75935-32-9Relevant academic research and scientific papers
Decomposition of gaseous phthalic anhydride from a vibrationally hot molecule formed by ArF laser irradiation
Yatsuhashi, Tomoyuki,Nakashima, Nobuaki
, p. 203 - 208 (2000)
ArF laser flash photolysis was used to study the photodecomposition of gaseous phthalic anhydride (PA). The experimental conditions (concentration of the ground-state PA, the inert gas pressure, and the laser fluence) strongly influenced the transient absorption profiles. Both biphenylene and triphenylene were detected as the final products. The results indicated that benzyne (1,3-cyclohexadien-5-yne) formation occurred during the photolysis. The quenching of biphenylene formation by a foreign gas showed that biphenylene was derived from a vibrationally excited (hot) intermediate. The hot PA, the vibrational temperature of which was 2700 K, and benzyne were determined to be intermediates of the PA decomposition reaction.
ONSH: Optimization of oxidative alkylamination reactions through study of the reaction mechanism
Verbeeck, Stefan,Herrebout, Wouter A.,Gulevskaya, Anna V.,Van Der Veken, Benjamin J.,Maes, Bert U. W.
scheme or table, p. 5126 - 5133 (2010/09/18)
(Figure presented) Oxidative alkylamination of electron-deficient (hetero)aromatic compounds, via the nucleophilic substitution of hydrogen, is a methodology that has made significant progress since the introduction of AgPy2MnO4 as oxidant. This oxidant generally gives good conversions and yields, whereas the use of KMnO4 only sometimes works equally well. In order to rationalize this, the reaction mechanism of oxidative alkylamination has been studied. 3-Nitropyridine (1), 1,3-dinitrobenzene (2), and quinazoline (3) were chosen as model substrates and n-butylamine and pyrrolidine as model alkylamines. The rate-limiting step of the mechanism for these substrate/alkylamine combinations was determined. With the use of 1H NMR spectroscopy thermodynamic properties of σ-- adduct formation were deduced and the effect of additives on the adduct formation was investigated. The fundamental insights resulting from these studies led to the identification of a cheap additive (tetrabutylammonium chloride), which in combination with the standard and cheap oxidant KMnO 4 generally gave excellent yields, similar to the ones previously obtained with more expensive AgPy2MnO4.
