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BENZOTHIACROWN ETHER FORMYL DERIVATIVES
1913
filtered off, the mother liquor was concentrated in vacuo, and the residue was
dissolved in 50 ml of ethyl acetate and washed successively with 5% aqueous
solutions of Na2SO3 and Na2CO3 and with water. The solvent was evapo-
rated in vacuo and the residue was chromatographed on a column with silica
gel(Kieselgel60, 0.063–0.100 mm, elution with benzene–MeCO 2Et, 20 : 1) to
give 8.3 g of diiodide 1c (85%). 1H NMR (500 MHz, CDCl3–CCl4): ꢀ 3.49 (m,
4H, 2CH2I), 4.38 (m, 4H, 2CH2O), 7.00 (d, 1H, H-6, J ¼ 8.1 Hz), 7.43 (s, 1H,
H-3), 7.47 (d, 1H, H-5, J ¼ 8.1 Hz), 9.86 (s, 1H, CH¼O); Anal. calcd for
C11H12I2O3: C, 29.62; H, 2.71. Found: C, 30.07; H, 2.69.
Preparation of crown compounds 3a–e (General procedure). At
75–85ꢁC, solutions of dihalide 1b,c (4.24 mmol) and dithiol 2a–e
(4.66 mmol), each in 10 ml of a solvent (EtOH/H2O, MeCN, MeCN/H2O,
DMF, DMF/H2O), were added simultaneously with stirring over a period
of 1 h to a mixture of M2CO3 (M ¼ Li, Na, K, Cs) (21.2 mmol) in 200 ml of a
solvent. The reaction mixture was kept at the specified temperature for
13–20 h, the solvent was evaporated, 100 ml of water was added to the
residue, and the products were extracted with a benzene–CHCl3 mixture
(10 : 1). The extracts were concentrated in vacuo and the residue was chro-
matographed on a column with silica gel (Kieselgel 60, 0.063–0.100 mm); the
products were eluted successively with benzene and a benzene–MeCO2Et
mixture (20 : 1).
3a: 1H NMR: ꢀ 2.98 (m, 4H, 2CH2S), 3.07 (s, 4H, 2CH2S), 4.42
(m, 4H, 2CH2O), 6.92 (d, 1H, H-6, J ¼ 8.1 Hz), 7.36 (s, 1H, H-3), 7.47
(d, 1H, H-5, J ¼ 8.1 Hz), 9.85 (s, 1H, CH¼O); Anal. calcd for C13H16O3S2:
C, 54.90; H, 5.67. Found: C, 54.78; H, 5.61; b) 3b, 3c were published in
1
Ref. [13]; c) 3d: H NMR, ꢀ 2.95 (m, 4H, 2CH2S), 3.05 (s, 4H, 2CH2S),
3.66 (m, 8H, 4CH2O), 3.78 (m, 4H, 2CH2O), 4.27 (m, 4H, 2CH2O), 6.96
(d, 1H, H-6, J ¼ 8.2 Hz), 7.39 (s, 1H, H-3), 7.45 (d, 1H, H-5, J ¼ 8.2 Hz),
9.85 (s, 1H, CH¼O); Anal. calcd for C19H28O6S2: C, 54.78; H, 6.78.
1
Found: C, 54.56; H, 6.81; d) 3e: H NMR ꢀ 2.81–2.94 (m, 6H, 3CH2S),
2.97–3.15 (m, 10H, 5CH2S), 4.27–4.39 (m, 4H, 2CH2O), 6.98 (d, 1H, H-6,
J ¼ 8.2 Hz), 7.41 (s, 1H, H-3), 7.47 (d, 1H, H-5, J ¼ 8.2 Hz), 9.86 (s, 1H,
CH¼O); Anal. calcd for C17H24O3S4: C, 50.46; H, 5.98. Found: C, 50.65;
H, 6.04.
ACKNOWLEDGMENT
The study was supported by the INTAS (96-1142), DFG (Grant
436RUS 113/56/0), RFBR-DFG (Grant 98-03-04137) and the Ministry
for Science and Technologies of Russia.