CHEMPHYSCHEM
ARTICLES
2
19
1
30.56 (CH=CH ), 148.21 ppm (C ); F NMR (282 MHz, CDCl , 258C,
C 38.47, H 4.64, N 8.41; found: C 38.29, H 4.26, N 8.28; yield: 98%;
white crystals.
2
3
À1
CFCl ): À79.32 ppm; IR (ATR): n¯ =1053, 1134, 1176, 1348 cm
;
3
+
HRMS (ESI/APCI): m/z: calcd for [C H N ]: 193.1699; found:
12
21
2
1
-Allyl-2-isopropyl-3-(2-methoxyethyl)-4,5-dimethylimidazolium
1
93.1697; yield: 95%; light yellow oil.
3
bis(trifluoromethylsulfonyl)imide
[C2O1 A i
C C m im][NTf ]
(11 c):
2
2
1
3
H NMR (300 MHz, CDCl , 258C, TMS): d=1.43 [d, J =7.2 Hz, 6H;
3
H,H
4/5
2
-Isopropyl-1-(2-methoxyethyl)-3,4,5-trimethylimidazolium bis(tri-
fluoromethylsulfonyl)imide [C2O1C C m im][NTf ] (7c): H NMR
300 MHz, CDCl3, 258C, TMS): d=1.45 [d,
CH(CH ) ], 2.23 (s, 3H; CH C ), 2.24 (s, 3H; CH C ), 3.31 (s, 3H;
OCH ), 3.53–3.66 (m, 1H; CH), 3.59 (t, J =5.1 Hz, 2H; CH O), 3.73
s, 3H, NCH ), 4.25 ppm (t, JH,H =5.1 Hz, 2H; NCH ); C NMR
3 2
75 MHz, CDCl , 258C, TMS): d=8.50 (CH C ), 8.86 (CH3C ), 18.60
3 3
CH(CH ) ], 25.31 (CH), 32.81 (NCH ), 45.70 (NCH ), 59.04 (OCH ),
3 2 3 2 3
4/5
CH(CH ) ], 2.19 (s, 3H; CH C ), 2.27 (s, 3H; CH C ), 3.33 (s, 3H;
OCH ), 3.55–3.66 [m, 1H; CH(CH ) ], 3.63 (t, JH,H =5.0 Hz, 2H;
CH O), 4.32 (t, JH,H =5.0 Hz, 2H; CH CH O), 4.74–4.78 (m, 2H;
CH CH=CH ), 4.95 (dd, J =18.2 Hz, J =1.1 Hz, 1H; CH=CH H ),
5
5
1
3 2
3
3
1
i3
2
2
3
3
3
3 2
(
J
=7.7 Hz, 6H;
H,H
4/5
3
4/5
2
2
2
3
2
3
3
3
2
3
2
2
H,H
H,H
E
Z
3
H,H
2
3
2
.39 (dd, JH,H =10.5 Hz,
J
=1.1 Hz, 1H; CH=CH H ), 5.87–
E Z
3
13
H,H
13
(
(
[
7
.98 ppm (m, 1H; CH=CH ); C NMR (75 MHz, CDCl , 258C, TMS):
4/5
4/5
2
3
4/5
4/5
d=8.28 (CH3C ), 8.93 (CH3C ), 19.56 [CH(CH ) ], 25.48 [CH(CH ) ],
3 2
3 2
4
5.88 (CH CH O), 47.79 (CH CH=CH ), 59.07 (OCH ), 69.97 (CH O),
2 2 2 2 3 2
1
4/5
0.13 (CH O), 119.98 (q, J =321.5 Hz; CF ), 125.70 (C ), 127.02
2 3
C ), 148.88 ppm (C ); F NMR (282 MHz, CDCl , 258C, CFCl ):
C,F
19
1
4/5
118.31 (CH=CH ), 119.91 (q, JC,F =321.5 Hz; CF ), 126.41 (C ),
4
/5
2
2
3
(
3
3
4/5
2
19
1
26.77 (C ), 130.39 (CH=CH ), 149.34 ppm (C ); F NMR (282 MHz,
À1
2
À79.37 ppm; IR (ATR): n¯ =1052, 1134, 1175, 1348 cm ; HRMS (ESI/
CDCl , 258C, CFCl ): À79.36 ppm; IR (ATR): n¯ =1054, 1135, 1178,
+
3
3
APCI): m/z: calcd for [C H N O ]: 211.1805; found: 211.1806;
12
23
2
À1
+
1
348 cm ; HRMS (ESI/APCI): m/z: calcd for [C H N O ]: 237.1961;
14 25 2
yield: 99%; white crystals.
found: 237.1960; yield: 99%; yellow oil.
