Rahimizadeh et al.
967
Yield: 0.39 g (38%); mp > 300 °C. IR (KBr): 2917, 2852,
13b,13c-Di(4-hydroxyphenyl)-2,3,9,10-tetramethyl-
5,7,12,13b,13c,14-hexahydro-5a,6a,12a,13a-tetra-aza-
benzo[5,6]azuleno[2,1,8-ija]benzo[f]azulene-6,13-dione (4b)
Yield: 0.98 g (67%); mp > 300 °C. IR (KBr): 3374 (br),
1691, 1615, 1515, 1464, 1279 cm–1. 1H NMR (DMSO-d6) δ:
2.09 (s, 12 H, 4 × CH3), 3.99 (d, J = 16 Hz, 4 H, 4 × CHH),
4.52 (d, J = 16 Hz, 4 H, 4 × CHH), 6.56 (d, J = 8 Hz, 4 H,
Ar–H), 6.81 (d, J = 8 Hz, 4 H, Ar–H), 6.94 (s, 4 H, Ar–H),
9.47 (s, 2 H, 2 × OH). EI-MS m/z (%): 586 (M+). Anal.
calcd. for C36H34N4O4: C, 73.70; H, 5.84; N, 9.55. Found:
C, 73.95; H, 6.02; N, 9.73.
1
1709, 1610, 1457, 1254 cm–1. H NMR (CDCl3) δ: 3.68 (s,
8 H, 2 × OCH2CH2O), 3.80 (t, J = 5 Hz, 4 H, 2 × OCH2),
4.02 (t, J = 5 Hz, 4 H, 2 × ArOCH2), 4.18 (d, J = 16 Hz, 4
H, 4 × CHH), 4.77 (d, J = 16 Hz, 4 H, 4 × CHH), 6.66 (d,
J = 8 Hz, 4 H, Ar–H), 6.93–7.30 (m, 12 H, Ar–H). EI-MS
m/z (%): 688 (M+). Anal. calcd. for C40H40N4O7: C, 69.75;
H, 5.85; N, 8.13. Found: C, 69.98; H, 5.91; N, 8.18.
Crown clip 5d
The title compound was obtained according to the general
procedure, starting with 4b and 6a.
13b,13c-Di(4-hydroxyphenyl)-1,2,3,4,8,9,10,11-octamethyl-
5,7,12,13b,13c,14-hexahydro-5a,6a, 12a,13a-tetraaza-
benzo[5,6]azuleno[2,1,8-ija] benzo[f]azulene-6,13-dione (4c)
Yield: 1.04 g (65%); mp > 300 °C. IR (KBr): 3381 (br),
1685, 1614, 1515, 1470, 1278 cm–1. 1H NMR (DMSO-d6) δ:
2.07 (s, 12 H, 4 × CH3), 2.34 (s, 12 H, 4 × CH3), 3.73 (d,
J = 16 Hz, 4 H, 4 × CHH), 4.94 (d, J = 16 Hz, 4 H, 4 ×
CHH), 6.55 (d, J = 8 Hz, 4 H, Ar–H), 6.90 (d, J = 8 Hz, 4
H, Ar–H), 9.42 (s, 2 H, 2 × OH). EI-MS m/z (%): 642 (M+).
Anal. calcd. for C40H42N4O4: C, 74.74; H, 6.59; N, 8.72.
Found: C, 74.48; H, 6.82; N, 8.55.
Yield: 0.44 g (45%); mp > 300 °C. IR (KBr): 2922, 1706,
1
1608, 1508, 1455, 1236 cm–1. H NMR (CDCl3) δ: 2.10 (s,
12 H, 4 × CH3), 3.63 (t, J = 4 Hz, 4 H, CH2OCH2), 4.08–
4.25 (m, 8 H, 4 × CHH, 2 × ArOCH2), 4.71 (d, J = 16 Hz, 4
H, 4 × CHH), 6.60 (d, J = 9 Hz, 4 H, Ar–H), 6.84 (d, J =
9 Hz, 4 H, Ar–H), 6.99 (s, 4 H, Ar–H). EI-MS m/z (%): 656
(M+). Anal. calcd. for C40H40N4O5: C, 73.15; H, 6.14; N,
8.53. Found: C, 73.40; H, 6.22; N, 8.41.
Crown clip 5e
The title compound was obtained according to the general
procedure, starting with 4b and 6b.
Synthesis of crown clips 5a–5i
Yield: 0.44 g (42%); mp > 300 °C. IR (KBr): 2920, 1708,
1
1610, 1509, 1457, 1253 cm–1. H NMR (CDCl3) δ: 2.13 (s,
General procedure
12 H, 4 × CH3), 3.65–3.84 (m, 8 H, OCH2CH2O, 2 ×
OCH2), 4.90–4.22 (m, 8 H, 4 × CHH, 2 × ArOCH2), 4.72 (d,
J = 16 Hz, 4 H, 4 × CHH), 6.63 (d, J = 8 Hz, 4 H, Ar–H),
6.92 (d, J = 8 Hz, 4 H, Ar–H), 7.02 (s, 4 H, Ar–H). EI-MS
m/z (%): 700 (M+). Anal. calcd. for C42H44N4O6: C, 71.98;
H, 6.33; N, 7.99. Found: C, 71.82; H, 6.37; N, 8.06.
