2678 J . Org. Chem., Vol. 64, No. 8, 1999
Shu et al.
38.65 (CH2), 32.73 (CH2), 32.65 (CH2), 25.28 (CH2), 12.42 (CH3);
FAB-MS m/z 701 (M+ + 1). Anal. Calcd for C48H44O5: C, 82.26;
H, 6.33. Anal. Calcd for C48H44O5‚1/2H2O: C, 81.21; H, 6.39.
Found: C, 81.40; H, 6.29.
25-Allyloxy-26-ben zyloxy-27-h yd r oxy-28-p r op oxyca lix-
[4]a r en e (6a ). A sample of 0.50 g (0.71 mmol) of 25-allyloxy-
26-benzyloxy-27-benzoyloxy-28-propoxycalix[4]arene (5a ) was
subjected to hydrolysis and yielded 0.35 g (81%) of color-
1
25-Ben zyloxy-26-b en zoyloxy-27-b u t oxy-28-p r op oxy-
ca lix[4]a r en e (5b). A sample of 0.67 g (1.0 mmol) of 25-
benzyloxy-26-benzoyloxy-27-butoxy-28-hydroxy-calix[4]arene
(4b) was alkylated with 0.48 mL (0.84 g, 4.9 mmol) of n-propyl
iodide and yielded 0.58 g (82%) of colorless crystals: mp 158-
159 °C; 1H NMR (CDCl3) δ 6.40-7.80 (m, 22 H), 4.84, 4.66
(AB, 2 H, J ) 10.9 Hz), 4.12-4.19 (m, 2 H), 3.82 (bd, 3 H, J )
12.3 Hz), 3.25-3.58 (m, 5 H), 3.10 (t, 2 H, J ) 13.5 Hz), 1.74-
1.84 (m, 2 H), 1.51-1.56 (m, 2 H), 1.10-1.45 (m, 2 H), 1.02 (t,
3 H, J ) 7.3 Hz), 0.53 (t, 3 H, J ) 7.6 Hz); 13C NMR (CDCl3)
δ 164.52 (Cq), 156.72 (Cq), 155.85 (Cq), 155.51 (Cq), 148.47 (Cq),
137.39 (Cq), 136.78 (Cq), 136.69 (Cq), 133.94 (Cq), 133.72 (Cq),
133.41(CH), 133.31 (Cq), 133.21 (Cq), 132.03 (CH), 131.86 (CH),
130.69 (CH), 130.08 (CH), 129.94 (CH), 129.04 (CH), 128.92
(CH), 128.82 (CH), 128.75 (CH), 128.36 (CH), 127.97 (CH),
127.75 (CH), 124.28 (CH), 122.65 (CH), 122.04 (CH), 121.66
(CH), 76.73 (CH2), 75.37 (CH2), 74.28 (CH2), 36.96 (CH2), 32.55
(CH2), 30.50 (CH2), 30.35 (CH2), 21.56 (CH2), 19.50 (CH2), 14.04
(CH3), 8.98(CH3); FAB-Ms m/z 717 (M+ + 1). Anal. Calcd for
less crystals: mp 106-107 °C; H NMR (CDCl3) δ 7.45-7.48
(m, 2 H), 7.32-7.38 (m, 3 H), 6.38-7.30 (m, 12 H), 5.09
(s, 1 H), 4.78-4.99 (m, 4 H), 4.54-4.58 (m, 2 H), 4.31-4.44
(m, 4 H), 3.72-3.78 (m, 2 H), 3.07-3.33 (m, 4 H), 1.83-
1.91 (m, 2 H), 1.18 (t, 3 H, J ) 7.5 Hz); 13C NMR (CDCl3) δ
155.85 (Cq), 154.20 (Cq), 154.07 (Cq), 153.27 (Cq), 137.29
(Cq), 137.15 (Cq), 136.23 (CH), 133.43 (Cq), 133.34 (Cq),
132.87 (Cq), 132.49 (Cq), 131.01 (Cq), 130.67 (Cq), 129.01 (CH),
128.58 (CH), 128.41 (CH), 128.31 (CH), 127.92 (CH), 127.85
(CH), 123.26 (CH), 123.21 (CH), 123.09 (CH), 119.20 (CH),
116.12 (CH2), 77.44 (CH2), 75.11 (CH2), 31.35 (CH2), 31.18
(CH2), 30.86 (CH2), 23.31 (CH2), 10.76 (CH3); FAB-MS m/z 597
(M+ + 1). Anal. Calcd for C41H40O4: C, 82.52; H, 6.76. Anal.
