M. L. Di Gioia et al. / Tetrahedron Letters 42 (2001) 7413–7415
7415
+
References
TOF MS: calcd for (C H O +H) 345.2066, found
21
28
4
345.2048.
1
2
3
4
5
6
7
. Monder, C.; Bradlow, H. L. Recent Prog. Horm. Res.
Compound 4b. Mp: 166–170°C, IR (KBr): 3416, 1663,
−
1 1
1
980, 36, 345.
. Weiss, G.; Monder, C.; Bradlow, H. L. J. Clin. Endocrinol.
976, 37, 811.
. Singer, C. J.; Iohan, F.; Monder, C. Endocrinology 1986,
19, 1356–1361.
. Beyler, R. E.; Hoffman, F. J. Am. Chem. Soc. 1957, 79,
297.
1640 cm , H NMR l (300 MHz, CDCl
CHO), 5.68 (1H, s, H-4), 5.57 (1H, s, OH-20; disappears in
D O), 1.18 (3H, s, 19-CH ), 0.98 (3H, s, 18-CH ), 2.90–
): 9.52 (1H, s,
3
1
2
3
3
13
0
1
3
2
.90 (25H, m), C NMR l (75 MHz, CDCl ): 199.27,
3
86.02, 170.67, 146.98, 141.88, 123.75, 53.95, 53.57, 46.05,
8.50, 33.45, 34.88, 34.62, 33.73, 32.54, 31.75, 25.02, 24.71,
0.81, 17.11, 15.35, ESI-TOF MS: calcd for (C H O +
1
9
21 28
3
+
H) 329.2117, found 329.2100.
. Herzog, H. L.; Gentles, M. J.; Marshall, H.; Hershberg, E.
B. J. Am. Chem. Soc. 1961, 83, 4073.
. Lewbart, M. L.; Monder, C.; Boyko, W. J.; Singer, C. J.;
Iohan, F. J. Org. Chem. 1989, 54, 1332–1338.
. Selected spectroscopic data:
Compound 5b. Mp: 147–150°C, IR (KBr): 3422, 1666,
−
1 1
1
640 cm , H NMR l (300 MHz, CDCl ): 9.76 (1H, s,
3
CHO), 5.94 (1H, s, OH-20; disappears in D O), 5.75 (1H,
2
s, H-4), 1.23 (3H, s, 19-CH ), 1.12 (3H, s, 18-CH ),
3
3
13
3
1
4
2
.00–0.90 (25H, m), C NMR l (75 MHz, CDCl3):
99.17, 183.72, 170.19, 150.33, 142.79, 123.87, 55.33, 52.94,
5.99, 39.15, 33.45, 34.88, 34.62, 33.69, 32.44, 31.55, 23.80,
Compound 4a. Mp: 149–152°C, IR (KBr): 3520, 3360,
−
1 1
1
670, 1636 cm , H NMR l (300 MHz, CDCl ): 9.57 (1H,
3
s, CHO), 5.69 (1H, s, H-4), 5.63 (1H, s, OH-20; disappears
in D O), 4.45 (1H, m, H-11), 1.47 (3H, s, 19-CH ), 1.25
1.28, 20.31, 17.15, 15.31, ESI-TOF MS: calcd for
2
3
+
(
C H O +H) 329.2117, found 329.2100.
13
21 28
3
(
3H, s, 18-CH ), 2.97–0.99 (24H, m), C NMR l (75
3
Compound 4c. Mp: 188–192°C, IR (KBr): 3422, 1704,
MHz, CDCl ): 199.57, 186.14, 172.07, 146.98, 141.58,
−1 1
3
1
665, 1648 cm , H NMR l (300 MHz, CDCl ): 9.54 (1H,
3
1
3
22.27, 68.47, 56.48, 55.47, 45.38, 44.93, 39.23, 34.72,
s, CHO), 5.70 (1H, s, H-4), 5.65 (1H, s, OH-20; disappears
in D O), 1.39 (3H, s, 19-CH ), 1.19 (3H, s, 18-CH ),
3.73, 32.58, 31.91, 30.80, 24.77, 24.65, 20.91, 17.82, ESI-
2
3
3
+
TOF MS: calcd for (C H O +H) 345.2066, found
13
21
28
4
3.20–0.85 (23H, m), C NMR l (75 MHz, CDCl3):
345.2048.
2
6
08.60, 199.52, 185.67, 168.29, 142.69, 142.14, 124.57,
3.21, 54.03, 53.22, 38.22, 35.47, 34.70, 33.63, 32.15, 32.07,
Compound 5a. Mp: 171–174°C, IR (KBr): 3420, 1654,
−
1 1
1
638 cm , H NMR l (300 MHz, CDCl ): 9.74 (1H, s,
3
29.59, 25.28, 24.55, 17.15, 156.77, ESI-TOF MS: calcd for
+
CHO), 5.86 (1H, s, OH-20; disappears in D O), 5.59 (1H,
2
(C H O +H) 343.1909, found 343.1891.
21
26
4
s, H-4), 4.42 (1H, m, H-11), 1.42 (3H, s, 19-CH ), 1.24
Compound 5c. Mp: 146–149°C, IR (KBr): 3424, 1702,
3
13
−1
1
13
(
3H, s, 18-CH ), 2.75–0.90 (24H, m), C NMR l (75
1664, 1646 cm , H and C NMR analyses were unsuc-
3
MHz, CDCl ): 199.26, 183.84, 171.56, 150.58, 142.69,
cessful because compound decomposed in deuteriochloro-
3
+
1
3
22.43, 65.78, 57.15, 56.07, 52.39, 48.84, 41.31, 34.95,
3.73, 32.46, 31.89, 29.02, 28.70, 27.63, 22.53, 15.19, ESI-
form, ESI-TOF MS: calcd for (C H O +H) 343.1909,
21
26
4
found 343.1891.