DESC:
FIELD OF THE DISCLOSURE:
The present disclosure relates to a process for purification of anthranilamide compounds.

BACKGROUND OF THE DISCLOSURE:
Pests and in particular insects, destroy growing as well as harvested crops, thereby causing considerable economic loss. A large number of pesticidal compounds are available against a variety of pests, however, the target pests possess ability to develop resistance to these compounds. Therefore, there is a dire need to develop novel and effective compounds having good pesticidal activity and showing a broad activity spectrum against different pests.

Anthranilamides are a new class of compounds with extremely potent insecticidal activity. These nitrogen-containing aromatic compounds selectively act on targeted ryanodine receptors (RyRs), which form calcium ion channels and are responsible for muscle function in insects. Based on the mechanism of action, these anthranilamide compounds are classified as ryanodine receptor modulator insecticides. Anthranilamide compounds can be represented by the structural formula (I):

Formula (I)
wherein, X is chlorine or a cyano group;
R1 is methyl, bromine or chlorine;
R2 is hydrogen or chlorine; and
R3 is selected from the group comprising methyl, ethyl, propyl, isopropyl, 1-cyclopropylethyl, and combinations thereof.

Furthermore, it has been observed that the preparation of anthranilamide compounds by processes known in the art, lead to formation of an impurity represented by formula (II) along with the desired anthranilamide compound.

Formula (II)
wherein, X, R1 and R3 have the same definitions as stated in formula (I) above. This impurity of formula (II) is very difficult to separate from the desired anthranilamide compound, due to structural similarities with the anthranilamide compound. However, if the impurity of formula (II) is not separated, it is carried forward in the formulation/composition along with the anthranilamide compound, thereby deteriorating the quality of the overall composition/formulation product.

Furthermore, another well-known application of insecticides is to control or reduce insect damage to the seeds during storage as well as to prevent damage to the seeds caused by insects present in the soil. However, it was observed that the use of anthranilamide compounds, as insecticides for seed treatment, comprising the impurity of formula (II) leads to phytotoxic effects on the treated seeds. Therefore, hampering performance of the treated seeds in the field i.e., on growth of the seedlings/plants. Therefore, it is important to develop a purification process, which ensures removal of the impurity of formula (II) from the anthranilamide compounds; which in turn will allow the use of these anthranilamide compounds as insecticides, without any adverse effects on the quality and field performance of treated seeds/crops. The purification method also needs to address the removal of the impurity of formula (II) from anthranilamides compound at large-scale production as the reaction conditions maintained at lab-scale synthesis may not always be feasible at a large/industrial scale.

OBJECTIVES OF THE DISCLOSURE:
It is a primary objective of the present disclosure to provide a process for purification of anthranilamide compound.

It is another objective of the present disclosure to provide anthranilamide compound of formula (I) having high purity.

It is yet another objective of the present disclosure to provide anthranilamide compound of formula (I) substantially free from an impurity of formula (II).

It is yet another objective of the present disclosure to provide a simple, cost-effective and industrially viable process for purification of anthranilamide compound of formula (I).

SUMMARY OF THE DISCLOSURE:
In one aspect, the present disclosure provides a process for purification of anthranilamide compound of formula (I):

Formula (I)
wherein, X is chlorine or a cyano group;
R1 is methyl, bromine or chlorine;
R2 is hydrogen or chlorine; and
R3 is selected from the group comprising methyl, ethyl, propyl, isopropyl, or 1-cyclopropylethyl.

In another aspect, the present disclosure provides a process for purification of anthranilamide compound of formula (I):

Formula (I)
wherein the purified anthranilamide compound is substantially free of an impurity of formula (II):

Formula (II)
wherein, X is chlorine or a cyano group;
R1 is methyl, bromine or chlorine;
R2 is hydrogen or chlorine; and
R3 is selected from the group comprising methyl, ethyl, propyl, isopropyl, or 1-cyclopropylethyl; and
the process comprising:
a) preparing a solution of a crude anthranilamide compound in a first organic solvent at a temperature ranging from about 40°C to about boiling point of the first organic solvent to obtain a purified anthranilamide compound of formula (I); and
b) isolating the purified anthranilamide compound of formula (I) from the solution of step a) by adding a second solvent;
wherein a weight ratio of the first organic solvent to the second solvent is in range from about 1:0.5 to about 3:1.

In yet another aspect, the present disclosure provides a composition comprising anthranilamide compound of formula (I) substantially free from an impurity of formula (II).

In yet another aspect, the present disclosure provides a method of treating a seed or a plant or its locus or a plant propagation material thereof, the method comprising applying to the seed or the plant or its locus or the plant propagation material thereof an effective amount of a composition comprising anthranilamide compound of formula (I) substantially free from an impurity of formula (II).

In yet another aspect, the present disclosure provides use of a composition comprising anthranilamide compound of formula (I) substantially free from an impurity of formula (II), as an insecticide.

In yet another aspect, the present disclosure provides use of the composition comprising anthranilamide compound of formula (I) substantially free from an impurity of formula (II), for seed/plant propagation material treatment.

BRIEF DESCRIPTION OF DRAWINGS:
Figure 1 discloses graphical representation of the emergence speed index of plants grown from seeds treated with the formulation disclosed in Examples 2 and 3.
Figure 2 discloses graphical representation of the vigour of plants grown from seeds treated with the formulation disclosed in Examples 2 and 3.
Figure 3 discloses graphical representation of the height (cm) of plants grown from seeds treated with the formulation disclosed in Examples 2 and 3.
Figure 4 discloses graphical representation of the phytotoxicity of plants grown from seeds treated with the formulation discloses in Examples 2 and 3.
Figure 5 discloses visual observation demonstrating the overall health of plants grown from the seeds treated with the formulations A and B. Figure 5a – (i) Formulation A for dose of 62.5 g a.i./100 kg of seeds; (ii) Formulation A for dose of 125 g a.i./100 kg of seeds; (iii) Formulation B for dose of 62.5 g a.i./100 kg of seeds; and (iv) Formulation B for dose of 62.5 g a.i./100 kg of seeds; eight days post sowing. Figure 5b – (i) Formulation A for dose of 62.5 g a.i./100 kg of seeds; (ii) Formulation A for dose of 125 g a.i./100 kg of seeds; (iii) Formulation B for dose of 62.5 g a.i./100 kg of seeds; and (iv) Formulation B for dose of 62.5 g a.i./100 kg of seeds; fifteen days post sowing.

DETAILED DESCRIPTION OF THE DISCLOSURE:
The present disclosure now will be described hereinafter with reference to the accompanying examples, in which embodiments of the disclosure are shown. This description is not intended to be a detailed catalogue of all the different ways in which the disclosure may be implemented, or all the features that may be added to the instant disclosure. Thus, the disclosure contemplates that in some embodiments of the disclosure, any feature or combination of features set forth herein can be excluded or omitted. In addition, numerous variations and additions to the various embodiments suggested herein will be apparent to those skilled in the art in light of the instant disclosure, which do not depart from the instant disclosure. Hence, the following descriptions are intended to illustrate some particular embodiments of the disclosure, and not to exhaustively specify all permutations, combinations and variations thereof.

Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this disclosure belongs. The terminology used in the description of the disclosure herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the disclosure.

For convenience, before further description of the present disclosure, certain terms employed in the specification and examples are described herein. These definitions should be read in light of the remainder of the disclosure and understood as by a person of ordinary skill in the art. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by a person of ordinary skill in the art. The terms used throughout this specification are defined as follows, unless otherwise limited in specific instances.

The use of the terms “a” and “an” and “the” and similar referents (especially in the context of the following claims) are to be construed to cover both the singular and the plural, unless otherwise indicated herein or clearly contradicted by context. The terms first, second etc. as used herein are not meant to denote any particular ordering, but simply for convenience to denote a plurality of, for example, layers.

As used herein, the terms “comprising”, “having”, “including”, and “containing” are to be construed as open-ended terms (i.e., meaning “including, but not limited to”) unless otherwise noted.

As used herein, the term “about” or “approximately” are inclusive of the stated value and means within an acceptable range of deviation for the particular value as determined by one of ordinary skill in the art, considering the measurement in question and the error associated with measurement of the particular quantity (i.e., the limitations of the measurement system). For example, “about” can mean within one or more standard deviations, or within ± 10% or ± 5% of the stated value.

