2152
C. Modrakowski et al.
PAPER
13C NMR (62.9 MHz, CDCl3): d = 0.64 (s, CH3Si), 14.16 (s,
CH3CH2), 22.62, 22.66, 29.33, 29.76, 31.62, 31.87, 32.15, 32.62,
32.86, 36.07, 125.48, 126.19, 128.29, 129.25, 130.32, 130.73,
135.79, 136.37, 136.68, 137.42, 139.48, 141.52, 142.21, 146.07, (2
signals missing).
129.90, 130.11, 130.79, 137.05, 137.58, 137.66, 138.26, 139.05,
141.07, 155.86, (1 signal missing).
MS (FAB, CH2Cl2–MNBA) m/z: 2113 (100) [M++H], 2057 (32.0)
[M+–C4H8], 2038 (17.0) [M+–C4H10O], 1957 (3.3) [M+–C8H14O2N].
Anal Calcd for C144H198N4O8 (2113.17): C, 81.85; H, 9.44; N, 2.65.
Found: C, 81.69; H, 9.46; N, 2.55.
MS (EI, 80 eV, 250–300 °C) m/z: 1771 (67.1) [M+], 1698 (6.7)
+
[M+–Si(CH3)3], 73 (19.7) [Si(CH3)3 ].
Anal Calcd for C124H170Si4 (1773.05): calcd C, 84.00; H, 9.66.
Found: C, 83.83; H, 9.61.
1,3,6,8-Tetrakis-(4’[3-ammoniopropyl]-2’,5’-dihexyl-biphenyl-
4-yl)pyrene Tetra-trifluoroacetate (16d)
To a solution of Boc protected 16c (2.0 g, 0.946 mmol) dissolved in
CHCl3 (50 mL) was added CF3COOH (6 mL) and the solution was
stirred for 3 h at r.t. Solvents were removed and crude product 16d
(1.7 g, 0.918 mmol, 97%) was freeze-dried with dioxane.
1,3,6,8-Tetrakis-(2’,5’-dihexyl-4’iodo-biphenyl-4-yl-)pyrene)
(16b)
To a solution of 16a (1.00 g, 0.56 mmol) in abs CH2Cl2 (40 mL) at
–78 °C was added a yellow solution of ICl (0.55g, 3.38 mmol) in
abs CH2Cl2 (20 mL) dropwise over 1h at –78 °C. The color changed
from yellow to dark blue and the mixture was stirred for 1h at –
78 °C. The mixture was poured into an aq solution of Na2SO3 (100
mL, c = 1 mol/L) with vigorous stirring. The layers were separated
and the aqueous phase was washed with CH2Cl2 (2 ¥ 30 mL). The
combined organic layers were dried (MgSO4), the CH2Cl2 was re-
moved and gave the yellow product 16b (1.07 g, 0.54 mmol, 96%),
which was recrystallized from Et2O.
1H NMR (270 MHz, DMSO): d = 0.69 (t, 12 H, J = 9 Hz, CH3), 0.82
(t, 12 H, J = 9 Hz, CH3), 0.89–1.62 (m, 64 H, CH2), 1.69–1.96 (m,
8 H, CH2), 2.31–2.70 (m, 24 H, CH2), 2.81–3.03 (m, 8 H, CH2), 7.00
(s, 4 H, Haromatic), 7.09 (s, 4 H, Haromatic), 7.36 (d, 4 H, J = 9 Hz, Har-
+
omatic), 7.58 (d, 8 H, J = 9 Hz, Haromatic), 7.84 (s, 12 H, NH3 ), 8.00 (s,
2 H, Hpyrene), 8.15 (s, 4 H, Hpyrene).
13C NMR (125.8 MHz, DMSO) d = 13.45, 13.52, 14.02, 21.68,
21.82, 28.03, 28.31, 28.51, 29.75, 30.42, 30.61, 30.96, 31.27, 31.94,
38.74, 118.23 (CF3), 124.51, 125.34, 127.32, 128.66, 129.62,
129.51, 130.08, 136.48, 136.90, 137.23, 137.52, 138.12, 138.47,
140.49, 158.66 (COO–), (1 signal missing).
