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N. Stuhr-Hansen et al. / Tetrahedron 67 (2011) 2633e2643
2.52 (2H, t, J 7.7 Hz), 6.97e7.06 (3H, m), 7.25e7.30 (2H, m), 7.38 (1H,
dd, J 5.3, 1.1 Hz), 7.45 (1H, dd, J 5.3, 1.8 Hz) ppm. 13C NMR (CDCl3)
126.45, 127.52, 132.16, 132.83, 134.13, 136.23, 137.60 ppm. 77Se NMR
(DMSO-d6) : 280 ppm.
d:
d
13.68, 22.38, 29.57, 30.06, 31.48, 36.22, 36.40, 122.01, 126.41, 127.77,
129.88, 130.99, 132.01, 132.19, 138.91 ppm. 77Se NMR (CDCl3)
316 ppm.
d:
4.11.9. 3-(N-Phthalimido)propyl 2-thienyl selenide 9i. Yield 0.76 g
(43%). Recrystallised from pentane to give colourless needles; mp
61e62 ꢁC. C15H13NO2SSe: found C 51.38% H 3.81% N 3.85% S 8.97%;
calcd C 51.43% H 3.74% N 4.00% S 9.15%. Mass spectrum (FAB þ, m/z):
4.11.3. p-Bromophenyl 2-thienyl selenide 9c. Yield 1.05 g (66%).
Recrystallised from pentane; faintly yellow solid; mp 50e51 ꢁC.
C10H7BrSSe: found C 37.34% H 2.01% S 9.92%; calcd 37.76% H 2.22% S
10.08%. Purity >98% (GCeMS). Mass spectrum (EI; m/z, relative
351 (Mþ) [80Se]. 1H NMR (CDCl3)
d: 1.95e2.11 (2H, t, J 7.0 Hz),
2.70e2.86 (2H, t, J 7.0 Hz), 3.72e3.87 (2H, t, J 7.0 Hz), 6.90e7.00 (1H,
m), 7.19e7.37 (2H, m), 7.64e7.84 (4H, m) ppm. 13C NMR (CDCl3)
24.86, 32.49, 39.13, 120.94, 123.01, 127.46, 131.21, 132.74, 133.69,
133.98, 167.03 ppm. 77Se NMR (CDCl3)
: 218 ppm.
d
:
intensity): 318 (Mþ, 35), 238 (100), 195 (5). 1H NMR (CDCl3)
d
: 7.03
(1H, dd, J 5.3, 3.5 Hz), 7.16 (2H, d, J 8.6 Hz), 7.28e7.33 (3H, m), 7.45
(1H, dd, J 5.3, 1.1 Hz) ppm. 13C NMR (CDCl3)
: 120.82, 122.45,
128.53, 131.49, 132.19, 132.45, 132.87, 137.22 ppm. 77Se NMR (CDCl3)
: 319 ppm.
d
d
4.11.10. m-Bis(2-thienylseleno)benzene 9j. Yield 1.35 g (67%). Upon
bulb-to-bulb distillation (air-bath 235 ꢁC,1 mmHg) the product was
obtained as a light-yellow oil [purity >98% (GCeMS)], which crys-
tallised into white crystals at room temperature; mp 63e65 ꢁC.
C14H10S2Se2: found C 42.31% H 2.59%; calcd 42.01% H 2.52%. Mass
spectrum (EI; m/z, relative intensity): 402 (Mþ, 38), 322 (3), 242
d
4.11.4. p-Chlorophenyl 2-thienyl selenide 9d. Yield 1.00 g (73%).
Bulb-to-bulb (air-bath 130 ꢁC, 1 mmHg) gave the product as a col-
ourless oil. Purity >98% (GCeMS). C10H7ClSSe: found C 43.63% H
2.61% S 11.31%; calcd 43.89% H 2.58% S 11.72%. Purity >98%
(GCeMS). Mass spectrum (EI; m/z, relative intensity): 274 (Mþ, 26),
(100).1H NMR (DMSO-d6)
(3H, several peaks), 7.33e7.34 (2H, m), 7.79 (2H, d, J 5.2 Hz) ppm. 13C
NMR (CDCl3) : 124.10,125.82,128.55,128.82,132.62,133.87,134.48,
138.18 ppm. 77Se NMR (DMSO-d6)
: 310 ppm.
