepare an efficient method which result a more stable, single polymorphic form which will not transform into any other form specifically crystal form-II.
In prior art process, crystalline form may contain contamination or mixture of other polymorphic forms having different physico-chemical properties which may affect formulation or in final treatment. Therefore, there is a need for a process which prepare polymorphic form-1 of Prothioconazole with absence of other polymorphic forms, especially form-II and any other impurities. There is also a need for a robust process which result in crystalline form-1 with industrial friendly and economically viable manner. Thus, the inventors of instant application motivated to develop an industrial, robust process for polymorphic form-1 of Prothioconazole. The present invention involves a single isolation step using economical reagents, solvents; and results in high chemical yield and purity of polymorphic form-1 of Prothioconazole. SUMMARY OF THE INVENTION
In one aspect the present invention provides a process for the preparation of crystalline polymorphic form-I of Prothioconazole of formula (I). ci
Figure imgf000004_0001
Figure imgf000004_0002
In another aspect the present invention provides an industrial process for the preparation of crystalline polymorphic form-1 of Prothioconazole of formula (I) comprising the step of: a) obtaining a prothioconazole of formula (I) by reacting compound of formula (II) with oxidizing agent in solvent(s) and filtering the reaction mixture;
Figure imgf000004_0003
b) providing a condition for crystallization of polymorphic form-1 of Prothioconazole; and c) isolating crystalline polymorphic form-1 of Prothioconazole.
In another aspect the present invention, wherein condition for crystallization comprising steps of: i) distilling filtrate od step (a) to minimum reaction volume; ii) cooling the reaction volume; iii) optionally seeding; and iv) cooling the mixture.
In another aspect the present invention provides an industrial process for the preparation of crystalline polymorphic form-1 of Prothioconazole of formula (I) comprising the step of: a) reacting compound of formula (II) with oxidizing agent in solvent(s) to obtain suspension of compound of formula (I);
Figure imgf000005_0001
b) crystallizing compound (I) obtained in step (a) by steps of: i) filtering; ii) distillation of solvent to minimum reaction volume, at suitable temperature; iii) cooling; iv) seeding; v) cooling; and vi) filtering to obtain crystalline polymorphic form-I.
DETAILED DESCRIPTION OF THE INVENTION
The present invention now will be described more fully hereinafter. The invention may be embodied in many different forms and should not be construed as limited to the embodiments set forth herein; rather, these embodiments are provided so that this disclosure will satisfy applicable legal requirements. As used in the specification, and in the appended claims, the singular forms “a,” “an,” “the,” include plural referents unless the context clearly indicates otherwise.
The term solvent used herein, refers to the single solvent or mixture of solvents.
In an embodiment, the present invention provides the preparation of crystalline Prothioconazole form-1 in one step, starting from compound of formula (II), thus the process is economical and industrially viable.
In another embodiment, the present invention provides a process for preparation of crystalline Prothioconazole form-1 which involve minimum reagent, solvents, avoiding critical and/or multiple purification processes and resulting into less effluent generation, thus makes process environment friendly, safer, and commercially viable.
In another embodiment, the present invention provides a process for the preparation of crystalline polymorphic form-1 of Prothioconazole with purity greater than 98%, preferably greater than 99%. In another embodiment of the present invention, wherein the oxidizing agent is selected from the group consisting of iron (III) chloride hexahydrate (FeCh.bEhO) with or without hydrochloric acid (HC1), hydrogen peroxide (H2O2), p-toluene sulfonic acid (p- TSA), acetic acid (AcOH), hydrochloric acid (HC1) and the like; or by using air along with solvent.
In another embodiment of present invention, wherein the oxidizing agent is used in 1 to 2 mol equivalent.
