METHODS FOR THE PREPARATION OF ETHYL 3-BROMO-1-(3-CHLOROPYRIDINI-2-YL)-1H-PYRAZOL-5-CARBOXYLATE

Abstract

This paper describes novel methods for synthesizing ethyl 3-bromo-1-(3-chloropyridin-2-yl)-1H-pyrazol-5-carboxylate.

Description

METHODS FOR THE PREPARATION OF ETHYL 3-BROMO-1-(3-CHLOROPYRIDINI-2-YL)-1H-PYRAZOL-5-CARBOXYLATE REFERENCE TO A RELATED APPLICATION This application claims the benefit of U.S. Provisional Application No. 262 / 933 553 filed on November 11, 2019. FIELD OF INVENTION This disclosure relates to novel methods for synthesizing ethyl 3-bromo-1-(3-chloropyridin-2-1I)-1Hpyrazol-5-carboxylate. The compounds prepared by the methods disclosed herein are useful for the preparation of certain anthranilamide compounds of interest as insecticides, such as, for example, the insecticides chlorantraniliprole and cyantraniliprole. BACKGROUND Ethyl 3-bromo-1-(3-chloropyridin-2-yl)-1 / - / -pyrazole-5-carboxylate is an intermediate in the production of 3-bromo-A / -[4-chloro-2-methyl-6-[(methyllamino)carbon¡l]phenyl]-1 -(3-chloro-2-pind¡nyl)-1 / - / -pyrazole-5carboxamide and 3-bromo-1 -(3-chloropyridin-2-yl)- / V-[4-cyano-2-methyl-6-[ / \ / -methylcarbamoyl]phenyl]-1 / - / -pyrazole-5carboxamide. As disclosed in patent WO03016283A1, 3-bromo-1-(3-chloropyridin-2-yl)-1 / 7-pyrazol-5-carboxylate is produced from ethyl 3-bromo-1-(3-chloropyridin-2-yl)-4,5-dihydro-1 / 7-pyrazol-5-carboxylate by an oxidation reaction in an acetonitrile system in the presence of potassium persulfate using sulfuric acid as a catalyst. The reported yield is approximately 75-80%. This disclosure provides novel methods for preparing ethyl 3-bromo-1-(3-chloropyridine-2-yl)-1-pyrazol-5-carboxylate and derivatives thereof. The benefits of the methods described herein compared to prior methods are numerous and include improved overall yield, reduced cost, and reduced process risks. The disclosed methods provide an overall yield of approximately 88%. BRIEF DESCRIPTION In one aspect, a method is provided herein for preparing a compound of Formula II, where frnacnn / zznz / E / YiAi r8OOC (Formula II) Rase selects between hydrogen and C1-C4 alkyl; and each of R2 - R7 is independently selected from hydrogen, halogen, C1-C4 alkyl and halogenated C1-C4 alkyl, comprising the method I) form a mixture comprising A) a first quantity of a compound of Formula I, where frnacnn / zznz / E / YiAi (Formula I) R1 is selected from hydrogen and C1-C4 alkyl; and each of R2 - R7 is independently selected from hydrogen, halogen, C1-C4 alkyl and halogenated C1-C4 alkyl; B) an oxidizing agent; and C) an organic solvent; II) heat the mixture; III) add an acid to the mixture; IV) add to the mixture a second quantity of the compound of Formula I; and V) to stop the reaction of the mixture. DETAILED DESCRIPTION OF THE DISCLOSURE As used herein, the terms “comprises,” “comprising,” “includes,” “having,” “containing,” “characterized by,” or any variation thereof, are intended to encompass a non-exclusive inclusion, subject to any limitations explicitly stated. For example, a composition, mixture, process, or method comprising a list of elements is not necessarily limited to those elements alone, but may include other elements not expressly listed or inherent in such composition, mixture, process, or method. The transitional phrase “consisting of” excludes any unspecified element, step, or ingredient. If it were in the claim, it would preclude the inclusion of materials other than those mentioned, except for impurities commonly associated with them. When the phrase “consisting of” appears in a clause within the body of a claim, rather than immediately following the preamble, it limits only the element set forth in that clause; other elements of the claim as a whole are not excluded. The transitional phrase “essentially consisting of” is used to define a composition or method that includes materials, steps, features, components, or elements, in addition to those explicitly disclosed, provided that these additional materials, steps, features, components, or elements do not materially affect the basic and novel feature(s) of the claimed invention. The expression “essentially consisting of” occupies an intermediate position between “comprising” and “consisting of.” When an invention or part thereof is defined by an open term or expression such as "comprising", it is readily understood that (unless otherwise indicated) the description should also be interpreted as describing such an invention using the expressions "consisting essentially of" or "consisting of". Furthermore, unless explicitly stated