WO2018024143A1

WO2018024143A1 - A process for preparing a novel formulation of sulfentrazone and use of the same

Info

Publication number: WO2018024143A1
Application number: PCT/CN2017/094622
Authority: WO
Inventors: James Timothy Bristow
Original assignee: Jiangsu Rotam Chemistry Co., Ltd
Priority date: 2016-08-05
Filing date: 2017-07-27
Publication date: 2018-02-08
Also published as: BR102017016862B1; AU2017100038A4; TWI742123B; CN109561687B; CN109561687A; BR102017016862A2; TW201808098A; AU2016210751B1

Abstract

A herbicidal composition for applying to a plant to control weeds, and including sulfentrazone with anti-photolysis agent, wherein the anti-photolysis agent is S-metolachlor, is provided. The amount of S-metolachlor to the amount of sulfentrazone is typically in a range of about 2: 1 to about 5: 1. The amount of sulfentrazone is preferably about 10％by weight to about 15.6％by weight, and the amount of S-metolachlor is preferable about 45％by weight to about 50％by weight of the herbicidal composition. The composition can also include a liquid diluent, a solid diluent, a wetting agent, a dispersant, or a thickening agent, and combinations thereof.

Description

A PROCESS FOR PREPARING A NOVEL FORMULATION OF SULFENTRAZONE AND USE OF THE SAME

CROSS-REFERENCE TO RELATED APPLICATION

This application claims priority to Australian Patent Application No. 2016210751, titled “A PROCESS FOR PREPARING A NOVEL FORMULATION OF SULFENTRAZONE AND USE OF THE SAME” , filed with IP Australia on August 5, 2016, the entire contents of which are incorporated herein by reference.

FIELD

The present invention relates to a novel formulation of 2', 4'-dichloro-5'- (4-difluoromethyl-4, 5-dihydro-3-methyl-5-oxo-1H-1, 2, 4-triazol-1-yl) methanesulfonanilide (Sulfentrazone) with an anti-photolysis agent, to processes for its preparation and to its use in agrochemical preparations.

BACKGROUND

2', 4'-dichloro-5'- (4-difluoromethyl-4, 5-dihydro-3-methyl-5-oxo-1H-1, 2, 4-triazol-1-y l) methanesulfonanilide (Sulfentrazone) is a protoporphyrinogen oxidase inhibitor. Sulfentrazone has a molecular formula of C₁₁H₁₀Cl₂F₂N₄O₃S. Its chemical structure is:

It is applied pre-emergence or pre-plant incorporated for soybean, sugarcane, tobacco, against annual broad-leaved weeds, some grasses and Cyperus spp.

Sulfentrazone, like other agricultural chemicals, can be formulated as concentrates in a variety of different formulations. However, it will readily undergo photolysis having half-life of less than 0.5 days. According to “Willut JM et al； in Picogram, Preprint Abstract, Iss. 52, Amer Chem Soc, Div Agrochem (1997) ” , direct photolysis of buffered aqueous solutions of sulfentrazone exposed to simulated sunlight occurs rapidly with half-lives of about 1 hour at pH 6 and pH 7, and 12 hours at pH 5.

Therefore, the content of sulfentrazone drops with time and adversely affects the function of sulfentrazone.

SUMMARY

It has been found that making proper selection of a formulation adjuvant surprisingly helps to stabilize the active ingredient in the formulation. More particularly, it was surprisingly found that S-metolachlor can significantly inhibit the photolysis of sulfentrazone. The half-life of the sulfentrazone can be prolonged, and thus the weeds are exposed to the formulation for an increased duration and the effectiveness of the formulation is enhanced. The present disclosure relates to embodiments of invention that provides a novel formulation of sulfentrazone that reduces or avoids the photolysis problems encountered.

S-Metolachlor (IUPAC name: A mixture of (aRS, 1S) -2-chloro-6'-ethyl-N- (2-methoxy-1-methylethyl) aceto-o-toluidide and (aRS, 1R) -2-chloro-6'-ethyl-N- (2-methoxy-1-methylethyl) aceto-o-toluidide) has the following chemical structures:

Accordingly, in one embodiment, the present invention relates to a novel formulation of 2', 4'-dichloro-5'- (4-difluoromethyl-4, 5-dihydro-3-methyl-5-oxo-1H-1, 2, 4-triazol-1-yl) methanesulfonanilide (Sulfentrazone) with an anti-photolysis agent, to processes for its preparation, and to its use in agrochemical preparations.

Surprisingly, it has been found that S-metolachlor can be used as an anti-photolysis agent for sulfentrazone.

