PROCESS FOR THE PREPARATION OF ANTHRANILAMIDES.

Abstract

The present invention provides a process for the preparation and purification of anthranilamides.

Description

PROCESS FOR THE PREPARATION OF ANTHRANILAMIDES Technical field of the invention The present invention relates to the preparation of anthranilamides. The present invention further provides anthranilamide that is free from impurities. In particular, the present invention provides a process for purifying anthranilamides that are free from impurities. Background of the invention Effective control of insect pests, such as arthropods, is essential for crop safety. Arthropods are a major class of pests that cause significant damage to crops and homes worldwide each year. Anthranylamides are a new class of compounds with extremely potent insecticidal activity. These nitrogen-containing aromatic compounds act selectively on specific ryanodine receptors in insects. Ryanodine receptors form calcium ion channels that are responsible for muscle function. Examples of anthranilamide insecticides include cyantraniliprole, chlorantraniliprole, cyclaniliprol, tetrachlorantraniliprole, and tetraniliprol. Chlorantraniliprole is a highly potent and selective activator of the insect ryanodine receptor with exceptional activity against a wide range of lepidopteran pests. It controls a broad spectrum of chewing pests (primarily lepidopteran, but also some species of coleopteran, dipteran, and isoptera) in a wide variety of crops, including fruits, vegetables, vines, cotton, sugarcane, rice, and pasture. U.S. Patent No. US 7232836 describes the preparation of chlorantraniliprole represented as a compound of Formula IV (Scheme I). cccQnn / Lznz / e / viAi Chlorantraniliprole (Formula IV) The intermediate 3-bromo-1-(3-chloropyridin-2-11)-1H-pyrazol-5-carboxylic acid is represented as compound of Formula I and the intermediate 2-amino-5-chloro-3-methylbenzoic acid is represented as compound of Formula II. The 2-[3-bromo-1-(3-chloropyridin-2-11)-1H-pyrazol-5-11]-6-chloro-8-methyl-4H-3,1-benzoxacin-4-one is designated as compound of Formula III. U.S. Patent No. 7247647 describes the preparation of cyantraniliprole (Formula represented as compound of Formula VII (Scheme II). cccQnn / Lznz / e / YiAi The intermediate 3-bromo-1-(3-chloropyridin-2-11)-1H-pyrazol-5-carboxylic acid is represented as compound of Formula I and the intermediate 2-amino-5-cyano-3-methylbenzoic acid is represented as compound of Formula V. The 2-[3-bromo-1-(3-chloropyridin-2-11)-1H-pyrazol-5-11]-6-cyano-8-methyl-4H-3,1-benzoxazin-4-one is designated as compound of Formula VI. The inventors of the present invention observed that the compound of Formula III is not physically stable enough to undergo adequate purification. It has further been observed that the impure compound of Formula III, upon subsequent reaction with methylamine, yields chlorantraniliprole with inconsistent physical and chemical properties, resulting in a product unsuitable for its intended use. Furthermore, it has been observed that the low solubility of anthranilamides in water and / or organic solvents makes it difficult to carry out adequate purification processes. Therefore, there is a need to develop improved methods of preparation and purification for anthranilamides. Objectives of the invention It is an objective of the present invention to provide anthranilamides that are free from impurities. Another objective of the present invention is to provide a process for the preparation of anthranilamides. Another objective of the present invention is to provide a process for preparing chlorantraniliprole that is free of impurities. Brief description of the invention The present invention provides compounds of Formula (A) that are substantially free of impurities: cccQnn / Lznz / e / viAi Formula A wherein R-ι, R2, R3 and R4 can independently be a hydrogen, halogen, cyano, amino, N-thio derivative, hydroxyl, alkyl or cycloalkyl (C1-C10) linear or branched unsubstituted or substituted, unsubstituted or substituted heterocyclic with halogen, cyano, amino, hydroxyl or linear or branched alkyl (C1-C10) and wherein m, n, pyq can be 0, 1, 2 or 3. The present invention provides a process for purifying the compound of Formula A, cccQnn / Lznz / e / YiAi Formula A wherein R1, R2, R3 and R4 can independently be a hydrogen, halogen, cyano, amino, N-thio derivative, hydroxyl, alkyl or linear or branched (C1-C10) cycloalkyl unsubstituted or substituted, unsubstituted or substituted heterocyclic with halogen, cyano, amino, hydroxyl or linear or branched (C1-C10) alkyl and wherein m, n, pyq can be 0, 1, 2 or 3; said process comprises purifying the compound of Formula A from an aqueous suspension comprising said compound of Formula A. The present invention provides a process for purifying the compound of the Formula A, cccQnn / Lznz / e / YiAi Formula A wherein Ri, R2, R3 and R4 can independently be a hydrogen, halogen, cyano, amino, N-thio derivative, hydroxyl, alkyl or cycloalkyl (C1-C10) linear or branched unsubstituted or substituted, unsubstituted or substituted heterocyclic with halogen, cyano, amino, hydroxyl or alkyl linear or branched (C1-C10) and wherein m, n, pyq can be 0, 1, 2 or 3; This process comprises the following stages: a) introducing a mixture of the reaction product comprising the compound of Formula A into a reactor; b) prepare a suspension of the mixture under aqueous conditions; c) shake the suspension for a predetermined time; d) separate the solids; e) optionally repeat steps b), c) and d); and f) dry to obtain the purified compound of Formula A. The present invention further provides chlorantraniliprole that is substantially free of impurities. The present invention provides a process for purifying chlorantraniliprole, said process comprising purifying chlorantraniliprole from an aqueous suspension comprising chlorantraniliprole. The present invention provides a process for purifying chlorantraniliprole, said process comprising the steps of: a) introducing a mixture of the reaction product comprising chlorantraniliprole into a reactor; b) preparing a suspension of the mixture under aqueous conditions; c) shake the suspension for a predetermined time; d) separate the solids; e) optionally repeat steps b), c) and d); and f) drying to obtain purified chlorantraniliprole. The present invention provides a process for preparing chlorantraniliprole that is free of impurities, said process comprising purifying chlorantraniliprole from an aqueous suspension comprising the reaction product of the compound of Formula III with methylamine. The present invention provides a process for preparing chlorantraniliprole that is free from impurities, said process comprising the steps of: a) react the compound of Formula III with methylamine in an organic solvent; b) separate and collect solids; c) prepare a suspension of the product from step b) under aqueous conditions; d) shake the suspension for a predetermined time; e) separate and collect solids; f) optionally repeat steps c), d) and e); and g) drying to obtain chlorantraniliprole substantially free of impurities. The present invention provides a process for preparing chlorantraniliprole that is substantially free of impurities, wherein purification of the compound of Formula III is not essential. cccQnn / Lznz / e / YiAi The present invention provides a process for preparing chlorantraniliprole that is substantially free of impurities, said process comprising purifying chlorantraniliprole from an aqueous suspension, said aqueous suspension comprising a hydrophilic solvent mixed with the reaction product of a compound of Formula III with methylamine. The present invention provides a process for