otherwise, “or” refers to an inclusive or, not an exclusive or. For example, a condition A or B is satisfied by any one of the following: A is true (or present) and B is false (or not present), A is false (or not present) and B is true (or present), and both A and B are true (or present). Furthermore, it is intended that the indefinite articles “a” and “one” preceding an element or component of the invention should not be restrictive with respect to the number of instances (i.e., occurrences) of the element or component. Therefore, “a” or “one” should be interpreted to include one or at least one, and the singular form of the word for the element or component should also include the plural, unless it is clear that the number is singular. As used herein, the term “approximately” means more or less than 10% of the value. The term “eq” refers to the amount of one substance that reacts with (or is equivalent to) an arbitrary amount of another substance in a given chemical reaction. The expression % of assay refers to the content of the desired compound divided by the total weight of the sample. The term halogen, whether used alone or in compound words or phrases such as haloalkyl or halogenated alkyl, includes fluorine, chlorine, bromine, or iodine. Furthermore, when used in compound words or phrases such as haloalkyl or halogenated alkyl, the alkyl group may be partially or fully substituted with halogen atoms, which may be the same or different. When a group contains a substituent that can be hydrogen, for example, R4, then when this substituent is considered to be hydrogen, it is recognized that this is equivalent to the group not being substituted. Certain compounds of this invention may exist as one or more stereoisomers. The various stereoisomers include enantiomers, diastereomers, atropisomers, and geometric isomers. A person skilled in the art will appreciate that a stereoisomer may be more active and / or may exhibit beneficial effects when enriched with respect to another stereoisomer or stereoisomers, or when separated from the other stereoisomer or stereoisomers. Furthermore, the person skilled in the art knows how to selectively separate, enrich, and / or prepare such stereoisomers. frnacnn / zznz / E / YiAi The achievements of this disclosure include: Implementation 1. A method for preparing a compound of Formula II, where frnacnn / zznz / E / YiAi (Formula II) Rs is selected from hydrogen and C1-C4 alkyl; and each of R2 - R7 is independently selected from hydrogen, halogen, C1-C4 alkyl and halogenated C1-C4 alkyl, comprising the method I) form a mixture comprising A) a first quantity of a compound of Formula I, where (Formula I) R1 is selected from hydrogen and C1-C4 alkyl; and each of R2 - R7 is independently selected from hydrogen, halogen, C1-C4 alkyl and halogenated C1-C4 alkyl; B) an oxidizing agent; and C) an organic solvent; II) heat the mixture; III) add an acid to the mixture; IV) add to the mixture a second quantity of the compound of Formula I; and V) to stop the reaction of the mixture. Implementation 2. The method of implementation 1, wherein the oxidizing agent is selected from hydrogen peroxide, organic peroxides, potassium persulfate, sodium persulfate, ammonium persulfate, potassium monopersulfate, sodium monopersulfate, potassium permanganate, and combinations thereof. Realization 3. The method of realization 1, wherein the oxidizing agent is potassium persulfate. Embodiment 4. The method of embodiment 1, wherein the oxidizing agent is present in the mixture in an amount in the range of approximately 1.0 eq to approximately 2.0 eq. Implementation 5. The method of implementation 1, wherein the oxidizing agent is present in the mixture in an amount in the range of approximately 1.3 eq to approximately 1.7 eq. Realization 6. The method of realization 1, wherein the oxidizing agent has a D50 particle size in the range of approximately 10 pm to approximately 200 pm. Realization 7. The method of realization 1, wherein the oxidizing agent has a D50 particle size in the range of approximately 20 pm to approximately 100 pm. Realization 8. The method of realization 1, wherein the oxidizing agent has a D50 particle size in the range of approximately 30 pm to approximately 80 pm. Realization 9. The method of realization 1, wherein the oxidizing agent has a D50 particle size in the range of approximately 40 pm to approximately 60 pm. Realization 10. The method of realization 1, wherein the solvent is selected from ethers, esters, aprotic organic solvents and combinations thereof. Realization 11. The method of realization 10, wherein the ether