Selective Synthesis of Primary Anilines from NH3 and Cyclohexanones by Utilizing Preferential Adsorption of Styrene on the Pd Nanoparticle Surface

Dehydrogenative aromatization is one of the attractive alternative methods for directly synthesizing primary anilines from NH3 and cyclohexanones. However, the selective synthesis of primary anilines is quite difficult because the desired primary aniline products and the cyclohexanone substrates rea...

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Bibliographic Details
Published in:Angewandte Chemie 2019-08, Vol.131 (32), p.11009-11013
Main Authors: Koizumi, Yu, Jin, Xiongjie, Yatabe, Takafumi, Miyazaki, Ray, Hasegawa, Jun‐ya, Nozaki, Kyoko, Mizuno, Noritaka, Yamaguchi, Kazuya
Format: Article
Language:English
Subjects:
Adsorption
Ammonia
Ammoniak
Aniline
Catalysis
Catalysts
Chemistry
Condensates
Cyclohexanone
Dehydrierende Aromatisierung
Dehydrogenation
Heterogene Katalyse
Hydrogen storage
Hydroxyapatite
Imines
Konkurrierende Adsorption
Nanoparticles
Styrene
Styrenes
Substrates
Surface chemistry
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Summary:Dehydrogenative aromatization is one of the attractive alternative methods for directly synthesizing primary anilines from NH3 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, Ca10(PO4)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 NH3 and cyclohexanones. The Pd/HAP catalyst was reused several times though its catalytic performance gradually declined. Primäre Aniline wurden in Anwesenheit adsorbierter Pd‐Nanopartikelkatalysatoren (z.B. Pd/HAP, HAP=Hydroxyapatit, Ca10(PO4)6(OH)2) selektiv synthetisiert, indem die konkurrierende Adsorption in heterogener Katalyse ausgenutzt wurde. Mit Styrol als Wasserstoffakzeptor können verschiedene strukturell vielfältige primäre Aniline selektiv aus den leicht zugänglichen Ausgangsstoffen NH3 und Cyclohexanonen synthetisiert werden.
ISSN:0044-8249
1521-3757
DOI:10.1002/ange.201903841