Melting point: 151 °C
1H NMR (270 MHz, CDCl3): d = 0.79 (t, 12 H, J = 9 Hz, CH3), 0.90
(t, 12 H, J = 9 Hz, CH3), 1.07–1.76 (m, 64 H, CH2), 2.59 (t, 8 H,
J = 9 Hz, CH2 benzylic), 2.71 (t, 8 H, J = 9 Hz, CH2 benzylic), 7.14 (s, 4
H, Haromatic), 7.48 (d, 8 H, J = 9 Hz, Haromatic), 7.72 (d, 8 H, J = 9 Hz,
MS (FAB, DMSO–MNBA) m/z: 1713 (100) [M++H–C8F12O8H4].
Anal Calcd for C132H170F12N4O8 (2168.72): C, 73.11; H, 7.90; N,
2.58. Found: C, 72.96, H, 7.85; N, 2.41.
Haromatic), 7.76 (s, 4 H, Haromatic), 8.12 (s, 2 H, Hpyrene), 8.31 (s, 4 H,
Hpyrene).
1,3,6,8-Tetrakis-(4’[3-{2-[2,6-bis-(3-{2-[2,6-bis-(3-tert-butoxy-
carbonylamino-propyl)-4’-pyren-1-yl-biphenyl-4-yl]-ethano-
ylamino}-propyl)-4’-pyren-1-yl-biphenyl-4-yl]-ethanoyl-
amino}propyl]-2’,5’-dihexyl-biphenyl-4-yl)-pyrene (17)
The procedure was analogous to the one described for 13a,b.
13C NMR (67.9 MHz, CDCl3): d = 14.10, 22.53, 22.62, 29.13,
30.37, 31.26, 31.51, 31.67, 32.29, 40.39, 99.61, 125.42, 126.10,
128.25, 129.11, 129.64, 130.40, 130.73, 137.04, 139.69, 139.92,
140.04, 140.26, 141.60, 142.68, (2 signals missing).
MS (EI, 80 eV, 380 °C) m/z: 1987 (85.5) [M+], 1860 (22.5) [M+-I),
Acid 13c (0.17 g, 0.087 mmol), HOBT (14.6 mg, 0.095 mmol),
deprotected 16d (43 mg, 0.020 mmol), DIPEA (21.6 mg, 29 l, 0.167
mmol) and EDC (18.3 mg, 0.095 mmol) and anhyd CH2Cl2 (20 mL)
were used. Chromatographic separation with CH2Cl2–MeOH (5%)
gave the product 17 (0.15 g, 0.016 mmol, 81%) as a yellow oil The
product was recrystallized with acetone.
1733 (3.7) [M+-2I].
Anal Calcd for C112H134I4 (1987.89): C, 67.67; H, 6.79. Found: C,
67.50, H, 6.62.
1,3,6,8 Tetrakis-[4’(3-tert-butoxycarbonylamino-propyl)-2’,5’-
dihexyl-biphenyl-4-yl)-pyrene (16c)
Rf (CH2Cl2–MeOH, 5%) = 0.65.
Protected allylamine 9 (2.64 g, 16.8 mmol) and 9-BBN (2.46 g,
20.16 mmol) were dissolved in abs THF (20 mL) and stirred r.t. for
12h. H2O (1 drop) was added and the solvent was removed. The res-
idue was dissolved in toluene (100 mL) and aqueous KOH (50 mL)
(c = 1 mol/L). 16b (3.36 g, 1.69 mmol) was added and the mixture
was degassed three times. Pd(PPh3)4 (155 mg, 0.134 mmol) was
added and followed by degassing three more times. The mixture
was refluxed for 2 days. After cooling to r.t. the layers were sepa-
rated, the aqueous layer was extracted with toluene (2 ¥ 50 mL).