is selected from tetrahydrofuran, 2-methyltetrahydrofuran, dioxane and combinations thereof. Realization 12. The method of realization 10, wherein the ester is selected from ethyl acetate, isopropyl acetate, dimethyl carbonate, butyl acetate, and combinations thereof. Implementation 13. The method of implementation 10, wherein the aprotic organic solvent is selected from / V,M-dimethylformamide, dimethylacetamide, dimethyl sulfoxide, 1,3-dimethyl-2-imidazolidine, acetonitrile and combinations thereof. Realization 14. The method of realization 10, wherein the aprotic organic solvent is acetonitrile. Realization 15. The method of realization 1, wherein the first amount of compound of Formula I is approximately 5% by weight to approximately 40% by weight of the total amount of compound of Formula I. Implementation 16. The method of implementation 1, wherein the first amount of compound of Formula I is present in the mixture at a concentration in the range of approximately 10% by weight to approximately 30% by weight of the total amount of compound of Formula I. Realization 17. The method of realization 1, wherein the acid is selected from organic acids, inorganic acids, and combinations thereof. Realization 18. The method of realization 17, wherein the organic acid is selected from acetic acid, propanoic acid, p-toluenesulfonic acid, benzoic acid, and combinations thereof. frnacnn / zznz / E / YiAi Realization 19. The method of realization 17, wherein the inorganic acid is selected from sulfuric acid, phosphoric acid, fuming sulfuric acid, hydrobromic acid, hydrochloric acid, and combinations thereof. Realization 20. The method of realization 17, wherein the inorganic acid is sulfuric acid. Realization 21. The method of realization 1, wherein the acid is present in the mixture in an amount in the range of approximately 0.05 eq to approximately 1.5 eq. Realization 22. The method of realization 1, wherein the acid is present in the mixture in an amount less than approximately 0.2 eq. Embodiment 23. The method of embodiment 1, wherein the step of the method in which the mixture is formed occurs at a temperature in the range of approximately 0 °C to approximately 60 °C. Embodiment 24. The method of embodiment 1, wherein the step of the method in which the mixture is formed occurs at a temperature in the range of approximately 15 °C to approximately 35 °C. Implementation 25. The method of implementation 1, wherein the step of the method in which the mixture is formed occurs at room temperature. Embodiment 26. The method of embodiment 1, wherein the step of the method in which the mixture is heated increases the temperature of the mixture to a temperature in the range of approximately 50 °C to approximately 82 °C. Embodiment 27. The method of embodiment 1, wherein the step of the method in which the mixture is heated increases the temperature of the mixture to a temperature in the range of approximately 55 °C to approximately 65 °C. Embodiment 28. The method of embodiment 1, wherein the step of the method in which a second quantity of the compound of Formula I is added to the mixture occurs at a temperature in the range of approximately 50 °C to approximately 82 °C. Embodiment 29. The method of embodiment 1, wherein the step of the method in which a second quantity of the compound of Formula I is added to the mixture occurs at a temperature in the range of approximately 65 °C to approximately 82 °C. Realization 30. The method of realization 1, wherein the step of the method in which a second quantity of the compound of Formula I is added comprises adding in discrete quantities the second quantity of the compound of Formula I. Embodiment 31. The method of embodiment 1, wherein the step of the method in which a second quantity of the compound of Formula I is added comprises continuously adding the second quantity of the compound of Formula I. Embodiment 32. The method of embodiment 1, wherein the step of the method in which a second quantity of the compound of Formula I is added comprises the dropwise addition of the second quantity of the compound of Formula I. Realization 33. The method of realization 1, wherein the step of the method in which a second quantity of the compound of Formula I is added occurs during a period of time in the range of approximately 3 hours to approximately 7 hours. frnacnn / zznz / E / YiAi Realization 34. The method of embodiment 1, wherein the step of the method in which a second quantity of the compound of Formula I is added occurs during a period of time in the range of approximately 3.5 hours to approximately 4.5 hours. Realization 