Premium
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 international edition
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.831
H-Index - 550
eISSN - 1521-3773
pISSN - 1433-7851
DOI - 10.1002/anie.201903841
Subject(s) - styrene , adsorption , nanoparticle , primary (astronomy) , chemical engineering , materials science , chemistry , nanotechnology , organic chemistry , copolymer , polymer , physics , astronomy , engineering
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.