S.P. Singh et al. / Tetrahedron 64 (2008) 1983e1997
1995
ArH ), 5.00 (d, J¼4.8 Hz, 1H, ArOCH2), 4.95 (d, J¼6.3 Hz,
1H, ArOCH2), 4.74 (s, 2H, ArOCH2), 4.72 (d, J¼5.1 Hz,
2H, ArOCH2), 4.50 (d, J¼15.6 Hz, 2H, ArOCH2), 4.30e
3.92 (m, 6H, OCH2CH3), 3.55e3.48 (m, 1H, NHCH2),
3.24e3.18 (m, 1H, NHCH2), 1.67e1.57 (m, 2H, NHCH2CH2),
1.38 (s, 9H, C(CH3)3), 1.33 (s, 9H, C(CH3)3), 1.31e1.27 (m,
4H, CH2CH2CH3), 1.25 (t, J¼7.5 Hz, 6H, CH3), 1.14 (t,
J¼7.2 Hz, 3H, CH3), 1.06 (s, 9H, C(CH3)3), 1.04 (s, 9H,
C(CH3)3), 0.92 (t, J¼7.2 Hz, 3H, CH3); 13C-DEPT 135
NMR (75 MHz, CDCl3) d (ppm): 135.6, 135.0, 134.7,
134.59, 134.51, 133.9, 133.1 (aromatic C ), 74.2, 70.5, 69.4,
66.0, 60.8, 60.7, 60.0 (ArOCH2 and OCH2CH3), 39.0
(NHCH2), 31.7 (NHCH2CH2), 31.3, 31.2, 31.06, 31.05
(C(CH3)3), 29.6 (NHCH2CH2), 20.2 (NHCH2CH2CH2),
14.28, 14.21, 14.0, 13.8 (CH2CH3). FAB-MS: m/z¼1091
[Mþ, 100%].
135.2, 134.1, 133.2 (aromatic CH), 74.2, 73.8, 66.1, 60.8
(ArOCH2 and OCH2CH3), 39.0, 38.8 (NHCH2), 32.0, 31.8
(NHCH2CH2), 31.3, 31.1, 31.0 (C(CH3)3), 20.5, 20.4
(NHCH2CH2CH2), 14.2, 11.3, 11.5 (CH2CH3). FAB-MS:
m/z¼1144 [Mþꢀ1, 100%].
4.3.16. Compound 7d (partial cone)
Method B (a), reaction time: 3 days, white solid (0.89 g,
81%) recrystallized from CHCl3/MeOH. Mp 218 ꢁC
(decomp.). IR (KBr, n/cmꢀ1): 3288, 1669. Anal. Calcd for
C64H92N4O8S4: C, 65.49; H, 7.90; N, 4.77. Found: C, 65.57;
1
H, 7.88; N, 4.78. H NMR (300 MHz, CDCl3) dH 8.62 (br s,
1H, CONH ), 7.91 (br s, 2H, CONH ), 7.79 (s, 2H, ArH ),
7.63 (s, 2H, ArH ), 7.49 (s, 2H, ArH ), 7.06 (s, 3H, ArH
and CONH ), 4.99 (s, 2H, ArOCH2), 4.89 (d, J¼13.2 Hz,
2H, ArOCH2), 4.39 (br s, 4H, ArOCH2), 3.45e3.41 (m, 4H,
NHCH2), 3.35e3.31 (m, 2H, NHCH2), 3.14 (br s, 2H,
NHCH2), 1.62e1.58 (m, 8H, CH2CH2CH3), 1.33 (br s, 18H,
C(CH3)3 and 8H, CH2CH3), 1.05 (s, 18H, C(CH3)3), 0.94 (br
s, 9H, CH3), 0.77 (br s, 3H, CH3). FAB-MS: m/z¼1171
[Mþþ1, 100%].
4.3.14. Compound 7b (partial cone)
Method B (a), reaction time: 4.5 h, white solid (0.47 g,
45%) purified by column chromatography (chloroform/ethyl
acetate 9.6:0.4), Rf¼0.72. Mp 203 ꢁC (decomp.). IR (KBr,
n/cmꢀ1): 3328, 1757, 1663. Anal. Calcd for C60H82NO10S4:
C, 64.37; H, 7.38; N, 2.50. Found: C, 64.47; H, 7.40; N,
2.49. 1H NMR (300 MHz, CDCl3) dH 8.35 (t, J¼11.7 Hz,
2H, CONH ), 7.77 (s, 2H, ArH ), 7.588 (s, 2H, ArH ),
7.582 (s, 2H, ArH ), 7.03 (s, 2H, ArH ), 4.95 (d, J¼15.3 Hz,
2H, ArOCH2), 4.76 (s, 2H, ArOCH2), 4.51 (d, J¼15.6 Hz, 2H,
ArOCH2), 4.33 (s, 2H, ArOCH2), 4.25 (q, J¼6.9 Hz, 2H,
OCH2CH3), 4.08 (q, J¼7.2 Hz, 2H, OCH2CH3), 3.54e3.43
(m, 2H, CONHCH2), 3.26e3.15 (m, 2H, CONHCH2), 1.57e
1.52 (m, 4H, NHCH2CH2CH2), 1.43e1.36 (m, 4H,
NHCH2CH2CH2), 1.35 (s, 9H, C(CH3)3), 1.33 (s, 9H,
C(CH3)3), 1.12 (t, J¼7.2 Hz, 6H, CH3), 1.05 (s, 18H,
C(CH3)3), 0.92 (t, J¼7.2 Hz, 6H, CH3); 13C-DEPT 135
NMR (75 MHz, CDCl3) d (ppm): 135.4, 135.1, 134.9, 134.4
(aromatic CH), 74.7, 69.8, 65.8, 61.2, 61.0 (ArOCH2 and
OCH2CH3), 39.4 (NHCH2), 32.1 (NHCH2CH2), 31.7, 31.5,
31.4 (C(CH3)3), 20.6 (CH2CH3), 14.7, 14.4, 14.1 (CH2CH3).
