838
F. Zeng et al. / Tetrahedron 58 (2002) 825±843
mmol) of 18-crown-6, and 0.72 g 01.95 mmol) of tetrabutyl-
ammonium iodide in 250 mL of acetone over 24 h gave
1.2 g 083%) of 13e as a white foam: glass transition 75±
Thus, the reaction of 0.113 g 00.15 mmol) of 8, 0.40 g
00.15 mmol) of 14, 0.12 g 00.87 mmol) of potassium carbo-
nate, 27 mg 00.12 mmol) of 18-crown-6, and 0.14 g 00.38
mmol) of tetrabutylammonium iodide in 50 mL of acetone
gave 0.39 g 078%) of 13f as a white foam after puri®cation
by chromatography 010±30% ethyl acetate/petroleum
1
808C; H NMR d 8.76 0s, 2H), 8.22 0s, 6H), 7.27 0dd,
J7.8 Hz, 0.9, 2H), 7.22 0d, J8.6 Hz, 2H), 7.15 0d, J
8.6 Hz, 2H), 7.05 0d, J7.8 Hz, 2H), 6.66 0d, J2 Hz,
2H), 6.46 0t, J2 Hz, 1H), 5.11 0s, 2H), 4.00 0t, J6.4 Hz,
4H), 3.50 0br s, 12H), 2.71 0m, 4H), 2.58 0m, 4H), 1.82 0m,
4H,), 1.49±1.28 0m, 32H), 0.88 0t, J6.3 Hz, 6H); 13C NMR
d 165.7, 160.6, 158.2, 148.9, 146.6, 142.0, 139.1, 137.6,
137.2, 135.2, 131.9, 130.3, 130.2, 130.0, 128.5, 128.1,
127.4, 126.7, 124.9, 114.7, 105.8, 100.8, 70.2, 68.1, 51.8,
31.9, 29.7, 29.66, 29.64, 29.45, 29.38, 29.32, 27.22, 26.1,
25.7, 22.7, 14.2. Anal. calcd for C78H91NO11: C, 76.88; H,
7.53; N, 1.15. Found: C, 76.89; H, 7.74; N, 1.12.
1
ether): H NMR d 8.79 0s, 2H), 8.42 0s, 2H), 8.39 0s, 4H),
7.41 0s, 8H), 7.29 0s, 16H), 7.17 0d, 4H), 7.08 0d, J8.4 Hz,
2H), 6.75±6.63 0m, 21H), 5.02 0s, 28H), 4.55 0s, 2H), 4.22 0t,
2H), 3.94 0t, 2H), 3.80 0m, 4H), 3.65 0br m, 18H), 2.80 0m,
4H), 2.65 0m, 4H), 1.35 0s, 144H); 13C NMR d 166.1, 160.4,
160.2, 160.1, 158.4, 151.5, 149.3, 147.0, 142.3, 141.2,
139.7, 139.5, 137.9, 137.5, 136.1, 135.7, 132.2, 130.7,
130.6, 130.4, 129.1, 128.4, 127.7, 127.0, 125.2, 122.4,
114.8, 106.8, 106.6, 101.9, 101.4, 71.4, 71.3, 71.0, 70.6,
70.4, 70.1, 69.7, 67.7, 52.0, 35.1, 31.8, 27.5, 25.9. FAB-
MS calcd for C222H267NO26: 3365.6. Found: 3366.1. Anal.
calcd for C222H267NO26´0.3CH2Cl2: C, 78.74; H, 7.95; N,
0.41. Found: C, 78.64; H, 7.92; N, 0.29.
4.1.24. 3,5-Bis23,5-bis23,5-bis23,5-di2tert-butyl)phenyl-
methoxy)phenylmethoxy)phenylmethoxy)phenylmeth-
oxyethoxyethoxyethanol. To a suspension of 0.19 g
07.8 mmol) of sodium hydride in 70 mL of tetrahydrofuran
was added 2.36 g 015.7 mmol) of triethylene glycol slowly.
The mixture was stirred for 30 min and 2 g 00.78 mmol) of
G3Br 7 was added. The mixture was re¯uxed for 3 h,
quenched with 30 mL of water, and extracted three times
with 200 mL of chloroform. The combined organic layers
were washed with 30 mL of brine, dried over anhydrous
sodium sulfate, and concentrated under reduced pressure.
The residue was puri®ed by chromatography to give
4.1.27. 3,5-Bis23,5-bis23,5-bis23,5-di2tert-butyl)phenyl-
methoxy)phenylmethoxy)phenylmethoxy)benzoic acid
215). The procedure used to prepare 1a was followed.
Thus, the hydrolysis of 0.20 g 00.079 mmol) of ester 16
in 17 mL of THF with 0.2 g 03.6 mmol) of potassium
hydroxide in 2 mL of water and 7 mL of methanol gave
0.18 g 090%) of 15 as a white foam after puri®cation by
chromatography 00.8±1% methanol/methylene chloride):
1H NMR 7.40 0t, 8H), 7.34 0d, 2H), 7.27 0d, 16H), 6.88 0t,
1H), 6.73 0d, 8H), 6.71 0d, 4H), 6.65 0t, J2 Hz, 4H), 6.62 0t,
J2 Hz, 2H), 5.00 0s, 28H), 1.33 0s, 144H); MALDI-MS
calcd for C169H218O16, 2505.6, found 2528.9 0M1Na1).
Anal. calcd for C169H218O16: C, 81.01; H, 8.77. Found: C,
81.01; H, 8.82.
