ꢂꢁꢁꢁ
B. Zhao et al.: Heteroarylthio derivatives of calix[4]areneꢀ
ꢀ21
5,17-Di-tert-butyl-11,23-bis[(2-pyridylthio)acetylamino]-25,
27-diethoxycalix[4]arene (6a)ꢀColorless solid; yield 80%; mp
6.78 (s, 2H), 4.31(d, J = 13 Hz, 4H), 4.11 (m, 4H), 3.84 (s, 4H), 3.29 (d,
J = 13 Hz, 4H), 2.47 (s, 12H), 1.68 (t, J = 7.5 Hz, 6H), 1.11 (s, 18H); 13C
NMR: δ 170.3, 167.1, 167.1, 149.3, 150.5, 147.7, 133.7, 130.4, 129.9, 126.0,
120.2, 116.7, 72.2, 35.8, 34.3, 32.1, 31.5, 24.2, 15.5. ESI-MS: Calcd for
C56H66N6O6S2: m/z 982.5, found: m/z 1005.6 (M+Na)+.
1
259–261°C; IR: 3441, 2927, 2845, 1679, 1565, 1488, 1198, 1028 cm-1; H
NMR: δ 9.51 (s, 2H), 8.48 (s, 2H), 8.45 (d, J = 5 Hz, 2H), 7.48 (t, J = 5.5
Hz, 2H), 7.20 (d, J = 5 Hz, 2H), 7.07 (s, 4H), 7.04 (t, J = 5.5 Hz, 2H),
6.99 (s, 4H), 4.32 (d, J = 13 Hz, 4H), 4.12 (m, 4H), 3.80 (s, 4H), 3.30
(d, J = 13 Hz, 4H), 1.70 (t, J = 7.5 Hz, 6H), 1.11 (s, 18H); 13C NMR: δ 167.6,
158.3, 150.5, 136.9, 149.0, 147.7, 134.0, 130.7, 130.1, 126.0, 122.8, 120.6,
120.2, 72.2, 35.1, 34.3, 32.1, 31.5, 15.6; ESI-MS: Calcd for C54H60N4O6S2:
m/z 924.4, found: m/z 925.4 (M+1)+.
5,17-Di-tert-butyl-11,23-bis[(4,6-dimethyl-2-pyrimidinylthio)
acetylamino]-25,27-dibutoxycalix[4]arene (7b)ꢀColorless solid;
yield 81%; mp 128–131°C; IR: 3329, 2960, 2872, 1686, 1584, 1483, 1266,
1196 cm-1; 1H NMR: δ 8.97 (s, 2H), 8.28 (s, 2H), 7.11 (s, 4H), 6.92 (s, 4H),
6.78 (s, 2H), 4.28 (d, J = 13 Hz, 4H), 3.96 (t, J = 7 Hz, 4H), 3.86 (s, 4H),
3.28 (d, J = 13 Hz, 4H), 2.47 (s, 12H), 2.05 (m, 4H), 1.67–1.69 (m, 4H),
1.26 (m, 6H), 1.07 (s, 18H); 13C NMR: δ 170.3, 167.6, 167.0, 150.5, 149.8,
147.5, 133.2, 130.0, 129.3, 126.0, 120.3, 116.7, 76.8, 35.6, 34.3, 32.3, 32.0,
31.5, 24.2, 19.5, 14.3. ESI-MS: m/z: Calcd for C60H74N6O6S2: m/z 1038.5,
found: m/z 1056.5 (M+H2O)+.
