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S. Makowiec et al.
SHORT PAPER
13C NMR (125 MHz, acetone-d6): d = 155.22, 135.33, 132.09,
129.72, 129.53, 129.09, 128.77, 57.23, 28.65, 28.49.
24 h. The precipitate was filtered, washed with MeCN (1 mL) and
Et2O (2 mL), and dried in a vacuum desiccator to yield 4a–g
(Table 1).
3-Allyl-5,6-dihydro[1,4]dithiino[2,3-d]thiazol-3-ium Tetrafluo-
roborate (3c)
References
Compound 2 (1.05 g, 6 mmol) was dissolved in allyl bromide (3 g,
24 mmol) and then sealed in a glass ampoule and heated to 62 °C
for 48 h. The solvent was removed under reduced pressure and the
residue was crystallized (MeOH–Et2O). The crude thiazolium bro-
mide (1.36 g, 4.6 mmol) was dissolved in CH2Cl2 and HBF4·OEt2
(0.626 mL, 4.6 mmol) was added. Solvent was removed under re-
duced pressure and a new portion of CH2Cl2 was added and evapo-
ration was repeated (5 ×). The crude product was recrystallized
(acetone–Et2O); yield: 1.36 g (75%); mp 78–80 °C.
1H NMR (500 MHz, acetone-d6): d = 10.12 (s, 1 H, CH), 6.07–6.23
(m, J = 5.8, 10, 18 Hz, 1 H, CH2=CH), 5.55 (dd, J = 10, 18, 2 H,
CH2=CH), 5.32 (d, J = 5.8 Hz, 2 H, NCH2), 3.61–3.74 (m, 4 H,
CH2CH2).
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13C NMR (125 MHz, acetone-d6): d = 154.98, 135.27, 129.45,
128.42, 122.81, 55.95, 28.83, 28.56.
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67, 354. (b) Kurmoo, M.; Graham, A. W.; Day, P.; Coles, S.
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Matsukawa, N.; Saito, G.; Mori, T.; Kusunoki, M.;
Sakaguchi, K. J. Am. Chem. Soc. 1993, 115, 11319.
(d) Geiser, U.; Schlueter, J. A.; Wang, H. H.; Kini, A. M.;
Williams, J. M.; Sche, P. P.; Zakowicz, H. I.; VanZile, M. L.;
Dudek, J. D. J. Am. Chem. Soc. 1996, 118, 9996.
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3-Ethyl-5,6-dihydro[1,4]dithiino[2,3-d]thiazol-3-ium Tetrafluo-
roborate (3d)
Compound 2 (1.22 g, 7 mmol) was dissolved in EtBr (10.68 g, 98
mmol) and then sealed in a glass ampoule and heated to 62 °C for
21 d. The solvent was removed under reduced pressure and the res-
idue was crystallized (MeOH–Et2O). The crude thiazolium bromide
(1.0 g, 3.52 mmol) was dissolved in CH2Cl2 and HBF4·OEt2 (0.48
mL, 3.52 mmol) was added. Solvent was removed under reduced
pressure and new portion of CH2Cl2 was added and evaporation was
repeated (5 ×). The crude product was recrystallized (CH2Cl2–
Et2O); yield: 0.69 g (34%); mp 107–108 °C.
1H NMR (500 MHz, acetone-d6): d = 10.11 (s, 1 H, CH), 4.62 (q,
J = 7.3 Hz, 2 H, CH2CH3), 3.76 (m, 2 H, CH2), 3.65 (m, 2 H, CH2),
1.66 (t, J = 7.3 Hz, 3 H, CH2CH3).
13C NMR (125 MHz, acetone-d6): d = 154.40, 134.66, 127.78,
49.80, 29.62, 29.46, 13.95.
Tetracyanoquinodimethane Charge Transfer Complexes of
3,3¢-Dialkyl-5,5¢,6,6¢-tetrahydro-3H,3¢H-[2,2¢]bi[1,4]dithi-
ino[2,3-d]thiazoles 4a–g; General Procedure
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2442.
Compound 3 (0.5 mmol) was dissolved under argon in thoroughly
degassed MeCN (10 mL). Et3N (51 mg, 0.5 mmol) was added to a
stirred soln, a deep red color appeared immediately. After 10 min a
soln of TCNQ (102 mg, 0.5 mmol, or 204 mg, 1 mmol, or 306 mg,
1.5 mmol) in MeCN (20, 40, or 60 mL) was added. After 3 h the
soln was concentrated to one fifth of its volume and refrigerated for
(16) Meneghetti, M.; Pecile, C. J. Chem. Phys. 1986, 84, 4149.
Synthesis 2008, No. 5, 696–698 © Thieme Stuttgart · New York