4232
M. Tian, H. Ihmels
PAPER
9-(p-N,N-Dimethylaminophenyl)benzo[b]quinolizinium Per-
chlorate (4d)
Catalyst: Pd(dppf)Cl2·CH2Cl2.
was observed. The yellow precipitate was collected, washed with
H2O, EtOAc, and Et2O. The analytically pure product was separated
by recrystallization of the precipitate from MeCN–EtOAc or by col-
umn chromatography (Al2O3, Activity I; MeCN) and subsequent re-
crystallization from MeCN–EtOAc.
Yield: 160 mg (40%); dark-red powder; mp >300 °C.
1H NMR (600 MHz, DMSO-d6): d = 3.04 (s, 6 H, CH3), 6.89 (d,
J = 8.9 Hz, 2 H, H-2¢, H-6¢), 7.80–7.86 (m, 1 H, H-3), 7.91 (d,
J = 9.3 Hz, 2 H, H-3¢, H-5¢), 7.95–8.02 (m, 1 H, H-2), 8.35–8.50 (m,
3 H, H-1, H-7, H-8), 8.51 (s, 1 H, H-10), 8.99 (s, 1 H, H-11), 9.14
(d, J = 6.9 Hz, 1 H, H-4), 10.24 (s, 1 H, H-6).
9-Phenylbenzo[b]quinolizinium Tetrafluoroborate (4a)
Catalyst: Pd(PPh3)2Cl2.
Yield: 152 mg (44%); yellow prisms; mp 203–204 °C.
1H NMR (600 MHz, DMSO-d6): d = 7.57 (t, J = 7.2 Hz, 1 H, H-4¢),
7.64 (dd, J = 7.9, 7.6 Hz, 2 H, H-3¢, H-5¢), 7.93–7.97 (m, 1 H, H-3),
8.02 (d, J = 7.3 Hz, 2 H, H-2¢, H-6¢), 8.08 (dd, J = 9.0, 7.2 Hz, 1 H,
H-2), 8.40 (dd, J = 9.0, 1.5 Hz, 1 H, H-8), 8.58 (d, J = 9.2 Hz, 1 H,
H-7), 8.60 (d, J = 9.5 Hz, 1 H, H-1), 8.71 (s, 1 H, H-10), 9.20 (s, 1
H, H-11), 9.27 (d, J = 7.0 Hz, 1 H, H-4), 10.42 (s, 1 H, H-6).
13C NMR (150 MHz, DMSO-d6): d = 122.2 (CHAr), 123.6 (CHAr),
124.6 (CHAr), 125.0 (Cq), 126.8 (CHAr), 127.7 (CHAr), 129.0
(CHAr), 129.5 (CHAr), 129.7 (CHAr), 130.5 (CHAr), 131.1 (CHAr),
134.4 (CHAr), 135.8 (Cq), 137.8 (Cq), 137.8 (Cq), 140.0 (CHAr),
145.3 (Cq).
13C NMR (150 MHz, DMSO-d6): d = 39.5 (CH3), 112.2 (CHAr),
119.4 (CHAr), 121.1 (CHAr), 123.0 (CHAr), 123.4 (Cq), 124.2 (Cq),
126.3 (CHAr), 128.2 (CHAr), 128.3 (CHAr), 129.5 (CHAr), 130.4
(CHAr), 133.8 (CHAr), 136.0 (Cq), 137.4 (Cq), 139.0 (CHAr), 145.1
(Cq), 151.0 (Cq).
MS (ESI+): m/z = 299 (100) [M]+.
Anal. Calcd for C21H19ClN2O4: C, 63.24; H, 4.80; N, 7.02. Found:
C, 62.94; H, 4.72; N, 7.07.
9-(3-Thienyl)benzo[b]quinolizinium Perchlorate (4e)
Catalyst: Pd(dppf)Cl2·CH2Cl2.
MS (ESI+): m/z (%) = 256 (100) [M]+.
Yield: 152 mg (42%); yellow needles; mp 238–240 °C (dec.).
