Karpov et al.
vis (CH3CN): λmax (ꢀ) 537 nm (37 100). UV/vis (ether): λmax (ꢀ)
491 nm (32200). Anal. Calcd for C16H16N2O2S (300.38): C,
63.98; H, 5.37; N, 9.33; S, 10.67. Found: C, 63.92; H, 5.31; N,
9.19; S, 10.95.
48.4 (CH2), 66.4 (CH2), 98.0 (CH), 114.3 (Cquat), 118.0 (Cquat),
123.5 (CH), 129.2 (CH), 130.9 (CH), 133.6 (CH), 139.4 (Cquat),
151.4 (Cquat), 152.6 (Cquat). Additional 13C NMR signals for the
minor isomer: δ 43.2 (CH2), 49.1 (CH2), 63.8 (CH2), 65.7 (CH2),
102.9 (CH), 128.8 (CH), 132.8 (CH). EI MS (70 eV, m/z (%)):
341 (M+, 100), 295 (M+ - NO2, 17), 209 (M+ - NO2, - C4H8-
NO, 27), 102 (4-CN - Ph, 11). IR (KBr): ν˜ 1579, 1429, 1303,
1227, 1170, 1110, 1023, 892 cm-1. UV/vis (CH3CN): λmax (ꢀ)
486 nm (21000). UV/vis (ether): λmax (ꢀ) 439 nm (18100). Anal.
Calcd for C17H15N3O3S (341.39): C, 59.81; H, 4.43; N, 12.31;
S, 9.39. Found: C, 59.56; H, 4.38; N, 12.17; S, 9.43.
(E )-D ie t h y l-[2-(5-n it r o t h ie n -2-y l)-1-p h e n y l-v in y l]-
a m in e (5b). E/ Z ) 9:1 (1H NMR, minor diastereomer not
entered). Red brown crystals with a metallic luster, mp 157-
1
158 °C. H NMR (CDCl3, 400 MHz): δ 1.15 (t, J ) 7.1 Hz, 6
H), 3.21 (q, J ) 7.1 Hz, 4 H), 5.63 (s, 1 H), 6.21 (d, J ) 4.6 Hz,
1 H), 7.22-7.26 (m, 2 H), 7.52-7.58 (m, 4 H). 13C NMR (CDCl3,
100 MHz): δ 13.2 (CH3), 44.1 (CH2), 93.1 (CH), 120.7 (CH),
129.00 (CH), 129.1 (Cquat), 129.9 (CH), 130.3 (CH), 130.3 (CH),
134.6 (Cquat), 154.4 (Cquat), 156.9 (Cquat). EI MS (70 eV, m/z
(%)): 302 (M+, 100), 273 (M+ - C2H5, 12), 256 (M+ - NO2,
66). 184 (M+ - NO2, - N(C2H5)2, 27). IR (KBr): ν˜ 1553, 1430,
1288, 1267, 1243, 1122, 1096, 1042 cm-1. UV/vis (CH3CN): λmax
(ꢀ) 533 nm (37100). UV/vis (ether): λmax (ꢀ) 485 nm (27000).
Anal. Calcd for C16H18N2O2S (302.40): C, 63.55; H, 6.00; N,
9.26; S, 10.60. Found: C, 63.20; H, 5.91; N, 9.16; S, 10.64.
(E)-1-[2-(5-Nit r ot h ia zol-2-yl)-1-p h en yl-vin yl]p yr r oli-
d in e (5g). Only the (E)-stereoisomer (1H NMR). Red crystals,
mp 132-133 °C. 1H NMR (CDCl3, 400 MHz): δ 1.80-2.20 (m,
4 H), 3.10-3.60 (m, 4 H), 5.96 (s, 1 H), 7.27-7.30 (m, 2 H),
7.59-7.63 (m, 3 H), 8.19 (s, 1 H). 13C NMR (CDCl3, 100 MHz):
δ 25.2 (CH2), 49.4 (CH2), 95.0 (CH), 127.7 (CH), 130.96 (CH),
130.99 (CH), 134.3 (Cquat), 141.2 (Cquat), 143.7 (CH), 158.5
(Cquat), 174.7 (Cquat). EI MS (70 eV, m/z (%)): 301 (M+, 40),
255 (M+ - NO2, 100), 232 (M+ - N(C2H4)2, 14). IR (KBr): ν˜
1548, 1456, 1264, 1207, 1175, 1108 cm-1. UV/vis (CH3CN): λmax
(ꢀ) 500 nm (17500). UV/vis (ether): λmax (ꢀ) 468 nm (14200).
