M. Tian, H. Ihmels
FULL PAPER
(400 MHz, CDCl3): δ = 2.76 (t, J = 5 Hz, 4 H, CH2), 2.88 (t, J
3
3
(CHar), 125.8 (CHar),127.8 (Cq), 130.2 (CHar), 130.3 (CHar), 134.0
(CHar), 137.9 (Cq), 138.2 (CHar), 139.0 (Cq), 145.0 (Cq), 151.8 (Cq)
3
= 8 Hz, 4 H, CH2), 3.28 (br. s, 2 H, NH2), 3.53 (t, J = 8 Hz, 4 H,
CH2), 3.64 (s, 4 H, CH2), 3.81 (t, J = 5 Hz, 4 H, CH2), 6.57 (d, ppm. MS (ESI+): m/z (%) = 520 (100) [M]+. C16H26N2O2S2·H2O
3
3J = 8 Hz, 2 H, CHar), 6.65 (d, J = 8 Hz, 2 H, CHar) ppm. 13C (574.20): calcd. C 60.66, H 6.32, N 7.32, S 11.17; found C 60.47,
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NMR (400 MHz, CDCl3): δ = 29.6 (2 CH2), 31.0 (2 CH2), 52.3 (2 H 6.38, N 7.30, S 11.19.
CH2), 70.7 (2 CH2), 74.1 (2 CH2), 114.2 (2 CHar), 117.0 (2 CHar),
9-{[4-(1,4,7,13-Tetraoxa-10-azacyclopentadecyl)phenyl]amino}-
137.0 (Cq), 140.6 (Cq) ppm. MS (ESI+): m/z (%) = 343 (3) [M +
benzo[b]quinolizinium Chloride (1d): Yield 335 mg (32%), purple
H]+. C16H26N2O2S2 (342.52): calcd. C 56.11, H 7.65, N 8.18, S
18.72; found C 56. 23, H 7.67, N 8.08, S 18.72.
1
needles; m.p. 246–248 °C. H NMR (400 MHz, MeOD): δ = 3.71–
3
3.56 (m, 16 H, CH2), 3.78 (t, J = 6 Hz, 4 H, CH2), 6.74–6.81 (m,
General Procedure for the Reaction of 9-Fluorobenzo[b]quinolizinium
Bromide with Donor-Substituted Aniline Derivatives: A solution of
9-fluorobenzo[b]quinolizinium bromide (556 mg, 2.00 mmol) and
the corresponding aniline derivative (2.00 mmol) in ethanol (5 mL)
was stirred under reflux under nitrogen for 72 h. After cooling the
reaction mixture to room temp., it was passed through an ion ex-
change resin (DOWEX®1 ϫ8 Cl–). The product was purified by
2 H, Ph-H), 7.08 (d, 4J = 2 Hz, 1 H, 10-H), 7.21–7.14 (m, 2 H, Ph-
3
4
H), 7.40–7.33 (m, 1 H, 3-H), 7.51 (dd, J = 9, J = 2 Hz, 1 H, 8-
H), 7.64–7.58 (m, 1 H, 2-H), 7.93 (d, 3J = 9 Hz, 1 H, 1-H), 8.08
3
3
(d, J = 9 Hz, 1 H, 7-H), 8.10 (s, 1 H, 11-H), 8.67 (d, J = 7 Hz, 1
H, 4-H), 9.50 (s, 1 H, 6-H) ppm. 13C NMR (100 MHz, CD3OD):
δ = 53.7 (CH2), 70.0 (CH2), 71.1 (CH2), 71.4 (CH2), 72.3 (CH2),
100.3 (CHar), 113.5 (CHar), 119.0 (CHar), 119.9 (CHar), 123.3 (Cq),
column chromatography (SiO2; CHCl3/MeOH, 10:1) and subse- 126.3 (2 CHar), 126.9 (CHar), 128.6 (Cq), 130.8 (CHar), 131.0
quent recrystallization from MeOH/ethyl acetate.
(CHar), 134.4 (CHar), 138.6 (CHar), 139.6 (Cq), 140.9 (Cq), 147.7
(Cq), 154.1 (Cq) ppm. MS (ESI+): m/z (%) = 489 (100) [M]+.
C29H34ClN3O4·0.5H2O (533.06): calcd. C 65.34, H 6.62, N 7.88;
found C 65.53, H 6.57, N 7.95.
9-{[2-(1,4-Dioxa-7,13-dithia-10-azacyclopentadecyl)phenyl]amino}-
benzo[b]quinolizinium Chloride (1a): Yield 116 mg (10%), orange-
red needles; m.p. 240–241 °C. 1H NMR (400 MHz, MeOD): δ =
2.68–2.75 (m, 8 H, CH2), 3.25–3.28 (m, 4 H, CH2), 3.64 (s, 4 H,
CH2), 3.72 (t, 3J = 5 Hz, 4 H, CH2), 7.19–7.24 (m, 2 H, Ph-H),
7.32–7.34 (m, 1 H, Ph-H), 7.41 (d, 4J = 2 Hz, 1 H, 10-H), 7.45–
7.47 (m, 1 H, 3-H), 7.56–7.58 (m, 1 H, Ph-H), 7.67–7.78 (m, 2 H,
2-H, 8-H), 7.91 (s, 1 H, CHCl3), 8.06 (d, 3J = 9 Hz, 1 H, 1-H), 8.20
Supporting Information (see footnote on the first page of this arti-
1
cle): H and 13C NMR spectra of all new compounds, spectra of
photometric titrations, and Job plot.
