1070-87-7Relevant academic research and scientific papers
Selective Formation of Solute Radicals in the Radiolysis of Neopentane-Cyclopentane Mixtures at 4 and 77 K as Studied by Capillary Gas Chromatography and ESR Spectroscopy
Tilquin, Bernard,Gourdin-Serveniere, Catherine,Miyazaki, Tetsuo,Fueki, Kenji
, p. 2029 - 2030 (1984)
The dimer yields in the radiolysis of the neo-C5H12-cyclo-C5H11 (1 molpercent) mixtures at 77 and 4 K have been measured by capillary gas chromatography.Analysis of the results indicates that cyclopentyl radicals are produced selectively at 77K, while their selective formation is suppressed at 4K.This result coincides well with the data obtained by ESR spectroscopy.
Reactions of aliphatic ketones R2CO (R = Me, Et, iPr, and tBu) with the MCl4/Li(Hg) system (M = U or Ti): Mechanistic analogies between the McMurry, Wittig, and Clemmensen reactions
Villiers, Claude,Ephritikhine, Michel
, p. 3043 - 3051 (2001)
Analysis of the products of the reactions of ketones R2CO (R = Me, Et, iPr, tBu) with the MCl4/Li(Hg) system (M = U, Ti) at 20°C revealed significant differences. For R = Me, the reaction proceeded exclusively (M = U) or preferentially (M = Ti) via a metallopinacol intermediate resulting from dimerization of ketyl radicals. Pinacol was liberated by hydrolysis, and tetramethylethylene was obtained after further reduction at 65°C. For R = iPr, formation of iPr2C=CiPr2 as the only coupling product, the nonproduction of this alkene by reduction of the uranium pinacolate [U]-OCR2CR2O-[U] (R = iPr) at 20°C, and the instability of the corresponding titanium pinacolate towards rupture of the pinacolic C-C bond indicated that reductive coupling of iPr2CO did not proceed by dimerization of ketyl radicals. Formation of 2,4-dimethyl-2-pentene was in favor of a carbenoid intermediate resulting from deoxygenative reduction of the ketyl. These results revealed that for sterically hindered ketones, McMurry reactions can be viewed as Wittig-like olefination reactions. For R = tBu, no coupling product was obtained and the alkane tBu2CH2 was the major product. The involvement of the carbenoid species [M]=CtBu2 was confirmed by its trapping with H2O, leading to tBu2CH2, and with the aldehydes RCHO, giving the cross-coupling products tBu2C=C(R)H (R = Me, tBu). Therefore, in the case of severely congested ketones, McMurry reactions present strong similarities to the Clemmensen reduction of ketones, owing to the involvement in both reactions of carbenoid species which exhibit similar reactivity. Wiley-VCH Verlag GmbH, 2001.
Formation of carbenoid intermediates in the reaction of ditertiobutyl ketone with low-valent titanium reagents
Villiers, Claude,Vandais, Alain,Ephritikhine, Michel
, p. 744 - 747 (2001)
Treatment of tBu2CO with TiCl4 and Li(Hg) in THF gave the hydrocarbon tBu2CH2 as the major product (40% yield); 60% of the total quantity of tBu2CH2 was lib
Tandem cyclopropanation with dibromomethane under Grignard conditions
Brunner, Gerhard,Eberhard, Laura,Oetiker, Juerg,Schroeder, Fridtjof
, p. 7543 - 7554 (2008/12/22)
(Chemical Equation Presented) Tertiary Grignard reagents and dibromomethane efficiently cyclopropanate allylic (and certain homoallylic) magnesium and lithium alcoholates at ambient temperature in ether solvents. Lithium (homo)allyl alcoholates are directly cyclopropanated with magnesium and CH 2Br2 under Barbier conditions at higher temperatures. The reaction rates depend on the substitution pattern of the (homo)allylic alcoholates and on the counterion with lithium giving best results. Good to excellent syn-selectivities are obtained from α-substituted substrates, which are in accord with a staggered Houk model. In tandem reactions, cyclopropyl carbinols are obtained from allyloxylithium or -magnesium intermediates, generated in situ by alkylation of conjugated aldehydes, ketones, and esters as well as from allyl carboxylates or vinyloxiranes. Using this methodology, numerous fragrance ingredients and their precursors were efficiently converted to the corresponding cyclopropyl carbinols.
Aliphatic Azo Compounds, XV cis- and trans-Tetracyclopropyl- and Tetra-tert-butylazomethanes
Bernloehr, Werner,Flamm-ter Meer, Manuela A.,Kaiser, Juergen H.,Schmittel, Michael,Beckhaus, Hans-Dieter,Ruechardt, Christoph
, p. 1911 - 1918 (2007/10/02)
The products and the kinetics of the thermolysis of the title compounds 3 and 5 were investigated.Like the trans-isomers, the cis-azo compounds also undergo homolytic decomposition without accompanying cis-trans-isomerization.The observed structure-reactivity relationships are discussed.On irradiation of trans-tetra-tert-butylazomethane (trans-5) at 60-120 deg C in benzene or chlorobenzene an almost quantitative yield of 1,1,2,2-tetra-tert-butylethane is obtained.
Thermolabile Hydrocarbons, XIX. Syntheses, Spectra, Structures, and Strain of Highly Branched Pentanes
Hellmann, Siegried,Beckhaus, Hans-Dieter,Ruechardt, Christoph
, p. 2219 - 2237 (2007/10/02)
The syntheses and spectroscopic properties of eight hydrocarbons R1R2CH-C(CH3)3 (3a-h) and of ten hydrocarbons R1R2R3C-C(CH3)3 (4a-k) (R = alkyl) are described.Their structures and strain enthalpies are discussed on the basis of force field calculations.
Thermolabile Hydrocarbons, XXI. Relationships between Thermal Stability and Strain of Non-Symmetrical Highly Branched Hydrocarbons
Hellmann, Siegried,Beckhaus, Hans-Dieter,Ruechardt, Christoph
, p. 2238 - 2249 (2007/10/02)
The pyrolysis reaction of 20 hydrocarbons 3 into radicals 4 and tert-butyl radicals was investigated by product analysis and kinetics.It is shown that the same relationships between the free enthalpies of activation and the strain energies observed earlier for the cleavage of symmetrically substituted CC bonds are valid for the cleavage of unsymmetrical substituted bonds.The introduction of the new concept "strain energy of dissociation" (difference in strain between the ground state 3 and the residual strain in the radical fragments 4 and 5) has proven to be particularly useful.It is now possible to predict the rate of homolytic cleavage of almost all simple CC bonds by force field calculations.