Anal. Calcd for C15H15N3O3S: C, 59.78; H, 5.02; N, 13.94; S,
10.64. Found: C, 59.89; H, 5.16; N, 13.55.
(E )-4-[2-(5-Nit r ot h ie n -2-yl)-1-p h e n yl-vin yl]m or p h o-
lin e (5c). E/ Z ) 20:1 (1H NMR, minor diastereomer not
entered). Crystals with a green metallic luster, mp 147-148
°C. 1H NMR (CDCl3, 400 MHz): δ 3.07 (t, J ) 4.9 Hz, 4 H),
3.71 (t, J ) 4.9 Hz, 4 H), 5.73 (s, 1 H), 6.33 (d, J ) 4.6 Hz, 1
H), 7.25-7.30 (m, 2 H), 7.48-7.56 (m, 4 H). 13C NMR (CDCl3,
100 MHz): δ 48.1 (CH2), 66.5 (CH2), 96.6 (CH), 122.6 (CH),
128.4 (Cquat), 129.3 (CH), 129.6 (CH), 130.1 (CH), 130.5 (CH),
134.3 (Cquat), 153.8 (Cquat), 155.1 (Cquat). EI MS (70 eV, m/z
(%)): 316 (M+, 100), 270 (M+ - NO2, 28), 184 (M+ - NO2, -
C4H8NO, 44). IR (KBr): ν˜ 1570, 1431, 1298, 1232, 1137, 1111,
1040, 1018 cm-1. UV/vis (CH3CN): λmax (ꢀ) 498 nm (21700).
UV/Vis (ether): λmax (ꢀ) 450 nm (20900). Anal. Calcd for
(E )-4-[2-(5-Nit r op yr id -2-yl)-1-p h e n yl-vin yl]m or p h o-
lin e (5h ). E/ Z ) 13:1 (1H NMR). Orange crystals, mp 109-
1
110 °C. H NMR (CDCl3, 400 MHz): δ 3.06 (t, J ) 4.8 Hz, 4
H), 3.68 (t, J ) 4.9 Hz, 4 H), 5.80 (s, 1 H), 6.10 (d, J ) 9.2 Hz,
1 H), 7.21-7.25 (m, 2 H), 7.32-7.41 (m, 3 H), 7.73 (dd, J )
2.6 Hz, J ) 9.2 Hz, 1 H), 9.06 (d, J ) 2.6 Hz, 1 H). Additional
1H NMR signals for the minor isomer: δ 3.14 (t, J ) 4.9 Hz,
4 H), 3.95 (t, J ) 4.9 Hz, 4 H), 5.41 (s, 1 H), 6.19 (d, J ) 4.5
Hz, 1 H). 13C NMR (CDCl3, 100 MHz): δ 46.7 (CH2), 66.6 (CH2),
104.1 (CH), 120.3 (CH), 128.6 (Cquat), 129.5 (CH), 129.6 (CH),
129.7 (CH), 129.9 (CH), 135.3 (Cquat), 145.1 (CH), 158.4 (Cquat),
164.5 (Cquat). Additional 13C NMR signals for the minor
isomer: δ 43.3 (CH2), 63.9 (CH2), 94.2 (CH), 126.1 (CH), 128.6
(CH), 130.8 (CH). EI MS (70 eV, m/z (%)): 311 (M+, 55), 265
(M+ - NO2, 16), 225 (M+ - C4H8NO, 100), 179 (M+ - NO2, -
C4H8NO, 62). IR (KBr): ν˜ 1581, 1558, 1508, 1337, 1280, 1244,
1198, 1107, 1022 cm-1. UV/vis (CH3CN): λmax (ꢀ) 426 nm
(20400). UV/vis (ether): λmax (ꢀ) 404 nm (23400). Anal. Calcd
for C17H17N3O3 (311.34): C, 65.58; H, 5.50; N, 13.50. Found:
C, 65.64; H, 5.63; N, 13.00.
