The Journal of Organic Chemistry
Note
atmosphere overnight; then it was cooled to room temperature and
dried under reduced pressure to give a brown solid. This solid was
suspended in dichloromethane (50 mL) and filtered through a short
pad of Celite, washing the solid with dichloromethane (2 × 25 mL).
solution, which was taken to dryness under reduced pressure to give
13 as a pale yellow powder. Yield: 0.077 g (0.096 mmol, 96%).
1
H NMR (400 MHz, 1:1 CDCl :CD OD): 8.10 (s, 2H), 8.05 (s,
3
3
2H), 7.75 (s, 4H), 7.31 (d, J = 8.6 Hz, 4H), 6.82 (d, J = 8.6 Hz, 4H),
5.85 (s, 2H), 3.95 (t, J = 6.4 Hz, 4H), 1.71−1.80 (m, 4H), 1.23−1.50
(m, 12H), 0.88 (t, J = 6.6 Hz, 6H) ppm. 13C NMR (100 MHz, 1:1
CDCl :CD OD): 160.4, 153.4, 147.7, 141.4, 140.4, 140.1, 135.3,
The resulting clear yellow filtrate was washed with K CO
(10%, 2
2
3(aq)
×
50 mL), dried (MgSO ), and taken to dryness under reduced
4
pressure. Purification by column chromatography (gradient: 4−7%
methanol in dichloromethane) gave 10 as an orange powder. Yield:
3
3
131.7, 131.5, 122.4, 114.8, 111.4, 68.6, 54.4, 32.1, 29.7, 26.2, 23.1, 14.2
+
0
.189 g (0.263 mmol, 53%).
H NMR (400 MHz, CDCl ): 7.87 (s, 2H), 7.37 (d, J = 8.7 Hz,
ppm. HRESI-MS (pos.): 739.3765, calcd. for [C H N O ·H] =
48 46 6 2
1
739.3761. mp > 260 °C.
Hexyl-Substituted Bis(imidazole) 14. Hexyl-substituted tetra-
3
4
H), 6.79−6.84 (m, 8H), 5.23 (s, 2H), 3.95 (t, J = 6.7 Hz, 4H), 3.26
(
(
br. s, 8H), 1.77 (app. qn, J = 6.7 Hz, 4H), 1.29−1.50 (m, 12H), 0.91
amine 11 (0.053 g, 0.10 mmol) and NH Cl (0.11 g, 2.0 mmol) were
4
t, J = 6.7 Hz, 6H) ppm. 13C NMR (75 MHz, CDCl ): 159.5, 152.0,
placed in a flask. Ethanol (10 mL) and trimethyl orthoformate (0.055
mL, 0.053 g, 0.50 mmol) were added, and the reaction mixture was
heated to reflux under a nitrogen atmosphere for 48 h. Drying the
solution under reduced pressure afforded a brown powder that was
suspended in saturated NaHCO3(aq), sonicated briefly, and then
filtered to give a pale brown powder. The solid was washed with
saturated NaHCO3(aq) (2 × 5 mL) and water (4 × 5 mL); then it was
dissolved using 2:1 CH Cl :CH OH to give a yellow solution, which
3
1
5
47.6, 140.2, 136.9, 131.95, 131.90, 131.2, 121.5, 114.3, 113.2, 68.2,
2.5, 31.7, 29.3, 25.8, 22.7, 14.2 ppm. HRESI-MS (pos.): 739.3755,
+
calcd. for [C H N O ·Na] = 739.3755. mp 178−180 °C. R (9:1
CH Cl :CH OH): 0.37.
34
52
8
9
f
2
2
3
Hexyl-Substituted Tetraamine 11. Hexaaminotriptycene·6HCl·
H O (0.71 g, 1.0 mmol) was suspended in methanol (50 mL) and
2
8
sonicated for 20 min to thoroughly disperse the insoluble compound.
The resulting milky white suspension was heated to reflux under a
nitrogen atmosphere, and a solution of 7,8-tetradecanedione (0.113 g,
2
2
3
was taken to dryness under reduced pressure to give 14 as a pale
brown powder. Yield: 0.052 g (0.093 mmol, 93%).
