460-12-8Relevant articles and documents
Site-Selective N-Dealkylation of 1,2,3-Triazolium Salts: A Metal-Free Route to 1,5-Substituted 1,2,3-Triazoles and Related Bistriazoles
Monasterio, Zaira,Irastorza, Aitziber,Miranda, José I.,Aizpurua, Jesus M.
supporting information, p. 2511 - 2514 (2016/06/09)
N3-Alkylation of 1-(pivaloyloxymethyl)-1,2,3-triazoles with alkyl triflates carrying latent "click" functionality, followed by a nucleophile-promoted N1-dealkylation of the resulting strongly electrophilic intermediate triazolium salts, provides an efficient route to 1,5-disubstituted 1,2,3-triazoles. The azide and alkyne groups incorporated by N-alkylation can be submitted to further copper-catalyzed azide-alkyne and Huisgen cycloadditions to provide bis(1,2,3-triazoles) with unprecedented 1,5/1,4 substitution patterns.
Kinetics of the reactions of hydroxyl radicals with diacetylene and vinylacetylene
Sommerer, J?rg,Olzmann, Matthias
, p. 495 - 505 (2015/04/14)
Highly unsaturated hydrocarbons like diacetylene (C4H2) or vinylacetylene (C4H4) are important intermediates in combustion that can have impact on soot formation. One of their major loss channels is reaction with hydroxyl radicals (OH). We studied the reactions C4H2 + OH → products (1) and C4H4 + OH → products (2) in a quasi-static reactor with helium as bath gas. The hydroxyl radicals were produced by laser flash-photolysis of nitric acid at a wavelength of 248 nm and detected by laser-induced fluorescence with excitation at 282 nm. The rate coefficients were obtained from the intensity-time profiles under pseudo-first order conditions with respect to OH. We found a virtually temperature-independent rate coefficient for reaction (1): k1 = (1.0 ± 0.3) × 10-11 cm3 s-1 (T = 290-670 K, P = 2.7-30.5 bar) and a weakly negative temperature-dependent rate coefficient for reaction (2): k2(T) = (6.4 ± 1.9) × 10-12 exp (486 K/T) cm3 s-1 (T = 295-740 K, P = 1.7-19.2 bar). For neither of the two reactions pressure dependence was observed. From comparisons with analogous reaction systems, we conclude that the dominating reaction pathway is OH addition, where in the case of C4H4 the double bond is preferred over the triple bond.
Formation of fulvene in the reaction of C2H with 1,3-butadiene
Lockyear, Jessica F.,Fournier, Martin,Sims, Ian R.,Guillemin, Jean-Claude,Taatjes, Craig A.,Osborn, David L.,Leone, Stephen R.
, p. 232 - 245 (2015/04/14)
Abstract Products formed in the reaction of C2H radicals with 1,3-butadiene at 4 Torr and 298 K are probed using photoionization time-of-flight mass spectrometry. The reaction takes place in a slow-flow reactor, and products are ionized by tunable vacuum-ultraviolet light from the Advanced Light Source. The principal reaction channel involves addition of the radical to one of the unsaturated sites of 1,3-butadiene, followed by H-loss to give isomers of C6H6. The photoionization spectrum of the C6H6 product indicates that fulvene is formed with a branching fraction of (57 ± 30)%. At least one more isomer is formed, which is likely to be one or more of 3,4-dimethylenecyclobut-1-ene, 3-methylene-1-penten-4-yne or 3-methyl-1,2-pentadien-4-yne. An experimental photoionization spectrum of 3,4-dimethylenecyclobut-1-ene and simulated photoionization spectra of 3-methylene-1-penten-4-yne and 3-methyl-1,2-pentadien-4-yne are used to fit the measured data and obtain maximum branching fractions of 74%, 24% and 31%, respectively, for these isomers. An upper limit of 45% is placed on the branching fraction for the sum of benzene and 1,3-hexadien-5-yne. The reactive potential energy surface is also investigated computationally. Minima and first-order saddle-points on several possible reaction pathways to fulvene + H and 3,4-dimethylenecyclobut-1-ene + H products are calculated.