The present invention relates to a method for the metal-free preparation of a biaryl compound by a photosplicing reaction and its use in the preparation of chemical compounds, preferably of active ingredients e.g. in the fields of pharmaceuticals and agrochemicals. In particular, it refers to a method for the regiocontrolled preparation of a biaryl compound of formula (I): Ar—Ar′ by photochemically reacting a precursor compound of formula (II): Ar—L—Ar′ to form a biaryl compound of general formula: Ar—L—Ar′(II).fwdarw.Ar—Ar′ (I) wherein Ar and Ar′, independently of each other, represent an unsubstituted or substituted C6-C20 aryl group or a heteroaryl group with 5-20 ring atoms selected from carbon, nitrogen, oxygen and sulfur, and L represents a group —X—Y—Z— as defined herein. The biaryl compounds are generally suitable as intermediates or key building blocks in a very broad spectrum of organic chemical syntheses and their respective utilities. Their use within the field of synthesis of active ingredients is an aspect of the invention, and their use in the preparation of pharmaceutically active ingredients is particularly preferred.

Some embodiments of the invention include inventive catalysts (e.g., catalysts of Formula (I)). Other embodiments include compositions comprising the inventive catalysts. Some embodiments include methods of using the inventive catalysts (e.g., in hydrofluorination of an organic compound). Further embodiments include methods for making the inventive catalysts. Additional embodiments of the invention are also discussed herein.

Some embodiments of the invention include inventive catalysts (e.g., catalysts of Formula (I)). Other embodiments include compositions comprising the inventive catalysts. Some embodiments include methods of using the inventive catalysts (e.g., in hydrofluorination of an organic compound). Further embodiments include methods for making the inventive catalysts. Additional embodiments of the invention are also discussed herein.

A preparative method for carboxylic acids is disclosed in the present invention. The method is characterized in that: compounds (II) are reacted in the presence of hydrogen peroxide and base to produce target products (I), as represented by the following reaction scheme: wherein R.sup.1 is aryl, pyridyl, pyrimidyl, pyridazinyl, pyrazinyl, benzothienyl, benzofuranyl, quinolinyl, isoquinolinyl, thiadiazolyl, C.sub.1-6 alkyl, C.sub.3-6 cycloalkyl, C.sub.2-6 alkenyl, C.sub.2-6 alkynyl and hydrogen; R.sup.2 is alkoxycarbonyl, alkylaminocarbonyl, aminocarbonyl, alkylthiolcarbonyl, cyano, sulfonyl, sulfinyl, carbonyl, aldehyde, carboxyl, nitro, alkyl and hydrogen; R.sup.3 is alkoxycarbonyl, alkyl amido carbonyl, aminocarbonyl, cyano, sulfonyl, sulfinyl, carbonyl, carboxyl and nitro. The present invention has the following main benefits: cheap and readily available starting materials, safe processes, high yield, good quality, which facilitates industrial production.

A regioselective N-Heterocyclic Carbene (NHC) catalyzed one step process for high yield synthesis of α-acyloxy carbonyl compounds is disclosed. ##STR00001##

A regioselective N-Heterocyclic Carbene (NHC) catalyzed one step process for high yield synthesis of α-acyloxy carbonyl compounds is disclosed. ##STR00001##

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.

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.

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.

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.