1
0.500 mmol) and triethylamine (1.7 mL, 1.2 g, 12 mmol) in
H NMR (400 MHz, 1:1 CDCl :CD OD): 7.97 (s, 2H), 7.93 (s,
3 3
chloroform (50 mL) was added in one portion. The resulting clear
yellow-orange solution was heated to reflux under a nitrogen
atmosphere overnight. It was cooled to room temperature and dried
under reduced pressure to give a brown solid. The solid was
suspended in dichloromethane (50 mL) and filtered through a short
pad of Celite, washing the solid with dichloromethane (2 × 25 mL).
2H), 7.70 (s, 4H), 5.79 (s, 2H), 2.91 (t, J = 7.8 Hz, 4H), 1.65−1.72,
13
(m, 4H), 1.23−1.45 (m, 12H), 0.84 (t, J = 6.7 Hz, 6H) ppm.
NMR (100 MHz, 1:1 CDCl :CD OD): 156.6, 147.2, 141.6, 140.1,
139.9, 135.9, 121.8, 111.4, 54.4, 35.6, 32.1, 29.9, 29.8, 23.0, 14.2 ppm.
C
3
3
+
HRESI-MS (pos.): 555.3234, calcd. for [C36H N ·H] = 555.3236.
38 6
mp > 260 °C.
The resulting clear yellow filtrate was washed with K CO
(10%, 2
Triptycene Bis(dimethylpyrazine) 15. Methoxyphenyl-substi-
tuted tetraamine 8 (0.029 g, 0.050 mmol) and butadione (0.018 mL,
0.017 g, 0.20 mmol) were placed in a round-bottom flask. A 1:1 v/v
2
3(aq)
×
50 mL), dried (MgSO ), and taken to dryness under reduced
4
pressure. Purification by column chromatography (gradient: 7−10%
methanol in dichloromethane) gave 11 as a yellow-orange powder.
mixture of CHCl and CH OH (10 mL) was added, and the resulting
3 3
1
Yield: 0.164 g (0.307 mmol, 61%). H NMR (300 MHz, CDCl ): 7.75
clear orange solution was heated to reflux under a nitrogen atmosphere
overnight, during which time the solution became yellow. The mixture
was cooled to room temperature, taken to dryness under reduced
pressure, and dried thoroughly to give 15 as a pale yellow powder.
3
(
s, 2H), 6.80 (s, 4H), 5.20 (s, 2H), 3.17 (br. s, 8H), 2.91 (t, J = 6.8 Hz,
4
6
1
H), 1.66−1.76 (m, 4H), 1.23−1.46 (m, 12H), 0.88 (t, J = 6.8 Hz,
H) ppm. 13C NMR (75 MHz, CDCl ): 155.4, 146.7, 139.9, 137.1,
3
31.8, 121.1, 113.2, 52.5, 35.4, 31.9, 29.5, 29.3, 22.7, 14.2 ppm. HREI-
Yield: 0.029 g (0.043 mmol, 85%).
+
1
MS: 534.3466, calcd. for [C H N ] = 534.3471. mp 183−185 °C. R
H NMR (400 MHz, CDCl ): 8.18 (s, 2H), 8.07 (s, 4H), 7.41 (d, J
3
34
42
6
f
(9:1 CH Cl :CH OH): 0.33.
= 8.7 Hz, 4H), 6.83 (d, J = 8.7 Hz, 4H), 6.00 (s, 2H), 3.81 (s, 6H),
2.68 (s, 12H) ppm. 13C NMR (100 MHz, CDCl
): 160.2, 153.3, 152.9,
143.9, 143.3, 140.2, 140.1, 131.7, 131.3, 123.7, 123.1, 113.9, 55.4, 53.2,
2
2
3
Methoxyphenyl-Substituted Bis(imidazole) 12. Methoxyphen-
yl-substituted tetraamine 8 (0.058 g, 0.10 mmol) and NH Cl (0.11 g,
3
4
+
2.0 mmol) were placed in a flask. Ethanol (10 mL) was added, and the
23.0 ppm. HRESI-MS (pos.): 679.2841, calcd. for [C44
H N O ·H] =
34 6 2
yellow suspension was heated to reflux under a nitrogen atmosphere.
