Abstract: The present disclosure relates to improved methods of synthesizing 6-aryl-4-aminopicolinates, such as arylalkyl and alkyl 4-amino-3-chloro-6-(4-chloro-2-fluoro-3-methoxyphenyl)pyridine-2-carboxylates.

Abstract: The present technology relates to processes, mixtures and intermediates useful for making picolinamide fungicides. The picolinamide compounds are prepared by processes that include coupling together a 4-methoxy-3-acyloxypicolinic acid with key 2-amino-L-alaninate esters derived from substituted 2-phenylethanols.

Abstract: Methods for preparing 5-fluoro-6-(bromo or chloro)picloram analogs, or derivatives thereof, from picloram acid, picloram ester, or the nitrile analog of picloram are provided. The methods include chemical process steps that: (1) introduce a phthaloyl group onto the 4-amino substituent of picloram acid, picloram ester, or the nitrile analog of picloram, (2) add 2 fluorine atoms at the 5,6-positions of the pyridine ring using halex fluorination chemistry, (3) remove the phthaloyl group, hydrolyze the ester or nitrile substituent, and add chlorine or bromine to the 6-position by treatment with an acid and water, and finally, (4) esterify the 5-fluoro-6-(bromo or chloro)picloram acid produced in step (3) to a 5-fluoro-6-(bromo or chloro)picloram ester.

Abstract: Methods for preparing 5-fluoro-6-(bromo or chloro)picloram analogs, or derivatives thereof, from picloram acid, picloram ester, or the nitrile analog of picloram are provided. The methods include chemical process steps that: (1) introduce a phthaloyl group onto the 4-amino substituent of picloram acid, picloram ester, or the nitrile analog of picloram, (2) add 2 fluorine atoms at the 5,6-positions of the pyridine ring using halex fluorination chemistry, (3) remove the phthaloyl group, hydrolyze the ester or nitrile substituent, and add chlorine or bromine to the 6-position by treatment with an acid and water, and finally, (4) esterify the 5-fluoro-6-(bromo or chloro)picloram acid produced in step (3) to a 5-fluoro-6-(bromo or chloro)picloram ester.

Abstract: A method for preparing phosphine-borane complexes from aryldihalophosphine includes mixing sodium borohydride, a solvent having at least 50 vol % glycol ethers, and the aryldihalophosphine to obtain a solution. The solution is maintained at a reaction temperature for a duration of time to obtain the phosphine-borane complexes. The solvent may include 1,2-dimethoxyethane and tetrahydrofuran. A ratio of tetrahydrofuran to 1,2-dimethoxyethane in the solvent may be from 0.1:1.0 to 2.5:1.0.

Abstract: Methods for preparing 5-fluoro-6-(bromo or chloro)picloram analogs, or derivatives thereof, from picloram acid, picloram ester, or the nitrile analog of picloram are provided. The methods include chemical process steps that: (1) introduce a phthaloyl group onto the 4-amino substituent of picloram acid, picloram ester, or the nitrile analog of picloram, (2) add 2 fluorine atoms at the 5,6-positions of the pyridine ring using halex fluorination chemistry, (3) remove the phthaloyl group, hydrolyze the ester or nitrile substituent, and add chlorine or bromine to the 6-position by treatment with an acid and water, and finally, (4) esterify the 5-fluoro-6-(bromo or chloro)picloram acid produced in step (3) to a 5-fluoro-6-(bromo or chloro)picloram ester.

Abstract: A method for forming 1,3,5,7-tetraalkyl-6-(2,4-dimethoxyphenyl)-2,4,8-trioxa-6-phosphaadamantane includes obtaining a solution comprising an ethereal solvent and an aluminum hydride, adding dichloro(2,4-dimethoxyphenyl)phosphine to the solution to produce 2,4-dimethoxyphenylphosphine, and reacting the 2,4-dimethoxyphenylphosphine with an acidic mixture comprising diones to produce 1,3,5,7-tetraalkyl-6-(2,4-dimethoxyphenyl)-2,4,8-trioxa-6-phosphaadamantane. The solution has a temperature from IN greater than ?20 C. to 50 C. throughout the method. Another method for forming 1,3,5,7-tetraalkyl-6-(2,4-dimethoxyphenyl)-2,4,8-tri-oxa-6-phosphaadamantane includes obtaining dichloro(2,4-dimethoxyphenyl)phosphine, forming 2,4-dimethoxyphenylphosphine by adding the dichloro(2,4-dimethoxyphenyl)phosphine to a solution comprising at least one solvent and an aluminum hydride, reacting the 2,4-dimethoxyphenylphosphine with a mixture to produce 1,3,5,7-tetraalkyl-6-(2,4-dimethoxyphenyl)-2,4,8-trioxa-6-phosphaadamantane.

Abstract: Improved methods of synthesizing 6-aryl-4-aminopicolinates, such as arylalkyl and alkyl 4-amino-3-chloro-6-(4-chloro-2-fluoro-3-methoxyphenyl)pyridine-2-carboxylates and arylalkyl and alkyl 4-amino-3-chloro-5-fluoro-6-(4-chloro-2-fluoro-3-methoxyphenyl)pyridine-2-carboxylates, are described herein. The improved methods include a direct Suzuki coupling step, which eliminates the protection/de-protection steps in the current chemical process, and therefore eliminates or reduces various raw materials, equipment and cycle time as well as modification of other process conditions including use of crude AP, use of ABA-diMe, and varying pH, catalyst concentration, solvent composition, and/or workup procedures. This includes synthesis of 2-aryl-6-aminopyrimidine-4-carboxylates.

