Compound 15b: 0.9 g of 14 was used in the reaction. Recrystallized from
1
dichloromethane/methanol; yield 1.14 g (77%); m.p. 208-211 °C; H NMR (500 MHz,
3
CDCl3): = 0.90 (t, JH, H = 6.9 Hz, 3 H, CH3), 1.27 (s, 10 H, CH2), 1.70 (br. 2H, CH2),
2.52 (s, 9 H, CH3), 3.71 (m, 2 H, CH2), 7.20 (d, 3JH, H = 8.7 Hz, 2 H, ArH), 7.22 (d, 3JH, H
3
3
= 8.7 Hz, 2 H, ArH), 7.37 (d, JH, H = 8.0 Hz, 6 H, ArH), 7.71 (d, JH, H = 8.0 Hz, 2 H,
ArH), 7.75 (d, 3JH, H = 8.4 Hz, 2 H, ArH), 7.82 (d, 3JH, H = 8.0 Hz, 4 H, ArH), 7.86 (d, 3JH,
= 8.4 Hz, 2 H, ArH), 7.91 (d, JH, H = 8.7 Hz, 2 H, ArH), 8.03 (d, 3JH, H = 8.7 Hz, 2 H,
3
H
ArH) ppm; 13C NMR (75.47 MHz, CDCl3): = 14.20, 21.89, 21.92, 22.72, 26.65, 29.04,
29.22, 31.81, 50.08, 128.75, 129.36, 129.53, 129.61, 129.80, 130.01, 130.10, 132.42,
132.58, 132.65, 135.72, 136.15, 138.89, 138.98, 139.88, 140.37, 141.64, 144.38, 145.81,
146.12 ppm. MS (ESI pos., CH3OH/CH2Cl2): m/z = 1158.05 [M+K]+ calcd monoisotopic
peak (12C47 H5079Br14N3 O1232S6K) 1158.05; 1142.07 [M+Na]+ calcd monoisotopic peak
1
16
(12C47 H5079Br14N3 O1232S6Na) 1142.08; elemental analysis calcd (%) for
C47H50BrN3O12S6 (1121.21): C 50.35, H 4.49, Br 7.13, N 3.75, S 17.16; found C 50.06, H
4.53, Br 7.30, N 3.69, S 17.30.
1
16
1
3
Compound 16: M.p. 142-144 °C; H NMR (300 MHz, CD3OD): = 0.93 (t, JH, H
=
7.0 Hz, 3 H, CH3), 1.29 (s, 10 H, CH2), 1.66 (br. 2H, CH2), 3.78 (m, 2 H, CH2), 7.08 (d,
3JH, H = 8.8 Hz, 4 H, ArH), 7.31 (d, 3JH, H = 8.7 Hz, 2 H, ArH), 7.67 (d, 3JH, H = 8.4 Hz, 2
H, ArH), 7.74 (d, 3JH, H = 8.8 Hz, 4 H, ArH), 7.95 (d, 3JH, H = 8.4 Hz, 2 H, ArH), 8.01 (d,
3JH, H = 8.7 Hz, 2 H, ArH) ppm; MS (EI, 80 eV): m/z = 814.07 [M]+.
Compound 17a: 1 g of 16 was used. Recrystallized from dichloromethane/methanol;
yield 1.4 g (74%); m.p. 267-269 °C; 1H NMR (500 MHz, (CD3)2SO): = 0.83 (t, 3JH, H
=
7.0 Hz, 3 H, CH3), 1.17 (s, 10 H, CH2), 1.62 (br. 2H, CH2), 3.77 (t, 3JH, H = 7.6 Hz, 2 H,
CH2), 7.44 (d, 3JH, H = 8.7 Hz, 2 H, ArH), 7.50 (d, 3JH,3H = 8.7 Hz, 4 H, ArH), 7.70 (d, 3JH,
= 8.4 Hz, 2 H, ArH), 7.92 (m, 6 H, ArH), 8.09 (d, JH, H = 8.7 Hz, 2 H, ArH), 8.17 (d,
H
3
3JH, H = 9.0 Hz, 8 H, ArH), 8.53 (d, JH, H = 9.0 Hz, 8 H, ArH) ppm; elemental analysis
calcd (%) for C56H49BrN8O24S8 (1554.45): C 43.27, H 3.18, Br 5.14, N 7.21, S 16.50;
found C 43.10, H 3.35, Br 5.19, N 7.52, S 16.74.
Compound 17b: 0.7 g of 16 was used. Purified by column chromatography (Rf = 0.39,
silica gel, CH2Cl2); yield 0.9 g (72%), m.p. 127-129 °C; 1H NMR (500 MHz, CDCl3): =
0.90 (t, 3JH, H = 7.0 Hz, 3 H, CH3), 1.26 (s, 10 H, CH2), 1.72 (br. 2 H, CH2), 2.50 (s, 12 H,
CH3), 3.72 (m, 2 H, CH2), 7.15 (d, 3JH, H = 8.8 Hz, 2 H, ArH), 7.20 (d, 3JH, H = 8.8 Hz, 4
H, ArH), 7.33 (d, 3JH, H = 8.0 Hz, 8 H, ArH), 7.70 (d, 3JH, H = 8.4 Hz, 2 H, ArH), 7.77 (d,
3JH, H = 8.7 Hz, 4 H, ArH), 7.78 (d, 3JH, H = 8.0 Hz, 8 H, ArH), 7.82 (d, 3JH, H = 8.4 Hz, 2
3
13
H, ArH), 8.02 (d, JH, H = 8.7 Hz, 2 H, ArH) ppm; C NMR (75.47 MHz, CDCl3):
=
14.22, 21.91, 22.74, 26.66, 29.05, 29.23, 30.11, 31.81, 50.16, 128.75, 129.49, 129.55,
129.62, 129.68, 129.85, 130.07, 132.40, 132.70, 136.12, 138.53, 139.72, 140.30, 142.05,
145.89 ppm; MS (ESI pos., CH3OH): m/z = 1467.18 [M+K]+ calcd monoisotopic peak
1
16
(12C60 H6179Br14N416O1632S8K) 1467.07; 1451.21 [M+Na]+ calcd monoisotopic peak
1
(12C60 H6179Br14N4 O1632S8Na) 1451.09; elemental analysis calcd (%) for
C60H61BrN4O16S8 (1430.57): C 50.37, H 4.30, Br 5.59, N 3.92, S 17.93; found C 50.26, H
4.42, Br 5.60, N 3.86, S 17.83.
S9