6516
B. A. Trofimov et al. / Tetrahedron Letters 45 (2004) 6513–6516
1612, 1596, 1567, 1468, 1434, 1365, 1316, 1250, 1224, 1164,
d 14.96 (br s, 1H), 8.86 (br s, 1H), 8.06 (m, 2H), 7.87–7.31
(m, 5H), 7.57–7.29 (m, 5H), 7.53 (m, 1H), 7.48 (m, 2H),
6.95 (m, 1H), 6.89 (s, 1H), 6.83 (m, 1H), 6.81 (m, 1H), 6.67
(m, 1H). Anal. Calcd for C29H22N2O: C, 84.03; H, 5.35;
N, 6.76. Found: C, 83.78; H, 5.67; N, 6.60.
1139, 1042, 1022, 930, 824, 806, 787, 692, 633. Anal. Calcd
for C17H15NO: C, 81.90; H, 6.06; N, 5.62. Found: C,
81.56; H, 6.20; N, 5.78.
2-(Benzoylethynyl)-5-phenylpyrrole––3c: orange crystals,
mp 182–183°C. 1H NMR (250.13MHz, CDCl3) d 9.04 (br
s, 1H), 8.22 (m, 2H), 7.65 (m, 1H), 7.59 (m, 2H), 7.56 (m,
2H), 7.46 (m, 2H), 7.35 (m, 1H), 6.97 (dd, 3J=3.6Hz,
1,1-Di(4,5,6,7-tetrahydroindol-2-yl)-2-thienoylethene––4d:
dark-red crystals, mp 210°C. 1H NMR (250.13MHz,
CDCl3) d 13.80 (br s, 1H), 8.16 (br s, 1H), 7.71 (dd,
3J=3.7Hz, 4J=1.2Hz, 1H), 7.51 (dd, 3J=4.9Hz,
4J=1.2Hz, 1H), 7.08 (dd, 3J=4.9Hz, 3J=3.7Hz, 1H),
4J=2.5Hz, 1H), 6.62 (dd, 3J=3.6Hz, 4J=2.8Hz, 1H). 13
C
NMR (62.9MHz, CDCl3) d 177.62, 137.50, 136.75,
133.80, 130.85, 129.32, 129.07, 128.50, 127.88,124.62,
122.54, 110.72, 108.24, 93.24, 89.12. IR (KBr, cmÀ1):
3309, 3061, 2166, 1628, 1605, 1596, 1574, 1538, 1509, 1475,
1456, 1382, 1315, 1291, 1245, 1218, 1172, 1075, 1042, 1022,
968, 901, 792, 759, 685, 650. Anal. Calcd for C19H13NO:
C, 84.11; H, 4.83; N, 5.16. Found: C, 83.75; H, 5.09; N,
5.51.
4
4
6.57 (d, J=2.2Hz, 1H), 6.56 (s, 1H), 6.44 (d, J=2.4Hz,
1H), 2.75 (m, 2H), 2.64 (m, 2H), 2.54 (m, 4H), 1.80 (m,
8H). Anal. Calcd for C23H24N2OS: C, 73.37; H, 6.42; N,
7.44; S 8.52. Found: C, 72.99; H, 6.64; N, 7.58; S, 8.86.
15. Amidation of 1-bromo-2-phenylacetylene with the two
vinylogous amides, 2,4-dimethyl-3-acetylpyrrole and 3-
benzoylpyrrole (10mol% CuSO4ÆH2O, 20mol% 1,10-
phenanthroline, 2.0equiv of K3PO4, toluene, 70–80°C,
18–36h) gave only 1-(2-phenylethynyl)pyrroles in 50% and
71% yields, respectively, see: Zhang, Y.; Hsung, R. P.;
Tracey, M. R.; Kurtz, K. C. M.; Vera, E. L. Org. Lett.
2004, 6, 1151–1154.
2-(Thienoylethynyl)pyrrole––3d: yellow crystals, mp 143–
1
144°C. H NMR (250.13MHz, CDCl3) d 8.93 (br s, 1H),
7.92 (dd, 3J=3.9Hz, 4J=1.2Hz, 1H), 7.67 (dd, 3J=4.9Hz,
4J=1.2Hz, 1H), 7.14 (dd, 3J=4.9Hz, 3J=3.9Hz, 1H),
6.96 (m, 1H), 6.83 (m, 1H), 6.28 (m, 1H). 13C NMR
(62.9MHz, CDCl3) d 169.71, 144.82, 134.84, 134.66,
128.36, 123.68, 120.77, 110.78, 110.03, 91.34, 87.05. IR
(KBr, cmÀ1): 3167, 3096, 3071, 3004, 2174, 1581, 1555,
1512, 1433, 1409, 1353, 1320, 1266, 1249, 1140, 1099, 1079,
1061, 1039, 996, 929, 883, 858, 820, 749, 728, 655, 598.