C
16H16N2O3S (316.38): C, 60.74; H, 5.10; N, 8.85; S, 10.13.
Found: C, 60.38; H, 5.07; N, 8.67; S, 10.54.
(E)-1-[2-(5-Nitr oth ien -2-yl)-1-p h en yl-vin yl]-(2R)-m eth -
oxym eth yl P yr r olid in e (5d ). Only the (E)-stereoisomer (1H
NMR). Deep red oil. 1H NMR (CDCl3, 400 MHz): δ 1.84-1.98
(m, 4 H), 3.07-3.26 (m, 7 H), 3.70-3.76 (m, 1 H), 5.53 (s, 1
H), 6.16 (d, J ) 4.6 Hz, 1 H), 7.14-7.26 (m, 2 H), 7.45-7.50
(m, 4 H). 13C NMR (CDCl3, 100 MHz): δ 22.0 (CH2), 27.4 (CH2),
48.5 (CH2), 57.3 (CH), 58.0 (CH3), 72.1 (CH2), 93.0 (CH), 119.9
(CH), 127.4 (CH), 128.3 (CH), 129.0 (CH), 129.2 (CH), 131.1
(Cquat), 133.9 (Cquat), 152.1 (Cquat), 155.4 (Cquat). EI MS (70 eV,
m/z (%)): 344 (M+, 19), 299 (M+ - CH2OCH3, 86), 267 (M+
-
OCH3, - NO2, 100). IR (KBr): ν˜ 1559, 1435, 1276, 1170, 1120,
1036 cm-1. UV/vis (CH3CN): λmax (ꢀ) 528 nm (24300). UV/vis
(ether): λmax (ꢀ) 485 nm (21000). HRMS calcd for C18H20N2O3S,
344.1190; found 344.1205.
(E,E)-2,5-Bis[2-(5-n itr oth ien -2-yl)-1-dieth ylam in o-vin yl]-
th iop h en e (5i). E,E/ E,Z ) 8:1 (1H NMR, minor diastereomer
not entered). Violet crystals, mp 206-207 °C. 1H NMR (CDCl3,
400 MHz): δ 1.24 (t, J ) 7.0 Hz, 12 H), 3.47 (q, J ) 7.0 Hz, 8
H), 5.78 (s, 2 H), 6.51 (d, J ) 4.5 Hz, 2 H), 7.24 (s, 2 H), 7.64
(d, J ) 4.5 Hz, 2 H). 13C NMR (CDCl3, 100 MHz): δ 13.3 (CH3),
44.6 (CH2), 96.0 (CH), 121.9 (CH), 129.6 (CH), 131.9 (CH),
138.7 (Cquat), 144.0 (Cquat), 145.0 (Cquat), 154.9 (Cquat). EI MS
(70 eV, m/z (%)): 532 (M+, 100), 486 (M+ - NO2, 39). IR
(KBr): ν˜ 1568, 1430, 1290, 1240, 1166, 1195, 1037 cm-1. UV/
Vis (CH3CN): λmax (ꢀ) 518 nm (44100). UV/Vis (ether): λmax
(ꢀ) 485 nm (21000). Anal. Calcd. for C24H28N4O4S3 (532.71): C
54.11, H 5.30, N 10.52, S 18.06. Found: C 53.90, H 5.12, N
10.18, S 17.95.