In another embodiment of present invention, wherein solvent(s) used is selected from water, aliphatic, alicyclic and aromatic hydrocarbons solvent which is selected from toluene, cyclohexane, methylcyclohexane, xylene, benzene, 2-methyltetrahydrofuran, methyl tert-butyl ether, isopropyl ether, dimethoxyethane, dimethoxymethane, 1,3- dioxane, 1,4-dioxane, ethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dibutyl ether, polyethylene glycol dimethyl ether, cyclic and acyclic ethers of one, several or a mixture in any proportions; in this embodiment hydrocarbon solvent is used in 6 to 10 volume; and lower alkyl alcohols, preferably C1-C4 alcohols which is selected from methanol, ethanol, isopropanol, n-butanol, in this embodiment alcoholic solvent is used in 0.1 to 1.0 volume.
In another embodiment of present invention, wherein solvent used are in combination of alcoholic solvent and hydrocarbon solvent; in this embodiment the combination of solvent is in ratio of 1:8 to 1:20 respectively.
In another embodiment of the present invention, wherein the oxidation step is performed at a temperature between 20°C to 40°C.
In another embodiment of the present invention, wherein condition for crystallization of compound (I) is performed by simple step such as filtration, distillation, cooling, seeding, and finally isolation by filtration to obtain crystalline polymorphic form-I.
In another embodiment of the present invention, wherein minimum reaction volume after distillation is 2-6 volume of total reaction volume. In another embodiment of the present invention, wherein temperature for distillation of solvent is 70°C to 100°C temperature.
In another embodiment of present invention, wherein minimum reaction volume is a volume which contains compound of formula (I) in a solution in an organic solvent.
In another embodiment of the present invention, wherein the minimum reaction volume is ‘essentially free’ from alcoholic solvent. The term “essentially free” means that the concentration of alcoholic solvent in the solution of compound of formula (I) does not exceed lwt.%, often 0.5wt.%.
In another embodiment of the present invention, wherein seeding is performed at 50°C to 70°C temperature; in this embodiment the seeding is performed using crystalline form-I.
In another embodiment of the present invention, wherein cooling temperature is 0°C to 70°C.
The preparation of the starting material used in the present invention are well known in prior art. The invention is further illustrated by the following examples, which should not be construed to limit the scope of the invention in anyway.
EXPERIMENTAL
1) Preparation of Prothioconazole form -I.
Figure imgf000007_0001
To the mixture of 2-[2-(l-chloro-cyclopropyl)-3-(2-chloro-phenyl)-2-hydroxy-propyl]- l,2,4-triazolidine-3-thione (3.28 Kg, 1.0 eq.) in toluene (8.0 vol), isopropyl alcohol (0.1 to l.OVol), a solution of FeCh.bEhO (2.0 eq.) in water (1.0 vol.) were added at 20°C to 30°C. The reaction mixture was stirred for 2-3 hrs. The completion of reaction is monitored by HPLC. After completion, the reaction mixture was filtered and separated the layers. The organic layer was washed with water and brine solution. The organic layer was distilled to obtain minimum reaction volume at 70°C to 100°C and stirred at for Ih. The resulting solution was cooled to 50°C to 70°C and seeded with crystalline polymorphic form-I. The precipitated polymorphic crystals were further cooled to 0°C to 10°C and filtered. The crystalline polymorphic form-1 were washed with toluene, dried to obtain pure crystalline polymorphic form-1 of Prothioconazole as an off-white to white solid (79.09% yield, HPLC purity >99.9%).
2) Preparation of Prothioconazole form -I.
Figure imgf000008_0001
To the mixture of 2-[2-(l-chloro-cyclopropyl)-3-(2-chloro-phenyl)-2-hydroxy-propyl]- l,2,4-triazolidine-3-thione (44.17 Kg, 1.0 eq.) in toluene (8.0 vol), isopropyl alcohol (0.1 tol.O vol), a solution of FeCh.bEhO (2.0 eq.) in water (1.0 vol.) were added at 20°C to 30°C. The reaction mixture was stirred for 2-3 hrs. The completion of reaction is monitored by HPLC. After completion, the reaction mixture was filtered and separated the layers. The organic layer was distilled at 70°C to 100°C to obtain minimum reaction volume and stirred at for Ih. The resulting solution was cooled to 50°C to 70°C and seeded with crystalline polymorphic form-1. The precipitated polymorphic crystals were further cooled to 0°C to 10°C and filtered. The crystalline polymorphic form-1 was washed with toluene, dried to obtain pure crystalline polymorphic form-1 of Prothioconazole as an off-white to white solid (35.5 Kg, 78% yield, HPLC purity >99.9%).

