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Selective Synthesis of Primary Anilines from NH 3 and Cyclohexanones by Utilizing Preferential Adsorption of Styrene on the Pd Nanoparticle Surface
Author(s) -
Koizumi Yu,
Jin Xiongjie,
Yatabe Takafumi,
Miyazaki Ray,
Hasegawa Junya,
Nozaki Kyoko,
Mizuno Noritaka,
Yamaguchi Kazuya
Publication year - 2019
Publication title -
angewandte chemie
Language(s) - English
Resource type - Journals
eISSN - 1521-3757
pISSN - 0044-8249
DOI - 10.1002/ange.201903841
Subject(s) - aniline , catalysis , chemistry , primary (astronomy) , cyclohexanone , styrene , nanoparticle , adsorption , aromatization , organic chemistry , polymer chemistry , combinatorial chemistry , materials science , nanotechnology , polymer , copolymer , physics , astronomy
Dehydrogenative aromatization is one of the attractive alternative methods for directly synthesizing primary anilines from NH 3 and cyclohexanones. However, the selective synthesis of primary anilines is quite difficult because the desired primary aniline products and the cyclohexanone substrates readily undergo condensation affording the corresponding imines (i.e., N ‐cyclohexylidene‐anilines), followed by hydrogenation to produce N ‐cyclohexylanilines as the major products. In this study, primary anilines were selectively synthesized in the presence of supported Pd nanoparticle catalysts (e.g., Pd/HAP, HAP=hydroxyapatite, Ca 10 (PO 4 ) 6 (OH) 2 ) by utilizing competitive adsorption unique to heterogeneous catalysis; in other words, when styrene was used as a hydrogen acceptor, which preferentially adsorbs on the Pd nanoparticle surface in the presence of N ‐cyclohexylidene‐anilines, various structurally diverse primary anilines were selectively synthesized from readily accessible NH 3 and cyclohexanones. The Pd/HAP catalyst was reused several times though its catalytic performance gradually declined.