OA20908A - An agrochemical composition. - Google Patents
An agrochemical composition. Download PDFInfo
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- OA20908A OA20908A OA1202200375 OA20908A OA 20908 A OA20908 A OA 20908A OA 1202200375 OA1202200375 OA 1202200375 OA 20908 A OA20908 A OA 20908A
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- crystal
- sulfentrazone
- metribuzin
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Abstract
The present invention provides a co-crystal of sulfentrazone and a triazinone herbicide and process for preparation thereof. The present invention also provides an agrochcmical composition comprising said co-crystal and process of preparation of an agrochemical composition and method of controlling weeds with said compositions.
Description
TITLE: AN AGROCHEMICAL COMPOSITION
Field of the invention
The present invention relates to an agrochemical composition. The present invention 5 more particularly relates to an agrochemical composition comprising co-crystal of sulfentrazone and triazinone herbicide.
Background of the invention
Co-crystals are multi-component crystalline Systems formed by intermol ecular 10 interactions without transfer of hydrogen ions. Co-crystals of organic compounds, or crystalline complexes, are multi-component Systems which comprise at least two different organic compounds. Co-crystallization is a manifestation of directed selfassembly of different components.
An agrochemical co-crystai can be defined as crystalline materials comprised of two 15 or more different active ingrédients or with one or more actives with other co-formers.
These compounds can be formed by intermolecular forces such as hydrogen bonding, π-stacking and van der Waal’s forces. Co-crystals may aiter or enhance several important physico-chemical characteristics of the substances like solubility, bioavaîlability, stab il ity, hygroscopicity, surface free energy, zêta potential, crystal 20 hardness, filterabîlity, filtration and flow ability. These properties hâve a significant influence on agrochemical formulation.
The use of agrochemical composition is a widespread and documented practice in the agricultural community. These agrochemical composition offer significant advantages over individual applications including improved and extended control, reduced 25 application rates and costs, shorter contact times for improved results, less stringent use restrictions, improved selectivity, improved spectrum for fungi, insects, weeds etc. which are controlled, and reduced residue problems.
However, the combined use of a plurality of active substances sometîmes lead to phenomenaof a physical and biological incompatibility, for example lackîng physical
stabiiity of a coformulation, décomposition of an active substance or antagonism of the active substances and therefore are to be tackled carefully.
Triazinone îs a heterocyclic compound with potentia! biological activity. Their principal mode of action is an inhibition of the électron transport in photosystem II 5 (Hîll reaction).
Sulfentrazone is a phenyl triazinone (also termed as aryl triazinone) herbicides that acts by inhibiting protoporphyrinogen oxidase (protox). Sulfentrazone mimîc half of the tetrapyrrole ring of protoporphyrinogen (the substrate of Protox) and compete for the catalytic site on the enzyme. The active compound sulfentrazone is also known for a 10 long time (ILS. Pat. No. 4,818,275) and is absorbed by the roots and foliage, with translocation primarily in the apoplasni, and limited movement in the phloem. It is used to control annual broad-leaved weeds, some grasses and Cyperus spp. in soya beans, sugar cane and tobacco. Applied as pre-emergence or pre-plant incorporation.
Metribuzin is a triazinone herbicide that inhibits photosynthesis in a susceptible plant 15 by binding to a protein of the photosystem II complex, which in turn, cause a chain of events where, eventually, plant lipids and proteins are attacked and oxidized by highly reactive free radicals. The active compound metribuzin has been known fora long time (U.S. Pat. No. 3,905,801) and is used both as pre- and post-emergence and has proved useful for the sélective control of weeds, in particular in soybean and potato.
It has been observed that while making a stable composition, especiafly the liquid composition of sulfentrazone and triazinone herbicide (e.g. metribuzin), physical incompatibîlity of these two active leads to an unstable composition. Such unstable composition is unacceptable from formulation part as well as application part. During formulation, such liquid composition may not pass quality check due to non-uniform 25 dispersion. And, during application, such liquid composition may not deliver uniform concentration of actives in the field and may cause nozzle choking of applicators.
Therefore, need exist to develop a stable system wherein sulfentrazone can be formulated with other triazinone herbicides as binary mixture. Also, need exist to develop a stable system wherein sulfentrazone and triazinone herbicides when formulated together, doesn’t show crystal growlh and remain stable during formulation and upon storage.
Object of the invention
It is an object of the présent invention to provide a co-crystal of sulfentrazone and a triazinone herbicide.
It is another object of the présent invention to provide an agrochemical composition of sulfentrazone and triazinone herbicide.
It is an object of the présent invention to provide an agrochemical composition of sulfentrazone and triazinone herbicide with long term storage stability.
It is another object of the présent invention to provide an agrochemical composition comprising a co-crystal of sulfentrazone and triazinone herbicide.
It is another object of the présent invention to provide an agrochemical composition comprising a co-crystal of sulfentrazone and metribuzin.
It is another object of the présent invention to provide a process for preparing agrochemical composition comprising a co-crystal of sulfentrazone and triazinone herbicide.
Summary of the invention
In an aspect of the présent invention provides a co-crystal of sulfentrazone and a triazinone herbicide.
In another aspect the présent invention provides a process for préparation of a cocrystal of sulfentrazone and a triazinone herbicide.
In another aspect, the présent invention provides an agrochemical composition comprises of a co-crystal of sulfentrazone and a triazinone herbicide.
In another aspect, the présent invention provides a process for préparation of an agrochemical composition comprises co-crystal of sulfentrazone and a triazinone herbicide.
In another aspect of the présent invention, a process for preparing an agrochemical composition comprising cocrystal of sulfentrazone and a triazinone herbicide said process comprising:
a) pre-treatment to sulfentrazone and a triazinone herbicide to form a co-crystal;
b) admixing co-crystal of step (a) with agrochemical excipients as required to obtain mixture; and
c) further processing the resultîng mixture of step (b) to obtain said composition. In an aspect of the présent invention, a process for preparing a liquid agrochemical composition comprising co-crystal of sulfentrazone and a triazinone herbicide said 10 process comprising:
a) pre-treatment to sulfentrazone and a triazinone herbicide to form a co-crystal;
b) admixing co-crystal of step (a) with agrochemical excipients as required in an aqueous condition to obtain mixture; and
c) further processing the resulting mixture of step (b) to obtain said composition 15 hi yet another aspect of the présent invention, an agrochemical composition comprises a co-crystal of sulfentrazone and metribuzin.
In another aspect of the présent invention, an agrochemical composition comprising a co-crystal of sulfentrazone and metribuzin wherein said composition comprises between 10-90% of sulfentrazone and 90-10% of metribuzin by weight.
In another aspect of the présent invention, an agrochemical composition comprising a co-crystal of sulfentrazone and metribuzin wherein the co-crystal exhibits atleast one of the characteristic-XRD reflexes at 20 values (± 0.2) of 7.8°, 11.8°, 14.1°, 17.8°, 22.1°, 23.4° and 24.4°.
In an aspect of the présent invention, a co-crystal of sulfentrazone and metribuzin is 25 provided.
In another aspect of the présent invention, a process for preparing a co-crystal of sulfentrazone and metribuzin by using any of the following methods:
i. solution crystallization, ii. dry grinding,
iiî. solvent drop grinding technique, iv. inelt crystallization, or
v. mixing sulfentrazone and a triazinone herbicide in an aqueous condition followed by providing energy.
In yet another aspect of the présent invention, a process for preparing an agrochemical composition comprising cocrystal of sulfentrazone and metribuzin said process comprising:
a) pre-treatment to sulfentrazone and metribuzin to form a co-crystal;
b) admixing co-crystal of step (a) with agrochemical excipients as required to 10 obtain mixture; and
c) further processing the resulting mixture of step (b) to obtain said composition In another aspect of the présent invention, a process for preparing a liquid agrochemical composition comprising co-crystal of sulfentrazone and metribuzin said process comprising;
(a) pre-treatment to sulfentrazone and metribuzin to form a co-crystal;
(b) admixing co-crystal of step (a) with agrochemical excipients in an aqueous condition to obtain said composition
In another aspect of the présent invention, a method of controlling weeds said method comprising applying to a plant, or its habitat, plant seed or soil, a herbicidally effective 20 amount of a composition comprising a co-crystal of sulfentrazone and a triazinone herbicide.
In another aspect ofthe présent invention, a method of controlling weeds said method comprising applying to a plant, or its habitat, plant seed or soil, a herbicidally effective 25 amount of a composition comprising a co-crystal of sulfentrazone and metribuzin.
Another aspect of the présent invention provides use of liquid agrochemical composition comprising co-crystal of sulfentrazone and a triazinone herbicide.
Brief description of the drawings
The présent invention can be understood by reference to the following figures:
Figure 1 : High Performance Liquid Chromatography (HPLC) chromatogram of cocrystal of sulfentrazone and metribuzin.
Figure 2: Fourier Transform Jnfrared (FTIR) spectrum of co-crystal of sulfentrazone and metribuzin.
Figure 3: Powder X Ray Diffraction (P-XRD) diffractogram of co-crystal of sulfentrazone and metribuzin.
Figure 4: Differential scanning calorimetry (DSC) thermogram of co-crystal of 10 sulfentrazone and metribuzin.
Figure 5: FTIR spectrum of co-crystal of sulfentrazone and metribuzin in suspension concen traie.
Figure 6: P-XRD diffractogram of co-crystal of sulfentrazone and metribuzin in suspension concentrate.
Figure 7: Single crystal structure (in baU and stick model) of co-crystal of sulfentrazone and metribuzin.
Detailed description of the invention
Surprisingly, inventors of the présent invention found that an agrochemical 20 composition of sulfentrazone and metribuzin can be formed when both the actives are allowed for pre-treatment that include interaction of two actives and further formulating using surfactants and other agrochemical excipients. Such pre-treatment facilitâtes intermolecular interaction between said actives and leads to the formation of a co-crystal of two actives. And, then such pre-formed co-crystal can be formulated 25 into desired products using surfactants and other agrochemical excipients. Further it has been observed by the inventors of the présent invention that when said agrochemical composition is formulated as liquid compositions comprising a co-crystal of sulfentrazone and triazinone herbicide, it does not suffer from particle growth issues
associated with Iiquid compositions and further noted that said compositions remain quite stable during longtime storage.
In the context of the présent invention the term ‘co-crystal s’ îs defined as “solids that are crystalline materîals composed of two or more molécules in the same crystal lattice”. Co-crystal is also defined as crystalline materials composed of two or more different molécules, în a defined stoichiometric ratio within the same crystal lattice and are associated by nonionic and noncovalent bonds.
Thus, in an embodiment, the présent invention provides an agrochemical composition comprising a co-crystal of sulfentrazone and a triazinone herbicide.
In an embodiment of the présent invention, there is provided an agrochemical composition comprising a co-crystal of sulfentrazone and a triazinone herbicide wherein said composition comprises between 10-90%of sulfentrazone and 90-10% of triazinone herbicide by weight.
