M.R. Banday et al. / European Journal of Medicinal Chemistry 45 (2010) 1459–1464
1463
JH ꢃH ¼ 2:8 Hz, HZC]CH–), 4.93 (dd, 1H, JH ꢃH ¼ 16:9 Hz,
36.43, 36.24, 36.05, 35.87, 34.76, 31.97, 31.05, 29.25, 29.21, 29.11,
28.80, 28.31, 28.09, 27.88, 26.78, 25.09, 24.36, 23.89, 22.92, 22.65,
21.09, 19.41, 18.78, 11.91.; ESI-MS found [M þ Na]þ 571.74; C38H64O3
[M þ Na]þ requires 591.57.
Z
E
E
JH ꢃH ¼ 2:8 Hz, HEC]CH–), 4.61 (m, 1H, C3b–H), 2.351–1.07 (br m,
E
Z
44H),1.01 (s, 3H, C10–CH3), 0.90 (d, 3H, J ¼ 6.5 Hz, C20–CH3), 0.86 (dd,
6H, J ¼ 6.6 Hz C25–(CH3)2), 0.67 (s, 3H, C13–CH3). 13C NMR (CDCl3, dC):
173.41, 139.77, 139.27, 122.67, 114.23, 73.75, 56.74, 56.17, 50.06, 42.37,
37.78, 39.59, 38.22, 37.06, 36.66, 36.25,35.88, 34.78, 33.89, 31.97,
31.91, 29.38, 29.30, 29.17, 29.15, 28.97, 28.32, 28.10, 27.88, 25.13,
24.36, 23.90, 22.92, 22.66, 21.10, 19.41, 18.79, 11.93; ESI-MS found
[M þ Na]þ 574.41; C38H64O2 [M þ Na]þ requires 575.35.
6.2.6. 3b
-Cholesteryloctadec-90-(Z)-enoate (12)
Viscous pale-yellow oil; Rf ¼ 0.70 (n-hexane/ethyl acetate,1:1 v/v,
as developer), isolated yield, 80%. IR (KBr, cmꢃ1): 2930, 2852, 1737,
1463; 1H NMR (CDCl3, dH): 5.36 (d, 1H, J ¼ 4.8 Hz, C6–H), 5.33 (m, 2H,
0
0
C9 H]C10 H), 4.62 (m, 1H, C3b–H), 2.31–1.07 (br m, 53H,), 1.01 (s, 3H,
-Cholesteryl-100,110-dibromo-undecanoate (8)
C10–CH3), 0.90 (d, 3H, J ¼ 6.5 Hz, C20–CH3), 0.88(dist. t, 3H, C18 H3),
0
6.2.2. 3
b
Off-white solid; Rf ¼ 0.77 (n-hexane/ethyl acetate, 1:1 v/v, as
developer), isolated yield, 94%. m.p, 84 ꢁC. IR (KBr, cmꢃ1): 2940,
2853, 1732, 1464; 1H NMR (CDCl3, dH): 5.36 (d, 1H, J ¼ 4.8 Hz, C6–H),
0.85 (dd, 6H, J ¼ 6.6 Hz C25–(CH3)2), 0.67 (s, 3H, C13–CH3). 13C NMR
(CDCl3, dC): 170.42, 139.77, 139.27, 127.67, 124.23, 88.10, 47.26, 44.89,
42.70, 42.50, 42.37, 39.78, 39.59, 37.22, 37.06, 36.40, 36.15, 36.09,
36.01, 35.88, 35.71, 34.78, 33.89, 31.97, 31.91, 29.38, 29.30, 29.17,
29.15, 28.97, 28.32, 28.10, 27.88, 25.13, 24.36, 24.08, 23.83, 22.89,
22.69, 22.63, 21.31, 20.18,19.41,18.66,14.21.; ESI-MS found [M þ Na]þ
674.03; C45H78O2 [M þ Na]þ requires 673.42.
0
4.61 (m, 1H, C3b–H), 4.16 (m, 1H, C10 –H), 3.85 (dd, 2H, J ¼ 10.0 Hz,
0
J ¼ 2.4 Hz, C11 –H2), 2.31–1.07 (br m, 44H),1.04 (s, 3H, C10–CH3), 0.94
(d, 3H, J ¼ 6.6 Hz, C20–CH3), 0.85 (dd, 6H, J ¼ 6.6 Hz C25–(CH3)2), 0.67
(s, 3H, C13–CH3). 13C NMR (CDCl3, dC): 173.37, 139.75, 122.68, 73.77,
56.73, 56.16, 53.20, 50.05, 42.36, 39.77, 39.58, 38.22, 37.05, 36.66,
36.43, 36.24, 36.05, 35.87, 34.76, 31.97, 31.05, 29.25, 29.21, 29.11,
28.80, 28.31, 28.09, 27.88, 26.78, 25.09, 24.36, 23.89, 22.92, 22.65,
21.09, 19.41, 18.78, 11.93.; ESI-MS found [M þ Na]þ 733.78/735.76/
737.69; C38H64O2Br2 [M þ Na]þ requires 733.35/735.35/737.35.
