R. D. Rogers et al.
Tetraphenylphosphonium 4,5-dinitroimidazolate (3g): Microcrystals from
acetone (92%), m.p. 159–1628C (DSC 2nd cycle m.p. 1458C); 1H NMR
(CDCl3): d = 7.00 (s, 1H), 7.58–7.65 (m, 8H), 7.72–7.79 (m, 8H), 7.88–
7.93 ppm (m, 4H); 13C NMR (CDCl3): d = 116.9 (d, J=89.9 Hz, 4C),
130.3 (d, J=12.6 Hz, 8C), 133.9 (d, J=10.3 Hz, 8C), 135.4 (d, J=2.8 Hz,
4C), 139.5, 139.6, 140.3 ppm; elemental analysis calcd (%) for
C27H21N4O4P: C 65.32, H 4.26, N 11.29; found: C 64.37, H 4.05, N 11.37.
Ethyltriphenylphosphonium 2,4,-dinitroimidazolate (4 f) monohydrate:
Light yellow microcrystals from acetone (96%); m.p. 68–708C (DSC 1st
cycle m.p. 708C); 1H NMR (CDCl3): d = 1.41 (dt, J=19.6, 7.4 Hz, 3H),
3.39 (dq, J=12.6, 7.4 Hz, 2H), 7.63–7.74 (m, 13H), 7.78–7.86 ppm (m,
3H); 13C NMR (CDCl3): d = 6.5, 16.4 (d, J=53.3 Hz, 1C), 117.1 (d, J=
85.9 Hz, 3C), 130.3, 130.4 (d, J=12.6 Hz, 6C), 133.0 (d, J=9.6 Hz, 6C),
135.1 (d, J=2.9 Hz, 3C), 147.0, 154.1 ppm; elemental analysis calcd (%)
for C23H23N4O5P: C 59.23, H 4.97, N 12.01; found: C 60.29, H 4.64, N
11.40.
Tetraphenylphosphonium 4,5-dicyanoimidazolate (3h): Microcrystals
from acetone (88%), m.p. 157–1598C (DSC 2nd cycle m.p. 1498C);
1H NMR (CDCl3): d = 7.37 (s, 1H), 7.56–7.64 (m, 8H), 7.71–7.78 (m,
8H), 7.87–7.92 ppm (m, 4H); 13C NMR (CDCl3): d = 116.9, 117.2 (d, J=
89.4 Hz, 4C), 130.5 (d, J=13.2 Hz, 8C), 134.1 (d, J=10.3 Hz, 8C), 135.6
(d, J=3.4 Hz, 4C), 148.9, 148.9 ppm; elemental analysis calcd (%) for
C29H21N4P: C 76.30, H 4.64, N 12.27; found: C 75.42, H 4.46, N 12.74.
Ethyltriphenylphosphonium 4,5-dinitroimidazolate (4g): Yellow micro-
crystals from acetone (95%); m.p. 91–938C (DSC 1st cycle m.p. 978C);
1H NMR (CDCl3): d = 1.39 (dt, J=19.8, 7.4 Hz, 3H), 3.25 (dq, J=12.7,
7.5 Hz, 2H), 7.00 (s, 1H), 7.59–7.73 (m, 12H), 7.79–7.85 ppm (m, 3H);
13C NMR (CDCl3): d
= 6.6, 16.6 (d, J=52.7 Hz, 1C), 117.2 (d, J=
86.4 Hz, 3C), 130.5 (d, J=12.6 Hz, 6C), 133.2 (d, J=9.7 Hz, 6C), 135.3
(d, J=3.5 Hz, 3C), 139.8 (d, J=5.7 Hz, 1C), 140.6 ppm; elemental analy-
sis calcd (%) for C23H21N4O4P: C 61.61, H 4.72, N 12.49; found: C 61.33,
H 4.74, N 12.36.
