SYNTHESIS
Papers
1446
13C NMR (CDCl3): δ = 12.59, 15.90, 19.54, 119.80, 123.32, 129.27,
129.52, 131.03, 131.28, 131.36, 131.48, 133.59, 135.32, 136.59,
136.64, 138.85, 149.35, 187.13, 187.58, 189.69.
1H NMR (CDCl3): δ = 1.34 (t, 3H, CH3, J = 7.1 Hz), 2.14 (s, 3H,
CH3), 2.65 (s, 6H, CH3), 4.29 (q, 2H, CH2, J = 7.1 Hz), 7.36–7.76
(m, 4H, Ar).
13C NMR (CDCl3): δ = 12.61, 14.71, 17.08, 19.45, 62.20, 118.65,
124.26, 131.06, 131.38, 131.41, 131.50, 135.12, 136.89, 139.54,
152.83, 159.97, 180.23, 184.72.
Anal. Calcd for C22H18N2OS4: C, 58.12; H, 3.99; N, 6.16; S, 28.21;
found C, 58.18; H, 3.92; N, 5.96; S, 28.42.
Anal. Calcd for C18H18N2O2S2Se2: C, 41.87; H, 3.51; N, 5.42. Found
C, 41.50; H, 3.46; N, 5.48.
1,2-Bis(2-selenoxo-2,3-dihydrothiazol-3-yl)benzene 14; General
Procedure:
14h R1 = CH3, R2 = CO2Et, R3 = CH3, R4 = CO2Et; yield: 0.68 g
(79%); mp 209–210°C; Rf = 0.43.
To a solution of 1,2-bis(2-thioxo-2,3-dihydrothiazol-3-yl)benzene
(1.5 mmol) in CHCl3 (20 mL) was added HC(OEt)3 (2 mL,
1H NMR (CDCl3): δ = 1.35 (t, 6H, CH3, J = 7.1 Hz), 2.61 (s, 6H,
CH3), 4.30 (q, 4H, CH2, J = 7.1 Hz), 7.39–7.80 (m, 4H, Ar).
13C NMR (CDCl3): δ = 14.21, 18.81, 61.82, 118.51, 131.05, 131.09,
135.27, 151.94, 159.45, 184.23.
•
12 mmol) and Et2O BF3 (2 mL, 16 mmol). The mixture was refluxed
for 15 min and stirred at r.t. overnight. Anhyd Et2O (25 mL) was
added to the solution, the resulting oil was washed several times with
Et2O, and 13 precipitated with the addition of EtOH. The salt was
dried under vacuum and used without further purification. A solution
of thiazolium salt 13 in anhyd MeCN (15 mL) was slowly added to a
mixture of NaBH4 (250 mg, 6.6 mmol) and selenium powder
(475 mg, 6 mmol) in degassed abs EtOH (100 mL). After stirring for
30 min, the mixture was poured into 2% AcOH (100 mL). The red
precipitate was filtered off and washed with CH2Cl2 several times.
The aqueous layer was separated from the filtrate and extracted with
CH2Cl2 (2 × 75 mL). The combined organic phases were washed
with water (3 × 100mL), dried (MgSO4) and the solvent was evapo-
rated. The residue was column chromatographed (silica gel, 80 g,
CH2Cl2) to yield 14 as yellow powder.
Anal. Calcd for C20H20N2O4S2Se2: C, 41.82; H, 3.51; N, 4.88; S,
11.16. Found C, 41.49; H, 3.42; N, 4.87; S, 11.02.
14i R1 = CH3, R2 = SCH3, R3 = CH3, R4 = CH3; yield: 0.40 g (54%);
mp 200°C; Rf = 0.50.
1H NMR (CDCl3) δ = 2.10 (s, 3H, CH3), 2.11 (s, 3H, CH3), 2.32 (s,
3H, CH3), 2.35 (s, 3H, CH3), 7.33–7.71 (m, 4H, Ar).
13C NMR (CDCl3) δ = 12.59, 17.11, 18.41, 20.77, 121.21, 124.02,
131.05, 131.14, 131.16, 131.29, 136.49, 136.62, 139.73, 148.16,
180.13, 183.57.
Anal. Calcd for C16H16N2S3Se2: C, 39.19; H, 3.29; N, 5.71. Found C,
38.69; H, 3.31; N, 5.66.
14a R1 = CH3, R2 = CH3, R3 = CH3, R4 = CH3; yield: 0.58 g (84%),
mp 252°C (dec); Rf = 0.26.
14j R1 = CH3, R2 = SCH3, R3 = CH3, R4 = SCH3; yield: 0.20 g
(26%); mp 192°C (dec); Rf = 0.70.
1H NMR (CDCl3): δ = 2.13 (s, 6H, CH3), 2.19 (s, 6H, CH3), 7.37–
7.73 (m, 4H, Ar).
1H NMR (CDCl3) δ = 2.32 (s, 6H, CH3), 2.33 (s, 6H, CH3), 7.37–
7.73 (m, 4H, Ar).
13C NMR (CDCl3): δ = 12.55, 17.33, 123.90, 131.05, 131.38,
136.85, 140.00, 180.24.
