Patent Application
20240032538
The present invention is included in the field of herbicidal formulations of the chemical compound flurochloridone: 3-chloro-4-(chloromethyl)-1-3-(trifluoromethyl)phenyl-2-pyrrolidone, especially in the form of a microemulsion at low concentrations.
The object of the present invention is the provision of an herbicidal composition of the active ingredient flurochloridone in low concentration in the form of a microemulsion that unexpectedly requires a lower application dose of the active ingredient per unit of crop area to which it is applied, achieving equal or better benefits than concentrated commercial formulations thereof.
Flurochloridone is a pre- and post-emergent herbicide used to control a wide spectrum of weeds, especially those with broad leaves.
Its systemic action is based on the penetration by cotyledons, young leaves or roots in order to completely translocate towards the leaves and stems, causing the death of the weeds.
Among the favorable characteristics of flurochloridone, it was found that it is activated with low soil moisture and is not washed away by the effect of rain.
The document closest to the present development corresponds to patent U.S. Pat. No. 9,339,030 which refers to a ready-to-use foamable composition that contains the product flurochloridone among its components, however there is no disclosure in said document about a possible obtaining of a flurochloridone composition in microemulsion form (ME).
In general, flurochloridone is marketed at 25% weight by volume as an emulsifiable concentrate (EC).
No antecedents have been found for commercialized products that comprise the compound flurochloridone as an active principle in compositions in the form of a microemulsion, therefore the present development implies an innovation in the art.
As a main variant of the invention mode, a flurochloridone composition in the form of a microemulsion is preferred, comprising from 5 to 20% weight by volume (w/v) of flurochloridone, a solvent or a mixture of polar or non-polar, soluble or insoluble solvents in water, comprising from 35 to 45% w/v, a polar cosolvent or mixture of polar cosolvents comprising from 8 to 13% w/v, a mixture of non-ionic surfactants comprising from 6% to 12% w/v, an anionic surfactant comprising from 9.5% to 10% w/v, a co-adjuvant comprising from 2% to 15.0% w/v, water from 2.0% to 28.0% w/v, and a defoamer comprising from 0.05% w/v to 0.5% w/v.
In the flurochloridone composition in the form of a microemulsion according to the above-indicated main variant, the solvent or solvent mixture that is polar or nonpolar, soluble or water-insoluble, comprising 35 to 45% w/v is selected as the solvent water-soluble cyclohexanone, dimethylsulfoxide (DMSO), dioxolane, methyl ethyl ketone (MEK), acetone, and as a solvent water-insoluble dibasic ester (DBE), or xylene; or mixtures thereof.
In the flurochloridone composition in the form of a microemulsion according to the indicated main variant, the polar cosolvent is selected from N-methylpyrrolidone, N-octylpyrrolidone or a mixture thereof.
In the flurochloridone composition in the form of a microemulsion according to the indicated main variant, the mixture of non-ionic surfactants comprising from 6% to 12% w/v is selected from polyalkylene oxide block copolymer (Atlas G5002L®) and 10 mol EO nonylphenol ethoxylate.
In the flurochloridone composition in the form of a microemulsion according to the variant above, the amount of polyalkylene oxide block copolymer in the composition ranges between 3.0% w/v to 7.0% w/v; or the amount of 10 mol EO nonylphenol ethoxylate in the composition ranges between 3% w/v to 5.0% w/v.
In the flurochloridone composition in the form of a microemulsion according to the main variant, where the anionic surfactant is selected from calcium dodecylbenzenesulfonate (FS Ca) at 60% or 70% w/w in isobutanol.
The flurochloridone composition in the form of a microemulsion according to the main variant, the co-adjuvant is selected from soybean oil fatty acid methyl esters (FAME) of vegetal oil as soybean oil, coconout oil, palm oil, palm kernel oil, corn oil, olive oil or oilseed rape and tallow.
In the flurochloridone composition in the form of a microemulsion according to the main variant, the defoamer comprises a silicone defoamer.
