ArCH2Ar), 2.50 (m, 4H, NCH2), 1.74 (m, 8H, CH2), 1.37 (m, 8H,
CH2), 0.89 (t, 6H, CH3).
(MgSO4) and evaporated. The residue was precipitated from
CHCl3/hexane to give 12 as a light yellow powder. Yield: 0.71 g,
81%; mp 155–158 °C; 1H NMR (400 MHz, CDCl3): 7.83 (m, 2H,
Phth), 7.72 (m, 2H, Phth), 6.06 (s, 4H, ArH), 6.05 (s, 2H, ArH),
6.03 (s, 2H, ArH), 4.32, 4.29 (2 × d, 4H, ArCH2Ar), 3.80–3.70 (m,
10H, NCH2 + OCH2), 3.14 (br s, 8H, NH2), 2.93 (d, 4H, ArCH2Ar),
1.90–1.81 (m, 8H, CH2), 1.78–1.71 (m, 2H, CH2), 1.45–1.40 (m,
2H, CH2), 0.97–0.90 (m, 9H, CH3).
5,11,17,23-Tetra-CMPO-25,27-bis(aminodecyloxy)-26,28-
dipropoxycalix[4]arene 2c. Obtained as a pale yellow powder as
described for 2b. Yield: 87%; mp 180–182 °C; (Found: C, 71.01;
H, 7.21; N, 4.76; C110H126N6O12P4·H2O requires C, 70.80; H 6.91;
N, 4.50%). 1H NMR (400 MHz, CDCl3): 8.92 (s, 2H, CONH), 8.79
(s, 2H, CONH), 7.72 (m, 16H, Ph2P), 7.39 (m, 24H, Ph2P), 6.64 (s,
4H, ArH), 6.46 (s, 4H, ArH), 4.32 (d, 4H, ArCH2Ar), 3.76 (m, 4H,
OCH2), 3.65 (b, 4H, NH2), 3.41 (m, 12H, COCH2PO + CH2), 3.02
(d, 4H, ArCH2Ar), 2.66 (t, 4H, NCH2), 1.78 (m, 8H, CH2), 1.42 (m,
4H, CH2), 1.26 (m, 24H, CH2), 0.90 (t, 6H, CH3).
5,11,17,23-Tetra-CMPO-25-phthalimidopentyloxy-26,27,28-
tripropoxycalix[4]arene 13. p-Nitrophenyl(diphenylphosphoryl)-
acetate (0.90 g) was stirred with 12 (0.30 g) in CHCl3 (25 ml)
containing triethylamine (0.1 g) for 18 h. Additional CHCl3
(10 ml) was added, the solution was washed repeatedly with 10%
aq. NaOH, dried (MgSO4) and evaporated. The pale yellow residue
was purified by column chromatography (CHCl3/methanol) and
precipitation from chloroform/hexane to give a white powder.
Yield: 0.54 g, 83%; mp 185–187 °C; 1H NMR (400 MHz, CDCl3):
8.95 (s, 4H, CONH), 7.81 (m, 2H, Phth), 7.74–7.68 (m, 16H,
Ph2P), 7.55–7.41 (m, 26H, Phth + Ph2P), 6.58 (s, 2H, ArH), 6.55
(s, 6H, ArH), 4.32, 4.29 (2 × d, 4H, ArCH2Ar), 3.81–3.68 (m, 10H,
NCH2 + OCH2), 3.45 (d, 8H, COCH2PO), 3.50 (t, 4H, NCH2), 3.05,
3.02 (2 × d, 4H, ArCH2Ar), 1.86–1.78 (m, 8H, CH2), 1.75–1.71(m,
2H, CH2), 1.42–1.38 (m, 2H, CH2), 0.94–0.87 (m, 9H, CH3).