Tetraphenylphosphonium tetrazolate (3i) monohydrate: Microcrystals
from acetone (85%), m.p. 308–3118C (DSC m.p. at Tdecomp 2908C);
1H NMR (CDCl3): d = 7.55–7.62 (m, 8H), 7.71–7.78 (m, 8H), 7.88–7.91
(m, 4H), 8.31 ppm (s, 1H); 13C NMR (CDCl3): d = 117.1 (d, J=89.4 Hz,
4C), 130.5 (d, J=13.2 Hz, 8C), 134.0 (d, J=10.3 Hz, 8C), 135.5 (d, J=
3.4 Hz, 4C), 149.6 (d, J=2.9 Hz, 1C); elemental analysis calcd (%) for
C25H23N4OP: C 70.41, H 5.44, N 13.14; found: C 71.64, H 5.04, N 13.52.
Ethyltriphenylphosphonium 4,5-dicyanoimidazolate (4h): Light yellow
oil (96%); DSC 2nd cycle m.p. À298C; 1H NMR (CDCl3): d = 1.40 (dt,
J=19.5, 7.3 Hz, 3H), 3.21 (dq, J=12.7, 7.4 Hz, 2H), 7.39 (s, 1H), 7.59–
7.66 (m, 6H), 7.68–7.74 (m, 6H), 7.81–7.86 ppm (m, 3H); 13C NMR
(CDCl3): d = 6.6, 16.6 (d, J=53.2 Hz, 1C), 116.9, 117.1 (d, J=85.9 Hz,
3C), 118.4, 130.5 (d, J=12.6 Hz, 6C), 133.1 (d, J=9.7 Hz, 6C), 135.4 (d,
J=3.4 Hz, 3C), 148.9 ppm (d, J=8.0 Hz, 1C); elemental analysis calcd
(%) for C25H21N4P: C 73.52, H 5.18, N 13.72; found: C 72.87, H 5.33, N
13.44.
Ethyltriphenylphosphonium 5-nitrobenzotriazolate (4a) monohydrate:
Light brown microcrystals from acetone (99%); m.p. 120–1228C (DSC
2nd cycle m.p. 1318C); 1H NMR (CDCl3): d = 1.29 (dt, J=19.8, 7.5 Hz,
3H), 3.18–3.30 (m, 2H), 7.51–7.65 (m, 12H), 7.72–7.85 (m, 4H), 7.83 (dd,
J=9.0, 2.2 Hz, 1H), 8.65 ppm (d, J=2.2 Hz, 1H); 13C NMR (CDCl3):
d=6.6, 16.3 (d, J=52.7 Hz, 1C), 114.3 (d, J=3.4 Hz, 1C), 115.2, 115.9,
117.2 (d, J=86.4 Hz, 3C), 130.3 (d, J=12.0 Hz, 6C), 133.0 (d, J=9.8 Hz,
6C), 135.1 (d, J=2.8 Hz, 3C), 141.3, 144.3, 148.5 ppm; elemental analysis
calcd (%) for C26H25N4O3P: C 66.09, H 5.33, N 11.86; found: C 65.56, H
4.89, N 11.35.
Ethyltriphenylphosphonium tetrazolate (4i) monohydrate: Light yellow
microcrystals from acetone (89%); m.p. 83–858C (DSC 1st cycle m.p.
518C); 1H NMR (CDCl3): d = 1.32 (dt, J=20.0, 7.6 Hz, 3H), 3.38 (dq,
J=12.7, 7.8 Hz, 2H), 7.62–7.72 (m, 12H), 7.76–7.82 (m, 3H), 8.30 ppm (s,
1H); 13C NMR (CDCl3): d = 6.4 (d, J=5.2 Hz, 1C), 16.0 (d, J=52.7 Hz,
1C), 117.5 (d, J=85.9 Hz, 3C), 130.3 (d, J=12.6 Hz, 6C), 133.1 (d, J=
10.3 Hz, 6C), 134.9 (d, J=2.9 Hz, 3C), 149.6 ppm (d, J=4.0 Hz, 1C); ele-
mental analysis calcd (%) for C21H23N4OP: C 66.65, H 6.13, N 14.81;
found: C 66.87, H 5.94, N 14.57.
