22635-62-7Relevant articles and documents
On the triggering of free radical reactivity of dimethyldioxirane
Curci, Ruggero,Dinoi, Anna,Fusco, Caterina,Lillo, Maria A.
, p. 249 - 252 (1996)
Performing the reaction in the presence of CCl3Br, and/or in inert gas atmosphere, dramatically changes the reation kinetics, rate-law and product distribution of adamantane oxyfunctionalization by dimethyldioxirane (1a). The kinetics of decomposition of the dioxirane is also markedly influenced by the addition of CCl3Br and by depletion of O2 gas. The data suggest that these conditions can trigger dioxirane radical reactions; these are widely different from the straightforward, highly selective concerted O-insertion into C-H bonds which would take place in the absence of CCl3Br and of conditions inducing radical reactivity.
Gold-Catalyzed Direct C(sp3)?H Acetoxylation of Saturated Hydrocarbons
Jo, Tae Geun,Klein, Johannes E. M. N.
, p. 4087 - 4091 (2021/08/25)
In this communication we report our studies towards the development of a gold-catalyzed direct acetoxylation of C(sp3)?H bonds. We achieve this through the use of the hypervalent iodine reagent PhI(OAc)2 in combination with a simple gold salt (HAuBr4) as the catalyst. Through a comparison of the reactivities of cyclooctane and adamantane we judge the reaction to proceed via hydride transfer. This is further substantiated through computational studies of the relative energies for the anions, radicals and cations derived from C?H bond cleavage of cyclooctane and adamantane relevant to the C?H cleaving step.
Mechanism of Hydrocarbon Functionalization by an Iodate/Chloride System: The Role of Ester Protection
Schwartz, Nichole A.,Boaz, Nicholas C.,Kalman, Steven E.,Zhuang, Thompson,Goldberg, Jonathan M.,Fu, Ross,Nielsen, Robert J.,Goddard, William A.,Groves, John T.,Gunnoe, T. Brent
, p. 3138 - 3149 (2018/04/14)
Mixtures of chloride and iodate salts for light alkane oxidation achieve >20% yield of methyl trifluoroacetate (TFA) from methane with >85% selectivity. The mechanism of this C-H oxygenation has been probed by examining adamantane as a model substrate. These recent results lend support to the involvement of free radicals. Comparative studies between radical chlorination and iodate/chloride functionalization of adamantane afford statistically identical 3°:2° selectivities (～5.2:1) and kinetic isotope effects for C-H/C-D functionalization (kH/kD = 1.6(3), 1.52(3)). Alkane functionalization by iodate/chloride in HTFA is proposed to occur through H-atom abstraction by free radical species including Cl? to give alkyl radicals. Iodine, which forms by in situ reduction of iodate, traps alkyl radicals as alkyl iodides that are subsequently converted to alkyl esters in HTFA solvent. Importantly, the alkyl ester products (RTFA) are quite stable to further oxidation under the oxidizing conditions due to the protecting nature of the ester moiety.
Synthesis of 1-(2-oxopropyl)adamantane from 1-bromo(chloro)adamantanes and isopropenyl acetate in the presence of iron and manganese compounds
Khusnutdinov,Shchadneva,Kislitsina,Veklov,Kutepov
, p. 1272 - 1275 (2015/01/08)
An efficient procedure has been developed for the synthesis of 1-(2-oxopropyl)adamantane by reaction of 1-bromo(chloro)adamantanes with isopropenyl acetate in the presence of manganese and iron compounds.
Synthesis of 1-acetyladamantane by reaction of 1-bromoadamantane with vinyl acetate and ethylidene diacetate catalyzed by Mn2(CO)10
Khusnutdinov,Shchadneva,Mukhametshina
scheme or table, p. 820 - 822 (2010/10/19)
A procedure has been developed for the synthesis of 1-acetyladamantane in 95% yield by reaction of 1-bromoadamantane with vinyl acetate or ethylidene diacetate in the presence of manganese complexes.
Simple vanadium(V) catalyst for oxidation of alkane with O2 under mild conditions
Kobayashi, Hirokazu,Yamanaka, Ichiro
, p. 114 - 115 (2007/10/03)
Selective oxidation of cyclohexane and adamantane was performed by simple V(5+) catalyst with 1 atm O2 in acetic acid at 338-393 K. UV-vis and electron spin resonance studies suggested that peroxide species on V(5+) functioned during the oxidation. The oxidation activity was enhanced three times for cyclohexane and 6.5 times for adamantane by addition of a small amount of CF3SO3H. Copyright
Process for producing oxygen-bearing compound
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Page/Page column 5-7, (2008/06/13)
Provided is a process for industrially advantageously producing an oxygen-bearing compound (e.g., an alcohol, a diol, a polyol, or a ketone) through oxidation of an alkane or an alcohol, which process requires no treatment for separation/removal of a catalyst and causes no equipment corrosion. Specifically, there are provided a process for producing an oxygen-bearing compound, including oxidizing an alkane in the presence of a catalyst containing at least one element selected from among transition metal elements belonging to Groups 5 and 8 to 10 of the periodic table, wherein the oxygen-bearing compound is an alcohol, a diol, a polyol, or a ketone; and a process for producing an oxygen-bearing compound, including oxidizing an alcohol in the presence of a catalyst containing at least one element selected from among transition metal elements belonging to Groups 5 and 8 to 10 of the periodic table, wherein the oxygen-bearing compound is a diol, a polyol, or a ketone.
N-Hydroxyphthalimide (NHPI)-catalyzed reaction of adamantane under nitric oxide atmosphere
Sakaguchi, Satoshi,Eikawa, Masahiro,Ishii, Yasutaka
, p. 7075 - 7078 (2007/10/03)
The reaction of adamantane under atmospheric nitric oxide in the presence of N-hydroxyphthalimide (NHPI) which serves as the radical catalyst in a mixed solvent of benzonitrile and acetic acid afforded 1-N-adamantylbenzamide as a principal product along with small amounts of 1-nitroadamantane and 1-hydroxyadamantane. On the other hand, 1-nitroadamantane was obtained in good yield upon treatment of adamantane with NO/O2.
Induced Homolysis of Dimethyldioxirane by Alkanes and Alkyl Radicals in Oxidation Processes. The Dramatic Role of Molecular Oxygen and Radical Inhibitors
Bravo, Anna,Fontana, Francesca,Fronza, Giovanni,Mele, Andrea,Minisci, Francesco
, p. 1573 - 1574 (2007/10/02)
The oxidation of alkanes by dimethyldioxirane is dramatically affected by the presence of molecular oxygen and radical inhibitors, supporting the hypothesis of a free-radical mechanism for these extraordinarily selective reactions; the factors affecting the free-radical selectivity are suggested.
