Synthesis of vicinal difluoro aromatics and intermediates thereof

A method for making aromatic compounds having two vicinal fluorine atoms comprising:

• (a) mixing an electrophilic fluorinating agent with a solution or suspension of a hydroxy aromatic compound in a polar aprotic solvent to form a difluoroketone derivative of an aromatic compound, said hydroxy aromatic compound having one, two or three rings, said rings being separate or fused and said rings optionally containing one or more heteroatoms and one or more substitutions in addition to hydroxy, said difluoroketone derivative having both fluorine atoms on a carbon vicinal to the ketone;
• (b) mixing a deoxofluorinating agent with the difluoroketone derivative of (a) in a second solvent to form a tetrafluoro derivative of an aromatic compound;
• and
• (c) mixing the tetrafluoro derivative of an aromatic compound of (b) with a reducing agent in a presence of a base to form an aromatic compound containing two vicinal fluorine atoms.

A method for making a vicinal difluoro halogenated aromatic compound, said method comprising:

• (a) mixing an electrophilic fluorinating agent with a solution or suspension of a halogen substituted hydroxy aromatic compound in a polar aprotic solvent to form a difluoroketone derivative of the halogen substituted hydroxy aromatic compound, said halogen substituted hydroxy aromatic compound having one, two or three rings, said rings being separate or fused and said rings optionally containing one or more heteroatoms and one or more substitutions in addition to hydroxy and halogen, said difluoroketone derivative having both fluorine atoms on a vicinal carbon adjacent to a ketone carbon;
• (b) mixing a deoxofluorinating agent with the difluoroketone derivative in a presence of a solvent to form a tetrafluoro derivative of the halogen substituted hydroxy aromatic compound, said tetrafluoro derivative having two fluorine atoms on each of the vicinal carbons;
• and
• (c) mixing the tetrafluoro derivative of the halogen substituted aromatic compound with a reducing agent in a presence of a base for a reaction time sufficient to form the vicinal difluoro halogenated aromatic compound containing two vicinal fluorine substituents and at least one additional halogen substituent, wherein the reducing agent is used in a reducing agent effective amount sufficient to retain the at least one additional halogen substituent.