10674
Z.-L. Wang et al. / Tetrahedron 64 (2008) 10670–10675
128.7, 128.3, 127.1, 126.5, 21.1; IR (KBr, cmꢁ1): 3022, 2920, 2862,
1595, 1488, 1443, 806, 772, 687; LRMS (EI, 70 eV) m/z (%): 226 (Mþ,
100), 211 (–CH3, 47).
(10), 405 (15), 257 (7), 255 (5), 93 (100); HRMS (EI) for
20H11Cl2F3N5OS (Mþ): calcd 496.0014, found 496.0012.
C
4.2.19. (Z)-3-(5-Amino-3-cyano-1-(2,6-dichloro-4-(trifluoro-
methyl)phenyl)-1H-pyrazol-4-ylthio)-N-methyl-
N-phenylacrylamide (24)
4.2.13. (Z)-2-(Styrylthio)aniline (17)
Yellow oil; 1H NMR (300 MHz, CDCl3)
d
: 7.58 (d, J¼7.8 Hz, 2H),
7.45–7.39 (m, 3H), 7.30–7.27 (m, 1H), 7.19 (t, J¼7.6 Hz, 1H), 6.79–
6.73 (m, 2H), 6.54 (d, J¼10.7 Hz, 1H), 6.19 (d, J¼10.7 Hz, 1H), 4.27 (br
Colorless solid, mp 233.9–234.8 ꢀC; 1H NMR (300 MHz, C3D6O)
d
: 8.09 (s, 2H), 7.50–7.40 (m, 2H), 7.37–7.30 (m, 3H), 6.69 (d,
J¼9.4 Hz, 1H), 6.16 (br s, 2H), 5.84 (d, J¼9.4 Hz, 1H), 3.30 (s, 3H);
13C NMR (75 MHz, C3D6O)
: 165.3, 151.1, 147.7, 143.9, 136.4, 133.5
s, 2H); 13C NMR (75 MHz, CDCl3)
d: 153.9, 135.3, 130.5, 128.8, 128.4,
127.7, 127.0, 126.2, 125.6, 121.9, 118.7, 115.3; IR (KBr, cmꢁ1): 3429,
3341, 1603, 1479, 1352, 751, 688; LRMS (EI, 70 eV) m/z (%): 227 (Mþ,
100); HRMS (EI) for C14H13NS (Mþ): calcd 227.0769, found 227.0769.
d
(q, J¼33.9 Hz, 1C), 130.8, 129.6, 127.4, 127.2, 126.4, 126.3, 122.4 (q,
J¼271.7 Hz, 1C), 115.0, 112.7, 95.7, 36.0; IR (KBr, cmꢁ1): 3456, 3341,
2930, 1629, 1573, 1495, 1387, 1315, 1140, 802, 698; LRMS (EI,
70 eV) m/z (%): 513 (5), 512 (Mþþ2, 3), 511 (6), 510 (Mþ, 3), 407
(10), 405 (14), 353 (4), 351 (6), 257 (7), 255 (10), 191 (27), 107
(100); HRMS (EI) for C22H15Cl2F3N4OS (Mþ): calcd 510.0296, found
510.0295.
4.2.14. 2-(4-Nitrostyrylthio)aniline (18)
Z/E¼1:1; Rufous solid, mp 65.1–66.5 ꢀC; 1H NMR (300 MHz,
CDCl3)
d
: 8.23 (d, J¼8.3 Hz, 1H), 8.08 (d, J¼8.3 Hz, 1H), 7.66 (d,
J¼8.3 Hz, 1H), 7.41 (d, J¼8.3 Hz, 1H), 7.32–7.18 (m, 2H), 6.86
(d, J¼15.4 Hz, 0.5H), 6.80–6.74 (m, 2H), 6.51–6.49 (m, 1H), 6.20 (d,
J¼15.4 Hz, 0.5H), 4.31 (br s, 1H), 4.28 (br s, 1H); 13C NMR (75 MHz,
4.2.20. (Z)-Phenyl(styryl)selane (26)9
CDCl3)
d: 148.4, 147.7, 146.1, 145.8, 143.0, 142.9, 136.4, 135.3, 134.1,
Colorless oil; 1H NMR (500 MHz, CDCl3)
d
: 7.59 (d, J¼8.0 Hz, 2H),
131.5, 131.1, 130.6, 129.1, 125.9, 124.1, 123.7, 118.9, 118.8, 116.6, 115.6,
115.5, 112.6; IR (KBr, cmꢁ1): 3437, 2924, 2861, 1599, 1493, 1337,
1206, 1096, 746, 674; LRMS (EI, 70 eV) m/z (%): 278 (Mþ, 20), 136
(100); HRMS (EI) for C14H12N2O2S (Mþ): calcd 272.0620, found
272.0619.