Anal. Calcd for C19H14BF4N·0.5H2O: C, 64.81; H, 4.29; N, 3.98.
Found: C, 64.47; H, 4.22; N, 3.79.
1H NMR (600 MHz, DMSO-d6): d = 7.82 (dd, J = 5.2, 2.9 Hz, 1 H,
H-4¢), 7.88–7.93 (m, 2 H, H-3, H-5¢), 8.02–8.07 (m, 1 H, H-2),
8.41–8.45 (m, 2 H, H-8, H-2¢), 8.49 (d, J = 9.0 Hz, 1 H, H-7), 8.55
(d, J = 8.7 Hz, 1 H, H-1), 8.66 (s, 1 H, H-10), 9.06 (s, 1 H, H-11),
9.22 (d, J = 6.9 Hz, 1 H, H-4), 10.31 (s, 1 H, H-6).
9-(p-Fluorophenyl)benzo[b]quinolizinium Tetrafluoroborate
(4b)
Catalyst: Pd(PPh3)2Cl2.
13C NMR (150 MHz, DMSO-d6): d = 121.9 (CHAr), 122.0 (CHAr),
124.0 (CHAr), 124.9 (Cq), 126.3 (CHAr), 126.3 (CHAr), 126.7
(CHAr), 128.5 (CHAr), 128.8 (CHAr), 130.1 (CHAr), 131.1 (CHAr),
134.3 (CHAr), 136.1 (Cq), 137.8 (Cq), 139.3 (CHAr), 139.6 (Cq),
139.9 (Cq).
Yield: 143 mg (40%); yellow prisms; mp 235–237 °C.
1H NMR (600 MHz, DMSO-d6): d = 7.44–7.51 (m, 2 H, H-2¢, H-6¢),
7.92–9.97 (m, 1 H, H-3), 8.05–8.10 (m, 3 H, H-2, H-3¢, H-5¢), 8.38
(dd, J = 9.1, 1.7 Hz, 1 H, H-8), 8.57 (d, J = 8.9 Hz, 1 H, H-7), 8.60
(d, J = 8.8 Hz, 1 H, H-1), 8.68 (s, 1 H, H-10), 9.17 (s, 1 H, H-11),
9.26 (d, J = 6.8 Hz, 1 H, H-4), 10.40 (s, 1 H, H-6).
MS (ESI+): m/z = 262 (100) [M]+.
13C NMR (150 MHz, DMSO-d6): d = 116.3 (d, J = 22 Hz, CHAr),
122.1 (CHAr), 123.4 (d, J = 1 Hz, CHAr), 124.5 (CHAr), 124.8 (Cq),
126.7 (CHAr), 128.9 (CHAr), 129.9 (d, J = 8 Hz, CHAr), 130.2
(CHAr), 131.1 (CHAr), 134.1 (d, J = 3 Hz, Cq), 134.3 (CHAr), 135.6
(Cq), 137.7 (Cq), 139.8 (CHAr), 144.0 (Cq), 163.0 (d, J = 248 Hz,
Cq).
Anal. Calcd for C17H12ClNO4S: C, 56.44; H, 3.34; N, 3.87; S, 8.86.
Found: C, 56.45; H, 3.29; N, 4.09; S, 8.59.
9-(2-Thienyl)benzo[b]quinolizinium Perchlorate (4f)
Catalyst: Pd(dppf)Cl2·CH2Cl2.
Yield: 100 mg (28%); yellow prisms; mp 214–216 °C (dec.).
MS (ESI+): m/z = 274 (100) [M]+.
