MARSAN BENOIT (CA)
HAMMAMI AMER (CA)
MARSAN BENOIT (CA)
| WO2005089390A2 | 2005-09-29 |
| US6365301B1 | 2002-04-02 | |||
| US4463071A | 1984-07-31 | |||
| US5552241A | 1996-09-03 | |||
| US6319428B1 | 2001-11-20 | |||
| US6853472B2 | 2005-02-08 |
| CLAIMS:
1. A compound of formula (I):
wherein R 2 is a hydrogen atom, a CrC 20 alkyl which is linear or branched, C 3 -Ci 2 cycloalkyl, C1-C12 heterocyclyl, C 2 -C 20 alkenyl, C 2 -C 20 alkynyl, C 6 -C 12 aryl, C 6 -C 20 aralkyl, C 6 -C 20 alkylaryl, and CrC 12 heteroaryl;
R 3 is a hydrogen atom, a C 1 -C 20 alkyl which is linear or branched, C 3 -Ci 2 cycloalkyl, CrC 12 heterocyclyl, C 2 -C 20 alkenyl, C 2 -C 20 alkynyl, C 6 -Ci 2 aryl, C 6 -C 20 aralkyl, C 6 -C 20 alkylaryl, and C 1 -C 12 heteroaryl;
R 4 is a hydrogen atom, a CrC 20 alkyl which is linear or branched, C 3 -C 12 cycloalkyl, C 1 -C 12 heterocyclyl, C 2 -C 20 alkenyl, C 2 -C 20 alkynyl, C 6 -C 12 aryl, C 6 -C 20 aralkyl, C 6 -C 20 alkylaryl, and C 1 -Ci 2 heteroaryl; and
R 5 is a hydrogen atom, a C 1 -C 20 alkyl which is linear or branched, C 3 -Ci 2 cycloalkyl, C 1 -C 12 heterocyclyl, C 2 -C 20 alkenyl, C 2 -C 20 alkynyl, C 6 -C 12 aryl, C 6 -C 20 aralkyl, C 6 -C 20 alkylaryl, and C1-C 1 2 heteroaryl, an effective protecting group for an amino group,
said heterocycles represented by Q + are as previously presented or substituted with 1 to 3 substituents chosen from -NO 2 , -CN -OH, -CF 3 -COR 4 , -SH, -OMe, -OCH 2 Ph, -SMe, -SPh, -SCH 2 Ph, -COOH, -COOR 4 , -NH 2 ,
C 2 -C 20 alkenyl, CrC 20 alkoxy, CrC 20 alkyl, C 2 -C 20 alkynyl, C 6 -C 20 aralkyl, C 6 - C12 aryl, C 3 -Ce cycloalkyl, CrC 20 aminoalkyl, CrC 6 hydroxyalkyl, C 2 -Ci 2 heteroaryl, CrCi 2 , vinyl, C 4 -C 20 alkylvinyl, C 4 -C 20 vinylalkyl, and C 3 -C 20 expoxyalkyl,
said alkyl, cycloalkyl, heterocyclyl, alkenyl, alkynyl, aryl, aralkyl, alkylaryl, and heteroaryl being unsubstituted or substituted with 1 to 3 substituents chosen from F, Cl, Br, I 1 OH, a CrC 6 alkoxy, a CrC 6 hydroxy alkyl, NO 2 , CN, CF 3 , SO 3 " , C n F 2n+1 , C 1 -C 12 alkyl which is linear or branched, C 6 -C 12 aryl, C n H 2n+I , Ph 2 P(O)-, Ph 2 P-, Me 2 P(O)-, Me 2 P, Ph 2 P(S), Me 2 P(S), Ph 3 P=N-, Me 3 P=N-, C 6 HsCpH 2P -, CpH 2 p+i C 6 H 4 -, CpH 2P+ IC 6 H 4 C n H 2n -, CH 2 = CHCpH 2 p— , CH 2 =CHC 6 H 5 -, CH 2 =CHC 6 H 4 CpH 2P+ I-, and CH 2 =CHCpH 2P C 6 H 4 - ^-^-C p H 2p - , where (1 < n, p < 48),
with the proviso that said compound of formula (I) is different than 1-methyl-1-propylpyrrolidinium imidosulfuryl fluoride.
2. The compound of claim 1 , wherein each of said Ri is F or Cl.
3. The compound of claim 1 , wherein each of said Ri is F.
4. The compound of any one of claims 1 to 3, wherein Q + is chosen from
R 2 R3 R 2 R3 R 2 R3 °2 R3
5. The compound of any one of claims 1 to 3, wherein Q + is chosen from
R 2 R 3 R 2 R 3 R 2 R 3
6. The compound of any one of claims 1 to 3, wherein Q + is chosen from
7. The compound of any one of claims 1 to 3, wherein Q + is chosen from
8. The compound of any one of claims 1 to 3, wherein Q + is
R2 V R 3
9. The compound of any one of claims 1 to 8, wherein R 2 is a C1-C20 alkyl which is linear or branched or a C3-C12 cycloalkyl.
10. The compound of claim 9, wherein R 2 is a Ci-C 20 alkyl which is linear or branched.
11. The compound of claim 10, wherein R 2 is a Ci-Cs alkyl which is linear.
12. The compound of any one of claims 1 to 11 , wherein R 3 is a Ci-C 20 alkyl which is linear or branched or a C 3 -Ci 2 cycloalkyl.
13. The compound of claim 12, wherein R 3 is a C1-C 20 alkyl which is linear or branched.
14. The compound of claim 13, wherein R 3 is a CrCs alkyl which is linear.
15. The compound of any one of claims 1 to 4, wherein R 4 is a Ci-C 2 o alkyl which is linear or branched or a C 3 -Ci 2 cycloalkyl.
16. The compound of claim 15, wherein R 4 is a C1-C 20 alkyl which is linear or branched.
17. The compound of claim 16, wherein R 4 is a Ci-Ce alkyl which is linear.
18. The compound of claim 17, wherein R 4 is a CrC 4 alkyl which is linear.
19. The compound of any one of claims 1 to 18, wherein said compound has a conductivity of at least 0.0001 mS cm '1 .
20. The compound of any one of claims 1 to 18, wherein said compound has a conductivity of at least 1 mS cm "1 .
21. The compound of any one of claims 1 to 18, wherein said compound has a conductivity of at least 10 mS cm "1 .
22. The compound of any one of claims 1 to 18, wherein said compound has a conductivity of about 0.0001 to about 100 mS cm "1 .
23. The compound of any one of claims 1 to 22, wherein said compound has a melting point below 100 0 C.
24. The compound of any one of claims 1 to 22, wherein said compound has a melting point below 40 ° C.
25. The compound of any one of claims 1 to 22, wherein said compound has a melting point below 25 ° C.
26. The compound of any one of claims 1 to 22, wherein said compound has a melting point of about 0 ° C to about 100 ° C.
27. A molten salt comprising at least one compound as defined in any one of claims 1 to 22.
28. An ionic liquid comprising at least one compound as defined in any one of claims 1 to 22.
29. An electrolyte comprising a compound as defined in any one of claims 1 to 26.
30. An electrochemical device comprising a compound as defined in any one of claims 1 to 26.
31. A battery comprising an anode, a cathode and a compound as defined in any one of claims 1 to 26.
32. Use of a compound as defined in any one of claims 1 to 22, as a molten salt.
33. Use of a compound as defined in any one of claims 1 to 22, as a solvent.
34. Use of a compound as defined in any one of claims 1 to 22, as an ionic liquid.
35. Use of a compound as defined in any one of claims 1 to 26, as an electrolyte.
36. Use of a compound as defined in any one of claims 1 to 26 in an electrochemical device.
37. Use of a compound as defined in any one of claims 1 to 26 in a battery.
38. A method of using a compound as defined in any one of claims 1 to 26, comprising contacting said compound with electrodes and using it as an electrolyte.
39. A method of using a compound as defined in any one of claims 1 to 26, comprising introducing said compound in the manufacture of a proton exchange membrane.
40. A method of using a compound as defined in any one of claims 1 to 26, comprising mixing said compound with a compound of formula (VIII) LiD
(VIII)
wherein
D is chosen from CF 3 SO 3 -, (FSO 2 ) 2 N-, (CF 3 SOa) 2 N-, (CF 3 CF 2 SO 2 ) 2 N-, (CF 3 SO 2 ) 3 C-, PF 6 " , CF 3 COO-, AsF 6 " , CH 3 COO-, (CN) 2 N-, NO 3 -, BF 4 -, CIO 4 -, (C 8 Hi 6 SOz) 2 N-, and C 3 H 3 N 2 " ,
so as to obtain a mixture and using said mixture as an electrolyte.
