Synthesis of fluorotrifluoromethylsulfonyl imide
The invention provides a method for producing fluorotrifluoromethylsulfonyl imide (FTFSI) by reacting non-fluorohalogenated trihalomethylsulfonyl imide (XTXSI) with hydrogen fluoride, where each X is independently a nonfluoro-halide, such as Cl, Br, or I.
1. A method for producing fluorotrifluoromethylsulfonyl imide (FTFSI) from a non-fluoro halogenated trihalomethylsulfonyl imide compound of the formula:
X 1 —SO 2 —NR 1 —SO 2 —C(X 2 ) 3 I
wherein
X 1 is non-fluoro halide;
each of X 2 is independently halide; and
R 1 is hydrogen, alkyl, or a nitrogen protecting group;
said method comprising reacting said non-fluoro halogenated trihalomethylsulfonyl imide compound with hydrogen fluoride under conditions sufficient to produce FTFSI while removing HX 1 , HX 2 or a combination thereof that is produced during the reaction.
2. The method according to claim 1 , wherein said reaction condition comprises hydrogen fluoride refluxing condition.
3. The method according to claim 2 , wherein said reaction condition comprises an ambient pressure condition.
4. The method according to claim 1 , wherein X 1 and X 2 are Cl.
5. The method according to claim 1 , wherein at least 2 equivalent of total hydrogen fluoride relative to said non-fluoro halogenated trihalomethylsulfonyl imide compound is added to the reaction.
6. The method according to claim 1 , wherein the yield of FTFSI is at least 90% by weight.
7. The method according to claim 1 , wherein said reaction condition comprises the presence of a catalyst.
8. The method according to claim 7 , wherein said catalyst comprises a Lewis acid.
9. The method according to claim 8 , wherein said Lewis acid comprises a salt of an alkaline metal, arsenic, antimony, bismuth, zinc, or a combination thereof.
10. The method according to claim 8 , wherein said Lewis acid is a salt of Bi(III) compound.
11. The method according to claim 7 , wherein about 0.5 equivalent or less of said catalyst is added to the reaction relative to the amount of said non-fluoro halogenated trihalomethylsulfonyl imide compound.
12. The method of claim 1 further comprising the step of producing said non-fluoro halogenated trihalomethylsulfonyl imide compound, said step comprising:
contacting sulfamic acid with thionylhalide of the formula: SO(X 1 ) 2 under conditions sufficient to produce a reactive intermediate, wherein each X 1 is non-fluoro halide; and
contacting the reactive intermediate with a trihalomethanesulfonic acid of the formula: (X 2 ) 3 SO 3 H under conditions sufficient to produce said non-fluoro halogenated trihalomethylsulfonyl imide, wherein each X 2 is independently a non-fluoro halide.
13. The method according to claim 12 , wherein X 1 is chloro.
14. The method according to claim 12 , wherein X 2 is chloro.
15. The method according to claim 1 , wherein R 1 is hydrogen.
16. A method for producing fluorotrifluoromethylsulfonyl imide (FTFSI) from a non-fluoro halogenated trihalomethylsulfonyl imide compound of the formula:
X 1 —SO 2 —NR 1 —SO 2 —C(X 2 ) 3 I
wherein
X 1 is non-fluoro halide;
each of X 2 is independently halide; and
R 1 is hydrogen, alkyl, or a nitrogen protecting group;
said method comprising reacting said non-fluoro halogenated trihalomethylsulfonyl imide compound with refluxing hydrogen fluoride to produce FTFSI.
17. A method for producing fluorotrifluoromethylsulfonyl imide (FTFSI) from a (chlorosulfonyl)(trichloromethylsulfonyl)imide compound of the formula:
Cl—SO 2 —NR 1 —SO 2 —CCl 3 I
wherein
R 1 is hydrogen, alkyl, or a nitrogen protecting group;
said method comprising reacting said (chlorosulfonyl)(trichloromethylsulfonyl)imide compound with hydrogen fluoride under conditions sufficient to produce FTFSI.
18. A method for producing fluorotrifluoromethylsulfonyl imide (FTFSI) from a non-fluoro halogenated trihalomethylsulfonyl imide compound of the formula:
X 1 —SO 2 —NR 1 —SO 2 —C(X 2 ) 3 I
wherein
X 1 is non-fluoro halide;
each of X 2 is independently halide; and
R 1 is hydrogen, alkyl, or a nitrogen protecting group;
said method comprising reacting said non-fluoro halogenated trihalomethylsulfonyl imide compound with hydrogen fluoride in the absence of a catalyst or in the presence of a catalyst selected from the group consisting of a salt of an alkaline metal, arsenic, antimony, bismuth, zinc, or a combination thereof, and under conditions sufficient to produce FTFSI.