Zeng et al.
17,23,29,35-Hexa-tert-butyl-37-[4′-(pyrid-2′′-yl)phenylmethoxy]-
39,41-dihydroxy-38,40,42-trimethoxycalix[6]arene (5). To a solution
of 5,11,17,23,29,35-hexa-tert-butyl-37,39,41-trihydroxy-38,40,42-
trimethoxycalix[6]arene (649 mg, 0.64 mmol) in THF (70 mL) was
added NaH (60% dispersion in mineral oil, 171 mg, 4.30 mmol) in
one portion. The resulting suspension was heated to 66 °C for 30
min, and then a solution of compound 3 (500 mg, 2.02 mmol) in
THF (50 mL) was added dropwise. The reaction mixture was stirred
at 66 °C overnight. The solvent was removed under reduced
pressure. The residue was dissolved in dichloromethane (50 mL)
and water (50 mL). The solution was stirred at room temperature
for 30 min. The organic layer was separated, and the aqueous layer
was extracted with dichloromethane (3 × 30 mL). The combined
organic phases were dried (anhydrous MgSO4); the solvent was
removed under reduced pressure; and the yellow residue was
purified by column chromatography (silica gel, DCM/acetone, from
100:2 to 100:8 v/v). Compound 4 (542 mg, 56% yield) was obtained
as a white powder, followed by compound 5 (50 mg, 7% yield) as
a white powder.
63% yield). A sample was crystallized from dichloromethane and
ethanol: mp 191-192 °C; 1H NMR (400 MHz, CDCl3) C3V
conformer, 8.73 (dd, 3H, J ) 2.0 Hz, 0.8 Hz), 8.01 (dd, 3H, J )
8.0 Hz, 2.0 Hz), 7.99-7.97 (m, 6H), 7.77 (dd, 3H, J ) 8.0 Hz, 0.8
Hz), 7.49-7.40 (m, 9H), 7.27 (s, 6H), 6.71 (s, 6H), 5.03 (s, 6H),
4.60 (d, 6H, J ) 15.2 Hz), 3.40 (d, 6H, J ) 15.2 Hz), 2.28 (s, 9H),
1.37 (s, 27H), 0.83 (s, 27H); Cs conformer, 8.69 (d, 1H, J ) 1.6
Hz), 8.67 (d, 2H, J ) 1.6 Hz), 7.85 (dd, 1H, J ) 8.4 Hz, 2.0 Hz),
7.81 (dd, 2H, J ) 8.4 Hz, 2.0 Hz), 7.70 (dd, 1H, J ) 8.4 Hz, 0.4
Hz), 7.64 (dd, 2H, J ) 8.0 Hz, 0.4 Hz), 7.18 (d, 2H, J ) 2.0 Hz),
7.12 (s, 2H), 7.05 (d, 2H, J ) 2.0 Hz), 6.93 (d, 2H, J ) 2.4 Hz),
6.77 (bs, 4H), 4.91 (d, 2H, J ) 11.6 Hz), 4.84 (s, 2H),
4.65 (d, 2H, J ) 11.6 Hz), 4.40 (d, 2H, J ) 15.2 Hz), 4.33 (d, 2H,
J ) 15.2 Hz), 4.12 (d, 2H, J ) 14.8 Hz), 3.67 (d, 2H, J ) 15.2
Hz), 3.47 (d, 2H, J ) 15.2 Hz), 3.33 (2H, partially overlapped
with C3V conformer), 2.39 (s, 6H), 2.23 (s, 3H), 1.27 (s, 9H), 1.16
(s, 18H), 1.00 (s, 9H), 0.99 (s, 18H); 13C NMR (100 MHz, CDCl3)
157.2, 154.4, 152.3, 151.4, 149.1, 146.2, 145.9, 139.2, 136.8, 133.7,
133.0, 131.6, 129.0, 128.7, 127.0, 123.8, 120.5, 120.2, 72.0, 60.2,
34.1, 31.6, 31.3, 30.0, 15.3; MS (MALDI) m/z 1517.9 (calcd
1517.9). Anal. Calcd for C105H117N3O6‚CH2Cl2: C, 79.47; H, 7.49;
N, 2.62. Found: C, 79.65; H, 8.78; N, 2.65.