41. The method of claim 40, further comprising using said electrolyte in a lithium-ion battery.
42. A process for preparing a compound of formula (Ia):
wherein each of said Ri is independently F or Cl, Q + is chosen from
wherein
R2 is a hydrogen atom, a C 1 -C2 0 alkyl which is linear or branched, C 3 -C 12 cycloalkyl, C1-C12 heterocyclyl, C2-C20 alkenyl, C2-C20 alkynyl, C 6 -Ci 2 aryl, C 6 -C 2 O aralkyl, C 6 -C 2 O alkylaryl, and C1-C12 heteroaryl;
R 3 is a hydrogen atom, a C1-C 2 0 alkyl which is linear or branched, C3-C 1 2 cycloalkyl, C1-C12 heterocyclyl, C2-C20 alkenyl, C2-C20 alkynyl, C 6 -Ci2 aryl, C 6 -C2o aralkyl, C 6 -C2o alkylaryl, and C1-C12 heteroaryl; and
R 4 is a hydrogen atom, a C1-C 2 0 alkyl which is linear or branched, C3-C12 cycloalkyl, C1-C12 heterocyclyl, C 2 -C 2 O alkenyl, C2-C20 alkynyl, C 6 -Ci 2 aryl, C6-C20 aralkyl, C 6 -C2o alkylaryl, and C1-C12 heteroaryl, said heterocycles represented by Q + are as previously presented or substituted with 1 to 3 substituents chosen from -NO 2 , -CN -OH, -CF 3 -COR 4 , -SH, -OMe, -OCH 2 Ph, -SMe, -SPh, -SCH 2 Ph, -COOH, -COOR 4 , -NH 2 ,
C 2 -C 20 alkenyl, CrC 20 alkoxy, Ci-C 20 alkyl, C 2 -C 20 alkynyl, C 6 -C 20 aralkyl, C 6 - Ci 2 aryl, C 3 -C 8 cycloalkyl, CrC 20 aminoalkyl, CrC 6 hydroxyalkyl, C 2 -Ci 2 heteroaryl, C 1 -C 12 , vinyl, C 4 -C 20 alkylvinyl, C 4 -C 20 vinylalkyl, and C 3 -C 20 expoxyalkyl,
said alkyl, cycloalkyl, heterocyclyl, alkenyl, alkynyl, aryl, aralkyl, alkylaryl, and heteroaryl being unsubstituted or substituted with 1 to 3 substituents chosen from F, Cl, Br, I, OH, a C r C 6 alkoxy, a Ci-C 6 hydroxy alkyl, NO 2 , CN, CF 3 , SO 3 " , C n F 2n+I , Ci-Ci 2 alkyl which is linear or branched, C 6 -Ci 2 aryl, C n H 2n+ I, Ph 2 P(O)-, Ph 2 P-, Me 2 P(O)-, Me 2 P, Ph 2 P(S), Me 2 P(S), Ph 3 P=N-, Me 3 P=N-, C 6 HsCpH 2P -, CpH 2p+ iC 6 H 4 — , CpH 2p +iC 6 H 4 C n H 2n — , CH 2 =CHCpH 2p — ,
CH 2
=CHC 6
Hs-,
O
comprising the step of reacting a compound of formula (II):
with a compound of formula (III):
R 6 ^ ^ R 6
Q (HI) wherein
Q + is as previously defined for formula (Ia); and
each of said R 6 is independently H, Li, Na, K, Cs, or (R 7 ) 3 Si-, each of said R 7 being independently a C1-C12 alkyl.
43. The process of claim 42, wherein said compound of formula (III) is a compound of formula (IV):
wherein
Q + is as previously defined in formula (I); and
each of said R 7 is independently a C1-C12 alkyl.
44. The process of claim 43, wherein each of said R 7 is the same.
45. The process of claim 43, wherein each of said R 7 is methyl.
46. The process of any one of claims 42 to 45, wherein said compounds of formulas (II) and (III) are reacted together at a temperature of about -78 to about 110 0 C.
47. The process of claim 46, wherein said temperature is about -5 to about 25 0 C.
48. The process of claim 46, wherein said temperature is about 15 to about 25 0 C.
49. The process of any one of claims 42 to 48, wherein each of said Ri is F.
50. The process of any one of claims 42 to 48, wherein each of said Ri is Cl.
51. A process for preparing a compound of formula (Ib):
wherein
Rs is F; and
Q + is chosen from
R 4 R 2
-N. A ^ tf^ N ri^ N-^N
C * eN)' ; ( θ N;D' ; ψ I ■ h I » and ψ I
R^ ^R 3 R 2 R 2 R 2
wherein
R 2 is a hydrogen atom, a C 1 -C20 alkyl which is linear or branched, C 3 -Ci 2 cycloalkyl, CrCi 2 heterocyclyl, C 2 -C 20 alkenyl, C 2 -C 20 alkynyl, C 6 -Ci 2 aryl, C 6 -C 20 aralkyl, C 6 -C 20 alkylaryl, and CrCi 2 heteroaryl;
R 3 is a hydrogen atom, a CrC 20 alkyl which is linear or branched, C 3 -Ci 2 cycloalkyl, Ci-Ci 2 heterocyclyl, C 2 -C 20 alkenyl, C 2 -C 20 alkynyl, C 6 -Ci 2 aryl, C 6 -C 20 aralkyl, C 6 -C 20 alkylaryl, and C1-C12 heteroaryl; and
R 4 is a hydrogen atom, a Ci-C 20 alkyl which is linear or branched, C 3 -Ci 2 cycloalkyl, CrCi 2 heterocyclyl, C 2 -C 20 alkenyl, C 2 -C 20 alkynyl, C 6 -Ci 2 aryl, C 6 -C 20 aralkyl, C 6 -C 20 alkylaryl, and CrCi 2 heteroaryl, said heterocycles represented by Q + are as previously presented or substituted with 1 to 3 substituents chosen from -NO 2 , -CN -OH, -CF 3 -COR 4 , -SH, -OMe, -OCH 2 Ph, -SMe, -SPh, -SCH 2 Ph, -COOH, -COOR 4 , -NH 2 ,
C 2 -C 2 O alkenyl, C1-C20 alkoxy, C1-C20 alkyl, C 2 -C 2 O alkynyl, C6-C 2 o aralkyl, C 6 - Ci 2 aryl, C 3 -C 8 cycloalkyl, CrC 20 aminoalkyl, C1-C 6 hydroxyalkyl, C 2 -Ci 2 heteroaryl, CrCi 2 vinyl, C 4 -C 2 O alkylvinyl, C 4 -C 20 vinylalkyl, and C 3 -C 20 expoxyalkyl,
said alkyl, cycloalkyl, heterocyclyl, alkenyl, alkynyl, aryl, aralkyl, alkylaryl, and heteroaryl being unsubstituted or substituted with 1 to 3 substituents chosen from F, Cl, Br, I 1 OH, a Ci-C 6 alkoxy, a d-C 6 hydroxy alkyl, NO 2 , CN 1 CF 3 , SO 3 " , C n F 2n+ I, Ci-Ci 2 alkyl which is linear or branched, C 6 -Ci 2 aryl, C n H 2n+ I, Ph 2 P(O)-, Ph 2 P-, Me 2 P(O)-, Me 2 P, Ph 2 P(S), Me 2 P(S), Ph 3 P=N-, Me 3 P=N-, C 6 HsCpH 2P -, CpH 2 p+iC 6 H 4 — , CpH 2 p+iC 6 H4C n H 2n — , CH 2 =CHCpH 2p — ,
CH 2 =CHC 6 Hs-, CH 2 =CHC 6 H 4 CpH 2 p+i—, and CH 2 =CHCpH 2 pC 6 H 4 — ^-^C p H 2p - , where: (1 < n, p < 48),
comprising the steps of :
a) reacting SO 2 CI 2 with a compound of formula (III):
Q (III)
wherein
Q + is as previously defined for formula (Ib); and each of said R 6 is independently H, Li, Na, K, Cs, or (R 7 )3Si-, each of said R 7 being independently a C-1-C12 alkyl
so as to obtain a compound of formula (Ic);
O O
Cl- -N- -Cl
o Q o (Ic)
wherein
Q + is as previously defined for formula (Ia); and
b) reacting said compound of formula (Ic) with a compound of formula MF, wherein M is Li, Na, K, or Cs, so as to obtain said compound of formula (Ib).