25-Phthalimidopentyloxy-27-propoxy-p-tert-butylcalix[4]-
arene-26,28-diol. A suspension of tert-butylcalix[4]arene mono-
propylether (3.0 g, 4.38 mmol), and K2CO3 (0.42 g, 3.04 mmol)
in acetonitrile (120 ml) was stirred under reflux for 1 h. 5-
Bromopentylphthalimide (1,43 g, 4.83 mmol) was added and the
mixture was refluxed for 2.5 days. After cooling it was filtered and
evaporated. The oily residue was triturated with methanol and the
white solid finally recrystallised from CHCl3/methanol: Yield 1.7 g,
1
39%; mp 139–142 °C. H NMR (400 MHz, CDCl3): 7.76 (s, 2H,
OH), 7.70 (m, 2H, Phth), 7.60 (m, 2H, Phth), 7.01 (s, 2H,ArH), 6.99
(s, 2H, ArH), 6.83 (s, 4H, ArH), 4.25, 4.15 (2 × d, 4H, ArCH2Ar),
3.97 (t, 2H, OCH2), 3.91 (t, 2H, OCH2), 3.78 (t, 2H, NCH2), 3.30,
3.20 (2 × d, 4H, ArCH2Ar), 2.07–2.01 (m, 4H, CH2), 1.87–1.83 (m,
4H, CH2), 1.29–1.25 (m, 21H, CH3 + t-Bu), 1.00 (s, 18H, t-Bu).
5,11,17,23-Tetra-CMPO-25-aminopentyloxy-26,27,28-
tripropoxycalix[4]arene 1. Hydrazine hydrate (1.4 ml) was
heated under reflux with 13 (0.3 g) in ethanol (15 ml) for 2 h.
After evaporation the residue was dissolved in a mixture of
CH2Cl2 and water. The aqueous layer was washed three times with
CH2Cl2, the organic layers were combined, washed with brine,
dried (MgSO4) and evaporated to give 1 as a white solid. Yield:
0.25 g, 91%; mp 180–183 °C; (Found: C, 67.66; H, 6.14; N, 4.51;
25-Phthalimidopentyloxy-26,27,28-tripropoxy-p-tert-
butylcalix[4]arene 10. Asuspension of the mixed diether described
above (1.7 g, 1.88 mmol) in DMF (60 ml) was stirred at RT for 1 h
with NaH (0.122 g, 4.83 mmol). Bromopropane (0.53 g, 4.31 mmol)
was then added and the mixture was stirred for 2 d at room tem-
perature. The solvent was removed under reduced pressure, and the
residue taken up with CH2Cl2 (60 ml). After washing with brine
(2 × 40 ml), the organic phase was dried (MgSO4) and evaporated.
Trituration with methanol gave 10 as a white solid. Yield: 0.65 g,
51%; mp 160–163 °C; 1H NMR (400 MHz, CDCl3): 7.85 (m, 2H,
Phth), 7.72 (m, 2H, Phth), 6.79 (s, 4H, ArH), 6.77 (s, 2H, ArH),
6.76 (s, 2H, ArH), 4.43, 4.37 (2 × d, 4H, ArCH2Ar), 3.88–3.73 (m,
8H, NCH2 + OCH2), 3.13, 3.09 (2 × d, 4H, ArCH2Ar), 2.08–1.98
(m, 4H, CH2), 1.87–1.83 (m, 8H, CH2), 1.84–1.76 (m, 2H, CH2),
1.53–1.47 (m, 2H, CH2), 1.10 (s, 27H, t-Bu), 1.10 (s, 9H, t-Bu),
1.00 (t, 9H, CH3).
1
C98H101N5O12P4·4H2O requires C, 67.77; H, 6.33; N, 4.16%). H
NMR (400 MHz, CDCl3, 55 °C): 8.87 (s, 4H, CONH), 7.79–7.72
(m, 16H, Ph2P), 7.54–7.42 (m, 24H, Ph2P), 6.61 (s, 2H, ArH), 6.58
(s, 6H, ArH), 4.36, 4.33 (2 × d, 4H, ArCH2Ar), 3.85–3.77 (m, 8H,
OCH2), 3.45 (d, 8H, COCH2PO), 3.07 (2 × d, 4H, ArCH2Ar), 2.72
(m, 2H, NCH2), 1.91–1.80 (m, 8H, CH2), 1.53–1.49 (m, 2H, CH2),
1.42–1.38 (m, 2H, CH2), 0.97–0.93 (m, 9H, CH3).
