ACCEPTED MANUSCRIPT
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J = 2.0 Hz, 2H), 6.58 (d, J = 2.0Hz, 2H), 7.10 (s, 2H), 7.19 (s, 2H), 7.64 (t, J = 5.6 Hz, 2H), 8.39 (t, J = 5.6 Hz, 1H); 13C NMR
(CDCl3, 100 MHz) δ: 30.9, 31.0, 31.2, 31.4, 31.6, 31.7, 33.8, 34.0, 34.3, 42.3, 42.4, 61.5, 75.5, 125.6, 126.6, 129.0, 131.1, 131.3,
135.0, 146.8, 147.6, 149.3, 151.0, 169.0, 171.0; IR (KBr) υ: 3381, 2961, 2868, 1659, 1555, 1481, 1194, 1124, 872 cm-1; MS m/z:
HRMS (ESI) Calcd: for C60H84N4NaO12 ([M+Na]+): 1075.5983, found: 1075.6011.
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5,11,17,23-tetra-tert-butyl-25,27-bis[N,N-di(2-hydroxyethyl)aminocarbonylmethoxyl]-calix[4]arene-26,28-diol (3d): White
powder, purified by column chromatography (SiO2, 1:3 petroleum ether/ethyl acetate), Mpꢂ250ꢃ, yield: 81%; 1H NMR
(DMSO-d6, 400 MHz) δ: 1.05, 1.19 (2s, 36H), 3.50 (q, J = 5.2 Hz, 8H), 3.62 (brs, 8H), 4.36 (d, J = 12.8 Hz, 4H), 4.71 (t, J = 4.8
Hz, 4H), 4.85 (s, 4H), 4.91 (t, J = 4.8 Hz, 4H), 6.92-6.95 (m, 4H), 7.01 (s, 4H), 8.27 (brs, 2H); 13C NMR (DMSO-d6, 100 MHz) δ:
31.3, 31.8, 33.9, 34.2, 59.2, 78.9, 79.2, 79.4, 79.6, 125.5, 125.8, 127.7, 133.2, 169.0; IR (KBr): 3393, 3309, 2961, 2869, 1653,
1636, 1486, 1363, 1193, 971 cm-1; MS m/z: HRMS (ESI) Calcd: for C56H78N2NaO10 ([M+Na]+): 961.5554, found: 961.5598.
25,27-bis[N,N-di(2-hydroxyethyl)aminocarbonylmethoxyl]-calix[4]arene-26,28-diol(3e): White powder, purified by column
chromatography (SiO2, 1:1 petroleum ether/ethyl acetate), Mp=225.7- 227.4 ꢃ, yield: 67 %; 1H NMR (DMSO-d6, 400 MHz) δ:
3.35 (d, J = 8.4 Hz, 4H), 3.44-3.48 (m, 8H ), 3.57-3.59 (m, 8H), 4.40 (d, J = 8.4Hz, 4H), 4.74(t, J=3.6 Hz, 2H), 4.89 (s, 4H), 4.93
(t, J = 3.6 Hz, 2H), 6.54(t, J = 5.2 Hz, 2H), 6.74 (t, J = 5.2 Hz, 2H), 6.98 (d, J = 5.2 Hz, 4H), 7.08 (d, J = 4.8 Hz, 4H), 8.41 (s,
2H); 13C NMR (DMSO-d6, 100 MHz) δ: 31.2, 59.0, 59.1, 128.1, 129.0, 129.2, 134.2, 154.2, 168.9; IR (KBr) υ: 3385, 1653, 1635,
1558, 1466, 1437, 1194, 1050, 755 cm-1; MS m/z: HRMS (ESI) Calcd: for C40H46N2NaO10 ([M+Na]+): 737.3045, found:
737.3087.
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5,11,17,23,29,35-hexa-tert-butyl-37,38,39,40,41,42-hexa[N-(2-hydroxyethyl)aminocarbonylmethoxyl]-calix[6]arene(3f):
White powder, purified by column chromatography (SiO2, 6:1 dichloromethane/methanol), Mpꢂ250ꢃ, yield: 68 %; 1H NMR
(DMSO-d6, 400 MHzꢄδ: 1.00 (s, 54H), 3.16 (brs, 12H), 3.40 (brs, 6H), 4.00 (brs, 24H), 4.72 (t, J = 5.2 Hz, 6H), 6.88 (s, 12H),
7.92 (s, 6H); 13C NMR (DMSO-d6, 100 MHz) δ: 29.9, 31.6, 34.3, 60.3, 72.3, 126.2, 132.8, 146.4, 152.8, 168.5; IR (KBr) υ: 3415,
2961, 2868, 1668, 1653, 1363, 1116, 874 cm-1; MS m/z: HRMS (ESI) Calcd: for C90H126N6NaO18 ([M+Na]+): 1601.9025, found:
1601.9038.