preparing chlorantraniliprole that is substantially free of impurities, said process comprising the steps of: a) prepare the compound of Formula III by reacting the compound of Formula I and the compound of Formula II in an organic solvent; b) optionally, purify the compound of Formula III; c) react the compound of Formula III with methylamine in an organic solvent; d) separate and collect solids; e) prepare a suspension of the product from step b) under aqueous conditions; f) shake the suspension for a predetermined time; g) separate and collect solids; h) Optionally, repeat steps e), f) and g); and i) drying to obtain impurity-free chlorantraniliprole. The present invention provides a process for purifying cyantraniliprole, said process comprising purifying cyantraniliprole from an aqueous suspension of cyantraniliprole. The present invention provides a process for purifying cyantraniliprole, said process comprising the steps of: a) introducing a mixture of the reaction product comprising cyantraniliprole into a reactor; b) prepare a suspension of the mixture under aqueous conditions; c) shake the suspension for a predetermined time; d) separate the solids; e) optionally repeat steps b), c) and d); and cccQnn / Lznz / e / YiAi f) drying to obtain purified cyantraniliprole. The present invention further provides a process for preparing cyantraniliprole that is free from impurities, said process comprising the steps of: a) react the compound of Formula VI with methi lamin in an organic solvent; b) separate and collect solids; c) prepare a suspension of the product from step b) under aqueous conditions; d) shake the suspension for a predetermined time; e) separate and collect solids; f) optionally repeat steps c), d) and e); and g) drying to obtain cyantraniliprole substantially free of impurities. The present invention further provides a process for preparing cyantraniliprole, said process comprising purifying cyantraniliprole from an aqueous suspension, said aqueous suspension comprising a hydrophilic solvent mixed with the reaction product of a compound of formula VI with methylamine. Detailed description It has been observed that many of the anthranilamides represented by the general structure of Formula A have low solubility in water or other hydrophilic solvents, making their isolation and purification problematic. Despite their low solubility in water and other hydrophilic solvents, the present inventors have surprisingly discovered that substantially pure anthranilamides, i.e., those substantially free from impurities, can be prepared by purifying the crude reaction product of the compound of Formula III with methylamine from an aqueous suspension. Based on this finding, the present inventors have made it possible to provide insecticidal anthranilamides that are free from impurities and a process for preparing substantially pure anthranilamides from them. cccQnn / Lznz / e / YiAi Chlorantraniliprole is an example of anthranilamides that are difficult to prepare and purify, resulting in variable physicochemical properties and making it challenging to optimize the preparation process. It has been observed that the compound of Formula III is not sufficiently stable to undergo effective purification processes, and that previous processes relying on purifying the compound of Formula III to obtain pure anthranilamides failed to yield substantially pure anthranilamides and resulted in yield losses, as has been made possible by the process of the present invention. Furthermore, the impure compound of Formula III, when reacted with methylamine, yields chlorantraniliprole with various impurities and inconsistent physical properties, and has been found to be ineffective for its intended use.The present invention finds that purifying anthranilamides from an aqueous suspension is a surprisingly better strategy for preparing substantially pure anthranilamides than starting with the pure compound of Formula III. The inventors of the present invention observed that, by following the process of the present invention, the purification of the compound of Formula III can be avoided or is not required, and the chlorantraniliprole could still be obtained substantially free of impurities. Therefore, the present invention provides compounds of Formula (A) that are free from impurities. cccQnn / Lznz / e / YiAi Formula Ά wherein R-ι, R2, R3 and R4 can independently be a hydrogen, halogen, cyano, amino, N-thio derivatives, hydroxyl, alkyl or cycloalkyl (C1-C10) linear or branched unsubstituted or substituted, unsubstituted or substituted heterocyclic halogen, cyano, amino, hydroxyl or linear or branched (C1-C10) alkyl or linear or branched (C1-C10) alkyl and wherein m, n, pyq can be 0, ! 2 or 3. In another aspect, the present invention also provides a process for purifying the compound of Formula A, cccQnn / Lznz / e / YiAi wherein R1, R2, R3 and R4 can independently be a hydrogen, halogen, cyano, amino, N-thio derivative, hydroxyl, alkyl or linear or branched (C1-C10) cycloalkyl unsubstituted or substituted, unsubstituted or substituted heterocyclic with halogen, cyano, amino, hydroxyl or linear or branched (C1-C10) alkyl and wherein m, n, pyq can be 0, 1, 2 or 3; said process comprises purifying the compound of Formula A from an aqueous suspension comprising said compound of Formula A. In one embodiment, the aqueous suspension of the compound of Formula A is provided in a reactor. In one embodiment, the aqueous suspension of the compound of Formula A comprises a mixture of the reaction product comprising the compound of Formula A. In one embodiment, the reaction product mixture is a reaction product of a compound of Formula III with methylamine. In one embodiment, the reaction product mixture is a reaction product of a compound of Formula III with methylamine carried out in an organic solvent. In one embodiment, the compound of Formula III is reacted with methylamine without being purified or isolated. In one embodiment, the aqueous suspension comprises a mixture of the reaction product in water. In one embodiment, purifying the compound of Formula A from an aqueous suspension comprising said compound of Formula A comprises stirring the aqueous suspension for a predetermined time before purifying said compound of Formula A. In one embodiment, the Formula III compound is a reaction product produced from a reaction between a Formula I compound and a Formula II compound. In one embodiment, the Formula III compound is a reaction product produced from a reaction between a Formula I compound and a Formula II compound carried out in an organic solvent. In one embodiment, the compound of Formula III is used without being isolated or purified from a reaction between a compound of Formula I and a compound of Formula II carried out in an organic solvent. cccQnn / Lznz / e / YiAi In one embodiment, purifying the compound of Formula A from an aqueous suspension comprising said compound of Formula A comprises stirring the aqueous suspension for a predetermined time and subsequently purifying said compound of Formula A. In one embodiment, purifying the compound of Formula A from an aqueous suspension comprising said compound of Formula A comprises stirring the aqueous suspension for a predetermined time, purifying said compound of Formula A, and separating said compound of Formula A from the aqueous suspension. In one embodiment, purifying the compound of Formula A from an aqueous suspension comprising said compound of Formula A comprises, repeatedly: (a) stirring the aqueous suspension for a predetermined time, (b) purifying said compound of Formula A, and (c) separating said compound of Formula A from the aqueous suspension. In one modality, steps (a), (b) and (c) can be repeated a plurality of times. In one embodiment, purifying the compound of Formula A from an aqueous suspension comprising said compound of Formula A comprises stirring the aqueous suspension for a predetermined time, purifying said compound of Formula A, separating said compound of Formula A from the aqueous suspension, and drying said separated compound of Formula A. In one embodiment, the present invention also provides a process for purifying the compound of Formula A, cccQnn / Lznz / e / YiAi cccQnn / Lznz / e / YiAi where R-ι, R2, R3 and R4 can independently be a hydrogen, halogen, cyano, amino, N-thio derivative, hydroxyl, alkyl or linear or branched (C1-C10) cycloalkyl unsubstituted or substituted, unsubstituted or substituted heterocyclic with halogen, cyano, amino, hydroxyl or linear or branched (C1-C10) alkyl and where m, n, pyq can be 0, 1, 2 or 3; This process comprises the following stages: a) introducing a mixture of the reaction product comprising the compound of Formula A into a reactor; b) prepare a suspension of the mixture under aqueous conditions; c) shake the suspension for a predetermined time; d) separate the solids; e) optionally repeat steps b), c) and d); and f) dry to obtain the purified compound of Formula A. In one embodiment, the compound of Formula A is when R1, R2, R3 and R4 can independently be a hydrogen, halogen, cyano, amino, N-thio derivatives, alkyl, halogen-substituted alkyl, cyano or unsubstituted or halogen-substituted heterocyclic amino, cyano, amino, hydroxyl or linear or branched (C1-C10) alkyl compounds, wherein m, n, pyq can be 0, 1, 2 or 3. In one form, the compound of Formula A is when Ri is CN, and CH3, R2 is Cl, R3 is Br and R4 is H and -CH3, where myq=2 as represented in the following structure. cccQnn / Lznz / e / YiAi In another form, the compound of Formula A is when R1 is Cl, and -CH3, R2 is Cl, R3 is Br and R4 is H and -CH3, where myq=2 as represented in the following structure. Chlorantraniliprole In another form, the compound of Formula A is when Ri is Cl and Br, R2 is Cl, R3 is Br and R4 is H and 1-cyclopropyl ethyl and where myq = 2 as represented in the following structure. cccQnn / Lznz / e / YiAi cyclaniliprol In yet another form, the compound of Formula A is when R1 is Cl, R2 is Cl, R3 is Br and R4 is H, and -CH3, where m, nyq = 2 as represented in the following structure. tetrachlorantraniliprole In another embodiment, the compound of Formula A is when Ri is CN, and -CH3, R2 is Cl, R3 is methyl of 5-(trifluoromethyl)-2H-tetrazol-2-1l] and R4 is H and -CH3, where myq=2 as represented in the following structure. cccQnn / Lznz / e / YiAi tetraniliprol In one modality, the term “impurities” refers to unreacted synthetic intermediates, reagents, solvents, organic and / or inorganic products of side reactions, organic and / or inorganic salts and / or other unwanted materials. Therefore, the statement that the compounds of the invention are substantially free from impurities is intended to mean that the aforementioned compound is substantially free from all unreacted synthetic intermediates, reagents, solvents, organic and / or inorganic products of side reactions, organic and / or inorganic salts and / or other unwanted materials. In one modality, the aqueous conditions of step b) refer to water or a mixture of water and one or more solvents. In a preferred embodiment, the aqueous conditions of step b) refer to water. In one embodiment, the suspension of step b) is prepared by mixing the reaction mass with water or with a mixture of water and one or more solvents. In one embodiment, the solvents are selected from the group comprising methanol, ethanol, n-propanol, n-butanol, acetone, ethyl acetate, dimethyl sulfoxide, acetonitrile, and dimethylformamide. In one embodiment, in step c), the reaction mass is stirred at a temperature of approximately 25 °C to approximately 80 °C. In a preferred embodiment, in step c), the reaction mass is stirred at a temperature of approximately 40 °C to approximately 60 °C. In one modality, in step c), the reaction mass is stirred for a period of at least 15 minutes. In a preferred embodiment, in step c), the reaction mass is stirred for a period of at least 30 minutes. In one modality, the separation of solids in stage d) is carried out by filtration, sedimentation, decantation or by solid-liquid centrifugation. In a preferred embodiment, the separation of solids in step d) is carried out by filtration. The present invention provides chlorantraniliprole that is substantially free of impurities. In one embodiment, the present invention provides chlorantraniliprole that is substantially free of impurities. In another embodiment, the present invention provides cyantraniliprole that is substantially free of impurities. cccQnn / Lznz / e / YiAi In another embodiment, the present invention provides chlorantraniliprole with a purity > 95% by weight. In another embodiment, the present invention provides chlorantraniliprole with a purity > 97% by weight. In another embodiment, the present invention provides cyantraniliprole with a purity > 95% by weight. In another embodiment, the present invention provides cyantraniliprole with a purity > 97% by weight. In one modality, the term “impurities” refers to unreacted synthetic intermediates, reagents, solvents, organic and / or inorganic products of side reactions, organic and / or inorganic salts and / or other unwanted materials. In another modality, synthetic intermediates comprise Formula I compound, Formula II compound and Formula III compound. In another modality, synthetic intermediates comprise Formula I compound, Formula V compound and Formula VI compound. In one form, the reagent includes methanesulfonyl chloride and methylamine. In one embodiment, the organic and / or inorganic products of side reactions include salts of the compound of Formula I with sulfonic acids and / or chlorides. In one embodiment, the organic and / or inorganic products of side reactions include salts of the compound of Formula I with methanesulfonyl chloride. cccQnn / Lznz / e / YiAi In another modality, the organic and / or inorganic products of secondary reactions include salts of the compound of Formula II with sulfonic acids and / or chlorides. In another modality, the organic and / or inorganic products of secondary reactions include salts of compounds of Formula V with sulfonic acids and / or chlorides. In yet another embodiment, the present invention provides chlorantraniliprole that is substantially free of compound of Formula I, compound of Formula II, compound of Formula III, salts of compound of Formula I with sulfonic acids and chlorides. In yet another embodiment, the present invention provides cyantraniliprole that is substantially free of compound of Formula I, compound of Formula V, compound of Formula VI, salts of compound of Formula I with sulfonic acids and chlorides. In one aspect, the present invention provides a process for purifying chlorantraniliprole, said process comprising purifying chlorantraniliprole from an aqueous suspension comprising chlorantraniliprole. In one embodiment, the aqueous suspension of chlorantraniliprole is provided in a reactor. In one embodiment, the aqueous suspension of chlorantraniliprole comprises a reaction product mixture comprising chlorantraniliprole. In one embodiment, the reaction product mixture is a reaction product of a compound of Formula III with methylamine. In one embodiment, the reaction product mixture is a reaction product of a compound of Formula III with methylamine carried out in an organic solvent. cccQnn / Lznz / e / YiAi In one embodiment, the compound of Formula III is reacted with methylamine without being