d: 7.07 (1H, s), 7.11e7.14 (2H, m), 7.16e7.20
238 (3), 194 (100). 1H NMR (CDCl3)
d
: 6.99e7.03 (1H, m), 7.16 (2H, d,
J 7.6 Hz), 7.23 (2H, d, J 7.6 Hz), 7.30 (1H, d, J 2.2 Hz), 7.42e7.49 (1H,
m) ppm. 13C NMR (CDCl3)
: 123.11, 126.20, 129.78, 132.26, 132.81,
133.19, 133.50, 137.84 ppm. 77Se NMR (CDCl3)
: 305 ppm.
d
d
d
d
4.11.11. p-Bis(2-thienylseleno)benzene 9k. Yield 1.27 g (63%). Upon
bulb-to-bulb distillation (air-bath 235 ꢁC,1 mmHg) the product was
obtained as a light-yellow oil [purity >98% (GCeMS)], which crys-
tallised into white crystals at room temperature; mp 80e81 ꢁC.
C14H10S2Se2: found C 42.39% H 2.52%; calcd 42.01% H 2.52%. Mass
spectrum (EI; m/z, relative intensity): 402 (Mþ, 23), 322 (5), 281 (3),
4.11.5. o-Nitrophenyl 2-thienyl selenide 9e. Yield 0.68 g (48%).
Recrystallised from pentane; yellow needles; mp 58e59 ꢁC.
C10H7NO2SSe: found C 42.32% H 2.41% N 4.83% S 11.29%; calcd
42.26% H 2.48% N 4.93% S 11.28%. Mass spectrum (EI; m/z, relative
intensity): 285 (Mþ, 46), 238 (17), 185 (100). 1H NMR (CDCl3)
d
: 7.05
(1H, d, J 8.0 Hz), 7.17e7.21 (1H, m), 7.26e7.43 (3H, m), 7.65 (1H, d, J
5.25 Hz), 8.31 (1H, d, J 8.0 Hz) ppm. 13C NMR (CDCl3)
: 123.73,
127.86, 129.17, 130.39, 131.37, 132.88, 135.17, 137.28, 146.34,
150.56 ppm. 77Se NMR (CDCl3)
: 384 ppm.
242 (100).1H NMR (DMSO-d6)
J 3.6 Hz), 7.75 (2H, d, J 5.5 Hz) ppm.13C NMR (CDCl3)
131.27,132.15,133.35,133.80 ppm. 77Se NMR (DMSO-d6)
d
: 7.11 (2H, m), 7.21 (4H, s), 7.39 (2H, d,
: 123.74,128.58,
: 306 ppm.
d
d
d
d
4.11.12. 2,5-Bis(methoxymethyl)-1,4-bis(2-thienylseleno)benzene
9l. Yield 0.88 g (36%). Recrystallised from heptane43 affording 9l as
colourless plates, mp 118e119 ꢁC. C18H18O2S2Se2: found C 44.14% H
3.63%; calcd C 44.27% H 3.71%. Mass spectrum (EI; m/z, relative
intensity): 490 (Mþ, 76), 457 (8), 406 (24), 322 (12), 279 (13), 247
4.11.6. 2,20-Dithienyl selenide 9f42. Yield 0.53 g (43%). Upon bulb-
to-bulb distillation (air-bath 175 ꢁC, 6.8 mmHg) the product was
obtained as a light-yellow oil. Purity >98% (GCeMS). Mass spec-
trum (EI; m/z, relative intensity): 246 (Mþ, 26), 201 (6), 166 (100).
(22), 171 (63), 127 (100). 1H NMR (DMSO-d6)
d
: 3.06 (6H, s), 4.23
(4H, s), 6.95 (2H, s), 7.15 (2H, dd, J 5.2, 3.4 Hz), 7.43 (2H, d, J 3.4 Hz),
7.80 (2H, d, J 5.2 Hz) ppm. 13C NMR (CDCl3)
: 57.89, 74.15, 122.99,
128.44, 130.22, 130.71, 132.22, 133.03, 137.39 ppm. 77Se NMR
(DMSO-d6) : 381 ppm.
1H NMR (CDCl3)
d
: 6.94 (2H, dd, J 5.3, 3.6 Hz), 7.26 (2H, dd, J 3.6,
1.2 Hz), 7.35 (2H, dd, J 5.3, 1.2 Hz) ppm. 13C NMR (CDCl3)
: 122.66,
127.33, 130.78, 133.85 ppm. 77Se NMR (CDCl3)
: 249 ppm.
d
d
d
d
4.11.7. 2,5-Dimethylphenyl 2-thienyl selenide 9g. Yield 0.95 g (71%).
