3776 J . Org. Chem., Vol. 64, No. 10, 1999
Notes
135-136 °C; 1H NMR (CDCl3, 400 MHz) δ 7.47 (s, 1H), 6.28 (s,
4 H), 6.18, 5.77 (two s, each 2H), 4.30 (d, J ) 12.8 Hz, 2H), 4.26
(d, J ) 12.3 Hz, 2H), 3.86-3.75 (m, 4 H), 3.68-3.60 (m, 4H),
3.21 (br s, 6H), 2.98 (d, J ) 13.5 Hz, 2H), 2.87 (d, J ) 13.2 Hz,
2H), 1.85-1.74 (m, 8 H), 1.42 (s, 9 H), 1.41-1.17 (m 16 H), 0.92-
0.87 (m, 12 H); 13C NMR (CDCl3, 100 MHz) δ 153.66, 150.61,
149.70, 136.66, 136.51, 134.83, 134.71, 131.53, 123.60, 79.06,
74.97, 74.84, 74.73, 31.08, 29.85, 29.56, 28.45, 28.39, 28.19, 22.74,
22.63, 14.08, 13.96; FD-MS, m/z 864.6 (100, M). Anal. Calcd for
C53H76N4O6: C, 73.58; H, 8.85; N, 6.48. Found: C, 73.37; H, 8.76;
N, 6.31.
Tetr a a m id oca lix[4]a r en e 3a . To a solution of the mono-
amine 2 (0.3 g, 0.28 mmol) in Ac2O (20 mL) was added Et3N
(0.5 mL) in one portion, and the reaction mixture was stirred at
room temperature overnight. The solvent was removed in vacuo,
and the residue was dissolved in EtOH (20 mL) and reprecipi-
tated with water. The precipitate was filtered off and dried in
vacuo. 3a : yield 0.23 g (74%); white solid; mp 144-145 °C; 1H
NMR (400 MHz, CDCl3) δ 7.06 (s, 1H), 6.95, 6.91, 6.36, 6.33,
6.16 (five s, each 2H), 6.10 (s, 1H), 4.34 (d, J ) 13.2 Hz, 4H),
3.95-3.85 (m, 4H), 3.70-3.59 (m, 4H), 3.05 (d, J ) 13.1 Hz, 4
H), 2.00 (s, 3H), 1.82-1.77 (m, 8H), 1.50 (s, 18H), 1.47-1.42 (m,
4H), 1.40 (s, 9H), 1.37-1.29 (m, 8 H), 1.25-1.14 (m, 4H), 0.95-
0.84 (m, 12H); FD-MS, m/z 1106.9 (100, M). Anal. Calcd for
C65H94N4O11‚H2O: C, 69.35; H, 8.60; N, 4.98. Found: C, 69.19;
H, 8.48; N, 4.76.
Tetr a a m id oca lix[4]a r en e 3b. To a stirred solution of the
amine 2 (0.2 g, 0.18 mmol) in dry THF (10 mL) was added phenyl
isothiocyanate (0.03 mL, 0.37 mmol) under nitrogen in one
portion, and the reaction mixture was stirred at room temper-
ature overnight. The solvent was removed in vacuo, and hexane
was added. The precipitate was filtered off and dried in vacuo.
3b: yield 0.2 g (92%); white solid; mp 135-136 °C; 1H NMR
(200 MHz, CDCl3) δ 7.36-7.18 (m, 8H), 7.09 (s, 1H), 6.95, 6.37,
6.28, 6.22 (four s, each 2H), 5.75 (s, 1H), 4.39 (d, J ) 13.2 Hz,
2H), 4.32 (d, J ) 12.6 Hz, 2H), 3.96-3.91 (m, 4 H), 3.74-3.67
(m, 2H), 3.63-3.57 (m, 2H), 3.11-3.03 (m, 4H), 1.87-1.76 (m,
8H), 1.60-1.23 (m, 43 H), 0.90 (t, J ) 6.4 Hz, 12 H); FD-MS,
m/z 1107.4 (9, M - OC4H9), 1065.3 (100, M - C7H6NS). Anal.