35. The method of realization 1, wherein the second quantity of the compound of Formula I is greater than the first quantity of the compound of Formula I. Realization 36. The method of realization 1, wherein the second quantity of the compound of Formula I is at least twice the first quantity of the compound of Formula I. Realization 37. The method of realization 1, wherein the second amount of compound of Formula I is approximately 70% by weight of the total amount of compound of Formula I. Realization 38. The method of realization 1, wherein the first amount of compound of Formula I is approximately 30% by weight of the total amount of compound of Formula I. Embodiment 39. The method of embodiment 1, wherein at least one step of the method further comprises detecting the O2 content of the mixture with an oxygen sensor. Realization 40. The method of embodiment 1, wherein the step of the method in which the mixture is heated occurs in the absence of O2. Realization 41. The method of realization 1, wherein the method produces less than approximately 0.5% by weight of O2. Realization 42. The method of realization 1, where the method does not produce O2. Embodiment 43. The method of embodiment 1, wherein at least one step of the method further comprises stirring the mixture. In one aspect, ethyl 3-bromo-1-(3-chloropyridin-2-yl)-1 / - / -pyrazol-5-carboxylate is prepared according to a method represented by Scheme 1. Scheme 1. Br Br frnacnn / zznz / E / YiAi In one respect, a compound of Formula II is prepared according to a method represented by Scheme 2. The R groups are as defined anywhere in this disclosure. Scheme 2. (Π) frnacnn / zznz / E / YiAi This aspect includes forming a mixture comprising a first quantity of a compound of Formula I, an oxidizing agent and an organic solvent, heating the mixture, adding an acid to the mixture, adding a second quantity of the compound of Formula I to the mixture and allowing the reaction of the mixture to complete. In one embodiment, the oxidizing agent is selected from hydrogen peroxide, organic peroxides, potassium persulfate, sodium persulfate, ammonium persulfate, potassium monopersulfate, sodium monopersulfate, potassium permanganate, and combinations thereof. In another embodiment, the oxidizing agent is potassium persulfate. In one embodiment, the oxidizing agent is present in the mixture in an amount ranging from approximately 1.0 eq to approximately 2.0 eq. In another embodiment, the oxidizing agent is present in the mixture in an amount ranging from approximately 1.3 eq to approximately 1.7 eq. In one embodiment, the oxidizing agent has a D50 particle size ranging from approximately 10 pm to approximately 200 pm. In another embodiment, the oxidizing agent has a D50 particle size ranging from approximately 20 pm to approximately 100 pm.In another embodiment, the oxidizing agent has a D50 particle size in the range of approximately 30 pm to approximately 80 pm. In another embodiment, the oxidizing agent has a D50 particle size in the range of approximately 40 pm to approximately 60 pm. In one embodiment, the solvent is selected from ethers, esters, aprotic organic solvents, and combinations thereof. In another embodiment, the solvent is an ether selected from tetrahydrofuran, 2-methyltetrahydrofuran, dioxane, and combinations thereof. In another embodiment, the solvent is an ester selected from ethyl acetate, isopropyl acetate, dimethyl carbonate, butyl acetate, and combinations thereof. In one embodiment, the solvent is an aprotic organic solvent selected from A / ,A / -dimethylformamide, dimethylacetamide, dimethyl sulfoxide, 1,3-dimethyl-2-imidazolidinone, acetonitrile, and combinations thereof. In another embodiment, the solvent is acetonitrile. In one embodiment, the first amount of the Formula I compound is approximately 5% by weight to approximately 40% by weight of the total amount of the Formula I compound. In another embodiment, the first amount of the Formula I compound is approximately 10% by weight to approximately 30% by weight of the total amount of the Formula I compound. In one embodiment, the acid is selected from inorganic acids, organic acids, and combinations thereof. In one embodiment, the acid is an organic acid selected from acetic acid, propanoic acid, p-toluenesulfonic acid, benzoic acid, and combinations thereof. In another embodiment, the acid is an inorganic acid selected from sulfuric acid, phosphoric acid, fuming sulfuric acid, hydrobromic acid, hydrochloric acid, and combinations thereof. In another embodiment, the acid is sulfuric acid. In one embodiment, the acid is