Aniline

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Noritaka Mizuno - One of the best experts on this subject based on the ideXlab platform.

  • selective synthesis of primary Anilines from nh3 and cyclohexanones by utilizing preferential adsorption of styrene on the pd nanoparticle surface
    Angewandte Chemie, 2019
    Co-Authors: Yu Koizumi, Xiongjie Jin, Kyoko Nozaki, Noritaka Mizuno, Takafumi Yatabe, Ray Miyazaki, Junya Hasegawa, Kazuya Yamaguchi
    Abstract:

    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.

  • selective synthesis of primary Anilines from cyclohexanone oximes by the concerted catalysis of a mg al layered double hydroxide supported pd catalyst
    Journal of the American Chemical Society, 2017
    Co-Authors: Xiongjie Jin, Yu Koizumi, Kazuya Yamaguchi, Kyoko Nozaki, Noritaka Mizuno
    Abstract:

    Although the selective conversion of cyclohexanone oximes to primary Anilines would be a good complement to the classical synthetic methods for primary Anilines, which utilize arenes as the starting materials, there have been no general and efficient methods for the conversion of cyclohexanone oximes to primary Anilines until now. In this study, we have successfully realized the efficient conversion of cyclohexanone oximes to primary Anilines by utilizing a Mg-Al layered double hydroxide supported Pd catalyst (Pd(OH)x/LDH) under ligand-, additive-, and hydrogen-acceptor-free conditions. The substrate scope was very broad with respect to both cyclohexanone oximes and cyclohexenone oximes, which gave the corresponding primary Anilines in high yields with high selectivities (17 examples, 75% to >99% yields). The reaction could be scaled up (gram-scale) with a reduced amount of the catalyst (0.2 mol %). Furthermore, the one-pot synthesis of primary Anilines directly from cyclohexanones and hydroxylamine was also successful (five examples, 66-99% yields). The catalysis was intrinsically heterogeneous, and the catalyst could be reused for the conversion of cyclohexanone oxime to Aniline at least five times with keeping its high catalytic performance. Kinetic studies and several control experiments showed that the high activity and selectivity of the present catalyst system were attributed to the concerted catalysis of the basic LDH support and the active Pd species on LDH. The present transformation of cyclohexanone oximes to primary Anilines proceeds through a dehydration/dehydrogenation sequence, and herein the plausible reaction mechanism is proposed on the basis of several pieces of experimental evidence.

  • Selective Synthesis of Primary Anilines from Cyclohexanone Oximes by the Concerted Catalysis of a Mg–Al Layered Double Hydroxide Supported Pd Catalyst
    2017
    Co-Authors: Xiongjie Jin, Yu Koizumi, Kazuya Yamaguchi, Kyoko Nozaki, Noritaka Mizuno
    Abstract:

    Although the selective conversion of cyclohexanone oximes to primary Anilines would be a good complement to the classical synthetic methods for primary Anilines, which utilize arenes as the starting materials, there have been no general and efficient methods for the conversion of cyclohexanone oximes to primary Anilines until now. In this study, we have successfully realized the efficient conversion of cyclohexanone oximes to primary Anilines by utilizing a Mg–Al layered double hydroxide supported Pd catalyst (Pd­(OH)x/LDH) under ligand-, additive-, and hydrogen-acceptor-free conditions. The substrate scope was very broad with respect to both cyclohexanone oximes and cyclohexenone oximes, which gave the corresponding primary Anilines in high yields with high selectivities (17 examples, 75% to >99% yields). The reaction could be scaled up (gram-scale) with a reduced amount of the catalyst (0.2 mol %). Furthermore, the one-pot synthesis of primary Anilines directly from cyclohexanones and hydroxylamine was also successful (five examples, 66–99% yields). The catalysis was intrinsically heterogeneous, and the catalyst could be reused for the conversion of cyclohexanone oxime to Aniline at least five times with keeping its high catalytic performance. Kinetic studies and several control experiments showed that the high activity and selectivity of the present catalyst system were attributed to the concerted catalysis of the basic LDH support and the active Pd species on LDH. The present transformation of cyclohexanone oximes to primary Anilines proceeds through a dehydration/dehydrogenation sequence, and herein the plausible reaction mechanism is proposed on the basis of several pieces of experimental evidence

Xiongjie Jin - One of the best experts on this subject based on the ideXlab platform.

