Conceptually New Carriers for DNA Delivery
FULL PAPER
1
1.36, N 3.43; found C 76.32, H 11.48, N 3.52. EI-MS (electro-
4-Nonadecyl-1-[(Z)-9-octadecenyl]pyridinium Chloride (2q): 1H
3
spray) calcd. for C26 46ClN 408.11; found 372.2 [M Ϫ Cl].
H
NMR (CDCl
3
): δ ϭ 0.88 (t, J ϭ 6.6 Hz, 6 H), 1.26 (br. m, 54 H),
3
1
.74 (br. m, 2 H), 1.99 (br. m, 6 H), 2.88 (t, J ϭ 7.6 Hz, 2 H), 4.97
1
(
-[(Z)-9-Octadecenyl]-4-pentylpyridinium Chloride (2k): 1H NMR
CDCl ): δ ϭ 0.75 (br. m, 6 H), 1.20 (br. m, 26 H), 1.59 (br. m, 2
H), 1.89 (br. m, 6 H), 2.74 (t, J ϭ 7.4 Hz, 2 H), 4.78 (br. m, 2 H),
3
3
(
t, J ϭ 7.2 Hz, 2 H), 5.34 (br. m, 2 H), 7.81 (d, JAB ϭ 6.6 Hz, 2
H), 9.36 (d, JAB ϭ 6.6 Hz, 2 H) ppm. 13C NMR (CDCl
3
3
): δ ϭ
2.6, 21.2, 24.6, 25.6, 27.6, 27.8, 28.2, 30.4, 34.4, 59.9, 126.3, 128.1,
3
3
1
1
2
3
3
5
6
2
5
.21 (br. m, 2 H), 7.79 (d, JAB ϭ 6.4 Hz, 2 H), 9.49 (d, JAB
ϭ
1
28.5, 142.9 ppm. C42
.12; found C 76.70, H 12.23, N 2.10. EI-MS (electrospray) calcd.
78ClN 632.54; found 596.3 [M Ϫ Cl].
2 2
H78ClN· / H O: calcd. C 76.48, H 12.38, N
.4 Hz, 2 H) ppm. 3C NMR (CDCl
4.5, 25.6, 27.5, 27.6, 27.7, 28.1, 28.9, 29.6, 30.3, 30.3, 31.0, 34.2,
9.4, 75.6, 126.5, 128.0, 128.4, 143.1, 161.2 ppm. C28 50ClN·2H O:
1
): δ ϭ 12.2, 12.5, 20.7, 21.0,
3
for C42
H
H
2
4
-[(Z)-10-Nonadecenyl]-1-[(Z)-9-octadecenyl]pyridinium
Chloride
calcd. C 71.22, H 11.53, N 2.97; found C 70.66, H 11.06, N 3.06.
EI-MS (electrospray) calcd. for C28H50ClN 436.16; found 400.6 [M
Ϫ Cl].
1
(
2r): H NMR (CDCl
3
): δ ϭ 0.87 (br. m, 6 H), 1.35 (br. m, 54 H),
3
1
4
.68 (br. m, 2 H), 2.10 (br. m, 10 H), 2.88 (t, J ϭ 7.7 Hz, 2 H),
3
3
.96 (t, J ϭ 7.3 Hz, 2 H), 5.34 (br. m, 4 H), 7.81 (d, JAB ϭ 6.6 Hz,
-Heptyl-1-[(Z)-9-octadecenyl]pyridinium Chloride (2l): 1H NMR
3
13
4
AB 3
2 H), 9.35 (d, J ϭ 6.6 Hz, 2 H) ppm. C NMR (CDCl ): δ ϭ
3
(CDCl
3
): δ ϭ 0.87 (t, J ϭ 6.4 Hz, 6 H), 1.27 (br. m, 30 H), 1.68
12.6, 21.2, 24.6, 25.7, 27.8, 28.0, 28.2, 30.4, 34.4, 126.3, 128.2,
3
(
br. m, 2 H), 1.99 (br. m, 6 H), 2.86 (t, J ϭ 7.6 Hz, 2 H), 4.94 (t, 128.5, 142.9 ppm. C H ClN: calcd. C 80.01, H 12.15, N 2.22;
J ϭ 7.2 Hz, 2 H), 5.32 (br. m, 2 H), 7.83 (d, JAB ϭ 6.8 Hz, 2 H),
4
2
76
3
3
found C 79.58, H 12.06, N 2.25. EI-MS (electrospray) calcd. for
3
.45 (d, JAB ϭ 6.8 Hz, 2 H) ppm. C NMR (CDCl ): δ ϭ 12.5, C H ClN 630.53; found 594.6 [M Ϫ Cl].
