Hypergolic Ionic Liquids
FULL PAPER
under reduced pressure to yield the crude product, which was dissolved
in acetone (5 mL), and diethyl ether (1–3 mL) was added to the solution
until permanent cloudiness was obtained. The solution was stored at
room temperature for 3 h and filtered. Additional diethyl ether (5 mL)
was added to the filtrate to form two phases. The upper phase was deca-
nted, and the residue was dried under vacuum at 708C to give the final
product.
(%) for C5H13N5O2 (175.19): C 34.28, H 7.48, N 39.98; found: C 33.53, H
7.67, N 39.04.
N-Butyl-N,N-dimethylhydrazinium nitrocyanamide (17): Colorless liquid
(1.05 g, 86%). 1H NMR: d=0.89 (t, J=14.6 Hz, 3H; CH3), 1.30 (m, 2H;
CH2), 1.71 (m, 2H; CH2), 3.20 (s, 6H; CH3), 3.38 (m, 2H; CH2),
5.86 ppm (s, 2H; NH2); 13C NMR: d=13.4, 19.1, 24.3, 55.3, 68.2,
117.0 ppm; IR (KBr): n˜ =3474, 3295, 3180, 2966, 2178, 2147, 1629, 1431,
1275, 1156, 1086, 955, 911, 796, 544 cmꢀ1; elemental analysis calcd (%)
for C7H17N5O2 (203.24): C 41.37, H 8.43, N 34.46; found: C 40.61, H 8.54,
N 34.10.
N,N,N-Trimethylhydrazinium dicyanamide (8): White solid (0.799 g,
94%). 1H NMR: d=3.25 (s, 9H; CH3), 6.06 ppm (s, 2H; NH2);
13C NMR: d=57.3, 119.0 ppm; IR (KBr): n˜ =3212, 3111, 3020, 2260,
2213, 2140, 1631, 1478, 1324, 1092, 943, 915,522 cmꢀ1; elemental analysis
calcd (%) for C5H11N5 (141.17): C 42.54, H 7.85, N 49.61; found: C 42.15,
H 7.85, N 49.19.
N-Allyl-N,N-dimethylhydrazinium nitrocyanamide (18): Amber liquid
(0.963 g, 86%). 1H NMR: d=3.20 (s, 6H; CH3), 4.05 (d, J=7.3 Hz, 2H;
CH2), 5.59 (m, 2H; CH2), 5.77 (s, 2H; NH2), 5.98 ppm (m, 1H; CH);
13C NMR: d=55.2, 70.7, 116.9, 125.6, 128.5 ppm; IR (KBr): n˜ =3464,
3297, 3176, 3039, 2180, 2141, 1627, 1436, 1276, 1157, 1088, 957, 887, 769,
544 cmꢀ1; elemental analysis calcd (%) for C6H13N5O2 (187.20): C 38.50,
H 7.00, N 37.41; found: C 38.28, H 7.16, N 36.82.
N-Ethyl-N,N-dimethylhydrazinium dicyanamide (9): Yellow supercooled
liquid (0.859 g, 92%). 1H NMR: d=1.28 (t, J=14.5 Hz, 3H; CH3), 3.16
(s, 6H; CH3), 3.44 (m, 2H; CH2), 5.88 ppm (s, 2H; NH2); 13C NMR: d=
8.0, 54.6, 63.6, 119.0 ppm; IR (KBr): n˜ =3441, 3276, 3160, 3035, 2247,
2203, 2142, 1633, 1471, 1323, 1087, 1015, 915, 525 cmꢀ1; elemental analysis
calcd (%) for C6H13N5 (155.20): C 46.43; H 8.44; N 45.12; found: C 45.51,
H 8.61, N 44.36.