52. The process of claim 51 , wherein said step (a) is carried out at a temperature of about -78 to about 11O 0 C.
53. The process of claim 52, wherein said temperature is about -5 to about 25 0 C.
54. The process of any one of claims 51 to 53, wherein said step (b) is carried out in the presence of an aprotic solvent.
55. The process of claim 54, wherein said aprotic solvent is a polar solvent.
56. The process of claim 54 or 55, wherein said aprotic solvent is nitromethane or acetonitrile.
57. The process of any one of claims 51 to 56, wherein said aprotic solvent is acetonitrile.
58. The process of any one of claims 51 to 57, wherein said compound of formula (III) is a compound of formula (IV):
wherein
Q + is as previously defined in formula (Ib); and
each of said R 7 is independently a C1-C-12 alkyl.
59. The process of claim 58, wherein each of said R 7 is the same.
60. The process of claim 59, wherein each of said R 7 is methyl.
61. A process for preparing a compound of formula (I):
wherein each of said Ri is independently F, Cl, -N(R 5 ^ or -CN; Q + is chosen from
wherein
R 2 is a hydrogen atom, a Ci-C 2 O alkyl which is linear or branched, C 3 -Ci 2 cycloalkyl, C1-C12 heterocyclyl, C 2 -C 20 alkenyl, C 2 -C 20 alkynyl, C 6 -Ci 2 aryl, C 6 -C 20 aralkyl, C 6 -C 20 alkylaryl, and CrCi 2 heteroaryl;
R 3 is a hydrogen atom, a C1-C20 alkyl which is linear or branched, C 3 -Ci 2 cycloalkyl, CrCi 2 heterocyclyl, C 2 -C 20 alkenyl, C 2 -C 20 alkynyl, C 6 -C 12 aryl, C 6 -C 20 aralkyl, C 6 -C 20 alkylaryl, and C 1 -Ci 2 heteroaryl;
R 4 is a hydrogen atom, a Ci-C 20 alkyl which is linear or branched, C 3 -C 12 cycloalkyl, C 1 -C 12 heterocyclyl, C 2 -C 20 alkenyl, C 2 -C 20 alkynyl, C 6 -C 12 aryl, Ce-C 20 aralkyl, C 6 -C 20 alkylaryl, and C 1 -C 12 heteroaryl; and
R 5 is a hydrogen atom, a C 1 -C 20 alkyl which is linear or branched, C 3 -Ci 2 cycloalkyl, C 1 -Ci 2 heterocyclyl, C 2 -C 20 alkenyl, C 2 -C 20 alkynyl, C 6 -Ci 2 aryl, C 6 -C 2 O aralkyl, C 6 -C 2 O alkylaryl, and CrCi 2 heteroaryl, an effective protecting group for an amino group,
said heterocycles represented by Q + are as previously presented or substituted with 1 to 3 substituents chosen from -NO 2 , -CN -OH, -CF3 -COR4, -SH, -OMe, -OCH 2 Ph, -SMe, -SPh, -SCH 2 Ph, -COOH, -COOR 4 , -NH 2 ,
C 2 -C 20 alkenyl, CrC 20 alkoxy, CrC 20 alkyl, C 2 -C 20 alkynyl, C 6 -C 20 aralkyl, C 6 - Ci 2 aryl, C 3 -C 8 cycloalkyl, CrC 20 aminoalkyl, CrC 6 hydroxyalkyl, C 2 -Ci 2 heteroaryl, CrCi 2 vinyl, C 4 -C 20 alkylvinyl, C 4 -C 20 vinylalkyl, and C 3 -C 20 expoxyalkyl,
said alkyl, cycloalkyl, heterocyclyl, alkenyl, alkynyl, aryl, aralkyl, alkylaryl, and heteroaryl being unsubstituted or substituted with 1 to 3 substituents chosen from F, Cl, Br, I, OH, a C 1 -C 6 alkoxy, a CrC 6 hydroxy alkyl, NO 2 , CN, CF 3 , SO 3 " , C n F 2n+I , CrCi 2 alkyl which is linear or branched, C 6 -Ci 2 aryl, C n H 2n+ I, Ph 2 P(O)-, Ph 2 P-, Me 2 P(O)-, Me 2 P, Ph 2 P(S), Me 2 P(S), Ph 3 P=N-, Me 3 P=N-, C 6 HsCpH 2P -, CpH 2 p+iC 6 H 4 — , CpH 2P+ IC 6 H 4 C n H 2n -, CH 2 =CHCpH 2p — ,
CH 2 =CHC 6 Hs-, CH 2 =CHC 6 H 4 CpH 2P+I -, and CH 2 =CHCpH 2p C 6 H 4 — , ^-^^C p H 2p - , where: (1 < n, p < 48),
comprising the step of reacting together a compound of formula (V) and a compound of formula (VI) :
wherein Ri and Q are as previously defined;
M + is chosen from Li + , Na + , K + , and Cs +
X- is chosen from F 1 Cl " , Br, I " , CH 3 COO-, PhCH 2 COO " , CN ' , CF 3 COO-, SO 4 2" , CF 3 SO 3 -, BF 4 -, PF 6 " , NO 3 " , CIO 4 " , SbF 6 " , and RuO 4 " .
62. The process of claim 61 , wherein said reaction is carried out in water so that the so-obtained product of formula (I) precipitates and the so-formed by product of formula M + X " is at least substantially soluble.
63. The process of claim 61 or 62, wherein M + is K + .
64. The process of any one of claims 61 to 63, wherein X " is F " , Cl " , Br " , or I " .
65. The process of any one of claims 61 to 63, wherein X " is Cl " , or Br " .
66. The process of any one of claims 61 to 65, wherein each of said Ri is Cl or F.
67. The process of any one of claims 61 to 65, wherein each of said Ri is F.
68. The process of any one of claims 61 to 65, wherein each of said Ri is Cl.
69. A process for preparing a compound of formula (Ib):
wherein
Re is F; and
Q + is chosen from
wherein
R 2 is a hydrogen atom, a C 1 -C 20 alkyl which is linear or branched, C 3 -C 12 cycloalkyl, C1-C 12 heterocyclyl, C2-C20 alkenyl, C2-C20 alkynyl, C 6 -C 12 aryl, C 6 -C 20 aralkyl, C 6 -C 2 O alkylaryl, and C1-C12 heteroaryl;
R 3 is a hydrogen atom, a C 1 -C 2 0 alkyl which is linear or branched, C3-C 12 cycloalkyl, C1-C12 heterocyclyl, C2-C20 alkenyl, C2-C20 alkynyl, C 6 -Ci 2 aryl, C 6 -C 2 O aralkyl, C 6 -C2o alkylaryl, and C1-C12 heteroaryl; and
R 4 is a hydrogen atom, a C 1 -C 2 0 alkyl which is linear or branched, C 3 -C 12 cycloalkyl, C1-C12 heterocyclyl, C2-C20 alkenyl, C2-C20 alkynyl, C 6 -CI 2 aryl, C6-C20 aralkyl, C6-C20 alkylaryl, and C1-C12 heteroaryl, said heterocycles represented by Q + are as previously presented or substituted with 1 to 3 substituents chosen from -NO 2 , -CN -OH, -CF 3 -COR 4 , -SH, -OMe, -OCH 2 Ph, -SMe, -SPh, -SCH 2 Ph, -COOH, -COOR 4 , -NH 2 ,
C 2 -C 20 alkenyl, Ci-C 20 alkoxy, CrC 20 alkyl, C 2 -C 20 alkynyl, Ce-C 20 aralkyl, C 6 - Ci 2 aryl, C 3 -C 8 cycloalkyl, CrC 20 aminoalkyl, CrC 6 hydroxyalkyl, C 2 -Ci 2 heteroaryl, C 1 -C1 2 , vinyl, C 4 -C 20 alkylvinyl, C 4 -C 20 vinylalkyl, and C 3 -C 20 expoxyalkyl;
said alkyl, cycloalkyl, heterocyclyl, alkenyl, alkynyl, aryl, aralkyl, alkylaryl, and heteroaryl being unsubstituted or substituted with 1 to 3 substituents chosen from F, Cl, Br, I 1 OH, a CrC 6 alkoxy, a CrC 6 hydroxy alkyl, NO 2 , CN, CF 3 , SO 3 " , C n F 2n+I , CrCi 2 alkyl which is linear or branched, C 6 -Ci 2 aryl, C n H2n+i, Ph 2 P(O)-, Ph 2 P-, Me 2 P(O)-, Me 2 P, Ph 2 P(S), Me 2 P(S), Ph 3 P=N-, Me 3 P=N-, C 6 HsCpH 2P -, CpH2p+iC 6 H 4 — , CpH 2p +iC 6 H4C n H 2n — , CH 2 = CHC p H 2 p— ,
CH 2 =CHC 6 H 5 -, CH 2 =CHC 6 H 4 CpH 2P+ I-, and CH 2 =CHC p H 2p C 6 H 4 - , ^-^-C p H 2p - , where: (1 < n, p < 48),
comprising the steps of :
a) reacting a compound of formula (Ha):
Rg ^~~ " S ^~^~ Rg
(Ha)
wherein each of said Rg is independently Cl, Br, or I
with a compound of formula (Ilia):
(Ilia)
wherein
T + is Li + , Na + , K + ,Cs + or H + and
each of said Re is independently H, Li, Na, K, Cs, or (R 7 ) 3 Si-, each of said R 7 being independently a C1-C12 alkyl.
