1402354-36-2Relevant academic research and scientific papers
Effect of the nitrogen substituent on the reactions of alane towards imino- and aminophenols: Generation of a dinuclear aluminoxane
Martinez, Gema,Cuenca, Tomas,Mosquera, Marta E. G.
, p. 3611 - 3617 (2012/09/08)
AlH3·NEtMe2 reacts with salicylaldimines 3,5-tBu2-2-(OH)C6H2CH=NR [R = C 6F5 (1a), 2,6-Me2C6H3 (1b); 0.5 equiv.] to give the bisphenoxido-amido-imino compounds [Al{3,5-tBu2-2-(O)C6H2CH=NR}{3,5-tBu 2-2-(O)C6H2CH2-NR}] [R = C 6F5 (4a), 2,6-Me2C6H3 (4b)]. When the substituent on the nitrogen is 2,6-Me2C 6H3, it is possible to isolate the bis(phenoxido-imino) hydride [AlH{3,5-tBu2-2-(O)C6H2CH=N-2,6-Me 2C6H3}2] (3) if the reaction is performed at low temperature. Compound 4a is converted in wet toluene at room temperature readily and quantitatively into the aluminoxane [(Al{3,5-tBu 2-2-(O)C6H2CH=NC6F 5}{3,5-tBu2-2-(O)C6H2CH 2-NHC6F5})2O] (5). The mononuclear bis(phenoxido-amino) hydrides [AlH{3,5-tBu2-2-(O)C6H 2CH2-NHR}2] [R = 2,6-Me2C 6H3 (6b), tBu (6c)] are obtained by treatment of AlH 3·NEtMe2 with aminophenols 3,5-tBu 2-2-(OH)C6H2CH2-NHR [R = 2,6-Me 2C6H3 (2b), tBu (2c); 0.5 equiv.] in toluene at -78 °C. Compound 6b evolves into [Al{3,5-tBu2-2-(O)C 6H2CH2-NH-2,6-Me2C6H 3}{3,5-tBu2-2-(O)C6H2CH 2-N-2,6-Me2C6H3}] (7), which can also be generated by the direct reaction of 2b with AlH3· NEtMe2 (0.5 equiv.) at room temperature. The molecular structures of 4b and 5 have been determined by X-ray diffraction analysis. Reaction of different phenol amines and phenol imines with alane leads to new phenoxido-amino, phenoxido-amido and phenoxido-imino derivatives. The result of these reactions depends heavily on the nitrogen substituent. When this group is an electron attractor, such as C6F5, the isolation of the dinuclear aluminoxane [(Al{3,5-tBu2-2-(O)C6H 2CH=NC6F5}{3,5-tBu2-2-(O)C 6H2CH2-NHC6F5}) 2O] is achieved. Copyright
