SYNTHESIS OF THE THIOPHENE SERIES 1,3-DISELENANES
1129
and 1 g of hydrazine hydrate were added and resulting
mixture was additionally heated at 77 80 C for 1.5 h.
Then the mixture was cooled to room temperature and
and self heating the reaction mixture to 3 C. After
keeping of the reaction mixture under argon for 0.5 h
it was heated to room temperature. Dark precipitate
formed was filtered off and treated as described above.
Compound IIc was obtained as light yellow crystals,
2
.23 g of methyl iodide was added. Reaction pro-
ceeded with heat evolution and discoloration of the
mixture. After the additional stirring for 20 min at
1
yield 1.1 g (44.7%), mp 88 89 C. H NMR spectrum,
3
0 35 C and cooling to room temperature the reaction
5
2
5
5
3
5
,
H
ppm: 2.09 d.d.t [1H, H , J(H H ) 14.8, J(H
a a e
a
mixture was diluted with water, extracted with me-
thylene chloride and filtered to remove unreacted
polymer (0.06 g). The extract was washed with water
4
a
5
(6 )
3
5
4 (6 )
) 10.54, J(H H ) 2.75 Hz], 2.21 d.t.t [1H,
a e
3
5
e
4 (6 )
a
3
5
4 (6 )
H , J(H H
6.51, J(H H ) 3.06 Hz], 2.97
e e
e
4
e
(6 )
2
4 (6 )
and dried over MgSO . The solution obtained con-
d.d.d [2H, H , J(He ) 13.45 Hz], 3.08 d.d.d (2H,
4
4
a
(6 )
2
4
2
3
2
2
tained thiophene and bis(methylseleno)propane VII in
H
), 5.63 d [1H, H , J(H H ) 0.98, J(H Se
a a a
1
:2 ratio (GLC). After the extract concentrating,
8
.8 Hz], thieno[2,3-b]thiophene system: 7.12 d [1H,
0
.71 g of the reddish brown liquid containing com-
pound VII was obtained. H NMR spectrum, , ppm:
4
3
5
4
5
1
H , J(H H ) 5.14 Hz], 7.27 d (1H, H ), 7.29 d (1H,
H ). C NMR spectrum, , ppm: 21.55 (C ), 25.04
(C ), 25.16 (C ), thieno[2,3-b]thiophene system:
1
1
3
13
2
1
2
2
.99 quintet (2H, C CH C), 2.01 s (3H, SeCH ),
C
2
3
3
+
4 (6 )
5
.62 t [2H, SeCH , J(CH CH Se) 7.22 Hz]. [M]
2
2
2
8
0
3
4
7
5
32 ( Se) (cf. [27]). Weight of the unreacted polymer
19.07 (C ), 120.02 (C ), 120.87 (C ), 127.61 (C ),
after drying was 0.05 g.
8
2
77
30.14 (C ), 145.84 (C ). Se NMR spectrum, Se,
2
-(1,3-Diselenan-2-yl)-5-chlorothiophene (IIb).
ppm: 410.82. Found, %: C 33.90; H 2.70; S 18.00;
Se 44.58. C H S Se . Calculated, %: C 34.09; H
A mixture of 1.30 g of compound Ib and 4.5 of
1
0
10
2
2
Me SiCl was cooled to 0 C and added dropwise at
+
80
3
2
.44; S 18.18; Se 44.88. [M] 354 ( Se). Calculated:
M 352.
The polymer VIa (Tables 1 and 3) was isolated
0
to 3 C to 1.8 g of freshly prepared propan-1,3-di-
selenol. After keeping the reaction mixture under
argon for 0.5 h it was heated to room temperature, and
the brown solid precipitated from the reaction mixture
was filtered off and treated as described above. Com-
pound IIb, 1.68 g (57%) was obtained as clear light
similarly to the above-mentioned polymers.
REFERENCES
1
yellow crystals, mp 74 75%. H NMR spectrum, ,
5
2
5
5
3
5
1. Clarembeau, M., Cravador, A., Dumont, W., He-
vesi, L., Krief, A., Lucchetti, J., and Ende, D. Van,
Tetrahedron, 1985, vol. 41, no. 21, p. 4793.
ppm: 2.04 d.t.t [1H, H , J(H H ) 14.9, J(H
a
a
e
a
4
(6 )
3
5
4 (6 )
5
H
) 10.3, J(H H ) 2.8 Hz], 2.2 d.t.t [1H, H ,
a e e
a
3
5
e
4 (6 )
3
5
4 (6 )
e
J(H H ) 6.7, J(H H ) 3.0 Hz], 2.96 d.d.d
a
a
2
. Krief, A. and Defrere, L., Tetrahedron Lett., 1996,
4
e
(6 )
2
4 (6 )
4 (6 )
a
[
H
2H, H
, J(He
H
) 13.4 Hz], 3.04 d.d.d (2H,
vol. 37, no. 44, p. 8011.
4
a
(6 )
2
4
2
3
), 5.46 d [1H, H , J(H H ) 0.83 Hz], thio-
a a
3. Krief, A. and Defrere, L., Tetrahedron Lett., 1996,
4
3
4
3
phene ring: 6.73 d [1H, H , J(H H ) 4.0 Hz], 6.88
vol. 37, no. 15, p. 2667.
3
13
d.d (1H, H ). C NMR spectrum, , ppm: 20.32
4. Krief, A. and Defrere, L., Tetrahedron Lett., 1996,
C
2
1
2
4 (6 )
1
[
5
1
(C ), J(C Se) 77.44 Hz]. 24.75 [C , J(C Se)
vol. 37, no. 44, p. 8015.
5
3
3.29 Hz], 25.08 (C ), thiophene ring: 125.59 (C ),
5. Geens, A. and Anteunis, M., Bull. Soc. Chim. Belg.,
4
5
2
77
1971, vol. 80, p. 639.
25.95 (C ), 129.41 (C ), 144.04 (C ). Se NMR
409.30 ppm. Found, %: C 29.69; H
6
7
8
. Geens, A., Swaelens, G., and Anteunis, M., J. Chem.
Soc., D, 1969, no. 9, p. 439.
spectrum,
.44; S 10.38; Se 47.64; Cl 10.41. C H ClSSe .
Se
2
8
9
2
. Pinto, B.M., Johnston, B.D., and Nagelkerke, R.,
Heterocycles, 1989, vol. 28, no. 1, p. 389.
Calculated.%: C 29.05; H 2.72; S 9.68; Se 47.81;
Cl 10.74. [M]+ 332 ( Se on Cl). M 330.5.
80
35
. Jensen, K.A. and Yenriksen, L., Chem. Scand. Acta
Chim., 1970, no. 9, p. 3213.
The polymer VIb (Tables 1 and 3) was isolated
analogously to the samples VI a and VI a.
9. Baudoux, G., Norberg, B., Wouters, J., Defrere, L.,
Krief, A., and Eurard, G., Acta Cryst., C, 1998,
vol. 54, no. 9, p. 1505.
2
-(1,3-Diselenan-2-yl)thieno[2,3-b]thiophene
IIc). Cooled mixture of 1.18 g of the aldehyde Ic and
.5 ml of Me SiCl was added dropwise at 0 to 5 C
(
4
1
0. Krief, A., Elie, B., and Willy, D., Tetrahedron Lett.,
3
1
993, vol. 34, no. 52, p. 8517.
to 1.41 g of the freshly prepared propan-1,3-diselenol.
Reaction proceeded vigorously with the heat evolution,
11. Mikolajczyk, M., Mikina, M., Graczyk, P.P., Wieczo-
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 76 No. 7 2006