1
Compound 4: mp 175-176 °C; H NMR (400 MHz, CDCl3)
C3V conformer, 8.69 (m, 3H), 8.01 (d, 6H, J ) 8.0 Hz), 7.75 (m,
6H), 7.64 (d, 6H, J ) 8.0 Hz), 7.27 (s, 6H), 7.21 (dd, 3H, J ) 8.4
Hz, 4.0 Hz), 6.70 (s, 6H), 5.04 (s, 6H), 4.63 (d, 6H, J ) 15.2 Hz),
3.40 (d, 6H, J ) 15.2 Hz), 2.29 (s, 9H), 1.38 (s, 27H), 0.83 (s,
27H); Cs conformer, 7.95 (d, 4H, J ) 8.4 Hz), 7.75 (m, 6H), 7.74
(m, 6H), 7.56 (d, 2H, J ) 8.4 Hz), 7.51 (d, 4H, J ) 8.4 Hz), 7.16
(s, 2H), 7.10 (d, 2H, J ) 2.4 Hz), 7.04 (d, 2H, J ) 2.4 Hz), 6.78
(s, 2H), 6.73 (d, 2H, J ) 2.4 Hz), 4.95 (d, 2H, J ) 12 Hz), 4.90 (s,
2H), 4.59 (d, 2H, J ) 12 Hz, overlapped with C3V conformer), 4.41
(d, 2H, J ) 16.0 Hz), 4.38 (d, 2H, J ) 16.0 Hz), 4.14 (d, 2H, J )
15.6 Hz), 3.78 (d, 2H, J ) 14.4 Hz), 3.50 (d, 2H, J ) 14.8 Hz),
3.32 (d, 2H, J ) 16.0 Hz), 2.30 (s, 6H), 2.07 (s, 3H), 1.32 (s, 9H),
1.16 (s, 18H), 1.12 (s, 27H); 13C NMR (100 MHz, CDCl3) 157.3,
154.6, 151.7, 149.6, 145.9, 138.9, 138.6, 136.7, 133.8, 133.2, 128.4,
128.0, 127.7, 127.0, 126.8, 123.7, 122.0, 120.6, 120.5, 74.3, 60.3,
34.2, 31.6, 31.2, 30.0, 18.4; MS (MALDI) m/z 1518.0 (calcd
1517.9). Anal. Calcd for C105H117N3O6‚H2O: C, 82.15; H, 7.81;
N, 2.74. Found: C, 82.35; H, 7.93; N, 2.70.
5,11,17,23,29,35-Hexa-tert-butyl-37,39,4l-tris{6′-[2-(9,9-di-n-
hexylfluorenyl)]pyrid-3′-ylmethoxy}-38,40,42-trimethoxycalix-
[6]arene (14). To a solution of 5,11,17,23,29,35-hexa-tert-butyl-
37,39,41-trihydroxy-38,40,42-trimethoxycalix[6]arene (1.27 g, 1.25
mmol) in THF (100 mL) was added NaH (60% dispersion in
mineral oil, 342 mg, 8.55 mmol) in one portion. The resulting
suspension was heated to 60 °C for 30 min. Then a solution of 13
(1.95 g, 3.86 mmol) in THF (30 mL) was added dropwise, and the
resulting mixture was stirred at 66 °C for 6 h. The reaction was
quenched by the dropwise addition of ethanol (5 mL). Workup as
described for 4, with column chromatography (silica gel, DCM/
acetone, from 100:1 to 100:3 v/v) gave compound 14 (2.13 g, 75%
1
yield) as a white powder: mp 140-141 °C; H NMR (400 MHz,
CDCl3) C3V conformer, 8.77 (d, 3H, J ) 2.0 Hz), 8.06 (dd, 3H, J
) 8.0 Hz, 2.0 Hz), 8.04-7.99 (m, 9H), 7.87 (d, 3H, J ) 8.0 Hz),
7.77 (d, 3H, J ) 8.0 Hz), 7.74 (dd, 3H, J ) 6.8 Hz, 1.6 Hz), 7.36-
7.30 (m, 6H), 7.29 (s, 6H), 6.71 (s, 6H), 5.07 (s, 6H), 4.60 (d, 6H,
J ) 15.2 Hz), 3.38 (d, 6H, J ) 15.2 Hz), 2.27 (s, 9H), 2.06-1.94
(m, 12H), 1.39 (s, 27H), 1.09-0.94 (m, 36H), 0.81 (s, 27H), 0.69
(t, 18H, J ) 6.8 Hz), 0.67-0.55 (m, 12H); Cs conformer, 7.19 (d,
2H, J ) 2.4 Hz), 7.16 (s, 2H), 7.10 (d, 2H, J ) 2.4 Hz), 6.98 (d,
2H, J ) 2.4 Hz), 6.81 (s, 2H), 6.78 (d, 2H, J ) 2.4 Hz), 4.92 (d,
2H, J ) 12.0 Hz), 4.87 (s, 2H), 4.73 (d, 2H, J ) 12.0 Hz), 4.44 (d,
2H, J ) 15.6 Hz), 4.37 (d, 2H, J ) 15.6 Hz), 4.15 (d, 2H, J )
14.4 Hz), 3.72 (d, 2H, J ) 14.8 Hz), 3.54 (d, 2H, J ) 14.4 Hz),
3.35 (2H, partially overlapped with C3V conformer), 2.42 (s, 6H),
2.20 (s, 3H), 1.30 (s, 9H), 1.19 (s, 18H), 1.05 (s, 9H), 1.00 (s,
18H); 13C NMR (100 MHz, CDCl3) 157.6, 154.6, 154.5, 151.6,
151.4, 149.1, 146.2, 145.8, 142.2, 140.7, 136.8, 133.7, 133.0,
131.4,128.1, 127.3, 126.8, 126.0, 123.8, 123.0, 121.3, 120.5, 120.2,
120.0, 119.9, 72.2, 60.3, 55.3, 40.4, 34.3, 34.1, 31.7, 31.49, 31.46,
30.0, 29.7, 23.8, 22.6, 14.0; MS (MALDI) m/z 2286.7 (calcd
2286.4). Anal. Calcd for C162H201N3O6‚H2O: C, 84.44; H, 8.88;
N, 1.82. Found: C, 84.60; H, 8.72; N, 1.90.
