Method of Synthesis of Arylsulfur Trifluorides and Use as in situ Deoxofluorination Reagent

A method of using 2,6-dimethyl-4-t-butylphenylsulfur trifluoride as in situ deoxofluorination reagent comprising the steps of:

• a. first providing a quantity of suitable solvent, an excess quantity of dried alkali metal fluoride, a quantity of bis(2,6-dimethyl-4-t-butylphenyl)disulfide, an excess quantity of bromine, and a quantity of suitable aldehyde or ketone;
• b. allowing said quantity of bis(2,6-dimethyl-4-t-butylphenyl)disulfide to react with said excess quantity of bromine and said excess quantity of dried alkali metal fluoride in said quantity of suitable solvent;
• c. allowing the reaction of step b to proceed for a two hour period at room temperature;
• d. adding said quantity of aldehyde or ketone;
• e. heating mixture to reflux until completion.

A method of using 2,4,6-trimethylphenylsulfur trifluoride as in situ deoxofluorination reagent comprising the steps of:

• a. first providing a quantity of suitable solvent, an excess quantity of dried alkali metalfluoride, a quantity of mesityl disulfide, an excess quantity of bromine, and a quantity of suitable substrate for deoxofluorination;
• b. allowing said quantity of mesityl disulfide to react with said excess quantity of bromine and said excess quantity of dried alkali metal fluoride in said quantity of suitable solvent;
• c. allowing the reaction of step b to proceed for a period of time at room temperature;
• d. adding said quantity of suitable substrate for deoxofluorination;
• e. heating mixture to reflux for until completion.

A method of preparing a compound of the formula (I)

• comprising the step of reacting a compound of formula (Ia) with a quantity of Bromine and an alkali metal fluoride,
• in which:
• R1α and R1β are independently a hydrogen atom or a primary or secondary alkyl group having from one to eight carbon atoms;
• R2α and R2β are independently a hydrogen atom or a primary, secondary, or tertiary alkyl group having from one to eight carbon atoms;
• R3 is a hydrogen atom, a halogen atom, or a primary, secondary, or tertiary alkyl group having from one to eight carbon atoms;
• wherein, when R3 is a hydrogen atom, at least two of R1α, R1α, R2α, and R2β are primary, secondary, or tertiary alkyl groups having from one to eight carbon atoms and the others are a hydrogen atom, and wherein, when R3 is a primary alkyl group having from one to eight carbon atoms, at least one of R1α, R1β, R2α, and R2β is a primary, secondary, or tertiary alkyl group having from one to eight carbon atoms and the others are a hydrogen atom, and wherein when at least two of R2α, R2β, and R3 are tertiary alkyl groups, the tertiary alkyl groups are non-adjacent.

A method of preparing a compound of formula (II):

• comprising the step of reacting a compound of formula (IIa) with Bromine and an alkali metal fluoride,
• in which:
• R1α and R1β are independently a hydrogen atom or a primary or secondary alkyl group having from one to eight carbon atoms;
• R3 is a hydrogen atom, a halogen atom, or a primary, secondary, or tertiary alkyl group having from one to eight carbon atoms;
• wherein when R3 is a hydrogen atom, R1α and R1β are independently a primary or secondary alkyl group having from one to eight carbon atoms, and wherein, when R3 is a primary alkyl group having one to eight carbon atoms, at least one of R1α and R1β is a primary or secondary alkyl group having from one to eight carbon atoms and the other is a hydrogen atom.