39167-46-9Relevant academic research and scientific papers
Breaking bonds with electrons: Stepwise and concerted reductive cleavage of C-S, C-Se and Se-CN bonds in phenacylthiocyanates and phenacylselenocyanates
Bouchet, Lydia M.,Peory, Alicia B.,Robert, Marc,Argüello, Juan E.
, p. 11753 - 11760 (2015/02/19)
The mechanistic aspects of the electrochemical reduction of phenacylthio- and selenocyanates have been studied. With phenacylthiocyanates (1), a change in the reductive cleavage mechanism is observed as a function of the substituent on the phenyl ring. While a stepwise mechanism involving the intermediacy of a radical anion is followed for substrates bearing a strong electron withdrawing group, such as cyano and nitro substituent (1d, 1e), and a concerted mechanism is favoured for compounds bearing an electron-donating or no substituent on the phenyl ring (1a-c). A regioselective bond cleavage leads to the fragmentation of the CH2-S bond with all compounds 1a-e, further yielding the corresponding 1,4-diketone (3) as products. Contrastingly, with phenacylselenocyanates (2), two different reductive cleavages occur involving the breaking of both the CH2-Se and Se-CN bonds. Several products are obtained, all coming from nucleophilic attack at the α (phenacyl) carbon or the selenium atom.
SYNTHESES WITH DIKETO SELENIDES
Nakayama, Juzo,Shibuya, Masahiro,Ikuina, Yoji,Murai, Fumito,Hoshino, Masamatsu
, p. 149 - 156 (2007/10/02)
We report a) a modified synthesis of diketo selenides, b) preparation of 2,5-diacylselenophenes by condensation of diketoselenides with glyoxal, c) preparation of poly-substituted selenophenes by intramolecular reductive coupling reaction of diketo selenides with low-valent titanium reagent under controlled conditions (0 degC) followed by dehydratation of the resulting 3,4-dihydroxyselenolanes, and d) formation of 2,5-dihydroselenophenes and 1,3-dienes by treatment of diketo selenides with the low-valent titanium reagent in refluxing tetrahydrofuran.
PREPARATION OF 2,5-DIACYLSELENOPHENES BY CONDENSATION 0F α,α'-DIKETOSELENIDES WITH GLYOXAL
Nakayama, Juzo,Shibuya, Masahiro,Hoshino, Masamatsu
, p. 909 - 912 (2007/10/02)
The reaction of selenium oxychloride with 2 equiv. of ketones affords α,α'-diketo selenide dichlorides (1) in excellent yields.Portionwise addition of 1 to a stirred two-phase mixture of an aqueous sodium dithionite solution and benzene gives α,α'-diketo
