Designed To React: Terminal Copper Nitrenes and Their Application in Catalytic C?H Aminations
Heteroscorpionate ligands of the bis(pyrazolyl)methane family have been applied in the stabilisation of terminal copper tosyl nitrenes. These species are highly active intermediates in the copper-catalysed direct C?H amination and nitrene transfer. Novel perfluoroalkyl-pyrazolyl- and pyridinyl-containing ligands were synthesized to coordinate to a reactive copper nitrene centre. Four distinct copper tosyl nitrenes were prepared at low temperatures by the reaction with SO2tBuPhINTs and copper(I) acetonitrile complexes. Their stoichiometric reactivity has been elucidated regarding the imination of phosphines and the aziridination of styrenes. The formation and thermal decay of the copper nitrenes were investigated by UV/Vis spectroscopy of the highly coloured species. Additionally, the compounds were studied by cryo-UHR-ESI mass spectrometry and DFT calculations. In addition, a mild catalytic procedure has been developed where the copper nitrene precursors enable the C?H amination of cyclohexane and toluene and the aziridination of styrenes.
The present invention discloses a preparation method for 6-chloro-2-trichloromethyl pyridine, in which 2-methyl pyridine hydrochloride or 2-chloromethyl pyridine is used as an initiator and a considerably excess amount of chlorine gas reacts with 2-methyl pyridine hydrochloride or 2-chloromethyl pyridine at a high temperature to form purer 6-chloro-2-trichloromethyl pyridine. The present invention provides a highly selective, high-yield and improved environmental-ly protective method.
-
Page/Page column 5
(2010/04/23)
MACROKINETIC RELATIONSHIPS OF HIGH-TEMPERATURE CHLORINATION OF 2-PICOLINE HYDROCHLORIDE
-
Emel'yanov, V. I.,Stul',B. Ya.
p. 2362 - 2365
(2007/10/02)
STRONG CHLORINATION OF 2-PICOLINE
The strong thermal and photochemical chlorination of 2-picoline hydrochloride at 80-150 deg.C was investigated.It occurs with change in the phase state of the reaction mixture.Among the chlorination products there were 17 compounds, 15 of which were isolated and identified.The main factor affecting the degree of chlorination is temperature, with increase in which the limiting degree of chlorination in the investigated range decreases.The penta-, hexa-, and heptachloro derivatives are formed mainly by initial chlorination of the pyridine ring with subsequent chlorination of the methyl group.
Kosorotov, V. I.,Stul', B. Ya.,Dzhagatspanyan, R. B.
p. 1845 - 1851
(2007/10/02)
More Articles about upstream products of 4377-37-1