In an embodiment of the présent invention, triazinone herbicide of the agrochemical 15 composition is selected from the group comprising of ametridione, amibuzin, ethiozin, hexazinone, isomethîozin, metamitron, metribuzin and trifiudimoxazin.
In an embodiment of the présent invention, triazinone herbicide is metamitron.
In an embodiment of the présent invention, triazinone herbicide amibuzin.
In a preferred embodiment of the présent invention, triazinone herbicide is metribuzin.
In an embodiment of the présent invention, sulfentrazone of the agrochemical composition comprising a co-crystal of sulfentrazone and a triazinone herbicide is from about 10%w/w to about 90% w/w sulfentrazone of the total weight of the agrochemical composition.
In an embodiment of the présent invention, sulfentrazone of the agrochemical 25 composition comprising a co-crystal of sulfentrazone and a triazinone herbicide is from about 20% w/w to about 80% w/w sulfentrazone and preferably, from about 40% w/w to about 60% w/w sulfentrazone of the total weight of the agrochemical composition.
In an embodiment of the présent invention, triazinone herbicide of the agrochemical composition comprising a co-crystal of sulfentrazone and triazinone herbicide is from
about 10 %w/w to about 90% w/w triazinone herbicide of the total weight of the agrochemical composition.
In an embodiment of the présent invention, triazinone herbicide of the agrochemical composition comprising a co-crystal of sulfentrazone and triazinone herbicide is from 5 about 20% w/w to about 80% w/w triazinone herbicide and preferably, from about 40% w/w to about 60% w/w triazinone herbicide of the total weight of the agrochemical composition.
According to an embodiment of the présent invention, a process for preparing an agrochemical composition comprising co-crystal of sulfentrazone and a triazinone 10 herbicide is provîded wherein, said process comprising steps of:
a) pre-treatment to sulfentrazone and a triazinone herbicide to form a co-crystal;
b) admixing co-crystal of step (a) with agrochemical excipients as required to obtain mixture; and
c) further processing the resulting mixture of step (b) to obtain said composition 15 As used herein after, the term “pre-treatment” refers to the process of allowing sulfentrazone and a triazinone herbicide to form a co-crystal prior to its incorporation in the agrochemical composition.
In an embodiment of the présent invention, pre-treatment comprises milling, grinding or providing suitable form of energy sufficient to allow the formation of co-crystal of 20 sulfentrazone and triazinone herbicide.
In an embodiment of the présent invention, pre-treatment comprises heating the mixture of sulfentrazone and triazinone herbicide and allowing the formation of cocrystal of sulfentrazone and triazinone herbicide.
In an embodiment of the présent invention, pre-treatment comprises subjecting the 25 mixture of sulfentrazone and triazinone herbicide to amorphization by way of grinding, melting, milling or other suitable means and allowing the formation of co-crystal of sulfentrazone and triazinone herbicide.
In an embodiment of the présent invention pre-treatment is provîded for sulfentrazone and a triazinone herbicide for an adéquate time period to form the co-crystal.
According to another embodiment ofthe présent invention, in the process for preparing an agrochemical composition comprising co-ctystal of sulfentrazone and a triazinone herbicide, the sequence of mixing co-crystal with agrochemical excipients is not fixed and may vary according to the preference of the formulator.
According to another embodiment of the présent invention, in the process for preparing an agrochemical composition comprising co-crystal of sulfentrazone and a triazinone herbicide, the mixture obtained in step (b) is subjected to particle size réduction by applying shear to the mixture of co-crystals and agrochemical excipients. Suitable deviees for this purpose are the deviees that offers millîng operation e.g. high shear mixers like ROSS H SM, Ultra-Turrax apparatus, and dissol vers, static mixers, e.g. Systems having mixing nozzles, bead miIIs, vibratory mi11s, agitator bead mills, colloid mills, cône mills, circulating mills (agitator bail mills with pin grinding System), disk mills, annular chamber mills, double cône mills, sprocket dispersers or homogenizers and other homogenizers.
According to another embodiment of the présent invention, in the process for preparing an agrochemical composition comprising co-crystal of sulfentrazone and a triazinone herbicide, further processing atstep (c) can be performed at ambient température conditions.
According to another embodiment of the présent invention, in the process for preparing 20 an agrochemical composition comprising co-crystal of sulfentrazone and a triazinone herbicide, further processing at step (c) can be performed at an elevated température conditions with température > 40°C, preferably >60°C.
According to another embodiment of the présent invention, in the process for preparing an agrochemical composition comprising co-crystal of sulfentrazone and a triazinone 25 herbicide, further processing at step (c) can be performed in low température conditions with température < 40°C, preferably < 20°C.
According to another embodiment of the présent invention, an agrochemical composition of the présent invention may be formulated as granular as well as liquid compositions.
In an embodiment there is provided a process for preparing a granular composition comprising a co-crystai of sulfentrazone and a triazinone herbicide.
In an embodiment of the présent invention, granular composition comprising a cocrystal of sulfentrazone and a triazinone herbicide is prepared by a process comprising:
a) pre-treatment to sulfentrazone and a triazinone herbicide to form a co-crystal;
b) admixing co-crystal of step (a) with agrochemîcal excipients as required to mixture;
c) optionally grinding and pulverizing; and further granuiating said mixture to obtain granular composition.
The step of granuiating the mixture is not particularly 1 imiting. Appropriate granuiating processes are conventional processes described in granuiating technology for example spray drying, fluidized bed granulation, agglomération, pan granulation and extrusion granulation.
In an embodiment of the présent invention, an agrochemîcal composition comprising 15 from about 10% to about 40% w/w co-crystal of sulfentrazone and metribuzin, from about 1% to about 20% solvent, from about 0.1% to about 20% non-ionic and anionic dispersing agents, from about 01.% to about 10% wetting agent, from about 0.1% to about 10% defoamer, from about 0.1% to about 30% thickener of the total weight of the agrochemîcal composition.
In an embodiment of the présent invention, an agrochemical composition comprising from about 10% to about 40% w/w co-crystal of sulfentrazone and metribuzin, from about 1% to about 20% diol, from about 0.1% to about 20% acrylic polymer, from about 0.1 % to about 20% alkali swellable polyacrylate, from about 0.1% to about 10% polyalkylene glycol ether, from about 0.1% to about 10% silicone defoamer, from 25 about 0.1% to about 30% thickener of the total weight of the agrochemîcal composition.
The présent invention relates to process for preparing a liquid agrochemîcal composition comprising co-crystal of sulfentrazone and a triazinone herbicide said process comprising:
(a) providing pre-treatment to sulfentrazone and a triazinone herbicide to form a co-crystal;
(b) admixing co-crystal of step (a) with agrochemical excipients as required in an aqueous condition to obtain mixture; and (c) further processing the resulting mixture of step (b) to obtain said composition
In an embodiment of the présent invention, pre-treatment comprises milling, grîndîng or providing suitable form of energy sufficient to allow the formation of co-crystal of sulfentrazone and triazinone herbicide.
In an embodiment of the présent invention, pre-treatment comprises heating the mixture of sulfentrazone and triazinone herbicide in aqueous conditions and allowing the formation of co-crystal of sulfentrazone and triazinone herbicide.
In an embodiment of the présent invention, pre-treatment comprises subjecting the mixture of sulfentrazone and triazinone herbicide in aqueous conditions to 15 amorphization by way of grinding, melting, milling or other suitable means and allowing the formation of co-crystal of sulfentrazone and triazinone herbicide.
In an embodiment ofthe présent invention, admixing of step b) is performed in aqueous conditions.
In an embodiment of the présent invention, processing of step c) is performed in 20 aqueous conditions to obtain the desired product.
The preferred methods for performing step b) and step c) are described previously.
In an embodiment of the présent invention, an agrochemical composition comprising a co-crystal of sulfentrazone and metribuzin.
In an embodiment of the présent invention, an agrochemical composition comprising 25 a co-crystal of sulfentrazone and metribuzin wherein said composition comprises between 10-90% of sulfentrazone and 90-10% of metribuzin by weight.
In an embodiment of the présent invention, sulfentrazone in the agrochemical composition comprising a co-crystal of sulfentrazone and metribuzin is from about
20% w/w to about 80% w/w sulfentrazone and preferably, from about 40% w/w to about 60% w/w sulfentrazone of the total weight of the agrochemical composition.
In an embodiment of the présent invention, metribuzin in the agrochemical composition comprising a co-crystal of sulfentrazone and metribuzin is from about 5 20% w/w to about 80% w/w metribuzin and preferably, from about 40% w/w to about
60% w/w metribuzin of the total weight of the agrochemical composition.
In an embodiment of the présent invention, an agrochemical composition comprising a eo-crystal of sulfentrazone and metribuzin wherein the co-crystal exhibîts atleast one of the characteristic-XRD reflexes at 20 values (± 0.2) of 7.8°, 1 1.8°, 14.1°, 17.8°, 10 22.1°, 23.4° and 24.4°.
In an embodiment of the présent invention, an agrochemical composition comprising from about 10% to about 40% w/w co-crystal of sulfentrazone and metribuzin, from about 1% to about 20% solvent, from about 0.1% to about 20% non-ionic and anionic dispersing agents, from about 01.% to about 10% wettîng agent, from about 0.1% to 15 about 10% defoamer, from about 0.1 % to about 30% thickener of the total weight of the agrochemical composition wherein said agrochemical composition is formulated as suspension concentrate.
In an embodiment of the présent invention, an agrochemical composition comprising from about 10% to about 40% w/w co-crystal of sulfentrazone and metribuzin, from 20 about 1% to about 20% diol, from about 0.1% to about 20% acryîic polymer, from about 0.1 % to about 20% aIkali swellabié polyacrylate, from about 01.% to about 10% polyalkylene glycol ether, from about 0.1% to about 10% silicone defoamer, from about 0.1% to about 30% xanthan gum of the total weight of the agrochemical composition wherein said agrochemical composition is formulated as suspension 25 concentrate.
In an embodiment of the présent invention, an agrochemical composition comprising a co-crystal of sulfentrazone and metribuzin wherein the co-crystal exhibits atleast one of the characteristic-XRD reflexes at 2 Θ values (± 0.2) of 7.8°, 1 1.8°, 14.1°, 17.8°, 22.1°, 23.4° and 24.4°.
In an embodiment of the présent invention, an agrochemical composition comprising a co-crystal of sulfentrazone and metribuzin, the molar ratio of sulfentrazone and metribuzin is 1: 9 to 9: 1.
In an embodiment of the présent invention, an agrochemical composition comprising a co-crystal of sulfentrazone and metribuzin, the molar ratio of sulfentrazone and metribuzin is 1:5 to 5: 1.
In an embodiment of the présent invention, an agrochemical composition comprising a co-crystal of sulfentrazone and metribuzin, the molar ratio of sulfentrazone and metribuzin is generally in the range from 2:1 to l :2, preferably from 1.5:1 to 1:1.5, and in particular from 1:1.