In another embodiment, the invention relates to a method of increasing the stability of sulfentrazone by applying an effective amount of S-metolachlor, to a composition containing sulfentrazone.

Of particular interest is the anti-photolysis compounds of S-metolachlor.

The weight ratio of the anti-photolysis compounds to sulfentrazone varies within wide limits and is typically in a range of about 2: 1 to about 5: 1, or about 2.5: 1 to about 4.75: 1, or about 3: 1 to about 4.5: 1, or about 3.5: 1 to about 4: 1, and most preferably 3.75: 1.

The amount of S-metolachlor in the formulation is a photolysis resistance providing effective amount and can be from about 10％by weight to about 80％by weight, or from about 20％by weight to about 70％by weight, or from about 30％by weight to about 60％by weight, or about 40％by weight to about 55％by weight of the formulation.

The amount of sulfentrazone in the formulation can be less than about 40％by weight of the formulation, or less than about 30％by weight of the formulation, or less than about 15％by weight of the formulation.

In one preferred embodiment, the amount of sulfentrazone is from about 10％by weight to about 15.6％by weight and the amount of S-metolachlor is from about 45％by weight to about 50％by weight of the formulation, and more preferably the amount of sulfentrazone is 12.8％by weight and the amount of S-metolachlor is 48％by weight of the formulation.

The herbicidal activity of sulfentrazone is known in the art and is used in commercial scale. Methods to formulate and use sulfentrazone-containing compositions are also known in the art. The formulations of sulfentrazone described herein according to embodiments of the present invention may be formulated and applied in an analogous manner.

In a further aspect, the present invention provides a herbicidal composition comprising sulfentrazone and an anti-photolysis agent as hereinbefore defined.

In another aspect, the invention furthermore provides processes for preparing compositions for controlling weeds comprising sulfentrazone and an anti-photolysis agent, and to methods for controlling weeds by applying a composition according to an embodiment of the invention.

In another embodiment, the invention provides a method for imparting photolysis resistance to a herbicidal composition comprising a herbicidally effective amount of sulfentrazone, comprising adding to the herbicidal composition a photolysis resistance providing effective amount of S-metolachlor.

DETAILED DESCRIPTION OF EMBODIMENTS

The composition of sulfentrazone and anti-photolysis agent can be converted in a known manner to the customary formulations, such as suspension concentrates (SC) , oil-based suspension concentrates (OD) , soluble granules (SG) , dispersible concentrates (DC) , emulsifiable concentrates (EC) , emulsion for seed treatment (ES) , flowable concentrate for seed treatment (FS) , granules, microgranules (MG) , suspo-emulsions (SE) , and water dispersible granules (WG) , using suitable auxiliaries and carriers or solvents.

Here, sulfentrazone should be present in a concentration of from about 0.1％to about 50％by weight of the composition or formulation, i.e., in an amount sufficient to achieve the required dosage upon application to a locus where herbicidal control is desired. The formulations are prepared, for example, by combining sulfentrazone and the anti-photolysis agent with water, solvents and/or carriers, using, if appropriate, emulsifiers and/or dispersants, and/or other auxiliaries.

The formulations according to embodiments of the invention can be prepared by mixing sulfentrazone and the S-metolachlor anti-photolysis agent with herbicidally acceptable additives, for example, liquid diluents, solid diluents, wetting agents, dispersants, thickening agent and other formulation ingredients.

Liquid diluents include, for example, water, N, N-dimethylmamide, dimethyl sulfoxide, N-alkylpyrrolidone, ethylene glycol, polypropylene glycol, propylene carbonate, dibasic esters, paraffins, alkylbenzenes, alkyl naphthalenes, glycerin, triacetine, oils of olive, castor, linseed, sesame, corn, peanut, cotton-seed, soybean, rape-seed and coconut； ketones, such as cyclohexanone, 2-heptanone, isophorone and 4-hydroxy-4-methyl-2-pentanone； acetates, such as hexyl acetate, heptyl acetate and octyl acetate； and alcohols, such methanol, cyclohexanol, decanol, benzyl alcohol, and tetrahydrofurfuryl alcohol.

Solid diluents can be water-soluble or water-insoluble. Water-soluble solid diluents include, but are not limited to, salts, such as alkali metal phosphates (e.g., sodium dihydrogen phosphate) , alkaline earth phosphates, sulfates of sodium, potassium, magnesium and zinc, sodium and potassium chloride, sodium acetate, sodium carbonate, sodium benzoate, and/or sugars and sugar derivatives such as sorbitol, lactose, sucrose and mannitol. Examples of water-insoluble solid diluents include, but are not limited to clays, synthetic and diatomaceous silicas, calcium and magnesium silicates, titanium dioxide, aluminum oxide, calcium oxide, and zinc oxide.