The use of any and all examples, or exemplary language (e.g., “such as”), is intended merely to better illustrate the disclosure and does not pose a limitation on the scope of the disclosure unless otherwise claimed. No language in the specification should be construed as indicating any non-claimed element as essential to the practice of the disclosure as used herein.

Those skilled in art will be aware that disclosure described herein is subject to variations and modifications other than those specifically described. It is to be understood that the disclosure described herein includes all such variations and modifications. The disclosure also includes all such steps, features, compositions, and methods referred to or indicated in this specification, individually or collectively, and any and all combinations of any two or more said steps or features.

The expression of various quantities in terms of “%” or “% w/v” or “% w/w” means the percentage by weight of the total solution or composition unless otherwise specified.

As used herein, the term “insecticide” refers to the ability of a substance to decrease or inhibit growth of insects.

As used herein, the term “room temperature” unless stated otherwise, essentially means temperature in a range from about 20°C to about 35°C, preferably from about 25°C to about 30°C.

As used herein, the term “purity” means purity as determined by the high-pressure liquid chromatography (HPLC).

As used herein, the term “anthranilamide compound” comprises all the insecticidal anthranilamide compounds comprising cyantraniliprole, chlorantraniliprole, cyclaniliprole, tetrachlorantraniliprole and the like. The term “anthranilamide compound” and “anthranilamide insecticide” have same meaning and are used interchangeably throughout the specification.

As used herein, the term “plant” or “crop” refers to all physical parts of a plant, including seeds, seedlings, saplings, roots, tubers, stems, stalks, foliage and fruits. The term plant includes transgenic and non-transgenic plants. This term also encompasses plant crops such as fruits. The term “plant” may further include the propagation material thereof, which may include all the generative parts of the plant such as seeds and vegetative plant material such as cuttings and tubers, which can be used for the multiplication of the plant. This includes seeds, tubers, spores, corms, bulbs, rhizomes, sprouts basal shoots, stolons, and buds and other parts of plants, including seedlings and young plants, which are to be transplanted after germination or after emergence from soil.

As used herein, the term “locus” of a plant is intended to embrace the place on which the plants are growing, where the plant propagation materials of the plants are sown or where the plant propagation materials of the plants will be placed into the soil.

As used herein, the term “plant propagation material” is understood to denote generative parts of a plant, such as seeds, vegetative material such as cuttings or tubers, roots, fruits, tubers, bulbs, rhizomes and parts of plants, germinated plants and young plants which are to be transplanted after germination or after emergence from the soil.

As used herein, the term “seed” means any resting stage of a plant that is physically detached from the vegetative stage of a plant. The term embraces seeds and plant propagules of all kinds including but not limited to true seeds, seed pieces, suckers, corms, bulbs, fruit, tubers, grains, cuttings, cut shoots and the like and means in a preferred embodiment true seed.

As used herein, the term “phytotoxicity” means a delay of seed germination, inhibition of plant growth or any adverse effect on plants caused by specific substances (phytotoxins) or growing conditions.

As described herein, the term “high yield” of compound means that the yield of a product produced by a process is increased by a measurable amount over the yield of the same product produced under the same conditions by another process, but without the improvement in the process as described herein.

As used herein, the term “crude anthranilamide” used herein means the anthranilamide compound obtained by methods known to any person skilled in art, having low HPLC purity.

As used herein, the term “substantially free from impurity” means the anthranilamide compound having purity of more than 99% and comprises less than 0.5% of impurity.

The inventors of the present disclosure through detailed investigation and study observed that presence of an impurity of formula (II) in technical anthranilamide compound led to deterioration in the quality of seeds treated with such anthranilamide compounds. It was observed that the presence of impurity of formula (II) in the anthranilamide formulation exhibited phytotoxicity by adversely affecting the field performance of the treated seeds such as delay of seed germination, inhibition of plant growth, etc. However, the removal of the impurity of formula (II) from final product was very difficult due to the structural similarities. This crucial problem was solved by the inventors of present disclosure by developing a process for purification of the crude anthranilamide compound to obtain anthranilamide compound of formula (I) substantially free from impurity of formula (II). The purified anthranilamide compound of formula (I) when used for seed treatment, did not show any phytotoxic effects and the plants grown from these seeds were healthier. Therefore, the present disclosure provide a large-scale purification process for anthranilamide compound of formula (I), wherein an impurity of formula (II) is considerably removed, and the formulated product using the purified anthranilamide compound ensures the required seed safety leading to proper germination and healthy seedlings/crops.

According to an embodiment, the present disclosure provides a process for purification of anthranilamide compounds. In another embodiment, the present disclosure provides a process for purification of anthranilamide compounds, their stereoisomers, salts, tautomers, n-oxides, and combinations thereof.

In another embodiment, the present disclosure provides a process for purification of anthranilamide compounds comprising ryanodine receptor modulators. In another embodiment, the ryanodine receptor modulators comprises diamide insecticides. In another embodiment, the diamide insecticides comprise chlorantraniliprole (CTPR), cyantraniliprole, cyhalodiamide, cyclaniliprole, flubendiamide, fluchlordiniliprole, tetrachlorantraniliprole, tetraniliprole, tiorantraniliprole, and combinations thereof.

According to an embodiment, the present disclosure provides a process for purification of an anthranilamide compound of formula (I):

Formula (I)
wherein, X is chlorine or a cyano group;
R1 is methyl, bromine or chlorine;
R2 is hydrogen or chlorine; and
R3 is selected from the group comprising methyl, ethyl, propyl, isopropyl, or 1-cyclopropylethyl.

In another embodiment, the present disclosure provides a process for purification of an anthranilamide compound of formula (I):

Formula (I)
wherein the purified anthranilamide compound is substantially free of an impurity of formula (II):

Formula (II)
wherein, X is chlorine or a cyano group;
R1 is methyl, bromine or chlorine;
R2 is hydrogen or chlorine; and
R3 is selected from the group comprising methyl, ethyl, propyl, isopropyl, or 1-cyclopropylethyl.

In another embodiment, the present disclosure provides a process for purification of an anthranilamide compound of formula (I):

Formula (I)
wherein the purified anthranilamide compound is substantially free of an impurity of formula (II):

Formula (II)
wherein, X is chlorine or a cyano group;
R1 is methyl, bromine or chlorine;
R2 is hydrogen or chlorine; and
R3 is selected from the group comprising methyl, ethyl, propyl, isopropyl, or 1-cyclopropylethyl;
the process comprising:
a) preparing a solution of a crude anthranilamide compound in a first organic solvent at a temperature ranging from about 40°C to about boiling point of the first organic solvent to obtain a purified anthranilamide compound of formula (I); and
b) isolating the purified anthranilamide compound of formula (I) from the solution of step a) by adding a second solvent;
wherein a weight ratio of the first organic solvent to the second solvent is in a range from about 1:0.5 to about 3:1.

According to an embodiment, the crude anthranilamide compound used as a starting material can be prepared by any available method known in the art. In another embodiment, the crude anthranilamide compound used as a starting material has purity of more than about 80%.

In an embodiment, the crude anthranilamide compound comprises more than 0.5% of impurity of formula (II). In another embodiment, the crude anthranilamide compound comprises from about 0.5% to about 5% of impurity of formula (II).

According to an embodiment, in step a) the solution is prepared from a slurry of the crude anthranilamide compound in the first organic solvent. In an embodiment, in step a) the solution is prepared by dissolving the crude anthranilamide compound in the first organic solvent.

In another embodiment, in step a) the solution is prepared by dissolving the crude anthranilamide compound in the first organic solvent at a temperature from about 40°C to about 200°C, preferably from about 40°C to about 180°C, more preferably from about 40°C to about 170°C.

In a preferred embodiment, in step a) the solution is prepared by dissolving the crude anthranilamide compound in the first organic solvent at a temperature from about 40°C to about boiling point of the first organic solvent. In a preferred embodiment, in step a) the solution is prepared by dissolving the crude anthranilamides compound in the first organic solvent at a temperature from about 60°C to about 90°C.

According to an embodiment, the first organic solvent is selected from amide solvents comprising dimethyl formamide (DMF), dimethyl acetamide (DMA),or combinations thereof.

In a preferred embodiment, the first organic solvent is dimethyl formamide (DMF). In a preferred embodiment, in step a) the solution is prepared by dissolving the crude anthranilamide compound in dimethyl formamide (DMF) at a temperature from about 40°C to about boiling point of dimethyl formamide (DMF).

