European Journal of Organic Chemistry
10.1002/ejoc.201800356
FULL PAPER
29
1
6-(3-Phenyl-2-propenylidene)-5α-androstan-17-one (3e):
3-Methoxy-16-(4-nitro-benzylidene)-estra-1,3,5(10)-triene-17-one (8f)
:
Yield: 98%. Light yellow solid, mp. 142-145 °C,
R
f
:
0.55 (silica,
Yield: 54%. Light yellow solid, mp. 218-219 °C, 0.47 (silica,
toluene/EtOAc 15:1). IR (KBr, (cm )): 2932, 2853, 1717, 1633, 1596,
f
R :
-1
-1
toluene/EtOAc 25:1). IR (KBr, (cm )): 2920, 2847, 1712, 1611, 1590,
1
1
7
=
448, 1279, 1098, 971, 760, 747. H-NMR (CDCl
3
, 500.15 MHz): δ =
1513, 1500, 1461, 1340, 1276, 1257, 1107, 1086, 1053, 1018, 991, 851,
1
.51 (d, J = 7.2 Hz, 2H, 2’,6’-H), 7.38 (t, J = 7.2 Hz, 2H, 3’,5’-H), 7.32 (t, J
7.2 Hz, 1H, 4’-H), 7.13-7.19 (m, 1H, C(O)C=CH-), 6.88-6.98 (m, 2H, Ar-
781, 687. H-NMR (CDCl
3
, 500.15 MHz): δ = 8.30 (d, J = 8.6 Hz, 2H,
3’,5’-H), 7.72 (d, J = 8.6 Hz, 2’,6’-H), 7.50-7.53 (brs, 1H, Ar-CH=), 7.25 (d,
J = 8.6 Hz, 1H, 1-H), 6.75-6.78 (dd, J = 2.4 Hz, 8.6 Hz, 1H, 2-H) 6.69 (d,
CH=, Ar-CH=CH-), 2.76-2.85 (ddd, J = 1.2 Hz, 6.4 Hz, 15.8 Hz, 1H, 15-
), 2.14-2.24 (ddd, J= 2.8 Hz, 12.7 Hz, 15.8 Hz, 1H, 15-H ), 0.76-1.97
m, 20H, ring protons), 0.93 (s, 3H, 19-H ), 0.86 (s, 3H, 18-H
CDCl , 125.78 MHz): δ = 209.7, 140.6, 137.4, 136.6, 132.2, 128.8 (3C),
27.1 (2C), 124.8, 55.0, 49.2, 48.4, 47.1, 38.6, 36.5, 34.7, 31.7, 31.2,
9.0, 28.8, 27.1, 26.8, 22.1, 20.2, 14.5, 12.3. HRMS: calculated for
H
a
b
J = 2.4 Hz, 1H, 4-H), 3.81 (s, 3H, OCH
3
), 1.46-3.06 (m, 13H, ring
13
13
(
(
3
3
). C-NMR
3
protons), 1.05 (s, 3H, 18-H ). C-NMR (CDCl , 125.78 MHz): δ = 208.7,
3
3
157.7, 147.6, 142.0, 140.0, 137.6, 131.8, 130.7 (2C), 130.3, 126.3, 123.9
1
2
(2C), 114.0, 111.7, 55.2, 48.4, 48.0, 44.0, 38.0, 31.7, 29.6, 29.2, 26.9,
+
25.9, 14.5. HRMS: calculated for C26
H
28NO
4
[M+H] 418.2018, found
+
28
C H37O [M+H] 389.2844, found 389.2846.
418.2015.
