607-53-4Relevant articles and documents
Combined Experimental and Theoretical Studies on the Radical Nucleophile Addition Reaction for Sulfide- and Selenide-Centered Anions
Bouchet, Lydia M.,Pe?é?ory, Alicia B.,Pierini, Adriana B.,Argüello, Juan E.
, p. 5035 - 5042 (2019/06/17)
The reactivity of sulfur- and selenium-centered nucleophiles toward 1-naphthyl radicals was studied in dimethylsulfoxide. The photostimulated reaction of sulfide anions, -SC(NH)C6H5 (1), -SC(NH)NH2 (2), and -SC(NH)CH3 (3), renders, after the addition of MeI, methyl 1-naphthylsulfide as a main product together with bis(1-naphthyl) sulfide and naphthalene under irradiation. Concordantly, the reaction of selenide anions, -SeC(NH)C6H5 (4), -SeC(NH)NH2 (5), and -SeCN (6), produces methyl 1-naphthyl selenide, bis(1-naphthyl) selenide, and naphthalene in the presence of potassium tert-butoxide anion (entrainment conditions). Absolute rate constants for the coupling of ions 1-6 to 1-naphthyl radicals were determined; as a general trend, the selenide-centered nucleophiles enhance in 2 times the reactivity of their sulfide analogues. From the mechanistic study, it is proposed that the unstable radical anion produced by the addition of the nucleophile to 1-naphthyl radical affords, after fragmentation, 1-naphthylsulfide/selenide anion. In addition, experimental results are discussed in terms of density functional theory calculations. There is a generally good agreement between the experimental and the calculated reactivities, the spin density being the main parameter to describe the difference found among the anions under study. Moreover, the calculations predict that anion -SeC(NH)CH3 (7) would be a good candidate for the synthesis of selenide derivatives.
Photoinduced nucleophilic substitution of aryl halides with potassium thioacetate - A one-pot approach to aryl methyl and diaryl sulfides
Schmidt, Luciana C.,Rey, Valentina,Penenory, Alicia B.
, p. 2210 - 2214 (2007/10/03)
Aryl methyl sulfides and diaryl sulfides were prepared by photoinduced reactions of potassium thioacetate with aryl halides under entrainment conditions. Without isolation, the arene thiolates obtained by the aromatic substitution were quenched with methyl iodide to afford the aryl methyl sulfides in 26-59% yields in a "one-pot" procedure together with the diaryl sulfides in variable yields (3-31 %). By optimization of the reaction conditions it was possible to improve the formation of the Ar2S, going from moderate to good yields (64-83%). Wiley-VCH Verlag GmbH & Co. KGaA, 2006.
One-Pot Two-Step Synthesis of Aryl Sulfur Compounds by Photoinduced Reactions of Thiourea Anion with Aryl Halides
Argueello, Juan E.,Schmidt, Luciana C.,Penenory, Alicia B.
, p. 4133 - 4136 (2007/10/03)
(Equation presented) The photoinduced reactions of aryl halides with the thiourea anion afford arene thiolate ions in DMSO. These species without isolation, and by a subsequent aliphatic nucleophilic substitution, S RN1 reaction, oxidation, or protonation, yield aryl methyl sulfides, diaryl sulfides, diaryl disulfides, and aryl thiols with good yields (50-80%). This is a simple and convenient approach which involves the use of the commercially available and inexpensive thiourea in a one-pot two-step process for the synthesis of aromatic sulfur compounds.