Wetting agents include, but are not limited to, alkyl sulfosuccinates, laureates, alkyl sulfate and phosphate esters, acetylenic diols, ethoxyfluorinated alcohols, ethoxylated silicones, alkyl phenol ethyloxylates, benzene sulfonates, alkyl-substituted benzene sulfonates, alkyl α-olefin sulfonates, naphthalene sulfonates, alkyl-substituted naphthalene sulfonates, condensates of naphthalene sulfonates and alkyl-substituted naphthalene sulfonates with formaldehyde, and alcohol ethoxylates, and salt forms of any of these. Alkyl naphthalene sulfonate, sodium salt is particularly preferred for the composition and formulation of the invention.

Dispersants include, but are not limited to, sodium, calcium and ammonium salts of lignosulfonates (optionally polyethoxylated) ； sodium and ammonium salts of maleic anhydride copolymers； sodium and ammonium salts of condensed phenolsulfonic acid； and naphthalene sulfonate-formaldehyde condensates and their sodium and ammonium salts. Of note are compositions comprising up to about 10％by weight of dispersant. Lignosulfonates, such as sodium lignosulfonates, are particularly preferred for the composition and formulation of the invention. Naphthalene sulfonate-formaldehyde condensates (and salts thereof) , such as condensation products of naphthalenesulfonic acid polymer with formaldehyde, sodium salt are particularly preferred for the composition and formulation of the invention.

Thickeners include, but are not limited to, guar gum, pectin, casein, carrageenan, xanthan gum, alginates, methylcellulose, hydroxyethylcellulose, hydroxypropylcellulose and carboxymethylcellulose. Synthetic thickeners include derivatives of the former categories, and also polyvinyl alcohols, polyacrylamides, polyvinylpyrrolidones, polyethers and their copolymers as well as polyacrylic acids and their salts. Alkylpolyvinylpyrrolidone is particularly preferred for the composition and formulation of embodiments of the invention.

Other formulation ingredients can be used in certain embodiments of the present invention, such as dyes, defoamers, drying agents, and the like. These formulation ingredients are known to one skilled in the art.

The sulfentrazone forming a component of formulations according to embodiments of the invention can be present in its commercially available formulations and use forms, prepared from these formulations, and as a mixture with other active compounds (such as insecticides, attractants, sterilizing agents, bactericides, acaricides, nematicides, fungicides, growth-regulating substances, herbicides, safeners, fertilizers and semiochemicals, and combinations thereof) . A mixture with other known active compounds (such as herbicides, fertilizers, growth regulators, safeners, semiochemicals, or with agents for improving plant properties) is also possible.

When used as herbicide according to embodiments of the invention, the active compound can be present in their commercially available formulations and use forms, in a form prepared from these formulations, or as a mixture with synergistic agents. Synergistic agents are compounds which increase the action of the active compounds, without it being necessary for the synergistic agent added to be active itself.

Any plants or plant parts susceptible to control or protection by sulfentrazone can be treated in accordance with embodiments of the invention. Plants are to be understood as meaning in the present context all plants and plant populations, such as desired and undesired wild plants or crop plants (including naturally occurring crop plants) . Crop plants can be plants which can be obtained by conventional breeding and optimization methods, by biotechnological and genetic engineering methods, or by combinations of these methods including the transgenic plants and the plant cultivars which may or may not be protected by plant breeders' rights. Plant parts are to be understood as meaning all parts and organs of plants either above or below the ground, such as shoot, leaf, flower and root. Examples of which may be mentioned include leaves, needles, stalks, stems, flowers, fruit bodies, fruits, seeds, roots, tubers and rhizomes. The plant parts also include harvested material, and vegetative and generative propagation material such as cuttings, tubers, rhizomes, offshoots and seeds.

Treatment according to an embodiment of the invention of the plants and plant parts with the active compounds is carried out directly (i.e., by direct application of the formulation to the plants or plant parts) or by applying the compounds to the surroundings, habitat, or storage space of the plants or plant parts, also known as application to the locus of the plants or plant parts. Examples of such application methods include dipping, spraying, vaporizing, fogging, broadcasting, painting on, and in the case of propagation material, applying one or more coats, particularly in the case of seed.