In a preferred embodiment, the first organic solvent is dimethyl acetamide (DMA). In a preferred embodiment, in step a) the solution is prepared by dissolving the crude anthranilamide compound in dimethyl acetamide (DMA) at a temperature from about 40°C to about boiling point of dimethyl acetamide (DMA).

According to an embodiment, in step b) the purified anthranilamide compound of formula (I) is isolated by adding a second solvent.

In an embodiment, the second solvent is selected from water, C1 to C4 alcohol, or combinations thereof. In an embodiment, the second solvent used is C1- C4 alcohol, selected from but not limited to methanol, ethanol, n-propanol, isopropanol, butanol, tert-butanol, or combinations thereof.

In a preferred embodiment, the second solvent is methanol. In a preferred embodiment, in step b) the purified anthranilamide compound of formula (I) is isolated by adding methanol.

In an embodiment, the second solvent is added at a temperature from about 40°C to about 100°C, preferably from about 40°C to about 90°C, more preferably from about 40°C to about 80°C, more preferably from about 40°C to about 70°C.

In an embodiment, the second solvent is added in a time period of about 0.25 hour to about 5 hours, preferably of about 0.5 hour to about 4 hours, more preferably of about 0.5 hour to about 3 hours.

In an embodiment, after adding the second solvent the solution of step a) is cooled to room temperature and the (product) purified anthranilamide compound of formula (I) is separated out.

In an embodiment, a weight ratio of the first organic solvent to the second solvent is in a range from about 1.1:0.5 to about 2.5:1, preferably from about 1.2:0.5 to about 1.2:1.

According to an embodiment, total solvent used for the process for purification of anthranilamide compound of formula (I) comprises a total amount of the first organic solvent and the second solvent. In an embodiment, the total solvent used for the process for purification of anthranilamide compound of formula (I) comprises a total amount of amide solvent and alcohol.

In an embodiment, the total solvent used for the process for purification of anthranilamide compound of formula (I) comprises a total amount of dimethyl formamide and methanol. In an embodiment, the total solvent used for the process for purification of anthranilamide compound of formula (I) comprises a total amount of dimethyl acetamide and methanol.

According to an embodiment, a weight ratio of total solvent used for process for purification with respect to the crude anthranilamide compound is in a range from about 1:1 to about 8:1, preferably from about 2:1 to about 6:1, more preferably from about 3:1 to about 5:1.

According to an embodiment, step a) and step b) of the process for purification of the anthranilamide compound of formula (I) may be, optionally, repeated.

The impurity of formula (II) is difficult to remove from anthranilamide compound of formula (I) due to structural similarities, this is even more difficult when the production is carried out at larger scale, wherein huge volumes of reagents and solvents are required to be added, thereby maintaining multiple parameters accurately might not even be feasible. The process of present disclosure provides a solution to this problem wherein dissolving the crude anthranilamide compound at a certain temperature and using a combination of specific solvents in particular ratio ensures substantial removal of the impurity of formula (II) from the crude anthranilamide compound. The process provided in the present disclosure is simple and industrially viable as multiple parameters are not required to be monitored/maintained.

It was found that use of a specific ratio of the first organic solvent to the second solvent at conditions disclosed in the present disclosure, keeps the impurity of formula (II) in solubilised state, whereas precipitating the desired anthranilamide compound of formula (I). The impurity of formula (II) and the anthranilamide compound of formula (I) are separated based on their solubility differences in different solvents.

According to an embodiment, the present disclosure provides an anthranilamide compound of formula (I):

Formula (I)
wherein, X is chlorine or a cyano group;
R1 is methyl, bromine or chlorine;
R2 is hydrogen or chlorine; and
R3 is selected from the group comprising methyl, ethyl, propyl, isopropyl, or 1-cyclopropylethyl.

In an embodiment, the present disclosure provides an anthranilamide compound of formula (I):

Formula (I)
wherein the anthranilamide compound of formula (I) is substantially free of an impurity of formula (II):

Formula (II)
wherein, X is chlorine or a cyano group;
R1 is methyl, bromine or chlorine;
R2 is hydrogen or chlorine; and
R3 is selected from methyl, ethyl, propyl, isopropyl, or 1-cyclopropylethyl.

According to an embodiment, the anthranilamide compound of formula (I) represents a compound wherein X is chlorine, R1 is methyl, R2 is hydrogen and R3 is methyl.

In another embodiment, the anthranilamide compound of formula (I) represents a compound wherein X is a cyano group, R1 is methyl, R2 is hydrogen and R3 is methyl.

In another embodiment, the anthranilamide compound of formula (I) represents a compound wherein X is chlorine, R1 is bromine, R2 is hydrogen and R3 is 1-cyclopropylethyl.

In yet another embodiment, the anthranilamide compound of formula (I) represents a compound wherein X is chlorine, R1 is chlorine, R2 is chlorine and R3 is methyl.

According to an embodiment, the present disclosure provides an anthranilamide compound of formula (I) having purity of more than about 90%, preferably more than about 92%, preferably more than about 95%, preferably more than about 98%, most preferably more than about 99%.

In another embodiment, the present disclosure provides highly pure anthranilamide compound of formula (I) having content of an impurity of formula (II) less than 0.5%, preferably less than 0.3%, more preferably less than 0.2%.

In a preferred embodiment, the anthranilamide compound of formula (I) comprises chlorantraniliprole (CTPR) compound of formula (Ia):

Formula (Ia)
wherein the chlorantraniliprole (CTPR) compound of formula (Ia) is substantially free of an impurity of formula (IIa):

Formula (IIa)
wherein the impurity of formula (IIa) comprises 3-Bromo-1-(5-bromo-3-chloro-2-pyridinyl)-N-[4-chloro-2-methyl-6-[(methylamino)carbonyl]phenyl]-1H-pyrazole-5-carboxamide.

In an embodiment of the present disclosure, anthranilamide compound of formula (I) purified according to the process of the present disclosure can be further characterised by parameters like particle size distribution and the likes thereof.

In an embodiment, the present disclosure provides an insecticidal composition comprising an anthranilamide compound of formula (I):

Formula (I)
wherein the anthranilamide compound of formula (I) substantially free of an impurity of formula (II):

Formula (II)
wherein, X is chlorine or a cyano group;
R1 is methyl, bromine or chlorine;
R2 is hydrogen or chlorine; and
R3 is selected from methyl, ethyl, propyl, isopropyl, or 1-cyclopropylethyl;
and at least one agrochemically acceptable excipient.

In a preferred embodiment, the present disclosure provides an insecticidal composition comprising chlorantraniliprole (CTPR) compound of formula (Ia):

Formula (Ia)
wherein the chlorantraniliprole (CTPR) compound of formula (Ia) substantially free of an impurity of formula (IIa):

Formula (IIa)
wherein the impurity of formula (IIa) comprises 3-Bromo-1-(5-bromo-3-chloro-2-pyridinyl)-N-[4-chloro-2-methyl-6-[(methylamino)carbonyl]phenyl]-1H-pyrazole-5-carboxamide; and
at least one agrochemically acceptable excipient thereof.

In an embodiment, the agrochemically acceptable excipient may be selected from the group comprising emulsifier(s), filler(s), anti-foaming agent(s), thickening agent(s), anti-freezing agent(s), surfactant(s), preservative(s), coloring agent(s), dispersing agent(s), wetting agent(s), solvent(s), and combinations thereof. However, it should be appreciated that any other agrochemically acceptable excipients, as known to a person ordinarily skilled in the art, may be used to serve its intended purpose.

In another embodiment, emulsifier(s) which can be advantageously employed herein can be readily determined by those skilled in the art and include various non-ionic, anionic, cationic, and amphoteric emulsifiers, or a blend of two or more emulsifiers. Examples of non-ionic emulsifiers useful in preparing the emulsifiable concentrates include the polyalkylene glycol ethers and condensation products of alkyl and aryl phenols, aliphatic alcohols, aliphatic amines or fatty acids with ethylene oxide, propylene oxides such as the ethoxylated alkyl phenols and carboxylic esters solubilized with the polyol or polyoxyalkylene. Cationic emulsifiers include quaternary ammonium compounds and fatty amine salts. Anionic emulsifiers include the oil-soluble salts (e.g., calcium) of alkylaryl sulfonic acids, oil-soluble salts or sulfated polyglycol ethers and appropriate salts of phosphated polyglycol ether, and combinations thereof.

