Dow Agrosciences LLC

Corteva Agriscience LLC

Dow Global Technolgoies LLC

Siyu Tu

Ronald B Leng

Xiaoyong Li

Gregory T Whiteker

Jossian Oppenheimer

James William Ringer

Shawn D Feist

Reetam Chakrabarti

Jason S Fisk

Mark Muehlfeld

Robert S Bauman

Mark A Nitz

Noormohamed Mohamed Niyaz

Chunming Zhang

Jeremy Kister

Rong Ling

Nicholas Martin Irvine

Abraham D Schuitman

Jayachandran Devaraj

John Robert Briggs

Jeffrey S Nissen

Yiyong He

Nugzar Ghavtadze

Aaron A Shinkle

Melissa Lee

Andrew M Camelio

Nicholas R Babij

Jessica L Klinkenberg

Yan Hao

Robert David Grigg

Xiaoyun Chen

Rongrong (Mandy) Lin

Elizabeth O Mccusker

Neeraj Sane

Daniel W Klosowski

Meng Guo

Rongrong [mandy] Lin

Tyler Davis

Matthew Robinson

Patrick T McGough

Haoquan Li

Matthew S Remy

James W Ringer

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.

Process for synthesis of picolinamides

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.

Preparation of halogen analogs of picloram

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 &#x2212;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. The mixture includes an acid selected from the group consisting of Lewis acids, sulfonic Bronsted acids, and mixtures thereof, an aromatic or non-aromatic hydrocarbons; and acetylacetone.

Methods for forming 1,3,5,7-tetraalkyl-6-(2,4-dimethoxyphenyl)-2,4,8-trioxa-6-phosphaadamantane

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.

Synthesis of 6-aryl-4-aminopicolinates and 2-aryl-6-aminopyrimidine-4-carboxylates by direct suzuki coupling

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.

Synthesis of 6-aryl-4-aminopicolinates and 2-aryl-6-aminopyrimidine-4-carboxylates by direct Suzuki coupling

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Midland, MI, United States of America

Siyu Tu