5,11,17,23-Tetranitro-25,26,27,28-tetraphthalimidopropoxy-
calix[4]arene 15. Tetraether 14 (1.6 g) was dissolved in dry CH2Cl2
(60 ml) at room temperature and mixed with 14 ml glacial acetic
acid. Then 100% nitric acid (4.0 ml) was added dropwise with
stirring. After 4 h, when the colour of the solution had changed
from black-violet to orange-yellow, water was added and stirring
continued for 1 h. The organic phase was separated, neutralized
with sodium carbonate solution, washed with brine, dried (MgSO4),
and evaporated. The residue was dissolved in the smallest amount
of CHCl3, methanol was added to precipitate 15 as a nearly white
5,11,17,23-Tetranitro-25-phthalimidopentyloxy-26,27,28-
tripropoxycalix[4]arene 11. Tetraether 10 (1.0 g) was dissolved in
dry CH2Cl2 (60 ml) at room temperature and mixed with glacial ace-
tic acid (11 ml). Then 100% nitric acid (3.2 ml) was added dropwise
with stirring. After 4 h, when the colour of the solution had changed
from black-violet to orange-yellow, water was added and stirring
continued for 1 h. The organic phase was separated, neutralized
with Na2CO3 solution, washed with brine, dried (MgSO4) and evap-
orated. The residue was dissolved in the smallest amount of CHCl3,
methanol was added to precipitate 11 as a nearly white powder.
1
powder. Yield: 0.51 g, 53%; mp > 330 °C; H NMR (400 MHz,
CDCl3): 7.72 (m, 8H, Phth), 7.64 (m, 8H, Phth), 7.54 (s, 8H, ArH),
4.62 (d, 4H,ArCH2Ar), 4.18 (t, 8H, OCH2), 3.92 (t, 8H, NCH2), 3.45
(d, 4H, ArCH2Ar), 2.36–2.31 (m, 8H, CH2); FD-MS m/z = 1354.2
(MH+, 100%, calc 1353.4).
1
Yield: 0.5 g, 88%; mp 164–167 °C; H NMR (400 MHz, CDCl3):
7.84 (m, 2H, Phth), 7.75 (m, 2H, Phth), 7.62 (s, 2H, ArH), 7.61 (s,
2H, ArH), 7.54 (s, 2H, ArH), 7.51 (s, 2H, ArH), 4.54, 4.50 (2 × d,
4H, ArCH2Ar), 4.00–3.92 (m, 8H, OCH2), 3.72 (t, 2H, NCH2), 3.42,
3.39 (2 × d, 4H, ArCH2Ar), 1.96–1.87 (m, 8H, CH2), 1.81–1.74 (m,
2H, CH2), 1.50–1.43 (m, 2H, CH2), 1.03–0.99 (m, 9H, CH3).
5,11,17,23-Tetraamino-25,26,27,28-tetraphthalimido-
propoxycalix[4]arene 16. A solution of 15 (0.50 g) in ethanol/
dioxane (1:1, 20 ml) was heated under reflux with SnCl2·H2O
(1.38 g) for 8 h. NaOH (10%) was added and the stirring continued
for 1 h. The aqueous solution was extracted with CH2Cl2 (2 × 70 ml)
and the organic phase was washed with water and brine, dried
(MgSO4) and evaporated. Precipitation from CHCl3/hexane gave
16 as a pale yellow powder. Yield 0.36 g, 80%; mp 166–170 °C. 1H
NMR (400 MHz, CDCl3): 7.70 (m, 8H, Phth), 7.59 (m, 8H, Phth),
6.03 (s, 8H, ArH), 4.35 (d, 4H, ArCH2Ar), 3.93 (t, 8H, OCH2), 3.87
(t, 8H, NCH2), 2.97 (d, 4H, ArCH2Ar), 2.76 (broad s, 8H, NH2),
2.30–2.23 (m, 8H, CH2); FD-MS m/z = 1233.0 (MH+, 100%, calc
1233.5).
5,11,17,23-Tetraamino-25-phthalimidopentyloxy-26,27,28-
tripropoxycalix[4]arene 12. A solution of 11 (0.5 g) in ethanol/
dioxane (1:1, 35 ml) was heated under reflux for 10 h with
SnCl2·H2O (1.98 g, 4.5 mole per mole NO2). NaOH (10%) was
then added at room temperature and stirring was continued for
1 h. The aqueous solution was extracted with CH2Cl2 (2 × 50 ml)
and the organic phase was washed with water and brine, dried
2 3 3 2
O r g . B i o m o l . C h e m . , 2 0 0 4 , 2 , 2 3 2 7 – 2 3 3 4