Ditosylate 6 (1.5 mmol) was added in small portions dur-
ing a period of 12 h to the refluxing mixture of 4 (1.5 mmol)
and K2CO3 (0.83 g, 6 mmol) in dry MeCN (60 mL). The re-
flux was continued for 3 days. Then, the solvent was evapo-
rated in vacuo, and the light-brown solid was partitioned
between aq. NaOH (5%, 75 mL) and CH2Cl2 (75 mL). The
organic layer was washed with water (75 mL), dried
(Na2SO4), and evaporated to dryness. After column chroma-
tography (eluent: CH2Cl2 – MeOH, 100:3, v/v), compound 5
was obtained as white powder.
Crown clip 5f
The title compound was obtained according to the general
procedure, starting with 4b and 6c.
Yield: 0.43 g (39%); mp > 300 °C. IR (KBr): 2917, 1714,
1
1609, 1509, 1452, 1251 cm–1. H NMR (CDCl3) δ: 2.12 (s,
Crown clip 5a
12H, 4 × CH3), 3.68–3.82 (m, 12 H, OCH2CH2OCH2CH2O,
2 × OCH2), 3.98–4.20 (m, 8 H, 4 × CHH, 2 × ArOCH2),
4.72 (d, J = 16 Hz, 4 H, 4 × CHH), 6.65 (d, J = 8 Hz, 4 H,
Ar–H), 6.94 (d, J = 8 Hz, 4 H, Ar–H), 7.01 (s, 4 H, Ar–H).
EI-MS m/z (%): 744 (M+). Anal. calcd. for C44H48N4O7: C,
70.95; H, 6.49; N, 7.52. Found: C, 71.12; H, 6.52; N, 7.36.
The title compound was obtained according to the general
procedure, starting with 4a and 6a.
Yield: 0.39 g (44%); mp > 300 °C. IR (KBr): 2917, 2849,
1
1703, 1509, 1455, 1233 cm–1. H NMR (CDCl3) δ: 3.68 (t,
J = 6 Hz, 4 H, CH2OCH2), 4.19–4.34 (m, 8 H, 4 × CHH, 2 ×
ArOCH2), 4.81 (d, J = 16 Hz, 4 H, 4 × CHH), 6.66 (d, J =
8 Hz, 4 H, Ar–H), 6.95–7.30 (m, 12 H, Ar–H). EI-MS m/z
(%): 600 (M+). Anal. calcd. for C36H32N4O5: C, 71.99; H,
5.37; N, 9.33. Found: C, 72.10; H, 5.42; N, 9.38.
Crown clip 5g
The title compound was obtained according to the general
procedure, starting with 4c and 6a.
Yield: 0.46 g (43%); mp > 300 °C. IR (KBr): 2925, 1705,
Crown clip 5b
1
1508, 1458, 1427, 1227 cm–1. H NMR (CDCl3) δ: 2.16 (s,
The title compound was obtained according to the general
procedure, starting with 4a and 6b.
12 H, 4 × CH3), 2.46 (s, 12 H, 4 × CH3), 3.67 (t, J = 4 Hz, 4
H, CH2OCH2), 3.97 (d, J = 16 Hz, 4 H, 4 × CHH), 4.28 (t,
J = 4 Hz, 4 H, 2 × ArOCH2), 5.17 (d, J = 16 Hz, 4 H, 4 ×
CHH), 6.61 (d, J = 9 Hz, 4 H, Ar–H), 6.93 (d, J = 8 Hz, 4
H, Ar–H). EI-MS m/z (%): 712 (M+). Anal. calcd. for
C44H48N4O5: C, 74.13; H, 6.79; N, 7.86. Found: C, 74.36; H,
6.87; N, 7.76.
Yield: 0.40 g (42%); mp > 300 °C. IR (KBr): 2925, 2854,
1706, 1512, 1454, 1256 cm–1. H NMR (CDCl3) δ: 3.65–
1
3.85 (m, 8 H, OCH2CH2O, 2 × OCH2), 4.05–4.30 (m, 8 H,
4 × CHH, 2 × ArOCH2), 4.78 6.91–7.30 (m, 12 H, Ar–H).
EI-MS m/z (%): 644 (M+). Anal. calcd. for C38H36N4O6: C,
70.79; H, 5.63; N, 8.69. Found: C, 70.51; H, 5.53; N, 8.83.
Crown clip 5h
Crown clip 5c
The title compound was obtained according to the general
procedure, starting with 4a and 6c.
The title compound was obtained according to the general
procedure, starting with 4c and 6b.
© 2007 NRC Canada