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3
Acknowledgments
(d, J = 9 Hz, 1 H, 7-H), 8.35 (s, 1 H, 11-H), 8.77 (d, J = 7 Hz, 1
H, 4-H), 9.67 (s, 1 H, 6-H) ppm.[10a]
Generous support by the Deutsche Forschungsgemeinschaft is
gratefully acknowledged.
9-{[2-(1,4,7,13-Tetraoxa-10-azacyclopentadecyl)phenyl]amino}-
benzo[b]quinolizinium Perchlorate (1b): Fully characterized as the
perchlorate salt, which was obtained by the addition of a saturated
aqueous solution of sodium perchlorate to the solution of the chlo-
ride in methanol, and subsequent recrystallization of the precipitate
from MeCN. Yield: 165 mg, 14%, orange prisms; m.p. 207–208 °C.
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1H NMR (400 MHz, CD3OD): δ = 3.21 (t, J = 5 Hz, 4 H, CH2),
3
3.53 (t, J = 5 Hz, 4 H, CH2), 3.57–3.61 (m, 4 H, CH2), 3.67–3.70
(m, 4 H, CH2), 3.74 (s, 4 H, CH2), 7.15–7.19 (m, 1 H, Ph-H), 7.21–
7.26 (m, 1 H, Ph-H), 7.39 (dd, 3J = 8, 4J = 1 Hz, 1 H, Ph-H), 7.44–
7.50 (m, 1 H, 3-H), 7.66–7.73 (m, 3 H, 2-H, 10-H, Ph-H), 7.99 (dd,
4
3
3J = 9, J = 2 Hz, 1 H, 1 H, 8-H), 8.08 (d, J = 9 Hz, 1 H, 1-H),
8.17 (d, 3J = 9 Hz, 1 H, 7-H), 8.37 (s, 1 H, 11-H), 8.79 (d, 3J =
7 Hz, 1 H, 4-H), 9.65 (s, 1 H, 9-H) ppm. 13C NMR (100 MHz,
CD3OD): δ = 55.7 (CH2), 69.7 (CH2), 71.1 (CH2), 71.3 (CH2), 71.4
(CH2), 102.1 (CHar), 120.0 (CHar), 120.4 (CHar), 120.6 (CHar),
123.8 (Cq), 124.9 (CHar), 125.6 (CHar), 126.0 (CHar), 127.0 (CHar),
129.7 (CHar), 130.2 (CHar), 130.9 (CHar), 134.4 (CHar), 137.6 (Cq),
138.6 (CHar), 139.5 (Cq), 140.6 (Cq), 144.2 (Cq), 151.2 (Cq) ppm.
MS (ESI+): m/z (%) = 489 (100) [M]+. C29H34ClN3O8 (588.05):
calcd. C 59.23, H 5.83, N 7.15; found C 59.01, H 5.85, N 7.22.
9-{[4-(1,4-Dioxa-7,13-dithia-10-azacyclopentadecyl)phenyl]amino}-
benzo[b]quinolizinium Chloride (1c): Yield 511 mg (46%), dark pur-
1
ple prisms; m.p. 240–244 °C. H NMR (600 MHz, [D6]DMSO): δ
= 2.75 (t, 3J = 5 Hz, 4 H, CH2), 2.83 (t, 3J = 8 Hz, 4 H, CH2),
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3
3.55–3.64 (m, 8 H, CH2), 3.71 (t, J = 5 Hz, 4 H, CH2), 6.71 (d, J
4
3
= 9 Hz, 2 H, Ph-H), 7.13 (d, J = 2 Hz, 1 H, 10-H), 7.23 (d, J =
3
4
9 Hz, 2 H, Ph-H), 7.44–7.48 (m, 1 H, 3-H), 7.58 (dd, J = 9, J =
2 Hz, 1 H, 8-H), 7.66–7.70 (m, 1 H, 2-H), 7.99 (d, J = 9 Hz, 1 H,
3
1-H), 8.16 (d, 3J = 9 Hz, 1 H, 7-H), 8.36 (s, 1 H, 11-H), 8.82 (d, 3J
= 7 Hz, 1 H, 4-H), 9.69 (s, 1 H, NH), 9.81 (s, 1 H, 6-H) ppm. 13C
NMR (150 MHz, [D6]DMSO): δ = 29.6 (2 CH2), 31.0 (2 CH2),
51.8 (2 CH2), 70.5 (2 CH2), 73.5 (2 CH2), 98.9 (CHar), 112.7 (2
CHar), 118.0 (CHar), 119.0 (CHar) 121.5 (Cq), 125.0 (2 CHar), 125.8
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Eur. J. Org. Chem. 2011, 4145–4153