Catalytic synthesis of N-substituted allylarylamines

Abstract Some N-substituted allylarylamines, for example, N-(1-methyl-2-butenyl) aniline (N-MBA) form, upon isomerization, not only ortho- , but also para- and 2,6-disubstituted derivatives, which does fit into generally accepted theory. The amino-Claisen rearrangement (ACR) of N-MBA is catalyzed by Lewis acids, cationites, arylamine hydrochlorides. This work presents the results studies ACR in solutions mineral acids. It was found that reaction must be carried out dilute solutions. At H 2 SO 4 concentrations 0.5 mol/L below, three parallel reactions are observed with formation aniline, 2-(1-methyl-2-butenyl) (2-MBA) 4-(1-methyl-2-butenyl) (4-MBA). main product all cases 2-MBA, content mixture exceeds amount 4-MBA 7 times, formed approximately equal amounts. Prolonged refluxing 2-MBA under conditions lead to its isomerization 4-MBA, i.e., para -isomer directly from N-MBA. 2,6-di-(1-methyl-2-butenyl) (DMBA) observed. In presence palladium catalysts, cyclizes 2,4-methyl quinoline, indicates ortho-arrangement substituents; cyclize these conditions. obtained compounds interest synthesis nitrogen-containing heterocycles other polyfunctional organic compounds.