13C NMR (CDCl3) δ = 18.36, 20.81, 121.50, 131.14, 131.25, 136.37,
147.95, 183.55.
Anal. Calcd for C16H16N2S2Se2: C, 41.93; H, 3.52; N, 6.11; S, 13.99.
Found C, 42.21; H, 3.54; N, 6.26; S, 14.41.
Anal. Calcd for C16H16N2S4Se2: C, 36.78; H, 3.08; N, 5.36; S, 24.54;
found C, 36.24; H, 2.93; N, 5.27; S, 24.37.
14b R1 = CH3, R2 = H, R3 = CH3, R4 = CH3; yield: 0.30 g (45%), mp
212°C; Rf = 0.25.
DTDAF; General Procedure:
1H NMR (CDCl3): δ = 2.08 (s, 3H, CH3), 2.14 (s, 3H, CH3), 2.29 (d,
3H, CH3, J = 1.0 Hz), 6.51 (d, 1H, =CH, J = 1.0 Hz), 7.34–7.70 (m,
4H, Ar).
A suspension of bis(thiazole-2(3H)-selone) 14 (0.1 mmol) in
degassed toluene (2 mL) and P(OEt)3 (34 µL, 0.2 mmol), freshly dis-
tilled, was heated to 110 ˚C under argon for 30 min. After cooling to
r.t., the DTDAF generated in the medium can be trapped in situ by
adding a solution of an acceptor.5
13C NMR (CDCl3): δ = 12.51, 17.06, 19.15, 112.77, 123.76, 130.93,
131.04, 131.16, 131.31, 135.83, 136.63, 139.79, 144.94, 180.07,
182.68.
Anal. Calcd for C15H14N2S2Se2: C, 40.55; H, 3.18; N, 6.30. Found C,
40.74; H, 3.23; N, 6.26.
(1) Tormos, G. V.; Bakker, M. G.; Wang, P.; Lakshmikantham, M.
V.; Cava, M. P.; Metzger, R. M. J. Am. Chem. Soc. 1995, 117,
8528, and references cited therein.
(2) For a recent review see: Schukat, G.; Fanghänel, E. Sulfur Rep.
1996, 18, 1.
(3) Hansen, T. K.; Becher, J. Adv. Mater. 1993, 5, 289.
(4) Bssaibis, M.; Robert, A.; Le Maguerès, P.; Ouahab, L.; Carlier,
R.; Tallec, A. J. Chem. Soc., Chem. Commun. 1993, 601.
(5) Bellec, N.; Lorcy, D.; Robert, A.; Carlier, R.; Tallec, A.; Rim-
baud, C.; Ouahab, L.; Clerac R.; Delhaes, P. Adv. Mater. 1997,
9, 1052.
14c R1 = H, R2 = H, R3 = CH3, R4 = CH3; yield: 0.54 g (83%); mp
245°C (dec); Rf = 0.38.
1H NMR (CDCl3): δ = 2.12 (s, 3H, CH3), 2.14 (s, 3H, CH3), 6.77 (d,
1H, =CH, J = 4.5 Hz), 7.45–7.99 (m, 4H, Ar), 8.16 (d, 1H, =CH, J =
4.5 Hz).
13C NMR (CDCl3): δ = 12.55, 15.10, 115.94, 123.53, 131.44,
131.51, 131.84, 132.17, 135.42, 135.75, 136.61, 139.17, 182.40,
183.25.
Anal. Calcd for C14H12N2S2Se2: C, 39.08; H, 2.81; N, 6.51; S, 14.90.
Found C, 39.18; H, 2.72; N, 6.50; S, 15.18.
(6) Lorcy, D.; Robert, A.; Carlier, R.; Tallec, A. Bull. Soc. Chim.
Fr. 1994, 131, 774.
(7) Bssaibis, M.; Robert, A.; Souizi, A. J. Chem. Soc., Chem. Com-
mun. 1993, 998.
(8) Bssaibis, M.; Robert, A.; Souizi, A. J. Chem. Soc., Perkin
Trans. 1 1994, 1469.
(9) Green, D. C. J. Org. Chem. 1979, 44, 1476.
(10) Svenstrup, N.; Becher, J. Synthesis 1995, 215.
(11) Moore, A. J.; Bryce, M. R.; Batsanov, A. S.; Cole, J. C.;
Howard, J. A. K. Synthesis 1995, 675.
14f R1 = CH3, R2 = H, R3 = CH3, R4 = H; yield: 0.28 g (44%), mp
200°C (dec); Rf = 0.25.
1H NMR (CDCl3): δ = 2.35 (d, 6H, CH3, J = 1.0 Hz), 6.53 (d, 2H,
=CH, J = 1.0 Hz), 7.41–7.77 (m, 4H, Ar).
Anal. Calcd for C14H12N2S2Se2: C, 39.08; H, 2.81; N, 6.51; S, 14.90.
Found C, 38.53; H, 2.76; N, 6.42; S, 14.50.
14g R1 = CH3, R2 = CO2Et, R3 = CH3, R4 = CH3; yield: 0.29 g
(37%), mp 172°C; Rf = 0.40.