present in the mixture in an amount ranging from approximately 0.05 eq to approximately 1.5 eq. In another embodiment, the acid is present in the mixture in an amount less than approximately 0.2 eq. In one embodiment, the step of the method in which the mixture is formed occurs at a temperature in the range of approximately 0 °C to approximately 60 °C. In another embodiment, the step of the method in which the mixture is formed occurs at a temperature in the range of approximately 15 °C to approximately 35 °C. In another embodiment, the step of the method in which the mixture is formed occurs at room temperature. In one embodiment, the step of the method in which the mixture is formed comprises stirring the mixture. In one embodiment, the step of the method in which the mixture is heated increases its temperature to a temperature in the range of approximately 50 °C to approximately 82 °C. In another embodiment, the step of the method in which the mixture is heated increases its temperature to a temperature in the range of approximately 55 °C to approximately 65 °C. In one embodiment, the step of the method in which the mixture is heated comprises stirring the mixture. In one embodiment, the step of the method in which a second quantity of the compound of Formula I is added to the mixture occurs at a temperature in the range of approximately 50 °C to approximately 82 °C. In another embodiment, the step of the method in which a second quantity of the compound of Formula I is added to the mixture occurs at a temperature in the range of approximately 50 °C to approximately 82 °C. In one embodiment, the step of the method in which a second quantity of the compound of Formula I is added comprises adding the second quantity of the compound of Formula I in discrete quantities. In one embodiment, the step of the method in which a second quantity of the compound of Formula I is added comprises continuously adding the second quantity of the compound of Formula I. In another embodiment, the step of the method in which a second quantity of the compound of Formula I is added comprises adding the second quantity of the compound of Formula I dropwise.In one embodiment, the step of the method in which a second quantity of the compound of Formula I is added occurs over a period of time in the range of approximately 3 hours to approximately 7 hours. In another embodiment, the step of the method in which a second quantity of the compound of Formula I is added occurs over a period of time in the range of approximately 3.5 hours to approximately 4.5 hours. In one embodiment, the step of the method in which a second quantity of the compound of Formula I is added comprises stirring the mixture. In one embodiment, the second amount of the compound of Formula I is greater than the first amount of the compound of Formula I. In another embodiment, the second amount of the compound of Formula I is at least twice the first amount of the compound of Formula I. In one embodiment, the second amount of the compound of Formula I is approximately 70% by weight of the total amount of the compound of Formula I. In another embodiment, the first amount of the compound of Formula I is approximately 30% by weight of the total amount of the compound of Formula I. In one embodiment, the second amount of the compound of Formula I is approximately 80% by weight of the total amount of the compound of Formula I. In another embodiment, the first amount of the compound of Formula I is approximately 20% by weight of the total amount of the compound of Formula I.In one embodiment, the second amount of the Formula I compound is approximately 90% by weight of the total amount of the Formula I compound. In another embodiment, the first amount of the Formula I compound is approximately 10% by weight of the total amount of the Formula I compound. In one embodiment, the second amount of the Formula I compound is approximately 95% by weight of the total amount of the Formula I compound. In another embodiment, the first amount of the Formula I compound is approximately 5% by weight of the total amount of the Formula I compound. In another embodiment, at least one step of the method further comprises detecting the O2 content of the mixture with an oxygen sensor. In one embodiment, the step of the method in which the mixture is heated occurs in the absence of O2. In one embodiment, the method produces less than approximately 0.5 wt% O2. In another embodiment, the method produces no O2. The low and / or undetectable O2 production increases the safety of the process. EXAMPLES Without going into further detail, it is