Anal. Calcd for C11H7NOS: C, 65.65; H, 3.51; N, 6.96; S,
15.93. Found: C, 65.80; H, 3.31; N, 6.57; S, 15.66.
16. (a) Shostakovsky, M. F.; Skvortsova, G. G.; Domnina, E.
S. Usp. Khim. 1969, 38, 892–916; (b) Trofimov, B. A.;
Korostova, S. E.; Shevchenko, S. G.; Polubentsev, E. A.;
Mikhaleva, A. I. Zh. Org. Khim. 1990, 26, 1110–1113; (c)
Trofimov, B. A. In The Chemistry of Heterocyclic Com-
pounds, Vol. 48: Pyrroles, Part II; Jones, R. A., Ed.; Wiley:
New York, 1992; pp 131–298.
2-(Thienoylethynyl)-4,5,6,7-tetrahydroindole––3e: dark-
yellow crystals, mp 147–148°C. 1H NMR (250.13MHz,
CDCl3) d 8.43 (br s, 1H), 7.87 (dd, 3J=3.7Hz, 4J=1.2Hz,
1H), 7.63 (dd, 3J=4.9Hz, 4J=1.2Hz, 1H), 7.11 (dd,
17. (a) Trofimov, B. A.; Stepanova, Z. V.; Sobenina, L. N.;
Ushakov, I. A.; Elokhina, V. N.; Mikhaleva, A. I.;
Vakulꢁskaya, T. I.; Toryashinova, D.-S. D. Mendeleev
Commun. 1998, pp 119–120; (b) Trofimov, B. A.; Stepa-
nova, Z. V.; Sobenina, L. N.; Mikhaleva, A. I.; Vak-
ulꢁskaya, T. I.; Elokhina, V. N.; Ushakov, I. A.;
Toryashinova, D.-S. D.; Kositsyna, E. I. Russ. Chem.
Bull. 1999, 48, 1542–1547; (c) Trofimov, B. A.; Stepanova,
Z. V.; Sobenina, L. N.; Mikhaleva, A. I.; Ushakov, I. A.;
Toryashinova, D.-S. D. Chem. Heterocycl. Compd. 1999,
35, 1107–1108; (d) Chipanina, N. N.; Stepanova, Z. V.;
Gavrilova, G. A.; Sobenina, L. N.; Mikhaleva, A. I. Russ.
Chem. Bull. 2000, 49, 1914–1917; (e) Trofimov, B. A.;
Sobenina, L. N.; Mikhaleva, A. I.; Ushakov, I. A.;
Vakulꢁskaya, T. I.; Stepanova, Z. V.; Toryashinova,
D.-S. D.; Malꢁkina, A. G.; Elokhina, V. N. Synthesis
2003, 1272–1278; (f) Stepanova, Z. V.; Sobenina, L. N.;
Mikhaleva, A. I.; Ushakov, I. A.; Elokhina, V. N.;
Vorontsov, I. I.; Antipin, M. Y.; Trofimov, B. A. Russ.
J. Org. Chem. 2003, 39, 1636–1643.
18. (a) Trofimov, B. A.; Mikhaleva, A. I. N-Vinylpyrroles;
Nauka: Novosibirsk, 1984, (in Russian); (b) Yurovskaya,
M. A.; Afanasꢁev, A. Z.; Bundel, Y. G. Khim. Geterotsikl.
Soedin., 1984, 1077–1079; (c) Pozharskii, A. F.; Anisi-
mova, V. A.; Tsupak, E. B. Practical Works on the
Chemistry of Heterocycles; Rostov University Publishers:
Rostov, 1988, p. 9; (d) Bean, G. P.. In The Synthesis of 1-
H Pyrroles, Part I; Jones, R. A., Ed.; Wiley: New York,
1990, pp 105; (e) Trofimov, B. A. Adv. Heterocycl. Chem.
1990, 51, 177–301; (f) Tedeschi, R. J. In Encyclopedia of
Physical Science and Technology; Academic: San Diego,
1992; Vol. 2, pp 27–65; (g) Puciova, M.; Ertl, P.; Toma, S.