In another embodiment, the filler(s) may include any or a combination of diatomaceous earth, kaolin, bentonite, precipitated silica, amorphous silica, attapulgite, and perlite, but not limited thereto. Fillers may be selected from insoluble fillers and soluble fillers.

In another embodiment, antifoaming agent(s) may be selected from polydimethoxysiloxane, polydimethylsiloxane, alkyl poly acrylates, castor oil, fatty acids, fatty acids esters, fatty acids sulfate, fatty alcohol, fatty alcohol esters, fatty alcohol sulfate, foot olive oil, mono & di glyceride, paraffin oil, paraffin wax, poly propylene glycol, silicones oil, vegetable fats, vegetable fats sulfate, vegetable oil, vegetable oil sulfate, vegetable wax, vegetable wax sulfate, agents based on silicon or magnesium stearate, and combinations thereof.

In another embodiment, thickening or gelling agent(s) may be selected from but not limited to molasses, granulated sugar, alginates, karaya gum, jaguar gum, tragacanth gum, polysaccharide gum, mucilage, xanthan gum or combination thereof. In another embodiment, the binder may be selected from silicates such as magnesium aluminium silicate, polyvinyl acetates, polyvinyl acetate copolymers, polyvinyl alcohols, polyvinyl alcohol copolymers, celluloses, including ethylcelluloses and methylcelluloses, hydroxymethyl celluloses, hydroxypropylcelluloses, hydroxymethylpropyl-celluloses, polyvinylpyrolidones, dextrins, malto-dextrins, polysaccharides, fats, oils, proteins, gum arabics, shellacs, vinylidene chloride, vinylidene chloride copolymers, calcium lignosulfonates, acrylic copolymers, starches, polyvinylacrylates, zeins, gelatin, carboxymethylcellulose, chitosan, polyethylene oxide, acrylimide polymers and copolymers, polyhydroxyethyl acrylate, methylacrylimide monomers, alginate, ethylcellulose, polychloroprene and syrups or mixtures thereof; polymers and copolymers of vinyl acetate, methyl cellulose, vinylidene chloride, acrylic, cellulose, polyvinylpyrrolidone and polysaccharide; polymers and copolymers of vinylidene chloride and vinyl acetate-ethylene copolymers; combinations of polyvinyl alcohol and sucrose; plasticizers such as glycerol, propylene glycol, polyglycols, and combinations thereof.

In another embodiment, anti-freezing agent(s) added to the composition may be alcohols selected from the group comprising of but not limited to ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 1,4-pentanediol, 3-methyl-1,5-pentanediol, 2,3-dimethyl-2,3-butanediol, trimethylol propane, mannitol, sorbitol, glycerol, pentaerythritol, 1,4-cyclohexanedimethanol, xylenol, bisphenols such as bisphenol A or the like. In addition, ether alcohols such as diethylene glycol, triethylene glycol, tetraethylene glycol, polyoxyethylene or polyoxypropylene glycols of molecular weight up to about 4000, diethylene glycol monomethylether, diethylene glycol monoethyl ether, triethylene glycol monomethylether, butoxyethanol, butylene glycol monobutylether, dipentaerythritol, tripentaerythritol, tetrapentaerythritol, diglycerol, triglycerol, tetraglycerol, pentaglycerol, hexaglycerol, heptaglycerol, octaglycerol.

In another embodiment, suitable preservative(s) are for example benzothiazoles, 1,2-benzisothiazolin-3-one, sodium dichloro-s-triazinetrione, sodium benzoate, potassium sorbate, 1,2-phenyl-isothiazolin-3-one, inter chloroxylenol paraoxybenzoate butyl and benzoic acid & combination thereof

In another embodiment, coloring agent(s) may be selected from iron oxide, titanium oxide and Prussian Blue, and organic dyestuffs, such as alizarin dyestuffs, azo dyestuffs or metal phthalocyanine dyestuffs, and trace elements, such as salts of iron, manganese, boron, copper, cobalt, molybdenum, zinc, and combinations thereof.

In another embodiment, the dispersing agent(s) used is selected from, but not limited to, group comprising of anionic, cationic or zwitterionic and/or non-ionic surface-active compounds (surfactants) or combinations thereof, preferably anionic surfactant is used.

In another embodiment, examples of anionic surfactant(s) include: anionic derivatives of fatty alcohols having 10-24 carbon atoms in the form of ether carboxylates, sulfonates, sulfates, and phosphates, and their inorganic salts (e.g., alkali metal and alkaline earth metal salts) and organic salts (e.g., salts based on amine or alkanolamine); anionic derivatives of copolymers consisting of EO(ethylene oxide), PO (propylene oxide) and/or BO (butylene oxide) units, in the form of ether carboxylates, sulfonates, sulfates, and phosphates, and their inorganic salts (e.g., alkali metal and alkaline earth metal salts) and organic salts (e.g., salts based on amine or alkanolamine) or acrylic/styrene copolymers, methacrylic copolymers; linear (C8-C15) alcohol derivative and their salts; alkyl aryl sulfonates including but not limited to alkyl benzenesulfonates; alkyl naphthalene sulfonates and salts thereof and salts of lignonsulfonic acid; derivatives of alkylene oxide adducts of alcohols, in the form of ether carboxylates, sulfonates, sulfates and phosphates, and their inorganic salts (e.g., alkali metal and alkaline earth metal salts) and organic salts (e.g., salts based on amine or alkanolamine); anionic derivatives of fatty acid alkoxylates, in the form of ether carboxylates, sulfonates, sulfates and phosphates, and their inorganic salts (e.g., alkali metal and alkaline earth metal salts) and organic salts (e.g., salts based on amine or alkanolamine); alkyl ether phosphate, alkyl sulfosuccinate mono ester and diester salts.

In another embodiment, the wetting agent(s) may include any or a combination of sulfosuccinates, naphthalene sulfonates, sulfated esters, phosphate esters, sulfated alcohol and alkyl benzene sulfonates, and combinations thereof.

In another embodiment, examples of suitable solvent(s) are water, oils of vegetable, or derivatives. In principle, solvent mixtures may also be used.

In a preferred embodiment, the insecticidal composition comprises the anthranilamide compound of formula (I) substantially free of an impurity of formula (II) in an amount ranging from about 1% w/w to about 80% w/w and the agrochemically acceptable excipient in an amount ranging from about 1% w/w to about 30% w/w of total weight of the composition. In a preferred embodiment, the insecticidal composition comprises the anthranilamide compound of formula (I) substantially free of an impurity of formula (II) in an amount ranging from about 10% w/w to about 80% w/w and the agrochemically acceptable excipient in an amount ranging from about 1% w/w to about 30% w/w of total weight of the composition.

According to an embodiment, the insecticidal composition comprising anthranilamide compound of formula (I) purified according to the process of the present disclosure may be present in a form of emulstifiable concentrate (EC), emulsion (EW), micro-emulsion (ME), suspension concentrates (SC), oil-based suspension concentrates (OD), flowable suspension (FS), water-dispersible granule (WDG or WG), water-dispersible powder (WP), granule (GR), encapsulated granule (CG), fine granule (FG), macrogranule (GG), aqueous suspo-emulsion (SE), capsule suspension (CS), microgranule (MG), and combinations thereof.

In an embodiment, the insecticidal composition comprising an anthranilamide compound of formula (I) purified according to process of the present disclosure is a seed treatment composition. In an embodiment, the insecticidal composition comprising an anthranilamide compound of formula (I) purified according to process of the present disclosure is a flowable suspension (FS).

In an embodiment, the present disclosure provides an insecticidal composition comprising an anthranilamide compound of formula (I) and at least one agrochemically acceptable excipient, in a form of a tank-mix or a ready-mix formulation.

According to an embodiment, the insecticidal composition comprising an anthranilamide compound of formula (I) purified according to process of the present disclosure and at least one agrochemically acceptable excipient; further comprises an additional agrochemical.

In an embodiment, the additional agrochemical is selected from the group comprising acaricides, algicides, avicides/bird repellents, bactericides, fungicides, herbicide safeners, herbicides, insect attractants, insect chemosterilants, insect repellents, insecticides, mammal repellents, molluscicides, nematicides, nitrification inhibitors, plant activators, plant growth regulators, rodenticides, synergists, virucides, and combinations thereof.