In an embodiment of the présent invention, an agrochemical composition comprising a co-crystal of sulfentrazone and metribuzin, the molar ratio of sulfentrazone and metribuzin is 1: 9 to 9: 1.
In an embodiment of the présent invention, an agrochemical composition comprising a co-crystal of sulfentrazone and metribuzin, the molar ratio of sulfentrazone and metribuzin is generally in the range from 2:1 to 1:2, preferably from 1.5:1 to 1:1.5, and in particular from 1:1.
In an aspect the présent invention provides a co-crystal comprising sulfentrazone and at least one triazinone herbicide.
In an embodiment of the présent invention, a co-crystal of sulfentrazone and metribuzin is provided.
In an embodiment the sulfentrazone and metribuzin are présent in co-crystal in a molar ratio from 2:1 to 1:2.
In an embodiment of the présent invention, a co-crystal of sulfentrazone and metribuzin wherein the co-crystal exhibits atleast one of the characteristic-XRD reflexes at 2 0 values (± 0.2) of 7.8°, 1 1.8°, 14.1°,] 7.8°, 22.1 23.4° and 24.4°.
In an embodiment the co-crystal is charaeterized by at least one of following
i. a powder X-ray diffraction pattern comprising at least one peaks at a diffraction angle of 20 values, 7.8°, 11.8°, 14.1°, 17.8°, 22.1°, 23.4° and 24.4° (± 0.2) or
u. a DSC thennogram comprising an endothermie peak with onset at 107.3°C and a peak at ! IO.5°C or iii. a single crystal X-ray diffraction having lattice parameters: a=22.2825(4) Â, b= 10.5240(2) Â, c=11.4659(2) Â, a= 90°, β= 93.5058°(7) and γ= 90°,
In an embodiment of the présent invention, a process for preparing a co-crystal of sulfentrazone and metribuzîn by using any of the following methods:
i. mixing sulfentrazone and a triazinone herbicide in an aqueous condition followed by providing energy;
îi. solution crystallization iii. dry grinding iv. solvent drop grinding technique
v. melt crystallization
In an embodiment of the présent invention, the co-crystai of sulfentrazone and metribuzîn herbicide can be obtained by any conventional processes known to the person skiIled in the art used for preparing such co-crystals.
The présent invention further provides a process for préparation of a co-crystal of sulfentrazone and a triazinone herbicide.
In an embodiment, the process for preparing a co-crystal of sulfentrazone and a triazinone herbicide wherein said co-crystal is obtained by solution crystallization or grinding or heating or solvent drop grinding or melt crystallization or mixing sulfentrazone and a triazinone herbicide in an aqueous condition.
In an embodiment of the présent invention, a process for preparing a co-crystal of sulfentrazone and metribuzîn by mixing sulfentrazone and metribuzîn involve suspending suifentrazone and metribuzin in water followed by providing energy sufficient to facilitate intermolecular interactions between suifentrazone and metribuzin.
In an embodiment of the présent invention, a process for preparing a co-crystal of S suifentrazone and metribuzin comprises mixing suifentrazone and metribuzin in an aqueous condition followed by providing energy.
In an embodiment of the présent invention, a process for preparing a co-crystal of suifentrazone and metribuzin comprises preparing a solution of suifentrazone and a triazinone herbicide using an organic solvent, water, or a mixture of water and an 10 organic solvent and triturating or precipitating with an anti-solvent to obtain said cocrystal of suifentrazone and a triazinone herbicide.
The solvent is selected from aliphatic alcohols, ketones, esters, ethers, polar protic solvents, polar aprotic solvents, halogenated solvents, aliphatic hydrocarbon or aromatic hydrocarbon and said anti-solvent is selected from aliphatic or aromatic 15 hydrocarbon solvents.
In an embodiment the process for preparing a co-crystal of suifentrazone and metribuzin comprises heating a mixture of suifentrazone and a triazinone herbicide to melt to obtain said co-crystal of suifentrazone and a triazinone herbicide.
In an embodiment of the présent invention, the process for preparing a co-crystal of 20 suifentrazone and metribuzin by solution crystallization involve completely dissolvsng suifentrazone and metribuzin in a suitable solvent, and further co-crystal lization is induced by coolîng or évaporation or précipitation.
In an embodiment the solvent can be selected from aliphatic alcohols, ketones, esters, ethers, polar protic solvents, polar aprotic solvents, halogenated solvents, aliphatic 25 hydrocarbon, and aromatic hydrocarbon.
In an embodiment the solvent can be selected from methanol, éthanol, isopropyl alcohol, acetone, dichloromethane, dichloroethane, dichloropropane, trichloroethane, chloroform, and ethyl acetate.
Τη an embodiment of the présent invention, co-crystalhzation mdnced by cooling involve, separately preparing the saturated solution of sulfentrazone and metribuzin at an elevated température. Afterwards, combining both the solutions at the same température and cooling down to 0° C. to 20° C., preferably to 3° C. to 8° C. (e.g. 5° C.). The so-formed co-crystals can be separated from the resulting suspension by conventional techniques (e.g. filtration).
In an embodiment of the présent invention, co-crystal lization induced by évaporation in volve partial or complété removal of solvent by using commonly used évaporation techniques (e.g. heating or reduced pressure).
In an embodiment of the présent invention, co-crystallization induced by précipitation involve complété dissolution of sulfentrazone and metribuzin in a suitable solvent The crystallization is induced by lowering the solubilîty of the soluté by addition of a solvent, in which the solubilîty of the sulfentrazone and solubilîty of metribuzin is preferably lower than 10 g/J and in particular lower than 2 g/l at room température (herein below referred to as “anti-solvent”). A convenient suitable anti-solvent is a nonpolar solvent, e.g. n-hexane, n-heptane, diethyl ether, petroleum ether, 1, 4-dîoxane, cyclohexanone, toluene or xylene.
In an embodiment of the présent invention, a process for preparing a co-crystal of sulfentrazone and metribuzin by dry grinding in volve combining sulfentrazone and metribuzin and subsequently applying shear forces.
In an embodiment of the présent invention, dry grinding process for preparing a cocrystal of sulfentrazone and metribuzin by applying shear forces is preferably performed at a température of at least 15° C., frequentiy at a température of at least 20° C., preferably at a température of at least 30° C., in particular of at least 35° C., e.g. from 15° C. to 80° C.
In an embodiment of the présent invention, a process for preparing a co-crystal of sulfentrazone and metribuzin by solvent drop grinding technique.
In an embodiment of the présent invention, a process for preparing a co-crystal of sulfentrazone and metribuzin by solvent drop grinding technique in volve organic solvent or a mixture of water and organic solvent where sulfentrazone and metribuzin hâve a comparable solubility.
More preference is given to organic solvents of the group 1, and to their mixtures with water. In the mixtures with water the relative amount of organic solvent and water may 5 vary from 200:1 to 1:200 (v/v), in particular from 1:5 to 1:100 (v/v).
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Suitable solvents are polar organic solvents as defined above.
An especially suitable organic solvent to be used alone or in mixture with water is an alcohol as mentioned above (Ci-C4-alkanols such as methanol, éthanol, n-propanol or isopropanol).
The solvent drop grinding process can be simply performed by pouring solvent onto the mixture of sulfentrazone and metribuzin in a drop-wise manner and applying shear forces (e.g. with a rotor-stator mill).
The solvent drop grinding process is usually performed ai a température of at least 5° C., preferably at least 10° C. and in particular at least 20° C., e.g. from 5 to 80° C., 15 preferably from 10 to 55° C., în particular from 20 to 40° C.
The time required for formation of the co-crystal by the solvent drop grinding process dépends on the température, the type of solvent and is generally 1 h. In any case, complété conversion is achieved after one week; however, the complété conversion will usually require not more than 24 h.
In an embodiment of the présent invention, a process for preparing a co-crystal of sulfentrazone and metribuzin by melt crystallization involve heating of sulfentrazone and metribuzin mixture in a porcelain dish on a paraffin oil bath maintained at 200°C. Further, incubating molten mass in a vessel containing 25 ml water at 90°C using water bath. The co-crystal thus obtained is dried at room température overnight and 25 further analyzed for its characterization.
In an embodiment of the présent invention, a process for preparing a co-crystal of sulfentrazone and metribuzin by mixing sulfentrazone and metribuzin in an aqueous condition followed by providing energy in volve milling the mixture of sulfentrazone and metribuzin in an aqueous condition, optionally in presence of other agrochemical excipients and allowing the co-crystal formation by interaction in aqueous conditions. In an embodiment of the présent invention, a process for preparing an agrochemical composition comprising co-crystal of sulfentrazone and metribuzin said process comprising:
a) pre-treatment to sulfentrazone and metribuzin to form a co-crystal;
b) admixing co-crystal of step (a) with agrochemical excipients as required to obtain mixture; and
c) further processing the resultîng mixture of step (b) to obtain said composition In an embodiment ofthe présent invention, pre-treatment comprises milling, grinding or providing suitable form of energy sufficient to allow the formation of co-crystal of sulfentrazone and metribuzin herbicide.
In an embodiment of the présent invention, pre-treatment comprises heating the mixture of sulfentrazone and metribuzin herbicide and allowing the formation of cocrystal of sulfentrazone and triazinone herbicide.
In an embodiment of the présent invention, pre-treatment comprises subjecting the mixture of sulfentrazone and metribuzin herbicide to amorphization by way of grinding, melting, milling or other suitable means and allowing the formation of cocrystal of sulfentrazone and triazinone herbicide.
In an embodiment of the présent invention, co-crystal thus formed in step (b) is then allowed to mix with suitable agrochemical excipients to obtain mixture and processed further to obtain the agrochemical composition in a suitable form.
The preferred methods for performing step b) and step c) are described previously.
In an embodiment, there is provided a process for preparing an agrochemical composition of a co-crystal of sulfentrazone and a triazinone herbicide, said process comprising:
a) pre-treatment to sulfentrazone and a triazinone herbicide to form a co-crystal;
b) admixing co-crystal of step (a) with agrochemically acceptable excipients to obtain said composition.
According to another embodiment of the présent invention, the process for preparing an agrochemical composition comprising:
a) pre-treatment to sulfentrazone and metribuzin by healing followed by cooling the mixture to room température to obtain co-crystal;
b) admixing co-crystal of step (a) with agrochemical excipients in presence of water to obtain homogeneous agrochemical composition.
Typically, the process for preparing an agrochemical composition comprising:
a) pre-treatment to sulfentrazone and metribuzin by heating at température in the range of about 70-80°C for about 1 hour followed by cooling the mixture to room température to obtain co-crystal;
b) admixing co-crystal of step (a) with agrochemical excipients in presence of water under high shear and adding one or more dispersing agent and/or wetting agent to obtain slurry.
c) optionally milling the slurry to achieve particle size as per spécification preferably dio < 1, d5o < 4, deo < 10 and dioo < 35 gm by maintain mil! température at < 25°C.
d) mixing the slurry for about 1 hour to get homogeneous agrochemical composition.
