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HETEROCYCLES, Vol. 65, No. 1, 2005
MS (APCI): m/z 347 ([M+1]+).
Anal. Calcd for C10H6N2S6: C, 34.66; H, 1.75; N, 8.08. Found: C,
34.48; H, 1.71; N, 7.83.
2,3-Dicyano-6,7-bis(ethylthio)tetrathiafulvalene (5b). This compound was obtained from the reaction
with 4,5-bis(ethylthio)-1,3-dithiole-2-thione (4b)7 under heating for 3.5 h as purple plates (from hexane);
yield 41 mg (22%), mp 150-152 oC; IR (KBr): ν 2360 (CN); 1H NMR (CDCl3): δ 1.34 (6H, t, J = 7.4
Hz, CH3 x 2), 2.88 (4H, q, J = 7.4 Hz, CH2 x 2); 13C NMR (CDCl3): δ 15.00, 30.81, 109.05, 118.77,
123.26, 128.30; MS (APCI): m/z 375 ([M+1]+).
Anal. Calcd for C12H10N2S6: C, 38.47; H, 2.69; N,
7.48. Found: C, 38.35; H, 2.84; N, 7.43.
2,3-Dicyano-6,7-bis(butylthio)tetrathiafulvalene (5c). This compound was obtained from the reaction
with 4,5-bis(butylthio)-1,3-dithiole-2-thione (4c) under heating for 4 h as purple flakes (from hexane);
yield 87 mg (36%), mp 105-107 oC; IR (KBr): ν 2360 (CN); 1H NMR (CDCl3): δ 0.95 (6H, t, J = 7.3
Hz, CH3 x 2), 1.37-1.60 (4H, m, CH2CH3 x 2), 1.60-1.74 (4H, m, SCH2CH2 x 2), 2.85 (4H, t, J = 7.2 Hz,
SCH2 x 2);
13C NMR (CDCl3): δ 13.54, 21.59, 31.71, 36.30, 100.01, 109.07, 118.76, 123.26, 128.26;
MS (APCI): m/z 431 ([M+1]+).
Anal. Calcd for C16H18N2S6: C, 44.62; H, 4.21; N, 6.50. Found: C,
44.46; H, 3.88; N, 6.30.
2,3-Dicyano-6,7-(ethylenedithio)tetrathiafulvalene (5d).14 This compound was obtained from the
reaction with 4,5-bis(ethylenedithio)-1,3-dithiole-2-thione (4d)7 under heating for 10 h. Methanol (40
mL) was added to the reaction mixture to precipitate purple solid, which was collected and washed with
o
methanol to give 5d as purple crystals (from chlorobenzene); yield 81 mg (47%), mp 236-238 C;
MS (APCI): m/z 345 ([M+1]+).
2,3-Dicyano-6,7-bis(methoxycarbonyl)tetrathiafulvalene (5e).
This compound was obtained from
the reaction with 4,5-bis(methoxycarbonyl)-1,3-dithiole-2-thione (4e)8 under heating for 6.5 h and the
chromatography was performed using petroleum ether-dichloromethane (2:1) as eluent to give as brown
o
needles (from hexane); yield 39 mg (21%), mp 193-194 C; IR (KBr): ν 2340 (CN); 1H NMR
(CDCl3): δ 3.87 (6H, s, CH3 x 2); 13C NMR (CDCl3): δ 53.75, 102.39, 108.79, 118.68, 131.72, 159.04;
MS (APCI): m/z 371 ([M+1]+).
Anal. Calcd for C12H6N2O4S4: C, 38.91; H, 1.63; N, 7.56. Found: C,
38.66; H, 1.54; N, 7.69.
N-Tosyl-2-[4,5-dicyano-1,3-dithiole-2-ylidene]-(1,3)-dithiolo[4,5-c]pyrrole (5f).
tosyl-(1,3)-dithiolo[4,5-c]pyrrole-2-thione (4f)9 (163 mg, 0.5 mmol) was carried out in the thrice amounts
of toluene (300 mL) under heating for 5 h. The product was chromatographed on a silica gel column
The reaction of N-
with petroleum ether-dichloromethane (2:1) as eluent to give 5f as brown microcrystals (from hexane-
o
toluene); yield 55 mg (25%), mp 270 C (decomp); IR (KBr): ν 2360 (CN); 1H NMR (CDCl3):