WO2022053116A1 - Metal prochloraz complexes and the production of them in water based suspension concentrates - Google Patents
Metal prochloraz complexes and the production of them in water based suspension concentrates Download PDFInfo
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- WO2022053116A1 WO2022053116A1 PCT/DK2020/050248 DK2020050248W WO2022053116A1 WO 2022053116 A1 WO2022053116 A1 WO 2022053116A1 DK 2020050248 W DK2020050248 W DK 2020050248W WO 2022053116 A1 WO2022053116 A1 WO 2022053116A1
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- prochloraz
- water based
- suspension concentrates
- complexes
- based suspension
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Classifications
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- 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
-
- 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
- A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
- A01N47/08—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having one or more single bonds to nitrogen atoms
- A01N47/28—Ureas or thioureas containing the groups >N—CO—N< or >N—CS—N<
- A01N47/38—Ureas or thioureas containing the groups >N—CO—N< or >N—CS—N< containing the group >N—CO—N< where at least one nitrogen atom is part of a heterocyclic ring; Thio analogues thereof
Definitions
- the present invention concerns a new procedure for producing water based suspension concentrates of the fimgicide l-[N-propyl-N-2-(2,4,6-tri-chloro-phenoxy)-ethyl-carbamoyl]-imidazole, known by the common name prochloraz, and the use of these water based suspension concentrates in combating fungi.
- Copper and zinc complexes of prochloraz chloride are typically formulated as water based suspension concentrates. While manganese prochloraz chloride is often formulated as a solid formulation, for instance as a wettable powder (GB 1567521A; US 4250179A; EP 0445656B1). There are at least two advantages of applying the metal complexes of prochloraz instead of the neat prochloraz.
- the metal complexes of prochloraz have high melting points, typically above I00°C, while prochloraz has a melting point around 48°C. Due to the low melting point it is difficult to formulate the neat prochloraz as a solid formulation and as a water based suspension concentrate.
- the metal complexes of prochloraz can be formulated as solid formulations and at least the cupric and zinc prochloraz chloride complexes can be formulated as water based suspension concentrates.
- the metal complexes of prochloraz are considered to be less phytotoxic than the neat prochloraz at least on some crops (GB 1567521A; US 4250179A; EP 0445656B1).
- the crystalline metal complexes of prochloraz were isolated by filtration and rinsed with a suitable solvent, e.g. ethanol or water. Afterwards, the isolated crystalline complexes of prochloraz were used in various formulation types, e.g. wettable powders and water-based suspension concentrates (EP 0445656B1)
- GB 1567521A it is described how to prepare and isolate for instance cupric and manganese complexes of prochloraz by adding a water solution of a cupric or manganese salt to an alcoholic solution of prochloraz. The crystalline metal complexes of prochloraz were afterwards rinsed using appropriate solvents.
- GB 1567521A it was also described that a solution of prochloraz in ethanol was added to an ethanolic solution of MnC12, 4H2O. The ethanol was removed by solvent evaporation. The residue was crystallized in ether. The crystallized compound was a manganese complex of prochloraz which contained chloride as the anion.
- the manganese and cupric complexes of prochloraz isolated according to GB 1567521A, were used for preparing wettable powders.
- the manganese prochloraz chloride it is considered difficult to use in a water-based suspension concentrate because the complex dissociates fast in water (EFSA Journal, 2011, 9(7) 2323, pp 11-12). Due to the low melting point of prochloraz, around 48°C, it is problematic if the dissociation takes place in a water based suspension concentrate. Therefore, the manganese prochloraz chloride compound is often formulated as a wettable powder.
- the copper and zinc prochloraz chloride complexes can be formulated as water based suspension concentrates because the copper and zinc complexes are stable in water and they do not to the same extent as the manganese prochloraz complex dissociate in water (FAO and WHO, Pesticide residues in food, Prochloraz, 1983).
- ft is popular to formulate pesticides as water based suspension concentrates because they don’t contain or do only contain minor amounts of organic solvents. Usually they have excellent pesticidal activity, and the lack of organic solvents and dust make them both operator and environmentally friendly. Therefore, it is highly desirable to formulate prochloraz metal complexes as water based suspension concentrates. Especially it will be an advantage to use the crystalline manganese prochloraz chloride complex in a water based suspension concentrate because the manganese ion is less problematic from an environmental point of view than the zinc and cupric ions are.
