Synthesis and Mass Spectrometric Analysis of Cyclostellettamines H, I, K and L
(m, 2 H, py-CH2CH2), 1.79 (quint, J = 7.1 Hz, 2 H, CH2CH2Cl), (C3), 143.8 (C2Ј), 145.5 (C4Ј) ppm. IR (KBr): ν = 3422 cm–1 s,
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2.60 (t, J = 7.7 Hz, 2 H, py-CH2), 3.56 (t, J = 6.7 Hz, 2 H, CH2Cl),
7.10–7.25 (m, 2 H, pyH5 and pyH4), 8.05–8.13 (m, 2 H, pyH6 and
2922 s, 2851 s, 1629 w, 1560 w, 1507 w, 1468 m, 1438 w, 1260 m,
1160 m, 1063 w, 1020 w, 962 w, 791 w, 760 w, 719 w, 678 m. HRMS:
calcd. for C33H55N2O2 511.4258; found 511.4262.
+
pyH2) ppm. IR (KBr): ν = 3084 cm–1 m, 2982 s, 2851 s, 1599 m,
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1560 m, 1472 s, 1420 s, 1309 m, 1268 s, 1213 m, 1152 s, 1010 s, 940
s, 862 m, 794 m, 718 s, 677 s. C16H26ClNO (283.84): calcd. C 67.70,
H 9.23, N 4.93; found C 67.70, H 8.97, N 4.77. M.p. 49–50 °C.
3-(14-Hydroxytetradecyl)-1-[10-(1-oxidopyridin-3-yl)decyl]pyridin-
ium Iodide (15h): Prepared from 12a (0.9 g, 3.08 mmol), 14e (0.83 g,
3.08 mmol) and NaI (0.55 g, 3.7 mmol) as described above for 15f.
Flash chromatography on SiO2 (9:1 CH2Cl2/methanol) yielded
1.57 g (78%) of 15h as a yellow solid. 1H NMR (250 MHz, [D6]
DMSO): δ = 1.18–1.72 (m, 38 H, 19×CH2), 1.83–1.98 (m, 2 H,
NCH2CH2), 2.53 (t, J = 7.3 Hz, 2 H, 3-CH2), 2.78 (t, J = 7.5 Hz,
3-(10-Chlorodecyl)pyridine N-Oxide (14e): Prepared from 13e
(1.46 g, 5 mmol) and m-chloroperbenzoic acid (1.29 g, 7.5 mmol,
77% active) as described above for 14b. Evaporation of the solvent
gave 1.14 g (83%) of 14e as a slightly yellow oil. 1H NMR
(250 MHz, CDCl3): δ = 1.23–1.48 (m, 12 H, 6×CH2), 1.51–1.68 2 H, 3Ј-CH2), 3.31–3.40 (m, 2 H, CH2OH), 4.32 (t, J = 5.1 Hz, 1
(m, 2 H, py-CH2CH2), 1.70–1.83 (m, 2 H, CH2CH2Cl), 2.56 (t, J H, OH; interchangeable with D2O), 4.56 (t, J = 7.3 Hz, 2 H,
= 7.6 Hz, 2 H, py-CH2), 3.52 (t, J = 6.7 Hz, 2 H, CH2Cl), 7.05–
NCH2), 7.19 (d, J = 8.0 Hz, 1 H, H4), 7.32 (dd, J = 7.6, J = 6.6 Hz,
7.21 (m, 2 H, pyH5 and pyH4), 8.03–8.10 (m, 2 H, pyH6 and 1 H, H5), 8.02–8.13 (m, 3 H, H2, H2Ј and H5Ј), 8.49 (d, J = 8.0 Hz,
pyH2) ppm. IR (NaCl): ν = 3064 cm–1 w, 2227 s, 2854 s, 1602 m,
1 H, H4Ј), 8.95 (d, J = 6.0 Hz, 1 H, H6Ј), 9.05 (s, 1 H, H2Ј) ppm.
13C NMR (62.5 MHz, [D6]DMSO): δ = 25.2, 25.4, 28.15, 28.20,
28.25, 28.55, 28.60, 28.62, 28.66, 28.80, 28.85, 28.94 and 29.0
(13 × CH2 ), 29.6 (3Ј-CH2 CH2 ), 29.8 (3-CH2 CH2 ), 30.5
(CH2CH2N), 31.5 (3Ј-CH2 + 3-CH2), 32.4 (CH2CH2OH), 60.5
(CH2OH + CH2N), 125.4 (C4), 125.9 (C5), 127.5 (C5Ј), 136.2 (C6),
138.0 (C2), 141.3 (C3Ј), 142.1 (C6Ј), 142.9 (C3), 143.8 (C2Ј), 145.0
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1506 m, 1480 w, 1436 s, 1273 s, 1159 s, 1014 s, 966 w, 862 w, 793
w, 761 w, 722 w, 681 m. C15H24ClNO (269.81): calcd. C 66.77, H
8.97, N 5.19 calcd. 13e·0.25H2O: calcd. C 65.68, H 9.00, N 5.11;
found C 65.69, H 9.15, N 5.13.