1
-(2-Allyloxyethyl)-2-isopropyl-3,4,5-trimethylimidazolium
bis(tri-
1
Characterization of Dicyanamide Ionic Liquids 6–11d
-Allyl-2-isopropyl-3,4,5-trimethylimidazolium dicyanamide
fluoromethylsulfonyl)imide [C2OAC1C m im][NTf ] (8c): H NMR
i3
2
2
3
(
300 MHz, CDCl3, 258C, TMS): d=1.43 [d, JH,H =7.2 Hz, 6H;
1
4/5 4/5
CH(CH ) ], 2.22 (CH C ), 2.23 (CH3C ), 3.58–3.70 [m, 1H; CH(CH ) ]
1
3
2
3
3 2
[
C C C m im][N(CN) ] (6d): H NMR (300 MHz, CDCl , 258C, TMS):
A 1 i3 2 2 3
3 4/5
3
3
3
5
1
5
.65 (t, J =5.0 Hz, 6H; CH O), 3.73 (m, 3H; NCH ), 3.93 (d, J
=
H,H
2
3
H,H
H,H
d=1.52 [d, J =7.2 Hz, 6H; CH(CH ) ], 2.27 (s, 3H; CH C ), 2.33
(
4
5
3
3
H,H
4/5
3 2
3
.4 Hz; OCH CH), 4.25 (t, J =5.0 Hz, 2H; NCH ), 5.18 (d, J
0.6 Hz, 1H; CH=CH H ), 5.19 (d, JH,H =17.3 Hz, 1H; CH=CH H ),
.79 ppm (ddt, JH,H =17.3, 10.6, 5.4 Hz, 1H; CH=CH ); C NMR
=
2
H,H
2
s, 3H; CH3C ), 3.45–3.58 [m, 1H; CH(CH ) ], 3.83 (s, 3H; NCH ),
3
3
2
3
Z
E
Z
E
3
.79–4.83 (m, 2H; NCH ), 4.94 (d, JH,H =17.1 Hz, 1H; CH=CH H ),
2 E Z
.38 (d, J =10.5 Hz, 1H; CH=CH H ), 5.89–6.02 ppm (m, 1H; CH=
3
13
2
3
4/5
4/5
H,H
E
Z
(
[
(
75 MHz, CDCl , 258C, TMS): d=8.47 (CH C ), 8.87 (CH3C ), 18.64
CH(CH ) ], 25.24 [CH(CH ) ], 32.81 (NCH ), 45.73 (NCH ), 67.81
OCH CH), 72.40 (CH O), 118.02 (CH=CH ), 120.00 (q, J =321.5 Hz;
13
4/5
3
3
CH2); C NMR (75 MHz, CDCl , 258C, TMS): d=8.69 (CH C ), 8.96
3
3
3
2
3 2
2
3
4/5
(CH3C ), 19.18 [CH(CH ) ], 25.42 [CH(CH ) ], 32.93 (NCH ), 47.58
1
3 2 3 2 3
2
2
2
C,F
4/5
4/5
(
1
2
NCH ), 118.36 (CH=CH ), 119.69 [N(CN) ], 126.02 (C ), 127.15 (C ),
4
/5
4/5
2
2
2
2
CF ), 125.75 (C ), 127.02 (C ), 133.79 (CH=CH ), 148.83 ppm (C );
2
3
2
30.42 (CH=CH ), 148.24 ppm (C ); IR (ATR): n¯ =749, 1301, 1522,
2
+
124, 2222 cm ; MS (ES): m/z (%): 193.3 (100) [M+H ]; yield: 97%;
1
9
F NMR (282 MHz, CDCl , 258C, CFCl ): À79.35 ppm; IR (ATR): n¯ =
À1
3
3
À1
+
1
054, 1135, 1179, 1348 cm ; MS (ES): m/z (%): 237.3 (100) [M+H ];
light yellow oil.
yield: 99%; yellow liquid.