1
6-(4-Nitro-benzylidene)-5α-androstan-17-one (3f):
3-Methoxy-16-(pyridin-2-ylmethylene)-estra-1,3,5(10)-triene-17-one (8g):
Yield: 43%. Yellow solid, mp. 181-182 °C, R : 0.49 (silica, toluene/EtOAc
5:1). IR (KBr, (cm )): 2995, 2935, 2914, 2844, 1720, 1633, 1610, 1495,
Yield: 77%. Dark yellow solid, mp. 195-196 °C, R : 0.53 (silica, n-
hexane/EtOAc 6:1). IR (KBr, (cm )): 2917, 2859, 1717, 1636, 1595, 1516,
f
f
-
1
-1
1
1
1341, 852, 796. H-NMR (CDCl
2H, 3’,5’-H), 7.68 (d, J = 8.7 Hz, 2H, 2’,6’-H), 7.43-7.47 (brs, 1H, Ar-CH=),
2.84-2.92 (ddd, J = 1.5 Hz, 6.4 Hz, 16.1 Hz, 1H, 15-H ), 2.41-2.51 (ddd, J
= 3.2 Hz, 12.7 Hz, 16.1 Hz, 1H, 15-H ), 0.76-2.03 (m, 20H, ring protons),
0.99 (s, 3H, 19-H ), 0.87 (s, 3H, 18-H
3
, 500.15 MHz): δ = 8.28 (d, J = 8.7 Hz,
3
1462, 1432, 1279, 1259, 1152, 1051, 868, 784, 619. H-NMR (CDCl ,
500.15 MHz): δ = 8.74 (d, J=4.4 Hz, 1H, 6’-H), 7.71-7.76 (m, 1H, 4’-H),
7.49 (d, J = 7.7 Hz, 1H, 3’-H), 7.43-7.46 (brs, 1H, Ar-CH=), 7.22-7.27 (m,
2H, 5’-H, 1-H), 6.74-6.78 (dd, J = 2.4 Hz, 8.6 Hz, 1H, 2-H), 6.69 (d, J =
a
b
13
3
3
). C-NMR (CDCl
3
, 125.78 MHz):
2.4 Hz, 1H, 4-H), 3.81 (s, 3H, OCH
(m, 12H, ring protons), 1.02 (s, 3H, 18-H
3
), 3.42-3.51 (m, 1H, 15-H
a
), 1.43-3.04
13
δ = 209.1, 147.5, 142.1, 140.4, 130.6 (2C), 129.9, 123.9 (2C), 54.9, 49.4,
3
). C-NMR (CDCl , 125.78
3
4
1
4
7.8, 47.0, 38.6, 36.5, 34.8, 31.7, 31.2, 29.4, 29.0, 28.7, 26.7, 22.1, 20.1,
MHz): δ = 210.1, 157.6, 155.1, 149.9, 140.4, 137.8, 136.3, 132.2, 130.9,
+
4.5, 12.3. HRMS: calculated for C26
H
34NO
3
[M+H] 408.2539, found
126.7, 126.3, 122.8, 113.9, 111.6, 55.2, 48.3, 48.0, 44.1, 38.1, 31.7, 29.7,
+
08.2533.
29.6, 26.9, 26.0, 14.6. HRMS: calculated for C25
H28NO
2
[M+H] 374.2120,
found 374.2115.
16-(Pyridin-2-ylmethylene)-5α-androstan-17-one (3g):
Yield: 75%. Pale brown solid, mp. 145-147 °C, R
hexane/EtOAc 6:1). IR (KBr, (cm )): 2922, 2849, 1717, 1638, 1585, 1565,
f
: 0.29 (silica, n-
3-Methoxy-16-(thien-2-ylmethylene)-estra-1,3,5(10)-triene-17-one (8h):
Yield: 52%. Light yellow solid, mp. 178-179 °C, 0.41 (silica,
-
1
f
R :
1
-1
1
4
7
7
2
2
467, 1451, 1081, 785. H-NMR (CDCl
3
, 500.15 MHz): δ = 8.72 (d, J =
toluene/EtOAc 25:1). IR (KBr, (cm )): 3110, 2972, 2920, 2858, 2844,
2821, 1708, 1615, 1503, 1464, 1449, 1417, 1376, 1316, 1235, 1187,
.1 Hz, 1H, 6’-H), 7.69-7.75 (td, J = 1.6 Hz, 7.7 Hz, 1H, 4’-H), 7.46 (d, J =
.7 Hz, 1H, 3’-H), 7.38-7.42 (m, 1H, Ar-CH=), 7.19-7.24 (dd, J = 4.1 Hz,
1
1166, 1102, 1086, 1034, 905, 863, 852, 822, 787, 717, 582, 517. H-
.7 Hz, 1H, 5’-H), 3.26-3.34 (ddd, J = 1.4 Hz, 6.3 Hz, 16.8 Hz, 1H, 15-H
.43-2.53 (ddd, J = 3.1 Hz, 12.9 Hz, 16.8 Hz, 1H, 15-H ), 0.76-2.01 (m,
