A. Shivanyuk, I. Thondorf, V. Bˆhmer et al.
FULL PAPER
Tri-tolylurea mono-Boc-calix[4]arene 5a: Yield 79%; m.p.: 115 1168C;
1H NMR (400 MHz, [D6]DMSO): d = 8.98 (s, 1H; NH), 8.31 (s, 2H;
NH), 8.10 (s, 2H; NH), 7.98 (s, 2H; NH), 7.28 (d, 2J = 8.5 Hz, 2H;
ArH), 7.14 (d, 2J = 8.24 Hz, 4H; ArH), 7.04 6.97 (m, 10H; ArH), 6.56
(s, 2H; ArH), 6.51 (s, 2H; ArH), 4.30 (d, 2J = 12.6 Hz, 2H; ArCH2Ar),
overnight. The precipitate formed was filtered off, washed with water
and methanol, and dried in vacuo. Compound 2a: yield 78%; white
solid. The spectra were as described in reference [13].
Tri-methoxyphenylurea monoacetamide calix[4]arene 2b: This com-
pound was prepared in the same way as 2a, from monoamine 6b, Ac2O,
and NEt3. Compound 2b: yield 90%; yellowish solid; m.p.: 187 1898C;
1H NMR (200 MHz, [D6]DMSO): d = 9.46 (s, 1H; NH), 8.19 (s, 1H;
NH), 8.15 (s, 2H; NH), 8.10 (s, 2H; NH), 8.06 (s, 1H; NH), 7.29 7.21 (m,
6H; ArH), 6.94 (s, 2H; ArH), 6.82 6.76 (m, 12H; ArH), 4.31 (d, 2J =
12.5 Hz, 4H; ArCH2Ar), 3.79 (t, 3J = 7.1 Hz, 8H; ArOCH2), 3.68 (s,
2
4.29 (d, J = 12.3 Hz, 2H; ArCH2Ar), 3.87 (brm, 4H; ArOCH2), 3.68 (t,
J = 6.4 Hz, 4H; ArOCH2), 3.08 (d, 2J = 12.9 Hz, 2H; ArCH2Ar), 3.02
(d, 2J = 12.5 Hz, 2H; ArCH2Ar), 2.17 (s, 3H; ArCH3), 2.19 (s, 6H;
ArCH3), 1.96 1.81 (m, 8H; CH2), 1.52 1.21 (m, 25H; CH2 and C(CH3)3),
0.93 0.90 ppm (m, 12H; CH3); FD-MS: m/z (%): 1264.2 (100) [M]+.
9H; ArOCH3), 3.07 (d, 2J
= 12.8 Hz, 4H; ArCH2Ar), 2.07 (s, 3H;
Tri-methoxyphenylurea mono-Boc-calix[4]arene 5b: Yield 79%; m.p.:
150 1518C; 1H NMR (200 MHz, [D6]DMSO): d = 8.83 (s, 1H; NH),
8.15 (s, 4H; NH), 8.08 (s, 2H; NH), 7.29 7.21 (m, 6H; ArH), 6.82 6.74
COCH3), 1.98 1.77 (m, 8H; CH2), 1.48 1.28 (m, 16H; CH2), 0.92 ppm (t,
3J = 6.5 Hz, 12H; CH3); FD-MS: m/z (%): 1255.4 (100) [M]+.
(m, 12H; ArH), 5.97 (s, 2H; ArH), 4.32 (d, 2J
=
13.2 Hz, 2H;
Tri-hexylurea monoacetamide calix[4]arene 2c: This compound was pre-
pared in the same way as 2a, from monoamine 6c, Ac2O, and NEt3.
Compound 2c: yield 75%; white powder; m.p.: 157 1598C; 1H NMR
(400 MHz, [D6]DMSO): d = 9.51 (s, 1H; NH), 8.36 (s, 2H; NH), 8.10 (s,
1H; NH), 7.32 (s, 2H; ArH), 7.15 (s, 2H; ArH), 6.71 (s, 2H; ArH), 6.60
(s, 2H; ArH), 6.24 (t, 3J = 5.5 Hz, 2H; NH), 6.17 (t, 3J = 5.2 Hz, 1H;
NH), 4.53 (d, 2J = 13.5 Hz, 2H; ArCH2Ar), 4.47 (d, 2J = 12.8 Hz, 2H;
ArCH2Ar), 4.23 (d, 2J
= 12.8 Hz, 2H; ArCH2Ar), 3.80 374 (m, 8H;
ArOCH2), 3.68 (s, 6H; ArOCH3), 3.67 (s, 3H; ArOCH3), 3.07 (d, 2J =
13.5 Hz, 2H; ArCH2Ar), 2.93 (d, 2J = 12.8 Hz, 2H; ArCH2Ar), 1.88
(brs, 8H; CH2), 1.54 (s, 9H; C(CH3)3), 1.36 (br s, 16H; CH2), 0.95
0.88 ppm (m, 12H; CH3); FD-MS: m/z (%): 1312.3 (100) [M]+.