3-(12-Hydroxydodecyl)-1-[10-(1-oxidopyridin-3-yl)decyl]pyridinium
Iodide (15f): Compound 14e (830 mg, 3.07 mmol) was added to a
solution of 12c (0.81 g, 3.07 mmol) and NaI (552 mg, 3.7 mmol) in
30 mL of butan-2-one and the mixture was refluxed for 40 h. The
solvent was then removed and the residue was adsorbed on SiO2.
Flash chromatography on SiO2 (9:1 CH2Cl2/methanol) yielded
1.27 g (66%) of 15f as a waxy solid. 1H NMR (250 MHz, [D6]
(C4Ј) ppm. IR (KBr): ν = 3384 cm–1 s, 3046 m, 2918 s, 2850 s, 1734
˜
w, 1630 m, 1604 m, 1570 w, 1505 w, 1466 s, 1438 m, 1364 w, 1314
w, 1263 s, 1161 s, 1054 m, 1019 w, 964 w, 917 w, 804 m, 761 w, 721
+
m, 683 s. HRMS: calcd. for C34H57N2O2 525.4415; found
525.4381.
DMSO): δ = 1.11–1.71 (m, 34 H, 17×CH2), 1.84–1.99 (m, 2 H, 3-(12-Hydroxydodecyl)-1-[11-(1-oxidopyridin-3-yl)undecyl]pyridin-
NCH2CH2), 2.53 (t, J = 7.5 Hz, 2 H, 3-CH2), 2.80 (t, J = 7.5 Hz, ium Iodide (15i): Prepared from 12c (0.74 g, 2.82 mmol), 14d (0.8 g,
2 H, 3Ј-CH2), 3.32–3.40 (m, 2 H, CH2OH), 4.33 (t, J = 5.0 Hz, 1
H, OH; interchangeable with D2O), 4.56 (t, J = 7.3 Hz, 2 H,
2.82 mmol) and NaI (0.51 g, 3.4 mmol) as described above for 15f.
Filtration of the precipitate yielded 1.53 g (85%) of 15i as an off-
NCH2), 7.19 (d, J = 7.8 Hz, 1 H, H4), 7.34 (t, J = 7.2 Hz, 1 H, white solid. 1H NMR (250 MHz, [D6]DMSO): δ = 1.15–1.71 (m, 36
H5), 8.03–8.14 (m, 3 H, H2, H2Ј and H5Ј), 8.49 (d, J = 8.0 Hz, 1
H, H4Ј), 8.95 (d, J = 6.0 Hz, 1 H, H6Ј), 9.05 (s, 1 H, H2Ј) ppm.
13C NMR (62.5 MHz, [D6]DMSO): δ = 25.3, 25.4, 28.15, 28.20,
28.25, 28.55, 28.60, 28.65, 28.80, 28.85, 28.90 and 29.0 (12×CH2),
H, 18×CH2), 1.83–1.98 (m, 2 H, NCH2CH2), 2.51 (t, J = 8.2 Hz, 2
H, 3-CH2), 2.79 (t, J = 7.5 Hz, 2 H, 3Ј-CH2), 3.34–3.40 (m, 2 H,
CH2OH), 4.38 (t, J = 4.5 Hz, 1 H, OH; interchangeable with D2O),
4.58 (t, J = 7.3 Hz, 2 H, NCH2), 7.19 (dt, J = 8.1, J = 1.3 Hz, 1
29.6 (3Ј-CH2CH2), 29.8 (3-CH2CH2), 30.5 (CH2CH2N), 31.5 (3Ј- H, H4), 7.32 (dd, J = 6.5, J = 7.5 Hz, 1 H, H5), 8.02–8.12 (m, 3
CH2 + 3-CH2), 32.4 (CH2CH2OH), 60.6 (CH2OH, CH2N), 125.4 H, H2, H2Ј and H5Ј), 8.49 (d, J = 8.1 Hz, 1 H, H4Ј), 9.00 (d, J =
(C4), 125.9 (C5), 127.5 (C5Ј), 136.1 (C6), 138.0 (C2), 141.3 (C3Ј), 6.0 Hz, 1 H, H6Ј), 9.10 (s, 1 H, H2Ј) ppm. 13C NMR (62.5 MHz,
142.1 (C6Ј), 142.9 (C3), 143.8 (C2Ј), 145.0 (C4Ј) ppm. IR (KBr): ν
[D6]DMSO): δ = 25.2, 25.4, 28.2, 28.3, 28.55, 28.60, 28.66, 28.73,
28.77, 28.82, 28.85, 28.90 and 29.0 (14×CH2), 29.6 (3Ј-CH2CH2),
29.8 (3-CH2CH2), 30.5 (CH2CH2N), 31.5 (3Ј-CH2 + 3-CH2), 32.4
(CH2CH2OH), 60.5 (CH2OH + CH2N), 125.4 (C4), 125.9 (C5),
127.5 (C5Ј), 136.2 (C6), 138.1 (C2), 141.3 (C3Ј), 142.2 (C6Ј), 142.9
˜
= 3422 cm–1 s, 3029 w, 2924 s, 2849 s, 1630 w, 1570 w, 1500 m,
1459 m, 1353 w, 1259 m, 1166 s, 1107 w, 1060 m, 1023 w, 953 w,
+
810 m, 761 m, 725 w, 689 m. HRMS: calcd. for C32H53N2O2
497.4102; found 497.4108.