Collect. Czech. Chem. Commun. 1994, 59, 175–185; (h)
Varlamov, A. V.; Voskresenskii, L. G.; Borisova, T. N.;
Chernyshev, A. I.; Levov, A. N. Chem. Heterocycl.
Compd. 1999, 35, 613–616; (i) Gilchrist, T. L. J. Chem.
Soc., Perkin Trans. 1, 2001, 2491–2515; (j) Mikhaleva, A.
I.; Schmidt, E. Y. In Selected Methods for Synthesis and
Modification of Heterocycles; Kartsev, V. G., Ed.; IBS:
Moscow, 2003; Vol. 1, pp 331–352.
3J=4.9Hz, J=3.7Hz, 1H), 6.58 (d, J=2.0Hz, 1H), 2.57
(m, 2H), 2.48 (m, 2H), 1.76 (m, 4H). 13C NMR (62.9MHz,
CDCl3) d 169.56, 145.09, 134.83, 134.21, 128.23, 120.24,
120.17, 107.60, 92.72, 89.82, 23.36, 23.15, 22.84, 22.67. IR
(KBr, cmÀ1): 3260, 3102, 3065, 2944, 2918, 2842, 2153,
1596, 1569, 1513, 1469, 1410, 1351, 1316, 1255, 1227, 1137,
1081, 1051, 1016, 943, 858, 823, 806, 760, 714, 667, 630.
Anal. Calcd for C15H13NOS: C, 70.56; H, 5.13; N, 5.48; S,
12.56. Found: C, 70.52; H, 5.48; N, 5.49; S, 12.90.
3
4
2-(Thienoylethynyl)-5-phenylpyrrole––3f: red-orange crys-
tals, mp 183–184°C. 1H NMR (250.13MHz, CDCl3) d
9.04 (br s, 1H), 7.95 (dd, 3J=3.7Hz, 4J=1.2Hz, 1H), 7.68
3
4
(dd, J=4.9Hz, J=1.2Hz, 1H), 7.58–7.31 (m, 5H), 7.17
(dd, 3J=4.9Hz, 3J=3.7Hz, 1H), 6.90 (dd,3J=3.6Hz,
4J=2.2Hz, 1H), 6.57 (dd, 3J=3.6Hz, 4J=2.4Hz, 1H).
IR (KBr, cmÀ1): 3298, 3066, 2169, 1597, 1558, 1512, 1462,
1406, 1354, 1315, 1302, 1245, 1225, 1194, 1057, 1044, 1022,
942, 919, 860, 784, 755, 724, 691, 652. Anal. Calcd for
C17H11NOS: C, 73.62; H, 4.00; N, 5.05; S, 11.56. Found:
C, 73.51; H, 4.26; N, 5.16; S, 11.70.
1,1-Di(pyrrol-2-yl)-2-benzoylethene––4a: red-orange oil.
1H NMR (250.13MHz, CDCl3) d 13.99 (br s, 1H), 8.67
(br s, 1H), 7.98 (m, 2H), 7.52 (m, 1H), 7.47 (m, 2H), 7.15
(m, 1H), 6.95 (m, 1H), 6.84 (s, 1H), 6.73 (m, 2H), 6.38 (m,
1H), 6.33 (m, 1H). Anal. Calcd for C17H14N2O: C, 77.84,
H, 5.38, N, 10.68. Found: C, 77.46; H, 5.49; N, 10.32.
1,1-Di(4,5,6,7-tetrahydroindol-2-yl)-2-benzoylethene––4b:
red crystals, mp 186–187°C. 1H NMR (250.13MHz,
CDCl3) d 14.00 (br s, 1H), 8.25 (br s, 1H), 7.97 (m, 2H),
7.50 (m, 1H), 7.48 (m, 2H), 6.65 (s, 1H), 6.62 (d,
4J=2.0Hz, 1H), 6.50 (d, 4J=2.2Hz, 1H), 2.81 (m, 2H),
2.68 (m, 2H), 2.60 (m, 2H), 2.58 (m, 2H), 1.84 (m, 8H).
Anal. Calcd for C25H26N2O: C, 81.05; H, 7.07; N, 7.56.
Found: C, 81.38; H, 7.45; N, 7.30.
1,1-Di(5-phenylpyrrol-2-yl)-2-benzoylethene––4c:
crystals, mp 204–205°C. H NMR (250.13MHz, CDCl3)
red
1