4705-87-7Relevant articles and documents
Carbenoid-mediated nucleophilic "hydrolysis" of 2-(dichloromethylidene)-1,1,3,3-tetramethylindane with DMSO participation, affording access to one-sidedly overcrowded ketone and bromoalkene descendants
Knorr, Rudolf,Menke, Thomas,Freudenreich, Johannes,Pires, Claudio
supporting information, p. 307 - 315 (2014/03/21)
2-(Dichloromethylidene)-1,1,3,3-tetramethylindane was " hydrolyzed" by solid KOH in DMSO as the solvent at ≥100 °C through an initial chlorine particle transfer to give a Cl,K-carbenoid. This short-lived intermediate disclosed its occurrence through a reversible proton transfer which competed with an oxygen transfer from DMSO that created dimethyl sulfide. The presumably resultant transitory ketene incorporated KOH to afford the potassium salt of 1,1,3,3-tetramethylindan-2-carboxylic acid (the product of a formal hydrolysis). The lithium salt of this key acid is able to acylate aryllithium compounds, furnishing one-sidedly overcrowded ketones along with the corresponding tertiary alcohols. The latter side-products (ca. 10%) were formed against a substantially increasing repulsive resistance, as testified through the diminished rotational mobility of their aryl groups. As a less troublesome further side-product, the dianion of the above key acid was recognized through carboxylation which afforded 1,1,3,3-tetramethylindan- 2,2-dicarboxylic acid. Brominative deoxygenation of the ketones furnished two one-sidedly overcrowded bromoalkenes. Some presently relevant properties of the above Cl,K-carbenoid are provided in Supporting Information File 1.
Synthesis and Reactions of Selenoketones
Ishii, Akihiko,Okazaki, Renji,Inamoto, Naoki
, p. 861 - 868 (2007/10/02)
A new, convenient method for the synthesis of selenoketones has been reported.The reaction of dimagnesium salts of ketone hydrazones with diselenium dichloride affords an intermediate tentatively assigned as tetraselenides, which are converted into seleno
PHOTOSENSITIZED DECOMPOSITIONS OF OXASILACYCLOPROPANE; UNUSUAL CARBENE FORMATION
Ando, Wataru,Hamada, Yoshitaka,Sekiguchi, Akira
, p. 5057 - 5060 (2007/10/02)
TCNE photo-sensitized decompositions of oxasilacyclopropane (1) generated carbene and silanone, while the DCA sensitized or direct photolysis of (1) gave silylene and indanone.
REACTIONS OF 1,1,3,3-TETRAMETHYLINDANE-2-SELONE WITH GRIGNARD AND ORGANOLITHIUM REAGENTS
Okazaki, Renji,Ishii, Akihiko,Inamoto, Naoki
, p. 5147 - 5150 (2007/10/02)
The title reaction afforded selenophilic, carbophilic, and reduction products depending on the kinds of the organometallic reagents and the heterophilic nature of the reaction was more conspicuous in the reaction with the selenoketone than with the corres
