B. A. Trofimo6 et al. / Tetrahedron Letters 44 (2003) 3501–3503
3503
1
4
starting 2,5-disubstituted pyrroles and their corre-
13. Typical procedure: A mixture of a CH-acid (3 mmol),
KOH (3 mmol) and DMSO (10 ml) was stirred for 0.5 h
at room temperature, a pyrrolecarbodithioate (2 mmol)
was added and the reaction mixture was heated at 110°C
for 1.5 h, then cooled to room temperature and an alkyl
halide (2 mmol) was added. The reaction mixture was
stirred at room temperature for 2 h and diluted with
brine (30 ml). The precipitated crystals were filtered off,
washed with water, dried, and finally purified chromato-
graphically (column with Al O , eluent–hexane). If crys-
1
1
sponding pyrrole-3-carbodithioates
have recently
become available and the selection of CH-acids is prac-
tically unlimited, the scope and utility of this synthesis
promises much.
Acknowledgements
2
3
The authors are grateful to the Russian Foundation for
Basic Research (grant No. 02-03-33017a) for financial
support.
tals did not form, the resultant solution was extracted
with diethyl ether, and the residue, after removal of the
ether, was purified by column chromatography.
3
5
2
-(2,2-Dicyano-1-ethylthioethenyl)-2,4,5-trimethylpyrrole
1
a. H NMR (CDCl ): l 8.14 (br. s, 1H, NH), 2.70 (q,
3
References
2
H, J=7.4 Hz, SCH ), 2.22 (s, 3H, Me ), 2.09 (s, 3H,
2
4
5
Me ), 1.95 (s, 3H, Me ), 1.13 (t, 3H, J=7.4 Hz, Me).
C H N S (245.34): calcd C, 63.64; H, 6.16; N, 17.13; S,
1
. (a) Burns, D. H.; Smith, K. M. J. Chem. Res. (S) 1990, 6,
78; (b) Murase, M.; Yoshida, S.; Hosaka, T.; Tobinaga,
S. Chem. Pharm. Bull. 1991, 39, 489; (c) Selim, M. A.
Aswan Sci. Technol. Bull. 1992, 13, 60; (d) Xiao, D.;
Ketcha, D. M. J. Heterocyclic Chem. 1995, 32, 499.
. (a) Bakhshi, A. K.; Lovleen, A. Superlattices Microstruct.
993, 13, 437; (b) Berlin, A.; Canavesi, A.; Pagani, G.;
Schiavon, G.; Zecchin, S.; Zotti, G. Synth. Met. 1997, 84,
51; (c) Entezami, A.; Rahmatpour, A. Eur. Polym. J.
998, 34, 871; (d) Kim, I. T.; Elsenbaumer, R. L. Macro-
13
15
3
1
13.07. Found: C, 63.40; H, 6.33; N, 16.96; S, 13.50.
3-(2,2-Dicyano-1-methylthioethenyl)-2-methyl-4,5,6,7-tetra-
1
hydroindole 5b. H NMR (CDCl ): l 8.00 (br. s, 1H,
NH), 2.38 (m, 4H, CH2 ), 2.27 (s, 6H, Me), 1.77 (m, 4H,
CH2 ). C H N S (257.36): calcd C, 65.34; H, 5.87; N,
3
4,7
2
5,6
14
15
3
1
1
1
3
6.33; S, 12.46. Found: C, 65.00; H, 6.39; N, 16.41; S,
2.07.
4
1
-(2,2-Dicyano-1-ethylthioethenyl)-2-methyl-4,5,6,7-tetra-
1
hydroindole 5c. H NMR (CDCl ): l 8.13 (br. s, 1H,
NH), 2.76 (q, 2H, J=7.4 Hz, SCH ), 2.49 (m, 2H, CH ),
3
molecules 2000, 33, 6407.
7
2
2
3
4
. (a) Gossauer, A. Die chemie der Pyrrole; Springer-Verlag:
Berlin-Heidelberg-New York, 1974; (b) Jones, R. A.;
Bean, G. P. The Chemistry of Pyrroles; Academic Press:
New York, 1989.
. (a) Hayes, R. T.; Wasielewski, M. R.; Gosztola, D. J.
Am. Chem. Soc. 2000, 122, 5563; (b) Harmjanz, M.; Gill,
H. S.; Scott, M. J. J. Am. Chem. Soc. 2000, 122, 10476;
c) Rurack, K. Angew. Chem., Int. Ed. 2001, 40, 385.
. Sour, A.; Boillot, M.-L.; Riviere, E.; Lesot, P. Eur. J.
Inorg. Chem. 1999, 12, 2117.