N-Propargyl-N,N-dimethylhydrazinium nitrocyanamide (19): Amber
liquid (0.948 g, 85%). 1H NMR: d=3.30 (s, 6H; CH3), 3.68 (s, 1H; CH),
4.41 (s, 2H; CH2), 5.98 ppm (s, 2H; NH2); 13C NMR: d=55.3, 59.0, 72.4,
82.6, 116.8 ppm; IR (KBr): n˜ =3460, 3270, 3178, 3041, 2980, 2248, 2181,
2142, 1625, 1434, 1277, 1157, 1091, 958, 893, 762, 543 cmꢀ1; elemental
analysis calcd (%) for C6H11N5O2 (185.18): C 38.91, H 5.99, N 37.82;
found: C 37.95, H 6.02, N 37.47.
N-Butyl-N,N-dimethylhydrazinium dicyanamide (10): Colorless liquid
1
(0.995 g, 90%). H NMR: d=0.91 (t, J=14.7 Hz, 3H; CH3), 1.31 (m, 2H;
CH2), 1.70 (m, 2H, CH2), 3.17 (s, 6H; CH3), 3.37 (m, 2H; CH2),
5.90 ppm (s, 2H; NH2); 13C NMR: d=13.4, 19.0, 24.1, 55.2, 67.8,
119.0 ppm; IR (KBr): n˜ =3433, 3264, 3156, 2966, 2877, 2248, 2201, 2141,
1633, 1475, 1325, 1092, 910, 522 cmꢀ1; elemental analysis calcd (%) for
C8H17N5 (183.25): C 52.43, H 9.35, N 38.22; found: C 51.85, H 9.52, N
38.35.
N-(2-Hydroxyethyl)-N,N-dimethylhydrazinium
nitrocyanamide
(20):
Amber liquid (1.00 g, 87%). 1H NMR: d=3.25 (s, 6H; CH3), 3.51 (t, J=
9.7 Hz, 2H; CH2), 3.89 (t, J=9.6 Hz, 2H; CH2), 5.10 (s, 1H; OH),
5.88 ppm (s, 2H; NH2); 13C NMR: d=55.6, 56.5, 70.2, 116.9 ppm; IR
(KBr): n˜ =3392, 3304, 3185, 3042, 2967, 2181, 2144, 1625, 1436, 1277,
N-Allyl-N,N-dimethylhydrazinium dicyanamide (11): Amber liquid
(0.896 g, 89%). 1H NMR: d=3.16 (s, 6H; CH3), 4.04 (d, J=7.2 Hz, 2H;
CH2), 5.62 (m, 2H; CH2), 5.95 (s, 2H; NH2), 6.03 ppm (m, 1H; CH);
13C NMR: d=54.8, 70.0, 119.1, 126.0, 127.5 ppm; IR (KBr): n˜ =3433,
3263, 3151, 3032, 2243, 2198, 2139, 1631, 1473, 1318, 1090, 958, 905, 772,
520 cmꢀ1; elemental analysis calcd (%) for C7H13N5 (167.21): C 50.28, H
7.84, N 41.88; found: C 49.31, H 7.97, N 41.83.
1158, 1083, 957, 769, 543 cmꢀ1
; elemental analysis calcd (%) for
C5H13N5O3 (191.19): C 31.41, H 6.85, N 36.63; found: C 30.86, H 6.85, N
36.29.
N-Cyanomethyl-N,N-dimethylhydrazinium nitrocyanamide (21): Yellow
1
liquid (0.952 g, 85%). H NMR: d=3.39 (s, 6H; CH3), 4.89 (s, 2H; CH2),
6.37 ppm (s, 2H; NH2); 13C NMR: d=56.0, 56.7, 112.0, 116.7 ppm; IR
(KBr): n˜ =3456, 3281, 3171, 3043, 2990, 2181, 2143, 1625, 1434, 1279,
1159, 1085, 962, 897, 764, 543 cmꢀ1; elemental analysis calcd (%) for
C5H10N6O2 (186.17): C 32.26, H 5.41, N 45.14; found: C 31.53, H 5.41, N
44.22.
