Anhydrous fluoride salts and reagents and methods for their production

1. A method of synthesizing an anhydrous fluoride salt having the formula [Q n M] x+ F x − , the method comprising a nucleophilic substitution of a fluorinated aromatic or fluorinated unsaturated organic compound with a salt having the formula [Q n M] x+ A x − in an inert polar, aprotic solvent wherein:

M is nitrogen or phosphorus;

Q groups are independently selected from the group consisting of an alkyl, an alkenyl, an alkynyl, an aryl, a heteroaryl, and a polymer;

n is an integer such that said [Q n M] carries at least one formal positive charge;

x is an integer defining the number of formal positive charge(s), +, carried by said [Q n M];

A − is an anionic nucleophile selected from the group consisting of cyanide, isothiocyanate, isocyanate, cyanate, thiocyanate, alkylthiolates, arylthiolates, or azide; and

F represents fluorine or a radioisotope thereof wherein the anhydrous fluoride salt contains less then 0.01% water of hydration.

2. The method of claim 1 wherein the nucleophilic substitution is conducted at a low temperature.

3. The method of claim 1 conducted at a temperature that is at least −35° C. and no greater than room temperature.

4. The method of claim 1 wherein said inert polar, aprotic solvent is tetrahydrofuran, dimethyl sulfoxide, diethyl ether, dioxane, dimethoxyethane, methyl tert-butyl ether, acetonitrile, acetone, methylethylketone, tetrahydrofuran, dimethylformamide, dimethylacetamide, N-methylpyrolidinone, butyronitrile, toluene, pyridine, benzonitrile, diphenyl ether, diethyl carbonate, or hexamethyiphosphoric triarmde.

5. The method of claim 1 wherein said fluorinated aromatic compound is a fluorinated benzene and said a fluorinated unsaturated organic compound is a fluorinated alkene or a fluorinated alkyne.

6. The method of claim 1 wherein said [Q n M] x+ A x − , is a tetraalkylammonium cyanide, a trialkylarylammonium cyanide, a dialkyldiarylammonium cyanide, an alkyltriarylammonium cyanide, or a tetraarylammonium cyanide.

7. The method of claim 6 wherein said tetraalkylammonium cyanide is tetrabutylammonium cyanide.

8. The method of claim 1 wherein said fluorinated aromatic compound is hexafluorobenzene, octafluoronaphthalene, octafluorotoluene, pentafluorobenzonitrile, pentafluoropyridine or decafluorobiphenyl.

9. A method for preparation of an anhydrous tetraalkylammonium fluoride salt, the method comprising reacting a fluorinated aromatic compound, in a nucleophilic aromatic substitution reaction, with a tetraalkylammonium cyanide in an inert polar, aprotic solvent, to produce the anhydrous tetraalkylammonium fluoride salt, that contains less than 0.01% water of hydration.

10. The method of claim 9 wherein said tetraalkyl ammonium fluoride salt is tetrabutylammonium fluoride.

11. The method of claim 9 wherein said tetraalkylammonium cyanide is tetrabutylammonium cyanide.

12. The method of claim 9 wherein said fluorinated aromatic compound is hexafluorobenzene.

13. A method for preparation of a fluorinated compound, the method comprising reacting an anhydrous organic fluoride salt, in a nucleophilic substitution reaction, with an alkyl halide, a tosylate, a triflate, a nitroaromatic, a chloroaromatic, or an aromatic triflate compound to produce a fluorinated compound that contains less than 0.01% water of hydration.

14. A method for deprotection of a silylated species, comprising reacting the silylated species with an anhydrous organic fluoride salt that contains less than 0.01% water of hydration to deprotect the silylated species.

15. A method as set forth in claim 14 wherein the silylated species is a silylated aromatic, a silylated heteroaromatic, a silylated alcohol, or a silylated amine.

16. The method of claim 1 wherein [Q n M] + is chiral.