CHEMPHYSCHEM
ARTICLES
3
13
(
m, 2H; CH ), 2.95 (s, 3H; CH ), 2.21 (s, 4H; CH ), 1.74–1.69 (m, 2H;
1.34 (m, 10H; CH ), 0.93 ppm (t, J(H,H)=6.7 Hz, 3H; CH ); C NMR
2 3
2
3
2
3
1
CH ), 1.28–1.21 (m, 8H; CH ), 0.79 ppm (t, J(H,H)=6.7 Hz, 3H;
CH3); C NMR (75 MHz, D O, 258C, TMS): d=64.3–64.1 (m, N-CH ),
(75 MHz, CD CN, 258C, TMS): d=119.9 (q, J(C,F)=320.8 Hz; CF ),
3 3
64.2 (N-CH ), 48.2 (N-CH ), 31.4 (CH ), 28.7 (CH ), 28.7 CH ), 25.9
2 3 2 2 2
2
2
1
3
2
2
4
8.1–47.9 (m, N-CH ), 30.7 (N-CH -CH ), 27.8 (N-(CH ) -CH ), 25.6 (N-
(CH ), 23.3 (CH ), 22.3 (CH ), 21.3 (CH -CH ), 13.4 ppm (CH -CH ); IR:
2 2 2 2 2 2 3
3
2
2
2 2
2
(
1
1
2
CH ) -CH ), 23.0 (CH -CH -CH ), 21.8 (CH -CH ), 21.3 (CH -CH ),
n˜ =739, 762, 788, 931, 1053, 1134, 1179, 1225, 1329 (S=O), 1348,
2
3
2
2
2
3
2
3
2
2
ꢁ
1
3.3 ppm (CH -CH ); IR: n˜ =726, 819, 912, 933, 957, 1002, 1050,
1468 (C-H), 2860, 2930 cm (C-H); MS negative mode: m/z (%):
2
3
ꢁ
ꢁ
105, 1134, 1160, 1236, 1301, 1341, 1374, 1392, 1462 (C-H), 2857,
280 (100) [M ], 147 (24) [CF NO S ]; MS positive mode (35 eV): m/z
3 2
ꢁ
1
+
+
+
+
925, 2959 cm (C-H); MS positive mode: m/z (%): 184 (100) [M ];
(%): 199 (18) [M +H], 198 (88) [M ], 86 (100) [C H N ]. DSC
5 12
measurements using cooling and heating rates of 5 Kmin
+
+
ꢁ1
MS (35 eV): m/z (%): 184 (42) [M ], 86 (100) [C H N ].
5
12
showed Tg at ꢁ82.98C, T
at ꢁ34.18C (broad peak), T at
recryst
m1
A solution of lithium bis(trifluoromethylsulfonyl)imide (105.8 g,
68 mmol) in water (100 mL ) was added under stirring to a solu-
ꢁ
17.98C, and T at ꢁ12.28C during heating. The refractive index
m2
3
ꢁ3
was 1.4288 at 258C and the density was 1.192 gcm .
tion of N,N-heptylmethylpyrrolidinium chloride (77.1 g, 351 mmol)
in water (70 mL). After the reaction mixture was stirred for 24 h at
room temperature, dichloromethane (100 mL) was added. The or-
ganic layer was separated and washed with water (4ꢁ70 mL). Sub-
sequently, the organic layer was dried over Na SO overnight. The
NonMPyrNTf2
N-Methylpyrrolidine (51.5 g, 605 mol) was dissolved in isopropanol
2
4
(70 mL) and 1-chlorononane (108.5 g, 647 mol) was added drop-
solvent was removed by evaporation. The HepMPyrNTf was dried
2
wise at room temperature for 1.5 h. After the reaction mixture was
stirred for 72 h at 1008C, the mixture was cooled to room tempera-
ture and the isopropanol was removed by evaporation. The residu-
al solid was taken into a column and washed with ethyl acetate
(1.5 L) at one drop per 4 s dropping rate. The product was washed
for 24 h in vacuo at 508C. Yield: 77% (125.3 g, 270 mmol), water
1
content: 0.083%; H NMR (300 MHz, CD CN, 258C, TMS): d=3.46–
3
3
2
0
2
.41 (m, 4H; CH ), 3.28–3.22 (m, 2H; CH ), 2.97 (s, 3H; CH ), 2.21–
2
2
3
.17 (m, 4H; CH ), 1.82–1.72 (m, 2H; CH ), 1.39–1.35 (m, 8H; CH ),
2
2
13
2
3