so as to obtain a compound of formula (VII);
wherein
each of said Rg is as previously defined for formula (Ha); and
T + is as previously defined for formula (Ilia); and b) reacting said compound of formula (VII) with a compound of formula Q-Rs 1 wherein Q and R 8 are as previously defined in formula (Ib), so as to obtain said compound of formula (Ib).
70. The process of claim 69, wherein said step (a) is carried out at a temperature of about -78 to about 11O 0 C.
71. The process of claim 70, wherein said temperature is about -5 to about 25 0 C.
72. The process of any one of claims 69 to 71 , wherein said step (b) is carried out in the presence of an aprotic solvent.
73. The process of claim 72, wherein said aprotic solvent is a polar solvent.
74. The process of claim 72 or 73, wherein said aprotic solvent is nitromethane or acetonitrile.
75. The process of claim 72 or 73, wherein said aprotic solvent is acetonitrile.
76. The process of any one of claims 69 to 75, wherein said compound of formula (Ilia) is a compound of formula (IVa):
(IVa)
wherein T + is as previously defined in formula (Ilia); and
each of said R 7 is independently a C1-C12 alkyl.
77. The process of claim 76, wherein each of said R 7 is the same.
78. The process of claim 76, wherein each of said R 7 is methyl.
79. The process of any one of claims 42 to 78, wherein Q + is chosen from
80. The process of any one of claims 42 to 78, wherein Q + is chosen from
81. The process of any one of claims 42 to 78, wherein Q + is chosen from
82. The process of any one of claims 42 to 78, wherein Q + is chosen from
83. The process of any one of claims 42 to 78, wherein Q + is chosen from
R2 R3
84. The process of any one of claims 42 to 83, wherein R2 is a C1-C20 alkyl which is linear or branched or a C3-C12 cycloalkyl.
85. The process of claim 84, wherein R 2 is a C1-C 20 alkyl which is linear or branched.
86. The process of claim 85, wherein R2 is a CrCs alkyl which is linear.
87. The process of any one of claims 42 to 86, wherein R 3 is a C1-C 20 alkyl which is linear or branched or a C3-C1 2 cycloalkyl.
88. The process of claim 87, wherein R 3 is a C 1 -C 20 alkyl which is linear or branched.
89. The process of claim 84, wherein R 3 is a Ci-Cs alkyl which is linear.
90. The process of any one of claims 42 to 79, wherein R 4 is a C 1 -C 20 alkyl which is linear or branched or a C 3 -Ci 2 cycloalkyl.
91. The process of claim 90, wherein R 4 is a C1-C 20 alkyl which is linear or branched.
92. The process of claim 90, wherein R 4 is a CrC 8 alkyl which is linear.
93. A composition comprising a compound as defined in any one of claims 1 to 26 and a compound of formula (VIII):
LiD
(VIII)
wherein
D is chosen from CF 3 SO 3 -, (FSO 2 ) 2 N-, (CF 3 SO 2 ^N-, (CF 3 CF 2 SO 2 )2N-, (CF 3 SO 2 ) 3 C-, PF 6 " , CF 3 COO " , AsF 6 -, CH 3 COO-, (CN) 2 N-, NO 3 -, BF 4 " , CIO 4 " , (C 8 H 16 SO 2 ) 2 N-, and C 3 H 3 N 2 ' .
94. Use of a composition as defined in claim 93 as an electrolyte. |
COMPOUNDS, IONIC LIQUIDS, MOLTEN SALTS AND USES THEREOF
FIELD OF THE INVENTION
The present document relates to the field of electrochemistry. In particular, it relates to compounds that are useful as electrolytes such as molten salts or ionic liquids.
BACKGROUND OF THE INVENTION
An electrolyte in an electrochemical cell may conduct electricity through the movement of ions, charged species, towards an electrode having opposite electrical charge to the ions. Typically, the electrolytes consist of a salt, dissolved in a solvent, which may be water (aqueous solution) or one or more organic compounds (non-aqueous solution). Alternatively, molten salts or ionic liquids, or room temperature molten salts (materials and mixtures which consist of an ionically bound liquid at ambient temperatures) may be used.
In recent years, highly conductive electrolyte salts that are molten at room temperature have been developed for electrochromic windows, variable reflectance mirrors, batteries, capacitors, and other important devices.
US 6,853,472 describes molten salts including lithium or quarternary ammonium cations, and perfluorinated anions selected from the group consisting of trifluoromethylsulfonate (CF 3 SO 3 ), bis(trifluoromethylsulfonyl)imide ((CF 3 SO 2 ^N " ), bis(perfluoroethylsulfonyl)imide ((CF 3 CF 2 SO 2 ^N " ) and tris(trifluoromethylsulfonyl)methide ((CF 3 SO2)3C " ).
WO 2005/089390 describes methyl-propyl-imidazolium-bis-fluoro- sulfonylimide (MPI-FSI) and ethyl-1-methyl-3-imidazolium-bis-fluoro- sulfonylimide (EMI-FSI) as suitable molten salt electrolytes.
It would therefore be highly desirable to be provided with compounds that would represent an alternative to the compounds previously mentioned.
SUMMARY OF THE INVENTION
In accordance with one aspect there is provided a compound of formula (I):
wherein
R 2 is a hydrogen atom, a C1-C20 alkyl which is linear or branched, C3-C12 cycloalkyl, C-1-C12 heterocyclyl, C2-C20 alkenyl, C 2 -C 2 O alkynyl, C 6 -Ci 2 aryl, C 6 -C 2 O aralkyl, C 6 -C 20 alkylaryl, and Ci-Ci 2 heteroaryl;
R 3 is a hydrogen atom, a CrC 20 alkyl which is linear or branched, C 3 -Ci 2 cycloalkyl, Ci-Ci 2 heterocyclyl, C 2 -C 20 alkenyl, C 2 -C 2 O alkynyl, C 6 -Ci 2 aryl, C 6 -C 20 aralkyl, C 6 -C 20 alkylaryl, and Ci-Ci 2 heteroaryl;
R 4 is a hydrogen atom, a Ci-C 2 o alkyl which is linear or branched, C 3 -Ci 2 cycloalkyl, CrCi 2 heterocyclyl, C 2 -C 20 alkenyl, C 2 -C 20 alkynyl, C 6 -Ci 2 aryl, C 6 -C 20 aralkyl, C 6 -C 20 alkylaryl, and CrCi 2 heteroaryl; and
R 5 is a hydrogen atom, a Ci-C 20 alkyl which is linear or branched, C 3 -Ci 2 cycloalkyl, CrCi 2 heterocyclyl, C 2 -C 20 alkenyl, C 2 -C 20 alkynyl, C 6 -Ci 2 aryl, C 6 -C 20 aralkyl, C 6 -C 20 alkylaryl, and CrCi 2 heteroaryl, an effective protecting group for an amino group,
the heterocycles represented by Q + are as previously presented or substituted with 1 to 3 substituents chosen from of -NO 2 , -CN -OH, -CF 3 -COR 4 , -SH, - OMe, -OCH 2 Ph, -SMe, -SPh, -SCH 2 Ph, -COOH, -COOR 4 , -NH 2 , C 2 -C 20 alkenyl, CrC 20 alkoxy, CrC 20 alkyl, C 2 -C 20 alkynyl, C 6 -C 20 aralkyl, C 6 -Ci 2 aryl, C 3 -C 8 cycloalkyl, CrC 20 aminoalkyl, CrC 6 hydroxyalkyl, C 2 -Ci 2 heteroaryl, CrCi 2 , vinyl, C 4 -C 20 alkylvinyl, C 4 -C 20 vinylalkyl, and C 3 -C 20 expoxyalkyl,
the alkyl, cycloalkyl, heterocyclyl, alkenyl, alkynyl, aryl, aralkyl, alkylaryl, and heteroaryl being unsubstituted or substituted with 1 to 3 substituents chosen from F, Cl, Br, I 1 OH, a CrC 6 alkoxy, a CrC 6 hydroxy alkyl, NO 2 , CN, CF 3 , SO 3 " , C n F 2n+ I, CrCi 2 alkyl which is linear or branched, C 6 -Ci 2 aryl, C n H 2n+I , Ph 2 P(O)-, Ph 2 P-, Me 2 P(O)-, Me 2 P, Ph 2 P(S), Me 2 P(S), Ph 3 P=N-, Me 3 P=N-, C 6 HsCpH 2P -, CpH 2p +iC 6 H 4 — , CpH 2p+ iC 6 H 4 C n H 2n — , CH 2 =CHCpH 2P -,
CH 2
=CHC 6
H 5
-, CH 2
=CHC 6
H 4
CpH 2P+
I- and CH 2
=CHC p
H 2p
C 6
H 4
- where (1 < n, p < 48),
The compounds previously presented represent a very interesting alternative to the compounds previously proposed in the prior art. In fact, these compounds can be simply and rapidly prepared at low costs.
