Catalytic Hydrogenation of Aromatic Nitrites

Hata, Kazuo; Watanabe, Kenichi

doi:10.1246/bcsj.32.861

Cited by 11 publications

(10 citation statements)

References 3 publications

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“…While an overall reaction scheme can involve disproportionation, reduction, condensation, hydrodenitrogenation and hydrodecarbonation, a simplified pathway is presented in Fig. 6 that applies to the published (liquid phase) catalytic studies [31,32] Fig. 7(A).…”

Section: Catalytic Responsementioning

confidence: 99%

“…This is a significant finding as reaction exclusivity to p-ABN has not been reported previously. The only gas phase study with which we can compare our results dates from the 1950s where Hata and Watanabe [32] investigated the hydrogenation of various aromatic nitriles (including the three NBN isomers) over a Ni-Cu catalyst at 523-573 K and reported the formation of aniline, toluidine and ABN (< 32% yield). We did not observe any activity in the reaction of benzonitrile over Au/ZrO2 or Au/Al2O3.…”

Section: Catalytic Responsementioning

confidence: 99%

“…The target amine product (p-aminobenzonitrile (p-ABN)) is used in the commercial production of a diversity of agrochemicals, pharmaceuticals, dyestuffs, urethanes and fine chemicals [26]. The literature [27][28][29][30][31][32][33] dealing with p-NBN hydrogenation is limited and has focused on batch liquid phase reactions at elevated pressures (up to 6 MPa [31]) where high selectivity to p-ABN is challenging. We can flag selectivities up to 97% achieved using Au/TiO2 and Au/Fe2O3 at near complete p-NBN conversion [27].…”

Section: Introductionmentioning

confidence: 99%

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Selective gas phase hydrogenation of p-nitrobenzonitrile to p-aminobenzonitrile over zirconia supported gold

Wang

Hao

Keane

2016

Applied Catalysis A: General

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The catalytic action of Au/ZrO2 in the gas phase hydrogenation of p-nitrobenzonitrile (p-NBN) to p-aminobenzonitrile (p-ABN) has been assessed against Au/Al2O3. Crystalline ZrO2 was prepared by precipitation of ZrOCl2 with aqueous NH3 and calcined to generate tetragonal and monoclinic phases. Catalyst and support were characterised by surface area/porosity, temperature-programmed reduction (TPR), H2 chemisorption/temperature programmed desorption (TPD), X-ray diffraction (XRD), transmission electron microscopy (TEM) and Xray photoelectron spectroscopy (XPS) measurements. Higher calcination temperatures (673-973 K) increased the monoclinic ZrO2 content with a decrease in surface area and pore volume. Introduction of Au by deposition-precipitation resulted in tetragonal→monoclinic transformation with post-TPR formation of Au particles in the 3-13 nm size range and electron transfer from ZrO2. Reaction over Au/ZrO2 delivered 100% p-ABN yield with higher turnover frequency (267 h-1) than Au/Al2O3 (109 h-1) attributed to greater H2 chemisorption capacity under reaction conditions and enhanced −NO2 activation. Au/ZrO2 outperformed benchmark Pd/Al2O3 and Ni/Al2O3, which generated p-aminotoluene via subsequent hydrogenation/hydrogenolysis.

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Section: Catalytic Responsementioning

confidence: 99%

Section: Catalytic Responsementioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Selective gas phase hydrogenation of p-nitrobenzonitrile to p-aminobenzonitrile over zirconia supported gold

Wang

Hao

Keane

2016

Applied Catalysis A: General

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“…A simplified pathway is presented in Figure 11.6 which applies to the published (liquid phase) catalytic studies. 122,123 Partially hydrogenated p-nitrosobenzonitrile and p-(cyanophenyl)-hydroxylamine 124 undergo condensation to 4,4 0 -dicyanoazobenzene. 122 The p-ABN formed can be hydrated to p-aminobenzylamide or hydrogenated to p-aminobenzylimine and p-aminobenzylamine with subsequent hydrogenolysis to p-aminotoluene (p-ATL).…”

Section: Hydrogenation Of P-nitrobenzonitrilementioning

confidence: 99%

“…122 The latter can also be generated via hydrogenolysis of 4,4 0 -diaminodibenzylamine as a condensation intermediate from p-aminobenzylimine and p-aminobenzylamine. 122,123 The catalytic action of Au/ZrO 2 and Au/Al 2 O 3 in gas phase hydrogenation of p-NBN may be assessed against Pd/Al 2 O 3 and Ni/Al 2 O 3 from the entries in Table 11.4. Reaction over both Au catalysts, with equivalent Au size (7-8 nm), was fully selective to p-ABN.…”