The combined organic layers were dried (MgSO4) and the solvent
removed. Chromatographic separation with hexanes–EtOAc, 3:1
gave the product 16c (2.64 g, 1.25 mmol, 74%) as yellow solid.
1H NMR (270 MHz, CDCl3): d = 0.72–0.98 (m, 24 H, 31, 31´),
1.07–2.00 (m, 264 H, 6, 12, 18, 27–30, 27´–30´, 21), 2.31–2.46 (m,
32 H, 17), 2.46–2.55 (m, 16 H, 11), 2.55–2.79 (m, 24 H, 5, 26, 26&
acute;), 2.84–3.10 (m, 32 H, 19), 3.14 - 3.31 (m, 24 H, 7, 13), 3.48
(s, 16 H, 15), 3.62 (s, 8 H, 8), 4.41 (s, 16 H, 20), 5.89 (s, 8 H, 14),
6.45 (s, 4 H, 8), 7.00 (s, 16 H, H16), 7.05– 7.21 (m, 16 H, 3, 4, 10),
7.24 (d, J = 9 Hz, 16 H, 24), 7.36 (d, J = 9 Hz, 8 H, 22), 7.46 (d,
J = 9 Hz, 8 H, 2), 7.62 (d, J = 9 Hz, 16 H, 25), 7.65–7.82 (m, 16 H,
1, 23), 7.93–8.43 (m, 114 H, Hpyrene). (Figure)
13C NMR (125.8 MHz, CDCl3): d = 14.08, 15.06, 22.48, 22.57,
28.28, 29.22, 29.49, 29.82, 30.69, 30.86, 31.03, 31.16, 31.48, 31.57,
31.70, 32.25, 32.70, 39.13, 39.43, 39.87, 43.63, 61.71, 66.45, 71.42,
78.93, 124.55, 124.77, 124.85, 124.94, 125.04, 125.16, 125.30,
125.92, 126.0, 127.32, 127.45, 127.58, 127.68, 128.07, 128.29,
129.24, 129.49, 129.69, 129.93, 130.19, 130.37, 130.49, 130.58,
130.83, 131.33, 134.24, 134.48, 136.95, 137.00, 137.07, 137.73,
137.77, 138.31, 138.35, 138.61, 139.05, 139.15, 139.60, 139.65,
139.71, 140.15, 140.27, 141.02, 155.87, 171.07, 171.24, (20 signals
missing).
Rf (hexanes–EtOAc, 3:1) = 0.11.
1H NMR (270 MHz, CDCl3): d = 0.77 (t, 12 H, J = 9 Hz, CH3), 0.86
(t, 12 H, J = 9 Hz, CH3), 1.10–1.72 (m, 100 H, CH3 Boc,CH2), 1.96
(quintet, 8 H, J = 9 Hz, CH2), 2.63 (quintet, 24 H, J = 9 Hz, CH2 ben-
zylic), 3.14–3.38 (m, 8 H, CH2), 4.61 (s, 4 H, NH), 7.10 (s, 4 H, Haro-
matic), 7.12 (s, 4 H, Haromatic), 7.50 (d, 8 H, J = 9 Hz, Haromatic), 7.74 (d,
8 H, J = 9 Hz, Haromatic), 8.15 (s, 2 H, Hpyrene), 8.31 (s, 4 H, Hpyrene).
13C NMR (125.7 MHz, CDCl3): d = 13.99, 22.50, 26.71, 27.53,
28.29, 29.12, 29.41, 29.56, 29.86, 31.15, 31.45, 31.64, 32.19, 32.62,
40.48, 41.69, 78.76, 125.29, 126.03, 128.08, 129.21, 129.57,
MS (FAB, MNBA–CH2Cl2–DMSO) m/z: 9441 (100) [M++Na].
Anal Calcd for C636H678N28O44 (9418.51): C, 81.11; H, 7.26; N,
4.16. Found: C, 80.79; H, 7.32; N, 3.96.
Synthesis 2001, No. 14, 2143–2155 ISSN 0039-7881 © Thieme Stuttgart · New York