purified or isolated. In one embodiment, the aqueous suspension comprises a mixture of the reaction product in water. In one embodiment, purifying chlorantraniliprole from an aqueous suspension comprising chlorantraniliprole comprises stirring the aqueous suspension for a predetermined time before purifying said chlorantraniliprole. In one embodiment, the Formula III compound is a reaction product produced from a reaction between a Formula I compound and a Formula II compound. In one embodiment, the Formula III compound is a reaction product produced from a reaction between a Formula I compound and a Formula II compound carried out in an organic solvent. In one embodiment, the compound of Formula III is used without being isolated or purified from a reaction between a compound of Formula I and a compound of Formula II carried out in an organic solvent. In one embodiment, purifying chlorantraniliprole from an aqueous suspension comprising chlorantraniliprole comprises stirring the aqueous suspension for a predetermined time and subsequently purifying said chlorantraniliprole. In one embodiment, purifying chlorantraniliprole from an aqueous suspension comprising said chlorantraniliprole comprises stirring the aqueous suspension for a predetermined time, purifying said chlorantraniliprole, and separating said chlorantraniliprole from the aqueous suspension. In one embodiment, purifying chlorantraniliprole from an aqueous suspension comprising said chlorantraniliprole repeatedly comprises: (a) stirring the aqueous suspension for a predetermined time, (b) purifying said chlorantraniliprole, and (c) separating the chlorantraniliprole from the aqueous suspension. cccQnn / Lznz / e / YiAi In one modality, steps (a), (b) and (c) can be repeated a plurality of times. In one embodiment, purifying chlorantraniliprole from an aqueous suspension comprising said chlorantraniliprole comprises stirring the aqueous suspension for a predetermined time, purifying the chlorantraniliprole, separating the chlorantraniliprole from the aqueous suspension, and drying said separated chlorantraniliprole. Therefore, the present invention provides a process for purifying chlorantraniliprole, said process comprising the steps of: a) introducing a mixture of the reaction product comprising chlorantraniliprole into a reactor; b) preparing a suspension of the mixture under aqueous conditions; c) shake the suspension for a predetermined time; d) separate and collect solids; e) optionally repeat steps b), c) and d); and f) drying to obtain chlorantraniliprole substantially free of impurities. In one embodiment, the chlorantraniliprole of step a) can be prepared from a reaction of the compound of Formula I, its derivatives or salts and the compound of Formula II, its derivatives or salts. In one modality, the aqueous conditions of step b) refer to water or a mixture of water and one or more solvents. In a preferred embodiment, the aqueous conditions of step b) refer to water. In one embodiment, the suspension of step b) is prepared by mixing the reaction mass with water or with a mixture of water and one or more solvents. In one embodiment, in step c), the reaction mass is stirred at a temperature of approximately 25 °C to approximately 80 °C. cccQnn / Lznz / e / YiAi In a preferred embodiment, in step c), the reaction mass is stirred at a temperature of approximately 40 °C to approximately 60 °C. In one modality, in step c), the reaction mass is stirred for a period of at least 15 minutes. In a preferred embodiment, in step c), the reaction mass is stirred for a period of at least 30 minutes. In one modality, the separation of solids in stage d) is carried out by filtration, sedimentation, decantation or by solid-liquid centrifugation. In a preferred embodiment, the separation of solids in step d) is carried out by filtration. In another embodiment, the present invention provides a process for purifying chlorantraniliprole, said process comprising the steps of: a) introducing a mixture of the reaction product comprising chlorantraniliprole into a reactor; b) prepare a suspension of the mixture in water; c) shake the suspension at 25°-60°C for at least 30 minutes; d) filter; e) optionally repeat steps b), c) and d); and f) drying to obtain chlorantraniliprole substantially free of impurities. In another embodiment, the present invention provides a process for purifying chlorantraniliprole, said process comprising the steps of: a) introducing a mixture of the reaction product comprising chlorantraniliprole into a reactor; b) prepare a suspension of the reaction mass in water; c) Stir at 25°-60°C for at least 30 minutes; d) filter; e) repeat steps b), c) and d) at least once; and f) drying to obtain chlorantraniliprole substantially free of impurities. cccQnn / Lznz / e / YiAi The present invention provides a process for preparing chlorantraniliprole that is substantially free of impurities. The present invention also provides a process for preparing chlorantraniliprole that is free of impurities, said process comprising purifying chlorantraniliprole from an aqueous suspension comprising the reaction product of the compound of Formula III with methylamine. In one embodiment, the aqueous suspension of chlorantraniliprole is provided in a reactor. In one embodiment, the aqueous suspension of chlorantraniliprole comprises a reaction product mixture comprising chlorantraniliprole. In one embodiment, the reaction product mixture is a reaction product of a compound of Formula III with methylamine. In one embodiment, the reaction product mixture is a reaction product of a compound of Formula III with methylamine carried out in an organic solvent. In one embodiment, the compound of Formula III is reacted with methylamine without being purified or isolated. In one embodiment, the aqueous suspension comprises a mixture of the reaction product in water. In one embodiment, purifying chlorantraniliprole from an aqueous suspension comprising chlorantraniliprole comprises stirring the aqueous suspension for a predetermined time before purifying said chlorantraniliprole. cccQnn / Lznz / e / YiAi In one embodiment, the Formula III compound is a reaction product produced from a reaction between a Formula I compound and a Formula II compound. In one embodiment, the Formula III compound is a reaction product produced from a reaction between a Formula I compound and a Formula II compound carried out in an organic solvent. In one embodiment, the compound of Formula III is used without being isolated or purified from a reaction between a compound of Formula I and a compound of Formula II carried out in an organic solvent. In one embodiment, purifying chlorantraniliprole from an aqueous suspension comprising chlorantraniliprole comprises stirring the aqueous suspension for a predetermined time and subsequently purifying said chlorantraniliprole. In one embodiment, purifying chlorantraniliprole from an aqueous suspension comprising said chlorantraniliprole comprises stirring the aqueous suspension for a predetermined time, purifying said chlorantraniliprole, and separating said chlorantraniliprole from the aqueous suspension. In one embodiment, purifying chlorantraniliprole from an aqueous suspension comprising said chlorantraniliprole repeatedly comprises: (a) stirring the aqueous suspension for a predetermined time, (b) purifying said chlorantraniliprole, and (c) separating the chlorantraniliprole from the aqueous suspension. In one modality, steps (a), (b) and (c) can be repeated a plurality of times. In one embodiment, purifying chlorantraniliprole from an aqueous suspension comprising said chlorantraniliprole comprises stirring the aqueous suspension for a predetermined