5076-20-0Relevant articles and documents
Red light-induced reaction of NO2 with 2,3-dimethyl-2-butene in a low-temperature argon matrix
Nakata, Munetaka
, p. 1455 - 1466 (1994)
Red light-induced oxygen atom transfer from NO2 to 2,3-dimethyl-2-butene has been investigated in a low-temperature argon matrix.The IR spectra of a reaction intermediate identified as an alkyl nitrite radical and two final products, tetramethyloxirane and 3,3-dimethyl-2-butanone (pinacolone), were observed.From analysis of the absorbance growth of the IR bands, first-order rate constants were determined by least-square fitting.Based on these results and those of our earlier works on NO2 photoreactions with other alkenes, a reaction mechanism is proposed that involves oxygen atom transfer from NO2 to the C=C bond of 2,3-dimethyl-2-butene to give a short-lived singlet oxirane biradical.Alkyl nitrite radical is produced by a recombination of the transient biradical with NO trapped in the cage of the matrix.Tetramethyloxirane and pinacolone emerge from secondary photolysis of the trapped alkyl nitrite radical.
METALLOPORPHYRIN-MEDIATED RADICAL CYCLOADDITIONS OF p-CYANO-N,N-DIMETHYLANILINE
Dicken, C. Michael,Lu, Fu-Lung,Bruice, Thomas C.
, p. 5967 - 5970 (1986)
Tetrahydroquinolines are formed via metalloporphyrin-catalyzed radical cycloadditions of olefins (2,3-dimethyl-2-butene and norbornene) and p-cyano-N,N-dimethylaniline; their synthesis, characterization and a mechanistic rationale of their formation are presented.
The reaction of permanganyl chloride with olefins: Intermediates and mechanism as derived from matrix-isolation studies and density functional theory calculations
Wistuba, Tobias,Limberg, Christian
, p. 4674 - 4685 (2001)
Density functional theory (DFT) calculations predict that the [2+3] addition of tetramethylethylene (TME) to the MnO2 moiety of MnO3Cl is thermodynamically favoured over [2+1] addition (epoxidation), while the kinetic barriers for bo
Cvetanovic
, p. 19,21 (1959)
Porphyrins in aqueous amphiphilic polymers as peroxidase mimics
Johnstone, Robert A. W.,Simpson, Anthony J.,Stocks, Paul A.
, p. 2277 - 2278 (1997)
Water-insoluble porphyrins dissolve in aqueous solutions of amphiphilic polymers to give systems which mimic the action of peroxidase enzymes.
Synthesis and reaction of cyano-substituted 1,2,4-trioxolanes
Kuwabara, Hajime,Ushigoe, Yoshihiro,Nojima, Masatomo
, p. 871 - 874 (1996)
Carbonyl oxides, derived from the ozonolyses of vinyl ethers, readily undergo [3 + 2] cycloadditions with acyl cyanides affording the corresponding cyano-substituted 1,2,4-trioxolanes in isolated yields of 34-88%. In competition experiments, a relative order of reactivity of the carbonyl oxide trapping agents was tentatively deduced; trifluoroacetophenone > α,α-diphenyl-N-methylnitrone (N-methyldiphenyl-methylideneamine N-oxide) > benzoyl cyanide > methyl benzoylformate > α,α,N-triphenylimine [N-(diphenylmethylidene)aniline] ? benzaldehyde. As expected from the electron-withdrawing ability of the cyano group, 3-cyano-3-phenyl-1,2,4-trioxolane oxidized not only triphenylphosphine but also methyl p-tolyl sulfide and 2,3-dimethylbut-2-ene very easily.
A General Regioselective Synthesis of Alcohols by Cobalt-Catalyzed Hydrogenation of Epoxides
Beller, Matthias,Junge, Kathrin,Leischner, Thomas,Li, Wu,Liu, Weiping
supporting information, p. 11321 - 11324 (2020/05/16)
A straightforward methodology for the synthesis of anti-Markovnikov-type alcohols is presented. By using a specific cobalt triphos complex in the presence of Zn(OTf)2 as an additive, the hydrogenation of epoxides proceeds with high yields and selectivities. The described protocol shows a broad substrate scope, including multi-substituted internal and terminal epoxides, as well as a good functional-group tolerance. Various natural-product derivatives, including steroids, terpenoids, and sesquiterpenoids, gave access to the corresponding alcohols in moderate-to-excellent yields.
Experimental investigation of the low temperature oxidation of the five isomers of hexane
Wang, Zhandong,Herbinet, Olivier,Cheng, Zhanjun,Husson, Benoit,Fournet, Rene,Qi, Fei,Battin-Leclerc, Frederique
, p. 5573 - 5594 (2014/08/18)
The low-temperature oxidation of the five hexane isomers (n-hexane, 2-methyl-pentane, 3-methyl-pentane, 2,2-dimethylbutane, and 2,3-dimethylbutane) was studied in a jet-stirred reactor (JSR) at atmospheric pressure under stoichiometric conditions between 550 and 1000 K. The evolution of reactant and product mole fraction profiles were recorded as a function of the temperature using two analytical methods: gas chromatography and synchrotron vacuum ultraviolet photoionization mass spectrometry (SVUV-PIMS). Experimental data obtained with both methods were in good agreement for the five fuels. These data were used to compare the reactivity and the nature of the reaction products and their distribution. At low temperature (below 800 K), n-hexane was the most reactive isomer. The two methyl-pentane isomers have about the same reactivity, which was lower than that of n-hexane. 2,2-Dimethylbutane was less reactive than the two methyl-pentane isomers, and 2,3-dimethylbutane was the least reactive isomer. These observations are in good agreement with research octane numbers given in the literature. Cyclic ethers with rings including 3, 4, 5, and 6 atoms have been identified and quantified for the five fuels. While the cyclic ether distribution was notably more detailed than in other literature of JSR studies of branched alkane oxidation, some oxiranes were missing among the cyclic ethers expected from methyl-pentanes. Using SVUV-PIMS, the formation of C 2-C3 monocarboxylic acids, ketohydroperoxides, and species with two carbonyl groups have also been observed, supporting their possible formation from branched reactants. This is in line with what was previously experimentally demonstrated from linear fuels. Possible structures and ways of decomposition of the most probable ketohydroperoxides were discussed. Above 800 K, all five isomers have about the same reactivity, with a larger formation from branched alkanes of some unsaturated species, such as allene and propyne, which are known to be soot precursors.