- Prochloraz and the metal complexes of prochloraz are mentioned in several documents about applying two or more pesticides to get additive or synergistic activity CN 1027771515A, CN 101380012A, CN 200810146216, CN 102017961A, CN 101971850A, CN 101796955B, CN 10653860A, CN 106982854, CN 102047898A, CN 108552202A, CN 103461368A, CN 101700033A, CN 101984809A, CN 103385250A, CN 107950577A, CN 102150678A, CN 101755808A/B, CN 101107931A, CN 101755837A, CN 1930966A, CN 1930973A, CN 101836654A, and CN 102669180A.
- compositions and the manufacturing procedures of water based suspension concentrates containing metal complexes of prochloraz, especially the manganese prochloraz chloride complex are provided in CN 1054775356 A.
- compositions of suspension concentrates of manganese prochloraz chloride and propineb are provided.
- compositions of suspension concentrates of metal complexes of prochloraz and the fungicide epoxiconazole are described in CN 102805096 A and CN 102823609 A.
- Suspension concentrates containing manganese prochloraz chloride and other fungicides are mentioned in CN 106857689 A.
- the metal prochloraz complexes are produced, rinsed and isolated before making the suspension concentrates.
- the already prepared metal prochloraz complexes for instance the manganese prochloraz chloride complex, are just added to the suspension concentrate as a part of the manufacturing process.
- ft will be a significant advantage if the crystalline metal prochloraz complexes can be produced as a part of the manufacturing of the water based suspension concentrate. It means it will not be necessary to produce and isolate the metal complex of prochloraz in advance in a separate manufacturing procedure. Producing the metal prochloraz complex in situ in the water based suspension concentrate will reduce the cost and the time of the production process.
- typically the prochloraz is more available for purchase than the metal prochloraz complexes are.
- Preferred examples according to the present invention are the complexes formed in situ in the water based suspension concentrate by reacting prochloraz, melted prochloraz or a solution of melted prochloraz with cupric, zinc or manganese chlorides or nitrates. It is preferred to add seed crystals of the metal prochloraz complex wanted before the formation of the complex takes place in the suspension concentrate vehicle.
- the manganese prochloraz complexes it is preferable to use an excess of manganese ions and/or chloride ions in the suspension concentrate, i.e. an excess of manganese and/or chloride in comparison with the amount of manganese and chloride necessary to form the manganese prochloraz chloride complex.
- the excess of manganese and/or chloride will ensure the concentration of free prochloraz in the water based suspension concentrate is low.
- the low concentration of prochloraz makes the suspension concentrate more stable because there is no melting of free prochloraz even at elevated temperatures, e.g. up to 45°C.
- phase solubility diagram is an efficient method to ensure that a sufficient excess of manganese and/or chloride ions are being applied in the water based suspension concentrate. This approach is outlined in example 1.
- a preferable way is to dissolve or disperse the dispersing agents and the metal salt, e.g. CuC12, MnC12, ZnC12 or Zn(NO3)2 with or without crystal water, in the water phase of the suspension concentrate. Seed crystals of the wanted metal prochloraz complexes can be added in order to speed up the crystallization process. Afterwards, the melted prochloraz is added to the water using stirring, e.g. high shear stirring or rotor/stator mixing. The melted prochloraz can be added as a neat liquid or together with solvents and dispersing agent(s).
- the metal salt e.g. CuC12, MnC12, ZnC12 or Zn(NO3)2
- the solvents and the dispersing agent can reduce the viscosity of the melted prochloraz making the mixing with water easier.
- the crystallization of the metal prochloraz complex typically takes minutes or a few hours. After the crystallization of the complex the suspension concentrate can be milled in order to get the particle size wanted, e.g. mean V (LASER) 2-4 pm.
- the B diagram type indicates, the manganese procloraz chloride complex is the solid phase present at equilibrium at MnC12, 4H2O concentrations higher than 30 g/1.