time, purifying the chlorantraniliprole, separating the chlorantraniliprole from the aqueous suspension, and drying said separated chlorantraniliprole. cccQnn / Lznz / e / YiAi The present invention provides a process for purifying cyantraniliprole, said process comprising purifying cyantraniliprole from an aqueous suspension of cyantraniliprole. The present invention provides a process for purifying cyantraniliprole, said process comprising the steps of: a) introducing a mixture of the reaction product comprising cyantraniliprole into a reactor; b) prepare a suspension of the mixture under aqueous conditions; c) shake the suspension for a predetermined time; d) separate the solids; e) optionally repeat steps b), c) and d); and f) drying to obtain purified cyantraniliprole. In one embodiment, the present invention provides a process for preparing chlorantraniliprole that is substantially free of impurities, said process comprising the steps of: a) react compound of Formula III and methylamine in an organic solvent; b) separate and collect solids; c) prepare a suspension of the product from step b) under aqueous conditions; d) shake for a predetermined time; e) separate and collect solids; f) optionally repeat steps c), d) and e); and g) drying to obtain chlorantraniliprole substantially free of impurities. In one embodiment, the reaction of step a) is carried out in an organic solvent selected from the group comprising acetonitrile, tetrahydrofuran, ethyl acetate, toluene, xylene, and dioxane. In a preferred embodiment, the reaction of step a) is carried out in ethyl acetate. cccQnn / Lznz / e / YiAi In one embodiment, in step a) methylamine is used as an aqueous solution. In one modality, the aqueous conditions of step c) refer to water or a mixture of water and one or more solvents. In a preferred embodiment, the aqueous conditions of step c) refer to water. In one embodiment, the suspension of step c) is prepared by mixing the reaction mass with water or with a mixture of water and one or more solvents. In one embodiment, in step d), the reaction mass is stirred at a temperature of approximately 25 °C to approximately 80 °C. In a preferred embodiment, in step d), the reaction mass is stirred at a temperature of approximately 40 °C to approximately 60 °C. In one modality, in step d), the reaction mass is stirred for a period of at least 15 minutes. In a preferred embodiment, in step d), the reaction mass is stirred for a period of at least 30 minutes. In one modality, the separation of solids from stage e) is carried out by filtration, sedimentation, decantation or by solid-liquid centrifugation. In a preferred embodiment, the separation of solids in step e) is carried out by filtration. The present invention also provides a process for preparing chlorantraniliprole that is substantially free of impurities, said process comprising purifying chlorantraniliprole from an aqueous suspension, said aqueous suspension comprising a hydrophilic solvent mixed with the reaction product of a compound of Formula III with methylamine. cccQnn / Lznz / e / YiAi In one embodiment, the hydrophilic solvents are selected from the group comprising methanol, ethanol, n-propanol, n-butanol, acetone, ethyl acetate, dimethyl sulfoxide, acetonitrile, and dimethylformamide. In a preferred embodiment, the present invention provides a process for preparing chlorantraniliprole that is substantially free of impurities, said process comprising the steps of: a) react compound of Formula III and aqueous solution of methylamine in an organic solvent; b) filter the reaction mass; c) prepare a suspension of the reaction mass in water; d) Stir at 25°-60°C for at least 30 minutes; e) filter; f) repeat steps c), d) and e) at least once; and g) dry to obtain purified chlorantraniliprole. The present invention further provides a process for preparing chlorantraniliprole that is substantially free of impurities, wherein purification of the compound of Formula III is not essential. The present invention provides a process for preparing chlorantraniliprole that is substantially free of impurities, said process comprising the steps of: a) prepare the compound of Formula III by reacting the compound of Formula I and the compound of Formula II in an organic solvent; b) optionally, purify the compound of Formula III; c) react the compound of Formula III with methylamine in an organic solvent; d) separate and collect solids; e) prepare a suspension of the product from step b) under aqueous conditions; f) shake the suspension for a predetermined time; g) separate and collect solids; h) Optionally, repeat steps e), f) and g); and i) drying to obtain chlorantraniliprole substantially free of impurities. cccQnn / Lznz / e / YiAi In one embodiment, the reaction of step a) is carried out in an organic solvent selected from the group comprising acetonitrile, tetrahydrofuran, ethyl acetate, toluene, xylene, and dioxane. In another modality, the reaction of step a) is carried out in the presence of a base. In one embodiment, the purification of step b) of the Formula III compound may be optional. In another modality, in step (b), the compound of Formula III can be partially purified. Even in another embodiment, according to the present invention, the purification of the compound of Formula III is not essential. In one embodiment, the purification of step b) of the Formula III compound can be avoided. In one embodiment, the process of the present invention yields chlorantraniliprole that is substantially free of impurities produced during the reaction of step a). In another embodiment, the process of the present invention avoids the purification of the less stable compound of Formula III. In one embodiment, the reaction of step c) is carried out in an organic solvent selected from the group comprising acetonitrile, tetrahydrofuran, ethyl acetate, toluene, xylene, and dioxane. In a preferred embodiment, the reaction of step c) is carried out in ethyl acetate. cccQnn / Lznz / e / YiAi In one embodiment, in step c) methylamine is used as an aqueous solution. In one embodiment, the aqueous conditions of step e) refer to water or a mixture of water and one or more solvents. In a preferred embodiment, the aqueous conditions of step e) refer to water. In one embodiment, the suspension of step e) is prepared by mixing the reaction mass with water or with a mixture of water and one or more solvents. In one embodiment, in step f), the reaction mass is stirred at a temperature of approximately 25 °C to approximately 80 °C. In a preferred embodiment, in step f), the reaction mass is stirred at a temperature of approximately 40 °C to approximately 60 °C. In one embodiment, in step f), the reaction mass is stirred for a period of at least 15 minutes. In a preferred embodiment, in step f), the reaction mass is stirred for a period of at least 30 minutes. In one modality, the separation of solids from stage g) is carried out by filtration, sedimentation, decantation or by solid-liquid centrifugation. In a preferred embodiment, the separation of solids from step g) is carried out by filtration. In one embodiment, the present invention provides chlorantraniliprole having a purity of at least approximately 97.0%. In one embodiment, the present invention provides chlorantraniliprole having a purity of at least approximately 97.5%. cccQnn / Lznz / e / YiAi In one embodiment, the present invention provides an anthranilamide insecticide having less than 0.5% of the intermediates of Formulas I, II, and III. In one embodiment, the present invention provides an anthranilamide insecticide having less than 0.2% of the intermediates of Formulas I, II, and III. In one embodiment, the present invention provides