Section: Hydrogenation Of P-nitrobenzonitrilementioning

confidence: 99%

Harnessing the Selective Catalytic Action of Supported Gold in Hydrogenation Applications

Wang¹,

Li²,

Keane³

2014

Heterogeneous Gold Catalysts and Catalysis

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Gold finds diverse uses that cut across the automotive, electronics, medicine, nanotechnology, space and engineering sectors. 1-3 Catalysis by gold is now a priority growth area in terms of technological applications. 4 This has resulted in a number of review articles that have considered different aspects of gold catalysis. [5][6][7][8][9][10][11][12][13][14][15][16][17][18][19] Bond and co-workers have provided an overview of the status of related research in 1999 and 2006, 5,6 focusing on physicochemical properties, synthesis, characterisation and applications, notably in CO oxidation and the water gas shift reaction. In a more recent article, Bond highlighted the reactivity of gold at the nanoscale in activating small molecules. 20 A number of reviews have examined the catalytic action of gold in selective oxidation and we can flag critical assessments by Hutchings, Edwards and co-workers (catalyst preparation and characterisation), 7 Chen and Goodman (use of Au/TiO 2 as model catalyst),

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Untersuchungen zur Chemie von Isoindolen und Isoindoleninen, XXVIII. 3‐Alkoxy‐1H‐isoindole — Synthesen und Eigenschaften

et al. 1988

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3-Alkoxy-1H-isdindole 1 mit Substituenten am carbocyclischen Teil wurden aus substituierten 2.3-Dihydro-lH-isoindol-1 -onen 4 durch regiospaifische 0-Alkylierung rnit Trialkyloxonium-tetrafluoroboraten oder Trinuormethansulfonsiiure-methylester zu 5 und nachfolgende NH-Deprotonierung synthetisiert. Aufgrund der spektroskopischen Befunde existieren die semicyclischen ImidsBure-alkylester 1 ausschiieBlich in der benzoiden 1H-Form; die tautomere 2H-Form 2 mit o-chinoider Struktur ist spektreskopisch nicht nachweisbar. 3-Alkoxy-1 H-isoindolc (1) sind ideale Modellverbindungen zum Studium von Struktur-und Reaktivitatsprohlemen und intcressanteBezugssubstanzcn fur dic Zuordnung und fur den Vergleich spektroskopischer Datcn. Die semicyclischen Irnidsaure-aIkylester*' 1 sind auBerdem attraktive Zwischenprodukte fur die Synthese substituierter und anellierter Hctarene mit benzoider oder o-chinoider Struktur. 1 2 3 1.la: R" = H, R Cli, 1 . l b R " = H, R := C?H5 Weitere Restc siche bei 4, 5Nach der Herstellung von l . l b durch Petcrsen und Tietze3' haben diese rcaktivcn Imidsaure-alkylestcr viclseitiges Interesse gefunden4-'\ und in zunehmendem M a k synthetische Bedeutung crlangt. Ncbcn dern einfachcn Vertreter l . l a (R = CH,) wurden von uns vor allem 3-Alkoxy-lH-isoindole 1.2 bis 1.7 rnit Substitucnten (R" = NOI, C€130, CH3, C1) am carbocyclischen Teil hcrgestellt und spektroskopisch untersucht, um den EinfluB von Acceptor-und Donator-Gruppen auf die thcrmische Stabilitat und die chemische Reaktivitit der tautomcren 1Hund 2H-lsoindolc 1 und 2 zu uberprufen.Bei Substituenten in 5.6-StelIung sollte die elektronische Wechselwirkung mit dem cyclisch konjugierten n-System bestimmend sein, wahrend bei Substituenten in 4,7-Stellung der sterische EinfluD uberwiegen durfte. Von besondercm Interesse ist die Frage, o b der elektronische EinfluB von Acceptor-Gruppen (R" = NOI, Chlor) am carbocyclischen System ausreicht, um eine Stabilititsumkehrung zu bewirken und eine Umlagerung der benzoiden 1H-Form 1 in die tautorncre o-chinoide 2I-/-Form 2 zu verursachcn". Der sta-Chem. Ber. 121, 243-252 (1988)

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Catalytic Hydrogenation of Aromatic Nitrites

Cited by 11 publications

References 3 publications

Selective gas phase hydrogenation of p-nitrobenzonitrile to p-aminobenzonitrile over zirconia supported gold

Selective gas phase hydrogenation of p-nitrobenzonitrile to p-aminobenzonitrile over zirconia supported gold

Harnessing the Selective Catalytic Action of Supported Gold in Hydrogenation Applications

Untersuchungen zur Chemie von Isoindolen und Isoindoleninen, XXVIII. 3‐Alkoxy‐1H‐isoindole — Synthesen und Eigenschaften

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