Tri-hexylurea mono-Boc-calix[4]arene 5c: Yield 80%; m.p.: 98 1008C;
1H NMR (400 MHz, [D6]DMSO): d = 8.84 (s, 1H; NH), 7.98 (s, 1H;
NH), 7.75 (s, 2H; NH), 6.90 (s, 2H; ArH), 6.80 (s, 2H; ArH), 6.49 (s,
2H; ArH), 6.46 (s, 2H; ArH), 5.81 (t, 3J = 5.8 Hz, 1H; NH), 5.66 (t, 3J
ArCH2Ar), 4.22 4.10 (m, 4H; ArOCH2), 3.90 (t, 3J
= 5.3 Hz, 2H;
ArOCH2), 3.87 (t, 3J = 6.2 Hz, 2H; ArOCH2), 3.37 (d, 2J = 13.5 Hz,
2H; ArCH2Ar), 3.27 3.14 (m, 8H; ArCH2Ar and NCH2), 2.17 (brs, 6H;
CH2), 1.99 1.95 (m, 2H; CH2), 1.69 1.58 (m, 12H; CH2), 1.50 (brs, 16H;
CH2), 1.17 (t, 3J = 6.2 Hz, 12H; CH3), 1.08 ppm (brs, 9H; CH3); FD-
MS: m/z (%): 1187.6 (100) [M]+.
2
= 5.5 Hz 2H; NH), 4.24 (d, J = 12.2 Hz, 4H; ArCH2Ar), 3.82 (brs, 4H;
3
ArOCH2), 3.65 (t, J = 6.6 Hz, 4H; ArOCH2), 3.01 2.89 (m, 10H; NCH2
and ArCH2Ar), 1.88 1.78 (m, 8H; CH2), 1.39 (s, 9H; C(CH3)3), 1.37 1.19
(m, 28H; CH2), 0.88 (t, 3J
= 6.6 Hz, 12H; CH3), 0.81 ppm (m, 9H;
CH3); FD-MS: m/z (%): 1245.5 (100) [M]+.
Tri-tolylurea monopropionamide calix[4]arene 2d: Propionyl chloride
(0.5 1 mL) was added to a vigorously stirred suspension of monoamine
2a (200 mg, 0.17 mmol) in EtOAc (20 mL) and Na2CO3 (1n, 40 mL). The
mixture was intensively stirred at room temperature for 2 h (reaction
monitored by TLC). The organic layer was separated, and washed with
Na2CO3 (1n, 50 mL) and water (2î50 mL). The solvent was removed in
vacuo, and the residue was dissolved in CHCl3 and reprecipitated with
hexane to give a white solid. Compound 2e: yield 85%; m.p.: 185
1878C; 1H NMR (400 MHz, [D6]DMSO): d = 9.30 (s, 1H; NH), 8.18 (s,
1H; NH), 8.14 (s, 2H; NH), 8.05 (s, 1H; NH), 8.02 (s, 2H; NH), 7.14 (d,
3J = 8.2 Hz, 2H; ArH), 7.09 (d, 3J = 8.4 Hz, 4H; ArH), 6.92 6.89 (m,
6H; ArH), 6.71 (s, 4H; ArH), 6.64 (s, 2H; ArH), 6.59 (s, 2H; ArH), 4.20
(d, 2J = 12.5 Hz, 4H; ArCH2Ar), 3.72 3.66 (m, 8H; ArOCH2), 2.98 (d,
2J = 12.5 Hz, 2H; ArCH2Ar), 2.95 (d, 2J = 12.5 Hz, 2H; ArCH2Ar),
2.09 (s, 9H; ArCH3), 1.78 (brs, 8H; CH2), 1.28 1.26 (m, 16H; CH2), 1.02
(t, 3J = 6.2 Hz, 3H; CH3), 0.88 0.81 ppm (m, 15H; CH3 and CH2); FD-
MS: m/z (%): 1221.9 (100) [M]+.
