Synthesis of bis(fluorosulfonyl)imide
The present invention provides methods for producing bis(fluorosulfonyl) compounds of the formula: F—S(O) 2 —Z—S(O) 2 —F I by contacting a nonfluorohalide compound of the formula: X—S(O) 2 —Z—S(O) 2 —X with bismuth trifluoride under conditions sufficient to produce the bis(fluorosulfonyl) compound of Formula I, where Z and X are those defined herein.
1. A method for producing a fluorinated compound of the formula: F—S(O) 2 —Z—S(O) 2 —F from a nonfluorohalide compound of the formula: X—S(O) 2 —Z—S(O) 2 —X, said method comprising contacting said nonfluorohalide compound with BiF 3 under conditions sufficient to produce said fluorinated compound and BiX 3 as a byproduct, wherein
each X is independently a halide, provided at least one of X is a non-fluoro halide;
Z is NR 1 or CR 2 R 3 ;
R 1 is H, alkali metal, alkyl, or a nitrogen protecting group; and
each of R 2 and R 3 is independently H, halide, alkyl, or haloalkyl.
2. The method of claim 1 further comprising the step of contacting BiX 3 with an oxygenating agent under conditions sufficient to produce Bi 2 O 3 .
3. The method of claim 2 , wherein said oxygenating agent comprises a metal carbonate, a hydroxide compound, water, oxygen, ozone, hydrogen peroxide, nitrous oxide, osmium tetraoxide, or a combination thereof.
4. The method of claim 3 further comprising the step of contacting Bi 2 O 3 with a fluorinating agent under conditions sufficient to produce BiF 3 .
5. The method of claim 4 , wherein BiF 3 used in producing said fluorinated compound comprises BiF 3 produced from Bi 2 O 3 .
6. The method of claim 5 , wherein said fluorinating agent comprises aqueous or anhydrous hydrofluoric acid, fluorine, or M′F, wherein M′ is alkali metal, alkaline earth metal, or a transition metal.
7. The method of claim 1 , wherein Z is NR 1 .
8. The method of claim 7 , wherein R 1 is H.
9. The method of claim 8 further comprising the steps of producing a metal salt of said fluorinated compound, said steps comprising contacting said fluorinated compound with a carbonate compound of the formula M[CO 3 ] m under conditions sufficient to produce said metal salt of said fluorinated compound, wherein M is an alkali metal, an alkaline earth metal, a transition metal, a lanthanide, or an actinide, and m is the oxidation state of M.
10. The method of claim 9 , wherein said metal salt of said fluorinated compound comprises a lithium salt, sodium salt, potassium salt, cesium salt, magnesium salt, or a mixture thereof.
11. The method of claim 9 , wherein said metal salt of said fluorinated compound is substantially halide free.
12. A method for producing a bis(fluorosulfonyl)imide of the formula:
F—S(O) 2 —NR 1 —S(O) 2 —F
said method comprising contacting a bis(nonfluorohalosulfonyl)imide of the formula:
X—S(O) 2 —NR 1 —S(O) 2 —X
with BiF 3 under conditions sufficient to produce said bis(fluorohalosulfonyl)imide,
wherein
each X is independently a halide provided at least one of X is a non-fluoro halide; and
R 1 is H, alkali metal, alkyl, or a nitrogen protecting group.
13. The method of claim 12 , wherein X is chloro and R 1 is H.
14. The method of claim 12 , wherein said method produces BiX 3 , and wherein said method further comprises the step of contacting BiX 3 with an oxygenating agent under conditions sufficient to produce Bi 2 O 3 , wherein said oxygenating agent comprises a metal carbonate, a hydroxide compound, water, oxygen, ozone, hydrogen peroxide, nitrous oxide, osmium tetraoxide, or a combination thereof.
15. The method of claim 14 further comprising the step of contacting Bi 2 O 3 with a fluorinating agent under conditions sufficient to produce BiF 3 .
16. The method of claim 15 , wherein BiF 3 used in producing said bis(fluorohalosulfonyl)imide comprises BiF 3 produced from Bi 2 O 3 .
17. The method of claim 12 , wherein R 1 is H, and said method further comprises contacting said bis(fluorosulfonyl)imide with a carbonate compound of the formula M[CO 3 ] m under conditions sufficient to produce a metal salt of bis(fluorosulfonyl)imide of the formula:
F—S(O) 2 —N(M)-S(O) 2 —F
wherein
M is an alkali metal, an alkaline earth metal, a transition metal, a lanthanide, or an actinide; and
m is the oxidation state of M.
18. The method of claim 17 , wherein M comprises lithium, sodium, potassium, cesium, or magnesium.
19. The method of claim 17 , wherein said metal salt of bis(fluorosulfonyl)imide is substantially halide free.