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.
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.