0H, ring protons), 0.97 (s, 3H, 19-H ), 0.86 (s, 3H, 18-H
, 125.78 MHz): δ = 210.5, 155.2, 149.9, 140.7, 136.2, 130.6, 126.4,
22.7, 55.0, 49.3, 47.8, 47.1, 38.6, 36.6, 34.9, 31.7, 31.3, 29.7, 29.0,
8.8, 26.8, 22.2, 20.2, 14.5, 12.3. HRMS: calculated for C25
a
),
3
NMR (CDCl , 500.15 MHz): δ = 7.65-7.72 (brs, 1H, Ar-CH=), 7.55 (d, J =
4.3 Hz, 1H, 5’-H), 7.35-7.41 (brs, 1H, 3’-H), 7.25 (d, J = 8.4 Hz, 1H, 1-H),
7.14-7.19 (m, 1H, 4’-H), 6.73-6.80 (m, 1H, 2-H), 6.67-6.73 (brs, 1H, 4-H),
b
13
3
3
). C-NMR
(
CDCl
3
3.82 (s, 3H, Ar-OCH
3
), 1.44-3.10 (m, 13H, ring protons), 1.00 (s, 3H, 18-
13
1
2
[
3
H ). C-NMR (CDCl , 125.78 MHz): δ = 209.3, 157.7, 140.0, 137.7,
3
H34NO
133.7, 132.4, 132.1, 129.6, 127.9, 126.3, 125.9, 114.0, 111.6, 55.2, 48.4,
+
M+H] 364.2640, found 364.2643.
48.2, 44.1, 38.0, 31.7, 29.7, 28.9, 26.9, 26.0, 14.7. HRMS: calculated for
+
C
24
H
27
O
2
S [M+H] 379.1732, found 379.1734.
1
6-(Thien-2-ylmethylene)-5α-androstan-17-one (3h):
2
3
Yield: 70%. Light yellow solid, mp. 157-160 °C, R : 0.63 (silica, n-
hexane/EtOAc 6:1). IR (KBr, (cm )): 2965, 2939, 2916, 2887, 2849, 1713,
f
16-Benzylidene-estra-1,3,5(10)-triene-17-one (10a)
Yield: 96%. White solid, mp. 248-250 °C, R : 0.49 (silica, toluene/EtOAc
5:1). IR (KBr, (cm )): 3361, 2933, 2918, 2874, 2853, 1703, 1611, 1505,
:
-
1
f
1
-1
1
(
619, 1451, 1280, 1259, 1246, 1097, 1016, 905, 832, 697. H-NMR
CDCl , 500.15 MHz): δ = 7.61-7.65 (brs, 1H, Ar-CH=), 7.52 (d, J = 4.9
Hz, 1H, 5’-H), 7.34 (d, J = 3.5 Hz, 1H, 3’-H), 7.14 (dd, J= 3.5 Hz, 4.9 Hz,
1
3
3
1491, 1456, 1216, 728, 694, 514. H-NMR (CDCl , 500.15 MHz): δ =
7.59 (d, J =7.4 Hz, 2H, 2’,6’-H), 7.49-7.53 (m, 1H, Ar-CH=), 7.43-7.49 (m,
2H, 3’,5’-H), 7.37-7.43 (m, 1H, 4’-H), 7.20 (d, J = 8.4 Hz, 1H, 1-H), 6.66-
6.72 (m, 1H, 2-H), 6.61-6.66 (brs, 1H, 4-H), 4.86-5.09 (brs, 1H, OH),
3 3
1.23-3.08 (m, 13H, ring protons), 1.04 (s, 3H, 18-H ). C-NMR (CDCl ,
1
2
H, 4’-H), 2.85-2.93 (ddd, J = 1.3 Hz, 6.6 Hz, 15.9 Hz, 1H, 15-H
.32 (ddd, J = 2.7 Hz, 12.4 Hz, 15.9 Hz, 1H, 15-H ), 0.78-1.97 (m, 20H,
), 0.87 (s, 3H, 18-H
a
), 2.23-
b
13
13
ring protons), 0.95 (s, 3H, 19-H
3
3
). C-NMR (CDCl
3
,
1
4
2
3
25.78 MHz): δ = 209.8, 140.1, 134.1, 132.1, 129.5, 127.8, 125.5, 55.0,
125.78 MHz): δ = 209.8, 153.6, 137.9, 136.0, 135.6, 133.4, 132.1, 130.3
9.4, 48.1, 47.1, 38.6, 36.6, 34.7, 31.7, 31.3, 29.1, 29.0, 28.8, 26.8, 22.1,
(2C), 129.3, 128.7 (2C), 126.5, 115.3, 112.9, 48.7, 47.9, 44.1, 38.0, 31.7,
+
+
0.2, 14.7, 12.3. HRMS: calculated for C24
H
33OS [M+H] 369.2252, found
26 2
29.5, 29.1, 26.8, 26.0, 14.6. HRMS: calculated for C25H O Na [M+Na]
69.2253.