- the isolated, water rinsed and dried solid phase from the sample containing 50 g/1 MnC12, 4H2O consisted of 92.0 % w/w prochloraz.
- the content of prochloraz in a Mn (Prochloraz)4 C12 complex is 92.3% w/w.
- the 92.0% result is in good agreement with the the theoretical content.
- the current example showed it was possible to formulate a water based suspension concentrate having Mn (Prochloraz)4 C12 as the stable solid phase.
- compositions and properties of various 250 g/1 prochloraz water based suspension concentrates for seed dressing are listed in the table below.
- product I and III compositions described in example 2 can be used for producing formulations containing other fungicides and insecticides in addition to prochloraz.
- a water based suspension concentrate of manganese prochloraz was produced having a composition like product I in example 2.
- the Atlas G5002L and the propyleneglycol were mixed with the melted prochloraz and afterwards this mixture was dispersed in the water phase of the suspension concentrate.
- the crystallization of the managanese prochloraz chloride complex took place in situ in the water phase within minutes after the addition of the mixture.
Abstract
Prochloraz is a member of the imidazole fungicides and it is used in various ways for crop protection, including seed dressing and post-harvest protection. The current invention relates to suspension concentrates of manganese prochloraz chloride complexes and other metal prochloraz complexes. The metal prochloraz complexes are produced in situ as an integrated part of the manufacturing of water based suspension concentrates.
Description
11-09-2020
Metal prochloraz complexes and the production of them in water based suspension concentrates
DESCRIPTION
The present invention concerns a new procedure for producing water based suspension concentrates of the fimgicide l-[N-propyl-N-2-(2,4,6-tri-chloro-phenoxy)-ethyl-carbamoyl]-imidazole, known by the common name prochloraz, and the use of these water based suspension concentrates in combating fungi.
Copper and zinc complexes of prochloraz chloride are typically formulated as water based suspension concentrates. While manganese prochloraz chloride is often formulated as a solid formulation, for instance as a wettable powder (GB 1567521A; US 4250179A; EP 0445656B1). There are at least two advantages of applying the metal complexes of prochloraz instead of the neat prochloraz. The metal complexes of prochloraz have high melting points, typically above I00°C, while prochloraz has a melting point around 48°C. Due to the low melting point it is difficult to formulate the neat prochloraz as a solid formulation and as a water based suspension concentrate. The metal complexes of prochloraz can be formulated as solid formulations and at least the cupric and zinc prochloraz chloride complexes can be formulated as water based suspension concentrates. In addition, the metal complexes of prochloraz are considered to be less phytotoxic than the neat prochloraz at least on some crops (GB 1567521A; US 4250179A; EP 0445656B1).
In GB 1567521A and EP 0445656B 1 the production and the isolation of the metal complexes of prochloraz are described in details. Two main strategies are described concerning the production and isolation. In EP 0445656B1 it is explicitly stated the crystalline Sn and Zn complexes of prochloraz are prepared and isolated by adding a water solution of SnC12 or ZnC12 to a clear alcoholic solution of prochloraz, in a molar ratio 1 :2, metal salt to prochloraz. While most common alcohols gave good results, alcohols such as ethanol and isopropanol were preferred.
According to the examples in EP 0445656B1, the crystalline metal complexes of prochloraz were isolated by filtration and rinsed with a suitable solvent, e.g. ethanol or water. Afterwards, the isolated crystalline complexes of prochloraz were used in various formulation types, e.g. wettable powders and water-based suspension concentrates (EP 0445656B1)
In GB 1567521A it is described how to prepare and isolate for instance cupric and manganese complexes of prochloraz by adding a water solution of a cupric or manganese salt to an alcoholic solution of prochloraz. The crystalline metal complexes of prochloraz were afterwards rinsed using appropriate solvents. In GB 1567521A it was also described that a solution of prochloraz in ethanol was added to an ethanolic solution of MnC12, 4H2O. The ethanol was removed by solvent evaporation. The residue was crystallized in ether. The crystallized compound was a manganese complex of prochloraz which contained chloride as the anion. The manganese and cupric complexes of prochloraz, isolated according to GB 1567521A, were used for preparing wettable powders. Regarding the manganese prochloraz chloride, it is considered difficult to use in a water-based suspension concentrate because the complex dissociates fast in water (EFSA Journal, 2011, 9(7) 2323, pp 11-12). Due to the low melting point of prochloraz, around 48°C, it is problematic if the
dissociation takes place in a water based suspension concentrate. Therefore, the manganese prochloraz chloride compound is often formulated as a wettable powder.