believed that a person skilled in the art using the foregoing description can derive the full benefit from the present invention. Therefore, the following examples are to be interpreted as merely illustrative and not limiting disclosure in any way. The starting material for the following examples may not necessarily have been prepared by a particular preparation process, the procedure for which is described in other examples. It is also understood that any numerical range mentioned herein includes all values ​​from the lowest to the highest. For example, if a range is stated as 10-50, it is intended that values ​​such as 12-30, 20-40, or 30-50, etc., are expressly listed in this specification.These are only examples of what is specifically intended, and it should be considered that all possible combinations of numerical values ​​between the lowest and highest values ​​listed, both inclusive, are expressly indicated in this application. Comparative example 1. Method for monitoring oxygen generation. 153 g of potassium persulfate, 450 g of acetonitrile, and other starting materials are added to a 2 L flask equipped with a condenser, thermometer, dropping funnel, and nitrogen inlet tube. An oxygen sensor is installed on the condenser. The air in the reactor is replaced with nitrogen flowing at a rate of 0.55 L / min. When the oxygen sensor indicates an oxygen level of 0.0%, the mixture is heated to 60 °C. Then, 4.0 g of sulfuric acid are added to the mixture, and the mixture is maintained under reflux heating. Throughout the process, the oxygen level is monitored and recorded. Comparative example 2. Single addition of ethyl 3-bromo-1-(3-chloropyridin-2-yl)-4,5-dihydro-1 / - / -pyrazol-5-carboxylate at the beginning of the reaction. 174 g of potassium persulfate (1.6 eq), 780 g of 17% ethyl 3-bromo-1-(3-chloropyridine-2-1)-4,5-dihydro-1H-pyrazol-5-carboxylate in acetonitrile, and 40 g of concentrated sulfuric acid (1.0 eq) are added to a reactor. The reaction mixture is stirred and heated to 65 °C. The reaction exhibits obvious exothermic release and is therefore self-heated under reflux. The reaction mixture is held under reflux for a further 3–4 hours to complete the reaction. No oxygen is detected throughout the process. 350 g of water are added to the mixture at 70 °C, and the phase is split with potassium bisulfate to remove wastewater. After separating the solvent and subsequent crystallization, approximately 107 g of the dry product is obtained in the form of ethyl 3-bromo-1-(3-chloropyridin-2-yl)-1 / 7-pyrazol-5-carboxylate with an assay of approximately 96% and a yield of approximately 78%. Example 1. Addition of ethyl 3-bromo-1-(3-chloropyridin-2-yl)-4,5-dihydro-1 / - / -pyrazol-5-carboxylate at the beginning of the reaction and after the beginning of the reaction. 100 g of 40% ethyl 3-bromo-1-(3-chloropyridine-2-1)-4,5-dihydro-1 / - / -pyrazol-5-carboxylate in acetonitrile, 153 g of potassium persulfate (1.4 eq) and 450 g of acetonitrile are added to a reactor. The reaction mixture is stirred and heated to 60 °C, and then 4.0 g of concentrated sulfuric acid (0.1 eq) is added to the mixture. The reaction mixture is refluxed for 1 hour, and then 230 g of 40% ethyl 3-bromo-1-(3-chloropyridine-2-yl)-4,5-dihydro-1-pyrazol-5-carboxylate in acetonitrile are added dropwise over a period of 3–5 hours. After all materials have been added, the reaction mixture is refluxed for another 1–2 hours to complete the reaction. No oxygen is detected during the entire process. 350 g of water at 70 °C is added to the mixture, and the phase is split with potassium bisulfate to remove wastewater.After separating the solvent and subsequent crystallization, approximately 120 g of the dry product is obtained in the form of ethyl 3-bromo-1-(3chloropyridine-2-1l)-1H-pyrazol-5-carboxylate with an assay of approximately 97% and a yield of approximately 88%. This written description uses examples to illustrate the present disclosure, including the best manner, and also to enable any person skilled in the art to put the disclosure into practice, which includes the preparation and use of any devices or systems and the performance of any methods incorporated therein. The patentable scope of the disclosure is defined by the claims and may include other examples that occur to those skilled in the art. These other examples are intended to be within the scope of the claims if they have structural elements that do not differ from the literal language of the claims or if they include equivalent structural elements with insubstantial differences from the literal language of the claims.