(C3), 143.9 (C2Ј), 145.0 (C4Ј) ppm. IR (KBr): ν = 3256 cm–1 m,
˜
3-(10-Hydroxydecyl)-1-[13-(1-oxidopyridin-3-yl)tridecyl]pyridinium
Iodide (15g): Prepared from 12e (0.67 g, 2.86 mmol), 14b (0.89 g,
2.86 mmol) and NaI (0.51 g, 3.4 mmol) as described above for 15f.
Flash chromatography on SiO2 (9:1 CH2Cl2/methanol) yielded
1.1 g (60 %) of 15g as orange solid. 1H NMR (250 MHz, [D6]
3067 w, 2917 s, 2848 s, 1630 w, 1603 w, 1560 w, 1492 w, 1468 m,
1431 m, 1330 w, 1269 m, 1215 m, 1156 s, 1079 m, 1016 w, 965
m, 906 w, 817 w, 801 w, 760 w, 720 w, 682 m. HRMS: calcd. for
+
C33H55N2O2 511.4258; found 511.4254.
DMSO): δ = 1.11–1.45 (m, 32 H, 16×CH2), 1.46–1.71 (m, 4 H, 3Ј- 3-(14-Hydroxytetradecyl)-1-[11-(1-oxidopyridin-3-yl)undecyl]-
CH2–CH2, 3-CH2–CH2), 1.83–1.98 (m, 2 H, NCH2CH2), 2.53 (t, J pyridinium Iodide (15j): Prepared from 12a (0.7 g, 2.4 mmol), 14d
= 7.4 Hz, 2 H, 3-CH2), 2.79 (t, J = 7.6 Hz, 2 H, 3Ј-CH2), 3.32–3.40 (0.68 g, 2.4 mmol) and NaI (0.43 g, 2.88 mmol) as described above
(m, 2 H, CH2OH), 4.30 (t, J = 5.1 Hz, 1 H, OH; interchangeable
with D2O), 4.55 (t, J = 7.3 Hz, 2 H, NCH2), 7.19 (dt, J = 7.8, J =
1.3 Hz, 1 H, H4), 7.34 (dd, J = 7.5, J = 6.5 Hz, 1 H, H5), 8.02–
for 15f. Flash chromatography on SiO2 (9:1 CH2Cl2/methanol)
yielded 0.85 g (53%) of 15h as a yellow solid. 1H NMR (250 MHz,
[D6]DMSO): δ = 1.15–1.72 (m, 40 H, 20×CH2), 1.82–1.98 (m, 2
8.12 (m, 3 H, H2, H2Ј and H5Ј), 8.48 (d, J = 8.2 Hz, 1 H, H4Ј), H, NCH2CH2), 2.52 (t, J = 7.7 Hz, 2 H, 3-CH2), 2.78 (t, J = 7.5 Hz,
8.93 (d, J = 6.0 Hz, 1 H, H6Ј), 9.03 (s, 1 H, H2Ј) ppm. 13C NMR 2 H, 3Ј-CH2), 3.32–3.40 (m, 2 H, CH2OH), 4.38 (t, J = 5.1 Hz, 1
(62.5 MHz, [D6]DMSO): δ = 25.2, 25.4, 28.1, 28.2, 28.3, 28.60,
28.65, 28.75, 28.80 and 28.9 (10×CH2), 29.6 (3Ј-CH2CH2), 29.8 (3- NCH2), 7.19 (d, J = 8.0 Hz, 1 H, H4), 7.32 (dd, J = 6.4, J = 7.6 Hz,
CH2CH2), 30.5 (CH2CH2N), 31.5 (3Ј-CH2 + 3-CH2), 32.4 1 H, H5), 8.02–8.13 (m, 3 H, H2, H2Ј and H5Ј), 8.48 (d, J = 8.1 Hz,
H, OH; interchangeable with D2O), 4.55 (t, J = 7.3 Hz, 2 H,
(CH2CH2OH), 60.6 (CH2OH + CH2N), 125.4 (C4), 125.9 (C5), 1 H, H4Ј), 8.94 (d, J = 6.0 Hz, 1 H, H6Ј), 9.04 (s, 1 H, H2Ј) ppm.
127.5 (C5Ј), 136.5 (C6), 138.0 (C2), 141.3 (C3Ј), 142.1(C6Ј), 142.9 13C NMR (62.5 MHz, [D6]DMSO): δ = 25.2, 25.4, 28.15, 28.23,
Eur. J. Org. Chem. 2006, 1285–1295
© 2006 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.eurjoc.org
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