16980-61-3Relevant articles and documents
Oxidation of 1,4-dimethylcyclohexane by perchloric acid catalyzed by polyphenylferrosiloxane
Kulikova,Levitsky,Shestakov,Shilov
, p. 435 - 437 (1998)
The reaction of oxidation of 1,4-dimethylcyclohexane (DMCH) by perchloric acid at ～20 °C catalyzed by polyphenylferrosiloxane has been found. The chromatographic analysis has revealed the formation of several products, including the tertiary alcohol with 100% retention of the configuration of the initial configuration. The specific feature of the process is the following: along with the high stereospecific formation of the tertiary alcohol, cis-trans isomerization in the starting 1,4-DMCH is observed. The data obtained are discussed on the basis of the mechanism, including the formation of a ferryl intermediate with the subsequent transfer of the oxygen atom to the tertiary C-H bond of 1,4-DMCH through the intermediate complex with the five-coordinated carbon.
Stereoselective oxidation of alkanes with: M -CPBA as an oxidant and cobalt complex with isoindole-based ligands as catalysts
Nesterova, Oksana V.,Kopylovich, Maximilian N.,Nesterov, Dmytro S.
, p. 93756 - 93767 (2016/10/21)
Two complexes with isoindole-core ligands of general formula [M{C6H4C(NH2)NC(ONCMe2)2}2](NO3)2 (M = Co for 1 and M = Ni for 2) were studied as catalysts for the mild stereoselective alkane oxidation with m-chloroperbenzoic acid (m-CPBA) as an oxidant and cis-1,2-dimethylcyclohexane (cis-1,2-DMCH) as a main model substrate. Complex 1 disclosed a pronounced activity, with high retention of stereoconfiguration of substrates (>98% for cis-1,2-DMCH) and highest cis/trans ratio of tertiary alcohols (products) of 56, under mild conditions. The best achieved yields of tertiary cis-alcohols were of 13.7 and 50.5%, based on the substrate (cis-1,2-DMCH) and the oxidant (m-CPBA) respectively. Kinetic experiments, high bond and stereoselectivity parameters, kinetic isotope effect of 7.2(2) in the oxidation of cyclohexane, and incorporation of 18O from H218O support the involvement of CoIVO high-valent metal-oxo intermediates as main C-H attacking species.
Oxidations by the system "hydrogen peroxide-[Mn2L 2O3][PF6]2 (L = 1,4,7-trimethyl-1,4, 7-triazacyclononane)-oxalic acid". Part 6. Oxidation of methane and other alkanes and olefins in water
Shul'pin, Georgiy B.,Nizova, Galina V.,Kozlov, Yuriy N.,Arutyunov, Vladimir S.,Dos Santos, Ana Cláudia M.,Ferreira, Ana Carolina T.,Mandelli, Dalmo
, p. 4498 - 4504 (2007/10/03)
Oxidation of alkanes with hydrogen peroxide in water solution at 10-50 °C is efficiently catalyzed by the cationic dinuclear manganese (IV) derivative [Mn2L2O3]2+ (1, with L = 1,4,7-trimethyl-1,4,7-triazacyclononane, TMTACN) in the form of the hexafluorophosphate salt ([1][PF6]2) if oxalic acid is present as a co-catalyst. Methane gives methanol and formaldehyde (turnover numbers, TONs, were 7 and 2, respectively, after reduction of the reaction mixture with ascorbic acid) whereas cyclohexane was oxidized with TONs up to 160 affording cyclohexyl hydroperoxide, cyclohexanone and cyclohexanol (the ketone was the main product, although at room temperature almost pure alkyl hydroperoxide was formed). In contrast to the oxidation in acetonitrile, the reaction with linear n-alkanes in water exhibits an unusual distribution of oxygenates. For example, in the oxidation of n-heptane the normalized reactivity of the methylene group in position 4 of the chain is 3-7 times higher than that of the CH2 group in position 2. Dec-1-ene is epoxidized by hydrogen peroxide in water (a biphasic system) catalyzed by [1][PF6] 2 and oxalic acid in the presence of a small amount of acetonitrile with TONs up to 1000 (no epoxidation has been detected in the absence of MeCN).