3
13
9
1
2
1
2
4
2
76
2.6, 21.0, 21.2, 24.6, 25.6, 25.7, 27.4, 27.6, 27.7, 27.8, 28.0, 28.1,
8.2, 28.3, 30.0, 30.4, 30.5, 31.1, 34.4, 59.7, 126.4, 128.1, 128.5,
43.0, 161.4 ppm. C30
.96; found C 76.36, H 11.73, N 3.04. EI-MS (electrospray) calcd.
54ClN 464.22; found 428.2 [M Ϫ Cl].
1
1
-[(Z)-9-Octadecenyl]-3-tridecylpyridinium Chloride (3a): H NMR
(CDCl ): δ ϭ 0.86 (br. t, 6 H), 1.26 (br. m, 40 H), 1.68 (br. m, 4
H), 1.97 (m, 6 H), 2.87 (t, 2 H), 5.03 (t, 2 H), 5.32 (m, 2 H), 8.02
1
3
H
54ClN· /
2
H
2
O: calcd. C 76.14, H 11.71, N
3
3
3
(
9
dd, JAB ϭ 8.1, JAB ϭ 5.9 Hz, 1 H), 8.20 (d, JAB ϭ 8.1 Hz, 1 H),
.24 (s, 1 H), 9.52 (d, JAB ϭ 5.9 Hz, 1 H) ppm. C NMR (CDCl ):
3
for C30
H
3
13
-Nonyl-1-[(Z)-9-octadecenyl]pyridinium Chloride (2m): 1H NMR
CDCl
H), 1.92 (br. m, 6 H), 2.80 (t, J ϭ 7.8 Hz, 2 H), 4.85 (t, J ϭ
δ ϭ 12.6, 21.7, 24.6, 25.7, 27.6, 27.7, 27.0, 28.0, 28.1, 29.0, 30.4,
): δ ϭ 0.80 (br. m, 6 H), 1.19 (br. m, 38 H), 1.61 (br. m, 2 30.6, 31.1, 31.3, 60.4, 126.4, 128.1, 128.5, 141.6, 142.9 ppm.
C H ClN·H O: calcd. C 76.34, H 12.10, N 2.47; found C 76.09,
4
(
3
3
3
36 66
2
3
H 12.10, N 2.42. EI-MS (electrospray) calcd. for C H ClN
7
.2 Hz, 2 H), 5.26 (br. m, 2 H), 7.83 (d, JAB ϭ 6.6 Hz, 2 H), 9.53
36 66
3
13
548.38; found 512.7 [M Ϫ Cl].
(
d, JAB ϭ 6.6 Hz, 2 H) ppm. C NMR (CDCl
3
): δ ϭ 12.5, 21.2,
1.1, 24.6, 25.7, 27.6, 27.6, 27.7, 28.0, 28.1, 28.2, 28.3, 30.2, 30.3,
0.4, 31.0, 34.3, 59.5, 75.7, 126.5, 128.1, 128.4, 143.2, 161.2 ppm.
