633303-45-4Relevant academic research and scientific papers
Reactions of stable α-chlorosulfanyl chlorides with C = S-functionalized compounds
Majchrzak, Agnieszka,Janczak, Aleksandra,Mloston, Grzegorz,Linden, Anthony,Heimgartner, Heinz
, p. 2272 - 2283 (2003)
The smooth reaction of 3-chloro-3-(chlorosulfanyl)-2,2,4,4-tetramethylcyclobutanone (3) with 3,4,5-trisubstituted 2,3-dihydro-1H-imidazole-2-thiones 8 and 2-thiouracil (10) in CH2Cl2/Et3N at room temperature yielded the corresponding disulfanes 9 and 11 (Scheme 2), respectively, via a nucleophilic substitution of Cl- of the sulfanyl chloride by the S-atom of the heterocyclic thione. The analogous reaction of 3-cyclohexyl-2,3-dihydro-4,5-diphenyl-1H-imidazole-2-thione (8b) and 10 with the chlorodisulfanyl derivative 16 led to the corresponding trisulfanes 17 and 18 (Scheme 4), respectively. On the other hand, the reaction of 3 and 4,4-dimethyl-2-phenyl-1,3-thiazole-5(4H)-thione (12) in CH2Cl2 gave only 4,4-dimethyl-2-phenyl-1,3-thiazol-5(4H)-one (13) and the trithioorthoester derivative 14, a bis-disulfane, in low yield (Scheme 3). At - 78°, only bis(1-chloro-2,2,4,4-tetramethyl-3-oxocyclobutyl)polysulfanes 15 were formed. Even at -78°, a 1:2 mixture of 12 and 16 in CH2Cl2 reacted to give 13 and the symmetrical pentasulfane 19 in good yield (Scheme 5). The structures of 11, 14, 17, and 18 have been established by X-ray crystallography.
Synthesis and reactions of a new cyclobutanethione derivative
Mloston, Grzegorz,Majchrzak, Agnieszka,Rutkowska, Marzena,Woznicka, Marta,Linden, Anthony,Heimgartner, Heinz
, p. 2624 - 2636 (2005)
The 3,3-dichloro-2,2,4,4-tetramethylcyclobutanethione (4b) was prepared from the parent diketone by successive reaction with PCl5 and Lawesson reagent in pyridine. This new thioketone 4b was transformed into 1-chlorocyclobutanesulfanyl chloride 5 and chloro 1-chlorocyclobutyl disulfide 9 by treatment with PCl5 and SCl2, respectively, in chlorinated solvents (Schemes 1 and 2). These products reacted with S- and P-nucleophiles by substitution of Cl- at the S-atom; e.g., the reaction with 4b yielded the di- and trisulfides 6b and 11, respectively. Surprisingly, only pentasulfide 12 was formed in the reaction of 9 with thiobenzophenone (Scheme 3). In contrast to 5 and 9, the corresponding chloro 1-chlorocyclobutyl trisulfide 13 could not be detected, but reacted immediately with the starting thioketone 4b to give the tetrasulfide 14 (Scheme 4). Oxidation of 4b with 3-chloroperbenzoic acid (mCPBA) yielded the corresponding thione oxides (=sulfine) 15, which underwent 1,3-dipolar cycloadditions with thioketones 3a and 4b (Scheme 5). Furthermore, 4b was shown to be a good dipolarophile in reactions with thiocarbonylium methanides (Scheme 6.) and iminium ylides (=azomethine ylides; Scheme 7). In the case of phenyl azide, the reaction with 4b gave the symmetrical trithiolane 25 (Scheme 8).