The invention may be used to control weeds such as Acanthospermum spp., Ageratum spp., Amaranthus spp., Bidens spp., Blainvillea spp., Brachiaria spp., Cenchrus spp., Chamaecrista spp., Commelina spp., Cynodon spp., Cyperus spp., Desmodium spp., Digitaria spp., Echinochloa spp., Eleusine spp., Emilia spp., Euphorbia spp., Galinsoga spp., Hyptis spp., Ipomoea spp., Nicandra spp., Panicum spp., Parthenium spp., Pennisetum spp., Portulaca spp., Rhynchelytrum spp., Richardia spp., Sida spp., Solanum spp., Spermacoce spp., Acanthospermum austral, Acanthospermum hispidum, Ageratum conyzoides, Amaranthus deflexus, Amaranthus hybridus, Amaranthus retroflexus, Amaranthus viridis, Bidens pilosa, Blainvillea latifolia, Brachiaria decumbens, Brachiaria plantaginea, Cenchrus echinatus, Chamaecrista rotundifolia, Commelina benghalensis, Cynodon dactylon, Cyperus rotundus, Desmodium tortuosum, Digitaria horizontalis, Echinochloa crusgalli, Eleusine indica, Emilia sonchifolia, Euphorbia heterophylla, Galinsoga parviflora, Hyptis suaveolens, Ipomoea grandifolia, Nicandra physaloides, Panicum maximum, Parthenium hysterophorus, Pennisetum setosum, Portulaca oleracea, Rhynchelytrum repens, Richardia brasiliensis, Sida glaziovii, Sida rhombifolia, Solanum americanum, Spermacoce alata, Spermacoce latifolia.

The benefits of embodiments of the present invention are most noticeable when the pesticidal composition and/or formulation is applied to kill weeds in growing crops of useful plants: cereals (wheat, barley, rye, oats, maize, rice, sorghum, triticale and related crops) ； fruit, such as pomes, stone fruit and soft fruit, such as apples, grapes, pears, plums, peaches, almonds, pistachio, cherries, and berries, for example strawberries, raspberries and blackberries, bell pepper, red pepper； leguminous plants (beans, lentils, peas, soybeans) ； oil plants (rape, mustard, sunflowers) ； cucurbitaceae (marrows, cucumbers, melons) ； fiber plants (cotton, flax, hemp, jute) ； citrus, such as calamondin, citrus citron, citrus hybrids (includes chironja, tangelo, tangor) , grapefruit, kumquat, lemon, lime, mandarin (tangerine) , sour orange, sweet orange, pummelo, and satsuma mandarin； vegetables (spinach, lettuce, asparagus, cabbages, carrots, onions, tomatoes, potatoes, paprika) ； coffee； sugarcane； as well as ornamentals (flowers, such as rose, shrubs, broad-leaved trees and evergreens, such as conifers) , preferably cereals, citrus, coffee, fiber plants, fruit, leguminous plants, oil plants, sugarcane, tobacco, tree, more preferably bean, canola, citrus, coffee, corn, cotton, eucalyptus, pineapple, soybean, sugarcane, sunflower, tobacco. Treatment of growing crops of maize and potatoes are particularly beneficial.

As used herein, the word “about” when used in connection with a numerical amount or range, means somewhat more or somewhat less than the stated numerical amount or range, to a deviation of ± 10％of the stated numerical amount or endpoint of the range.

“Locus” and “surrounding, ” as used herein, refers to the place on which the plants are growing, the place on which the plant propagation materials of the plants are sown or the place on which the plant propagation materials of the plants will be sown.

All percentages are given in weight ％unless otherwise indicated.

Embodiments of the present invention will now be described by the following examples which are provided for illustrative purposes only, and not intended to limit the scope of the disclosure.

Examples

The photolysis stability of sulfentrazone in these compositions was determined by continuously irradiating samples with UV light from a UV lamp, and then comparing the sulfentrazone content before and after irradiating to determine relative percentage of photolysis. The relative percentage of photolysis was calculated by the following equation:

Sulfentrazone content was determined by assaying the compositions with high-pressure liquid chromatography (HPLC) using reversed-phase columns and eluants.

Examples 1-Samples were prepared as follows:

Sulfentrazone and S-metolachlor were dissolved in acetone.

Table 1.

Example 19

An emulsifiable concentrate was prepared having the following composition:

Examples 1 to 18 were subjected to a test to determine their photolysis stability, using the following procedure:

20 mL of the solution was added to a quartz tube. The tube was continuously irradiated with UV light from a UV lamp. Aliquots (100 μL) of the solution were removed from the tube at 2 hours and 8 hours. The concentration of sulfentrazone in each aliquot was determined by HPLC.

The results are summarized in Table 2 below.

