75501-28-9Relevant academic research and scientific papers
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
, 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.
Alkenyl bromides by brominative deoxygenation of ketones in one or two steps
Von Roman,Ruhdorfer,Knorr
, p. 985 - 992 (2007/10/02)
The conversion of ketones into alkenyl bromides is accomplished in one or two steps by 2,2,2-tribromo-2,2-dihydro-1,3,2-benzodioxaphosphole or by the dibromomethyl methyl ether prepared therefrom. Investigations of the scope and limitations provide some hints for the preparative planning and improvement.
On the Formation and Reactivity of Di-tert-alkyl Substituted Phenylalkenes
Knorr, Rudolf,Lattke, Ernst,Raepple, Edith
, p. 1207 - 1215 (2007/10/02)
Molecular rearrangements occur during the attempted syntheses of α-bromo-β,β-di-tert-alkylstyrenes; the resulting structures are elucidated.A hydrocarbon dimer with allenic structure accompanies the formation of the Grignard reagent from an α-bromostyrene