The copper and zinc prochloraz chloride complexes can be formulated as water based suspension concentrates because the copper and zinc complexes are stable in water and they do not to the same extent as the manganese prochloraz complex dissociate in water (FAO and WHO, Pesticide residues in food, Prochloraz, 1983). ft is popular to formulate pesticides as water based suspension concentrates because they don’t contain or do only contain minor amounts of organic solvents. Usually they have excellent pesticidal activity, and the lack of organic solvents and dust make them both operator and environmentally friendly. Therefore, it is highly desirable to formulate prochloraz metal complexes as water based suspension concentrates. Especially it will be an advantage to use the crystalline manganese prochloraz chloride complex in a water based suspension concentrate because the manganese ion is less problematic from an environmental point of view than the zinc and cupric ions are.
Prochloraz and the metal complexes of prochloraz are mentioned in several documents about applying two or more pesticides to get additive or synergistic activity CN 1027771515A, CN 101380012A, CN 200810146216, CN 102017961A, CN 101971850A, CN 101796955B, CN 10653860A, CN 106982854, CN 102047898A, CN 108552202A, CN 103461368A, CN 101700033A, CN 101984809A, CN 103385250A, CN 107950577A, CN 102150678A, CN 101755808A/B, CN 101107931A, CN 101755837A, CN 1930966A, CN 1930973A, CN 101836654A, and CN 102669180A.
In the above-listed documents about combinations of various pesticides there are no detailed information about the composition or how to produce water based suspension concentrates of metal complexes of prochloraz.
Details about the compositions and the manufacturing procedures of water based suspension concentrates containing metal complexes of prochloraz, especially the manganese prochloraz chloride complex, are provided in CN 1054775356 A. In this document the compositions of suspension concentrates of manganese prochloraz chloride and propineb are provided.
Similarly the compostions of suspension concentrates of metal complexes of prochloraz and the fungicide epoxiconazole are described in CN 102805096 A and CN 102823609 A. Suspension concentrates containing manganese prochloraz chloride and other fungicides are mentioned in CN 106857689 A.
In the documents mentioned above the metal prochloraz complexes are produced, rinsed and isolated before making the suspension concentrates. The already prepared metal prochloraz complexes, for instance the manganese prochloraz chloride complex, are just added to the suspension concentrate as a part of the manufacturing process. ft will be a significant advantage if the crystalline metal prochloraz complexes can be produced as a part of the manufacturing of the water based suspension concentrate. It means it will not be necessary to produce and
isolate the metal complex of prochloraz in advance in a separate manufacturing procedure. Producing the metal prochloraz complex in situ in the water based suspension concentrate will reduce the cost and the time of the production process. In addition, typically the prochloraz is more available for purchase than the metal prochloraz complexes are.
Preferred examples according to the present invention are the complexes formed in situ in the water based suspension concentrate by reacting prochloraz, melted prochloraz or a solution of melted prochloraz with cupric, zinc or manganese chlorides or nitrates. It is preferred to add seed crystals of the metal prochloraz complex wanted before the formation of the complex takes place in the suspension concentrate vehicle. As regards the manganese prochloraz complexes, it is preferable to use an excess of manganese ions and/or chloride ions in the suspension concentrate, i.e. an excess of manganese and/or chloride in comparison with the amount of manganese and chloride necessary to form the manganese prochloraz chloride complex. The excess of manganese and/or chloride will ensure the concentration of free prochloraz in the water based suspension concentrate is low. The low concentration of prochloraz makes the suspension concentrate more stable because there is no melting of free prochloraz even at elevated temperatures, e.g. up to 45°C.
The construction of a phase solubility diagram is an efficient method to ensure that a sufficient excess of manganese and/or chloride ions are being applied in the water based suspension concentrate. This approach is outlined in example 1.