.94 ppm (t, J(H,H)=6.7 Hz, 3H; CH ); C NMR (75 MHz, CD CN,
58C, TMS): d=119.9 (q, J(C,F)=320.8 Hz, CF ), 64.3 (N-CH ), 48.2
3
3
1
and subsequently dried in vacuo. Yield: 76% (113.5 g, 458 mmol);
3
2
1
m.p. 1838C; H NMR (300 MHz, CD CN, TMS): d=3.74–3.56 (m, 14;
(
N-CH ), 31.2 (CH ), 28.4 (CH ), 25.9 (CH ), 23.2 (CH ), 22.2 (CH ), 21.3
3
3
2
2
2
2
2
2
ꢁN-CH ), 3.57–3.44 (m, 2H; N-CH ), 3.13 (s, 3H; N-CH ), 2.17 (s,
(
1
CH ), 13.3 ppm (CH -CH ); IR: n˜ =739, 762, 788, 930, 1053, 1134,
2
2
3
2
2
3
ꢁ1
4H; CH -CH ), 1.84–1.62 (m, 2H; N-CH -CH ), 1.45–1.15 (m, 12H;
2 2 2 2
178, 1225, 1330 (S=O), 1348, 1468 (C-H), 2862, 2932 cm (C-H);
3
13
+
CH -(CH ) -CH ), 0.89 ppm (t, J(H,H)=6.7 Hz; 3H, CH3); C NMR
2 2 6 3
MS positive mode (40 eV): m/z (%): 184 (10) [M ], 86 (100)
[
(
cooling and heating rates of 5 Kmin showed Tg at ꢁ85.38C
during heating. The refractive index was 1.4277 at 258C and the
density was 1.279 gcm .
+
ꢁ
(75 MHz, CD CN, 258C, TMS): d=64.5 (2ꢁN-CH ), 64.2 (N-CH ), 48.5
3 2 2
(N-CH ), 32.4 (N-CH -CH ), 29.9 (N-(CH ) -CH ), 29.7 (N-(CH ) -CH ),
3 2 2 2 2 2 2 3 2
29.6 (N-(CH ) -CH ), 26.9 (CH -(CH ) -CH ), 24.2 (CH -CH -CH ), 23.2
2 4 2 2 2 2 3 2 2 3
C H N ]; MS negative mode (35 eV): m/z (%): 280 (20) [M ], 211
5
12
ꢁ
ꢁ
74) [CF NO S ], 147 (100) [CF NO S ]. DSC measurements using
3
4
2
3
2
ꢁ
1
(
CH -CH ), 22.0 (N-CH -CH -N), 14.3 ppm (-CH -CH ); IR: n˜ =588,
2 3 2 2 2 3
ꢁ
3
619, 723, 826, 911, 934, 1005, 1235, 1303, 1378, 1464, 1750, 2854,
ꢁ
1
+
2
8
922, 2955 cm ; MS: m/z (%): 212 (100) [M ]; MS (40 eV): m/z (%):
+
+
6 (100) [C H N ], 212 (10) [M ].
5
12
OctMPyrNTf2
A
solution of lithium bis(trifluoromethysulfonyl)imide (93.3 g,
N-Methylpyrrolidine (165.4 g, 1.9 mol) was dissolved in isopropanol
3
25 mmol) in water (50 mL) was added under stirring to a solution
(
160 mL) and 1-chlorooctane (308.4 g, 2.0 mol) was added drop-
wise at 48C for 1.5 h. After the reaction mixture was stirred for
4 h at 828C, the mixture was cooled to room temperature. The re-
of N,N-nonylmethylpyrrolidinium chloride (74.6 g, 301 mmol) dis-
solved in water (250 mL). After the reaction mixture was stirred at
room temperature for 72 h, dichloromethane (80 mL) was added
and the organic layer was washed with water (6ꢁ50 mL). Subse-
quently, the organic layer was dried over Na SO overnight, and
the solvent was removed by evaporation in vacuo. The product
was dried in vacuo at room temperature for 1 day. Yield 99%
(146.1 g, 297 mmol), water content: 0.023%; H NMR (300 MHz,
CDCl , 258C, TMS): d=3.48 (t, J(H-H)=5.5 Hz; 4H, 2ꢁN-CH ), 3.35–
3.19 (m, 2H; N-CH ), 3.01 (s, 3H; N-CH ), 2.25 (m, 4H; CH -CH ),
1.75 (m, 2H; N-CH -CH ), 1.45–1.16 (m, 12H; CH -(CH ) -CH ),
2 2 2 2 6 3
0.88 ppm (t, 1 J(H,H)=6.6 Hz; 3H, CH ); C NMR (75 MHz, CDCl3,
2
sidual solid was washed seven times with ethyl acetate (200 mL).