Claims

CLAIM:
1) An industrial process for the preparation of crystalline polymorphic form-I of Prothioconazole of formula (I) comprising the step of: ci
Figure imgf000009_0001
Figure imgf000009_0002
I a) obtaining a prothioconazole of formula (I) by reacting compound of formula (II) with oxidizing agent in solvent(s) and filtering the reaction mixture;
Figure imgf000009_0003
b) providing a condition for crystallization of polymorphic form-1 of Prothioconazole; and c) isolating crystalline polymorphic form-1 of Prothioconazole.
2) The process as claimed in claim 1, wherein condition for crystallization comprising the steps of: i) distilling filtrate of step (a) to minimum reaction volume; ii) cooling the reaction volume; iii) optionally seeding; and iv) cooling the mixture.
3) The process as claimed in claim 1, wherein oxidizing agent is selected from the group consisting of iron (III) chloride hexahydrate (FeCh.bEhO) with or without hydrochloric acid (HC1), hydrogen peroxide (H2O2), p-toluene sulfonic acid (p-TSA), acetic acid (AcOH), hydrochloric acid (HC1), and air with solvent.
4) The process as claimed in claim 1, wherein solvent(s) is selected from water, aliphatic, alicyclic and aromatic hydrocarbons solvent selected from toluene, cyclohexane, methylcyclohexane, xylene, benzene, 2-methyltetrahydrofuran, methyl tert-butyl ether, isopropyl ether, dimethoxyethane, dimethoxymethane, 1,3-dioxane, 1,4-dioxane, ethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dibutyl ether, polyethylene glycol dimethyl ether, cyclic and acyclic ethers of one, several or a mixture in any proportions; lower alkyl alcohol selected from methanol, ethanol, isopropanol, and n-butanol. ) The process as claimed in claim 1, wherein solvent(s) used for step (a) is combination of alcoholic solvent and hydrocarbon solvent. ) The process as claimed in claim 2, wherein minimum reaction volume is 2-6 of total reaction volume at a temperature 70°C to 100°C. ) The process as claimed in claim 2, wherein cooling temperature for step (iii) is 50°C to 60°C; and cooling temperature for step (v) is 0°C to 10°C. ) The process as claimed in claim 2, wherein seed crystal is crystalline polymorphic form-I of Prothioconazole. ) The process as claimed in claim 1, wherein isolation of crystalline polymorphic form-1 is carried out at 0°C to 10°C by filtration and washing the crystal of form-1 with precooled hydrocarbon solvent selected from alicyclic and aromatic hydrocarbons solvent selected from toluene, cyclohexane, methylcyclohexane, xylene, 2-methyltetrahydrofuran, methyl tert-butyl ether, isopropyl ether, dimethoxyethane, dimethoxymethane, 1,3 -dioxane, and 1,4-dioxane.
PCT/IB2023/052630 2022-03-18 2023-03-17 An industrial process for the manufacturing of crystalline polymorphic form-i of prothioconazole WO2023175577A1 (en)

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108912062A (en) * 2018-06-21 2018-11-30 南通泰禾化工股份有限公司 A kind of preparation method of triazolinthione derivative
CN111662240A (en) * 2020-06-08 2020-09-15 山东潍坊润丰化工股份有限公司 Preparation method of high-purity prothioconazole
IN201921042108A (en) * 2019-10-17 2021-04-23

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108912062A (en) * 2018-06-21 2018-11-30 南通泰禾化工股份有限公司 A kind of preparation method of triazolinthione derivative
IN201921042108A (en) * 2019-10-17 2021-04-23
CN111662240A (en) * 2020-06-08 2020-09-15 山东潍坊润丰化工股份有限公司 Preparation method of high-purity prothioconazole

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