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.
Oxidative bromination of alkenes mediated with nitrite in ionic liquids
Kuznetsova, Lidia I.,Kuznetsova, Nina I.,Zudin, Vladimir N.,Utkin, Viktor A.,Trebushat, Dmitry V.,Fedotov, Martin A.,Larina, Tatyana V.
, p. 1499 - 1506,8 (2014/11/08)
The oxidative bromination of C2-C8 alkenes with HBr-NaNO2-O2 in solutions of BMImBr, HMImBr or BMImBF 4 containing 16-28 wt% H2O was studied using volumetric method, GC-MS analysis, 14N NMR and UV-VIS spectroscopy. The optimal conditions to conduct the reaction at high selectivity for 1,2-dibromoalkanes in BMImBr were determined. The composition of ionic liquid affects the catalytic performance. Although in BMImBF4 the reaction runs with equal rate as in bromide ionic liquid, the fraction of bromohydrin in the reaction products increases to 20 %. Generated from NaNO2, NOx operated as a catalyst in the oxidation of Br- and was oxidized to catalytically inert NO3 - anions when complete conversion of HBr was attained. Graphical Abstract: Oxidative bromination of alkenes [Figure not available: see fulltext.]
