10 min) to yield, after purification by column chromatography
on silica gel (hexane–ether 4:1), E-7b (1.6[4] g, 92%). IR (neat)
n 3070, 2980, 1712, 1622, 1447, 1365, 1307, 1175, 1039, 978,
126.91, 128.45, 129.09, 132.01, 132.16, 133.93, 136.þ41, 147.28,
=
172.90 (2 C O); MS (EI, 70 eV) m/z (%) 283 (M , 85), 136
(100). HR-MS found: 283.0663; calcd for C16H13O2NS:
283.0667. Anal. calcd for: C16H13O2NS: C, 67.82; H, 4.62;
N, 4.94; found: C. 68.12; H, 4.62; N, 4.89%.
859, 652 cmꢂ1 1H NMR (270 MHz, CDCl3) d 1.31 (t, 3H,
;
3J 6.9 Hz, OCH2CH3), 1.74 (m, 4H), 2.27 (m, 2H), 2.69 (m,
3
3
2H), 4.23 (q, 2H, J 6.9 Hz, OCH2), 5.91 (d, 1H, J 15.8 Hz),
7.87 (d, 1H, 3J 15.8 Hz); 13C NMR (67.9 MHz, CDCl3) d
14.29, 21.82, 24.30, 27.17, 38.15, 60.41, 118.87, 131.21, 132.70,
144.29, 167.08; MS (EI, 70 eV) m/z (%) 260 ([81Br]Mþ, 14),
258 ([79Br]Mþ, 14), 215 ([81Br]Mþ ꢂ C2H5O, 10), 213
([79Br]Mþ ꢂ C2H5O, 10), 179 (91), 151 (100). HR-MS found:
258.0253; calcd for C11H15O792Br: 258.0255. Anal. calcd for:
C11H15O2Br: C, 50.98; H, 5.83; found: C. 50.95; H, 5.80%.
8g–b. IR (KBr) n 3064, 2916, 1764, 1699, 1633, 1495, 1391,
1161, 1135, 902, 803, 754, 698 cmꢂ1
;
1H NMR (270 MHz,
4
CDCl3) d 2.51 (s, 3H, CH3), 3.61 (d, 2H, J 1.5 Hz), 6.78 (d,
1H, 3J 3.7 Hz), 7.06 (d, 1H, 4J 1.5 Hz), 7.33–7.52 (m, 6H);
13C NMR (67.8 MHz, CDCl3) d 15.58, 36.14, 115.67, 125.77,
126.60, 126.90, 128.33, 129.07, 132.35, 135.15, 136.þ91, 148.57,
=
172.83 (2 C O); MS (EI, 70 eV) m/z (%) 283 (M , 69), 136
(100). HR-MS found: 283.0668; calcd for C16H13O2NS:
283.0667.
Ethyl 3-(20-bromocyclopent-10-enyl)acrylate (E-7d). 6d (1.02
g, 5.82 mmol) and 2b (2.55 g, 7.31 mmol) were reacted (10
min, 100 ꢀC) to yield, after purification by column chromato-
graphy on silica gel (hexane–ether 4:1), E-7d (1.07 g, 75%). IR
(neat) n 2976, 2848, 1712, 1628, 1365, 1304, 1167, 1083, 1040,
Methyl 3-(Z)-(50-methylthien-20-yl)-2-phenylacrylate (8e–a).
A mixture of 1s (874 mg, 6.9 mmol) and 2g (3.5 g, 8.5 mmol)
was placed into a 30 mL Erlenmeyer flask (borosilicate, nar-
row-mouthed, top covered with Saran Wrap1 [polyvinylidene
chloride]) and was irradiated for 3 min in a microwave oven
at 500 W. The mixture was transferred to silica gel and sub-
mitted to column chromatography (hexane–ether 3:1) to yield
8e–a (0.23 g, 13%). IR (neat) n 3058, 2948, 1707, 1612, 1450,
1206, 1165 cmꢂ1;1H NMR (270 MHz, CDCl3) d 2.24 (s, 3H,
CH3), 3.68 (s, 3H, COOCH3), 6.52 (d, 1H, 3J 3.6 Hz), 6.90
1
3
979, 858 cmꢂ1; H NMR (270 MHz, CDCl3) d 1.32 (t, 3H, J
7.2 Hz, CH3), 2.00–2.06 (m, 2H), 2.45–2.52 (m, 2H), 2.79–2.84
(m, 2H), 4.23 (q, 2H, 3J 7.2 Hz), 5.84 (d, 1H, 3J 15.8 Hz), 7.57
3
(d, 1H, J 15.8 Hz); 13C NMR (67.9 MHz, CDCl3) d 14.23,
21.51, 31.00, 41.43, 60.47, 120.90, 130.03, 136.86, 137.74,
166.99; MS (EI, 70 eV) m/z (%) 246 [81Br]Mþ, 15), 244 ([79Br]
Mþ, 15), 201 ([81Br]Mþ ꢂ C2H5O, 9), 199 ([79Br]Mþ ꢂ C2H5O,
11), 165 (48), 137 (100). HR-MS found: 244.0091; calcd for
C10H13O279Br: 244.0099.