. (a) Trofimov, B. A. The Chemistry of Heterocyclic Com-
pounds. Pyrroles; Wiley: New York, 1992; Vol. 48; (b)
Sobenina, L. N.; Demenev, A. P.; Mikhaleva, A. I.;
Trofimov, B. A. Usp. Khim. 2002, 71, 641. See also Russ.
Chem. Rev. 2002, 71, 563.
. Hartke, K.; Radau, S. Liebigs Ann. Chem. 1974, 2110.
. Tominaga, Y.; Matsuoka, Y.; Oniyama, Y.; Uchimura,
Y.; Komiya, H.; Hirayama, M.; Kohra, S.; Hosomi, A. J.
Heterocyclic Chem. 1990, 27, 647.
4
2
2
2.41 (m, 2H, CH ), 2.27 (s, 3H, Me ), 1.75 (m, 4H,
5,6
CH2 ), 1.14 (t, 3H, J=7.4 Hz, Me): C H N S (271.38)
calcd for: C, 66.39; H, 6.31; N, 15.48; S, 11.82. Found: C,
15
17
3
66.64; H, 6.29; N, 15.53; S, 12.07.
3
-(2,2-Dicyano-1-ethylthioethenyl)-2-methyl-5-phenyl-
1
pyrrole 5d. H NMR (CDCl ): l 9.20 (br. s, 1H, NH),
3
4
7
2
3
.45, 7.37, 7.25 (m, 5H, Ph), 6.46 (d, 1H, J=2.9 Hz, H ),
.92 (q, 2H, J=7.4 Hz, SCH ), 2.40 (s, 3H, Me ), 1.18 (t,
H, J=7.4 Hz, Me). C H N S (293.39): calcd C, 69.59;
(
2
2
5
17
15
3
H, 5.15; N, 14.32; S, 10.93. Found: C, 69.20; H, 5.29; N,
6
14.58; S, 11.28.
3
-(2-Carbamoyl-2-cyano-1-ethylthioethenyl)-2-methyl-5-
1
phenylpyrrole 5e. H NMR (CDCl ): l 8.57 (br. s, 1H,
NH), 7.44, 7.36, 7.25 (m, 5H, Ph), 6.33 (d, 1H, J=2.8 Hz,
H ), 6.13 (br. s, 1H, CONH ), 5.63 (br. s 1H, CONH ),
3
4
2
2
7
8
2
2
3
6
5
3
.62 (q, 2H, J=7.4 Hz, SCH ), 2.32 (s, 3H, Me ), 1.12 (t,
H, J=7.4 Hz, Me). C H N OS (311.40): calcd C,
5.57; H, 5.50; N, 13.49; S, 10.30. Found: C, 65.23; H,
.23; N, 13.80; S, 10.78.
2
17
17
3
9
. Sobenina, L. N.; Mikhaleva, A. I.; Sergeeva, M. P.;
Petrova, O. V.; Aksamentova, T. N.; Kozyreva, O. B.;
Toryashinova, D. S. D.; Trofimov, B. A. Tetrahedron
-(2-Carbethoxy-2-cyano-1-ethylthioethenyl)-2-methyl-5-
1
phenylpyrrole 5f. H NMR (CDCl ): l 8.40 (br. s, 1H,
NH), 7.38, 7.30, 7.18 (m, 5H, Ph), 6.26 (d, 1H, J=2.9 Hz,
H ), 4.32 (q, 2H, J=7.1 Hz, CH CO ), 2.64 (q, 2H,
J=7.4 Hz, SCH ), 2.28 (s, 3H, Me ), 1.37 (t, 3H, J=7.4
3
1
995, 51, 4223.
4
1
0. Dell’Erba, C.; Giglio, A.; Mugnoli, A.; Novi, M.;
Petrillo, G.; Stagnaro, P. Tetrahedron 1995, 51, 5181.
1. Trofimov, B. A.; Sobenina, L. N.; Mikhaleva, A. I.;
Demenev, A. P.; Tarasova, O. A.; Ushakov, I. A.;
Zinchenko, S. V. Tetrahedron 2000, 56, 7325.
2. Trofimov, B. A.; Vitkovskaya, N. M.; Kobychev, V. B.;
Larionova, E. Y.; Sobenina, L. N.; Mikhaleva, A. I.;
Demenev, A. P. Sulfur Lett. 2001, 24, 181.
2
2
2
2
Hz, Me), 1.11 (t, 3H, J=7.4 Hz, Me). C H N O S
1
19 20
2
2
(
340.44): calcd C, 67.03; H, 5.92; N, 8.23; S, 9.40. Found:
C, 67.43; H, 5.60; N, 8.41; S, 9.73.
1
4. Trofimov, B. A.; Tarasova, O. A.; Mikhaleva, A. I.;
Kalinina, N. A.; Sinegovskaya, L. M.; Henkelman, J.
Synthesis 2000, 11, 1585.
1