1630-94-0Relevant articles and documents
Solvent perturbs the reactivity of tert-butylcarbene
Ruck, Rebecca T.,Jones Jr., Maltland
, p. 2277 - 2280 (1998)
Two different sources of tert-butylcarbene are used to generate this reactive intermediate in a variety of solvents. Two products, 1,1- dimethylcyclopropane and 2-methyl-2-butene are formed. Solvents able to form an ylid or complex with the carbene strongly favor the alkene product.
tert-BUTYLCARBENE FROM 1,1-DIIODONEOPENTANE
Fukushima, Motoo,Jones, Maitland,Brinker, Udo H.
, p. 3211 - 3214 (1982)
When 1,1-diiodoneopentane is passed through a hot tube containing methyllithium-coated Pyrex chips, 1,1-dimethylcyclopropane and 2-methyl-2-butene are produced in near quantitative yield.The ratio of products indicates that the intermediate carbene is the same as is produced from thermal or photosensitized decomposition of tert-butyldiazomethane but different from that formed by direct irradiation of the diazo compound.
Generation of methylene by the liquid phase oxidation of isobutene with nitrous oxide
Semikolenov, Sergey,Ivanov, Dmitry,Babushkin, Dmitry,Malykhin, Sergey,Kharitonov, Alexander,Dubkov, Konstantin
, p. 3589 - 3595 (2018)
The application of nitrous oxide as an alternative oxidant provides new opportunities for selective oxidation of olefins. Here, we studied for the first time the thermal oxidation of isobutene with N2O in the liquid phase. The study revealed that the oxidation proceeds via 1,3-dipolar cycloaddition of N2O to the C[dbnd]C bond by two routes forming unstable 4,5-dihydro-[1,2,3]-oxadiazole intermediates. The main route (the contribution of 91%) includes the addition of the N2O oxygen to the second carbon atom in olefin. In this case, the oxadiazole decomposes with the C–C bond cleavage yielding acetone, methylene (:CH2), and N2. The methylene then readily reacts with isobutene and benzene (solvent). The minor route involves the addition of the N2O oxygen to the first carbon atom and the oxadiazole decomposition with a hydrogen shift leading to isobutanal and N2. The main distinctive feature of the studied reaction is the formation of methylene in high yield.
Rate coefficients of hydroxyl radical reaction with dimethyl ether and methyl tert-butyl ether over an extended temperature range
Arif,Dellinger,Taylor
, p. 2436 - 2441 (2007/10/03)
Rate coefficients of the reaction of hydroxyl (OH) radicals with CH3OCH3 (k1) and CH3OC(CH3)3 (k2) over an extended temperature range are reported. Measurements were performed using a laser photolysis-laser-induced fluorescence technique under slow flow conditions at a total pressure of 740±10 Torr. Arrhenius plots of the data exhibited significant curvature and were fitted in the form of k(T) = ATB exp(-C/T). The resulting modified Arrhenius expressions (error limits ±2σ) that best described these extended temperature measurements and prior low-temperature measurements were (in units of cm3 molecule-1 s-1) k1(295-650 K) = (1.05±0.10)×10-17T2.0 and exp[(328±32)/T] and k2(293-750 K) = (1.15±0.11)×10-17T2.04 exp-[(266±41)/T]. Comparison of our measurements for k1 with previous, overlapping low-temperature measurements indicated generally good agreement. Our measurements for k2, although consistent with previous room temperature measurements, exhibited a larger temperature dependence than previously reported. High-temperature oxidation mechanisms for these oxygenated fuel components are proposed. Support for the mechanisms is presented in the form of product analysis studies in high-temperature tubular flow reactors. For CH3OC(CH3)3, these studies suggest that H abstraction from the tert-butyl group is an important high-temperature oxidation pathway.