According to an embodiment of the présent invention, the process for preparing an agrochemical composition comprising:
a) preparing an aqueous mixture of agrochemically suitable excipients to obtain a homogeneous solution.
b) adding metribuzin and sulfentrazone in the homogeneous solution of step (a) to obtain a slurry;
c) optionally milling the slurry.
d) heating the slurry of step (b) or (c) and cooling to room température.
e) optionally charging other agrochemical excipient to the slurry of step (d) and mixing to get homogeneous agrochemical composition.
According to an embodiment of the présent invention, the process for preparing an agrochemical composition comprising:
a) preparing an aqueous solution ofagrochemically suitable excipients, preferably an anionîc and non-ionic dîspersing agents a mixer under high shear to obtain a homogeneous solution.
b) adding metribuzin and sulfentrazone in the homogeneous solution of step (a) to obtain a slurry;
c) optionally milling the slurry to achieve particle size as per spécification of dio < 1, dîo < 4, dw i 10 and dioo < 35 pm and maintaining the mi 11 température at <25°C.
d) heating the slurry of step (b) or (c) at température range of 70 to 80°C, mixing for about 1 hour and cooling to room température;
e) charging other agrochemical excipient for example thickener gel to the slurry of step (b) or step (d) or and mixing to get homogeneous agrochemical composition.
The process comprises optionally following the step (c) after step (d)to achieve particle size spécification of step (c);
The step (e) comprises preparing a thickener (2% solution) gel by charging a vessel with Proxel GXL and Rhodopol 23, mixing for 30 minutes and adding water and continue mixing for 1 hour.
In an embodiment of the présent invention, steps in the process for preparing an 25 agrochemical composition comprising co-crystal of sulfentrazone and metribuzin may not be fixed and can be in any order to achieve an agrochemical composition according to the présent invention.
In an embodiment of the présent invention, the agrochemical compositions of the présent invention may be in a solid or liquid form.
According to preferred embodiment, the agrochemical compositions of the présent invention is a liquid formulation.
According to an embodiment of the présent invention, the liquid agrochemical composition may be fonnulated as suspension concentrate (SC), as an émulsion concentrate (EW), as an oil-based suspension concentrate (OD), and/or suspoemulsions (SE).
According to the preferred embodiment of the présent invention, the liquid agrochemical composition is fonnulated as suspension concentrate (SC).
The présent invention relates to process for preparing a liquid agrochemical composition comprising co-crystal of sulfentrazone and metribuzin said process comprising:
(a) pie-treatment to sulfentrazone and metribuzin to form a co-crystal;
(b) admixing co-crystal of step (a) with agrochemical excipients as required in an aqueous condition to obtain mixture; and (c) further processing the resulting mixture of step (b) to obtain said composition
In an embodiment of the présent invention, steps in the process for preparing a liquid agrochemical composition comprising co-crystal of sulfentrazone and metribuzin may not be ftxed and can be in any order to achieve liquid agrochemical composition according to the présent invention.
In another embodiment of the présent invention, co-crystal of a liquid agrochemical composition is obtained by “pre-treatment” mean a process that allows sulfentrazone and a triazinone herbicide to form a co-crystal prior to its incorporation into the liquid agrochemical composition.
In an embodiment of the présent invention, pre-treatment of sulfentrazone and metribuzin involve bringing together and milling, grinding or heating or providing suitable form of energy sufficîent to allow the formation of co-crystal of sulfentrazone and metribuzin.
In one embodiment, slurry of agrochemical excipients was first prepared and milled and then sulfentrazone and metribuzin were added at an elevated température (54°C60°C) and mi lied along with the slurry of agrochemical excipients. Then, further processing was carried by adding thickeners to make the suspension concentrate.
In another embodiment, slurry of agrochemical excipients was first prepared, then sulfentrazone and metribuzin were added at an elevated température (54°C-60°C) and then mi lied along with the slurry of agrochemical excipients. Further processing was carried by adding thickeners to make the suspension concentrate.
In another embodiment, sulfentrazone and metribuzin are mtxed and grinded and then allowing to melt ( 125°C-14O°C) by providing heat to obtain co-crystal. The co-crystal is then cooled and crushed under milling condition. Separately prepared slurry of agrochemical excipients is then added to the mixture and agaîn taken for milling. Finally, further processing is carried by adding thickeners to make the suspension.
In another embodiment, sulfentrazone and metribuzin are mîxed and grinded to obtain mixture. The mixture is heated dynamically (54°C-70°C) then separately prepared slurry of agrochemical excipients is added to the mixture and again taken for milling. Finally, further processing is carried by adding thickeners to make the suspension. The présent invention provides a liquid agrochemical composition comprising;
(a)a co-ctystal of sulfentrazone and triazinone herbicide;
(b) aciylate polymer; and (c) glycerol.
According to an embodimentofthe présent invention, liquid agrochemical composition comprises acrylate polymer.
According to an embodiment of the présent invention, acrylate polymer is seiected from the group comprising of polymers of methyl aciylate, méthacrylates, ethyl acrylate, 2-chloroethyl vinyl ether, 2-ethylhexyl acrylate, hydroxyethyl méthacrylate, butyl aciylate, butyl méthacrylate, and trimethylolpropane triacrylate (TMPTA). Acrylic polymers include, but are not limited to, Modified styrene/maleic anhydride copolymer (Envi-Pol 871), PAPI 27 Polymeric MDI, polymethyl méthacrylate, polyacrylates, polyacrylate salts such as sodium polyacrylate, poiy(vinyl acetate) (PVAc), and polyacrylamide.
In an embodiment of the présent invention, the Iiquid agrochemical composition may further comprise of urea.
According to an embodiment of the présent invention, Iiquid agrochemical composition comprises from about 0.1% w/w to about 40% w/w, preferably from about 0.1% w/w to about 30% w/w acrylate polymer of the total weight of the Iiquid agrochemical composition.
According to preferred embodiment of the présent invention, Iiquid agrochemical composition comprises from about 1% w/w to about 30% w/w, preferably from about 0.1% w/w to about 30% w/w glycerol of the total weight of the Iiquid agrochemical composition.
According to an embodiment of the présent invention, the Iiquid agrochemical composition comprises of water.
According to an embodiment of the présent invention, the Iiquid agrochemical composition comprises from about 0.1% to about 99% w/w, preferably from about 10% to about 70% w/w water of the total weight of the Iiquid agrochemical composition.
In an embodiment of the présent invention, the Iiquid agrochemical composition may further comprise agrochemical excipients selected from one or more anionic and nonion ic surfactants, antifreeze agent, wetting agents, fillers, surfactants, anticaking agents, pH-regu latin g agents, préservât ives, biocîdes, antifoaming agents, colorants and other formulation aids.
Suitable anionic surfactants include polyacrylates, alkylbezenesulfonates (Example: TERWET 1004) such as dodecylbenzenesulfonates, for example calcium dodecylbenzensulfonate, ethoxylated and/or propoxylated di- or tri- styryl phénol phosphates, ethoxylated and/or propoxylated di- or tri-styrylphenol sulfates, phenyl sulfanâtes, alkynaphtalenesuîphonates, ethoxylated and/or propoxylated alcohol phosphate esters, ethoxylated and/or propoxylated alkylaryl phosphate esters, taurates, suphosuccinates, and polycarboxylates. Sodium alkylnaphthalene sulfonate formalin condensate or modified styrene-maleic anhydride copolymer). Examples of the commercially available alkyl naphthalene sulfonate sodium formalîn condensate include Morwet D425, TERSPERSE 2020, Agrosurf WG-2300 and the like. Examples of the commercially available modified styrene-maleic anhydride copolymer TERSPERSE 2612.
Suitable non-ionic surfactants include alkoxylated surfactants and block copolymer surfactants. Examples of useful alkoxylated surfactants for the invention include castor oil ethoxylate, tridecyl alcohol ethoxylate, nonyl phénol ethoxylate, octyl phénol ethoxylate, tristryl phénol ethoxylate, phosphate ester ethoxylate, tallow amine ethoxylate, cocoa amine ethoxylate, and oleyl amine ethoxylate.
Suitable antifreeze agents that can be added to the liquid agrochemical composition are liquid polyols, for example ethylene glycol and propylene glycol.
Suitable pH regulating agents can be citric acid or phosphoric acid.
Wetting agents that can be added to the liquid agrochemical composition of the présent invention include, but are not limited to: poiyary(alkoxylated phosphate esters and their potassium salts (e.g., Soprophor® FLK, Stepfac TSP PE- K. Other suitable wetting agents include sodium dioctylsulfosuccinates (e.g., Geropon® SDS, Aérosol® OT) and ethoxylated alcohols (e.g., Trideth-6; Rhodasurf® BC 610; Tersperse® 4894).
Optionally, about 0.1 wt % to about 5.0 wt % of antifoaming or defoamers are employcd to stop any unwanted foam generated while manufacturing suspension concentrate composition of the présent application. The preferred antifoaming agent is selected from the group consisting of silicone-based compounds, alcohols, glycol ethers, minerai spirits, acetylene diols, polysiloxanes, organosiloxanes, siloxane glycols, reaction products of Silicon dioxide and organesiloxane polymer, polydimethylsiloxanes or polyalkylene glycols alone or in combination. Defoamers that are suitable include AGNIQUE DFM DIS; SAG-IO; SAG-1000AP; SAG-1529; SAG-1538; SAG-1571; SAG-1572; SAG-1575; SAG-200I; SAG-220; SAG-290; SAG-30; SAG-30E; SAG-330; SAG-47; SAG-5440; SAG-7133 and SAG-770.
Exampies of thickening agents based on anionic heteropolysaccharides from the xanthan gum group are inter alla the Rhodopol 23®, Rhodopol G®, Rhodopol 50 MD®, Rhodicare T®, Kelzan®, Kelzan S® and Satiaxane CX9I®.
Preservatives used may be benzisothiazolinone (Proxei GXL) or phénols, 2-bromo-2nitropropane-l,3-diol, also known as Bronopol (Bioban BP 30), 5-chioiO-2-methyl-4isothiazolin-3-one & 2 methyl-4-isothiazolin -3 one (Kathon CG/lCP),Glutaraldehyde (Ucarcide 50), Chloromethylisothiazoiinone (CMIT)/Methylisothiazolinone (MIT) (Isocil Ultra l .5), 2.2-dibromo-3-nitrilopropioamide (Reputain 20), Natamycin & Nisin, Bronopol/CMIT/MIT (Mergal 721K3).
Suitable colorants (for example in red, blue and green) are, preferably, pigments, which are sparingly soluble in water, and dyes, which are water-soluble. Examples are inorganic coloring agents (for example iron oxide, titanium oxide, and iron hexacyanoferrate) and organic coloring agents (for example aiizarin, azo and phthalocyanin coloring agents).
