- C-H functionalization of sp3centers with aluminum: A computational and mechanistic study of the baddeley reaction of decalin
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Decalin undergoes reaction with aluminum trichloride and acetyl chloride to form a tricyclic enol ether in good yield, as first reported by Baddeley. This eye-catching transformation, which may be considered to be an aliphatic Friedel-Crafts reaction, has not previously been studied mechanistically. Here we report experimental and computational studies to elucidate the mechanism of this reaction. We give supporting evidence for the proposition that, in the absence of unsaturation, an acylium ion acts as a hydride acceptor, forming a tertiary carbocation. Loss of a proton introduces an alkene, which reacts with a further acylium ion. A concerted 1,2-hydride shift/oxonium formation, followed by elimination, leads to formation of the observed product.
- Lyall, Catherine L.,Sato, Makoto,Uosis-Martin, Mario,Asghar, Syeda Farina,Jones, Matthew D.,Williams, Ian H.,Lewis, Simon E.
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supporting information
p. 13745 - 13753
(2015/02/05)
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- Lifetime of acyloxy radicals produced by decomposition of acetylpropionyl peroxide
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The authors consider thermolysis of 0.5 M solutions of acetylpropionyl peroxide in CCl4 and 333 and 343 K as well as photolysis of 0.5 M solutions of acetylpropionyl peroxide in CCl4 and 253-333 K and photolysis of methanol solutions of acetylpropionyl peroxide with added 1 m CCl4 at temperature of 193-253 K.The effects of chemical nuclear polarization and reaction yields were analyzed to determine the decarboxylation rate constants of acyloxy radicals that were produced by thermolysis and photolysis of acetylpropionyl peroxide. - Keywords: acyloxy radical; decarboxylating rate constant; chemical nuclear polarization.
- Skakovskii, E. D.,Lamotkin, S. A.,Tychinskaya, L. Yu.
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p. 319 - 324
(2007/10/03)
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- Chlorination of Carboxylic Acid Derivatives. IX. Liquid Phase Chlorination of Aliphatic C2-C8 Alkyl Acetates. EI Mass Spectra of Monochlorinated Esters
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A series of aliphatic alkyl acetates from ethyl to octyl acetate was chlorinated in the liquid phase in order to obtain monochlorinated products.The chlorination of esters was carried out with chlorine in the liquid phase in the absence and in the presence of benzene and with sulfuryl chloride in the presence of Bz2O2.The products were determined by gas-liquid chromatography and gas-liquid chromatography-mass spectrometry.Chlorination is appreciably deactivated at the 1-position, particularly with SO2Cl2, the deactivation at the 2-position being strongest with Cl2 in the presence of benzene.The amounts of 1-chloro and ω-chloro isomers constituted the greatest disparity between the chlorination methods.The most characteristic mass spectral fragment ions of the 35 chlorinated alkyl acetates are given.
- Korhonen, Ilpo O. O.
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