chlorantraniliprole having less than 0.5% of the intermediates of Formulas I, II and III. In one embodiment, the present invention provides chlorantraniliprole having less than 0.2% of the intermediates of Formulas I, II and III. In one embodiment, the present invention provides an anthranilamide insecticide having less than 1.0% of the salts of the intermediates of Formulas I, II, and III. In one embodiment, the present invention provides an anthranilamide insecticide having less than 0.5% of the salts of the intermediates of Formulas I, II and III. In one embodiment, the present invention provides chlorantraniliprole having less than 1.0% of the salts of the intermediates of Formulas I, II and III. In one embodiment, the present invention provides chlorantraniliprole having less than 0.5% of the salts of the intermediates of Formulas I, II and III. In these forms, the salts of the intermediates of Formulas I, II or III include the salts of these methanesulfonyl chloride intermediates. In one embodiment, the present invention provides an anthranilamide insecticide having less than 2.0% inorganic impurities. cccQnn / Lznz / e / YiAi In one embodiment, the present invention provides an anthranilamide insecticide having less than 0.5% inorganic impurities. In one embodiment, the present invention provides chlorantraniliprole having less than 2.0% inorganic impurities. In one embodiment, the present invention provides chlorantraniliprole having less than 0.5% inorganic impurities. The present invention further provides a process for preparing cyantraniliprole that is free from impurities, said process comprising the steps of: a) react compound of Formula VI with methylamine in an organic solvent; b) separate and collect solids; c) prepare a suspension of the product from step b) under aqueous conditions; d) shake the suspension for a predetermined time; e) separate and collect solids; f) optionally repeat steps c), d) and e); and g) drying to obtain cyantraniliprole substantially free of impurities. The present invention further provides a process for preparing cyantraniliprole, said process comprising purifying cyantraniliprole from an aqueous suspension, said aqueous suspension comprising a hydrophilic solvent mixed with the reaction product of a compound of Formula VI with methylamine. The advantages and other parameters of the present invention are illustrated by the examples given below. However, the scope of the present invention is not limited by the examples in any way. Anyone skilled in the art will appreciate that the present invention includes the aforementioned examples and may be further modified and altered within the technical scope of the present invention. cccQnn / Lznz / e / YiAi Examples: Example 1: Preparation of the Formula III compound Methanesulfonyl chloride (56 g) in acetonitrile (108 g) was added to the mixture of compound of Formula I (54 g), compound of Formula II (35 g), and pyridine (73 g) in acetonitrile (162 g) with stirring at 5–10 °C, followed by stirring for 3 hours at 25 °C. The mixture was then filtered and washed with acetonitrile, followed by drying to obtain compound of Formula III (75 g, yield = 93%). Example 2: Preparation of chlorantraniliprole The Formula III compound (75 g) was stirred in ethyl acetate (225 g) in a reactor at 15–20 °C while stirring. Aqueous methylamine solution (43 g) was added to the reaction mixture after 2 hours at 15–25 °C and stirred for 3 hours. The mass was then cooled to 30 °C, filtered, and washed with ethyl acetate to obtain chlorantraniliprole (98 g, ~93% purity). Example 3: Purification of chlorantraniliprole 98 g of chlorantraniliprole (as prepared in Example 2) and 200 g of water were loaded into a reactor. The mixture was stirred at 40–50 °C for one hour. The mixture was then filtered. The wet mixture was then loaded back into the reactor, and 200 g of water was added. The suspension was stirred at 40–50 °C for one hour. The mixture was then filtered and washed with hot water. The resulting wet mixture was dried at 70 °C. 51 g, 97.5% purity. Example 4: Preparation of the Formula III compound Methanesulfonyl chloride (56 g) was added to tetrahydrofuran (75 g) in a mixture of compound of Formula I (54 g), compound of Formula II (35 g), and pyridine (73 g) in tetrahydrofuran (75 g) with stirring at 5–10 °C, followed by stirring for 3 hours at 25 °C. The mixture was then filtered and washed with acetonitrile followed by drying to obtain compound of Formula III (68 g, yield = 84.3%). Example 5: Preparation of chlorantraniliprole The Formula III compound (68 g) was stirred in ethyl acetate (175 g) in a reactor at 15–20 °C while stirring. Aqueous methylamine solution (41 g) was added to the reaction mixture after 2 hours at 15–25 °C and stirred for 3 hours. The mixture was then cooled to 30 °C, 200 g of water was added, and it was held for 1 hour. Afterward, it was filtered and washed with ethyl acetate to obtain chlorantraniliprole (58 g, 93% purity). Example 6: Purification of chlorantraniliprole 58 g of chlorantraniliprole (as prepared in Example 5), 200 g of water, and 100 g of ethyl acetate were loaded into a reactor. The mixture was stirred at 40–50 °C for one hour. Afterward, the mixture was filtered and washed with hot water. The resulting wet mixture was dried at 70 °C. 49 g, 97.5% purity. Example 7: Analytical results of chlorantraniliprole prepared and purified by the process according to the present invention The analytical results of chlorantraniliprole prepared (Example 2) and purified (Example 3) by the present invention are presented in the following table (Table 1): Table 1: cccQnn / Lznz / e / YiAi Chlorantraniliprole Sample (% purity) Intermediates (%) Salts of intermediates (%) Inorganics (%) Other (%) Example 2 93 0.5-1 1-2 2-4 <1 Example 3 >97 <0.2 <0.5 <0.5 <0.1 The intermediates include the compound of Formula I, the compound of Formula II, and the compound of Formula III. Salts of intermediates include the salt of the compound of Formula I with methanesulfonyl chloride. Inorganic components include chlorides. Traces of solvents, bases, and other unidentified impurities are also removed by the process of the present invention. From previous experiments, it is established that the process according to the present invention can be used to produce chlorantraniliprole of high purity and consistent properties. Example 8: Preparation of the compound of Formula VI Methanesulfonyl chloride (60 g) in acetonitrile (115 g) was added to the mixture of compound of Formula I (55 g), compound of Formula V (38 g), and pyridine (75 g) in acetonitrile (165 g) with stirring at 5–10 °C, followed by stirring for 4 hours at 25 °C. The mixture was then filtered and washed with acetonitrile, followed by drying to obtain compound of Formula VI (73 g, yield = 92%). Example 9: Preparation of cyantraniliprole (Formula Vil) The compound of Formula VI (73 g) was stirred in ethyl acetate (220 g) in a reactor at 15–20 °C while stirring. Aqueous methylamine solution (43 g) was added to the reaction mixture after 2 hours at 15–25 °C and stirred for 3 hours. The mass was then cooled to 30 °C, filtered, and washed with ethyl acetate to obtain cyantraniliprole (95 g, ~93% purity). Example 10: Purification of cyantraniliprole (Formula Vil) 95 g of cyantraniliprole (as prepared in Example 6) and 200 g of water were loaded into a reactor. The mixture was stirred at 35–40 °C for one hour. The mixture was then filtered. The wet mixture was then loaded into the reactor and 200 g of water was added. The suspension was stirred at 35–40 °C for one hour. The mixture was then filtered and washed with hot water. The resulting wet mixture was dried at 70 °C. (49 g, 97.5% purity).