1H NMR (600 MHz, DMSO-d6): d = 7.32 (dd, J = 4.9, 3.7 Hz, 1 H,
H-4¢), 7.88 (dd, J = 5.0, 0.9 Hz, 1 H, H-3¢), 7.89–7.92 (m, 1 H, H-
3), 8.01 (dd, J = 3.5, 0.9 Hz, 1 H, H-5¢), 8.04 (dd, J = 9.0, 7.4 Hz, 1
H, H-2), 8.36 (dd, J = 8.9, 1.6 Hz, 1 H, H-8), 8.46–8.52 (m, 2 H, H-
1, H-7), 8.55 (s, 1 H, H-10), 9.10 (s, 1 H, H-11), 9.20 (d, J = 7.0 Hz,
1 H, H-4), 10.30 (s, 1 H, H-6).
Anal. Calcd for C19H13BF5N: C, 63.19; H, 3.63; N, 3.88. Found: C,
62.79; H, 3.30; N, 3.89.
9-(p-Methoxyphenyl)benzo[b]quinolizinium Perchlorate (4c)
Catalyst: Pd(dppf)Cl2·CH2Cl2.
13C NMR (150 MHz, DMSO-d6): d = 120.7 (CHAr), 122.0 (CHAr),
124.0 (CHAr), 124.8 (Cq), 126.7 (CHAr), 128.2 (CHAr), 129.0
(CHAr), 129.1 (CHAr), 129.4 (CHAr), 130.1 (CHAr), 131.3 (CHAr),
134.3 (CHAr), 135.9 (Cq), 137.9 (Cq), 138.7 (Cq), 139.6 (CHAr),
141.1 (Cq).
Yield: 312 mg (81%); yellow prisms; mp 218–220 °C.
1H NMR (600 MHz, DMSO-d6): d = 3.88 (s, 3 H, CH3), 7.16–7.22
(m, 2 H, H-2¢, H-6¢), 7.88–7.94 (m, 1 H, H-3), 7.98–8.08 (m, 3 H,
H-2, H-3¢, H-5¢), 8.40 (dd, J = 9.0, 1.6 Hz, 1 H, H-8), 8.53 (d,
J = 9.3 Hz, 1 H, H-7), 8.56 (d, J = 8.8 Hz, 1 H, H-1), 8.64 (s, 1 H,
H-10), 9.12 (s, 1 H, H-11), 9.23 (d, J = 6.9 Hz, 1 H, H-4), 10.36 (s,
1 H, H-6).
13C NMR (150 MHz, DMSO-d6): d = 55.4 (CH3), 114.9 (CHAr),
121.9 (CHAr), 122.0 (CHAr), 124.1 (CHAr), 124.8 (Cq), 126.7
(CHAr), 128.8 (CHAr), 129.1 (CHAr), 129.7 (Cq), 130.2 (CHAr),
131.0 (CHAr), 134.3 (CHAr), 136.0 (Cq), 137.7 (Cq), 139.7 (CHAr),
144.9 (Cq), 160.7 (Cq).
MS (ESI+): m/z = 262 (100) [M]+.
Anal. Calcd for C17H12ClNO4S: C, 56.44; H, 3.34; N, 3.87; S, 8.86.
Found: C, 56.38; H, 3.28; N, 3.83; S, 8.59.
9-(3-Furyl)benzo[b]quinolizinium Perchlorate (4g)
Catalyst: Pd(dppf)Cl2·CH2Cl2.
Yield: 50 mg (15%); yellow powder; mp 234–236 °C (dec.).
MS (ESI+): m/z = 286 (100) [M]+.
1H NMR (600 MHz, DMSO-d6): d = 7.29–7.34 (m, 1 H, H-4¢),
7.88–7.93 (m, 1 H, H-3), 7.93–7.96 (m, 1 H, H-5¢), 8.05 (dd, J = 8.5,
7.0 Hz, 1 H, H-2), 8.32 (dd, J = 9.0, 1.2 Hz, 1 H, H-8), 8.49 (d,
J = 8.9 Hz, 1 H, H-7), 8.56 (s, 1 H, H-2¢), 8.57 (d, J = 9.0 Hz, 1 H,
Anal. Calcd for C20H16ClNO5: C, 62.26; H, 4.18; N, 3.63. Found: C,
62.50; H, 3.86; N, 3.68.
Synthesis 2009, No. 24, 4226–4234 © Thieme Stuttgart · New York