Table 2

Throughout the specification and the claims that follow, unless the context requires otherwise, the words “comprise” and “include” and variations such as “comprising” and “including” will be understood to imply the inclusion of a stated integer or group of integers, but not the exclusion of any other integer or group of integers.

The reference to any prior art in this specification is not, and should not be taken as, an acknowledgement of any form of suggestion that such prior art forms part of the common general knowledge.

Claims

A herbicidal composition comprising:

a herbicidally effective amount of sulfentrazone, and

a photolysis inhibiting effective amount of S-metolachlor, wherein the amount of S-metolachlor to the amount of sulfentrazone is in a range of about 2: 1 to about 5: 1.
The herbicidal composition according to claim 1, wherein the amount of S-metolachlor to the amount of sulfentrazone is in a range of about 2.5: 1 to about 4.75: 1.
The herbicidal composition according to claim 1, wherein the amount of S-metolachlor to the amount of sulfentrazone is in a range of about 3: 1 to about 4.5: 1.
The herbicidal composition according to claim 1, wherein the amount of S-metolachlor to the amount of sulfentrazone is in a range of about 3.5: 1 to about 4: 1.
The herbicidal composition according to claim 1, wherein the amount of S-metolachlor to the amount of sulfentrazone is 3.75: 1.
The herbicidal composition according to claim 1, wherein the amount of sulfentrazone is less than about 40％by weight of the composition.
The herbicidal composition according to claim 1, wherein the amount of sulfentrazone is less than about 30％by weight of the composition.
The herbicidal composition according to claim 1, wherein the amount of sulfentrazone is less than about 15％by weight of the composition.
The herbicidal composition according to claim 1, wherein the amount of S-metolachlor is from about 10％by weight to about 80％by weight of the composition.
The herbicidal composition according to claim 1, wherein the amount of S-metolachlor is from about 20％by weight to about 70％by weight of the composition.
The herbicidal composition according to claim 1, wherein the amount of S-metolachlor is from about 30％by weight to about 60％by weight of the composition.
The herbicidal composition according to claim 1, wherein the amount of S-metolachlor is from about 40％by weight to about 55％by weight of the composition.
The herbicidal composition according to claim 1, wherein the amount of sulfentrazone is from about 10％by weight to about 15.6％by weight and the amount of S-metolachlor is from about 45％by weight to about 50％by weight of the composition.
The herbicidal composition according to claim 1, wherein the amount of sulfentrazone is 12.8％by weight and the amount of S-metolachlor is 48％by weight of the composition.
The herbicidal composition according to any one of claims 1 to 14, wherein the composition is formulated as a suspension concentrate (SC) , an oil-based suspension concentrate (OD) , a soluble granule (SG) , a dispersible concentrate (DC) , an emulsifiable concentrate (EC) , an emulsion for seed treatment (ES) , a flowable concentrate for seed treatment (FS) , a granule, a microgranule (MG) , a suspo-emulsion (SE) , or a water dispersible granule (WG) .
The herbicidal composition according to claim 15, further comprising one or more auxiliaries selected from the group consisting of a liquid diluent, a solid diluent, a wetting agent, a dispersant, a thickening agent, and combinations thereof.
A method for controlling weeds, comprising applying to a plant or plant part, or the surroundings thereof, an effective amount of the herbicidal composition according to any one of claims 1 to 16.
A method for imparting photolysis resistance to a herbicidal composition comprising a herbicidally effective amount of sulfentrazone, comprising adding to the herbicidal composition a photolysis resistance providing effective amount of S-metolachlor, wherein the amount of S-metolachlor to the amount of sulfentrazone is in a range of about 2: 1 to about 5: 1.
The method according to claim 18, wherein the amount of S-metolachlor to the amount of sulfentrazone is in a range of about 2.5: 1 to about 4.75: 1.
The method according to claim 18, wherein the amount of S-metolachlor to the amount of sulfentrazone is in a range of about 3: 1 to about 4.5: 1.
The method according to claim 18, wherein the amount of S-metolachlor to the amount of sulfentrazone is in a range of about 3.5: 1 to about 4: 1.
The method according to claim 18, wherein the amount of S-metolachlor to the amount of sulfentrazone is 3.75: 1.
The method according to claim 18, wherein the amount of sulfentrazone is from about 10％by weight to about 15.6％by weight and the amount of S-metolachlor is from about 45％by weight to about 50％by weight of the composition.
The method according to claim 18, wherein the amount of sulfentrazone is 12.8％by weight and the amount of S-metolachlor is 48％by weight of the composition.