Claims

1. Compounds of Formula (A) that are substantially free from impurities: cccQnn / Lznz / e / YiAi Formula A characterized in that R-ι, R2, R3 and R4 can independently be a hydrogen, halogen, cyano, amino, N-thio derivative, hydroxyl, alkyl or cycloalkyl (C1-C10) linear or branched unsubstituted or substituted, unsubstituted or substituted heterocyclic with halogen, cyano, amino, hydroxyl or alkyl linear or branched (C1-C10) and wherein m, n, pyq can be 0, 1, 2 or 3.

2. A compound of Formula A that is substantially free from impurities according to claim 1 characterized in that R1 is CN, and CH3, R2 is Cl, R3 is Br and R4 is H and -CH3 and wherein myq = 2.

3. A compound of Formula A that is substantially free from impurities according to claim 1 characterized in that R1 is Cl, and -CH3, R2 is Cl, R3 is Br and R4 is H and -CH3 and wherein myq = 2.

4. A compound of Formula A that is substantially free of impurities according to claim 1 characterized in that Ri is OI and Br, R2 is Cl, R3 is Br and R4 is H and 1-cyclopropyl ethyl and wherein myq = 2.

5. A compound of Formula A that is substantially free from impurities according to claim 1 characterized in that R1 is C, R2 is Cl, R3 is Br and R4 is H and -CH3 where m, nyq = 2.