In accordance with another aspect there is provided a process for preparing a compound of formula (I):
wherein each of the Ri is independently F 1 CI, -N(Rs) 2 , or -CN,
Q + is chosen from
wherein
R2 is a hydrogen atom, a C1-C2 0 alkyl which is linear or branched, C3-C12 cycloalkyl, C1-C12 heterocyclyl, C2-C20 alkenyl, C2-C2 0 alkynyl, C6-C12 aryl, C6-C20 aralkyl, C6-C20 alkylaryl, and C1-C12 heteroaryl;
R3 is a hydrogen atom, a Ci-C 20 alkyl which is linear or branched, C 3 -Ci 2 cycloalkyl, C1-C12 heterocyclyl, C 2 -C 2 O alkenyl, C2-C20 alkynyl, C 6 -Ci 2 aryl, C6-C20 aralkyl, C 6 -C 2 O alkylaryl, and C1-C12 heteroaryl;
R 4 is a hydrogen atom, a C1-C20 alkyl which is linear or branched, C 3 -Ci 2 cycloalkyl, C1-C12 heterocyclyl, C 2 -C 20 alkenyl, C 2 -C 20 alkynyl, C 6 -Ci 2 aryl, C 6 -C 20 aralkyl, C 6 -C 20 alkylaryl, and CrCi 2 heteroaryl; and
R5 is a hydrogen atom, a CrC 20 alkyl which is linear or branched, C 3 -Ci 2 cycloalkyl, C 1 -C 12 heterocyclyl, C 2 -C 20 alkenyl, C 2 -C 20
alkynyl, C 6 -Ci 2 aryl, C 6 -C 2 O aralkyl, C 6 -C 20 alkylaryl, and CrCi 2 heteroaryl, an effective protecting group for an amino group,
the heterocycles represented by Q + are as previously presented or substituted with 1 to 3 substituents chosen from -NO 2 , -CN -OH, -CF 3 -COR 4 , -SH,
-OMe, -OCH 2 Ph, -SMe, -SPh, -SCH 2 Ph, -COOH, -COOR 4 , -NH 2 , C 2 -C 20 alkenyl, CrC 20 alkoxy, CrC 20 alkyl, C 2 -C 20 alkynyl, C 6 -C 20 aralkyl, C 6 -Ci 2 aryl, C 3 -Cs cycloalkyl, CrC 20 aminoalkyl, CrC 6 hydroxyalkyl, C 2 -Ci 2 heteroaryl, CrCi 2 , vinyl, C 4 -C 20 alkylvinyl, C 4 -C 20 vinylalkyl, and C 3 -C 20 expoxyalkyl,
the alkyl, cycloalkyl, heterocyclyl, alkenyl, alkynyl, aryl, aralkyl, alkylaryl, and heteroaryl being unsubstituted or substituted with 1 to 3 substituents chosen from F, Cl, Br, I, OH, a d-C 6
alkoxy, a CrC 6
hydroxy alkyl, NO 2
, CN, CF 3
, SO 3 '
, C n
F 2n+
I, CrCi 2
alkyl which is linear or branched, C 6
-Ci 2
aryl, C n
H 2n+
I, Ph 2
P(O)-, Ph 2
P-, Me 2
P(O)-, Me 2
P, Ph 2
P(S), Me 2
P(S), Ph 3
P=N-, Me 3
P=N-, CeHsCpH 2P
-, CpH 2p+
iC 6
H 4
— , CpH2p+iC 6
H 4
C n
H 2n
— ,
CH 2 =CHC 6 H 5 -, CH 2 =CHC 6 H 4 CpH 2P+ I- and CH 2 =CHC p H 2p C 6 H 4 - __C p H 2p - , where (1 < n, p < 48),
comprising the step of reacting together a compound of formula (V) and a compound of formula (VI) :
wherein
Ri and Q are as previously defined;
M + is chosen from Li + , Na + , K + , and Cs +
X ' is chosen from P 1 Cl " , Br " , I " , CH 3 COO-, PhCH 2 COO-, CN " , CF 3 COO-, SO 4 2" , CF 3 SO 3 -, BF 4 " , PF 6 ' , NO 3 ' , CIO 4 " , SbF 6 " , and RuO 4 " .
Such a process is useful and efficient to prepare, at low costs, compounds of general formula (I). This process is simple and can easily be carried out.
According to another aspect, there is provided a process for preparing a compound of formula (Ia):
wherein
R 2 is a hydrogen atom, a C 1 -C 20 alkyl which is linear or branched, C3-C12 cycloalkyl, C1-C12 heterocyclyl, C2-C20 alkenyl, C2-C20 alkynyl, C 6 -Ci 2 aryl, C6-C 2 0 aralkyl, C6-C20 alkylaryl, and C1-C12 heteroaryl;
R3 is a hydrogen atom, a C1-C 20 alkyl which is linear or branched, C3-C12 cycloalkyl, C1-C12 heterocyclyl, C2-C20 alkenyl, C 2 -C 2 O alkynyl, C6-C1 2 aryl, C6-C 2 0 aralkyl, C6-C 2 0 alkylaryl, and C1-C12 heteroaryl; and
R 4 is a hydrogen atom, a C 1 -C 2 O alkyl which is linear or branched, C3-C12 cycloalkyl, C 1 -C 12 heterocyclyl, C 2 -C20 alkenyl, C2-C20 alkynyl, C6-C12 aryl, C6-C20 aralkyl, Cβ-C∑o alkylaryl, and C1-C12 heteroaryl,
the heterocycles represented by Q + are as previously presented or substituted with 1 to 3 substituents chosen from -NO 2 , -CN -OH, -CF 3 -COR 4 , -SH,
-OMe, -OCH 2 Ph, -SMe, -SPh, -SCH 2 Ph, -COOH, -COOR 4 , -NH 2 , C 2 -C 20 alkenyl, CrC 20 alkoxy, CrC 20 alkyl, C 2 -C 20 alkynyl, Ce-C 20 aralkyl, C 6 -Ci 2 aryl, C3-C 8 cycloalkyl, CrC 20 aminoalkyl, CrC 6 hydroxyalkyl, C 2 -Ci 2 heteroaryl, CrCi 2 , vinyl, C 4 -C 20 alkylvinyl, C 4 -C 20 vinylalkyl, and C 3 -C 20 expoxyalkyl,
the alkyl, cycloalkyl, heterocyclyl, alkenyl, alkynyl, aryl, aralkyl, alkylaryl, and heteroaryl being unsubstituted or substituted with 1 to 3 substituents chosen from F, Cl, Br, I, OH, a CrC 6 alkoxy, a CrC 6 hydroxy alkyl, NO 2 , CN, CF 3 , SO 3 " , C n F 2n+1 , CrCi 2 alkyl which is linear or branched, C 6 -Ci 2 aryl, C n H 2n+I , Ph 2 P(O)-, Ph 2 P-, Me 2 P(O)-, Me 2 P, Ph 2 P(S), Me 2 P(S), Ph 3 P=N-, Me 3 P=N-, CeHsCpH 2P -, CpH 2p+ i C 6 H 4 -, CpH 2P+ IC 6 H 4 C n H 2n -, CH 2 =CHC p H 2p -,
CH 2 =CHC 6 Hs-, CH 2 =CHC 6 H 4 CpH 2 p + i—, and CH 2 =CHC p H 2p CeH 4 — v - 7 ^C p Ha,- , where (1 < n, p < 48), O F F
comprising the step of reacting a compound of formula (II):
O
R 1 S Ri
O (II) wherein each of the Ri is as previously defined,
with a compound of formula (III):
(III)
wherein
Q + is as previously defined for formula (Ia); and
each of Re is independently H, Li, Na, K, Cs 1 or (R 7 ) 3 Si-, each of the R 7 being independently a C1-C12 alkyl.