According to an embodiment of the présent invention, compositions of the présent invention comprises co-crystal of sulfentrazone and metribuzin and one or more pesticides other than the two components of said co-crystal.
Pesticides may be selected from herbicides, fungicides, insecticides, nematicides, acaricides, plant growth regulators, and safeners.
Preferably the pesticide is an herbicide selected from isoxazolidinone herbicide, a urea herbicide, a triazine herbicide, a hydroxybenzonitrile herbicide, a thiocarbamate herbicide, a pyridazine herbicide, chloroacetanilide herbicides; benzothiazole herbicides; carbanilate herbicides, cyciohexene oxime herbicides; picolinic acid herbicides; pyridine herbicides; quinolinecarboxylic acid herbicides; chlorotriazine herbicides, aryloxyphenoxypropionic herbicides, oxadiazolone herbicides, phenylurea herbicides, sulfoanilide herbicides, triazolopyrimidine herbicides, amide herbicides, pyridazine herbicides, dinitroaniline herbicides or combinations thereof.
Preferably the pesticide is a fungicide selected from amide fungicides, acylamino acid fungicides, an il ide fungicides, benzamide fungicides, sulfonamide fungicides, strobilurin fongicides, aromatic fongicides, benzimidazole fongicides, carbamate fongicides, carbanilate fongicides, conazole fongicides (imidazoles triazoles), copper fongicides, dithiocarbamate fongicides, imidazole fongicides, organophosphorus fongicides, oxazole fongicides, pyrazole fongicides, pyridine fongicides or combinations thereof.
Preferably the insecticide is selected from arsenical insecticides, botanical insecticides, carbamate insecticides, benzofuranyl methyl carbamate insecticides, dimethylcarbamate insecticides, insecticides, dinitrophenol insecticides, fluorine insecticides, fonnamidine insecticides, fomigant insecticides, inorgamc insecticides, insect growth regulators, benzoylphenylurea chitin synthesis inhibitors, macrocyclic lactone insecticides, neonicotinoid insecticides, nereistoxin analogue insecticides, organochlorine insecticides, organophosphorus insecticides, organothiophosphate insecticides, heterocyclic organothiophosphate insecticides, phenyl organothiophosphate insecticides, phosphonate insecticides, phosphonothioate insecticides, phosphoramidate insecticides, phosphoramidothioate insecticides, phosphorodiamide insecticides, oxadiazine insecticides, oxadiazolone insecticides, phthalimide insecticides, physical insecticides, pyrazole insecticides, pyrethroid insecticides, pyrethroid ether insecticides, py ri mid inami ne insecticides, pyrrole insecticides, quaternary ammonium insecticides, sulfoximîne insecticides, tetramic acid insecticides, tetronic acid insecticides, thiazole insecticides, thiazohdine insecticides and thiourea insecticides.
Preferably the nematicide is selected froin abamectin, carvacrol, benomyl, carboforan, carbosulfan, cloethocarb, alanycarb, aldîcarb, aldoxycarb, oxamyl, tîrpate, carbon disulfide, cyanogen, 1,2-dichloropropane, 1.3-dichloropropene, dimethyl disulfide, methyl bromide, methyl iodide, sodium tetrathiocarbonate, diamidafos, fenamiphos, fosthietan, phosphamidon, cadusafos, chlorpyrifos, dichlofenthion, dimethoate, ethoprophos, fensulfothion, fosthiazate, heîerophos isamidofos, isazofos, phorate, phosphocarb, terbufos, thionazin, triazophos, imieyafos, mecarphon, acetoprole, benclothîaz, chloropicrin, dazomet, DBCP, DCIP, fluazaindolizine, fl Lien sulfone, furfural, metam, methyl isothiocyanate, tioxazafen, xylenols.
Preferably the safener is selected from benoxacor, BPCMS, cloquintocet, cyometriml, cyprosulfamide, dîchlormid, dicyclonon, dietholate, fenchlorazole, fenclorim, 5 flurazole, fluxofenim, furilazole, isoxadifen, jiecaowan, jiecaoxi, mefenpyr, mephenate, metcamifen, naphthalic anhydride and oxabetrinil.
In an embodiment of the present invention, a liquîd agrochemical composition comprising from about 10% to about 40% w/w co-crystal of sulfentrazone and metribuzin, from about 1 % to about 20% acrylic polymer and from about 1 % to about 10 20% glycerol of the total weight of the liquid agrochemical composition.
In an embodiment of the present invention, a liquid agrochemical composition comprising from about 10% to about 40% w/w co-crystal of sulfentrazone and metribuzin,, from about 1 % to about 20% acrylic polymer and from about 1 % to about 15 20% glycerol of the total weight of the liquid agrochemical composition wherein said agrochemical composition is formulated as suspension concentrate.
In an embodiment of the present invention, a liquid agrochemical composition comprising from about 10% to about 40% w/w co-crystal of sulfentrazone and 20 metribuzin, from about 1% to about 20% alkali swellable polyacrylate, from about 0.1 % to about 30% glycerol and from about 10% to about 30% water of the total weight of the liquid agrochemical composition wherein said liquid agrochemical composition is formulated as suspension concentrate.
Compositions according to the present invention can also be prepared by tank-mixing 25 the active ingrédient with auxiiiaries suitable for the formulation of these active ingrédients or altematively may be sold as a kit of parts containing actives and other ingrédients that may be mixed prior to spraying.
According to an embodiment of the present invention a method of controlling weeds is provided wherein said method comprising applying to a plant, or its habitat, plant seed
or soil, an effective amount of a composition comprising a co-crystal of sulfentrazone and a triazinone herbicide.
According to an embodiment of the présent invention a method of control ling weeds is provided wherein said method comprising applying to a plant, or its habitat, plant seed 5 or soil, an effective amount of a composition comprising a co-crystal of sulfentrazone and metribuzin.
The herbicidal composition of the présent invention maybe used to target weeds among the crops such corn, rice, wheat, barley, rye, oat, sorghum, cotton, soybean, peanut, buckwheat, beet, rapeseed, sunflower, stigar cane, tobacco, etc.; vegetables. 10 solanaceous vegetables such as eggplant, tomato, pimento, pepper, potato, etc., cucurbit vegetables such as cucumber, pumpkin, zucchini, water melon, melon, squash, etc., cruciferous vegetables such as radish, white turnip, horseradish, kohlrabi, Chinese cabbage, cabbage, leaf mustard, broccoli, cauliflower, etc., asteraceous vegetables such as burdock, crown daisy, artichoke, lettuce, etc, liliaceous vegetables such as green 15 on ion, on ion, garlic, and asparagus, ammiaceous vegetables such as carrot, parsley, celery, parsnip, etc., chenopodiaceous vegetables such as spinach, Swiss chard, etc., lamiaceous vegetables such as Perilla frutescens, mint, basil, etc, strawbeny, sweet potato, Dioscorea japonica, colocasia, etc., flowers, foliage plants, turf grasses, fiuits. pome fruits such apple, pear, quince, etc, stone fleshy fruits such as peach, plum, 20 nectarine. Prunus munie, cherry fruit, apricot, prune, etc., citrus fruits such as oiange, lemon, rime, grapefruit, etc., nuts such as chestnuts, walnuts, hazelnuts, almond, pistachio, cashew nuts, macadam ia nuts, etc. berries such as blueberry, cranberry, blackberry, raspberry, etc., vines, kaki fruit, olive, plum, banana, oil palm, coffee, date palm, coconuts, etc. , trees other than fruit trees; tea, mulbeny, flowering plant, trees 25 such as ash, birch, dogwood, Eucalyptus, Gînkgo biloba, lilac, maple, Quercus, poplar, Judas tree, Liquidambar formosana, plane tree, zelkova, Japanese arborvitae, fir wood, hemlock, juniper, Pinus, Picea, and Taxus cuspidate, etc.
Thus, in another aspect, the présent invention provides a method of controlling weeds at a locus, the method comprising a co-crystal of sulfentrazone and metribuzîn to the locus.