6. A compound of Formula A that is substantially free of impurities according to claim 1 characterized in that R1 is CN, and -CH3, R2 is Cl, R3 is methyl of 5-(trifluoromethyl)-2H-tetrazol-2-yl] and R4 is H and -CH3 wherein myq -2.

7. Compounds of Formula (A) according to claim 1 that are substantially free from impurities characterized in that the impurities include unreacted synthetic intermediates, reagents, solvents, organic and / or inorganic products of side reactions, organic and / or inorganic salts and / or other unwanted materials.

8. A process for purifying the compound of Formula A, cccQnn / Lznz / e / YiAi Formula A characterized in that R-ι, R2, Rsy R4 can independently be a hydrogen, halogen, cyano, amino, N-thio derivative, hydroxyl, alkyl or cycloalkyl (C1-C10) unsubstituted or substituted, unsubstituted or substituted heterocyclic halogen, cyano, amino, hydroxyl or linear or branched (C1-C10) alkyl and wherein m, n, pyq can be 0, 1, 2 or 3; the process comprising purifying the compound of Formula A from an aqueous suspension of the compound of Formula A.

9. A process for purifying the compound of Formula A, cccQnn / Lznz / e / YiAi wherein R1, R2, R3 and R4 can independently be a hydrogen, halogen, cyano, amino, N-thio derivative, hydroxyl, alkyl or linear or branched (C1-C10) cycloalkyl unsubstituted or substituted, unsubstituted or substituted heterocyclic halogen, cyano, amino, hydroxyl or linear or branched (C1-C10) alkyl and wherein m, n, pyq can be 0, 1, 2 or 3; according to claim 8, the process comprises the steps of: a) introducing a mixture of the reaction product of the compound of Formula A into a reactor; b) preparing a suspension of the mixture under aqueous conditions; c) stirring the suspension for a predetermined time; d) separating the solids; e) optionally repeating steps b), c) and d); yf) dry to obtain the purified compound of Formula A.

10. A process according to claim 9 characterized in that the aqueous conditions comprise water or a mixture of water and one or more solvents.

11. Chlorantraniliprole substantially free of impurities.

12. Chlorantraniliprole according to claim 11, substantially free from impurities, characterized in that the impurities include unreacted synthetic intermediates, reagents, solvents, organic and / or inorganic products of side reactions, organic and / or inorganic salts, and / or other unwanted materials.

13. Chlorantraniliprole according to claim 11, which is substantially free from impurities, characterized in that the impurities include compound of Formula I, compound of Formula II, compound of Formula III, salts of the compound of Formula I with sulfonic acids and chlorides.

14. Chlorantraniliprole according to claim 11 having a purity of at least approximately 97.0%.

15. Chlorantraniliprole according to claim 11 having less than 0.5% of intermediates of Formula I, II and III.

16. Chlorantraniliprole according to claim 11 having less than 0.5% of the intermediate salts of Formula I, II and III.

17. A process for purifying chlorantraniliprole, the process comprising purifying chlorantraniliprole from an aqueous suspension of chlorantraniliprole. cccQnn / Lznz / e / YiAi 18. A process for purifying chlorantraniliprole according to claim 17, the process comprising the steps of: a) introducing a reaction product mixture comprising chlorantraniliprole into a reactor; b) preparing a suspension of the mixture under aqueous conditions; c) stirring the suspension for a predetermined time; d) separating the solids; e) optionally repeating steps b), c) and d); and f) drying to obtain purified chlorantraniliprole.

19. A process for preparing chlorantraniliprole that is free from impurities, the process comprising the steps of: a) reacting the compound of Formula III with methylamine in an organic solvent; b) separating and collecting solids; c) preparing a suspension of the product of step b) under aqueous conditions; d) stirring the suspension for a predetermined time; e) separating and collecting solids; f) optionally repeating steps c), d) and e); and g) drying to obtain chlorantraniliprole substantially free from impurities.

20. A process for preparing chlorantraniliprole according to claim 19, characterized in that purification of the compound of Formula III is not essential.

21. A process for preparing chlorantraniliprole according to claim 19, the process comprising purifying chlorantraniliprole from an aqueous suspension, the aqueous suspension comprising a hydrophilic solvent mixed with the reaction product of a compound of Formula III with methylamine.

22. A process for preparing chlorantraniliprole according to claim 19, the process comprising the steps of: a) preparing the compound of Formula III by reacting the compound of Formula I and the compound of Formula II in an organic solvent; b) optionally, purifying the compound of Formula III; c) reacting the compound of Formula III with methylamine in an organic solvent; d) separating and collecting solids; e) preparing a suspension of the product of step b) under aqueous conditions; f) stirring the suspension for a predetermined time; g) separating and collecting solids; h) optionally, repeating steps e), f) and g); i) drying to obtain impurity-free chlorantraniliprole.

23. A process for purifying cyantraniliprole, the process comprising purifying cyantraniliprole from an aqueous suspension of cyantraniliprole.

24. A process for purifying cyantraniliprole according to claim 23, the process comprising the steps of: a) introducing a reaction product mixture comprising cyantraniliprole into a reactor; b) preparing a suspension of the mixture under aqueous conditions; c) stirring the suspension for a predetermined time; d) separating the solids; e) optionally repeating steps b), c) and d); and f) drying to obtain purified cyantraniliprole.

25. A process for preparing cyantraniliprole that is free from impurities, the process comprising the steps of: a) reacting the compound of Formula VI with methylamine in an organic solvent; b) separating and collecting solids; c) preparing a suspension of the product of step b) under aqueous conditions; d) stirring the suspension for a predetermined time; e) separating and collecting solids; f) optionally repeating steps c), d) and e); and g) drying to obtain cyantraniliprole substantially free from impurities.

26. A process for preparing cyantraniliprole according to claim 25, the process comprising purifying cyantraniliprole from an aqueous suspension, the aqueous suspension comprising a hydrophilic solvent mixed with the reaction product of a compound of formula VI with methylamine.