Regarding the in situ formation of a metal prochloraz chloride or nitrate complex in a water based suspension concentrate a preferable way is to dissolve or disperse the dispersing agents and the metal salt, e.g. CuC12, MnC12, ZnC12 or Zn(NO3)2 with or without crystal water, in the water phase of the suspension concentrate. Seed crystals of the wanted metal prochloraz complexes can be added in order to speed up the crystallization process. Afterwards, the melted prochloraz is added to the water using stirring, e.g. high shear stirring or rotor/stator mixing. The melted prochloraz can be added as a neat liquid or together with solvents and dispersing agent(s). The solvents and the dispersing agent can reduce the viscosity of the melted prochloraz making the mixing with water easier. The crystallization of the metal prochloraz complex typically takes minutes or a few hours. After the crystallization of the complex the suspension concentrate can be milled in order to get the particle size wanted, e.g. mean V (LASER) 2-4 pm.
The ingredients listed in the table above were mixed in 100 ml PET bottles, and the samples were equilibrated at 23°C on a rotor (carousel). Parts of the samples were filtered through 0.45 pm nylon (NY) filters after 2 and 7 weeks of equilibration. The concentrations of prochloraz in the filtered samples as a function of MnC12, 4H2O concentration are depicted in the figure below. After both 2 and 7 weeks of equilibration the solubility diagrams were of the B type according to Higuchi and Connors, Phase-Solubility techniques, Adv. Anal. Chem. Inbstr., 4, 117-212, 1965. The B diagram type indicates, the manganese procloraz chloride complex is the solid phase present at equilibrium at MnC12, 4H2O concentrations higher than 30 g/1. The isolated, water rinsed and dried solid phase from the sample containing 50 g/1 MnC12, 4H2O consisted of 92.0 % w/w prochloraz. The content of prochloraz in a Mn (Prochloraz)4 C12 complex is 92.3% w/w. The 92.0% result is in good agreement with the the theoretical content. The current example showed it was possible to formulate a water based suspension concentrate having Mn (Prochloraz)4 C12 as the stable solid phase. There was no problem as regards the dissociation of the complex when the concentration of manganse and/or chloride was sufficiently high, i.e. there was an excess amount of manganse and/or chloride in the suspension concentrate compared with what was needed to form the manganse prochloraz chloride complex.
Example 2
The compositions and properties of various 250 g/1 prochloraz water based suspension concentrates for seed dressing are listed in the table below.
The order of addition of the ingredients is shown in the table above (1-12). Prochloraz was melted at 60°C before it was added, and high shear stirring was used in order to disperse the melted prochloraz in the formulation. Prochloraz remained as droplets/liquid in product IV, while it crystallized immediately in product I, probably due to the presence of MnC12, 4H2O. Product I and III were easily milled whereas product II and IV were sticky and the milling wasn’t possible. Probably it was the lack of an excess amount of manganese and/or chloride in product II which triggered the dissociation of the manganese prochloraz complex and the melting of free prochloraz in the product.
Example 3
The product I and III compositions described in example 2 can be used for producing formulations containing other fungicides and insecticides in addition to prochloraz.
For instance it is possible to produce homogenous and stable water-based suspension concentrates containing 250 g/1 prochloraz, 50 g/1 kresoksim-methyl and 50 g/1 tebuconazole or containing 150 g/1 prochloraz, 250 g/1 thiomethoxam and 50 g/1 flutriafol.
Example 4
Using a formulation template similar to the template for product I in example 2 and using excessive amounts of CuC12, ZnC12 or Zn(NO3)2 instead of MnC12, 4H2O water based suspension concentrates of copper and zinc prochloraz complexes were produced. The copper and zinc prochloraz complexes were produced in situ as a part of the suspension concentrate production process.
Example 5
A water based suspension concentrate of manganese prochloraz was produced having a composition like product I in example 2. However, the Atlas G5002L and the propyleneglycol were mixed with the melted prochloraz and afterwards this mixture was dispersed in the water phase of the suspension concentrate. The crystallization of the managanese prochloraz chloride complex took place in situ in the water phase within minutes after the addition of the mixture.