According to another aspect, there is provided a process for preparing a compound of formula (Ib):
Rs is F; and
Q + is chosen from
wherein
R 2 is a hydrogen atom, a C 1 -C 20 alkyl which is linear or branched, C3-C12 cycloalkyl, C1-C12 heterocyclyl, C2-C20 alkenyl, C2-C20 alkynyl, C 6 -C^ aryl, C6-C20 aralkyl, C6-C20 alkylaryl, and C- 1 -C12 heteroaryl;
R 3 is a hydrogen atom, a C1-C20 alkyl which is linear or branched, C3-C12 cycloalkyl, C1-C12 heterocyclyl, C2-C20 alkenyl, C2-C20 alkynyl, C 6 -Ci 2 aryl, C 6 -C 2 O aralkyl, C 6 -C 2 O alkylaryl, and Ci-C-| 2 heteroaryl; and
R 4 is a hydrogen atom, a Ci-C 2O alkyl which is linear or branched, C 3 -Ci 2 cycloalkyl, C1-C12 heterocyclyl, C 2 -C 20 alkenyl, C 2 -C 20 alkynyl, C 6 -Ci 2 aryl, C 6 -C 20 aralkyl, Ce-C 20 alkylaryl, and CrCi 2 heteroaryl,
the heterocycles represented by Q + are as previously presented or substituted with 1 to 3 substituents chosen from -NO 2 , -CN -OH, -CF 3 -COR 4 , -SH, -OMe, -OCH 2 Ph, -SMe, -SPh, -SCH 2 Ph, -COOH, -COOR 4 , -NH 2 , C 2 -C 20 aikenyl, d- C 20 alkoxy, Ci-C 2 o alkyl, C 2 -C 2 O alkynyl, C6-C20 aralkyl, C 6 -Ci 2 aryl, C 3 -C 8 cycloalkyl, C 1 -C 20 aminoalkyl, CrC 6 hydroxyalkyl, C 2 -Ci 2 heteroaryl, Ci-Ci 2 vinyl, C4-C20 alkylvinyl, C4-C20 vinylalkyl, and C 3 -C 20 expoxyalkyl,
the alkyl, cycloalkyl, heterocyclyl, aikenyl, alkynyl, aryl, aralkyl, alkylaryl, and heteroaryl being unsubstituted or substituted with 1 to 3 substituents chosen from F, Cl, Br, I, OH, a C 1 -C 6 alkoxy, a C 1 -C 6 hydroxy alkyl, NO 2 , CN, CF 3 , SO 3 " , C n F 2n +-!, CrCi 2 alkyl which is linear or branched, C 6 -Ci 2 aryl, C n H 2n +i, Ph 2 P(O)-, Ph 2 P-, Me 2 P(O)-, Me 2 P, Ph 2 P(S), Me 2 P(S), Ph 3 P=N-, Me 3 P=N-, C 6 H5CpH 2 p— , CpH 2p +i C 6 H 4 -, CpH2p+iC 6 H4C n H 2n — , CH 2 = CHC p H 2p — ,
CH 2 =CHC 6 H 5 -, CH 2 =CHC 6 H 4 CpH 2P+ I-, and CH 2 =CHC p H 2p C 6 H 4 - ^-C p H 2p - , where (1 < n, p < 48),
comprising the steps of :
a) reacting SO 2 CI 2 with a compound of formula (III):
R 6 . -R 6
• N'
(III)
wherein
Q + is as previously defined for formula (Ib); and
each of the R 6 is independently H, Li, Na, K, Cs, or (Rr) 3 Si-, each of the R 7 being independently a Ci-Ci 2 alkyl
so as to obtain a compound of formula (Ic);
O o
Cl- -N- -Cl
I l
O (Ic)
wherein
Q + is as previously defined for formula (Ib); and
b) reacting the compound of formula (Ic) with a compound of formula MF, wherein M is Li, Na, K, or Cs, so as to obtain the compound of formula (Ib).
According to another aspect, there is provided a process for preparing a compound of formula (Ib):
o o
r\g O IN O r\g
0 Q ° (Ib)
wherein
Re is F; and
Q + is chosen from
wherein
R 2 is a hydrogen atom, a C1-C 20 alkyl which is linear or branched, C 3 -Ci 2 cycloalkyl, C1-C12 heterocyclyl, C2-C2 0 alkenyl, C2-C2 0 alkynyl, C 6 -Ci 2 aryl, C6-C20 aralkyl, C 6 -C 2 O alkylaryl, and C1-C12 heteroaryl;
R3 is a hydrogen atom, a C1-C20 alkyl which is linear or branched, C3-C12 cycloalkyl, Ci-Ci 2 heterocyclyl, C 2 -C 2O alkenyl, C 2 -C 20 alkynyl, C 6 -Ci 2 aryl, C 6 -C 2 O aralkyl, C 6 -C2o alkylaryl, and CrCi 2 heteroaryl; and
R 4 is a hydrogen atom, a Ci-C 20 alkyl which is linear or branched, C3-C12 cycloalkyl, C1-C12 heterocyclyl, C2-C20 alkenyl, C2-C2 0 alkynyl, C 6 -Ci 2 aryl, C 6 -C 20 aralkyl, C 6 -C 20 alkylaryl, and C 1 -C1 2 heteroaryl, the heterocycles represented by Q + are as previously presented or substituted with 1 to 3 substituents chosen from -NO 2 , -CN -OH, -CF 3 -COR 4 , -SH, -
OMe, -OCH 2 Ph, -SMe, -SPh, -SCH 2 Ph, -COOH, -COOR 4 , -NH 2 , C 2 -C 20 alkenyl, CrC 20 alkoxy, CrC 20 alkyl, C 2 -C 20 alkynyl, Ce-C 20 aralkyl, Ce-Ci 2 aryl, C 3 -C 8 cycloalkyl, CrC 20 aminoalkyl, C1-C6 hydroxyalkyl, C 2 -Ci 2 heteroaryl, CrCi 2 , vinyl, C 4 -C 20 alkylvinyl, C 4 -C 20 vinylalkyl, and C 3 -C 20 expoxyalkyl,
the alkyl, cycloalkyl, heterocyclyl, alkenyl, alkynyl, aryl, aralkyl, alkylaryl, and heteroaryl being unsubstituted or substituted with 1 to 3 substituents chosen from F, Cl, Br, I 1 OH, a CrC 6 alkoxy, a CrC 6 hydroxy alkyl, NO 2 , CN, CF 3 , SO 3 " , C n F 2n+ I, CrCi 2 alkyl which is linear or branched, C 6 -Ci 2 aryl, C n H 2n+ I, Ph 2 P(O)-, Ph 2 P-, Me 2 P(O)-, Me 2 P, Ph 2 P(S), Me 2 P(S), Ph 3 P=N-, Me 3 P=N-, C 6 HsCpH 2P -, CpH 2p+ i C 6 H 4 -, CpH 2 p + iC 6 H 4 C n H 2n — , CH 2 =CHC p H 2 p— ,
CH 2 =CHC 6 Hs-, CH 2 = CHC 6 H 4 CpH 2 p+i— , and CH 2 =CHCpH 2 pC 6 H 4 — , ^ 7 -C p H 2P - , where: (1 < n, p < 48),
comprising the steps of :
a) reacting a compound of formula (Ha):
wherein
each of the R 9 is independently Cl, Br, or I
with a compound of formula (Ilia):
R 1 6 v θ ^^6
(Ilia)
wherein
T + is Li + , Na + , K + ,Cs + or H + and
each of the R 6 is independently H, Li, Na, K, Cs, or (RrbSi-, each of the Rγ being independently a C1-C12 alkyl.
so as to obtain a compound of formula (VII);
wherein
each of the Rg is as previously defined for formula (Ha); and
T + is as previously defined for formula (Ilia); and
b) reacting the compound of formula (VII) with a compound of formula Q-Rs, wherein Q and R 8 are as previously defined in formula (Ib), so as to obtain the compound of formula (Ib).