Calcd for C41H40O4‚1/4H2O: C, 81.90; H, 6.79. Found: C, 82.08;
H, 6.79.
25-Ben zyloxy-27-bu toxy-26-h yd r oxy-28-p r op oxyca lix-
[4]a r en e (6b). A sample of 0.40 g (0.56 mmol) of 25-benzyloxy-
26-benzoyloxy-27-butoxy-28-propoxycalix[4]arene (5b) was sub-
jected to hydrolysis and yielded 0.29 g (85%) of colorless
crystals: mp 117-118 °C; 1H NMR (CDCl3) δ 7.50-7.52 (m, 2
H), 7.35-7.38 (m, 2 H), 6.36-7.17 (m, 12 H), 4.86, 4.74 (AB, 2
H, J ) 10.9 Hz), 4.71 (s, 1 H), 4.32-4.45 (m, 4 H), 3.72-3.75
(m, 4 H), 3.17-3.30 (m, 4 H), 1.78-1.81 (m, 2 H), 1.52-1.63
(m, 2H), 1.41-1.49 (m, 2 H), 0.98 (t, 3 H, J ) 7.3 Hz), 0.64 (t,
3 H, J ) 7.5 Hz); 13C NMR (CDCl3) δ 156.83 (Cq), 154.18 (Cq),
154.08 (Cq), 153.24 (Cq), 137.08 (Cq), 137.07 (Cq), 133.48 (Cq),
132.88 (Cq), 132.46 (Cq), 131.26 (Cq), 130.99 (Cq), 129.14 (Cq),
129.12 (Cq), 128.60 (CH), 128.43 (CH), 128.37 (CH), 128.00
(CH), 127.95 (CH), 127.89 (CH), 127.83 (CH), 127.80 (CH),
122.94 (CH), 119.31 (CH), 77.76 (CH2), 76.59 (CH2), 75.69
(CH2), 32.35 (CH2), 30.87 (CH2), 30.79 (CH2), 30.68 (CH2), 22.31
(CH2), 19.59 (CH2), 14.04 (CH3), 9.39 (CH3); FAB-MS m/z 613
(M+ + 1). Anal. Calcd for C42H44O4: C, 82.32; H, 7.24. Found:
C, 82.00; H, 7.44.
25-Allyloxy-26-ben zyloxy-28-bu toxy-27-h yd r oxyca lix-
[4]a r en e (6c). A sample of 0.30 g (0.42 mmol) of 25-allyloxy-
26-benzyloxy-27-benzoyloxy-28-butoxycalix[4]arene (5c) was
subjected to hydrolysis and yielded 0.21 g (81%) of colorless
crystals: mp 114-116 °C; 1H NMR (CDCl3) δ 4.46-7.48 (m, 2
H), 7.34-7.39 (m, 3 H), 6.39-7.25 (m, 13 H), 5.05 (s, 1 H),
4.95-4.99 (m 2 H), 4.88, 4.82 (AB, 2 H, J ) 11.3 Hz), 4.54-
4.60 (m, 2 H), 4.32-4.44 (m, 4 H), 3.77-3.79 (m, 2 H), 3.08-
3.33 (m, 4 H), 1.92-2.02 (m, 2 H), 1.52-1.54 (m, 2 H), 0.98 (t,
3 H, J ) 7.4 Hz); 13C NMR (CDCl3) δ 155.89 (Cq), 154.25 (Cq),
154.07 (Cq), 153.29 (Cq), 137.31 (CH), 137.28 (Cq), 137.16 (Cq),
136.29 (Cq), 133.43 (Cq), 133.35 (Cq), 132.89 (Cq), 132.51 (Cq),
131.01 (Cq), 130.65 (Cq), 129.03 (CH), 129.00 (CH), 128.60 (CH),
128.34 (CH), 127.95 (CH), 127.89 (CH), 127.87 (CH), 127.84
(CH), 123.12 (CH), 119.22 (CH), 116.02 (CH2), 77.59 (CH2),
75.84 (CH2), 75.13 (CH2), 32.22 (CH2), 31.34 (CH2), 31.16 (CH2),
30.86 (CH2), 19.50 (CH2), 14.03 (CH3); FAB-MS m/z 611 (M+
+ 1). Anal. Calcd for C42H42O4: C, 82.59; H, 6.93. Found: C,
82.27; H, 6.93.