5,17-Di-tert-butyl-11,23-bis[(2-pyridylthio)acetylamino]-25,
27-dibutoxycalix[4]arene (6b)ꢀColorless solid; yield 79%; mp
259–263°C; IR: 3432, 2962, 2876, 1668, 1559, 1482, 1414, 1242, 1031 cm-1;
1H NMR: δ 9.47 (s, 2H), 8.45 (d, J = 5 Hz, 2H,), 8.43 (s, 2H), 7.49 (t, J = 5.5
Hz, 2H), 7.21 (d, J = 5 Hz, 2H), 7.07 (s, 4H), 7.05 (t, J = 5.5 Hz, 2H), 6.99
(s, 4H), 4.32 (d, J = 13 Hz, 4H), 4.12 (m, 4H), 3.81 (s, 4H), 3.30 (d, J = 13
Hz, 4H), 2.03 (m, 4H), 1.75–1.78 (m, 4H), 1.28 (m, 6H), 1.11 (s, 18H); 13
C
5,17-Di-tert-butyl-11,23-bis[(4,6-dimethyl-2-pyrimidinylthio)
acetylamino]-25,27-dibenzyloxycalix[4]areneꢀ(7c)ꢀColorless
solid; yield 81%; mp 115–118°C; IR: 3249, 2965, 2882, 1678, 1596, 1489,
1257, 1186 cm-1; 1H NMR: δ 9.16 (s, 2H), 7.60 (s, 2H), 7.59 (m, 5H), 7.37–
7.38 (m, 5H), 7.13 (s, 4H), 6.92 (s, 4H), 6.83 (s, 2H), 5.00 (s, 4H), 4.22
(d, J = 13 Hz, 4H), 3.88 (s, 4H), 3.22 (d, J = 13 Hz, 4H), 2.47 (s, 12H),
1.01 (s, 18H); 13C NMR: δ 170.5, 167.8, 167.1, 149.8, 150.9, 150.4, 148.5,
130.4, 130.1, 129.3, 128.5, 119.0, 137.4, 133.5, 128.6, 124.9, 124.2, 121.7,
76.3, 35.8, 34.6, 32.9, 32.0, 24.3. ESI-MS: Calcd for C66H70N6O6S2: m/z
1106.5, found: m/z 1124.6 (M+H2O)+.
NMR: δ 167.6, 158.3, 149.0, 137.0, 120.6, 150.5, 147.7, 134.0, 130.7, 130.1,
126.0, 122.8, 120.3, 72.2, 35.1, 34.4, 32.1, 31.8, 31.5, 20.4, 15.6. ESI-MS:
Calcd for C58H68N4O6S2: m/z 980.5, found: m/z 981.4 (M+1)+.
5,17-Di-tert-butyl-11,23-bis[(2-pyridylthio)acetylamino]-25,
27-dibenzyloxycalix[4]arene (6c)ꢀColorless solid; yield 70%; mp
107–109°C; IR: 3369, 2957, 2853, 1682, 1560, 1481, 1454, 1286, 1124 cm-1;
1H NMR: δ 9.48 (s, 2H), 8.46 (d, J = 5 Hz, 2), 7.72 (s, 2H), 7.58–7.60
(m, 5H), 7.47 (t, J = 5.5 Hz, 2H), 7.38 (m, 5H), 7.21 (d, J = 5 Hz, 2H), 7.11
(s, 4H), 7.03 (t, J = 5.5 Hz, 2H), 6.96 (s, 4H), 5.00 (s, 4H), 4.21 (d, J = 13
Hz, 4H), 3.84 (s, 4H), 3.22 (d, J = 13 Hz, 4H), 1.02 (s, 18H); 13C NMR: δ
167.3, 158.3, 150.0, 136.7, 122.6, 149.5, 148.8, 147.5, 132.8, 129.9, 128.9,
125.8, 119.9, 128.9, 128.1, 78.2, 34.9, 34.1, 31.8, 31.3. ESI-MS: Calcd for
C64H64N4O6S2: m/z 1048.4, found: 1049.4 (M+1)+.
Acknowledgments: We thank the Young Scholars of Hei-
longjiang Province of China (grant no. QC2009C61) and the
Program for Young Teachers Scientific Research in Qiqihar
University (grant no. 2010K-M23) for financial support.
5,17-Di-tert-butyl-11,23-bis[(4,6-dimethyl-2-pyrimidinylthio)
acetylamino]-25,27-diethoxycalix[4]arene (7a)ꢀColorless solid;
yield 76%; mp 142–144°C; IR: 3441, 2927, 2845, 1689, 1565, 1488, 1198,
1028 cm-1; 1H NMR: δ 8.96 (s, 2H), 8.39 (s, 2H), 7.17 (s, 4H), 6.96 (s, 4H),
Received October 7, 2012; accepted November 21, 2012; previously
published online January 16, 2013
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