1
Compound 5: mp 172-173 °C; H NMR (400 MHz, CDCl3)
8.71-8.68 (m, 1H), 8.04 (d, 2H, J ) 8.0 Hz), 7.79 (d, 1H, J ) 8.0
Hz), 7.74 (td, 1H, J ) 7.6 Hz, 2.0 Hz), 7.50 (d, 2H, J ) 8.0 Hz),
7.23-7.21 (m, 1H), 7.20 (s, 2H), 7.17 (s, 2H), 7.07 (d, 2H, J )
2.4 Hz), 6.95 (s, 4H), 6.94 (s, 2H), 6.88 (d, 2H, J ) 2.4 Hz), 4.72
(s, 2H), 4.30 (d, 2H, J ) 14.4 Hz), 3.94 (d, 2H, J ) 14.4 Hz), 3.86
(d, 2H, J ) 15.6 Hz), 3.82 (d, 2H, J ) 14.4 Hz), 3.75 (d, 2H, J )
15.2 Hz), 3.72 (d, 2H, J ) 13.6 Hz), 3.67 (s, 6H), 2.68 (s, 3H),
1.27 (s, 9H), 1.18 (s, 18H), 1.12 (s, 9H), 0.97 (s, 18H); 13C NMR
(100 MHz, CDCl3) 157.5, 153.4, 152.8, 152.3, 149.8, 149.5, 146.7,
146.5, 146.2, 142.1, 139.0, 138.5, 136.7, 133.2, 132.7, 132.5, 128.2,
127.1, 127.0, 126.9, 126.6, 126.0, 125.34, 125.29, 125.1, 121.9,
120.6, 74.7, 61.4, 60.5, 34.2, 34.1, 33.8, 31.8, 31.5, 31.4, 31.2, 30.8;
MS (MALDI) m/z 1182.7 (calcd 1182.7). Anal. Calcd for C81H99-
NO6: C, 82.26; H, 8.44; N, 1.18. Found: C, 82.50; H, 8.52; N,
1.15.
5,11,17,23,29,35-Hexa-tert-butyl-37,39,4l-tris(6′-phenylpyrid-
3′-ylmethoxy)-38,40,42-trimethoxycalix[6]arene (9). To a solution
of 5,11,17,23,29,35-hexa-tert-butyl-37,39,41-trihydroxy-38,40,42-
trimethoxycalix[6]arene (1.02 g, 1.0 mmol) in THF (150 mL) was
added NaH (60% dispersion in mineral oil, 342 mg, 8.55 mmol) in
one portion. The resulting suspension was heated to 46 °C for 30
min, and then compound 8 (756 mg, 3.05 mmol) was added in one
portion. The reaction mixture was stirred at 46 °C overnight.
Workup as described for 4 gave 9 as a white powder (0.953 g,
Acknowledgment. We thank CENAMPS for funding this
work.
Supporting Information Available: Synthetic details and
characterization data for compounds 1-3, 6-8, and 11-13; a table
1
of variable-temperature H NMR data and copies of the spectra
for compound 4 at +60, +30, 0, -30, and -60 °C; and an X-ray
crystallographic file for 4. This material is available free of charge
(25) Cyclometalated fluorenylpyridine complexes have been described:
(a) Ostrowski, J. C.; Robinson, M. R.; Heeger, A. J.; Bazan, G. C. Chem.
Commun. 2002, 784-785. (b) Tavasli, M.; Bettington, S.; Bryce, M. R.;
Al Attar, H. A.; Dias, F. B.; King, S.; Monkman, A. P. J. Mater. Chem.
2005, 15, 4963-4970.
JO0614341
9594 J. Org. Chem., Vol. 71, No. 26, 2006