25-Allyloxy-27-ben zyloxy-26-h yd r oxy-28-p r op oxyca lix-
[4]a r en e (6d ). A sample of 0.61 g (0.87 mmol) of 25-allyloxy-
26-benzoyloxy-27-benzyloxy-28-propoxycalix[4]arene (5d ) was
subjected to hydrolysis and yielded 0.45 g (87%) of colorless
crystals: mp 142-143 °C; 1H NMR (CDCl3) δ 7.52-7.54 (m, 2
H), 7.38-7.40 (m, 3 H), 6.41-7.18 (m, 12 H), 6.08-6.22 (m, 1
H), 5.20-5.46 (m, 2 H), 4.87 (s, 1 H), 4.86, 4.76 (AB, 2 H, J )
14.1 Hz), 4.32-4.45 (m, 6 H), 3.75 (t, 2 H, J ) 8.5 Hz), 3.20-
3.34 (m, 4 H), 1.86-2.14 (m, 2 H), 0.64 (t, 3 H, J ) 7.5 Hz);
13C NMR (CDCl3) δ 156.82 (Cq), 154.03 (Cq), 153.83 (Cq), 153.25
(Cq), 137.27 (Cq), 137.00 (Cq), 136.95 (Cq), 133.97 (CH), 133.53
(Cq), 132.83 (Cq), 132.66 (Cq), 131.10 (Cq), 130.88 (Cq), 129.11
(CH), 128.60 (CH), 128.43 (CH), 128.24 (CH), 128.02 (CH),
127.97 (CH), 127.90 (CH), 127.85 (CH), 123.33 (CH), 122.92
(CH), 119.30 (CH), 117.72 (CH2), 77.44 (CH2), 76.59 (CH2),
76.39 (CH2), 30.98 (CH2), 30.84 (CH2), 22.32 (CH2), 9.42 (CH3);
FAB-MS m/z 597 (M+ + 1). Anal. Calcd for C41H40O4: C, 82.52;
H, 6.76. Found: C, 82.57; H, 6.92.
C
49H48O5: C, 82.09; H, 6.75. Anal. Calcd for C49H48O5‚1/4H2O:
C, 81.58; H, 6.78. Found: C, 81.70; H, 6.67.