2
-Isopropyl-1-(2-methoxyethyl)-3,4,5-trimethylimidazolium dicyan-
1
1
-Allyl-3-ethyl-2-isopropyl-4,5-dimethylimidazolium bis(trifluorome-
amide [C2O1
TMS): d=1.51 [d, JH,H =7.7 Hz, 6H; CH(CH
C
1
C
i3
m
2
3
im][N(CN)
2
] (7d): H NMR (300 MHz, CDCl
], 2.30 (s, 3H; CH
), 3.57–3.66 (m, 1H; CH), 3.64
, 258C,
3
4/5
1
thylsulfonyl)imide [C C C m im][NTf ] (9c): H NMR (300 MHz,
3
)
2
C ),
3
A
2
i3
2
2
3
4/5
CDCl , 258C, TMS): d=1.42 (d, J =7.3 Hz, 3H; CH CH ), 1.45 [d,
2.32 (s, 3H; CH
3
C
), 3.34 (s, 3H; OCH
(t, JH,H =5.0 Hz, 2H; CH O), 3.81 (s, 3H, NCH
); C NMR (75 MHz, CDCl , 258C, TMS): d=8.84
], 25.36 (CH), 32.99 (NCH ),
O), 119.78 [N(CN) ], 125.69
3
3
H,H
2
3
3
4/5
3
3
JH,H =7.2 Hz, 6H; CH(CH ) ], 2.19 (s, 3H; CH C ), 2.27 (s, 3H;
2
), 4.35 ppm (t, JH,H =
3
3 2
3
4
/5
3
13
4/5
CH3C ), 3.41–3.55 [m, 1H; CH(CH ) ], 4.16 (t, JH,H =7.3 Hz, 3H;
CH CH ), 4.73–4.74 (m, 2H; CH CH=CH ), 4.89 (d, J =17.1 Hz, 1H;
5.0 Hz, 2H; NCH
2
3
3 2
3
4/5
(CH
C
3
), 9.16 (CH
C
), 18.87 [CH(CH
)
3
2
3
2
2
H,H
3
2
3
3
CH=CH H ), 5.35 (d, J =10.5 Hz, 1H; CH=CH H ), 5.99 ppm (ddt,
45.85 (NCH
2
), 59.19 (OCH
3
), 70.02 (CH
2
2
E
Z
H,H
E
Z
3
13
4/5
4/5
2
JH,H =17.1, 10.5, 4.4 Hz, 1H; CH=CH ); C NMR (75 MHz, CDCl3,
(C ), 126.98 (C ), 148.94 ppm (C ); IR (ATR): n¯ =1052, 1134, 1175,
1348 cm ; HRMS (ESI/APCI): m/z: calcd for [C12
2
4/5
4/5
À1
+
2
58C, TMS): d=8.29 (CH3C ), 8.43 (CH3C ), 15.33 (CH CH ), 19.70
H
23
N
2
O ]: 211.1805;
2
3
[
1
1
CH(CH ) ], 25.38 [CH(CH ) ], 41.06 (CH CH ), 47.62 (CH CH=CH ),
found: 211.1806; yield: 99%; white crystals.
3
2
3 2
2
3
2
2
4/5
1
18.14 (CH=CH ), 119.96 (q, JC,F =321.5 Hz; CF ), 126.04 (C ),
2
3
1
-(2-Allyloxyethyl)-2-isopropyl-3,4,5-trimethylimidazolium dicyana-
4
/5
2
19
26.88 (C ), 130.53 (CH=CH ), 147.95 ppm (C ); F NMR (282 MHz,
2
1
mide [C2OAC1C m im][N(CN) ] (8d): H NMR (300 MHz, CDCl , 258C,
TMS): d=1.50 [d, J =7.2 Hz, 6H; CH(CH ) ], 2.30 (CH C ), 2.31
i3
2
2
3
4/5
CDCl , 258C, CFCl ): À79.36 ppm; IR (ATR): n¯ =1054, 1137, 1180,
3
3
3
À1
+
H,H
3 2
3
1
2
334, 1349 cm ; HRMS (ESI/APCI): m/z: calcd for [C H N ]:
13 23 2
4/5
3
(CH3C ), 3.62–3.77 [m, 1H; CH(CH ) ], 3.70 (t, JH,H =5.0 Hz, 6H;
3 2
07.1856; found: 207.1850; yield: 98%; white crystals.