37,38,39,40,41,42-hexa[N-(2-hydroxyethyl)aminocarbonylmethoxyl]calix[6]arene(3g): White powder, purified by column
chromatography (SiO2, 10:1 ethyl acetate/methanol), Mpꢂ250ꢃ, yield: 72 %; 1H NMRꢅDMSO-d6, 400 MHzꢄδ: 3.18 (s, 12H),
3.38 (s, 6H), 4.11 (d, J = 22.8 Hz, 24H), 4.73 (s, 6H), 6.81 (s, 12H), 6.93 (s, 6H), 7.95 (s, 6H); 13C NMR (DMSO-d6, 100 MHz) δ:
29.8, 41.6, 56.5, 60.1, 72.2, 125.2, 129.4, 134.0, 154.7, 168.2; IR (KBr) υ: 3420, 3303, 2960, 1662, 1653, 1558, 1480, 1190,
1041, 974 cm-1; MS m/z: HRMS (ESI) Calcd: for C66H78N6NaO18 ([M+Na]+): 1265.5270, found: 1265.5247.
5,11,17,23,29,35-hexa-tert-butyl-37,38,39,40,41,42-hexa[N,N-di(2-hydroxyethyl)aminocarbonylmethoxyl]-calix[6]arene(3h).
White powder, purified by column chromatography (SiO2, 1:2 dichloromethane/methanol), Mpꢂ250ꢃ, yield: 96.82%; 1H
NMR(DMSO-d6, 400 MHz) δ: 0.94, 1.17 (2s, 54H), 3.30-3.53(m, 42H), 3.92 (d, J = 34.8 Hz, 12H), 4.57-4.87 (m, 16H),
6.74-7.10 (m, 12H); 13C NMR (DMSO-d6, 100 MHz) δ: 30.0, 31.7, 34.2, 34.3, 34.4, 58.4, 59.4, 132.9, 146.0, 169.1; IR (KBr) υ:
3385, 2956, 2867, 1653, 1635, 1482, 1189,1049, 874 cm-1; MS m/z: HRMS (ESI) Calcd: for C78H102N6NaO24 ([M+Na]+):
1529.6843, found: 1529.6818.
37,38,39,40,41,42-hexa[N,N-di(2-hydroxyethyl)aminocarbonylmethoxyl]calix[6]arene (3i): White powder, purified by
column chromatography (SiO2, 1:2 dichloromethane/methanol), Mpꢂ250ꢃ, yield: 58 %; 1H NMRꢅDMSO-d6, 400 MHzꢄδ:
3.36-3.43 (m, 24H), 3.44-3.50 (m, 24H), 4.05 (s, 12H), 4.72-4.76 (m, 12H), 4.94 (t, J = 5.2Hz, 6H), 6.76-6.92 (m, 18H); 13C
NMR (DMSO-d6, 100 MHz) δ: 30.0, 59.1, 59.3, 60.2, 61.0, 71.7, 124.6, 129.2, 134.4, 155.7, 168.6; IR (KBr) υ: 3377, 2955,
1657, 1645, 1481, 1194, 1045, 872 cm-1; MS m/z: HRMS (ESI) Calcd: for C78H102N6Na2O24 ([M+2Na]2+): 1889.0497, found:
945.0259.
5,11,17,23,29,35,41,47-octa-tert-butyl-49,50,51,52,53,54,55,56-octa[N-(2-hydroxyethyl)aminocarbonylmethoxyl]calix[8]
arene(3j). purified by column chromatography (SiO2, 6:1 dichloromethane/methanol), White powder: Mpꢂ250ꢃ, yield: 53 %;
1H NMR (DMSO-d6, 400 MHz) δ: 1.00 (s, 72H), 3.15 (brs, 16H ), 3.38 (s, 16H), 4.00 (brs, 24H), 4.71 (brs, 8H), 6.87 (s, 16H),
7.91 (s, 8H); 13C NMR (DMSO-d6, 100 MHz) δ: 31.5, 34.3, 41.6, 60.1, 72.0, 132.7, 146.3, 152.7, 168.4; IR (KBr) υ: 3413, 2960,