In an embodiment, the additional agrochemical is selected from a fungicide or an insecticide.

In an embodiment, the additional agrochemical is a fungicide selected from a multisite contact fungicide or a systemic fungicide.

In an embodiment, the additional agrochemical is an insecticide. In an embodiment, the insecticide used may be selected from, but not limited to alkyl halide insecticides; aminopyrimidine insecticides; aminotriazene insecticides; antibiotic insecticides; aromatic hydrocarbon insecticides; arylpyrrole insecticides; benzimidazole insecticides; benzoylurea insecticides; beta-ketonitrile insecticides; botanical insecticides; alkaloid insecticides; carbamate insecticides; dimethylcarbamate insecticides; oxime carbamate insecticides; phenyl carbamate insecticides; diacylhydrazine insecticides; diamide insecticides; dinitrophenol insecticides; dithiolane insecticides; fumigant insecticides, inorganic insecticides; arsenical insecticides; fluoride insecticides; isoxazoline insecticides; juvenile hormone mimics; juvenile hormones;macrocyclic lactone insecticides, milbemycin insecticides, spinosyn insecticides; meta-diamide insecticides; methoxyacrylate insecticides; neonicotinoid insecticides; nitroguanidine insecticides, nitromethylene insecticides, pyridylidene insecticides, and sulfoximine insecticides; nereistoxin analogue insecticides; organochlorine insecticides; chlorinated cyclodiene insecticides; organophosphorus insecticide; organophosphate insecticides; organothiophosphate insecticides; aliphatic amide organothiophosphate insecticides; aliphatic organothiophosphate insecticides; aryl organothiophosphate insecticides; arylalkyl organothiophosphate insecticides; phenyl organothiophosphate insecticides; phosphonate insecticides; phosphonothioate insecticides; phosphoramidate insecticides; phosphorodiamide insecticides; oxadiazine insecticides; oxadiazolone insecticides; perfluroalkyl sulfonamide insecticides; phenol insecticides; precocenes; pyrazole insecticides; phenylpyrazole insecticides; pyrazolecarboxamide insecticides; pyrethrin insecticides; pyrethroid insecticides; pyrethroid ether insecticides; pyrethroid isovalerate ester insecticides; pyrethroid oxime insecticides; pyridine azomethine insecticides; pyrimidinamine insecticides; pyropene insecticides; salicylanilide insecticides; semicarbazone insecticides; steroid insecticides; tetramic acid insecticides; tetronic acid insecticides; thiocarbonate insecticides; thiourea insecticides; and unclassified insecticides; or combinations thereof.