7.58–7.39 (m, 4H), 7.33–7.24 (m, 4H), 6.98 (d, J¼10.0, 1H), 6.78 (d,
J¼10.5 Hz, 1H); 13C NMR (125 MHz, CDCl3)
d: 137.3, 132.8, 131.7,
130.1, 129.4, 128.4, 128.3, 127.7, 127.3, 124.0; LRMS (EI, 70 eV) m/z
(%): 262 (Mþþ2, 13), 260 (Mþ, 67), 258 (35), 245 (8), 180 (77), 179
(75), 178 (43), 169 (24), 165 (29), 152 (6), 102 (37), 77 (100).
4.2.15. (Z)-2-(2-(Pyridin-4-yl)vinylthio)aniline (19)
4.2.21. (Z)-(2-Methoxystyryl)(phenyl)selane (27)
Yellow solid, mp 121.9–122.8 ꢀC; 1H NMR (300 MHz, CDCl3)
d:
Yellow oil; 1H NMR (300 MHz, CDCl3)
d
: 7.55 (d, J¼7.2 Hz, 2H),
8.62 (d, J¼6.1 Hz, 2H), 7.42 (d, J¼6.1 Hz, 2H), 7.41 (d, 1H), 7.24–7.18
7.40 (d, J¼7.5 Hz, 1H), 7.28–7.23 (m, 4H), 7.19 (d, J¼10.3, 1H), 6.99 (t,
(m, 1H), 6.79–6.73 (m, 2H), 6.48 (dd, J¼10.8 Hz, 10.8 Hz, 2H), 4.29
J¼7.5 Hz, 1H), 6.87 (d, J¼8.1 Hz, 1H), 6.78 (d, J¼10.3 Hz, 1H), 3.84 (s,
(br s, 2H); 13C NMR (75 MHz, CDCl3)
d
: 149.9, 147.7, 143.6, 135.3,
3H); 13C NMR (75 MHz, CDCl3)
d: 156.6, 132.6, 129.2, 128.9, 128.6,
134.4, 130.9, 123.6, 122.9, 118.8, 116.7, 115.4; IR (KBr, cmꢁ1): 3435,
3296, 3023, 2923,1589,1474,1409,1310,1240,1153, 825, 744; LRMS
(EI, 70 eV) m/z (%): 228 (Mþ, 29), 195 (8), 136 (100); HRMS (EI) for
C13H12N2S (Mþ): calcd 228.0721, found 228.0721.
127.4, 126.2, 125.8, 123.9, 120.5, 120.2, 110.6, 55.4; IR (KBr, cmꢁ1):
3049, 2939, 2840, 1691, 1586, 1464, 1250, 1033, 749, 682; LRMS (EI,
70 eV) m/z (%): 292 (Mþþ2, 13), 291 (11), 290 (Mþ, 67), 289 (9), 288
(32), 287 (14), 286 (13), 259 (–OCH3, 7), 211 (16), 210 (100); HRMS
(EI) for C15H14OSe (Mþ): calcd 290.0210, found 290.0210.
4.2.16. (4-Fluorophenyl)(styryl)sulfane (20)
Z/E¼7.5:1; light-yellow oil; 1H NMR (300 MHz, CDCl3)
d: 7.58–
4.2.22. (Z)-(4-Nitrostyryl)(phenyl)selane (28)9
7.34 (m, 7H), 7.36–7.30 (m, 2H), 7.09, 6.86 (dd, J¼15.4 Hz, 15.4 Hz,
Yellow oil; 1H NMR (500 MHz, CDCl3)
d
: 8.14 (d, J¼7.5 Hz, 2H),
0.24H), 6.61, 6.44 (dd, J¼10.8 Hz, 10.8 Hz, 1.76H); 13C NMR (75 MHz,
7.59 (d, J¼7.0 Hz, 2H), 7.47 (d, J¼16.0,1H), 7.39–7.37 (m, 5H), 6.72 (d,
CDCl3)
d: 1264.0, 160.7, 136.4, 136.3, 132.6, 132.5, 131.4, 131.3, 131.2,
J¼16.0 Hz, 1H); 13C NMR (125 MHz, CDCl3)
d: 143.2, 133.9, 133.1,
130.0, 128.7 (2C), 128.4, 127.6, 127.2 (1C), 127.1, 126.5, 126.0, 123.9,
116.4 (d, J¼21.9 Hz, 1C), 116.3 (d, J¼21.9 Hz, 1C); IR (KBr, cmꢁ1):
3033, 1591, 1486, 945, 826; LRMS (EI, 70 eV) m/z (%): 230 (Mþ, 100);
HRMS (EI) for C14H11FS (Mþ): calcd 230.0566, found 230.0565.
