179990-85-3Relevant academic research and scientific papers
Selective electrolytic fluorinations in 70% HF/30% pyridine
Lee, Sarah M.,Roseman, Jamie M.,Zartman, C. Blair,Morrison, Eamonn P.,Harrison, Sean J.,Stankiewicz, Corrie A.,Middleton
, p. 65 - 70 (1996)
The selective fluorination of compounds containing benzylic hydrogen atoms was accomplished by electrolysis in a mixture of 70% HF and 30% pyridine (Olah's reagent) using a square wave alternating current (1.76-2.75 V, 0.02-0.05 Hz) and Pt electrodes. This method can be used in the laboratory to prepare conveniently gram-size quantities of monofluorinated products. An ion radical mechanism has been proposed.
Fragmentations of Protonated Acetophenones via Intermediate Ion-Molecule Complexes
Filges, U.,Gruetzmacher, Hans-Fr.
, p. 444 - 450 (1987)
Protonated acetophenones, substituted with a methoxymethyl group in the para and meta positions, have been generated by electron impact induced fragmentation of the correspondingly substituted 2-phenylpropan-2-ols.The metastable ions, formed in the second field-free region of a VG ZAB2F mass spectrometer, react unimolecularly by elimination of CH3OH, formation of CH3CO+ and CH3O+=CH2 ions, loss of CH3COOCH3, and loss of CH2O.The mechanisms of these fragmentations have been elucidated with the aid of deuterated analogues of the protonated acetophenones.It is shown that these reactions are initiated by an endothermic transfer of the proton at the carbonyl group of the protonated acetophenones to the benzene ring.A further migration of the proton to the ether O atom of the methoxymethyl side-chain leads eventually to the elimination of CH3OH.Protolytic bond cleavages of either side-chain gives rise to the CH3CO+ and CH3O+=CH2 ions.At low internal energies both these ions may be trapped by the aromatic neutral fragment in ion-molecule complexes.Reactions within these complexes result in the energetically favourable losses of CH3COOCH3 and CH2O, respectively.With respect to these reactions, the protonated acetophenones behave analogously to the correspondingly substituted and protonated benzaldehydes.
Triplet-sensitized photoreactivity of a geminal diazidoalkane
Upul Ranaweera, Ranaweera A. A.,Sankaranarayanan, Jagadis,Casey, Lydia,Ault, Bruce S.,Gudmundsdottir, Anna D.
supporting information; experimental part, p. 8177 - 8188 (2011/12/22)
Photolysis of 1 in chloroform yielded 2 as the major product and a small quantity of 3. Laser flash photolysis demonstrated that upon irradiation, the first excited triplet state of the ketone (T1K) of 1 is formed and decayed to form radical 4, which has a λmax at 380 nm (t = 2 μs). Radical 4 expelled a nitrogen molecule to yield imine radical 5 (λmax at 300 nm). Density functional theory (DFT) calculations showed that the transition state barrier for the formation of 5 is approximately 4 kcal/mol. In comparison, photolysis of 1 in argon matrices resulted in triplet nitrene 6, which was further characterized with 15N and D isotope labeling and DFT calculations. Prolonged irradiation of 6 yields triplet imine nitrene 7.