3
(d, 1H, J 3.6 Hz), 7.17 (m, 2H), 7.36 (m, 3H), 7.89 (s, 1H);
13C NMR (67.8 MHz, CDCl3) d 15.55, 52.20, 125.17, 127.67,
128.34, 129.00, 130.05, 134.11, 134.34, 135.38, 136.59, 146.04,
168.19; MS (EI, 70 eV) m/z (%) 258 (Mþ, 100); 199 (Mþ ꢂ
C3H7O, 53); 184 (Mþ ꢂ C3H6O2 , 31), 165 (14), 141 (33).
HR-MS found: 258.0712; calcd for C15H14O2S: 258.0715.
Anal. calcd for: C15H14O2S: C, 69.74; H, 5.46; found: C.
69.56; H, 5.32%.
(Z)- and (E)-3-ethoxycarbonyl-4-(50-methylthien-20-yl)but-3-
enoic acid (8d–a and 8d–b). 1s (0.87 g, 6.9 mmol) and 2e
(3.49 g, 8.6 mmol) were reacted (100 ꢀC, 15 min) to give, after
purification by column chromatography (ether–CHCl3 2:1),
8d–a (545 mg, 31%) and 8d–b (68 mg, 4%).
8d–a. IR (KBr) n 3500–2800, 1697 (v br), 1455, 1092, 930, 676,
1
574, 551, 517, 461 cmꢂ1; H NMR (270 MHz, CDCl3) d 1.32
(t, 3H, J 6.9 Hz, OCH2CH3), 2.51 (s, 3H, CH3), 3.77 (s, 2H,
3
3
3
CH2), 4.27 (q, 2H, J 6.9 Hz, OCH2CH3), 6.77 (d, 1H, J 3.6
Hz), 7.13 (d, 1H, 3J 3.6 Hz), 7.26 (s, 1H), 10.31 (br s, 1H,
COOH); 13C NMR (67.9 MHz, CDCl3) d 14.20, 15.58, 33.62,
61.22, 119.57, 126.15, 133.56, 134.79, 135.51, 145.44, 167.69,
176.66; MS (FAB, 3-nitrobenzyl alcohol) m/z (%) 255
(MHþ, 75), 209 (Mþ ꢂ C2H5O, 100), 181 (62), 136 (34). HR-
MS (FAB) found: 255.0689; calcd for C12H15O4S (MHþ):
255.0691.
References
1
2
K. Tanaka and F. Toda, Chem. Rev., 2000, 100, 1025.
(a) A. Loupy, L. Perreux, M. Liagre, K. Burle and M. Moneuse,
Pure Appl. Chem., 2001, 73, 161; (b) H. E. Blackwell, Org. Biomol.
Chem., 2003, 1, 1251.
3
4
F. Toda and H. Akai, J. Org. Chem., 1990, 55, 3446.
W. Liu, Q. Xu, Y. Ma, Y. Liang, N. Dong and D. Guan,
J. Organomet. Chem., 2001, 625, 128.
1
3
8d–b. H NMR (270 MHz, CDCl3) d 1.27 (t, 3H, J 7.2 Hz,
5
(a) C. Xu, G. Chen, C. Fu and X. Huang, Synth. Commun., 1995,
25, 2229; (b) C. Xu, G. Chen and X. Huang, Org. Prep. Proced.
Int., 1995, 27, 559.