1
1.24 g 060%) of G30OCH2CH2)3OH as a white foam: H
NMR d 7.43 0t, J1.6 Hz, 8H), 7.31 0d, J1.6 Hz, 16H),
6.77 0d, J8 Hz, 8H), 6.75 0d, J2 Hz, 4H), 6.68 0t, J
2 Hz, 4H), 6.65 0d, J2 Hz, 2H), 6.64 0t, 2H), 6.62 0t,
1H), 5.03±5.01 02s, 28H), 4.54 0s, 1H), 3.72±3.58 0m,
12H), 1.36 0s, 144H); 13C NMR d 160.7, 160.4, 160.2,
151.2, 141.0, 139.5, 139.2, 135.9, 122.6, 122.5, 106.8,
106.7, 101.8, 101.4, 73.3, 72.7, 71.3, 70.9, 70.88, 70.6,
70.4, 70.3, 69.6, 62.0, 35.1, 31.7. Anal. calcd for
C175H232O18: C, 80.11; H, 8.91. Found: C, 80.37; H, 8.90.
4.1.28. Methyl 3,5-bis23,5-bis23,5-bis23,5-di2tert-butyl)-
phenylmethoxy)phenylmethoxy)phenylmethoxy)benzo-
ate 216). The procedure used to prepare 13a was followed.
Thus, the reaction of 0.53 g 00.43 mmol) of G2-Br 5, 34 mg
00.20 mmol) of methyl 3,5-dihydroxybenzoate, 0.138 g
01 mmol) of potassium carbonate, and 13 mg 00.05 mmol)
of 18-crown-6 in 25 mL of acetone gave 0.42 g 082%) of 16
4.1.25. 10-23,5-Bis23,5-bis23,5-bis23,5-di2tert-butyl)phenyl-
methoxy)phenylmethoxy)phenylmethoxy)phenyl)-3,6,9-
trioxydecyl bromide 214). The procedure used to prepare 5
was followed. Thus, the reaction of 0.55 g 00.21 mmol) of
G30OCH2CH2)3OH, 207 mg 00.63 mmol) of carbon tetra-
bromide, 165 mg 00.63 mmol) of triphenylphosphine
afforded 0.52 092%) of 14 as a white foam after puri®cation
by chromatography 05±15% ethyl acetate/petroleum ether):
1H NMR d 7.41 0t, J1.7 Hz, 8H), 7.29 0d, J1.7 Hz, 16H),
6.75 0d, J2.1 Hz, 8H), 6.73 0d, J2.1 Hz, 4H), 6.66 0t,
J2.1 Hz, 4H), 6.63 0m, 4H), 6.58 0t, 1H), 5.01±4.97 02s,
28H), 4.52 0s, 2H), 3.77 0t, J6.3 Hz, 2H), 3.68±3.61 0m,
8H), 3.42 0t, J6.3 Hz, 2H), 1.34 0s, 144H); 13C NMR d
160.8, 160.5, 160.4, 151.3, 141.2, 139.7, 139.5, 136.1,
122.7, 122.6, 106.9, 106.8, 101.9, 101.5, 73.4, 71.5, 71.4,
71.1, 71.0, 70.9, 70.5, 70.3, 69.8, 35.2, 31.9, 30.7. Anal.
calcd for C175H231BrO17: C, 78.24; H, 8.67; Br, 2.97.
Found: C, 78.25; H, 8.89; Br, 3.30.
1
as a white foam: H NMR 7.43 0t, J2 Hz, 8H), 7.33 0d,
J2 Hz, 2H), 7.29 0d, J2 Hz, 16H), 6.86 0t, J2 Hz, 1H),
6.76 0d, J2 Hz, 8H), 6.73 0d, 4H), 6.67 0t, J2 Hz, 4H),
6.63 0t, J2 Hz, 2H), 5.02 0s, 28H), 3.91 0s, 3H), 1.36 0s,
144H); 13C NMR d 166.9, 160.7, 160.4, 160.0, 151.3, 139.2,
139.1, 135.9, 132.3, 122.6, 122.5, 108.7, 107.3, 106.7,
102.0, 101.8, 71.3, 70.5, 70.4, 52.5, 35.1, 31.8. Anal.
calcd for C170H220O16: C, 81.04; H, 8.80. Found: C, 81.22;
H, 8.81.
4.1.29. Dimethyl 5-23,5-bis23,5-di2tert-butyl)phenyl-
methoxy)phenylmethoxy)isophthalate 218a). The pro-
cedure used to prepare 13a was followed. Thus, the
reaction of 0.159 g 00.26 mmol) of G1-Br 4, 50 mg 00.24
mmol) of dimethyl 5-hydroxyisophthalate, 65.6 mg 00.48
mmol) of potassium carbonate, 15 mg 00.06 mmol) of
18-crown-6, and 0.72 g 01.95 mmol) of tetrabutyl-
ammonium iodide in 30 mL of acetone gave 0.17 g 098%)
4.1.26. 2,12-Bis23,5-bis2methoxycarbonyl)phenyl)-7-24-
23,5-bis23,5-bis23,5-bis23,5-di2tert-butyl)phenylmethoxy)-
phenylmethoxy)phenylmethoxy)phenylmethoxy)ethoxy-
ethoxyethoxyphenyl)-5,6,8,9-tetrahydrodibenz[c,h]acri-
dine 213f). The procedure used to prepare 13a was followed.
1
of 18a as a white foam: H NMR d 8.31 0t, 1H), 7.85 0d,
J1.5 Hz, 2H), 7.42 0t, J2 Hz, 2H), 7.29 0d, J2 Hz, 4H),
6.74 0d, J2 Hz, 2H), 6.71 0t, 1H), 5.11 0s, 2H), 5.02 0s, 4H),