The interaction of piperylene and its chlorine derivatives with aromatic amines
Authors:   Bashkir State University, Mustafin Akhat G. , Zimin Yury S. ,   Bashkir State University, Abdrakhmanov Ildus B. ,   Ufa Institute of Chemistry – Subdivision  of the Ufa Federal Research Centre of the Russian Academy of Sciences, Sharafutdinov Vakil M. ,   Branch of Ufa State Petroleum Technological University  in Sterlitamak
Published: March 2021

The article considers the possibility of introducing a pentenyl radical into the structure of aromatic amines by the interaction of the latter with piperylene and its chlorine derivatives, 4-chloro-2-pentene and 3,4-dichloro-2-pentene. Direct alkenylation of aniline with piperylene in the presence of Lewis acids leads to C-alkenyl arylamines. The most effective catalyst is AlCl3. Along with the expected 2- and 4-(1-methyl-2-butenyl) anilines, the formation of 2,4-di- and 2,4,6-tri-(1-methyl-2-butenyl) anilines is observed, the latter being virtiually the only product in the reaction with a 5-fold excess of piperylene. In addition to Lewis acids, H3PO4 deposited on kieselguhr or silica gel, as well as polyphosphoric acid, were used to catalyze this reaction. Under the action of these catalysts, ortho- and para-alkenylated anilines are mainly formed, and the yield of the ortho-isomer, reaching 34%, always exceeds the yield of the para-product. It is possible that, under these conditions, N-alkenylation occurs simultaneously with direct C-alkenylation followed by an amino rearrangement. The yield of the 2,4-dialkenyl product does not exceed 8%, and trialkenylated aniline is completely absent. The optimal reaction temperature is in the range of 180-200 °C, at higher temperatures the yield of the target products decreases due to the polymerization of piperylene. Various aniline derivatives are also involved in the reaction with piperylene. When one of the ortho positions in the arylamine molecule is occupied, as in ortho-toluidine or in 2-chloroaniline, a mixture of the three products is formed in comparable amounts. The reaction of meta-toluidine with piperylene also leads to the mixture of three products, and the substitution does not affect the 2-position between the amino and methyl groups. If both ortho-positions are occupied, as in 2-methyl-6-ethylaniline, the reaction is quite successfully under way in the para-position (yield is 61%). To increase the selectivity of the process, the alkylation of aromatic amines is best carried out not by piperylene, but by its chlorine derivatives. The reaction of aniline with 4-chloro-2-pentene takes place in the environment of triethylamine and leads to N-(1-methyl-2-butenyl) aniline with a yield of 80%. Other primary and secondary arylamines react in the same way. The reaction with 3,4-dichloro-2-pentene proceeds under more severe conditions. If the reaction of aromatic amines with 4-chloro-2-pentene is carried out not in triethylamine medium, but in an excess of arylamine itself as a solvent, then not N- but C-substituted products are formed. The reaction proceeds as a consequitive-simultameous process. In the first stage, N-alkenylation occurs with the formation of N-(1-methyl-2-butenyl) arylamine followed by an amino rearrangement of Claisen under the catalytic action of evolved HCl. Alongside with the obvious predominance of ortho-substituted arylamine (64-82%), para-isomers and, in some cases 5-12% of 2,4- or 2,6-disubstituted compounds were found in the reaction products. The amino rearrangement in the interaction of arylamines with 3,4-dichloro-2-pentene proceeds with exceptional ortho-selectivity. Alkyl groups at nitrogen and ortho positions accelerate, and ortho-chloro, para-methyl, 2,4-dimethyl substituents slow down the process, while the meta-methyl group has no significant effect. The same dependence was observed in the case of 4-chloro-2-pentene. Thus, pentenyl fragment can be introduced in various ways into the structure of aromatic amines: by direct interaction with piperylene in the presence of catalysts, N-alkenylation of 4-chloro-2-pentene and 3,4-dichloro-2-pentene in triethylamine medium and reaction of arylamines with chlorine derivatives of piperylene, accompanied by an amino rearrangement of Claisen.