31706-56-6Relevant articles and documents
A concise method for the synthesis of 2-tetralone by titanium tetrachloride-promoted cyclization of 4-aryl-2-hydroxybutanal diethyl acetal
Hon, Yung-Son,Devulapally, Rammohan
scheme or table, p. 5713 - 5715 (2009/12/09)
4-Aryl-2-hydroxybutanal diethyl acetal, prepared from the reaction of benzyl Grignard reagent and glycidaldehyde diethyl acetal, was treated with titanium tetrachloride to give 2-tetralone in good yield. This highly efficient transformation involves tande
Transition state imbalance in proton transfer from phenyl ring-substituted 2-tetralones to acetate ion
Yao, Xudong,Gold, Mark A.,Pollack, Ralph M.
, p. 6220 - 6225 (2007/10/03)
Rate constants for the acetate ion-catalyzed ketonization of phenyl-substituted 2-tetralone enols have been determined by stopped-flow UV spectroscopy. From these rate constants and the keto - enol equilibrium constants, the rate constants (k-2) for enolization were calculated. A Bronsted plot of these rate constants (log k-2) vs the acidity of the appropriate 2-tetralone (pKaK) is linear, with a slope ( - αE) of - 0.78 ± 0.03, except for the point corresponding to 6-nitro-2-tetralone (4b). Rate constants for the ionization of 2-tetralone by substituted acetates were determined directly by NMR, giving a corresponding Bronsted βE of 0.54 ± 0.03. Both the negative deviation of the point for 4b from the correlation line for αE and the inequality between αE and βE indicate an imbalanced transition state for the proton abstraction of 2-tetralone by acetate ion. This reaction is impeded by a thermodynamic barrier of 11 kcal/mol, along with an intrinsic kinetic barrier of 14 kcal/mol. A comparison of the transition states for proton abstraction of 2-tetralone by hydroxide ion and by acetate ion shows similar transition state imbalance and intrinsic kinetic barriers for both reactions. The relevance of these results to the mechanism of enzymatic acceleration of enolization is discussed.
The Intramolecular Buchner Reaction of Aryl Diazoketones. Substituent Effects and Scope in Synthesis
Kennedy, Michael,McKervey, M. Anthony,Maguire, Anita R.,Tuladhar, Sarbajna M.,Twohig, M. Fiona
, p. 1047 - 1054 (2007/10/02)
Rhodium(II) acetate-catalysed cyclisation of α-diazoketones derived from 3-arylpropionic acid produces bicyclodecatrienones or 2-tetralones depending on the substitution pattern of the aryl ring in the precursor; the former products are transformed into the latter catalytically with trifluoroacetic acid.Precursors with methyl, methoxy, and acetoxy substituents have been examined, efficient cyclisation occurring in all cases.When the precursor contains a meta-methoxy substituent, 2-tetralones are obtained directly.The efficient conversion of 3-phenylpropionicacid into trans-1-methylbicyclodecan-2-one is also described, partial asymmetric synthesis having been realised through the use of rhodium (S)-mandelate as the cyclisation catalyst.Cyclisations of diazoketones derived from 4-phenylbutyric acid and 5-phenylpentanoic acid have also been studied; the former provides a new entry into the bicycloundecane system whereas the latter produces a 2,3-disubstituted cyclopentanone via C-H insertion.Aspects of the cycloheptatriene-norcaradiene equilibrium in fused ring systems are discussed.