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.
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-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.