The term "alkyl" as used herein refers to linear or branched radicals. Examples of such radicals include, but are not limited to, methyl, ethyl, n- propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, pentyl, iso-amyl, hexyl and the like. For example, the alkyl can be a methyl.
The term "aryl" has used herein refers to a cyclic or polycyclic aromatic ring. The aryl group can be a phenyl or napthyl.
The term "heteroaryl" has used herein refers to an aromatic cyclic or fused polycyclic ring system having at least one heteroatom chosen from N, O, and S. For example, the heteroaryl groups include, but are not limited to, furyl, thienyl, pyridyl, quinolinyl, isoquinolinyl, indolyl, isoindolyl, triazolyl, pyrrolyl, tetrazolyl, imidazolyl, pyrazolyl, oxazolyl, thiazolyl, benzofuranyl, benzothiophenyl, carbazolyl, benzoxazolyl, pyrimidinyl, benzimidazolyl, quinoxalinyl, benzothiazolyl, naphthyridinyl, isoxazolyl, isothiazolyl, purinyl, quinazolinyl, among others.
The term "heterocyclyl" includes non-aromatic rings or ring systems that contain at least one ring having at least one hetero atom (such as nitrogen, oxygen or sulfur). For example, this term can include all of the fully saturated and partially unsaturated derivatives of the above mentioned heteroaryl groups. Examples of heterocyclic groups include, without limitation, pyrrolidinyl, tetrahydrofuranyl, morpholinyl, thiomorpholinyl, piperidinyl, piperazinyl, thiazolidinyl, isothiazolidinyl, and imidazolidinyl.
In the compounds and processes previously presented, Q + can be chosen from
R 2 R?
θ/ ®/
// λ and fl
O
Alternatively, Q + can be chosen from:
R2 X R 3 R2 N R 3 R 2 R 3
According to another example Q + can be chosen from
R 2 can be a C 1 -C 20 alkyl which is linear or branched or a C3-C12 cycloalkyl. According to one example, R2 can be a C1-C20 alkyl which is linear or branched. According to another example, R 2 can be a C-i-Cβ alkyl which is linear. R 3 can be a C1-C20 alkyl which is linear or branched or a C 3 -Ci 2 cycloalkyl. According to one example, R 3 can be a C1-C20 alkyl which is linear
or branched .Accord ing to another example, R 3 is a CrC 8 alkyl which is linear. R 4 can be a C1-C2 0 alkyl which is linear or branched or a C3-C12 cycloalkyl.According to one example, R 4 can be a C1-C20 alkyl which is linear or branched.According to another example, R 4 can be a Ci-Ce alkyl which is linear. According to a further example, R 4 can be a CrC 4 alkyl which is linear.
The compounds previously presented can have a conductivity of at least 0.0001 mS cm "1 . For example, the conductivity can be of at least 1 mS cm "1 , or of at least 10 mS cm "1 . Alternatively, they can have a conductivity of about 0.0001 to about 100 mS cm "1 . The compounds can have a melting point below 100 ° C. For example, the melting point can be below 40 ° C, or below 25 ° C. Alternatively, the compounds can have a melting point of about 0 0 C to about 100 ° C. For example, the Ri group can be a halogen atom. According to one example, Ri is F or Cl. According to another example, Ri is F.
The compounds previously presented can be used as a molten salt, an ionic liquid or an electrolyte. These compounds can also be used in an electrochemical device such as a battery.
In the process for preparing the compounds represented by formula (I), the reaction can be carried out in water so that the so-obtained product of formula (I) precipitates and the so-formed byproduct of formula M + X " is at least substantially soluble. For example, M + can be K + . For example, X " can be F " , Cl " , Br " , or I " . According to another example, X " is Cl " , or Br " . Each of the Ri can be a halogen atom. According to another example, Ri can be Cl " or F " . According to another example, Ri can be F " .
In the process for preparing compounds represented by formula (Ia), the compound of formula (III) can be a compound of formula (IV):
wherein
Q + is as previously defined in formula (I); and
each of the R 7 is independently a C1-C12 alkyl.
For example, each of the R 7 can be the same. According to one example, R 7 can be methyl. The compounds of formulas (II) and (III) can be reacted together at a temperature of about -78 to about 110 ° C.The temperature can be for example about -5 to about 25 ° C, or about 15 to about 25 0 C. Ri can be F or Cl. According to one example, Ri can be F.
In the process for preparing compounds represented by formula (Ib), step (a) can be carried out at a temperature of about -78 to about 110 ° C. For example, the temperature can be about -5 to about 25 ° C or about 15 to about 25 0 C. Step (b) can be carried out in the presence of an aprotic solvent. For example, the aprotic solvent can be a polar solvent such as nitromethane or acetonitrile. According to one example, the compound of formula (III) can be a compound of formula (IV):
wherein
Q + is as previously defined in formula (Ib); and
each of the R 7 is independently a C1-C12 alkyl.
Each of the R 7 can be the same. For example, R 7 can be a methyl.
In the process for preparing compounds represented by formula (Ib), the compound of formula (Ilia) can be a compound of formula (IVa):
wherein
T + is as previously defined in formula (Ilia); and
each of the R 7 is independently a C 1 -C 12 alkyl.
Each of the R 7 can be the same.For example, each of the R 7 can be a methyl.
In accordance with another aspect there is provided a molten salt comprising a compound as defined in the present invention.
In accordance with another aspect there is provided an ionic liquid comprising a compound as defined in the present invention.
In accordance with another aspect, there is provided an electrolyte comprising a compound as defined in the present invention.
In accordance with another aspect, there is provided an electrochemical device comprising a compound as defined in the present invention.
In accordance with another aspect, there is provided a battery comprising a compound as defined in the present invention.
In accordance with another aspect, there is provided a method of using a compound as previously defined, which comprises contacting the compound with electrodes and using it as an electrolyte.
In accordance with another aspect, there is provided a method of using a compound as previously defined, which comprises introducing the compound in the manufacture of a proton exchange membrane.
The compounds previously described can be used in many applications. For example, they can be used as solvents for organic and organometallic syntheses and catalysis. They can also be used as electrolytes (for example in electrochemistry or in fuel and solar cells), as lubricants, as a stationary phase for chromatography, as matrices for mass spectrometry, supports for the immobilization of enzymes, in separation technologies, as liquid crystals, templates for the synthesis of mesoporous, nano-materials and ordered films, materials for embalming and tissue preservation, etc.
The compounds previously mentioned can be used in various solutions (dry cleaning, metal extraction, personal care, embalming, household products, coatings, etc.) and in electrochemistry ( batteries, solar panel, ion propulsion, fuel cells, electro-optics, etc.). The can also be used in view of their various interesting properties for heat transfer or as lubricants. They can also be used in drug delivery, biomass processing, biocides etc.
The compounds previously mentioned can also be useful for preparing compositions for lithium-ions batteries.