129.9, 129.7, 128.8, 128.4, 127.8, 126.2, 124.2; LRMS (EI, 70 eV) m/z
(%): 305 (Mþþ2, 65), 303 (Mþ, 32), 288 (10), 259 (31), 258 (15), 257
(17), 225 (49), 214 (8), 195 (8), 179 (35), 178 (100).
Acknowledgements
4.2.17. (Z)-(4-Chlorophenyl)(styryl)sulfane (21)
Colorless solid, mp 66.3–67.4 ꢀC; 1H NMR (300 MHz, CDCl3)
d:
We thank the Zhejiang Provincial Natural Science Foundation of
China (Y407116) and National Natural Science Foundation of China
(No 20572020) for financial support.
7.51 (d, J¼7.7 Hz, 2H), 7.42–7.25 (m, 7H), 6.63 (d, J¼10.7 Hz, 1H),
6.42 (d, J¼10.7 Hz, 1H); 13C NMR (75 MHz, CDCl3)
d: 136.2, 134.7,
133.3, 131.2, 129.3, 128.7, 128.3, 128.0, 127.3, 125.1; IR (KBr, cmꢁ1):
3071, 2926, 1588, 1441, 1386, 1087, 821, 772, 676; LRMS (EI, 70 eV)
m/z (%): 248 (Mþþ2, 36), 246 (Mþ, 100), 211 (–Cl, 38); HRMS (EI) for
C14H11ClS (Mþ): calcd 246.0270, found 246.0270.
Supplementary data
Supplementary data associated with this article can be found in
4.2.18. 3-(5-Amino-3-cyano-1-(2,6-dichloro-4-(trifluoromethyl)-
phenyl)-1H-pyrazol-4-ylthio)-N-phenylacrylamide (23)
References and notes
Z/E¼3.3:1; colorless solid, mp 216.3–217.5 ꢀC; 1H NMR
(300 MHz, CD3COCD3) d: 9.39 (br s, 0.77H), 9.21 (br s, 0.23H), 8.13
1. (a) Ager, D. J. Chem. Soc. Rev. 1982, 11, 493; (b) Metzner, P.; Thuillier, A. Sulfur
Reagents in Organic Synthesis; Academic: London, 1994; (c) Fernndez, F.; Khiar,
N. Chem. Rev. 2003, 103, 3651; (d) Dubbaka, S. R. Angew. Chem., Int. Ed. 2005, 44,
7674; (e) Kondo, T.; Mitsudo, T. Chem. Rev. 2000, 100, 3205; (f) Alonso, F.; Be-
letskaya, I. P.; Yus, M. Chem. Rev. 2004, 104, 3079; (g) Beller, M.; Seayad, J.;
Tillack, A.; Jiao, H. Angew. Chem., Int. Ed. 2004, 43, 3368.
2. Rh: (a) Cao, C.; Fraser, L. R.; Love, J. A. J. Am. Chem. Soc. 2005, 127, 17614; (b)
Shoai, S.; Bichler, P.; Kang, B.; Buckley, H.; Love, J. A. Organometallics 2007, 26,
5778; Rh or Pd: (c) Ogawa, A.; Ikeda, T.; Kimura, K.; Hirao, T. J. Am. Chem. Soc.
1999, 121, 5108; Pd: (d) Kondoh, A.; Yorimitsu, H.; Oshima, K. Org. Lett. 2007, 9,
(s, 1.54H), 8.08 (s, 0.46H), 7.75–7.65 (m, 2H), 7.35–7.28 (m, 2H),
7.10–7.03 (m, 1H), 6.88–6.83 (m 1H), 6.27–6.21 (m, 3H); 13C NMR
(75 MHz, CD3COCD3) d: 168.7, 155.6, 152.2, 145.2, 143.8, 141.1, 138.3
(q, J¼34.1 Hz, 1C), 135.3, 133.3, 131.0, 126.9 (q, J¼271.0 Hz, 1C), 127.9,
123.5, 122.4, 117.3, 99.9; IR (KBr, cmꢁ1): 3405, 3323, 1613, 1538,
1499, 1443, 1391, 1316, 1172, 1139, 823, 756, 691, 626; LRMS (EI,
70 eV) m/z (%): 499 (2), 498 (Mþþ2, 3), 497 (10), 496 (Mþ, 1), 407