25-Allyloxy-26-ben zyloxy-27-ben zoyloxy-28-bu toxycalix-
[4]a r en e (5c). A sample of 0.67 g (1.0 mmol) of 25-benzyloxy-
26-benzoyloxy-27-butoxy-28-hydroxy-calix[4]arene (4b) was
alkylated with 0.43 mL (0.60 g, 5.0 mmol) of allyl bromide and
yielded 0.61 g (86%) of colorless crystals: mp 152-153 °C; 1H
NMR (CDCl3) δ 6.37-7.72 (m, 17 H), 5.42-5.58 (m, 1 H), 4.69-
4.88 (m, 4 H), 4.00-4.17 (m, 4 H), 3.71-3.87 (m, 3 H), 3.56-
3.62 (m, 1H), 3.38-3.49 (m, 2 H), 3.14 (d, 1 H, J ) 13.2 Hz),
2.98 (d, 1 H, J ) 13.2 Hz), 1.79-1.81 (m, 2 H), 1.46-1.56 (m,
2 H), 0.99 (t, 3 H, J ) 7.4 Hz); 13C NMR (CDCl3) δ 164.52 (Cq),
156.11 (Cq), 155.82 (Cq), 155.58 (Cq), 148.42 (Cq), 137.97 (Cq),
137.49 (CH), 136.98 (Cq), 133.94 (Cq), 133.65 (Cq), 133.38 (Cq),
133.24 (CH), 132.17 (Cq), 131.93 (CH), 131.78 (CH), 130.76
(CH), 130.69 (CH), 129.89 (CH), 129.82 (CH), 128.99 (CH),
128.87 (CH), 128.77 (CH), 128.26 (CH), 127.92 (CH), 127.78
(CH), 124.13 (CH), 122.87 (CH), 122.12 (CH), 121.75 (CH),
113.23 (CH2), 76.25 (CH2), 74.35 (CH2), 73.72 (CH2), 37.01
(CH2), 32.51 (CH2), 31.11 (CH2), 31.01 (CH2), 29.70 (CH2), 19.47
(CH2), 14.01(CH3); FAB-MS m/z 715 (M+ + 1). Anal. Calcd for
C
49H46O5: C, 82.32; H, 6.49. Anal. Calcd for C49H46O5‚1/4H2O:
C, 81.81; H, 6.51. Found: C, 81.82; H, 6.54.
25-Allyloxy-26-b en zoyloxy-27-b en zyloxy-28-p r op oxy-
ca lix[4]a r en e (5d ). A sample of 0.66 g (1.0 mmol) of 25-allyl-
oxy-26-benzoyloxy-27-benzyloxy-28-hydroxycalix[4]arene (4c)
was alkylated with 0.48 mL (0.84 g, 4.9 mmol) of n-propyl
iodide and yielded 0.59 g (84%) of colorless crystals: mp 156-
158 °C; 1H NMR (CDCl3) δ 6.40-7.76 (m, 22 H), 6.08-6.20
(m, 1 H), 5.29-5.39 (m, 2 H), 4.84, 4.66 (AB, 2 H, J ) 10.9
Hz), 4.19-4.21 (m, 1 H), 4.13-4.17 (3d, 3 H), 3.81 (bd, 2 H, J
) 14.1 Hz), 3.45 (bd, 2 H, J ) 13.8 Hz), 3.31-3.33 (m, 2 H),
3.04-3.14 (m, 2 H), 1.26-1.30 (m, 2 H), 0.52 (t, 3H, J ) 7.6
Hz); 13C NMR (CDCl3) δ 164.29 (Cq), 156.44 (Cq), 155.24 (Cq),
154.98 (Cq), 148.15 (Cq), 137.13 (Cq), 136.42 (Cq), 134.23 (CH),
133.69 (Cq), 133.57 (CH), 133.18 (Cq), 132.92 (Cq), 131.81 (Cq),
131.56 (CH), 128.79 (CH), 128.71 (CH), 128.52 (CH), 128.44
(CH), 128.09 (CH), 127.71 (CH), 127.52 (CH), 122.39 (CH),
121.76 (CH), 116.99 (CH2), 76.43 (CH2), 75.06 (CH2), 75.01
(CH2), 36.70 (CH2), 30.30 (CH2), 30.27 (CH2), 21.34 (CH2), 8.81
(CH3); FAB-MS m/z 701 (M+ + 1). Anal. Calcd for C48H44O5:
C, 82.26; H, 6.33. Anal. Calcd for C48H44O5‚1/4H2O: C, 81.73;
H, 6.36. Found: C, 81.87; H, 6.36.
Gen er a l P r oced u r e for 25,26,27-Tr ia lk oxy-28-h yd r oxy-
ca lix[4]a r en es 6a -d . A solution of 0.71 mmol of 25,26,27-
trialkoxy-28-benzoyloxycalix[4]arene (5a -d ) in 10 mL of THF
was added to a solution of 1.25 g of KOH in 5 mL of H2O and
10 mL of EtOH, and the mixture was then refluxed for 4 h.
The solvent was removed, and the residue was treated with
CH3OH to induce an off-white solid. Further recrystallization
from CHCl3 and CH3OH afforded the corresponding hydrolysis
products 6a -d .