FAB-MS: m/z¼1117 [Mþꢀ1, 100%].
4.3.17. Compound 8b (partial cone)
Method B (a), reaction time: 4.5 h, white solid (0.46 g,
42%) purified by column chromatography (chloroform/ethyl
acetate 9.8:0.2), Rf¼0.70. Mp 130 ꢁC. IR (KBr, n/cmꢀ1):
3332, 1759, 1668. Anal. Calcd for C64H90N2O10S4: C,
65.38; H, 7.72; N, 2.38. Found: C, 65.54; H, 7.73; N, 2.38.
1H NMR (300 MHz, CDCl3) dH 8.32 (br t, 2H, CONH ),
7.78 (s, 2H, ArH ), 7.57 (s, 2H, ArH ), 7.56 (s, 2H, ArH ),
7.03 (s, 2H, ArH ), 4.95 (d, J¼15.3 Hz, 2H, ArOCH2), 4.76
(s, 2H, ArOCH2), 4.50 (d, J¼15.3 Hz, 2H, ArOCH2), 4.33
(s, 2H, ArOCH2), 4.29 (q, J¼7.2 Hz, 2H, OCH2CH3), 4.07
(q, J¼7.0 Hz, 2H, OCH2CH3), 3.51e3.45 (m, 2H, NHCH2),
3.22e3.15 (m, 2H, NHCH2), 1.64e1.60 (m, 8H,
NHCH2(CH2)2), 1.34 (s, 9H, C(CH3)3), 1.33 (s, 9H,
C(CH3)3), 1.31e1.24 (m, 8H, (CH2)2CH3 and 3H, eCH3),
1.11 (t, J¼7.0 Hz, 3H, CH3), 1.05 (s, 18H, C(CH3)3), 0.86
(br t, 6H, CH3); 13C-DEPT 135 NMR (75 MHz, CDCl3)
d (ppm): 135.0, 134.8, 134.5, 133.9 (aromatic CH), 74.3,
69.4, 65.4, 60.7, 60.5 (ArOCH2 and OCH2CH3), 39.2
(NHCH2), 31.5 (NHCH2CH2), 31.3, 31.2, 31.0 (C(CH3)3),
29.6, 26.7, 22.5 (CH2CH2CH2CH3), 14.2, 14.0, 13.9
(CH2CH3). FAB-MS: m/z¼1174 [Mþ, 100%].
4.3.15. Compound 7c (partial cone)
Method B (a), reaction time: 4.5 h, white solid (0.22 g,
21%) puirified by column chromatography (chloroform/ethyl
acetate 9.6:0.4), Rf¼0.56. Mp 224 ꢁC (decomp.). IR (KBr,
n/cmꢀ1): 3327, 1753, 1663. Anal. Calcd for C62H87N3O9S4:
C, 64.94; H, 7.65; N, 3.66. Found: C, 65.08; H, 7.66; N,
4.3.18. Compound 8c (partial cone)
1
3.66. H NMR (300 MHz, CDCl3) dH 8.69 (t, J¼5.7 Hz, 1H,
Method B (a), reaction time: 6 h, white solid (0.18 g, 16%)
purified by column chromatography (chloroform/ethyl acetate
9.6:0.4), Rf¼0.53. Mp 169 ꢁC (decomp.). IR (KBr, n/cmꢀ1):
3324, 1753, 1661. Anal. Calcd for C68H99N3O9S4: C, 66.36;
H, 8.11; N, 3.41. Found: C, 66.51; H, 8.10; N, 3.43. 1H
NMR (300 MHz, CDCl3) dH 8.67 (br s, 1H, CONH ), 8.16
(br s, 2H, CONH ), 7.82 (s, 2H, ArH ), 7.58 (s, 2H, ArH ),
7.46 (s, 2H, ArH ), 7.03 (br s, 2H, ArH ), 5.02 (s, 2H,
ArOCH2), 4.99 (d, J¼15.2 Hz, 2H, ArOCH2), 4.46 (d,
J¼15.2 Hz, 2H, ArOCH2), 4.33 (s, 2H, ArOCH2), 4.06 (q,
J¼7.0 Hz, 2H, OCH2CH3), 3.51e3.44 (m, 4H, NHCH2),
CONH ), 8.17 (t, J¼5.4 Hz, 2H, CONH ), 7.83 (s, 2H, ArH ),
7.59 (s, 2H, ArH ), 7.47 (d, 2H, ArH ), 7.03 (d, 2H, ArH ),
5.03 (s, 2H, ArOCH2), 4.99 (d, J¼15.3 Hz, 2H, ArOCH2),
4.46 (d, J¼15.3 Hz, 2H, ArOCH2), 4.41 (s, 2H, ArOCH2),
4.09 (q, J¼7.2 Hz, 2H, OCH2CH3), 3.56e3.41 (m, 4H,
NHCH2), 3.27e3.16 (m, 2H, NHCH2), 1.74e1.61 (m, 6H,
NHCH2CH2), 1.45e1.38 (m, 6H, NHCH2CH2CH2), 1.35 (s,
9H, C(CH3)3), 1.34 (s, 9H, C(CH3)3), 1.12 (t, J¼6.9 Hz, 3H,
CH3), 1.03 (s, 18H, C(CH3)3), 0.93 (t, J¼7.2 Hz, 9H, CH3);
13C-DEPT 135 NMR (75 MHz, CDCl3) d (ppm): 136.2,