381.1831, found 381.1832.
2
3
3
-Methoxy-16-benzylidene-estra-1,3,5(10)-triene-17-one (8a):
0.53 (silica,
toluene/EtOAc 15:1). IR (KBr, (cm )): 2975, 2921, 2856, 2842, 1711,
16-(Thien-2-ylmethylene)-estra-1,3,5(10)-triene-17-one (10h) :
Yield: 93%. Light yellow solid, mp. 158-159 °C,
R
f
:
f
Yield: 84%. Pale yellow solid, mp. 260-261 °C, R : 0.46 (silica,
-1
toluene/EtOAc 5:1).
1
1
8
7
3
6
3
626, 1608, 1502, 1448, 1316, 1247, 1235, 1187, 1166, 1089, 1034, 943,
65, 822, 773, 687, 521. H-NMR (CDCl
.4 Hz, 2H, 2’,6’-H), 7.49-7.54 (brs, 1H, Ar-CH=), 7.46 (t, J = 7.4 Hz, 2H,
’,5’-H), 7.40 (t, J = 7.4 Hz, 1H, 4’-H), 7.26 (d, J = 8.6 Hz, 1H, 1-H), 6.75-
.79 (dd, J = 2.3 Hz, 8.6 Hz, 1H, 2-H), 6.68-6.71 (m, 1H, 4-H), 3.82 (s,
3
H-NMR (CDCl , 500.15 MHz): δ = 7.66-7.72 (brs, 1H, Ar-CH=), 7.55 (d,
J = 4.7 Hz, 1H, 5’-H), 7.38 (d, J = 2.8 Hz, 1H, 3’-H), 7.14-7.23 (m, 2H, 1-
H, 4’-H), 6.66-6.72 (m, 1H, 2-H), 6.61-6.66 (brs, 1H, 4-H), 4.83-4.93 (brs,
1
3
, 500.15 MHz): δ = 7.60 (d, J =
13
1H, OH), 1.24-3.08 (m, 13H, ring protons), 1.00 (s, 3H, 18-H
(CDCl , 125.78 MHz): δ = 209.4, 153.6, 140.0, 138.0, 133.7, 132.4, 132.1,
129.7, 127.9, 126.5, 126.0, 115.3, 112.9, 48.4, 48.2, 44.1, 38.0, 31.7,
3
). C-NMR
3
1
3
H, OCH
3
), 1.44-3.08 (m, 13H, ring protons), 1.04 (s, 3H, 18-H
3
). C-
+
NMR (CDCl
3
, 125.78 MHz): δ = 209.6, 157.7, 137.7, 136.1, 135.7, 133.2,
29.5, 28.9, 26.8, 26.0, 14.7. HRMS: calculated for C23
25 2
H O S [M+H]
132.1, 130.3 (2C), 129.2, 128.7 (2C), 126.3, 114.0, 111.6, 55.2, 48.6,
365.1575, found 365.1573.
4
C
7.9, 44.1, 38.0, 31.7, 29.7, 29.2, 26.9, 26.0, 14.6. HRMS: calculated for
+
H O
26 29 2
[M+H] 373.2168, found 373.2166.
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