Reilly Industries, Inc.

Reilly Tar and Chemical Corporation

Eric F Scriven

James G Keay

Gerald L Goe

Ramiah Murugan

Tony Yantao Zhang

Donald W McQuigg

Edward E Sowers

James R Stout

Michael L Prunier

Steven J Quimby

Charles R Hopper

William R Roder

L Mark Huckstep

Joel R Calvin

Ernest Crowe

Marudai Balasubramanian

Joe W Curtis

Lowell M Huckstep

Described are preferred processes for producing extrusion-granulated supernucleophilic 4-amino-substituted pyridine catalysts, and granular products obtainable therefrom. Also described are preferred activation-substitution-deactivation processes for producing 4-aminopyridine compounds, which involve the use of acrylic acid or acrylamide or analogs thereof for activation, and substitution steps conducted under mild basic conditions in an excess of the amine reagent for 4-substitution. Such processes provide improved reacted masses which are more readily processed to recover the products in pure, heat-stable form. Further, described are processes for preparing 4-substituted-pyridines via pyridine betaines.

Supernucleophilic 4-substituted-pyridine catalysts, and processes useful

Described are preferred processes for preparing heterocycles having one or more nitrogen and/or oxygen heteroatoms, utilizing a 1,3-dihalopropene as an effective 3-carbon fragment. Preferred processes yield pyridines, quinolines, oxazoles, pyrimidines and pyrazoles, depending upon the other reactant or reactants utilized with the 1,3-dihalopropene.

Preparation of heterocycles using 1,3-dihalopropenes

H.sub.2 O.sub.2 -catalyzed polymerizations for linear polyvinylpyridines

Disclosed are preferred processes for producing .alpha.-2-pyridyl.alpha.-aryl carbinol or .alpha.-4-pyridyl .alpha.-aryl carbinol compounds.

Processes for producing .alpha.-pyridyl carbinols

Described are preferred pitches which comprise a blend of coal tar pitch, petroleum pitch and gilsonite pitch, and preferred processes and compositions which can be used to form such pitches. The pitches have substantially reduced contents of polyaromatic hydrocarbons (PAH's) relative to standard coal tar pitches, and are thus more favorable from health, safety and environmental standpoints.

Low PAH pitch and process for same

Described are preferred processes for preparing 2-halo-5-substituted pyridine compounds. Preferred processes can be conducted in a one-step, one-pot fashion, and involve the reaction of a formamide and a halogenating agent with a nitrile such as cis-2-pentenonitrile or with a combination of reactants including an aldehyde such as n-propionaldehyde and a nitrile or an amide. Preferred processes provide for convenient and advantageous preparations of 2-chloro-5-methylpyridine, which serves as an intermediate to important insecticidal compounds.

Process for preparing 2-halo-5-substituted pyridines

Disclosed are preferred processes for the preparation of 2-halo-nicotinic acid derivatives of formula (IV): ##STR1## by cyclocondensation of a 4-halo-4-cyanocarbonyl compound of formula (III): ##STR2## wherein X is Cl or Br; Y is a carbonyl group and R.sup.1, R.sup.2 and R.sup.3 are each, independently, H, Cl, Br or an organic radical. Further preferred aspects include the preparation of the above-noted 4-halo-4-cyanocarbonyl compound via Michael addition of a 2-halonitrile with an .alpha.,.beta.-unsaturated aldehyde or ketone, and the preparation of the 2-halonitrile by redistribution of halogen between a 2,2-dihalonitrile and a parent nitrile.

Processes for producing 2-Halo-nicotinic acid derivatives and precursors

Processes for preparing pyridyl-substituted hydrazoles, dihydrothiadiazones or aminotriazinones by reaction of iminopyridines preformed in situ or otherwise with hydrazides or carbazides, or their sulfur counterparts, or with aminotriazinones.

Preparation of hydrazones, dihydrothiadiazoles and triazinones

Imines are synthesized by the hydrogenation of pyridinecarbonitriles with amines in the presence of a rhodium-loaded catalyst. The resulting imines are stable and may be transiminated and then hydrogenated to form selected secondary amine products or may be hydrolyzed to aldehydes. Further, a very useful class of unsymmetrical secondary amines represented by the formula RCH.sub.2 NHAr (in which R is not aliphatic and Ar is aromatic and not attached to R), which has heretofore been accessible only with some difficulty, can be synthesized by processes herein disclosed utilizing the reductive intermolecular coupling of nitriles and primary aromatic amines.

Processes for the synthesis of unsymmetrical secondary amines

Described are preferred processes for producing linear polyvinylpyridines. The processes involve the use of hydrogen peroxide to initiate polymerization of vinylpyridine monomers in an alcohol/water solvent. Processes of the invention provide good reaction rates and conversions, and are particularly advantageous in achieving control of the M.sub.w 's of the final product polymers.

H2O2-catalyzed solution polymerizations for linear polyvinylpyridines

Described are unique polymerization processes for preparing linear polyvinylpyridine polymers as well as unique linear polyvinylpyridine polymer compositions. The processes involve the use of an alkylpyridine anion as an anionic polymerization catalyst and result in linear polyvinylpyridines having alkylpyridine end groups homologous to the pendant pyridines of the polymer. Processes of the invention are particularly advantageous in preparing relatively low molecular weight linear polyvinylpyridines without the need to use large amounts of catalyst to achieve the same.

Linear polyvinylpyridine polymers and processes

Processes for the synthesis of imines, aldehydes, and unsymmetrical

Disclosed are preferred processes for preparing a 2-halo-5-halomethylpyridine compound. The preferred processes involve cyclocondensing a 2-halo-2-halomethyl aldehyde or ketone of the formula (II) ##STR1## to form a 2-halo-2-halomethylpyridine compound of the formula (III) ##STR2## wherein X is Cl or Br, Y is a cyano group or an aminocarbonyl group, and R, R.sup.1, R.sup.2 and R.sup.3 are, independently, H or an organic radical which does not interfere with the cyclocondensation.

Process for preparing 2-halo-5-halomethylpyridines

A cross-linked polymer-supported 4-(N-benzyl-N-methylamino) pyridine material and process for its preparation in high yield and having effective physical and catalytic properties. The polymer supported catalyst is characterized by the suspension copolymerization of an organic phase containing the corresponding vinyl-substituted pyridine monomer, a styrene monomer, and a suitable cross-linking agent and free radical-generating catalyst in the presence of an aqueous phase containing a cellulose ether derivative as the stabilizing agent. A purified acid salt of the vinyl-substituted pyridine monomer useful in polymerizations and stable for storage as either a solid or an aqueous solution.

4-(N-benzyl-N-methylamino)pyridine acid salts and use in preparation of

A cross-linked polymer-supported 4-(N-benzyl-N-methylamino) pyridine material and process for its preparation in high yield and having effective physical and catalytic properties. The polymer-supported catalyst is characterized by the suspension copolymerization of an organic phase containing the corresponding vinyl-substituted pyridine monomer, a styrene monomer, and a suitable cross-linking agent and free radical-generating catalyst in the presence of an aqueous phase containing a cellulose ether derivative as the stabilizing agent. A purified acid salt of the vinyl-substituted pyridine monomer useful in polymerizations and stable for storage as either a solid or an aqueous solution.

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Greenwood, IN, United States of America

Eric F Scriven