Claims
1. A production procedure for water based suspension concentrate compositions of a crystalline complex of the formula (M (Prochloraz)n )2+ 2A', in which M is copper, manganese or zinc, n is 2 or 4, and A is chloride or nitrate, by which the crystalline complex is formed in situ during the preparation of the water based suspension concentrate compositions by adding melted prochloraz or a solution of prochloraz to the water phase of the suspension concentrates during the preparation of these.
2. A production procedure according to claim 1 for water based suspension concentrates containing one or more insecticides and/or one or more additional fungicides.
3. A production procedure according to claim 1 for water based suspension concentrates containing thiomethoxam and flutriafol.
4. A production procedure according to claim 1 for water based suspension concentrates containing tebuconazole and kresoksim methyl.
5. A production procedure according to claim 1 in which a surplus of M2+ and/or A" is used compared with the molar ratio used in the formula (M (Prochloraz)n )2+ 2A".
6. A method for controlling a phytopathogenic fungus which comprises applying to seeds, plants, their habitats or to post-harvest products, suspension concentrates produced according to claim 1.
7. A method for controlling a phytopathogenic fungus which comprises applying to seeds, plants, their habitats or to post-harvest products, suspension concentrates produced according to claim 1 and 2.
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Citations (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4250179A (en) * | 1977-03-26 | 1981-02-10 | The Boots Company Limited | Metal complex imidazole fungicides, and methods of controlling fungi with them |
GB1591212A (en) * | 1977-03-31 | 1981-06-17 | Nippon Soda Co | 1-(n-phenyl-2-alkylimidoyl) imidazole compounds and their use in fungicides |
EP0445656A1 (en) * | 1990-03-05 | 1991-09-11 | Makhteshim Chemical Works Limited | Novel fungicidal imidazole complexes |
WO2011157725A2 (en) * | 2010-06-16 | 2011-12-22 | Basf Se | Aqueous active ingredient composition |
CN104365651A (en) * | 2014-11-03 | 2015-02-25 | 联保作物科技有限公司 | Prochloraz microcapsule suspending agent and compound preparation thereof |
CN104529663A (en) * | 2015-01-23 | 2015-04-22 | 广东省农业科学院农业资源与环境研究所 | Special fertilizer-pesticide mixture for litchi, and preparation method and application thereof |
RU2656965C1 (en) * | 2015-12-21 | 2018-06-07 | Общество с ограниченной ответственностью "Альфа Химгрупп" | Fungicidal composition for the wheat seeds presowing treatment |
CN109438356A (en) * | 2018-11-29 | 2019-03-08 | 江苏乐斯化学有限公司 | A kind of purification process of Prochloraz raw medicine |
-
2020
- 2020-09-11 WO PCT/DK2020/050248 patent/WO2022053116A1/en active Application Filing
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US4250179A (en) * | 1977-03-26 | 1981-02-10 | The Boots Company Limited | Metal complex imidazole fungicides, and methods of controlling fungi with them |
GB1591212A (en) * | 1977-03-31 | 1981-06-17 | Nippon Soda Co | 1-(n-phenyl-2-alkylimidoyl) imidazole compounds and their use in fungicides |
EP0445656A1 (en) * | 1990-03-05 | 1991-09-11 | Makhteshim Chemical Works Limited | Novel fungicidal imidazole complexes |
WO2011157725A2 (en) * | 2010-06-16 | 2011-12-22 | Basf Se | Aqueous active ingredient composition |
CN104365651A (en) * | 2014-11-03 | 2015-02-25 | 联保作物科技有限公司 | Prochloraz microcapsule suspending agent and compound preparation thereof |
CN104529663A (en) * | 2015-01-23 | 2015-04-22 | 广东省农业科学院农业资源与环境研究所 | Special fertilizer-pesticide mixture for litchi, and preparation method and application thereof |
RU2656965C1 (en) * | 2015-12-21 | 2018-06-07 | Общество с ограниченной ответственностью "Альфа Химгрупп" | Fungicidal composition for the wheat seeds presowing treatment |
CN109438356A (en) * | 2018-11-29 | 2019-03-08 | 江苏乐斯化学有限公司 | A kind of purification process of Prochloraz raw medicine |
Non-Patent Citations (2)
Title |
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