In accordance with another aspect there is provided a composition comprising a compound of formula (I) and a compound of formula (VIII):
(I) wherein each of the Ri is independently F, Cl, -N(Rs^, or -CN; Q + is chosen from
wherein
D is chosen from CF 3 SO 3 -, (FSO 2 ) 2 N- ,(CF 3 SO 2 )2N-, (CF 3 CF 2 SO 2 ) 2 N-, (CF 3 SO 2 ) 3 C-, PF 6 " , CF 3 COO-, AsF 6 " , CH 3 COO " , (CN) 2 N " , NO 3 " , BF 4 " , CIO 4 " , (C 8 H 16 SO 2 ) 2 N " , and C 3 H 3 N 2 "
R 2 is a hydrogen atom, a C 1 -C2 0 alkyl which is linear or branched, C 3 - Ci 2 cycloalkyl, Ci-Ci 2 heterocyclyl, C 2 -C 20 alkenyl, C 2 -C 20 alkynyl, C 6 -Ci 2 aryl, C 6 -C 20 aralkyl, C 6 -C 20 alkylaryl, and Ci-Ci 2 heteroaryl;
R 3 is a hydrogen atom, a CrC 20 alkyl which is linear or branched, C 3 -Ci 2 cycloalkyl, CrCi 2 heterocyclyl, C 2 -C 20 alkenyl, C 2 -C 20 alkynyl, C 6 -Ci 2 aryl, C 6 -C 20 aralkyl, C 6 -C 20 alkylaryl, and C1-C12 heteroaryl;
R 4 is a hydrogen atom, a CrC 20 alkyl which is linear or branched, C 3 -Ci 2 cycloalkyl, C1-C1 2 heterocyclyl, C 2 -C 20 alkenyl, C 2 -C 20 alkynyl, C 6 -Ci 2 aryl, C 6 -C 20 aralkyl, C 6 -C 20 alkylaryl, and CrCi 2 heteroaryl; and
R 5 is a hydrogen atom, a CrC 20 alkyl which is linear or branched, C 3 -Ci 2 cycloalkyl, C1-C12 heterocyclyl, C 2 -C 20 alkenyl, C 2 -C 20 alkynyl, C 6 -Ci 2 aryl, C 6 -C 20 aralkyl, C 6 -C 20 alkylaryl, and CrCi 2 heteroaryl, an effective protecting group for an amino group,
the heterocycles represented by Q + are as previously presented or substituted with 1 to 3 substituents chosen from of -NO 2 , -CN -OH, -CF 3 -COR 4 , -SH, - OMe, -OCH 2 Ph, -SMe, -SPh, -SCH 2 Ph, -COOH, -COOR 4 , -NH 2 , C 2 -C 20 alkenyl, CrC 20 alkoxy, CrC 20 alkyl, C 2 -C 20 alkynyl, C 6 -C 20 aralkyl, C 6 -Ci 2 aryl, C 3 -Ce cycloalkyl, CrC 20 aminoalkyl, CrC 6 hydroxyalkyl, C 2 -Ci 2 heteroaryl, CrCi 2 , vinyl, C 4 -C 20 alkylvinyl, C 4 -C 20 vinylalkyl, and C 3 -C 20 expoxyalkyl,
the alkyl, cycloalkyl, heterocyclyl, alkenyl, alkynyl, aryl, aralkyl, alkylaryl, and heteroaryl being unsubstituted or substituted with 1 to 3 substituents chosen from F, Cl, Br, I 1 OH, a CrC 6 alkoxy, a CrC 6 hydroxy alkyl, NO 2 , CN, CF 3 , SO 3 " , C n F 2n+ I, CrCi 2 alkyl which is linear or branched, C 6 -Ci 2 aryl, C n H 2n+I ,
Ph 2 P(O)-, Ph 2 P-, Me 2 P(O)-, Me 2 P, Ph 2 P(S), Me 2 P(S), Ph 3 P=N-, Me 3 P=N-, CeHsCpH 2P -, CpH 2 p+iC6H4— , CpH 2P+ ICeH 4 C n H 2n -, CH 2 =CHC p H 2p — ,
CH 2 =CHC 6 H 5 -, CH 2 =CHC 6 H 4 CpH 2P+1 -, and CH 2 =CHC p H 2p C 6 H 4 - ^^C p H 2p - where (1 < n, p < 48),
In accordance with another aspect, there is provided a method of using a compound as previously defined, which comprises mixing the compound with a compound of formula (VIII) so as to obtain a mixture and using said mixture as an electrolyte, for example in a lithium-ion battery.
DETAILED DESCRIPTION OF OF THE INVENTION
The following examples are given in a non-limitative manner.
EXAMPLE 1
O
H 3 C^CH 3
Compound 1
2 g (14.81 mM) of sulfuryl chloride are charged under argon into a 500 ml_ flask and mixed with 50 ml_ of anhydrous acetonitrile. Then, the mixture is cooled at -20 0 C. 14.81 ml_ of a potassium hexamethyldisilazane (KHMDS) solution (0.5 M in toulene) is added dropwise over 5 minutes at -20 0 C under argon. The mixture is stirred at room temperature for 12h. Then, the solvent is removed under vacuum and the resulting brown crude is dissolved in 100 mL acetonitrile and mixed with 1.72 g (29.08 mM) of anhydrous KF. The reaction mixture is heated and stirred over 12h. Then, the solid particles are filtered- out and the solvent is removed under vacuum and replaced by 100 mL of
distilled water. The aqueous solution is charged into a 500 ml_ flask and mixed with 100 ml_ of an aqueous solution of 1.68 g (7.4 mM) of N 1 N- dimethyl-pyrrolidinium iodide. The resulting compound 1 is then extracted by dichloromethane and isolated in pure form.
EXAMPLE 2
O Q O
I l ^ I l
F-S-N-S-F
Il Il
O O
Compound 2
Potassium bis(fluoromethanesulfonimide) KFSI is prepared as previously described and 2.2 g (10 mM) of this compound are used to prepare an aqueous solution by charging it into a 500 ml_ flask and dissolving it into 50 mL of distilled water. 2.41 g (10 mM) of N.N-ethylmethylpyrrolidinium iodide is dissolved into 50 mL of distilled water and then mixed with KFSI solution. The N,N-ethylmethylpyrrolidinium iodide exchanges anions with KFSI in water. The Potassium iodide stays in the aqueous phase and the desired molten salt 2 is decanted. The organic layer is decanted, extracted with 40 mL of CH 2 CI 2 and then washed with 80 mL of distilled H 2 O and dried over anhydrous MgSO 4 . After concentration with a rotative evaporator, the translucent ionic liquid obtained is dried under vacuum at 60 0 C for 3 hours. Its purity is confirmed by NMR ( 1 H, 13 C, 19 F) and cyclic voltammetry.
EXAMPLE 3
O Q O
I l V -^ I l
F-S-N-S-F
Il Il
O O
Compound 3
Potassium bis(fluoromethanesulfonimide) KFSI is prepared as previously described and 2.2 g (10 mM) of this compound are used to prepare an aqueous solution by charging it into a 500 ml_ flask and dissolving it into 50 mL of distilled water. 2.37 g (10 mM) of N,N-ethylmethylpyrrolium iodide was dissolved into 50 mL of distilled water and then mixed with KFSI solution. The N,N-ethylmethylpyrrolium iodide exchanges anions with KFSI in water. The potassium iodide stays in the aqueous phase and the desired molten salt 3 is decanted. The organic layer was decanted, extracted with 40 mL of CH 2 CI 2 and then washed with 80 mL of distilled H 2 O and dried over anhydrous MgSO 4 . After concentration with a rotative evaporator, the translucent ionic liquid obtained is dried under vacuum at 60 0 C for 3 hours. Its purity is confirmed by NMR (1 H, 13C, 19F) and cyclic voltammetry.
EXAMPLE 4
CH 3
@/
N
W
O O I l Q w O I l
F-S-N-S-F
Il I l
O O
Compound 4
Potassium bis(fluoromethanesulfonimide) KFSI is prepared as previously described and 2.2 g (10 mM) of this compound are used to prepare an aqueous solution by charging it into a 500 ml_ flask and dissolving it into 50 mL of distilled water. 2.13 g (10 mM) of, N-methyloxazolinium iodide is dissolved into 50 mL of distilled water and then mixed with KFSI solution. The N-methyloxazolinium iodide exchanges anions with KFSI in water. The potassium iodide stays in the aqueous phase and the desired molten salt 4 is decanted. The organic layer is decanted, extracted with 60 mL of CH2CI2 and then washed with 100 mL of distilled H2O and dried over anhydrous MgSO 4 . After concentration with a rotative evaporator, the translucent ionic liquid obtained is dried under vacuum at 60 0 C for 3 hours. Its purity is confirmed by NMR ( 1 H, 13 C, 19 F) and cyclic voltammetry.
The person skilled in the art would clearly recognize that all the references cited in this application are hereby incorporated by references. The person skilled in the art would also recognize that various modifications, adaptations, and variations may be brought to the previously presented preferred embodiments without departing from the scope of the following claims.