3314-83-8Relevant academic research and scientific papers
Regioselective Synthesis of Vinyl Halides, Vinyl Sulfones, and Alkynes: A Tandem Intermolecular Nucleophilic and Electrophilic Vinylation of Tosylhydrazones
Ojha, Devi Prasan,Prabhu, Kandikere Ramaiah
, p. 18 - 21 (2015/07/28)
A diazo species is trapped in an intermolecular fashion by two independent ion species in tandem at the carbene center to install an electrophile and a nucleophile on the same carbon. This metal-free concept, which is unprecedented, has been illustrated by regioselective synthesis of a variety of vinyl halides, vinyl sulfones, and alkyne derivatives. (Chemical Equation Presented).
Dissociation of the disilatricyclic diallylic dianion [(C 4Ph4SiMe)2]-2 to the silole anion [MeSiC4Ph4]- by halide ion coordination or halide ion nucleophilic substitution at the silicon atom
Hong, Jang-Hwan
experimental part, p. 8451 - 8462 (2011/12/03)
The reductive cleavage of the Si-Si bond in 1,1-bis(1-methyl-2,3,4,5- tetraphenyl-1-silacyclopentadiene) [(C4Ph4SiMe) 2] (1) with either Li or Na in THF gives the silole anion [MeSiC 4Ph4]- (2). The head-to-tail dimerization of the silole anion 2 gives crystals of the disilatricyclic diallylic dianion [(C4Ph4SiMe)2]-2 (3). The derivatization of 3 (crystals) with bromoethane (gas) under reduced pressure provides [(MeSiC4Ph4Et)2] (4) quantitatively. The reverse addition of 3 in THF to trimethylsilyl chloride, hydrogen chloride, and bromoethane in THF gives 1-methyl-1-trimethylsilyl-1-silole [Me 3SiMeSiC4Ph4] (6), 1-methyl-2,3,4,5- tetraphenyl-1-silacyclo-3-pentenyl-1-methyl-1-silole [C4Ph 4H2SiMe-MeSiC4Ph4] (7), and 1-methyl-2,5-diethyl-2,3,4,5-tetraphenyl-1-silacyclo-3-pentenyl-1-methyl-1- silole [C4Ph4Et2SiMe-MeSiC4Ph 4] (8), respectively. The reaction products unambiguously suggest that the silole anion [MeSiC4Ph4]- is generated by coordination of the chloride ion at the silicon atom in 3 or by the nucleophilic substitution of either chloride or bromide ion at one of two silicon atoms in 3. The quenching reaction of 3 dissolved in THF with water gives 1,2,3,4-tetraphenyl-2-butene, the disiloxane of 1-methyl-2,3,4,5- tetraphenyl-1-silacyclo-3-pentenyl [O(MeSiC4Ph4) 2] (10) and methyl silicate.
Synthesis of dialkenyl dichalcogenides via alkenechalcogenolate ions generated by treating ketone p-Toluenesulfonylhydrazones with a base and elemental chalcogen
Shimada, Kazuaki,Asahida, Mitsuharu,Takahashi, Ken,Sato, Yoshitaka,Aoyagi, Shigenobu,Takikawa, Yuji,Kabuto, Chizuko
, p. 513 - 514 (2007/10/03)
Alkeneselenolate and alkenetellurolate ions were generated by treating ketone p-toluenesulfonylhydrazones possessing an α-methylene or an α-methine group with t-BuOK and elemental selenium or tellurium, respectively, at 110-150°C, and were converted into dialkenyl dichalcogenides by aerobic oxidation.
REDUCTIVE COUPLING OF BENZOIC ACID HALIDES AND ESTERS USING LOW-VALENT TITANIUM
Dang, Y.,Geise, H. J.
, p. 375 - 380 (2007/10/02)
The reductive coupling of (substituted) benzoic acid chlorides and esters is achieved using low-valent titanium, generated from TiCl3 and LiAlH4.Both acid chlorides and esters seem to follow the same two reaction pathways: one path via tolanes to stilbenes, the other via benzils to complex mixtures of products arising from reduction and further coupling reactions.Although the exact product balance depends upon the reaction conditions the major product is (substituted) cis-stilbene.