In an embodiment, the insecticide used may be selected from, but not limited to alkyl halide insecticides such as carbon tetrachloride, chloroform, 1,2-dichloropropane, ethylene dibromide, ethylene dichloride, methyl bromide, methyl iodide, methylchloroform, methylene chloride, tetrachloroethane; aminopyrimidine insecticides such as dicyclanil; aminotriazene insecticides such as cyromazine; antibiotic insecticides such as allosamidin; aromatic hydrocarbon insecticides such as naphthalene, triarathene; arylpyrrole insecticides such as chlorfenapyr; benzimidazole insecticides such as fenazaflor; benzoylurea insecticides such as bistrifluron, chlorbenzuron, chlorfluazuron, dichlorbenzuron, diflubenzuron, flucycloxuron, flufenoxuron, hexaflumuron, lufenuron, novaluron, noviflumuron, penfluron, teflubenzuron, triflumuron; beta-ketonitrile insecticides such as thiapronil; botanical insecticides such as allicin, azadirachtin, carvacrol, d-limonene, quassia, rhodojaponin-III, rotenone, thuringiensin, triptolide; alkaloid insecticides such as anabasine, matrine, nicotine, nornicotine, oxymatrine, ryania, sabadilla, sanguinarine; carbamate insecticides such as bendiocarb, benfuracarb, carbofuran, carbosulfan, carbaryl, decarbofuran, formetanate, formparanate, furathiocarb; dimethylcarbamate insecticides such as dimetan, dimetilan, hyquincarb, isolan, pirimicarb, pyramat, pyrolan; oxime carbamate insecticides, alanycarb, aldicarb, aldoxycarb, butocarboxim, butoxycarboxim, methomyl, nitrilacarb, oxamyl, tazimcarb, thiocarboxime, thiodicarb, thiofanox; phenyl carbamate insecticides such as allyxycarb, aminocarb, bufencarb, butacarb, carbanolate, cloethocarb, 2-chlorophenyl methylcarbamate (CPMC), dicresyl, dimethacarb, dioxacarb, 4-(ethylsulfanyl)phenyl methylcarbamate (EMPC), ethiofencarb, fenethacarb, fenobucarb, isoprocarb, methiocarb, metolcarb, mexacarbate, promacyl, promecarb, propoxur, trimethacarb, 3,5-dimethylphenyl methylcarbamate (XMC), xylylcarb; diacylhydrazine insecticides such as chromafenozide; furan tebufenozide; halofenozide, methoxyfenozide, tebufenozide, yishijing; diamide insecticides such as chlorantraniliprole, cyantraniliprole, cyhalodiamide, cyclaniliprole, flubendiamide, fluchlordiniliprole, tetrachlorantraniliprole, tetraniliprole, tiorantraniliprole; dinitrophenol insecticides such as dinex, dinoprop, dinosam, 2-methyl-4,6-dinitrophenol (DNOC); dithiolane insecticides such as isoprothiolane; formamidine insecticides such as amitraz, chlordimeform, medimeform, and semiamitraz; fumigant insecticides such as acrylonitrile, allyl isothiocyanate, calcium cyanide, carbon disulfide, carbonyl sulfide, chloropicrin, cyanogen, dimethyl disulfide, ethyl formate, ethylene oxide, hydrogen cyanide, methyl isothiocyanate, phosphine, sodium cyanide, sulfuryl fluoride, inorganic insecticides such as borax, boric acid, calcium polysulfide, copper naphthenate, copper oleate, diatomaceous earth, mercurous chloride, potassium thiocyanate, silica gel, sodium thiocyanate; arsenical insecticides such as calcium arsenate, copper arsenate, lead arsenate, Paris green, potassium arsenite, sodium arsenite; fluoride insecticides such as barium hexafluorosilicate, cryolite, sodium fluoride, sodium silicofluoride, sulfuryl fluoride; isoxazoline insecticides such as afoxolaner, esafoxolaner, fluralaner, fluxametamide, isocycloseram, lotilaner, mivorilaner, sarolaner, tigolaner, Umifoxolaner; juvenile hormone mimics such as dayoutong, diofenolan, epofenonane, fenoxycarb, hydroprene, kinoprene, Methoprene, pyriproxyfen, triprene; juvenile hormones such as juvenile hormone I, juvenile hormone II, juvenile hormone III; macrocyclic lactone insecticides such as avermectin insecticides (e.g., abamectin, doramectin, emamectin, eprinomectin, ivermectin, selamectin), milbemycin insecticides (e.g., lepimectin, moxidectin), and spinosyn insecticides (e.g., spinetoram, Spinosad); meta-diamide insecticides such as broflanilide, cyproflanilide, modoflaner; methoxyacrylate insecticides such as flupyroxystrobin; neonicotinoid insecticides such as butenolide insecticides (e.g., flupyradifurone), cyano imidamide insecticides (e.g., acetamiprid, thiacloprid), mesoionic insecticides (e.g., dicloromezotiaz, fenmezoditiaz, triflumezopyrim); nitroguanidine insecticides (e.g., clothianidin Dinotefuran, imidacloprid, imidaclothiz, thiamethoxam), nitromethylene insecticides (e.g., cycloxaprid, nitenpyram, nithiazine, paichongding), pyridylidene insecticides (e.g., flupyrimin), and sulfoximine insecticides (e.g., sulfoxaflor); nereistoxin analogue insecticides such as bensultap, cartap, polythialan, thiocyclam, thiosultap; organochlorine insecticides such as 1,1'-(2,2,2-trichloroethane-1,1-diyl)bis(4-bromobenzene) (bromo-DDT), camphechlor, 1,1'-(2,2,2-trichloroethane-1,1-diyl)bis(4-chlorobenzene) (DDT), 1,1'-(2,2,2-trichloroethane-1,1-diyl)bis(4-chlorobenzene) (pp'-DDT), 1,1'-(2,2,2-trichloroethane-1,1-diyl)bis(4-fluorobenzene) (DFDT), p-dichlorobenzene, 1,1'-(2,2-dichloroethane-1,1-diyl)bis(4-ethylbenzene) (ethyl-DDD), 1,2,3,4,5,6-hexachlorocyclohexane (HCH), (1R,2S,3r,4R,5S,6r)-1,2,3,4,5,6-hexachlorocyclohexane (gamma-HCH), lindane, methoxychlor, 1,1'-(2,2-dichloroethane-1,1-diyl)bis(4-chlorobenzene) (TDE); chlorinated cyclodiene insecticides such as aldrin, bromociclen, chlorbicyclen, chlordane, chlordecone, dieldrin, dilor, endosulfan, alpha-endosulfan, endrin, (1aR,2R,2aS,3S,6R,6aR,7S,7aS)-3,4,5,6,9,9-hexachloro-1a,2,2a,3,6,6a,7,7a-octahydro-2,7:3,6-dimethanonaphth[2,3-b]oxirene (HEOD), heptachlor, (1R,4S,4aS,5S,8R,8aR)-1,2,3,4,10,10-hexachloro-1,4,4a,5,8,8a-hexahydro-1,4:5,8-dimethanonaphthalene (HHDN), isobenzan, isodrin, kelevan, mirex; organophosphorus insecticide; organophosphate insecticides such as bromfenvinfos, calvinphos, chlorfenvinphos, crotoxyphos, dichlorvos, dicrotophos, dimethylvinphos, fospirate, heptenophos, methocrotophos, mevinphos, monocrotophos, naled, naftalofos, phosphamidon, propaphos, tetraethyl diphosphate (TEPP), tetrachlorvinphos; organothiophosphate insecticides such as, chlorphoxim, dioxabenzofos, phoxim, phoxim-methyl, sulfotep; aliphatic amide organothiophosphate insecticides such as amidithion, cyanthoate, dimethoate, ethoate-methyl, formothion, mecarbam, morphothion, omethoate, prothoate, sophamide; aliphatic organothiophosphate insecticides such as acethion, acetophos, amiton, cadusafos, carbophenothion, chlorethoxyfos, chlormephos, demephion, demephion-O, demephion-S, demeton, demeton-O, demeton-S, demeton-methyl, demeton-O-methyl, demeton-S-methyl, demeton-S-methylsulphon, dioxathion, disulfoton, ethion, ethoprophos, fosmethilan, S-[(ethanesulfinyl)methyl] O,O-di(propan-2-yl) phosphorodithioate (IPSP), isothioate, malathion, methacrifos, methylacetophos, oxydemeton-methyl, oxydeprofos, oxydisulfoton, phenkapton, phorate, terbufos, thiometon; aryl organothiophosphate insecticides such as butathiofos, chlorprazophos, chlorpyrifos, chlorpyrifos-methyl, coumaphos, coumithoate, diazinon, etrimfos, flupyrazofos, isazofos, isoxathion, lirimfos, pirimioxyphos, pirimiphos-ethyl, pirimiphos-methyl, primidophos, pyraclofos, pyrazophos, pyrazothion, pyridaphenthion, pyrimitate, quinalphos, quinalphos-methyl, quinothion, tebupirimfos, triazophos; arylalkyl organothiophosphate insecticides such as athidathion, azamethiphos, azinphos-ethyl, azinphos-methyl, colophonate, dialifos, dithicrofos, endothion, lythidathion, menazon, methidathion, phenthoate, phosalone, phosmet, prothidathion, thicrofos, zolaprofos; phenyl organothiophosphate insecticides such as azothoate, bromophos, bromophos-ethyl, chlorthiophos, cyanophos, cythioate, dicapthon, dichlofenthion, etaphos, famphur, fenchlorphos, fenitrothion, fensulfothion, fenthion, fenthion-ethyl, heterophos, jodfenphos, mesulfenfos, parathion, parathion-methyl, phosnichlor, profenofos, prothiofos, sulprofos, temephos, trichlormetaphos-3, trifenofos, xiaochongliulin; phosphonate insecticides such as butonate, trichlorfon; phosphonothioate insecticides such as cyanofenphos, (RS)-[O-ethyl O-(4-nitrophenyl) phenylphosphonothioate] (EPN), fonofos, leptophos, mecarphon, trichloronat; phosphoramidate insecticides such as acephate, chloramine phosphorus, crufomate, fenamiphos, fosthietan, isocarbophos, isofenphos, isofenphos-methyl, mephosfolan, methamidophos, phosfolan, phosfolan-methyl, phosglycin, pirimetaphos, propetamphos; phosphorodiamide insecticides such as dimefox, mipafox, schradan; phosphorotriamide insecticides such as mazidox, triamiphos; oxadiazine insecticides such as indoxacarb; oxadiazolone insecticides such as metoxadiazone; perfluroalkyl sulfonamide insecticides such as flursulamid, sulfluramid; phenol insecticides such as pentachlorophenol; precocenes such as precocene I, precocene II, precocene III; pyrazole insecticides; phenylpyrazole insecticides such as acetoprole, ethiprole, fipronil, flufiprole, pyrafluprole, pyriprole, vaniliprole; pyrazolecarboxamide insecticides such as dimpropyridaz, tolfenpyrad; pyrethrin insecticides such as pyrethrins, cinerins, cinerin I, cinerin II, jasmolin, jasmolin II, pyrethrin I, pyrethrin II; pyrethroid insecticides such as acrinathrin, allethrin, bioallethrin, esdépalléthrine, barthrin, bifenthrin, kappa-bifenthrin, bioethanomethrin, bromethrin, butethrin, chlorempenthrin, cyclethrin, cycloprothrin, cyfluthrin, beta-cyfluthrin, cyhalothrin, gamma-cyhalothrin, lambda-cyhalothrin, cypermethrin, alpha-cypermethrin, beta-cypermethrin, theta-cypermethrin, zeta-cypermethrin, supermethrin, cyphenothrin, deltamethrin, dimefluthrin, dimethrin, empenthrin, d-fanshiluquebingjuzh, chloroprallethrin, fenfluthrin, fenpirithrin, fenpropathrin, furamethrin, furethrin, heptafluthrin, d-teflumethrin, imiprothrin, japothrins, kadethrin, methothrin, metofluthrin, epsilon-metofluthrin, momfluorothrin, epsilon-momfluorothrin, pentmethrin, permethrin, biopermethrin, transpermethrin, phenothrin, prallethrin, profluthrin, proparthrin, pyresmethrin, renofluthrin, meperfluthrin, resmethrin, bioresmethrin, cismethrin, tefluthrin, kappa-tefluthrin, terallethrin, tetramethrin, tetramethylfluthrin, tralocythrin, tralomethrin, transfluthrin; pyrethroid ether insecticides such as etofenprox, flufenprox, halfenprox, protrifenbute, silafluofen; pyrethroid isovalerate ester insecticides such as brofenvalerate, brofluthrinate, fenvalerate, esfenvalerate, flucythrinate, fluvalinate, tau-fluvalinate, valerate; pyrethroid oxime insecticides such as sulfoxime, thiofluoximate; pyridine azomethine insecticides such as pymetrozine, pyrifluquinazon; pyrimidinamine insecticides such as flufenerim, pyrimidifen; pyropene insecticides such as afidopyropen; salicylanilide insecticides such as closantel; semicarbazone insecticides such as metaflumizone; steroid insecticides such as a-ecdysone, ecdysterone; tetramic acid insecticides such as spidoxamat, spiropidion, spirotetramat; tetronic acid insecticides such as spirodiclofen, spiromesifen; thiocarbonate insecticides such as O,O-diethyl 2-(dithioperoxy)-1,3-dithiodicarbonate (EXD), sodium tetrathiocarbonate; thiourea insecticides such as diafenthiuron; urea insecticides such as flucofuron, sulcofuron; and unclassified insecticides such as benzpyrimoxan, buprofezin, crotamiton, fenoxacrim, fentrifanil, flometoquin, flonicamid, fluhexafon, hydramethylnon, indazapyroxamet, jiahuangchongzong, malonoben, maltodextrin, nicofluprole, nifluridide, oxazosulfyl, plifenate, pyridaben, pyridalyl, rafoxanide, tartar emetic, triazamate, trichlophenidine, and tyclopyrazoflor, and combinations thereof.