OCH2CH3), 2.49 (s, 3H, CH3), 3.43 (s, 2H), 4.15 (q, 2H, 3J
3
7.2 Hz, OCH2), 6.70 (d, 1H, J 3.6 Hz), 6.96 (s, 1H), 7.13 (d,
1H, 3J 3.6 Hz), 10.31 (br s, COOH); 13C NMR (67.9 MHz,
CDCl3) d 14.11, 15.51, 40.91, 60.83, 116.91, 124.87, 135.56,
136.28, 137.19, 146.90, 166.41, 171.50; MS (EI, 70 eV) m/z
(%) 254 (Mþ, 47), 210 (96), 181 (74), 136 (100). HR-MS found:
254.0607; calcd for C12H14O4S: 254.0613.
6
7
A. Spinella, T. Fortunati and A. Soriente, Synlett, 1997, 93.
V. P. Balema, J. W. Wiench, M. Pruski and V. K. Pecharsky,
J. Am. Chem. Soc., 2002, 124, 6244.
8
(a) T. Thiemann, K. Umeno, D. Ohira, E. Inohae, T. Sawada and
S. Mataka, New J. Chem., 1999, 23, 1067; (b) T. Thiemann, K.
Umeno, E. Inohae and S. Mataka, Rep. Inst. Adv. Mater. Study,
Kyushu Univ., 2000, 14(1), 17; T. Thiemann, K. Umeno, E. Inohae
and S. Mataka, Chem. Abs., 2000, 113, 335 380w; (c) T.
Thiemann, K. Umeno, J. Wang, K. Arima, M. Watanabe, Y.
Tabuchi, Y. Tanaka, H. Gorohmaru and S. Mataka, J. Chem.
Soc., Perkin Trans. 1, 2002, 2090.
(E)- and (Z)-3-(50-methylthien-20-ylmethylidene)-N-phenyl-
(4H)-maleimide (8g-a and 8g–b). 1s (0.87 g, 6.9 mmol) and 2h
(3.75 g, 8.6 mmol) were reacted. While the reaction is exother-
mic, it was found beneficial to submit the melt to additional
heating (10 min, 100 ꢀC). Thereafter, methanol (20 mL) was
added to the melt and precipitated 8g–a (1.82 g) was filtered
off. Thereafter the filtrate was concentrated in vacuo and the
residue was submitted to column chromatography on silica
gel (ether–CHCl3 2:1) to give additional 8g–a (combined yield:
1.87 g, 96%) and 8g–b (58 mg, 3%).
9
For typical examples, see: (a) E. J. Corey, D. A. Clark, G. Goto,
A. Marfat, C. Mioskowski, B. Samuelsson and S. Hammerstro¨m,
`
J. Am. Chem. Soc., 1980, 102, 1436 (for DME); (b) S. Fliszar,
R. F. Hudson and G. Salvadori, Helv. Chim. Acta, 1964, 47,
159 (for chloroform).
10 For typical examples, see: (a) D. Spitzner and H. Swoboda,
Tetrahedron Lett., 1986, 27, 1281 (for benzene); (b) T. Thiemann,
D. Ohira, Y. Q. Li, T. Sawada, S. Mataka, K. Rauch, M.
Noltemeyer and A. de Meijere, J. Chem. Soc., Perkin Trans. 1,
2000, 2968 (for benzene); (c) J.-P. Surivet, J.-N. Volle and J. M.
8g–a. IR (KBr) n 1767, 1704, 1641, 1502, 1385, 1175, 898, 807,
1
699 cmꢂ1; H NMR (270 MHz, CDCl3) d 2.58 (s, 3H, CH3),
`
Vatele, Tetrahedron: Asymmetry, 1996, 7, 3305 (for toluene).
4
3
3.63 (d, 2H, J 2.3 Hz), 6.85 (d, 1H, J 3.6 Hz), 7.21 (d, 1H,
3J 3.6 Hz), 7.33–7.51 (m, 5H), 7.83 (t, 1H, 4J 2.3 Hz); 13C
NMR (67.8 MHz, CDCl3) d 15.87, 34.15, 118.95, 126.45,
11 (a) C. Ruchardt, P. Panse and S. Eichler, Chem. Ber., 1967, 100,
¨
1144; (b) D. P. Marriott and S. R. Bantick, Tetrahedron Lett.,
1981, 22, 3657.
T h i s j o u r n a l i s Q T h e R o y a l S o c i e t y o f C h e m i s t r y a n d t h e
C e n t r e N a t i o n a l d e l a R e c h e r c h e S c i e n t i f i q u e 2 0 0 4
N e w . J . C h e m . , 2 0 0 4 , 2 8 , 5 7 8 – 5 8 4
583