Binary Carbon Sulfides Based on the .alpha.-C3S5 Subunit and Related C-S-O, C-S-Cl, and C-S-N Compounds

Pyridyl-substituted [1,3]Dithiolo-[4,5-b][1,4]dithiine-2-thiones

“…A method has been described for obtaining substituted 4,5-ethylenedithio-1,3-dithiol-2-thiones, based on the reaction observed by the authors of [10,11] between alkenes and isotrithionedithiol, a compound to which they assigned a polymeric structure (C 3 S 5 ) x . As we established in [12], isotrithionedithiol, synthesized by oxidation of a solution of sodium isotrithionedithiolate Na 2 C 3 S 5 in DMF by a methanol solution of iodine at 0°C, has a dimer structure: C 6 S 10 , which is consistent with X-ray diffraction data [13] and allows us to hypothesize the possibility of a Diels-Alder type reaction between isotrithionedithiol and alkenes (Scheme 1).Accordingly, the aim of this work was to study the products of condensation of isotrithionedithiol with 2-and 4-vinylpyridines, obtained by the method of O. Neiland and J. Becher, and also with 2-ethynylpyridine. In the latter case, a bicyclic conjugated system is formed.…”

“…UV spectrum (MeCN), λ max , nm (log ε): 408 (3.65), shoulder 327, 308 (3.61), 257 (3.69). 13 C NMR spectrum (CD 2 Cl 2 ), δ, ppm: 35.30 (SCH 2 ); 49.74 (CHPy); 123.03 (C (3)pyrid ); 123.75 (C (5)pyrid ); 124.24 (C=C); 137.50 (C (4)pyrid ); 150.25 (C (6)pyrid ); 156.91 (C (2)pyrid ); 208.88 (C=S).…”

“…UV spectrum (MeCN), λ max , nm (log ε): 406 (3.56), 268 (3.42). 13 2-Ethynylpyridine (0.5 ml, 5.14 mmol) was added to isotrithionedithiol (0.5 g, 1.27 mmol) in benzene (25 ml). The reaction mixture was boiled under reflux for 17 h. After cooling, the solution was filtered, and the solvent was evaporated on a rotary evaporator.…”

“…1 H NMR spectrum (benzene-d 6 ), δ, ppm (J, Hz): 6.84 (1H, s, HCS); 7.28 (1H, ddd, J = 7.5, J = 4.8, J = 1, H (5)pyrid ); 7.30 (1H, dd, J = 7.5, J = 1, H (3)pyrid ); 7.60 (1H, dt, J = 8 and J = 1, H (4)pyrid ); 8.60 (1H, dd, J = 4.8 and J = 1, H (6)pyrid ). 13 C NMR spectrum (benzene-d 6 ), δ, ppm (J, Hz): 120.05 (C (3)pyrid ); 121.5 (C (6) ); 122.67 (C (5)pyrid ); 123.89 (C (3a) or C (7a) ); 137.18 (C (4)pyrid ); 142.2 (C (5) ); 149.84 (C (6)pyrid ); 156.6 (C (2)pyrid ); we could not identify C (7a) or C (3a) due to the low signal-to-noise ratio of the C=S signal. Found, %: C 39.42; H 1.92; N 4.57.…”

Notizen: C4S8 2- and C16S18 4-: Intermediates in the Synthesis of PoIy(Carbon Sulfide)

“…The polym er (C 8S82~)" (1) is obtained in a two step process starting with the base hydrolysis of the tricyclic b is(dithiocarbonate) C6S80 2 [6 ] which gives N a2C4S" [1]. A ddition of PPh4Cl to these so lutions gives (P P h 4)2C4S" which upon heating at 80 °C is converted in 1 [1].…”