The target weeds may be selected fromUrticaceae weeds: Urtica urens, Polygonaceae weeds: Polygonum convolvulus, Polygonum lapathifolium, Polygonum pensylvanicum, Polygonum persicaria, Polygonum longisetum, Polygonum aviculare, Polygonum arenastrum, Polygonum cuspidatum, Rumex japon icus, Rumex cnspus, Rutnex obtusîfoiius, Rumex acetosa; Portulacaceae weeds: Portulaca oleracea;
Caryophyllaceae weeds: Stellaria media, Cerastium holosteoides, Cerastium glomeratum, Spergula arvensis, Silene gallica
Molluginaceae weeds: Mollugo verticillata; Chenopodiaceae weeds: Chenopodium album, Chenopodium ambrosioides, Kochia scoparia, Salsola kali, Atriplex spp.;
Amaranthaceae weeds: Amaranthus retroflexus, Amaranthus viridis, Amaranthus lividus, Amaranthus spinosus, Amaranthus hybridus, Amaranthus palmen, Amaranthus rudis, Amaranthus patulus, Amaranthus tuberculatos, Amaranthus blitoides, Amaranthus deflexus, Amaranthus quitensis, Alternanthera philoxeroides, Alternanthera sessilis, Alternanthera tenella; Papaveraceae weeds: Papaver rhoeas, Argemone Mexicana; Brassicaceae weeds: Raphanus raphanistrum, Raphanus sativus,
Sinapis arvensis, Capsella bursa-pastoris, Brassica juncea, Brassica campestns, Descurainia pinnata, Rorippa islandica, Rorippa sylvestris, Thlaspi arvense, Myagrum rugosum, Lepidium virginicum, Coronopus didymus; Dinebra weeds: Dmebra Americana, Dinebra aquatic, Dinebra aristidoides, Dinebra bromoides , Dinebra calycina, Dinebra caudata, Dinebra chinensis, Dinebra chloride. Dmebra chondrosioides, Dinebra coerulescens, Dinebra cristata, Dinebra curti pendu la, Dinebra decipiens, Dinebra divaricate, Dinebra divaricatissima, Dinebra dura, Dinebra guineensis, Dinebra hirsute, Dinebra hirta, Dinebra juncifolia , Dinebra ligulata, Dinebra lima, Dinebra melicoides, Dinebra nealleyi, Dinebra neesii, Dinebra panicea, Dinebra panicoides, Dinebra pubescens, Dinebra repens, Dinebra scabra, Dmebra secunda, Dinebra simoniana, Dinebra southwoodii, Dinebra squarrosa, Dinebra srilankensis , Dinebra tuaensis, Dinebra verticillate, Dinebra rétro flexa.. Dinebra haareri , Dinebra marquisensis, Dinebra perrieri , Dinebra polycarpha, Dinebra somalensis Capparaceae weeds: Cleome affinis; Fabaceae weeds: Aeschynomene indica. Aeschynomene rudis, Sesbania exaltata, Cassia obtusifolia, Cassia occidentalis, Desmodium tortuosum, Desmodium adscendens, Trifolium repens, Pueraria lobata, Vicia angusti folia, Indigo fera hirsuta, Indigo fera truxil Iensis, Vigna sinensis; Oxalidaceae weeds: Oxalîs corniculata, Oxalis strica, Oxalîs oxyptera; Geraniaceae weeds: Géranium carolinense, Erodium cicutarium; Euphorbiaceae weeds: Euphorbia helioscopia, Euphorbia inaculate, Euphorbia humistrata, Euphorbia esula, Euphorbia heterophylla, Euphorbia brasi 1 iensis, Acalypha australis, Croton glandulosus, Croton lobatus, Phyllanthus corcovadensis, Ricinus commuais; Malvaceae weeds: Abutilon theophrasti, Sida rhombiforia, Sida cordifolia, Sida spinosa, Sida glaziovii, Sida santaremnensis, Hibiscus trionum, Anoda cristala, Malvastrum coromandelianum
Sterculiaceae weeds: Waltheria indica; Violaceae weeds: Viola arvensis, Viola tricolor; Cucurbitaceae weeds: Sicyos angulatus, Echinocystis lobata, Momordica charantia; Lythraceae weeds: Lytbrum salicaria; Apîaceae weeds: Hydrocotyle sibthorpioides; Sapindaceae weeds: Cardiospermum halicacabum; Primulaccae weeds: Anagallis arvensis; Asclepiadaceae weeds: Asclepias syriaca, Ampelamus albidus; Rubiaceae weeds: Galium aparine, Galium spurium var. echinospermon, Spermacoce latifolia, Richardia brasîl iensis, Borreria alata; Convolvulaceae weeds: Ipomoea nil, Ipomoea hederacea, Ipomoea purpurea, Ipomoea hederacea var. integriuscula, Ipomoea lacunosa, Ipomoea triloba, Ipomoea acuminata, Ipomoea hederifolia, Ipomoea coccinea, Ipomoea quamoclit, Ipomoea grandifolia, Ipomoea aristolochiafoiia, 25 Ipomoea cairica, Convolvulus arvensis, Calystegia hederacea, Calystegia japonica, Merremia hedeacea, Merremia aegyptia, Merremiacissoides, Jacquemontia tamnifolia; Boraginaceae weeds: Myosotis arvensis; Lamiaceae weeds: Lamium puipuieum, Lamium ampiexicaule, Leonotis nepetaefolia, Hyptis suaveolens. Hyptis lophanta, Leonurus sîbiricus, Stachys arvensis; Solanaceae weeds: Datura stramonium, Solanum nigrum. Solarium americanum, Solanum ptycanthum, Solarium sarrachoides, Solanum rostratum, Solanum aculeatissimum, Solanum sisymbriifolium, Solanum carolinense, Physalis angulata, Physalîs subglabrata, Nicandra physaloides; Scrophulariaceae weeds: Veronica hederaefolia, Veronica persica, Veronica arvensis; Plantaginaceae weeds: Plantago asiatica; Asteraceae weeds: Xanthium pensylvanicum, Xanthium occidentale, Helianthus an nous, Matricaria chamomilla, Matricaria perforata, Chrysanthemum segetum, Matricaria matricarioides, Artemisia princeps, Artemisia vulgaris, Artemisia verlotorum, solidago altissima, Taraxacum officinale, Galinsoga ciliata, Galinsoga parviflora, Senecio vulgaris, Senecio brasiliensis, Senecio grisebachii, Conyza bonariensis, Conyza canadensis, Ambrosia artemisiaefolia, Ambrosia trifida, Bidens pilosa, Bîdens frondosa, Bidens subalternans. Cîrsium arvense, Cirsium vulgare, Silybum marianum, Carduus nutans, Laetuca seiriola, Sonchus oleraceus, Sonchus asper, Wedelia glauca, Melampodium perfoliatum, Emilia sonchifolia, Tagetes minuta, Blainvillea latifolia, fridax procumbens, Porophyllum ruderale, Acanthospermum australe, Acanthospermum hispidum, Cardiospeimum halicacabum. Agératum conyzoides, Eupatorium perfoliatum, Eclipta alba, Erechtites hieracifolia, Gamochaeta spicata, Gnaphalium spicatum, Jaegeria hirta, Parthenium hysterophorus, Siegesbeckia oriental is, Soliva sessilis; Liliaceae weeds; A Ilium canadense, Allium vineale; Commelinaceae weeds: Commelina communis, Commelina bengharensis, Commelina erecta; Poaceae weeds: Echinochloa crus-galli, Setaria viridis, Setaria faberi, Setaria glauca, Setaria genicuîata, Digitaria ciliaris, Digitarîa sanguinalis, Digitaria horizontalis, Digitaria insularis, Eleusine indica, Poa annua, Alospecurus aequalis, Alopecurus myosuroîdes, Avena fatua, Sorghum halepense, Sorghum vulgare, Agropyron repens, Lolium mukiflorum, Lolium peienne, Lolium rigidum, Bromus secalinus, Bromus tectorum, Hordeum jubatum, Aegilops cylindrica. Phalaris arundinacea, Phalaris minor, Apera spica-venti, Panicum dichotomifiorum, Panicum texanum, Panicum maximum, Brachiaria platyphylla, Brachiaria ruziziensis, Brachiaria plantaginea, Brachiaria decumbens, Biachiaiia brizantha, Brachiaria humidicola, Cenchrus echînatus, Cenchrus pauciflorus, Enochloa villosa, Pennisetum setosum, Chions gayana, Eragrostis pilosa, Rhynchehirum repens, Dactyloctenium aegyptium, Ischaemum rugosum, Oryza saliva, Paspalum notatum, Paspalum maritimum, Pennisetum clandestinum, Pennisetum setosum, Rottboellia cochinchinensis; Cyperaceae weeds: Cyperus microiria, Cyperus iria, Cyperus odoratus, Cyperus rotundus, Cyperus esculentus, Kyllinga gracillima, Equisetaceae weeds: Equiselum arvense, Equisetum palustre, Trianthema weeds and the like.
In preferred embodiment the composition ofthe présent invention is applied in soybean crop and is effective against several broadleaved weeds and grassy weeds, viz. velvetleaf, redroot pigweed, common lambsquaters, tumble pigweed and giant foxtail. In an embodiment, composition may be applied in a tank mix or as a pie-mixed composition.
In an embodiment, composition of the présent invention may be applied either pre-or post-emergent. In a preferred embodiment, the composition of the présent invention may be used pre-emergent, and pre-plant. The advantage of the composition is surprisingly good residual effects, and quick burndown ofthe weeds when applied preplant or pre-emergent.
According to an embodiment of the présent invention, methods of application of agrochemical compositions as well as the mixtures according to the présent invention are not particularly limiting. It can be simultaneous application of either a pre-mix or tank mix of active ingrédients with auxiliaries suitable for the formulation or it can be a sequential application of one after the other.
According to an embodiment of the présent invention, use of agrochemical composition comprising co-crystal of sulfentrazone and a triazinone herbicide.
According to an embodiment of the présent invention, use of agrochemical composition comprising co-crystal of sulfentrazone and metribuzin.
According to an embodiment of the présent invention, use of liquid agrochemical composition comprising co-crystal of sulfentrazone and metribuzin.
According to an embodiment of the présent invention, a kit is provided wherein kit comprises a co-crystal of sulfentrazone and a triazinone herbicide; and other agrochemical excipients.
According to an embodiment of the présent invention, a kît is provided wherein kît 5 comprises a co-crystal of sulfentrazone and triazinone herbicide.
According to an embodiment of the présent invention, a kit comprising co-crystal of sulfentrazone and metribuzin.
The invention shall now be described with reference to the following spécifie examples. Tt should be noted that the examples appended below illustrate rather than 10 limit the invention and that those ski lied in the art will be able to design many alternative embodiments withoui départing from the scope of the présent invention.
EXAMPLES
Example 1: Préparation of the co-crystal of sulfentrazone and metribuzin
For a 1:1 co-crystal of sulfentrazone and metribuzin, 193.5 g of sulfentrazone and 107 15 g of metribuzin were charged into a round bottom flask. To this mixture was added 150 ml of dichloroethane. The solution was stirred at 30 °C overnight, 1000 ml hexane was added and stirred to obtain solid which were filtered and dried under vacuum to get 268 g of crystals. HPLC analysis: mctribuzin-33.48% (w/w) and sulfentrazone-65.31% (w/w) which corresponds to about 1:1 of metribuzin: sulfentrazone (mole: mole). (Fig.
I).
Spectroscopic analysis of Co-crystal
The co-crystal prepared according to Example-1 is further characterized by FT-IR (Fig.
). The FT-IR. spectrum of co-crystal of sulfentrazone and metribuzin is found to exhibit at least 3 characteristic values, particularly at least 5 characteristic values, or ail 25 the values selected from (±4 cm'1) 3314, 3264, 2970, 1736, 1685, 1630, 1521, 1494, 1467, 1420, 1392, 1367, 1348, 1332, 1303, 1262, 1193, 1163, 11 16, 1098, 1072,976, 942, 893, 877, 824, 796, 764, 740, 670, 661, 645, 602, 570, 458, in particular from (±4 cm'1) 3314, 3264, 1736, 1685, 1630, 1521, 1494, 1467, 1420, 1392, 1367, 1348, 1332, 1163, ! 116, 1098, 1072, 976 and 824.
Crystallographic analysis of the Co-crystal
The co-crystal prepared according to Example-1 is characterized by PXRD. (Fig. 3) The co-crystal of sulfentrazone and metribuzin shows an X-ray powder diffractogram at25°C. (PXRD conditions: Instrument: Brukermake 2lld génération D2 Phaser Powder 5 X-Ray diffractometer; Operated at: 30.0 kV, 10 inA; Radiation: Cu-Κα; Wavelength:
.54060 °A, Scan Range: 2-40 20, Step size: 0.02°). The co-crystal of sulfentrazone and metribuzin shows at least 3, in particular at least 4 and more preferably ail of the following reflexes, given in the following table 1 as 2Θ values:
Table 1
| PXRD of the co-crystal of Sulfentrazone and Metribuzin (Example-1) (25 °C, Cu-K.cc radiation, 1.54060 Â) | |
| 20 values [°] | d[A°l |
| 7.9 ± 0.2 | 11.1 ±0.2 |
| 1 1.8 ±0.2 | 7.4 ±0.2 |
| 12.1 ±0.2 | 7.2 ± 0.2 |
| 14.1 ± 0.2 | 6.2 ± 0.2 |
| 17.9 ±0.2 | 4.9 ± 0.2 |
| 20.5 ±0.2 | 4.3 ± 0.2 |
| 22.2 ±0.2 | 4.0 ± 0.2 |
| 23.3 ±0.2 | 3.8 ±0.2 |
| 24.5 ± 0.2 | 3.6 ±0.2 |
3S
Single crystal X-ray diffraction
Single crystal X-ray analysis détermines the atomic and molecular structure of a cocrystal, încluding the molar relationship between the two compounds forming the cocrystal. The single crystal X-ray diffraction data of the co-crystal of sulfentrazone and S metribuzin was collected on a Bruker D8 QUEST PHOTON-100 Detector. The structures were solved using direct methods, refined and expanded by Fourier techniques with SHELXTL-PLUS software package. Single crystal X-ray diffraction showing hydrogen bonding interaction forming co-crystal of sulfentrazone and metribuzin is given in Fig. 7.