N-Propargyl-N,N-dimethylhydrazinium dicyanamide (12): Amber liquid
(0.878 g, 89%). 1H NMR): d=3.25 (s, 6H; CH3), 3.65 (s, 1H; CH), 4.37
(s, 2H; CH2), 5.98 ppm (s, 2H; NH2); 13C NMR: d=55.2, 58.9, 72.3, 82.7,
119.3 ppm; IR (KBr): n˜ =3433, 3268, 3159, 3035, 2978, 2247, 2202, 2142,
1624, 1472, 1321, 1092, 995, 896, 665, 524 cmꢀ1; elemental analysis calcd
(%) for C7H11N5 (165.20): C 50.89, H 6.71, N 42.39; found: C 50.04, H
6.79, N 41.76.
Acknowledgements
N-(2-Hydroxyethyl)-N,N-dimethylhydrazinium dicyanamide (13): Amber
liquid (0.922 g, 90%). 1H NMR: d=3.24 (s, 6H; CH3), 3.50 (t, J=
10.1 Hz, 2H; CH2), 3.86 (m, 2H; CH2), 5.24 (t, J=9.2 Hz, 1H; OH),
5.99 ppm (s, 2H; NH2); 13C NMR: d=55.0, 56.1, 69.7, 119.0 ppm; IR
(KBr): n˜ =3286, 3161, 3034, 2964, 2247, 2202, 2140, 1628, 1471, 1325,
1084, 957, 913, 662, 522 cmꢀ1; elemental analysis calcd (%) for C6H13N5O
(171.20): C 42.09, H 7.65, N 40.91; found: C 41.56, H 7.76, N 40.73.
The authors gratefully acknowledge the support of DTRA (HDTRA1-
07-1-0024), NSF (CHE-0315275), and ONR (N00014-06-1-1032).
[3] O. de Bonn, A. Hammerl, T. M. Klapçtke, P. Mayer, H. Piotrowski,
N-Cyanomethyl-N,N-dimethylhydrazinium dicyanamide (14): Dark red
liquid (0.904 g, 91%). H NMR: d=3.35 (s, 6H; CH3), 4.81 (s, 2H; CH2),
1
6.29 ppm (s, 2H; NH2); 13C NMR: d=56.1, 56.8, 111.9, 119.3 ppm; IR
(KBr): n˜ =3269, 3145, 3038, 2983, 2247, 2198, 2140, 1714, 1621, 1464,
1295, 1084, 900, 788, 525 cmꢀ1; elemental analysis calcd (%) for C6H10N6
(166.18): C 43.36, H 6.07, N 50.57; found: C 42.65, H 6.17, N 49.72.
[5] A. Osmont, L. Catoire, T. M. Klapçtke, G. L. Vaghjiani, M. T. Swi-
N,N,N-Trimethylhydrazinium dicyanamide (15): White solid (0.887 g,
1
92%). H NMR: d=3.26 (s, 9H; CH3), 6.03 ppm (s, 2H; NH2); 13C NMR
d=57.3, 116.6 ppm; IR (KBr): n˜ =3462, 3301, 3220, 3113, 3021, 2190,
1630, 1446, 1292, 1159, 1089, 945, 771, 547 cmꢀ1; elemental analysis calcd
(%) for C4H11N5O2 (161.16): C 29.81, H 6.88, N 43.46; found: C 29.35, H
6.75, N 42.98.
[8] I. Frank, A. Hammerl, T. M. Klapçtke, C. Nonnenberg, H. Zewen,
N-Ethyl-N,N-dimethylhydrazinium nitrocyanamide (16): Colorless solid,
(0.945 g, 90%). 1H NMR: d=1.28 (t, J=14.5 Hz, 3H; CH3), 3.17 (s, 6H;
CH3), 3.45 (m, 2H; CH2), 5.81 ppm (s, 2H; NH2); 13C NMR: d=8.2, 54.8,
64.1, 116.9 ppm; IR (KBr): n˜ =3468, 3300, 3176, 2246, 2181, 2142, 1629,
1434, 1277, 1157, 1082, 1015, 961, 873, 769 cmꢀ1; elemental analysis calcd
[10] Y. Ishikawa, M. J. McQuaid, J. Mol. Struct. 2007, 825–846, 119–124.
Chem. Eur. J. 2010, 16, 3114 – 3120
ꢂ 2010 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
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