Bulb-to-bulb (air-bath 190 ꢁC, 0.6 mmHg) gave the product as
a colourless oil. Purity >98% (GCeMS). C12H12SSe: found C 53.96% H
4.52%; calcd 53.96% H 4.53%. Purity >98% (GCeMS). Mass spectrum
(EI; m/z, relative intensity): 268 (Mþ, 61), 253 (3), 238 (2), 188 (81),
174 (47), 155 (18), 143 (11), 103 (42), 91 (22), 77 (100). 1H NMR
Supplementary data
Supplementary data associated with this article can be found in
(CDCl3)
7.02e7.08 (2H, several peaks), 7.29 (1H, dd, J 3.6, 1.2 Hz), 7.47 (1H,
dd, J 5.2, 1.2 Hz) ppm. 13C NMR (CDCl3)
: 20.09, 22.49, 122.47,
126.10, 127.13, 127.91, 129.52, 130.92, 132.25, 132.72, 136.81,
138.29 ppm. 77Se NMR (CDCl3)
: 278 ppm.
d: 2.19 (3H, s), 2.38 (3H, s), 6.90e6.93 (2H, several peaks),
References and notes
d
1. Pitombo, L. R. M. Chem. Ber. 1959, 92, 745.
2. Freudendahl, D. M.; Shahzad, S. A.; Wirth, T. Eur. J. Org. Chem. 2009, 1649.
3. Nicolaou, K. C.; Claremon, D. A.; Barnette, W. E.; Seits, S. P. J. Am. Chem. Soc.
1979, 101, 3704.
d
4. Gassman, P. G.; Miura, A.; Miura, T. J. Org. Chem. 1982, 47, 951.
5. Lindgren, G.; Schmid, G. H. Chem. Scr. 1984, 23, 98.
4.11.8. 2,5-Bis(methoxymethyl)phenyl 2-thienyl selenide 9h. Yield
0.67 g (41%). Bulb-to-bulb (air-bath 200 ꢁC, 2 mmHg) gave the
product as a colourless oil. Purity >98% (GCeMS). C14H16O2SSe:
found C 51.54% H 4.94%; calcd 51.38% H 4.93%. Purity >98%
(GCeMS). Mass spectrum (EI; m/z, relative intensity): 328 (Mþ, 73),
295 (47), 244 (82), 184 (26), 171 (30), 119 (30), 91 (96), 45 (100). 1H
6. Yoshida, M.; Sasage, S.; Kawamura, K.; Suzuki, T.; Kamigata, N. Bull. Chem. Soc.
Jpn. 1991, 64, 416.
7. (a) Tiecco, M.; Testaferri, L.; Tingoli, M.; Marini, F.; Mariggio, S. Tetrahedron
1994, 50, 10549; (b) Engman, L.; Eriksson, P. Heterocycles 1996, 43, 861.
8. Henriksen, L. Tetrahedron Lett. 1994, 35, 7057.
9. Henriksen, L.; Stuhr-Hansen, N. Synth. Commun. 1996, 26, 1897.
10. Henriksen, L.; Stuhr-Hansen, N. Phosphorus, Sulfur Silicon 1998, 136e138, 175.
11. Stuhr-Hansen, N.; Henriksen, L. Synth. Commun. 1997, 27, 89.
12. Brust, M.; Stuhr-Hansen, N.; Nørgaard, K.; Christensen, J. B.; Nielsen, L. K.;
Bjørnholm, T. Nano. Lett. 2001, 1, 189.
NMR (DMSO-d6) d: 3.17 (3H, s), 3.29 (3H, s), 4.26 (2H, s), 4.50 (2H, s),
7.03 (1H, d, J 1.4 Hz), 7.13e7.18 (2H, several peaks), 7.34 (1H, d, J
7.7 Hz), 7.44 (1H, dd, J 3.6, 1.1 Hz), 7.47 (1H, dd, J 5.2, 1.1 Hz) ppm. 13C
NMR (CDCl3)
d: 58.66, 59.32, 73.76, 74.91, 122.08, 125.19, 126.24,
13. Rheinboldt, H.; Giesbrecht, E. Chem. Ber. 1955, 88, 666.