In an embodiment, the additional insecticide used is be selected from, but not limited to macrocyclic lactone insecticides, neonicotinoid insecticides; nitroguanidine insecticides, pyrethroid insecticides or combinations thereof. In an embodiment, the additional insecticide used is nitroguanidine insecticide.

According to an embodiment, the insecticidal composition comprises an additional insecticide in an amount from about 1% w/w to about 80% w/w, preferably from about 1% w/w to about 50% w/w of total weight of the composition.

In a preferred embodiment, the additional insecticide is clothianidin in an amount from about 1% w/w to about 50% w/w of total weight of the composition.

In a preferred embodiment, the present disclosure provides an insecticidal composition comprising chlorantraniliprole (CTPR) compound of formula (Ia);

Formula (Ia)
wherein the chlorantraniliprole (CTPR) compound of formula (Ia) is substantially free of an impurity of formula (IIa);

Formula (IIa)
wherein the impurity of formula (IIa) comprises 3-Bromo-1-(5-bromo-3-chloro-2-pyridinyl)-N-[4-chloro-2-methyl-6-[(methylamino)carbonyl]phenyl]-1H-pyrazole-5-carboxamide; and
an additional insecticide;
at least agrochemically acceptable excipient thereof.

According to an embodiment, the present disclosure provides use of the anthranilamide compound of formula (I) as an insecticide for controlling the growth of insects.

In another embodiment, the present disclosure provides use of the high purity anthranilamide compound of formula (I) for improving plant growth. In another embodiment, the present disclosure provides use of the high purity anthranilamide compound of formula (I) for improving seed vigour.

In accordance with the present disclosure, improved plant growth refers to an increase in root length, shoot length, seedling weight, biomass production, seed germination index as well as reduction in phytotoxicity and other such properties that indicate healthy plant growth relative to plants which have not been treated by agrochemical combinations comprising anthranilamide compound of formula (I) and at least one agrochemically acceptable excipient thereof.

In yet another aspect of the present disclosure, there is provided a use of the composition comprising anthranilamide compound of formula (I) substantially free of an impurity of formula (II) as an insecticide.

In yet another aspect of the present disclosure, there is provided a use of the composition comprising anthranilamide compound of formula (I) substantially free of an impurity of formula (II) for seed/plant propagation material treatment.

In an embodiment, the composition comprising anthranilamide compound of formula (I) substantially free of an impurity of formula (II) is used for improving the overall health of the plant.

In an embodiment, the present disclosure provides a method for treating a seed or a plant propagation material thereof, the method comprising applying to the seed or the plant propagation material thereof, an effective amount of an insecticidal composition comprising an anthranilamide compound of formula (I), substantially free of an impurity of formula (II).

In an embodiment, the present disclosure provides a method for improving the growth or rate of growth of a plant, the method comprising applying to the plant or seed or plant propagation materials or locus thereof, an effective amount of an insecticidal composition comprising an anthranilamide compound of formula (I), substantially free of an impurity of formula (II).

In an embodiment, the present disclosure provides a method for improving the vigour of a plant or a seed or a plant propagation material, the method comprising applying to the plant or seed or plant propagation materials thereof, an effective amount of an insecticidal composition comprising an anthranilamide compound of formula (I), substantially free from an impurity of formula (II).

In an embodiment, the method for improving the vigour of a plant or a seed or a plant propagation material controls the phytotoxic effect on the plant or the seed or the plant propagation materials treated an effective amount of an insecticidal composition comprising an anthranilamide compound of formula (I) substantially free from an impurity of formula (II).

In an embodiment, the method of the present disclosure further enhances greening in crop plants, the method comprising applying an effective amount of an insecticidal composition comprising anthranilamide compound of formula (I) substantially free of an impurity of formula (II) to the plant or to the plant propagation material thereof, or to the locus of plant or intended plant growth.

In another embodiment, the method of the present disclosure further improves the germination of the seed by applying an insecticidal composition comprising an anthranilamide compound of formula (I) substantially free of an impurity of formula (II), to said plant or plant propagation material or the locus thereof.

Thus, in an embodiment, the present invention provides a seed treated with anthranilamide compound of formula (I) substantially free of an impurity of formula (II).

In another embodiment, the present invention provides a seed treated with anthranilamide compound of formula (I) substantially free of an impurity of formula (II), such that at least a portion of the applied anthranilamide compound of formula (I) substantially free of an impurity of formula (II) is adhered to the plant propagation material.

According to an embodiment, the present disclosure provides a method for seed/plant propagation material treatment, wherein the anthranilamide compound of formula (I) is applied in a range from about 1 g a.i./ha to about 100 g a.i./ha, preferably from about 1 g a.i./ha to about 70 g a.i./ha, preferably from about 1 g a.i./ha to about 50 g a.i./ha, more preferably from about 1 g a.i./ha to about 30 g a.i./ha.

According to an embodiment, an insecticidal composition made by using the anthranilamide compound of formula (I) purified by a process of the present disclosure may be applied in a range from about 10 g/ha to about 300 g/ha, preferably from about 50 g/ha to about 200 g/ha, more preferably from about 100 g/ha to about 180 g/ha.

In an embodiment, the present invention provides a method for treatment of seeds, wherein at least 98% of the sown seeds are germinated within 10 days of sowing.

According to an embodiment of the present disclosure, the anthranilamide compound of formula (I) purified by a process of the present disclosure is stable, over time and at various temperatures during the purification process of the compound.

It will be understood that the specification and examples are illustrative but not limitative of the present disclosure and that other embodiments within the spirit and scope of the disclosure will suggest themselves to those skilled in the art. Other embodiments can be practiced that are also within the scope of the present disclosure. The following examples illustrate the disclosure, but by no means intend to limit the scope of the claims.

Advantages of the present invention:
1. The present invention provides an anthranilamide compound (I) substantially free of impurity of formula (II).
2. The present invention provides a large-scale purification process for anthranilamide compound (I) substantially free of impurity of formula (II).
3. Said process is technically simple and industrially viable process.
4. Said process provides anthranilamide compound (I) substantially free of impurity of formula (II) which on using for plants/seeds/plant propagation materials treatment, did not show any phytotoxic effects and the plants grown were healthier.

EXAMPLES:
Analytical method:
Samples were analysed by high performance liquid chromatography (HPLC) with an ultraviolet (UV) detector using Cosmosil 5 C18-MS-II (250 mm x 4.6 mm, 5.0 µm).

Example 1: Purification of Chlorantraniliprole (CTPR) compound of formula (Ia)
A mixture of 4.12 kg chlorantraniliprole (having HPLC purity of 96.18%) and 9.06 kg dimethyl formamide was heated to a temperature range from about 70°C to about 75°C for 30 minutes to get a solution. To this solution was then added 7.4 kg methanol at a temperature range from about 50°C to about 60°C within 1 hour. The mixture was then cooled down to a temperature range from about 25°C to about 30°C. The slurry thus obtained was filtered and dried to obtain chlorantraniliprole compound of formula (Ia) having HPLC purity of 99.42%. The product specification of the starting material and final product has been disclosed in Table 1.

Table 1: Product specification of starting material and final product
Sr. No. Compound Chlorantraniliprole (CTPR) used as starting material Purified Chlorantraniliprole (CTPR) obtained in Example 1
1 Chlorantraniliprole (CTPR) compound of formula (Ia) 96.18% 99.42%
2 Impurity of formula (IIa) 0.853% 0.19%
3 Other unknown impurities 2.96% 0.39%

Example 2: Determination of bio-efficacy
Two compositions of chlorantraniliprole (CTPR) compound of formula (Ia) flowable concentrate (FS) formulations were compared to evaluate the bio-efficacy of the chlorantraniliprole compound. The compositions were prepared by any standard method known to a person ordinarily skilled in the art. The compositions, Formulation A, Formulation B and C have been disclosed in detail.