3
CH O), 3.81 (m, 3H; NCH ), 3.97 (d, J =5.5 Hz; OCH CH), 4.35 (t,
2
3
H,H
2
3
3
JH,H =5.0 Hz, 2H; NCH ), 5.20 (d, JH,H =10.8 Hz, 1H; CH=CH H ),
2
Z
E
1
,3-Diallyl-2-isopropyl-4,5-dimethylimidazolium bis(trifluoromethyl-
3
3
5
.21 (d, J =16.9 Hz, 1H; CH=CH H ), 5.81 ppm (ddt, J =16.9,
H,H Z E H,H
1
sulfonyl)imide [C C C m im][NTf ] (10c): H NMR (300 MHz, CDCl ,
2
CH3C ), 3.36–3.51 [m, 1H; CH(CH ) ], 4.75–4.77 (m, 4H; NCH ), 4.86
13
A
A
i3
2
2
3
1
0.8, 5.5 Hz, 1H; CH=CH ); C NMR (75 MHz, CDCl , 258C, TMS):
3
2
3
58C, TMS): d=1.40 [d, J =7.2 Hz, 6H; CH(CH ) ], 2.20 (s, 6H;
4/5
4/5
H,H
3 2
d=8.78 (CH3C ), 9.11 (CH3C ), 18.86 [CH(CH ) ], 25.21 [CH(CH ) ],
4
/5
3 2
3 2
3 2
2
3
2.98 (NCH ), 45.82 (NCH ), 67.67 (OCH CH), 72.36 (CH O), 118.14
3 2 2 2
3
4
3
(
dt, JH,H =17.1 Hz, JH,H =1.9 Hz, 2H; CH=CH H ), 5.35 (dt, JH,H
=
4/5
4/5
E
Z
(CH=CH ), 119.69 [N(CN) ], 125.69 (C ), 126.95 (C ), 133.60 (CH=
4
3
2
2
1
1
0.8 Hz, JH,H =1.9 Hz, 2H; CH=CH H ), 5.95 ppm (ddt, JH,H =17.1,
0.8, 4.1 Hz, 2H; CH=CH ); C NMR (75 MHz, CDCl , 258C, TMS):
2
E
Z
CH2), 148.82 ppm (C ); IR (ATR): n¯ =1111, 1311, 1523, 2130,
13
2
3
À1
+
2
232 cm ; HRMS (ESI/APCI): m/z: calcd for [C H N O ]: 237.1961;
14 25 2
4
/5
d=8.37 (CH3C ), 19.65 [CH(CH ) ], 25.47 [CH(CH ) ], 47.64 (CH CH=
CH ), 118.07 (CH=CH ), 119.83 (q, J =321.9 Hz; CF ), 126.74 (C ,
C ), 130.45 (CH), 148.60 ppm (C ); F NMR (282 MHz, CDCl , 258C,
3 2
3 2
2
found: 237.1965; yield: 96%; yellow liquid.
1
4
2
2
C,F
19
3
5
2
1-Allyl-3-ethyl-2-isopropyl-4,5-dimethylimidazolium
dicyanamide
3
À1
1
CFCl ): À79.31 ppm; IR (ATR): n¯ =1053, 1138, 1177, 1347 cm
;
[C C C m im][N(CN) ] (9d): H NMR (300 MHz, CDCl , 258C, TMS):
3
A
2
i3
2
2
3
+
3
3
HRMS (ESI/APCI): m/z: calcd for [C H N ]: 219.1856; found:
d=1.47 (d, JH,H =7.2 Hz, 3H; CH CH ), 1.53 [d,
J
=7.7 Hz, 6H;
14
23
2
2
3
H,H
4
/5
4/5
2
19.1848; elemental analysis calcd (%) for C H F N O S (499.49):
CH(CH ) ], 2.27 (s, 3H; CH C ), 2.35 (s, 3H; CH3C ), 3.49–3.56 [m,
16
23
6
3
4
2
3 2
3
ꢀ
2013 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
ChemPhysChem 2013, 14, 3503 – 3516 3515