Single crystal X-ray diffraction data and refinement for the co-crystal of sulfentrazone and metribuzin is given in the following table 2:
Table 2
| Empirical formula | C19H24NSO4S2CI2F2 | |
| Formula weight | 601.49 gm/mol | |
| Température | 294.15 K | |
| Wavelength | 0.71073 Â | |
| Crystal system | Monoclinic | |
| Space group | P 2t/c | |
| Unit cell dimensions | a=22.2825(4) Â | a= 90° |
| b=10.5240(2) Â | 93.505847) | |
| c=l 1.4659(2) Â | γ= 90° | |
| Volume | 2683.73 (8) Â3 | |
| Z | 4 | |
| Density(calculated) | 1.4885 g/cc | |
| Absorption coefficient | 0.454 mm'1 | |
| Θ range for data collection | 5.26° to 50° | |
| Reflections collected | 18592 |
| Independent reflections | 4631 [Rirlt=0.0306], [R5igllia-0.0687] |
| Final R indices [Ι>=2σ(Ι) | R 1=0.0939, wR2=0.2592 |
Thermal Analysis of the co-crystal
DSC-measurement of the co-crystal was carried out on a Mettler-Toledo DSC 3 STARe system and STARe software was used to analyze the DSC data. A closed 5 aluminum pan with 40 microliter capacity was used and the measurement was carried out under nitrogen flow with a heating rate of 10°C/min and a sample weight of 5 to 10 mg.
DSC of the co-crystal exhibit an endothermie peak with onset at 107.3°C and peak at 110.5°C. (Fig. 4) and spécifie heat of fusion(normalized) is between -69 JgA-l to -81 10 JgA-1 The endothermie peak seen in DSC does not match with the individual melting points of sulfentrazone and metribuzin. Hence, analysis using DSC indieates cocrystallization.
Example 2: Suspension Concentrate (SC) composition of co-crystal of
Sulfentrazone and Metribuzin
| Ingrédients | Quantity (%w/w) |
| Sulfentrazone-Metribuzin Co-crystal | 13.867 |
| Metribuzin | 22.43 |
| Propylene glycol | 5 |
| Polyalkylene glycol ether | 1 |
| Alkali swellable polyacrylate | 5 |
| Acrylic polymer | 2 |
| Silicone defoamer | 0.2 |
| Clay | 0.3 |
| Xanthan gum (2% gel) | 7.5 |
| l,2-benzisothiazolin-3-one | 0.1 |
| Water | Q.S. |
| Total | 100 |
5g propylenc glycol, 1g polyalkylene glycol ether, 5 g alkali swellable polyacrylate, 2 g acrylic polymer was agitated with 42.60 g water for at least i hr. 0.2 g silicone defoamerwas added to above stated mixture and subjected to agitation. 13.867 gof co5 crystal of sulfentrazone and metribuzin and 22.43 g Metribuzin was added and subjected to homogenization forât least 1 hr followed by milling. 7.5 gof 2 % Xanthan gum gel was added and the mixture was subjected to homogenization for at least 1 hr. The homogenized mixture was then set for uniform gelling. The composition obtaincd was then characterized by analytical techniques viz. FT-IR (Fig. 5) and P-XRD (Fig.
6).
Example 3: 26.77% Sulfentrazone and 8.93% Metribuzin SC
| Ingrédients | Quantity (w/w%) |
| Sulfentrazone (98% purity) | 9.1 |
| Metribuzin | 27.6 |
| Glycerin | 5 |
| Polyalkylene glycol ether | 1 |
| Alkali sweliable polyacrylate | 4.7 |
| Acrylic polymer | 2.3 |
| Silicone defoamer | 0.2 |
| Clay | 0.3 |
| Xanthan gum | 0.15 |
| Water | Q.S. |
| Total | 100 |
27.85g Metribuzin and 9.30g Sulfentrazone technical were mixed to make homogeneous powder. The powder was then kept in incubator at 54 °C for 14 days to facilitate co-crystal formation. Separalely, slurry was prepared in water by adding 5.0g glycerin, 1.0g polyalkylene glycol ether, 2.3g acrylic polymer, 4.70g alkali swellabie 5 polyacrylate, to the slurry préparation and stirred for 30 min to make the solution homogène us. Further, 0.2g silicone defoamer and 0.3g clay, were added one by one in sequence under continuous stirring. Homogeneous powder of Metribuzin and Sulfentrazone kept for pre-treatment was then charged under continuous stirring in the slurry obtained in the above step. The slurry' was stirred for 30 min to break lumps and 10 kept cooling down below 15 °C and was taken for bead milling. After slurry reaches the desired particle size (D90 <10 micron) it was taken for GelIification. 2% aqueous gel obtained by adding 8g xanthan gum and 0.2g bronopol.
Examplc 4: 26.77% Sulfentrazone and 8.93% Metribuzin SC
| Ingredicnt(s) | Quanti ty (%w/w) |
| Metribuzin Tech @ 97% | 27.85 |
| Sulfentrazone Tech @ 98% | 9.30 |
| Alkali swellabie polyacrylate | 4.70 |
| Polyalkylene glycol ether | 1.00 |
| Acrylic polymer | 2.30 |
| 1,2-benzisothiazolin-3-one | 0.20 |
| Silicone defoamer | 0.20 |
| Clay | 0.30 |
| Glycerin | 5.00 |
| Xanthan gum | 8.00 |
| Water | Q.S. |
| Total | iOO |
Metribuzin and Sulfentrazone in above quantity were mixed to make homogeneous powder. The powder thus obtained was melted on oil bath at 105-110 °C. after that it was allowed to cool at room température to obtain flakes. The flakes were then grinded to obtain a power. Separately, slurry was prepared in water by adding glycerin, 5 polyalkylene glycol ether, acrylic polymer, alkali swellable polyacrylate, to die slurry préparation and stirred for 30 min to make the solution homogenous. Further, silicone defoamer, clay, and l,2-benzisothiazolin-3-one are added one by one in sequence under continuous stirring. The powder of Metribuzin and Sulfentrazone obtained from pre-treatment was then charged under continuous stirring in the slurry obtained in the 10 above step. The slurry was stirred for 30 min to break lumps and kept to cool down below 15 °C and was taken for bead milling. After slurry reaches the desired particle size (D90 <10 micron) it was taken for Gellîfication. 2% aqueous gel obtained by adding 8g xanthan gum and ],2-benzisothiazolin-3-one.
Example 5: SC composition of Sulfentrazone and Metribuzin
| Ingrédients | Quantity (%w/w) |
| Sulfentrazone | 8.98 |
| Metribuzin | 27.22 |
| Propylene glycol | 5 |
| Polyalkylene glycol ether | 1 |
| Alkali swellable polyacrylate | 5 |
| Acrylic polymer | 2 |
| Silicone defoamer | 0.2 |
| l ,2-benzisothiazolin-3-one | 0.2 |
| Clay | 0.3 |
| Xanthan gum (2% gel) | 7.5 |
| Water | Q.S. |
| Total | 100 |
g propylene glycol J g polyalkylene glycol ether, 5 g alkali swellable polyacrylate and 2 g acrylic polymer were agitated with 42.60 g water for at least i hr. 0.2 g silicone defoamer was added to above stated mixture and subjected to agitation. 8.98 g Sulfentrazone and 27.22 g Metribuzin were added and subjected to homogenization for at least 1 hr. followed by milling. 7.5 g of 2 % Xanthan gum gel was added and the mixture was subjected to homogenization for at ieast 1 hr. The homogenized mixture was then set for uniform gelling.
Example 6: Sulfentrazone and Metribuzin SC
| Ingrcdient(s) | Quanti ty (%wAv) |
| Metribuzin Tech @ 97% | 27.85 |
| Sulfentrazone Tech @ 98% | 9.3 |
| Alkali swellable polyacrylate | 4.7 ___ |
| Polyalkylene glycol ether | 1 |
| Acrylic polymer | 2.3 |
| 1,2-benzisothiazolin-3-one | 0.2 |
| Silicone defoamer | 0.2 |
| Clay | 0.3 |
| Glycerin | 5 |
| Xanthan gum | 8 |
| Water | Q.S. |
| Total | 100 |
Thermoregulatory vessel equipped with a high mixer was charge with partial water and stated to agitate. alkali swellable polyacrylate, acrylic polymer, polyalkylene glycol ether, silicone defoamer, partial amount of Glycerin and clay was added to obtain solution. The solution was then allowed to cool < 25°C. Metribuzin and Sulfentiazone 15 was added to the solution under high shear to obtain mixture. The mixture was then taken for milling (Partîcle size spécification of dlO < 1, d50 <4, d90 < 10 and d100 <
μιη) at mill température at < 25°C to obtain miiled base. The miiled base was returned to mixing vessel heated to 54°C and mixing carried for approximately 1 hour. Separately, thickener was prepared by charging a vessel with Glycerin, 1,2benzisothiazolin-3-one, xanthan guin and water and mixed for 30 minutes. Thickener 5 was added to mill base. The final composition was adjusted with water and released quality check and packaging.
Example 7: Sulfentrazone and Metribuzin SC
| Ingrédients | Quantity (%w/w) |
| Sulfentrazone (98% purity) | 12.1 |
| Metribuzin | 24.6 |
| Glycerin | 5 |
| Polyalkylene glycol ether | 1 |
| Aikali swellable polyacrylate | 6 |
| Acrylic poiymer | 3 |
| Xanthan gum (2% gel) | 7.5 |
| Clay | 0.15 |
| Water | Q.S. |
| Total | 100_____________ |
Metribuzin, Sulfentrazone, Glycerin, polyalkylene glycol ether, aikali swellable polyacrylate, acrylic poiymer, xanthan gum, clay and water were mixed in above quantity and processed as per the process given in Example-6 to obtain suspension concentrate composition of co-crystals comprising sulfentrazone and metribuzin.
Examplc 8: Sulfentrazone and Metribuzin SC
| Ingrédients | Quantity (w/w%) |
| Sulfentrazone (98% purity) | 9.1 |
| Metribuzin | 27.6 |
| Giycerin | 5 |
| Polyalkylene glycol ether | ! ________ |
| Alkali swellable polyacrylate | 6 |
| Acrylic polymer | 3 |
| Silicone defoamer | 0.2 _ |
| Clay | 0.3 |
| Xanthan gum | 0.15 |
| Water Total__ | Q.S. 100 |
Metribuzin, Sulfentrazone, Giycerin, Polyalkylene glycol ether, alkali swellable polyacrylate, acrylie polymer, silicone defoamer, xanthan gum, clay and water were mixed in above quantity and processed as per the process given in Example-6 to obtaîn 5 suspension concentrate composition of co-crystals comprising sulfentrazone and metribuzin.