In the flurochloridone composition in the form of a microemulsion according to the stated main variant, it is preferred that it comprises the following list of components:
In the flurochloridone composition in the form of a microemulsion according to the stated main variant, it is preferred that it comprises the following list of components:
In the flurochloridone composition in the form of a microemulsion according to the stated main variant, it is preferred that it comprises the following list of components:
In the flurochloridone composition in the form of a microemulsion according to the stated main variant, it is preferred that it comprises the following list of components:
The present invention relates to compositions of flurochloridone in the form of a microemulsion with a concentration of the active principle between 5 and 20% w/v.
The technical grade flurochloridone is a solid that is marketed at a concentration of 96-97 p/p with a very low solubility in water of 21.9 ppm (mg/L) at 20° C.
Microemulsion compositions are formulations containing very small emulsified oily droplets, which give rise to a transparent formulation that is thermodynamically stable in a wide range of temperatures because the droplets have a very small size that varies in a range of 0.01. μm to 0.05 μm in diameter. Therefore, unlike other emulsion systems, where oily droplets can coalesce slowly over time causing phase separation, this does not happen in microemulsion formulations.
Microemulsions are made up of immiscible liquids and appropriate amounts of surfactant and cosurfactant.
The present microemulsion formulation of flurochloridone is composed of water immiscible liquids that comprise an organic aprotic solvent of a water-soluble formulation selected from cyclohexanone, dimethylsulfoxide (DMSO), dioxolane, methyl ethyl ketone (MEK), acetone, and as a water-insoluble solvent dibasic ester (DBE), or xylene.
Dibasic ester comprises a mixture of 10 to 30% w/w dimethyl adipate with 40 to 70% w/w dimethyl glutarate and 10 to 30% w/w dimethyl succinate.
The present formulation further comprises a water-soluble cosolvent selected from N-methylpyrrolidone and N-octylpyrrolidone, or their mixture.
Among the surfactants for the formulation of the flurochloridone microemulsion composition of the present development are preferred: mixture of non-ionic surfactants such as polyalkylene oxide block copolymer marketed as ATLAS G5002L® and 10 mol EO nonylphenol ethoxylate.
A preferred anionic surfactant is calcium dodecylbenzenesulfonate (FS Ca) at 60% or 70% w/w in isobutanol.
The flurochloridone microemulsion also contains fatty acid methyl esters of vegetal oil as soybean oil, coconout oil, palm oil, palm kernel oil, corn oil, olive oil or oilseed rape and tallow as co-adjuvants; the co-adjuvants give them an anti-evaporation and adherence power to agricultural applications; this property is essential to avoid the separation into phases of active ingredients within the mixing tank at the application time of agrochemicals.
In order to avoid the foam formation during the formulation of the flurochloridone composition in the form of a microemulsion, defoamers selected from silicones are added, among others.
Finally, the flurochloridone composition in the form of a microemulsion contains water that facilitates the formation of a transparent formulation in the present case.
Based on the previous components, the following microemulsions were prepared, where the amounts in % w/v are described in the following tables:
In all the previous formulations, the technical grade drug was added in order to obtain the desired weight by volume concentrations.
The previous formulations in microemulsions showed excellent stability, passing the water emulsion tests without separation of components.
The following tests were carried out with the previous microemulsion formulations, which were carried out confidentially until the moment of filing of this application:
Products to evaluate: (Flurochloridone 12.5% ME) in pre-emergence of sunflower cultivation.
Work report:
The wind was 20 km/h in favor, relative humidity of 39% and 32° C. of ambient temperature.
As a first result, it must be said that phytotoxicity symptoms were observed in the crop in treatments 4,5 and 6. The symptoms were thickening of the veins and chlorosis in the first leaves, but these symptoms were diluted with time.
Table 1 shows the Lecherón control at 35 days after application. Although the density of the weed was not very important in the test, very good controls could be seen with all the evaluated doses of the herbicide. Likewise, treatment 5 was highlighted, ending with totally clean plots on this weed.
Different letters between columns indicate meaningful differences between treatments.
The control of SONOL births is shown in Table 2. In general, the control was good for all the doses evaluated, but at 70 days the control of dose 1 decreased. This data is very interesting because this weed has its presence and abundance greatly increased in recent years, being one of the most problematic weeds in sunflower cultivation.