6.2.7. 3b
-Cholesteryl-120-(R)-hydroxyoctadec-90-(Z)-enoate (13)
Viscous colorless oil; Rf ¼ 0.67 (n-hexane/ethyl acetate, 1:1 v/v,
as developer), isolated yield, 75%. IR (nujol, cmꢃ1): 3452, 2935,
2863,1737,1463; 1H NMR (CDCl3, dH) 5.41 (m, 2H, C9 H]C10 H), 5.36
(d, 1H, J ¼ 4.6 Hz, C6–H), 4.87 (m, 1H, OH, D2O exchangeable), 4.61
0
0
-cholesteryl-undec-100-enoate (9)
(m, 1H, C3b–H), 3.61 (m, 1H, C12 H–OH), 2.31–1.04 (br m, 51H,), 1.01
0
6.2.3. 5a,6
b
-Dibromo-3
b
White amorphous compound; Rf ¼ 0.78 (n-hexane/ethyl acetate,
1:1 v/v, as developer), isolated yield, 90%. m.p, 82 ꢁC. IR (KBr, cmꢃ1):
2932, 2850, 1738, 1466; 1H NMR (CDCl3, dH): 5.73 (tdd, 1H,
JHꢃ90CH ¼ 6:7 Hz, JHꢃH ¼ 10:1 Hz, JHꢃH ¼ 16:9 Hz, CH2]CH–),
(s, 3H, C10–CH3), 0.94 (d, 3H, J ¼ 6.5 Hz, C20–CH3), 0.89 (dist. t, 3H,
0
C18 H3), 0.85 (dd, 6H, J ¼ 6.6 Hz C25–(CH3)2), 0.67 (s, 3H, C13–CH3).
13C NMR (CDCl3, dC): 170.42, 139.77, 139.27, 127.67, 124.23, 77.10,
68.5, 47.46, 44.39, 42.20, 42.10, 42.07, 39.75, 39.59, 37.21, 37.06,
36.43, 36.25, 36.19, 36.11, 35.83, 35.72, 34.75, 33.39, 31.91, 29.38,
29.33, 29.17, 29.15, 28.37, 28.22, 28.10, 27.33, 25.13, 24.46, 24.18,
23.83, 22.89, 22.69, 22.63, 21.31, 20.18, 19.41, 18.66, 13.67.; ESI-MS
found [M þ Na]þ 690.07; C45H78O3 [M þ Na]þ requires 689.42.
2
Z
E
4.95 (dd, 1H, JH ꢃH ¼ 10:1 Hz, JH ꢃH ¼ 2:8 Hz, HZC]CH), 4.88 (dd,
Z
Z
E
1H, JH ꢃH ¼ 16:9 Hz, JH ꢃH ¼ 2:8 Hz, HEC]CH–), 4.75 (m, 1H, C3b
–
E
E
Z
H), 3.63 (t, 1H, J ¼ 4.8 Hz, C6–H), 2.23–1.07 (br m, 44H,), 1.01 (s, 3H,
C10–CH3), 0.82 (t, 3H, J ¼ 6.6 Hz, C20–CH3), 0.79 (dd, 6H, J ¼ 6.4 Hz
C25–(CH3)2), 0.63 (s, 3H, C13–CH3). 13C NMR (CDCl3, dC): 173.27,
139.25, 114.23, 88.19, 71.79, 56.20, 56.10, 55.17, 47.21, 42.72, 41.98,
41.90, 39.61, 39.54, 37.24, 36.54, 36.16, 35.81, 34.61, 33.86, 31.03,
30.84, 29.35, 29.26, 29.12, 28.94, 28.22, 28.07, 26.27, 25.04, 24.09,
23.84, 22.89, 22.63, 21.32, 20.21, 18.71, 12.25. ESI-MS found
[M þ Na]þ 733.75/735.79/737.76; C38H63O2Br2 [M þ Na]þ requires
733.35/735.35/737.35.
6.2.8. 3b
-Cholesteryl-90-(R)-hydroxyoctadec-120-(Z)-enoate (14)
Viscous colorless oil; Rf ¼ 0.8 (n-hexane/ethyl acetate, 1:1 v/v, as
developer), isolated yield, 98%. IR (nujol, cmꢃ1): 3449, 2922, 2859,
1737, 1466; 1H NMR (CDCl3, dH) 5.40 (m, 2H, C11 H]C12 H), 5.33
(d, 1H, J ¼ 4.8 Hz, C6–H), 4.64 (m, 1H, OH, D2O exchangeable), 4.57
0
0
0
(m, 1H, C3b–H), 3.60 (m, 1H, C9 H–OH,), 2.31–1.07 (br m, 51H,), 1.01
(s, 3H, C10–CH3), 0.92 (d, 3H, J ¼ 6.5 Hz, C20–CH3), 0.88 (dist. t, 3H,
,100,110-Tetrabromo-3
b
-cholesteryl-undecanoate (10)
C18 H3), 0.85 (dd, 6H, J ¼ 6.6 Hz C25–(CH3)2), 0.67 (s, 3H, C13–CH3).