Example 9: Sulfentrazone and Metribuzin SC
| Ingrédients | Quantity (w/w%) |
| Sulfentrazone | 9.17 |
| Metribuzin | 18.56 |
| Giycerin | 5 |
| Polyalkylene glycol ether | 1 |
| Alkali swellable polyacrylate | 6 _ |
| Acrylic polymer | 3 _ |
| Clay_______________________ | 0.3 _ |
| Xanthan gum | 0.15 |
| Water Total | Q. S. 100 |
Process: Thermoregulatory vessel equipped with a high mixer was charged with partial water and stated to agitate. Alkali swellable polyacrylate, acrylic polymer, polyalkylene glycol ether, silicone defoamer, partial amount of Glycerin and clay were added to obtain a solution. The solution was then allowed to cool < 25°C. Metribuzin and Sulfentrazone was added to the solution under high shear to obtain mixture. The material was mi lied to the required parti cle size and measure wet sieve rétention according to in-process spécification at température 25°C or less than 25°C during the milling process. Thickener was added to mill base. The final composition wasadjusted with water and released quaiity check and packaging.
Example 10
Stability Study of Suspension Concentrate Composition
Stability features associated with the composition developed according to the present invention were studied. The compositions described in Example-3 and Example-4 were taken further to evaluate physicochemical parameters. It was found that the compositions of Example-3 and Example-4 remained stable when tested at ambient conditions i.e. room température and pressure. The compositions also passed 14 days and 28 days Acceierated Heat Stability (AHS) test and remained flowable suspension in off-white appearance. Amount of active content also been evaluated at ail three stages (ambient, 14 days AH S and 28 days A HS). It was found that active content remained almost constant without any significant détérioration or loss. The composition also passed wet sieve testing as no crystals were observed to be retained on wet sieve. Particle size of composition was analysed and found to be ncaily constant suggesting little/ negligible particle size growth or crystal formation. (Table 3)
Table 3
| Example 3 | Example 4 | |||||
| Parameters | Ambient | 14 Days AHS at 54 °C | 28 Days AHS at 54 °C | Ambient | 14 Days AHS at 54 DC | 28 Days AHS at 54 °C |
| Description | Off white col or suspension concentrate. | Compiles | Compiles | Off white col or suspension concentrate. | Compiles | Compiles |
| Active content Metribuzin (%w/w) Sulfentrazone | 27.31 9.13 | 27.25 9.11 | 26.54 8.87 | 27.31 9.07 | 27.23 9.12 | 27.32 9.19 |
| pH of 1% Aq. Solution | 6.33 | 6.24 | 6.28 | 5.95 | 6.00 | 6.01 |
| Suspensibility (Gravimétrie) % w/w | 93.7 | 91 | 90 | 96 | 93 | 91 |
| Wet sieve test material retains on75 micron (% w/w) | Nil | NIL | NIL | Nil | 0.3 | 0.5 |
| Particle size distribution (in micron) | DIO=1.1 D50=2.8 | DI 0=2.8 D50=8.2 | DI 0=1.0 D50=2.7 | DI 0=2.0 D50=6.2 | DI 0=2.2 D50=7.2 | |
| Density @ 20 °C | 1.116 | — | — |
Example 11
Bio-efficacy Data
The pre-emergence study was conducted on soyabean crop to test the efficacy of the agrochemîcal composition developed according to the présent invention against several 5 broadleaved weeds and grassy weeds, viz. velvetleaf, redroot pigweed, common lambsquaters, tumble pigweed and giant foxtail. The composition of Example-7 with co-crystal of sulfentrazone and metribuzin in 1:2 ratio was tested in soyabean field at the rate of 630g a.i. The composition found to be effective on velvetleaf, redroot pigweed, common lambsquaters, tumble pigweed and giant foxtail at ail intervals from 10 14DAA (14 days after application) to 35DAA (35days after application). More than 60% control was observed for velvetleaf; 100% control of redroot pigweed was observed by the agrochemical composition of the présent invention, bimilarly, moie than 90% control was observed for common lambsqauters and tumble pigweed. A good control of giant foxtail as also observed from 50-83% at 35DAA-21DAA observation 15 as represented in below table.
Table 4
Composition of Example-7 @630g a.i.
| 14DAA | 21DAA | 28DAA | 35DAA | |
| Velvetleaf % Control | 80 | 68 | 68 | 64 |
| Redroot Pigweed % Control | - | 100 | 100 | 100 |
| Common Lambsquaters % Control | - | 98 | 96 | 96 |
| Tumble Pigweed % Control | • | 100 | 100 | 99 |
| Giant Foxtail % Control | - | 83 | 78 | 50 |
Therefore, inventors of the présent invention found that an agrochemical composition made of a co-crystal of sulfentrazone and a triazinone herbicide resulted into a stable composition, The formation of a co-crystal of sulfentrazone and triazinone herbicide, particularly metribuzin prior to the incorporation in the agrochemical composition 5 imparted physical stability to the system. The acrylate polymer and glycerol in said agrochemical composition of co-crystal provîded good performance over time, low or no sédimentation, and little particle size dégradation. It is to be understood that the invention is not to be limited to the details of the above embodiments, which are described by way of example only.
Claims (24)
- !. A co-crystal comprising sulfentrazone and at least one triazînone herbicide.
- 2. The co-crystal as claimed in claim 1 wherein said triazinone herbicide is selected from the group comprising ametridione, amibuzin, ethiozin, hexazinone, isomethiozin, metamitron, metribuzin or trifludimoxazin.
- 3. The co-crystal as claimed in claim 1 wherein said triazinone herbicide is metribuzin.
- 4. The co-crystal as claimed in claim 1 being a co-crystal of sulfentrazone and metribuzin.
- 5. The co-crystal as claimed in claim 1, wherein the molar ratio of sulfentrazone and at least one triazinone herbicide in said co-crystal is from 1: 9 to 9: I.
- 6. The co-crystal as claimed in claim 5 wherein said sulfentrazone and metribuzin are présent in a molar ratio from 2:1 to 1:2.
- 7. A co-crystal of sulfentrazone and metribuzin.
- 8. The co-crystal as claimed in claim 7 wherein said co-crystal is characterized by a powder X-ray diffraction pattern comprising at least one peak at a diffraction angle of 20 values, 7.8°, 11.8°, 14.1I7.8°, 22.1% 23.4° and 24.4° (± 0.2).
- 9. The co-crystal as claimed in claim 7 wherein said co-crystal is charactei ized by at least one of following a powder X-ray diffraction pattern comprising at least one peaks at a diffraction angle of 2Θ values, 7.8°, 11.8°, 14.1 1 7.8°, 22.1 °, 23.4° and 24.4° (± 0.2) or a DSC thermogram comprising an endothermie peak with onset at 107.3°C and a peak at 110.5°C or;a single crystal X-ray diffraction having lattice parameters: a=22.2825(4) À, b=l0.5240(2) Â, c=11.4659(2) Â, a= 90°, β= 93.5058°(7) and γ= 90°.
- 10. A process for preparing a co-crystal of sulfentrazone and a triazinone herbicide wherein said co-crystal is obtained by solution crystallization or grinding or heating or solvent drop grinding or melt crystallization or mixing sulfentrazone and a triazinone herbicide in an aqueous condition.
- 11. The process as claimed in claim 10 comprises preparing a solution of sulfentrazone and a triazinone herbicide using an organic solvent, water, or a mixture of water and an organic solvent and triturating or precipitating with an anti-solvent to obtain said co-crystal of sulfentrazone and a triazinone herbicide.
- 12. The process as claimed in claim 11 wherein said solvent is selected from aliphatic alcohols, ketones, esters, ethers, polar protic solvents, polar aprolic solvents, halogenated solvents, aliphatic hydrocarbon or aromatic hydrocarbon and said anti-solvent is selected from aliphatic or aromatic hydrocarbon solvents.
- 13. The process as claimed in claim 10 wherein said process comprises heating a mixture of sulfentrazone and a triazinone herbicide to melt to obtain said cocrystal of sulfentrazone and a triazinone herbicide.
- 14. An agrochemical composition comprising a co-crystal of sulfentrazone and a triazinone herbicide.
- 15. The composition as claimed in claim 14 wherein said co-crystal is a co-crystal of sulfentrazone and metribuzin.
- 16. The composition as claimed in claim 15 wherein said composition comprising a co-crystal of sulfentrazone and metribuzin, characterized by a powder X-ray diffraction pattern comprising at least one peaks at a diffraction angle of 20 values, 7.8°, 11.8°, 14.1°, I7.8°, 22.1 23.4° and 24.4° (± 0.2).
- 17. The composition as claimed in claim 15 wherein said co-crystal comprises 1090% of sulfentrazone and 90-10% of triazinone herbicide by weighl of the composition.
- 18. The composition as claimed in claim 15 wherein said composition is a liquid composition.
- 19. An agrochemical formulation comprising the composition of claim 15 which is a suspension concentrate.
- 20, A process for preparing an agrochemical composition of a co-crystal of sulfentrazone and a triazinone herbicide, said process comprising:a) pre-treatment to sulfentrazone and a triazinone herbicide to form a cocrystal;b) admixing co-crystal of step (a) with agrochemically acceptable excipients to obtain said composition.
- 21. The process as claimed in claim 20 wherein said process comprises;a) pre-treatment to sulfentrazone and metribuzin by heating followed by cooling the mixture to room température to obtain co-crystal;b) admixing co-crystal of step (a) with agrochemical excipients in piesence of water to to obtain homogeneous agrochemical composition,
- 22. The process for preparing agrochemical composition as claimed in claim 19 comprisesa) preparing an aqueous mixture of agrochemically suitable excipients to obtain a homogeneous solution.b) adding metribuzin and sulfentrazone in the homogeneous solution of step (a) to obtain a slurry;c) optionally milling the slurry.d) heating the slurry' of step (b) or (c) and cooling to room température.e) optionally charging other agrochemical excipient to the slurry of step (d) and mixing to get homogeneous agrochemical composition.
- 23. A method of controlling weeds comprising applying to a plant, or its habitat, plant seed or soil, a herbicidally effective amount of a co-crystal of sulfentrazone and a triazinone herbicide.
- 24. The method as claimed in claim 23 wherein said method comprising applying to a plant, or its habitat, plant seed or soil, a herbicidally effective amount of a composition comprising a co-crystal of sulfentrazone and metribuzin.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| IN202021012142 | 2020-03-20 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| OA20908A true OA20908A (en) | 2023-06-27 |
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