64372-87-8Relevant articles and documents
The thermal isomerisation benzoazetine - 6-methylene-2,4-cyclohexadien-1-imine: A photoelectron investigation
Pfister-Guillouzo, Genevieve,Gracian, Francoise,Senio, Anna,Letulle, Marguerite,Ripoll, Jean-Louis
, p. 5753 - 5756 (1992)
The flash vacuum thermolyses of 1,2,3,4-tetrahydroquinoline 3, o-aminobenzylalcohol 4 and o-aminobenzylamine 5 were performed at temperatures from 923 to 1273 K and monitored by photoelectron spectrometry. While thermolyses at 923-1073 K led to the until now undescribed benzoazetine 2a, 6-methylene-2,4- cyclohexadien-1-imine 1a was obtained at 1173-1273 K.
Metal- and Protection-Free [4 + 2] Cycloadditions of Alkynes with Azadienes: Assembly of Functionalized Quinolines
Saunthwal, Rakesh K.,Patel, Monika,Verma, Akhilesh K.
, p. 2200 - 2203 (2016/06/01)
A base promoted, protection-free, and regioselective synthesis of highly functionalized quinolines via [4 + 2] cycloaddition of azadienes (generated in situ from o-aminobenzyl alcohol) with internal alkynes has been discovered. The reaction tolerates a wide variety of functional groups which has been successfully extended with diynes, (2-aminopyridin-3-yl)methanol, and 1,4-bis(phenylethynyl)benzene to afford (Z)-phenyl-2-styrylquinolines, phenylnaphthyridine, and alkyne-substituted quinolines, respectively. The proposed mechanism and significant role of the solvent were well supported by isolating the azadiene intermediate and deuterium-labeling studies.
Intramolecular Hydrogen Transfer in (2-Aminophenyl)carbene and 2-Tolylnitrene. Matrix Isolation of 6-Methylene-2,4-cyclohexadien-1-imine
Morawietz, Jens,Sander, Wolfram,Traeubel, Michael
, p. 6368 - 6378 (2007/10/03)
Flash vacuum pyrolysis (FVP) or matrix photolysis of 2-(diazomethyl)phenylamine, 1-azido-2-methylbenzene (2-tolyl azide), o-aminobenzyl alcohol, or 2-indolinone provide entries into the C7H7N hypersurface.The matrix-isolated (argon, 10 K) products have been characterized by IR and UV-vis spectroscopy in combination with high level (MP2/6-31G(d) and HF/6-31G(d,p)) ab-initio calculations.FVP (500-800 deg C) of the first three of these precursors produces high yields of E/Z-mixtures of 6-methylene-2,4-cyclohexadien-1-imine (o-iminoquinone methide), while the bicyclic isomer benzoazetine is not formed under these conditions.FVP of 2-tolyl azide at very high temperatures (>900 deg C) leads to the formation of benzaldimine and benzonitrile.Photolysis of the matrix-isolated precursors allows one to selectively generate the E- and Z-isomer of the iminoquinone methide as well as benzoazetine.In addition, 2-tolylnitrene and 1-aza-3-methyl-1,2,4,6-cycloheptatetraene are produced as intermediates in the photolysis of 2-tolyl azide.The nitrene is thermally stable up to 80 K (in xenon matrix), although the hydrogen migration to give (E)-o-iminoquinone methide is calculated to be exothermic by 42 kcal/mol.Irradiation of 2-(diazomethyl)phenylamine directly yields the quinone methide while (o-aminophenyl)carbene, which is the most reasonable intermediate, is not observed.