Ethyltriphenylphosphonium 5-nitrobenzimidazolate (4b) monohydrate:
Red oil (98%); DSC 1st cycle m.p. 888C; 1H NMR (CDCl3): d = 1.28
(dt, J=19.8, 7.4 Hz, 3H), 3.15 (dq, J=12.6, 7.4 Hz, 2H), 7.50–7.58 (m,
7H), 7.61–7.68 (m, 6H), 7.76–7.81 (m, 3H), 7.89 (dd, J=8.8, 2.2 Hz, 1H),
8.26 (s, 1H), 8.48 ppm (d, J=2.2 Hz, 1H); 13C NMR (CDCl3): d = 6.4,
16.3 (d, J=52.1 Hz, 1C), 113.5, 114.1, 115.2, 117.2 (d, J=85.9 Hz, 3C),
130.3 (d, J=12.6 Hz, 6C), 132.9 (d, J=9.7 Hz, 6C), 135.1 (d, J=2.9 Hz,
3C), 139.2, 144.8, 151.8, 158.1 ppm; elemental analysis calcd (%) for
C27H26N3O3P: C 68.78, H 5.13, N 8.91; found: C 67.43, H 5.61, N 7.94.
N-Phenylpyridinium 5-nitrobenzotriazolate (5a) monohydrate: Black mi-
crocrystals from acetone (96%); m.p. 79–818C (DSC 1st cycle m.p.
758C); 1H NMR ([D6]DMSO): d = 7.73–7.76 (m, 4H), 7.83 (dd, J=9.0,
2.1 Hz, 1H), 7.88–7.92 (m, 2H), 8.29–8.34 (m, 2H), 8.62 (d, J=2.0 Hz,
1H), 8.79 (t, J=7.8 Hz, 1H), 9.36 ppm (d, J=5.6 Hz, 2H); 13C NMR
([D6]DMSO): d = 113.5 (d, J=3.4 Hz, 1C), 115.0, 115.7, 124.7, 128.1,
130.2, 131.2, 140.7, 142.8, 143.8, 144.9, 146.6, 147.8 ppm; elemental analy-
sis calcd (%) for C17H15N5O3: C 60.53, H 4.48, N 20.76; found: C 59.92, H
4.21, N 21.11.
Ethyltriphenylphosphonium 4-nitro-1,2,3-triazolate (4c): Light yellow mi-
crocrystals from acetone (99%); m.p. 90–928C (DSC 2nd cycle m.p.
978C); 1H NMR (CDCl3): d = 1.38 (dt, J=19.8, 7.4 Hz, 3H), 3.44 (dq,
J=12.8, 7.5 Hz, 2H), 7.65–7.72 (m, 12H), 7.70–7.84 (m, 3H), 8.07 ppm (s,
1H); 13C NMR (CDCl3): d = 6.6 (d, J=5.2 Hz, 1C), 16.4 (d, J=52.7 Hz,
1C), 117.4 (d, J=86.5 Hz, 3C), 130.1, 130.4 (d, J=12.6 Hz, 6C), 133.2 (d,
J=9.7 Hz, 6C), 135.1 (d, J=2.9 Hz, 3C), 154.5 ppm; elemental analysis
calcd (%) for C22H21N4O2P: C 65.34, H 5.23, N 13.85; found: C 64.36, H
5.13, N 13.71.
N-Phenylpyridinium 4-nitro-1,2,3-triazolate (5c): Microcrystals from ace-
tone (94%); m.p. 129–1318C (DSC 2nd cycle m.p. 1358C); 1H NMR
([D6]DMSO): d = 7.73–7.76 (m, 3H), 7.89–7.92 (m, 2H), 8.02 (s, 1H),
8.30–8.34 (m, 2H), 8.80 (t, J=7.8 Hz, 1H), 9.36 ppm (d, J=5.5 Hz, 2H);
13C NMR ([D6]DMSO): d = 124.7, 128.1, 129.5, 130.2, 131.2, 142.8, 144.9,
146.6, 154.1 ppm; elemental analysis calcd (%) for C13H11N5O2: C 57.99,
H 4.12, N 26.01; found: C 57.75, H 3.95, N 26.28.