Subsequently, the solvent was removed by evaporation. Yield:
2
4
1
2
0% (86.5 g, 370 mmol); m.p. 1858C; H NMR (300 MHz, D O, 258C,
2
TMS): d=3.50–3.38 (m, 4H; CH ), 3.30–3.25 (m, 2H; CH ), 2.99 (s,
2
2
3
1
H; CH ), 2.16 (s, 4H; CH ), 1.77–1.72 (m, 2H; CH ), 1.31–1.24 (m,
0H; CH2), 0.83 ppm (t, J(H,H)=6,6 Hz, 3H; CH3); C NMR
1
3
2
2
3
13
3
3
2
(
75 MHz, D O, 258C, TMS): d=64.3 (N-CH ), 48.1 (N-CH ), 31.2 (CH ),
2 2 3 2
2 3 2 2
2
8.4 (CH ), 28.4 (CH ), 25.8 (CH ), 23.2 (CH ), 22.2 (CH ), 21.3 (CH -
2 2 2 2 2 2
CH ), 13.6 ppm (CH -CH ); IR: n˜ =724, 913, 932, 960, 1003, 1046,
13
2
2
3
3
ꢁ1
1
304, 1378, 1407, 1463 (C-H), 2854, 2923, 2957 cm (C-H); MS posi-
tive mode (35 eV): m/z (%): 86 (100) [C H N ]; MS: m/z (%): 198
100) [M ].
1
2
58C, TMS): d=119.9 (q, J(C,F)=319 Hz, CF ), 64.8 (N-CH ), 64.4
3
2
+
5
12
(N-CH ), 48.2 (N-CH ), 31.7 (N-CH -CH ), 29.2 (N-(CH ) -CH ), 29.0 (N-
2 3 2 2 2 2 2
ꢁ
(
(CH ) -CH ), 28.9 (N-(CH ) -CH ), 26.1 (CH -(CH ) -CH ), 23.7 (CH -CH -
2 3 2 2 4 2 2 2 2 3 2 2
CH ), 22.6 (CH -CH ), 21.4 (N-CH -CH -N), 14.0 ppm (-CH -CH ); IR:
n˜ =511, 569, 600, 614, 653, 739, 762, 788, 932, 1052, 1133, 1177,
A solution of lithium bis(trifluoromethylsulfonyl)imide (111.5 g,
3
2
3
2
2
2
3
3
88 mmol) in water (100 mL) was added under stirring to a solution
ꢁ
1
1
(
(
5
225, 1330, 1348, 1467, 2858, 2928 cm ; MS (35 eV): m/z (%): 212
of N,N-octylmethylpyrrolidinium chloride (86.50 g, 370 mmol) dis-
solved in water (100 mL). After the reaction mixture was stirred for
+
+
+
100) [M ], 86 (100) [C H N ], 212 (17) [M ]; MS: m/z (%): 280
5 12
100) [M ]. DSC measurements using cooling and heating rates of
ꢁ
2
4 h at room temperature, dichloromethane (120 mL) was added.
The organic layer was separated and washed with water (7ꢁ
00 mL). Subsequently, the organic layer was dried over Na SO4
ꢁ
1
Kmin showed T at ꢁ80.88C, T
at ꢁ34.98C, T at ꢁ8.18C,
g
recryst
m1
and Tm2 at ꢁ4.68C during heating. The refractive index was 1.4307.
1
2
overnight. The solvent was removed by evaporation. The OctM-
PyrNTf was dried in vacuo at 808C for 5 days. Yield: 86% (152.5 g,
2
DecMPyrNTf2
1
3
2
2
90 mmol), water content: 0.033%; H NMR (300 MHz, CD CN,
3
58C, TMS): d=3.46–3.41 (m, 4H; CH ), 3.28–3.23 (m, 2H; CH ),
N-Methylpyrrolidine (93.7 g, 1.1 mol) was dissolved in isopropanol
(120 mL) and 1- chlorodecane (207.5 g, 2.2 mol) was added drop-
2
2
.98 s, 3H; CH ), 2.19 (s, 4H; CH ), 1.82–1.74 (m, 2H; CH ), 1.37–
3
2
2
ꢀ
2013 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
ChemPhysChem 2013, 14, 1899 – 1908 1906