58ClN·2H O: calcd. C 72.75, H 11.83, N 2.65; found C 72.72,
H 12.01, N 2.68. EI-MS (electrospray) calcd. for C32 58ClN
2
3
C
1
-[(Z)-9-Octadecenyl]-3-pentadecylpyridinium Chloride (3b): 1H
NMR (CDCl ): δ ϭ 0.86 (br. t, 6 H), 1.25 (br. m, 44 H), 1.68 (br.
m, 4 H), 1.98 (d, 6 H), 2.88 (t, 2 H), 5.03 (t, 2 H), 5.32 (m, 2 H),
3
32
H
2
H
3
3
3
8
1
.03 (dd, JAB ϭ 8.1, JAB ϭ 5.9 Hz, 1 H), 8.20 (d, JAB ϭ 8.1 Hz,
492.27; found 456.6 [M Ϫ Cl].
3
13
H), 9.23 (s, 1 H), 9.52 (d, JAB ϭ 5.9 Hz, 1 H) ppm. C NMR
): δ ϭ 12.6, 21.2, 24.6, 25.7, 27.6, 27.7, 27.8, 28.0, 28.2,
29.0, 30.4, 30.6, 31.3, 60.4, 126.4, 128.1, 128.5, 142.6, 142.9 ppm.
70ClN·H O: calcd. C 76.78, H 12.21, N 2.36; found C 76.78,
1
(CDCl
3
1
-[(Z)-9-Octadecenyl]-4-undecylpyridinium Chloride (2n): H NMR
3
(CDCl
3
): δ ϭ 0.88 (t, J ϭ 6.4 Hz, 6 H), 1.27 (br. m, 38 H), 1.71
br. m, 2 H), 1.99 (br. m, 6 H), 2.88 (t, J ϭ 7.8 Hz, 2 H), 5.34 (br.
m, 2 H), 7.82 (d, JAB ϭ 6.6 Hz, 2 H), 9.39 (d, JAB ϭ 6.6 Hz, 2
): δ ϭ 12.6, 21.2, 24.6, 25.6, 27.6, 27.7,
7.8, 28.1, 30.4, 34.4, 59.8, 126.3, 128.1, 128.5, 142.9, 161.5 ppm.
3
C
38
H
2
(
3
3
H 12.27, N 2.28. EI-MS (electrospray) calcd. for C38H70ClN
576.43; found 540.2 [M Ϫ Cl].
H) ppm. 1 C NMR (CDCl
2
C
3
3
-Heptadecyl-1-[(Z)-9-octadecenyl]pyridinium Chloride (3c): 1H
NMR (CDCl ): δ ϭ 0.88 (br. t, 6 H), 1.26 (br. m, 48 H), 1.74 (br.
m, 4 H), 2.00 (d, 6 H), 2.90 (t, 2 H), 4.95 (t, 2 H), 5.34 (m, 2 H),
3
1
34
H
62ClN· /
2
H
2
O: calcd. C 77.15, H 12.00, N 2.65; found C 76.93,
62ClN
3
H 11.98, N 2.65. EI-MS (electrospray) calcd. for C34
H
520.33; found 484.5 [M Ϫ Cl].
3
3
3
8
1
.03 (dd, JAB ϭ 8.3, JAB ϭ 6.1 Hz, 1 H), 8.24 (d, JAB ϭ 8.3 Hz,
3
13
H), 9.11 (s, 1 H), 9.22 (d, JAB ϭ 6.1 Hz, 1 H) ppm. C NMR
): δ ϭ 12.6, 21.2, 24.5, 25.7, 27.6, 27.8, 28.0, 28.2, 28.9, 30.4,
1.3, 60.6, 126.4, 128.1, 128.5, 142.8, 143.3 ppm. C40 74ClN·H O:
1
-[(Z)-9-Octadecenyl]-4-pentadecylpyridinium Chloride (2o): 1H
(CDCl
3
3
NMR (CDCl
3
): δ ϭ 0.88 (t, J ϭ 6.4 Hz, 6 H), 1.26 (br. m, 46 H),
3
H
2
3
1.71 (br. m, 2 H), 2.00 (br. m, 6 H), 2.87 (t, J ϭ 7.6 Hz, 2 H), 4.96
calcd. C 77.18, H 12.31, N 2.25; found C 77.24, H 12.46, N 2.18.