Triurea monoamine calix[4]arenes 6a c: TFA (20 mL) was added in one
portion to a solution of 5a c (0.3 mmol) in CH2Cl2 (20 mL). The reaction
mixture was stirred at room temperature for 2 h and was then diluted
with toluene (50 mL). The solvent was evaporated to dryness in vacuo to
give the crude product as a yellowish powder. Precipitation from CHCl3/
hexane gave the desired amines 6a c as their triflate salts.
Tri-tolylurea monoamine calix[4]arene 6a: Yield 98%; m.p.>3008C; 1H
NMR (400 MHz, [D6]DMSO): d = 9.27 (brs, 2H; ArNH2), 8.54 (s, 2H;
3
NH), 8.47 (s, 2H; NH), 8.34 (s, 1H; NH), 8.18 (s, 1H; NH), 7.28 (d, J =
8.2 Hz, 4H; ArH), 7.22 (d, 3J = 8.2 Hz, 2H; ArH), 7.14 (s, 2H; ArH),
7.04 7.00 (m, 6H; ArH), 6.94 (s, 2H; ArH), 6.63 (s, 2H; ArH), 6.53 (s,
2H; ArH), 4.35 (d, 2J = 13.5 Hz, 2H; ArCH2Ar), 4.31 (d, 2J = 13.5 Hz,
2H; ArCH2Ar), 3.94 3.84 (m, 4H; ArOCH2), 3.75 (t, 3J = 6.7 Hz, 2H;
ArOCH2), 3.70 (t, 3J = 6.7 Hz, 2H; ArOCH2), 3.19 (d, 2J = 12.9 Hz,
2H; ArCH2Ar), 3.11 (d, 2J
= 13.2 Hz, 2H; ArCH2Ar), 2.21 (s, 6H;
ArCH3), 2.19 (s, 3H; ArCH3), 1.95 1.85 (m, 8H; CH2), 1.43 1.30 (m,
16H; CH2), 0.92 ppm (t, 3J = 6.7 Hz, 12H; CH3); FD-MS: m/z (%):
1161.5 (100) [M]+.
Tri-tolylurea monovaleramide calix[4]arene 2e: This compound was pre-
pared in the same way as 2d, from monoamine 6a (200 mg, 0.17 mmol)
and valeroyl chloride (0.5 1 mL). Yield 80%; white powder: m.p.: 196
1988C; 1H NMR (400 MHz, [D6]DMSO): d = 9.42 (s, 1H; NH), 8.26 (s,
1H; NH), 8.19 (s, 2H; NH), 8.14 (s, 1H; NH), 8.10 (s, 2H; NH), 7.26 (d,
3J = 8.2 Hz, 2H; ArH), 7.21 (d, 3J = 8.2 Hz, 4H; ArH), 7.04 7.01 (m,
6H; ArH), 6.83 (s, 4H; ArH), 6.76 (s, 2H; ArH), 6.71 (s, 2H; ArH), 4.32
Tri-methoxyphenylurea monoamine calix[4]arene 6b: Yield 88%; m.p.>
3008C; 1H NMR (200 MHz, [D6]DMSO): d = 9.31 (brs, 2H; ArNH2),
3
8.20 (s, 4H; NH), 8.10 (s, 2H; NH), 7.27 (d, J = 8.7 Hz, 2H; ArH), 7.22
3
(d, J = 8.8 Hz, 4H; ArH), 6.82 6.74 (m, 12H; ArH), 5.97 (s, 2H; ArH),
4.31 (d, 2J
= = 12.8 Hz, 2H;
12.5 Hz, 2H; ArCH2Ar), 4.25 (d, 2J
(d, 2J
= =
12.5 Hz, 4H; ArCH2Ar), 3.84 3.77 (m, 8H), 3.10 (d, 2J
ArCH2Ar), 3.80 374 (m, 8H; ArOCH2), 3.68 (s, 6H; ArOCH3), 3.67 (s,
3H; ArOCH3), 3.07 (d, 2J = 13.5 Hz, 2H; ArCH2Ar), 2.93 (d, 2J =
12.8 Hz, 2H; ArCH2Ar), 1.88 (brs, 8H; CH2), 1.36 (brs, 16H; CH2),
0.91 ppm (t, 3J = 6.5 Hz, 12H; CH3); FD-MS: m/z (%): 1209.4 (100)
[M]+.