Ethyltriphenylphosphonium 4-nitroimidazolate (4d) monohydrate: Light
yellow microcrystals from acetone (98%); m.p. 89–918C (DSC 2nd cycle
m.p. 1008C); 1H NMR (CDCl3): d = 1.35 (dt, J=19.8, 7.4 Hz, 3H), 3.44
(dq, J=12.7, 7.5 Hz, 2H), 7.28 (s, 1H), 7.60–7.72 (m, 12H), 7.78–7.84 (m,
3H), 7.89 ppm (s, 1H); 13C NMR (CDCl3): d = 6.5 (d, J=5.2 Hz, 1C),
16.3 (d, J=52.7 Hz, 1C), 117.3 (d, J=86.2 Hz, 3C), 130.4 (d, J=12.6 Hz,
6C), 132.3, 133.1 (d, J=10.3 Hz, 6C), 135.1 (d, J=2.9 Hz, 3C), 146.7 (d,
J=4.0 Hz, 1C), 148.3 ppm; elemental analysis calcd (%) for
C23H24N3O3P: C 65.55, H 5.74, N 9.97; found: C 66.57, H 5.40, N 9.85.
N-Phenylpyridinium 3,5-dinitro-1,2,4-triazolate (5e): Microcrystals from
acetone (88%); m.p. 158–1608C (DSC 2nd cycle m.p. 1678C); 1H NMR
([D6]DMSO): d = 7.73–7.77 (m, 3H), 7.88–7.92 (m, 2H), 8.30–8.35 (m,
2H), 8.80 (t, J=7.8 Hz, 1H), 9.36 ppm (d, J=5.5 Hz, 2H); 13C NMR
([D6]DMSO):
d = 124.7, 128.1, 130.2, 131.2, 142.8, 145.0, 146.6,
162.9 ppm; elemental analysis calcd (%) for C13H10N6O4: C 49.69, H 3.21,
N 26.74; found: C 49.53, H 2.99, N 26.27.
Ethyltriphenylphosphonium 3,5-dinitro-1,2,4-triazolate (4e): Microcrys-
tals from acetone (96%), m.p. 124–1258C (DSC 2nd cycle m.p. 1278C);
1H NMR (CDCl3): d = 1.44 (dt, J=19.8, 7.6 Hz, 3H), 3.38 (dq, J=12.6,
7.4 Hz, 2H), 7.64–7.75 (m, 12H), 7.79–7.86 ppm (m, 3H); 13C NMR
(CDCl3): d = 6.6 (d, J=5.7 Hz, 1C), 16.6 (d, J=53.3 Hz, 1C), 117.2 (d,
J=86.5 Hz, 3C), 130.5 (d, J=12.6 Hz, 6C), 133.2 (d, J=9.7 Hz, 6C),
135.3 (d, J=3.5 Hz, 3C), 163.2 ppm; elemental analysis calcd (%) for
C22H20N5O4P: C 58.80, H 4.49, N 15.58; found: C 58.63, H 4.35, N 15.19.
N-Phenylpyridinium 2,4-dinitroimidazolate (5 f): Light yellow microcrys-
tals from acetone (93%), m.p. 140–1428C (DSC 2nd cycle m.p. 1438C);
1H NMR ([D6]DMSO): d = 7.71 (s, 1H), 7.74–7.77 (m, 3H), 7.89–7.92
(m, 2H), 8.30–8.35 (m, 2H), 8.80 (t, J=7.8 Hz, 1H), 9.37 ppm (d, J=
5.7 Hz, 2H); 13C NMR ([D6]DMSO): d
= 100.1, 124.8, 128.1, 130.2,
130.3, 131.2, 142.8, 145.0, 146.6, 146.8 ppm; elemental analysis calcd (%)
for C14H11N5O4: C 53.68, H 3.54, N 22.36; found: C 53.99, H 3.40, N
22.29.
1582
ꢁ 2010 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Chem. Eur. J. 2010, 16, 1572 – 1584