Abstract: Improved methods of synthesizing 6-aryl-4-aminopicolinates, such as arylalkyl and alkyl 4-amino-3-chloro-6-(4-chloro-2-fluoro-3-methoxyphenyl)pyridine-2-carboxylates and arylalkyl and alkyl 4-amino-3-chloro-5-fluoro-6-(4-chloro-2-fluoro-3-methoxyphenyl)pyridine-2-carboxylates, are described herein. The improved methods include a direct Suzuki coupling step, which eliminates the protection/de-protection steps in the current chemical process, and therefore eliminates or reduces various raw materials, equipment and cycle time as well as modification of other process conditions including use of crude AP, use of ABA-diMe, and varying pH, catalyst concentration, solvent composition, and/or workup procedures. This includes synthesis of 2-aryl-6-aminopyrimidine-4-carboxylates.

Abstract: A method for forming 1,3,5,7-tetraalkyl-6-(2,4-dimethoxyphenyl)-2,4,8-trioxa-6-phosphaadamantane includes obtaining a solution comprising an ethereal solvent and an aluminum hydride, adding dichloro(2,4-dimethoxyphenyl)phosphine to the solution to produce 2,4-dimethoxyphenylphosphine, and reacting the 2,4-dimethoxyphenylphosphine with an acidic mixture comprising diones to produce 1,3,5,7-tetraalkyl-6-(2,4-dimethoxyphenyl)-2,4,8-trioxa-6-phosphaadamantane. The solution has a temperature from IN greater than ?20 C. to 50 C. throughout the method. Another method for forming 1,3,5,7-tetraalkyl-6-(2,4-dimethoxyphenyl)-2,4,8-tri-oxa-6-phosphaadamantane includes obtaining dichloro(2,4-dimethoxyphenyl)phosphine, forming 2,4-dimethoxyphenylphosphine by adding the dichloro(2,4-dimethoxyphenyl)phosphine to a solution comprising at least one solvent and an aluminum hydride, reacting the 2,4-dimethoxyphenylphosphine with a mixture to produce 1,3,5,7-tetraalkyl-6-(2,4-dimethoxyphenyl)-2,4,8-trioxa-6-phosphaadamantane.

Abstract: Improved methods of synthesizing 6-aryl-4-aminopicolinates, such as arylalkyl and alkyl 4-amino-3-chloro-6-(4-chloro-2-fluoro-3-methoxyphenyl)pyridine-2-carboxylates and arylalkyl and alkyl 4-amino-3-chloro-5-fluoro-6-(4-chloro-2-fluoro-3-methoxyphenyl)pyridine-2-carboxylates, are described herein. The improved methods include a direct Suzuki coupling step, which eliminates the protection/de-protection steps in the current chemical process, and therefore eliminates or reduces various raw materials, equipment and cycle time as well as modification of other process conditions including use of crude AP, use of ABA-diMe, and varying pH, catalyst concentration, solvent composition, and/or workup procedures. This includes synthesis of 2-aryl-6-aminopyrimidine-4-carboxylates.

Abstract: Improved methods of synthesizing 6-aryl-4-aminopicolinates, such as arylalkyl and alkyl 4-amino-3-chloro-6-(4-chloro-2-fluoro-3-methoxyphenyl)pyridine-2-carboxylates and arylalkyl and alkyl 4-amino-3-chloro-5-fluoro-6-(4-chloro-2-fluoro-3-methoxyphenyl)pyridine-2-carboxylates, are described herein. The improved methods include a direct Suzuki coupling step, which eliminates the protection/de-protection steps in the current chemical process, and therefore eliminates or reduces various raw materials, equipment and cycle time as well as modification of other process conditions including use of crude AP, use of ABA-diMe, and varying pH, catalyst concentration, solvent composition, and/or workup procedures. This includes synthesis of 2-aryl-6-aminopyrimidine-4-carboxylates.

Abstract: Improved methods of synthesizing 6-aryl-4-aminopicolinates, such as arylalkyl and alkyl 4-amino-3-chloro-6-(4-chloro-2-fluoro-3-methoxyphenyl)pyridine-2-carboxylates and arylalkyl and alkyl 4-amino-3-chloro-5-fluoro-6-(4-chloro-2-fluoro-3-methoxyphenyl)pyridine-2-carboxylates, are described herein. The improved methods include a direct Suzuki coupling step, which eliminates the protection/de-protection steps in the current chemical process, and therefore eliminates or reduces various raw materials, equipment and cycle time as well as modification of other process conditions including use of crude AP, use of ABA-diMe, and varying pH, catalyst concentration, solvent composition, and/or workup procedures. This invention was expanded to include synthesis of 2-aryl-6-aminopyrimidine-4-carboxylates.

Abstract: Improved methods of synthesizing 6-aryl-4-aminopicolinates, such as arylalky and alkyl 4-amino-3-chloro-6-(4-chloro-2-fluoro-3-methoxyphenyl)pyridine-2-carboxylates and arylalkyl and alkyl 4-amino-3-chloro-5-fluoro-6-(4-chloro-2-fluoro-3-methoxyphenyl)pyridine-2-carboxylates, are described herein. The improved methods include a direct Suzuki coupling step, which eliminates the protection/de-protection steps in the current chemical process, and therefore eliminates or reduces various raw materials, equipment and cycle time as well as modification of other process conditions including use of crude AP, use of ABA-diMe, and varying pH, catalyst concentration, solvent composition, and/or workup procedures. This invention was expanded to include synthesis of 2-aryl-6-aminopyrimidine-4-carboxylates.