Calcd for C70H97N5O10S‚H2O: C, 68.99; H, 8.19; N, 5.74. Found:
C, 68.98; H, 8.09; N, 5.60.
Tr ia m in oca lix[4]a r en e 4. To a stirred solution of 3a (0.2 g,
0.18 mmol) in CH2Cl2 (20 mL) was added TFA (20 mL) in one
portion. The reaction mixture was stirred at room temperature
for 2 h and then diluted with toluene (50 mL). The solvent was
evaporated in vacuo to dryness, and the powder obtained was
dried in vacuo at 100 °C for 3 h. 4: yield 0.2 g (97%); yellow
solid; mp 251-252 °C; 1H NMR (400 MHz, DMSO-d6) δ 9.71 (s,
1 H), 7.19, 6.86, 6.20, 6.16 (four s, each 2H), 4.29 (d, J ) 13.0
Hz, 4H), 3.95-3.80 (m, 4H), 3.77-3.65 (br m, 4H), 3.22 (d, J )
13.1 Hz, 2H), 3.12 (d, J ) 13.0 Hz, 2H), 1.98 (s, 3H), 1.90-1.74
(m, 8H), 1.50-1.19 (m, 16H), 0.95-085 (m, 12H); FD-MS, m/z
806.9 (100, M). Anal. Calcd for C56H73N4O11F9: C, 58.51; H, 6.41;
N, 4.88. Found: C, 58.47; H, 6.21; N, 4.78.
1
F igu r e 1. Section of the H NMR spectra (500 MHz, CDCl3,
rt) of monoamine 2 and diamine 5.
pure product was isolated by flash column chromatography
(EtOAc/hexane 6/4) where it was eluted after a small fraction
of tetra-BOC-calix[4]arene 3c. 2: yield 0.75 g (54%); yellowish
powder: mp 130-131 °C; 1H NMR (CDCl3, 500 MHz) δ 7.38 (s,
1H), 7.08, 6.83, 6.34, 6.10, 5.71 (five s, each 2H), 4.37, 4.33 (two
d, J ) 13.4 Hz, each 2H), 3.95-3.86 (m, 4H), 3.69, 3.65 (two t,
J ) 6.6 Hz, each 2H), 3.08, 3.01 (two d, J ) 13.7 Hz, each 2H),
1.91-1.76 (m, 8 H), 1,54 (s, 18 H), 1.51-1.45 (m, 4H), 1,43 (s,
9H), 1.41-1.31 (m, 8H), 1.28-1.18 (m, 4H), 0.96-089 (m, 12H);
13C NMR (CDCl3, 100 MHz) δ 153.64, 153.50, 153.08, 136.80,
134.28, 134.15, 131.81, 124.01, 119.38, 119.36, 115.23, 80.01,
79.10, 75.06, 74.83, 71.06, 70.73, 29.94, 29.89, 29.58, 29.47, 28.54,
28.49, 28.36, 28.04, 22.71, 22.58, 14.06, 13.93; FD-MS, m/z 1065.4
(20, M), 965.0 (100, M-BOC). Anal. Calcd for C63H92N4O10‚H2O:
C, 69.84; H, 8.74; N, 5.17. Found: C, 69.93, H, 8.57, N, 5.04.
Tetr a -BOC-ca lix[4]a r en e 3c: yield 20 %; white solid: mp
199-200 °C; 1H NMR (CDCl3, 200 MHz) δ 6.59 (s, 8H), 6.15 (s,
4H), 4.34 (d, J ) 13.4 Hz, 4H), 3.68 (t, J ) 6.4 Hz, 8H), 3.06 (d,
J ) 13.2 Hz, 4H), 1.91-1.72 (m, 8H), 1,48 (s, 36H), 1.38-1.25
(m, 16 H), 0.96-0.83 (m, 12H); FD-MS, m/z 1165.4 (100, M).
Anal. Calcd for
C68H100N4O12: C, 70.06, H, 8.65, N, 4.81;
Found: C, 70.03; H, 8.60; N, 4.83.