Trimethyl orthoformate (0.055 mL, 0.053 g, 0.50 mmol) was then
added, and the reaction mixture was heated to reflux under a nitrogen
atmosphere for 48 h. Drying under reduced pressure gave a brown
powder, which was suspended in saturated NaHCO3(aq), sonicated
briefly, and then filtered. The pale brown powder was washed with
saturated NaHCO3(aq) (2 × 5 mL) and water (4 × 5 mL); then it was
dissolved using 2:1 CH Cl :CH OH to give a yellow solution. Upon
679.2821. mp > 260 °C. R (19:1 CH Cl :CH OH): 0.49.
f
2
2
3
Triptycene Bis(triptycene) 16. Methoxyphenyl-substituted tetra-
amine 8 (0.029 g, 0.050 mmol) and triptycene quinone (0.028 g, 0.10
mmol) were placed in a round-bottom flask. A 1:1 v/v mixture of
CHCl and CH OH (10 mL) was added, and the resulting clear
3 3
orange solution was heated to reflux under a nitrogen atmosphere
overnight. The mixture was cooled to room temperature, taken to
dryness under reduced pressure, and purified by preparative TLC
2
2
3
drying under reduced pressure, compound 12 was obtained as a pale
(19:1 CH Cl :CH OH) to give 16 as a pale yellow powder. Yield:
2 2 3
brown powder. Yield: 0.048 g (0.080 mmol, 80%).
0.045 g (0.042 mmol, 84%).
1
1
H NMR (400 MHz, 1:1 CDCl :CD OD): 8.04 (s, 2H), 7.99 (s,
H NMR (300 MHz, CDCl ): 8.26 (s, 4H), 8.23 (s, 2H), 8.04 (s,
3
3
3
2
3
1
1
H), 7.42 (d, J = 7.4 Hz, 4H), 6.83 (d, J = 7.4 Hz, 4H), 5.83 (s, 2H),
4H), 7.44−7.49 (m, 8H), 7.39 (d, J = 8.7 Hz, 4H), 7.04−7.10 (m, 8H)
6.82 (d, J = 8.7 Hz, 4H), 6.07 (s, 2H), 5.63 (s, 4H), 3.80 (s, 6H) ppm.
13
.78 (s, 6H) ppm. C NMR (100 MHz, 1:1 CDCl :CD OD): 160.9,
3
3
13
53.2, 148.0, 141.6, 140.4, 139.8, 135.91, 135.85, 131.7, 122.3, 114.2,
C NMR (100 MHz, CDCl ): 160.3, 153.1, 146.9, 143.5, 143.30,
3
11.5, 55.6, 54.4 ppm. HRESI-MS (pos.): 599.2190, calcd. for
143.28, 142.7, 142.6, 142.2, 140.5, 131.6, 131.3, 126.4, 124.3, 124.2,
123.7, 122.2, 113.9, 55.4, 53.6, 53.1 ppm. HRESI-MS (pos.):
+
[
C H N O ·H] = 599.2195. mp > 260 °C.
38
26
6
2
+
Hexyloxyphenyl-Substituted Bis(imidazole) 13. Hexyloxy-
1075.3730, calcd. for [C H N O ·H] = 1075.3761. mp > 260 °C.
76
46
6
2
phenyl-substituted tetraamine 10 (0.072 g, 0.10 mmol) and NH Cl
R (19:1 CH Cl :CH OH): 0.57.
4
f
2
2
3
(
0.11 g, 2.0 mmol) were placed in a flask. Ethanol (10 mL) and
Triptycene Bis(di-tert-butylpyrene) 17. Methoxyphenyl-substi-
t
trimethyl orthoformate (0.055 mL, 0.053 g, 0.50 mmol) were added,
and the reaction mixture was heated to reflux under a nitrogen
atmosphere for 48 h. Drying under reduced pressure gave a yellow
powder. This was suspended in saturated NaHCO3(aq), sonicated
briefly, and then filtered to give a yellow powder, which was washed
with saturated NaHCO3(aq) (2 × 5 mL), and water (4 × 5 mL). The
solid was dissolved using 2:1 CH Cl :CH OH to give a yellow
tuted tetraamine 8 (0.029 g, 0.050 mmol) and di- Bu-pyrene dione
(0.034 g, 0.10 mmol) were placed in a round-bottom flask. A 1:1 v/v
mixture of CHCl and CH OH (10 mL) was added, and the resulting
3
3
clear orange solution was heated to reflux under a nitrogen atmosphere
overnight. During this time, a pale yellow powder precipitated from
the reaction mixture. The mixture was cooled to room temperature,
taken to dryness under reduced pressure, and purified by preparative
2
2
3
F
J. Org. Chem. XXXX, XXX, XXX−XXX