(E)-1-[2-(5-Nit r ot h ien -2-yl)-1-b u t yl-vin yl]p yr r olid in e
(5e). Only the (E)-stereoisomer (1H NMR). Crystals with a blue
1
metallic luster, mp 100-101 °C. H NMR (CDCl3, 400 MHz):
δ 0.99 (t, J ) 7.0 Hz, 3 H), 1.50-1.64 (m, 4 H), 1.96-2.02 (m,
4 H), 2.62-2.67 (m, 2 H), 3.36-3.46 (m, 4 H), 5.36 (s, 1 H),
6.42 (d, J ) 4.7 Hz, 1 H), 7.73 (d, J ) 4.7 Hz, 1 H). 13C NMR
(CDCl3, 100 MHz): δ 13.8 (CH3), 23.0 (CH2), 25.2 (CH2), 29.0
(CH2), 31.2 (CH2), 48.3 (CH2), 92.6 (CH), 120.3 (CH), 131.1
(CH), 128.2 (Cquat), 155.6 (Cquat), 156.2 (Cquat). EI MS (70 eV,
m/z (%)): 280 (M+, 6), 217 (M+ - NO2, - CH3, - 2H, 100). IR
(KBr): ν˜ 1557, 1442, 1286, 1162, 1126, 1092, 1042 cm-1. UV/
vis (CH3CN): λmax (ꢀ) 545 nm (43700). UV/vis (ether): λmax (ꢀ)
499 nm (20400). Anal. Calcd for C14H20N2O2S (280.39): C,
59.97; H, 7.19; N, 9.99; S, 11.44. Found: C, 59.80; H, 7.08; N,
9.96; S, 11.57.
r a c-2-(5-Nit r ot h ie n -2-ylid e n e )-1,5-d im e t h ylp yr r oli-
d in e (5j). Only the (E)-stereoisomer (1H NMR). Violet crystals,
1
mp 127-128 °C. H NMR (CDCl3, 400 MHz): δ 1.23 (d, J )
6.4 Hz, 3 H), 1.67-1.76 (m, 1 H), 2.24-2.34 (m, 1 H), 2.79-
2.95 (m, 5 H), 3.64-3.72 (m, 1 H), 5.37 (s, 1 H), 6.44 (d, J )
4.8 Hz, 1 H), 7.76 (d, J ) 4.8 Hz, 1 H). 13C NMR (CDCl3, 100
MHz): δ 19.2 (CH3), 29.2 (CH2), 31.1 (CH2), 31.3 (CH3), 60.8
(CH), 87.0 (CH), 119.1 (CH), 131.4 (CH), 141.7 (Cquat), 157.6
(Cquat), 157.8 (Cquat). EI MS (70 eV, m/z (%)): 238 (M+, 100),
223 (M+ - CH3, 62), 208 (M+ - 2CH3, 27), 192 (M+ - NO2,
21), 150 (M+ - 2CH3, - NO2, 19). IR (KBr): ν˜ 1585, 1447, 1325,
1299, 1251, 1168, 1131, 1034 cm-1. UV/vis (CH3CN): λmax (ꢀ)
532 nm (34300). UV/vis (ether): λmax (ꢀ) 487 nm (29200). Anal.
(E)-4-{2-[5-Nit r ot h ien -2-yl]-1-(4-cya n o)p h en yl-vin yl}-
m or p h olin e (5f). E/ Z ) 4:1 (1H NMR). Red crystals, mp 222-
1
223 °C. H NMR (CDCl3, 400 MHz): δ 2.94 (t, J ) 4.9 Hz, 4
H), 3.66 (t, J ) 4.9 Hz, 4 H), 5.70 (s, 1 H), 6.28 (d, J ) 4.6 Hz,
1 H), 7.41 (d, J ) 8.4 Hz, 2 H), 7.51 (d, J ) 4.6 Hz, 1 H), 7.73
(d, J ) 8.4 Hz, 2 H). Additional 1H NMR signals for the minor
isomer: δ 3.18 (t, J ) 4.8 Hz, 2 H), 3.22 (t, J ) 4.9 Hz, 2 H),
3.74 (t, J ) 4.8 Hz, 2 H), 3.96 (t, J ) 4.9 Hz, 2 H), 5.21 (s, 1
H), 5.92 (d, J ) 4.6 Hz, 1 H). 13C NMR (CDCl3, 100 MHz): δ
1510 J . Org. Chem., Vol. 68, No. 4, 2003