Tetr a a m id oca lix[4]a r en e 6a . Compound 6a was prepared
in the same way as 3a from diamine 5 (0.3 g, 0.31 mmol), Ac2O
(20 mL), and Et3N (0.5 mL). 6a : yield 0.3 g (94%); white solid;
1,2-Di-BOC-ca lix[4]a r en e 5. Compound 5 was prepared in
the same way as 2 from the tetraamino calixarene 1 (2.0 g, 2.60
mmol) and BOC-anhydride (1.13 g, 5.20 mmol). Isolation and
purification by flash column chromatography (EtOAc/hexane
1/1): yield 1.2 g (48%); yellowish powder; mp 133-134 °C; 1H
NMR (CDCl3, 500 MHz) δ 7.01, 6.62, 6.42 (three s, each 2H),
6.04 (d, J ) 3.6 Hz, 4 H), 4.36 (d, J ) 13.7 Hz, 1H), 4.33 (d, J )
13.4 Hz, 2H), 4.30 (d, J ) 13.1 Hz, 1H), 3.81-3.61 (m, 8 H),
3.08 (d, J ) 13.7 Hz, 1H), 3.01 (d, J ) 13.4 Hz, 2H), 2.91 (d, J
) 13.1 Hz, 1H), 1.89-1.69 (m, 8 H), 1,48 (s, 18H), 1.42-1.30
(m, 16H), 0.95-0.83 (m, 12H); 13C NMR (CDCl3, 100 MHz) δ
154.03, 153.72, 150.15, 139.69, 135.69, 135.63, 135.50, 131.68,
122.09, 115.59, 115.50, 79.42, 74.93, 74.75, 31.08, 29.71, 28.38,
28.32, 28.29, 22.26, 14.02; MALDI-TOF-MS, m/z 965.0 (100, M).
Anal. Calcd for C58H84O8N4‚H2O: C, 70.84; H, 8.82; N, 5.70.
Found: C, 70.77; H, 8.77; N, 5.70.
1
mp 165-166 °C; H NMR (CDCl3, 200 MHz) δ 7.36 (br s, 2H),
6.70-6.69 (br m, 4H), 6.54 (s, 4H), 6.30 (s, 2H), 4.35 (d, J )
13.0 Hz, 4H), 3.82-3.72 (m, 8H), 3.05 (d, J ) 13.1 Hz, 4H), 2.05
(s, 6H), 1.92-1.70 (m, 8H), 1.45 (s, 18H), 1.35-1.32 (m, 16H),
0.90 (t, J ) 6.6 Hz, 12H); FD-MS, m/z 974.8 (36, M - Ac), 874.6
(100, M - Ac - BOC) 1048.9 (24, M). Anal. Calcd for
C62H88N4O10: C, 70.96; H, 8.45; N, 5.34. Found: C, 70.70; H,
8.14; N, 5.23.
Tetr a a m id oca lix[4]a r en e 6b. To a vigorously stirred sus-
pension of diamine 5 (0.3 g, 0.31 mmol) in EtOAc (30 mL) and
Na2CO3 (1 N, 50 mL) was added p-methylbenzoyl chloride (3-5
mL) in two portions. The mixture was intensively stirred at room
temperature for 20-30 min. The organic layer was separated
washed with Na2CO3 (1N, 50 mL) and water (2 × 50 mL).
Solvent was removed in vacuo, and the residue was dissolved
in CH2Cl2 and reprecipitated with hexane. The white precipitate
was filtered off, washed with hexane, and dried in vacuo. 6b:
yield 0.28 g (83%); white solid; mp 161-162 °C; 1H NMR (CDCl3,
200 MHz) δ 7.73 (d, J ) 8.3 Hz, 4H), 7.19 (m, 6H), 6.95, 6.87,
6.62, 6.57 (four d, J ) 2.5 Hz, each 2 H), 6.30 (br s, 2H), 4.41 (d,
Mon o-BOC-ca lix[4]a r en e 9. Compound 9 was prepared in
the same way as 2 from the tetraamino calixarene 1 (1.0 g, 1.30
mmol) and BOC-anhydride (0.282 g, 1.30 mmol). Isolation and
purification by flash column chromatography (EtOAc/hexane 1/1,
followed by EtOAc): yield 0.4 g (36%); yellowish powder; mp