Tri-hexylurea monoamine calix[4]arene 6c: Yield 99%, mp>3008C; 1H
NMR (400 MHz, [D6]DMSO): d = 9.26 (brs, 2H; NH2), 8.38 (s, 2H;
NH), 8.06 (s, 1H; NH), 7.33 (s, 2H; ArH), 7.14 (s, 2H; ArH), 6.69 (s,
2H; ArH), 6.62 (s, 2H; ArH), 6.25 (t, 3J = 5.1 Hz, 2H; NH), 6.17 (t, 3J
12.5 Hz, 2H; ArCH2Ar), 3.07 (d, 2J = 12.5 Hz, 2H; ArCH2Ar), 2.21 (s,
9H; ArCH3), 2.19 2.16 (m, 2H; COCH2), 1.89 (m, 8H; CH2), 1.51 1.43
(m, 2H; CH2), 1,39 1.38 (m, 16H; CH2), 1.25 1.19 (m, 2H; CH2), 0.94
0.91 (m, 12H; CH3), 0.82 ppm (t, 3J = 6.2 Hz, 3H; CH3); FD-MS: m/z
(%): 1250.0 (100) [M]+.
Tri-tolylurea mono-p-methylbenzamide calix[4]arene 2 f: This compound
was prepared in the same way as 2d, from monoamine 6a and p-methyl-
benzoyl chloride. Yield 86%; Brown solid: m.p.: 260 2618C; 1H NMR
(400 MHz, [D6]DMSO): d = 9.86 (s, 1H; NH), 8.23 (s, 1H; NH), 8.20 (s,
1H; NH), 8.16 (s, 2H; NH), 8.06 (s, 2H; NH), 7.78 (d, 3J = 7.9 Hz, 2H;
ArH), 7.29 (s, 2H; ArH), 7.23 7.15 (m, 8H; ArH), 7.03 6.97 (m, 6H;
ArH), 6.89 (s, 2H; ArH), 6.71 (d, 3J = 2.0 Hz, 2H; ArH), 6.66 (d, 3J =
2.1 Hz, 2H; ArH), 4.34 (d, 2J = 13.2 Hz, 2H; ArCH2Ar), 4.30 (d, 2J =
2
2
= 5.0 Hz, 1H; NH), 4.55 (d, J = 12.8 Hz, 2H; ArCH2Ar), 4.50 (d, J =
12.5 Hz, 2H; ArCH2Ar), 4.18 4.06 (m, 4H; ArOCH2), 3.95 (t, 3J
=
3
2
6.2 Hz, 2H; ArOCH2), 3.87 (t, J = 6.0 Hz, 2H; ArOCH2), 3.36 (d, J =
12.5 Hz, 2H; ArCH2Ar), 3.29 3.17 (m, 8H; ArCH2Ar and NCH2), 2.19
2.05 (m, 6H; CH2), 2.00 1.97 (m, 2H; CH2), 1.69 1.58 (m, 12H; CH2),
3
13.5 Hz, 2H; ArCH2Ar), 3.89 3.83 (m, 4H; ArOCH2), 3.76 (t, 3J
=
1.50 (brs, 16H; CH2), 1.15 (t, J = 6.3 Hz, 12H; CH3), 1.12 1.07 ppm (m,
9H; CH3); FD-MS: m/z (%): 1143.8 (100) [M]+.
7.0 Hz, 4H; ArOCH2), 3.12 3.08 (m, 4H; ArCH2Ar), 2.30 (s, 3H;
ArCH3), 2.20 (s, 3H; ArCH3), 2.18 (s, 6H; ArCH3), 1.96 1.84 (m, 8H;
CH2), 1.39 1.37 (m, 16H; CH2), 0.92 ppm (t, 3J = 6.2 Hz, 12H; CH3);
FD-MS: m/z (%): 1283.2 (100) [M]+.
Tri-tolylurea monoacetamide calix[4]arene 2a: NEt3 (0.5 mL) was added
in one portion to a solution of the monoamine 6a (200 mg, 0.17 mmol) in
Ac2O (20 mL), and the reaction mixture was stirred at room temperature
2146
¹ 2004 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Chem. Eur. J. 2004, 10, 2138 2148