Claims

1. A method for preparing a compound of Formula II, wherein R1 (Formula II) is selected from hydrogen and C1-C4 alkyl; and each of R2 - R7 is independently selected from hydrogen, halogen, C1-C4 alkyl and halogenated C1-C4 alkyl, the method comprising: I) forming a mixture comprising: A) a first amount of a compound of Formula I, wherein R1 (Formula I) is selected from hydrogen and C1-C4 alkyl; and each of R2 - R7 is independently selected from hydrogen, halogen, C1-C4 alkyl and halogenated C1-C4 alkyl; B) an oxidizing agent; and C) an organic solvent; II) heating the mixture; III) adding an acid to the mixture; IV) adding a second amount of the compound of Formula I to the mixture; and V) allowing the reaction of the mixture to complete.

2. The method of claim 1, wherein the oxidizing agent is selected from hydrogen peroxide, organic peroxides, potassium persulfate, sodium persulfate, ammonium persulfate, potassium monopersulfate, sodium monopersulfate, potassium permanganate, and combinations thereof.

3. The method of claim 1, wherein the oxidizing agent is present in the mixture in an amount in the range of approximately 1.0 eq to approximately 2.0 eq.

4. The method of claim 1, wherein the oxidizing agent has a D50 particle size in the range of approximately 10 pm to approximately 200 pm.

5. The method of claim 1, wherein the solvent is selected from ethers, esters, aprotic organic solvents and combinations thereof.

6. The method of claim 1, wherein the first amount of the compound of Formula I is approximately 5% by weight to approximately 40% by weight of the total amount of the compound of Formula I.

7. The method of claim 1, wherein the acid is selected from organic acids, inorganic acids, and combinations thereof.

8. The method of claim 1, wherein the acid is present in the mixture in an amount in the range of approximately 0.05 eq to approximately 1.5 eq.

9. The method of claim 1, wherein the acid is present in the mixture in an amount less than approximately 0.2 eq.

10. The method of claim 1, wherein the step of the method in which the mixture is formed occurs at a temperature in the range of approximately 0 °C to approximately 60 °C.

11. The method of claim 1, wherein the step of the method in which the mixture is heated increases the temperature of the mixture to a temperature in the range of approximately 50 °C to approximately 82 °C.

12. The method of claim 1, wherein the step of the method in which a second quantity of the compound of Formula I is added comprises adding the second quantity of the compound of Formula I in discrete quantities.

13. The method of claim 1, wherein the step of the method in which a second quantity of the compound of Formula I is added comprises continuously adding the second quantity to the compound of Formula I.

14. The method of claim 1, wherein the step of the method in which a second quantity of the compound of Formula I is added comprises the dropwise addition of the second quantity of the compound of Formula I. frnacnn / zznz / E / YiAi 15. The method of claim 1, wherein the step of the method in which a second quantity of the compound of Formula I is added occurs during a period of time in the range of approximately 3 hours to approximately 7 hours.

16. The method of claim 1, wherein the second quantity of the compound of Formula I is greater than the first quantity of the compound of Formula I.

17. The method of claim 1, wherein the second quantity of the compound of Formula I is at least twice the first quantity of the compound of Formula I.

18. The method of claim 1, wherein the second quantity of the compound of Formula I is at least 70% by weight of the total quantity of the compound of Formula I.

19. The method of claim 1, wherein the first amount of the compound of Formula I is less than 30% by weight of the total amount of the compound of Formula I.

20. The method of claim 1, wherein at least one step of the method further comprises stirring the mixture.