Dow Agrosciences LLC

Dow Global Technolgoies LLC

Corteva Agriscience LLC

Dowelanco

Ronald B Leng

Siyu Tu

James William Ringer

Jason S Fisk

Xiaoyong Li

Jossian Oppenheimer

Shawn D Feist

Reetam Chakrabarti

Douglas C Greminger

Abraham D Schuitman

Mark Muehlfeld

Mark A Nitz

Robert S Bauman

Gregory T Whiteker

Noormohamed Mohamed Niyaz

Chunming Zhang

Jeremy Kister

Rong Ling

Eric W Otterbacher

Nicholas Martin Irvine

David Bruce Gorman

Herbert Nathan Praay

Jayachandran Devaraj

Nugzar Ghavtadze

Aaron A Shinkle

Melissa Lee

William Jack Kruper, Jr

Daniel J Murray

William Gerald Stobby

John Wesley Hull, Jr

Yiyong He

Ted A Morgan

Mark Alan Barger

William J Kruper

Shari Kram

Xinrui Yu

Bruce A King

Daniel A Beaudoin

Avani Maulik Patel

James R McConnell

Eung Kyu Kim

Brian D Scherzer

Megan E Donaldson

Brian Murdoch

Julie L Maurer

Mark W Zettler

David J Couling

Derrick G Wetters

Todd William Toyzan

Richard E Tobey

Rongrong (Mandy) Lin

Rongrong [mandy] Lin

Douglas C Bland

James W Ringer

Jr John Wesley Hull

Ted Andrew Morgan

Daniel Joseph Murray

Douglas Carl Greminger

Brian David Scherzer

Derrick Godfrey Wetters

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

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

A method of preparing benzyl 4-amino-3-chloro-5-fluoro-6-(4-chloro-2-fluoro-3-methoxyphenyl)picolinate (I) from benzyl 4,5-difluoro-6-(4-chloro-2-fluoro-3-methoxyphenyl)picolinate (II) is described. The method includes the use of amination and chlorination process steps to provide the compound of Formula I.

Method of preparing benzyl 4-amino-3-chloro-5-fluoro-6-(4-chloro-2-fluoro-3-methoxyphenyl)picolinate

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

Cyhalofop is prepared by coupling 2-(4-hydroxyphenoxy)propionic acid and 3,4-difluorobenzonitrile with base in a polar aprotic solvent in the presence of a phase-transfer catalyst.

Process for the manufacture of R-(+)-2-(4-(4-cyano-2-fluorophenoxy)phenoxy)propionic acid esters

Brominated organic polymer solutions from a bromination reaction are devolatilized in a devolatilizing extruder. A starting organic polymer is brominated in solution to form a brominated polymer solution. This solution is combined with a second thermoplastic polymer to form a concentrated solution. The solvent and other volatile compounds are removed from the concentrated solution in a devolatilizing extruder to form a devolatilized polymer blend.

Melt devolatilization extrusion processs

A process to produce polycarbamate comprising providing urea in liquid form; and adding the urea in liquid form to a polyol in a reduced gradient profile to form polycarbamate product is provided. Also provided are: (a) a reaction product of the process and (b) an apparatus for operating the process.

Process to produce polycarbamate using a gradient feed of urea

Unsaturated organic compounds are brominated with a quaternary ammonium tribromide or a quaternary phosphonium tribromide, especially when the bromination is conducted in a chlorinated solvent. A quaternary ammonium or quaternary phosphonium monobromide salt is produced in the reaction, together with some amount of quaternary ammonium or quaternary phosphonium monochloride salt. The monochloride salt is converted to the corresponding quaternary ammonium monobromide salt by reacting it with a source of bromide ions. The monobromide salt is then reacted with bromine to regenerate the quaternary ammonium or phosphonium tribromide, which is recycled into the bromination reaction. This process reduces the amount of chlorine that is incorporated into the brominated product.

Process for brominating unsaturated organic compounds with removal of quaternary ammonium or quaternary phosphonium monochlorides

A polybutadiene brominating method uses a quaternary ammonium tribromide as the brominating agent. The brominating is performed in solution, and dual extractions recover the spent brominating agent and recombine it with fresh bromine to regenerate an active tribromide. Solvent and aqueous extraction streams can be purified and recycled as needed.

Process for brominating butadiene/vinyl aromatic copolymers

Butadiene copolymers are brominated in solution using bromine as the brominating agent. The bromination is conducted in the presence of an excess of an aliphatic alcohol, relative to the amount of bromine that is used. The bromination proceeds rapidly at mild conditions, and is selective in that only aliphatic carbon-carbon double bonds are brominated, and unwanted bromination at tertiary carbon atoms is largely or completely avoided. The resulting brominated polymers are characterized in having very good thermal stability.

Cyhalofop esters are prepared by coupling 2-(4-hydroxyphenoxy)-propionic acid with 3,4-difluorobenzonitrile with base in a polar aprotic solvent (optionally including a phase-transfer catalyst), alkylating with alkyl halide, removing the polar aprotic solvent (optionally using cyhalofop ester as a flux), removing salt by aqueous extraction of molten cyhalofop ester without a solvent, and removing residual water by heating under reduced pressure.

Brominated polybutadiene polymers are recovered from a bromination reaction solution by forming the solution into droplets, thermally stripping the solvent from the droplets, and then washing the resulting particles. The washed particles are then recovered from the washing liquid. The droplets can be dispersed into a gaseous medium such as air and then transferred into a nonsolvent liquid for washing, or can be formed directly into the nonsolvent liquid. The process forms a particulate polymer material that is easily filterable and has low levels of volatile impurities and inorganic salts. Brominated polybutadiene polymers recovered in this manner are often very thermally stable.

Process for recovering brominated butadiene polymers from solution

Chloropyrimidine compounds, such as 4,6-dichloro-2-ethoxypyrimidine, were prepared in good yield and good purity from the corresponding hydroxypyrimidine compounds in the absence of organic solvents and with a reduced amount of phosphorus oxychloride by carrying out the reaction in the presence of a trialkylamine compound and phosphorus trichloride. The additions of hydroxypyrimidine compound and trialkylamine compound could be made in segments. The chloropyrimidine compounds produced were recovered in an improved manner by adding chlorine to convert the chlorophosphoric acid by-products and phosphorus trichloride to phosphorus oxychloride, diluting the mixture with additional chloropyrimidine compound and removing the phosphorus oxychloride by distillation, combining the residue with water and a base, distilling the trialkylamine compound from the resulting mixture, and removing the aqueous phase.

Chloropyrimidine process

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Ronald B Leng