0
6.2.4. 5
a
,6
b
Off-white solid; Rf ¼ 0.74 (n-hexane/ethyl acetate, 1:1 v/v, as
developer), isolated yield, 74%. m.p, 88 ꢁC. IR (KBr, cmꢃ1): 2945,
2886, 1732, 1465; 1H NMR (CDCl3, dH): 4.82 (m, 1H, C3b–H), 4.16 (m,
13C NMR (CDCl3, dC): 170.42, 139.72, 139.19, 127.64, 124.23, 78.33,
67.53, 46.23, 44.77, 42.71, 42.39, 42.37, 39.76, 39.44, 37.22, 37.16,
36.20, 36.15, 36.00, 35.88, 35.71, 34.34, 33.99, 31.65, 31.11, 29.38,
29.34, 29.30, 29.06, 29.02, 28.81, 28.32, 28.10, 27.32, 25.33, 24.36,
24.76, 23.13, 22.89, 22.21, 22.13, 21.31, 20.18, 19.41, 14.19.; ESI-MS
found [M þ Na]þ 690.09; C45H78O3 [M þ Na]þ requires 689.42.
0
0
1H, C10 –H), 3.84 (dd, 2H, J ¼ 10.0 Hz, J ¼ 2.4 Hz, C11 –H2), 3.63 (t,1H,
J ¼ 4.8 Hz, C6–H), 2.58–1.07 (br m, 44H,), 1.00 (s, 3H, C10–CH3), 0.90
(d, 3H, J ¼ 6.6 Hz, C20–CH3), 0.85 (dd, 6H, J ¼ 6.6 Hz C25–(CH3)2),
0.64 (s, 3H, C13–CH3). 13C NMR (CDCl3, dC): 173.18, 71.79, 56.19,
56.14, 56.09, 47.26, 44.89, 42.70, 42.50, 39.67, 39.60, 39.53, 39.48,
37.22, 36.52, 36.40, 36.15, 36.09, 36.01, 35.79, 35.71, 34.71, 34.56,
31.64, 31.01, 30.83, 29.23, 29.17, 28.77, 28.05, 26.95, 26.75, 24.99,
23.83, 22.63, 21.41, 18.70, 11.91.; ESI-MS found [M þ Na]þ 891.31/
893.67/895.81/897.73/899.91; C38H63O2Br4 [M þ Na]þ requires
891.35/893.35/895.35/897.35/899.35.
6.3. Pharmacology
Antibacterial activity and antifungal activity of the synthesized
compounds was completed by disk diffusion method and measured
by Halo Zone Test [29,30]. The MIC of synthesized compounds
against bacterial and fungal strains was performed by macro dilution
test and results were observed visually and spectrophotometrically.
6.2.5. 3b
-Cholesteryl-100,110-epoxyundecnoate (11)
White solid; Rf ¼ 0.74 (n-hexane/ethyl acetate, 1:1 v/v, as devel-
oper), isolated yield, 72%. m.p, 94 ꢁC. IR (KBr, cmꢃ1): 2932, 2854,
1732, 1464, 1174; 1H NMR (CDC3l, dH): 5.36 (d, 1H, J ¼ 4.4 Hz, C6–H),
Acknowledgements
The authors thank the chairman, Department of Chemistry,
AMU, Aligarh, for providing necessary facilities and SAIF Panjab
University, Chandigarh for recording the spectra. We thank the
University Grants commission for financial support in part by
a grant from Major Research Project [UGC-Scheme-F. No. 33-263/
2007 (SR)].
0
4.61 (m, 1H, C3b–H), 2.90 (m, 1H, C10 –H), 2.75 (dd, 2H, J ¼ 10.1 Hz,
0
J ¼ 2.6 Hz, C11 –H2), 2.31–1.05 (br m, 44H),1.01 (s, 3H, C10–CH3), 0.95
(d, 3H, J ¼ 6.4 Hz, C20–CH3), 0.85 (dd, 6H, J ¼ 6.6 Hz C25-(CH3)2), 0.67
(s, 3H, C13–CH3). 13C NMR (CDCl3, dC): 173.18, 139.75, 122.68, 73.77,
56.73, 56.16, 53.20, 50.05, 42.36, 39.77, 39.58, 38.22, 37.05, 36.66,