38256-01-8Relevant articles and documents
Structural effects on the thermochemical properties of carbonyl compounds. II. Enthalpies of combustion, vapour pressures and enthalpies of sublimation, and standard enthalpies of formation in the gaseous phase, of 1-adamantyl methyl ketone and of 1,1'-diadamantyl ketone
Abboud, J.-L. M.,Jimenez, P.,Roux, M. V.,Turrion, C.,Lopez-Mardomingo, C.,Sanz, G.
, p. 217 - 223 (1992)
The energies of combustion of 1-adamantyl methyl ketone, and 1,1'-diadamantyl ketone have been determined using a static bomb calorimeter.The vapour pressures have been measured over a temperature range of about 17 K by the Knudsen-effusion technique.From the experimental results the following quantities for the two compounds, at T = 298.15 K, have been derived: table.Structural effects on ΔfHmdeg(g) for these and other ketones have been discussed.
Deoxygenation of dithiirane 1-oxides with Lawesson's reagent leading to the corresponding dithiiranes
Ishii, Akihiko,Yamashita, Remi,Saito, Masashi,Nakayama, Juzo
, p. 1555 - 1558 (2003)
3,3-Disubstituted dithiirane 1-oxides were efficiently reduced with Lawesson's reagent (LR) to give the corresponding dithiiranes. X-ray diffraction analysis of 3,3-di(1-adamantyl)dithiirane is reported. Reaction of 34S-labeled 3,3-di(1-adamant
Trifluoroacetylation and ionic hydrogenation of [2-(3-alkoxy-thienyl)]di(1-adamantyl)methanols
Lomas, John S.,Vauthier, Edouard,Vaissermann, Jacqueline
, p. 1399 - 1408 (2007/10/03)
Lithiation of 3-alkoxythiophenes followed by reaction with di(1-adamantyl) ketone leads to anti-[2-(3-alkoxy-thienyl)]di(1-adamantyl)methanols where the C-OH proton is intramolecularly hydrogen-bonded to the alkoxy group. The structure of the 3-methoxy derivative was confirmed by a single crystal X-ray diffraction study. Reaction of this alcohol with trifluoroacetic acid (TFA) and trifluoroacetic anhydride (TFAA) in dichloromethane gives a trifluoroacetate, the initially formed carbocation undergoing an intramolecular 1,5-hydride shift to give a carboxonium ion. However, in the absence of anhydride, trifluoroacetate is formed to the extent of about 15% only. Ionic hydrogenation with TFA and an organosilane in dichloromethane gives syn- and anti-[2-(3-methoxythienyl)]-diadamantylmethanes by reduction of the carbocation, with a preference for the isomer with the Ad2CH hydrogen close to methoxy. The corresponding 3-ethoxy compound behaves quite differently: in TFA-dichloromethane a trifluoroacetate is formed which then eliminates acetaldehyde to give anti-[2-(3-hydroxythienyl)]diadamantylmethane. In the presence of an organosilane syn- and anti-[2-(3-ethoxythienyl)]diadamantylmethanes are formed together with the 3-hydroxy derivative. Isotope labelling experiments show that the anti deoxygenation product is obtained by reduction of both the carbocation and the carboxonium ion. The 3-isopropoxy derivative reacts sluggishly with TFA and, with an organosilane, tends to give preferentially the less stable, syn deoxygenation product. The activation energies for syn to anti rotation in the [2-(3-alkoxythienyl)]diadamantylmethanes indicate significant differences in the steric effects of the alkoxy groups.