Comparative test of herbicides in Sunflower Pre-emergence (Flurochloridone 12.5% ME) Campaign 2015/16
Products to evaluate: Flurochloridone 12.5% in Sunflower pre-emergence
Tests design: Complete randomized blocks with plots 3 m wide by 8 m long and 3 replications.
The weeds that appeared in the test were Conyza sumatrensis “black branch” and Carduus acanthoides “Chilean thistle”.
Table 2 shows the controls on the black branch. At 19 days, treatments 3, 4 and 5 showed an acceptable control greater than 80%. It was seen that some controlled plants in the fallow were beginning to sprout and on this sprout the control was lower. At 54 days, the controls dropped because there was a very important black branch emergence flow, in any case the trend was the same and no final differences were seen between treatments 3, 4 and 5.
Thistle control was slightly superior to that of black branch. There were also many births of this weed. At 19 days after application, all treatments exceeded 80% control. After 54 days, the control residuality was maintained in the treatments with the highest doses and in the chemical witness (treatments 4 and 5) without showing meaningful differences.
Although the final black branch controls were not totally effective, the higher doses of the product achieved a good initial control, which is where the critical period in sunflower is defined.
Regarding thistle, it was very clear how residual control increased when the dose of flurochloridone was increased.
In this test and these conditions, no notable effects of phytotoxicity were observed in sunflower.
In pre-emergence treatments in the Sunflower crop in full coverage, evaluated in the control of broad leaf weeds common in the Pampean region, susceptible to the chemical molecule under study.
At the time of application, the lot was found to be clean of weeds, 2 days after sowing. Afterwards, sampling was made at 15 and 30 days after application, then recording of the emergence of seedlings susceptible to control (species and quantity) was performed.
Individuals present per square meter, average value of the three repetitions from each treatment
Different letters indicate meaningful differences (p<=0.05)
Different letters indicate meaningful differences (p<=0.05)
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With the following analysis of variance:
Different letters indicate meaningful differences (p<=0.05)
Different letters indicate meaningful differences (p<=0.05)
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With the following analysis of variance:
Different letters indicate meaningful differences (p<=0.05)
Different letters indicate meaningful differences (p<=0.05)
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With the following analysis of variance:
Different letters indicate meaningful differences (p<=0.05)
Different letters indicate meaningful differences (p<=0.05)
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With the following analysis of variance:
Different letters indicate meaningful differences (p<=0.05)
Different letters indicate meaningful differences (p<=0.05)
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The product evaluated in this study exhibited a performance comparable to a good extent to that shown by the chemical witness, directly dependent on the test dose and the biological characteristics of each weed species present and taking into account the differences in concentration and formulation of the tested products.
The formulation of flurochloridone 12.5% ME had an efficient control over the weeds evaluated in the test. The 5 l/ha dose of flurochloridone 12.5% ME (treatment 3) showed the same performance compared to the doses of the commercial witness (flurochloridone 25% EC 4 l/ha). From these results we can conclude that the reduction of active ingredient per hectare translates into 37.5% compared to the chemical witness of proven efficacy in the market.
The formulation of flurochloridone 12.5% ME had an efficient control over the weeds evaluated in the test. The 5 l/ha dose of flurochloridone 12.5% ME (treatment 4) showed the same performance compared to the doses of the commercial witness (flurochloridone 25% EC 4 l/ha). From these results we can conclude that the reduction of active ingredient per hectare translates into 37.5% compared to the chemical witness of proven efficacy in the market.
The formulation of flurochloridone 12.5% ME had an efficient control over the weeds evaluated in the test. The 5 l/ha dose of flurochloridone 12.5% ME (treatment 4) showed the same performance compared to the doses of the commercial witness (flurochloridone 25% EC 4 l/ha). From these results we can conclude that the reduction of active ingredient per hectare translates into 37.5% compared to the chemical witness of proven efficacy in the market.
| Number | Date | Country | Kind |
|---|---|---|---|
| P20200103543 | Dec 2020 | AR | national |
| Filing Document | Filing Date | Country | Kind |
|---|---|---|---|
| PCT/IB2021/055323 | 6/16/2021 | WO |