EI-MS (electrospray) calcd. for C40H74ClN 604.49; found 568.6 [M
Ϫ Cl].
3
3
(
t, J ϭ 7.2 Hz, 2 H), 5.33 (br. m, 2 H), 7.82 (d, JAB ϭ 6.6 Hz, 2
H), 9.39 (d, JAB ϭ 6.6 Hz, 2 H) ppm. 13C NMR (CDCl
3
): δ ϭ
2.6, 21.2, 24.6, 25.7, 27.7, 27.8, 28.2, 30.4, 34.4, 59.8, 126.3, 128.1,
28.5, 142.9, 161.5 ppm. C38 70ClN·11/2H O: calcd. C 76.01, H
1.75, N 2.33; found C 76.05, H 11.96, N 2.31. EI-MS (electro-
70ClN 576.43; found 540.3 [M Ϫ Cl].
3
1
1
1
H
2
-Nonadecyl-1-[(Z)-9-octadecenyl]pyridinium Chloride (3d): 1H
NMR (CDCl ): δ ϭ 0.88 (br. t, 6 H), 1.25 (br. m, 52 H), 1.65 (br.
m, 4 H), 2.00 (m, 6 H), 2.89 (t, 2 H), 5.04 (t, 2 H), 5.32 (m, 2 H),
3
3
spray) calcd. for C38
H
3
3
3
8
1
.00 (dd, JAB ϭ 7.8, JAB ϭ 6.1 Hz, 1 H), 8.19 (d, JAB ϭ 7.8 Hz,
4
-Heptadecyl-1-[(Z)-9-octadecenyl]pyridinium Chloride (2p): 1H
3
13
H), 9.15 (s, 1 H), 9.52 (d, JAB ϭ 6.1 Hz, 1 H) ppm. C NMR
): δ ϭ 12.6, 21.2, 27.5, 27.8, 28.2, 29.0, 30.4, 30.6, 31.3,
0.5, 126.3, 142.8 ppm. C42 78ClN·H O: calcd. C 77.54, H 12.31,
3
3
NMR (CDCl ): δ ϭ 0.87 (t, J ϭ 6.0 Hz, 6 H), 1.25 (br. m, 52 H),
1
(CDCl
3
3
.71 (br. m, 2 H), 1.98 (br. m, 6 H), 2.86 (t, J ϭ 7.6 Hz, 2 H), 4.95
6
H
2
3
3
(
t, J ϭ 7.1 Hz, 2 H), 5.33 (br. m, 2 H), 7.79 (d, JAB ϭ 6.6 Hz, 2
N 2.25; found C 77.35, H 12.59, N 2.11. EI-MS (electrospray)
calcd. for C42 78ClN 632.54; found 597.1 [M Ϫ Cl].
H), 9.35 (d, JAB ϭ 6.6 Hz, 2 H) ppm. 13C NMR (CDCl
3
): δ ϭ
2.6, 21.2, 24.6, 25.7, 27.7, 27.8, 27.9, 28.2, 30.4, 34.4, 59.8, 126.3,
28.1, 128.5, 142.9, 161.5 ppm. C40 74ClN·H O: calcd. C 77.18, H 3-[(Z)-10-Nonadecenyl]-1-[(Z)-9-octadecenyl]pyridinium
2.31, N 2.25; found C 76.97, H 12.33, N 2.23. EI-MS (electro-
74ClN 604.49; found 568.3 [M Ϫ Cl].
3
H
1
1
1
H
2
Chloride
): δ ϭ 0.85 (br. t, 6 H), 1.25 (br. m, 44 H),
1.70 (br. m, 4 H), 2.00 (s, 10 H), 2.87 (t, 2 H), 5.03 (t, 2 H), 5.32
1
(3e): H NMR (CDCl
3
spray) calcd. for C40
H
Eur. J. Org. Chem. 2004, 835Ϫ849
www.eurjoc.org
2004 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
845