In Formulation A, the chlorantraniliprole compound of formula (Ia) was prepared using the purified chlorantraniliprole compound having HPLC purity of 99.42% according to the process of Example 1. In Formulation B, the chlorantraniliprole compound used is the starting material of Example 1 having HPLC purity of 96.18%. These formulations have been disclosed in Table 2. In Formulation C, the chlorantraniliprole compound of formula (Ia) was prepared using the purified chlorantraniliprole compound having HPLC purity of 99.42% according to the process of Example 1.
Table 2: Formulations A, B and C
Sr. No. Ingredients Quantity (% w/w)
Formulation A Formulation B Formulation C
1 Chlorantraniliprole 50.00 50.00 24.18
2 Clothianidin - - 24.18
3 Dispersing agents 5.50 5.50 5.50
4 Dye 4.00 4.00 4.00
5 Xanthan gum 0.05 0.05 0.05
6 Biocide 0.10 0.10 0.25
7 Water Q.S. Q.S. Q.S.
Total 100 100 100

Several experiments were performed to exemplify Formulation A & C prepared using the chlorantraniliprole compound of formula (Ia) purified according to process of the present disclosure and it was observed that the Formulation A & C did not show any phytotoxicity in terms of seed germination, plant growth or any adverse effect on plants or on the growing conditions.

Field Trials:
Field trials were carried out for determination of efficacy and phytotoxicity of formulations A and B. The formulations were applied such that the concentration of the active ingredient was 65.5 g a.i/100 kg of seeds and 125 g a.i/100 kg of seeds. The treatment details have been disclosed in Table 3.
Table 3: Experimental details for field trail
Sr. No. Particular Details
1 Crop Soybean
2 Condition Greenhouse (Sand)
3 Application Seed treatment
4 Seed quantity 50 seeds/pot
5 Dose 62.5 g a.i./100 kg of seeds
125 g a.i./100 kg of seeds

Methodology:
The emergence speed index (IVE), vigour, height of plant and phytotoxicity was recorded in a greenhouse, on soyabean seeds sown in pots filled with untreated agricultural sand. To establish the effect of purity of active ingredient, experiments were conducted using formulations A and B. For both formulations, study was performed on two different doses 62.5 g a.i./100 kg of seeds and 125 g a.i./100 kg of seeds. To simulate field conditions, no temperature or humidity control was applied in the greenhouse during the study period. About 50 seeds were placed in a pot and covered sand. The sand was then packed gently, and pots were placed in a watering bath, to supply water from below the pots whenever needed. This was intended to avoid disturbing seed placement by watering from above.

Emergence speed index (IVE):
Daily emergence was counted and continued until constant readings were obtained. The speed emergence index (IVE) was calculated using conventional method. Observations were made on 8th day after sowing.
Speed emergence index of 33.3% was recorded for formulation A for both doses of62.5 g a.i./100 kg of seeds and 125 g a.i./100 kg of seeds.
On the contrary, speed emergence index of 16.8% and 16.3% was recorded for formulation B for doses of 62.5 g a.i./100 kg of seeds and 125 g a.i./100 kg of seeds, respectively.
This clearly indicated the positive impact of purity of the active ingredient on the emergence of treated seeds. The graphical representation of the same has been provided in Figure 1.

Vigour:
The vigour was measured using conventional method on the scale of (0–5) wherein rating 5 corresponds to most healthy plants/seedlings showing better physiological traits; whereas rating 0 corresponds to poor health of plants/seedlings. Observations were made on 8th day, 11th day, 13th day and 15th day after sowing seeds treated with formulation B for dose of 62.5 g a.i./100 kg of seeds and 125 g a.i./100 kg of seeds.
The vigour rating observed was (maximum) 1.6 on the scale of 0-5. Whereas seeds treated with formulation A for both doses of 62.5 g a.i./100 kg of seeds and 125 g a.i./100 kg of seeds showed average rating of 3, which is substantially more than that of seeds treated with formulation B. The graphical representation of the same is provided in Figure 2.

Height:
The height of seedlings were measured in centimetres on day 11 and day 15 post sowing, and it was observed that seeds treated with formulation B for dose of 62.5 g a.i./100 kg of seeds and 125 g a.i./100 kg of seeds grew only to the height of 1.5 cm to 3.9 cm; whereas seeds treated with formulation A for both doses of 62.5 g a.i./100 kg of seeds and 125 g a.i./100 kg of seeds were taller with a height of 7.8 cm to 11.5 cm. The graphical representation of the same is provided in Figure 3.

Phytotoxicity:
By assessing percentage phytotoxicity that combines all symptoms on scale of (0-100) where rating 0 indicates no phytotoxicity and rating 100 indicates most phytotoxic. The traits of the plants germinated from seeds treated with formulation A and B, for both doses of 62.5 g a.i./100 kg of seeds and 125 g a.i./100 kg of seeds were observed on day 8, day 11, day 13 and day 15. It was observed that the plants from seeds treated with formulation A showed no phytotoxicity whereas plants from seeds treated with formulation B showed phytotoxicity of 49% to 75%, which is very high. The graphical representation of the same is provided in Figure 4.

Furthermore Figure 5 discloses the visual observation demonstrating the overall health of plants grown from the seeds treated with formulations A and B each. Figure 5a discloses the health of plants eight days post sowing and Figure 5a discloses the health of plants fifteen days post sowing.

It was observed that the (FS) formulation A exhibited no phytotoxicity and better emergence speed index, growth and vigour in plants grown from seeds treated with said formulation as compared to plants grown from seeds treated with (FS) formulation B.
,CLAIMS:
1. A process for purification of an anthranilamide compound of formula (I):

Formula (I)
wherein the purified anthranilamide compound is substantially free of an impurity of formula (II):

Formula (II)
wherein, X is chlorine or a cyano group;
R1 is methyl, bromine or chlorine;
R2 is hydrogen or chlorine; and
R3 is selected from the group comprising methyl, ethyl, propyl, isopropyl or 1-cyclopropylethyl;
the process comprising:
a) preparing a solution of a crude anthranilamide compound in a first organic solvent at a temperature from about 40°C to about boiling point of the first organic solvent to obtain a purified anthranilamide compound of formula (I); and
b) isolating the purified anthranilamide compound of formula (I) from the solution of step a) by adding a second solvent;
wherein a weight ratio of the first organic solvent to the second solvent is in a range from about 1:0.5 to about 3:1.

2. The process as claimed in claim 1, wherein the first organic solvent is selected from an amide solvent comprising dimethyl formamide (DMF), dimethyl acetamide (DMA), or combinations thereof.

3. The process as claimed in claim 1, wherein the second solvent is selected from water, C1 to C4 alcohol, or combinations thereof.

4. The process as claimed in claim 3, wherein the second solvent is methanol.

5. An anthranilamide compound of formula (I):

Formula (I)
wherein the anthranilamide compound of formula (I) is substantially free of an impurity of formula (II):

Formula (II)
wherein, X is chlorine or a cyano group;
R1 is methyl, bromine or chlorine;
R2 is hydrogen or chlorine; and
R3 is selected from methyl, ethyl, propyl, isopropyl, or 1-cyclopropylethyl.

6. An insecticidal composition comprising an anthranilamide compound of formula (I):

Formula (I)
wherein the anthranilamide compound of formula (I) is substantially free from
an impurity of formula (II):

Formula (II)
wherein, X is chlorine or a cyano group;
R1 is methyl, bromine or chlorine;
R2 is hydrogen or chlorine; and
R3 is selected from methyl, ethyl, propyl, isopropyl, or 1-cyclopropylethyl; and
at least one agrochemically acceptable excipient.

7. The composition claimed in claim 6, wherein the composition is a seed treatment composition.

8. The composition as claimed in claim 7, wherein the composition further comprises an additional agrochemical.

9. The composition as claimed in claim 8, wherein the additional agrochemical is an insecticide.

10. A method for treating a seed or a plant propagation material thereof, the method comprising applying to the seed or the plant propagation material, an effective amount of an insecticidal composition comprising an anthranilamide compound of formula (I), substantially free from an impurity of formula (II).

11. A method for improving the growth or rate of growth of a plant, the method comprising applying to the plant or a seed or a plant propagation material or a locus thereof, an effective amount of an insecticidal composition comprising an anthranilamide compound of formula (I), substantially free from an impurity of formula (II).

12. A method for improving the vigour of a plant or a seed or a plant propagation material thereof, the method comprising applying to the plant or the seed or the plant propagation material, an effective amount of an insecticidal composition comprising an anthranilamide compound of formula (I), substantially free from an impurity of formula (II).

13. The method as claimed in claim 12, wherein the method controls phytotoxic effect on the plant or the seed or the plant propagation material thereof, treated with the insecticidal composition comprising an anthranilamide compound of formula (I), substantially free from an impurity of formula (II).