  • selective synthesis of primary Anilines from nh3 and cyclohexanones by utilizing preferential adsorption of styrene on the pd nanoparticle surface
    Angewandte Chemie, 2019
    Co-Authors: Yu Koizumi, Xiongjie Jin, Kyoko Nozaki, Noritaka Mizuno, Takafumi Yatabe, Ray Miyazaki, Junya Hasegawa, Kazuya Yamaguchi
    Abstract:

    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.

  • selective synthesis of primary Anilines from cyclohexanone oximes by the concerted catalysis of a mg al layered double hydroxide supported pd catalyst
    Journal of the American Chemical Society, 2017
    Co-Authors: Xiongjie Jin, Yu Koizumi, Kazuya Yamaguchi, Kyoko Nozaki, Noritaka Mizuno
    Abstract:

    Although the selective conversion of cyclohexanone oximes to primary Anilines would be a good complement to the classical synthetic methods for primary Anilines, which utilize arenes as the starting materials, there have been no general and efficient methods for the conversion of cyclohexanone oximes to primary Anilines until now. In this study, we have successfully realized the efficient conversion of cyclohexanone oximes to primary Anilines by utilizing a Mg-Al layered double hydroxide supported Pd catalyst (Pd(OH)x/LDH) under ligand-, additive-, and hydrogen-acceptor-free conditions. The substrate scope was very broad with respect to both cyclohexanone oximes and cyclohexenone oximes, which gave the corresponding primary Anilines in high yields with high selectivities (17 examples, 75% to >99% yields). The reaction could be scaled up (gram-scale) with a reduced amount of the catalyst (0.2 mol %). Furthermore, the one-pot synthesis of primary Anilines directly from cyclohexanones and hydroxylamine was also successful (five examples, 66-99% yields). The catalysis was intrinsically heterogeneous, and the catalyst could be reused for the conversion of cyclohexanone oxime to Aniline at least five times with keeping its high catalytic performance. Kinetic studies and several control experiments showed that the high activity and selectivity of the present catalyst system were attributed to the concerted catalysis of the basic LDH support and the active Pd species on LDH. The present transformation of cyclohexanone oximes to primary Anilines proceeds through a dehydration/dehydrogenation sequence, and herein the plausible reaction mechanism is proposed on the basis of several pieces of experimental evidence.

  • Selective Synthesis of Primary Anilines from Cyclohexanone Oximes by the Concerted Catalysis of a Mg–Al Layered Double Hydroxide Supported Pd Catalyst
    2017
    Co-Authors: Xiongjie Jin, Yu Koizumi, Kazuya Yamaguchi, Kyoko Nozaki, Noritaka Mizuno
    Abstract:

    Although the selective conversion of cyclohexanone oximes to primary Anilines would be a good complement to the classical synthetic methods for primary Anilines, which utilize arenes as the starting materials, there have been no general and efficient methods for the conversion of cyclohexanone oximes to primary Anilines until now. In this study, we have successfully realized the efficient conversion of cyclohexanone oximes to primary Anilines by utilizing a Mg–Al layered double hydroxide supported Pd catalyst (Pd­(OH)x/LDH) under ligand-, additive-, and hydrogen-acceptor-free conditions. The substrate scope was very broad with respect to both cyclohexanone oximes and cyclohexenone oximes, which gave the corresponding primary Anilines in high yields with high selectivities (17 examples, 75% to >99% yields). The reaction could be scaled up (gram-scale) with a reduced amount of the catalyst (0.2 mol %). Furthermore, the one-pot synthesis of primary Anilines directly from cyclohexanones and hydroxylamine was also successful (five examples, 66–99% yields). The catalysis was intrinsically heterogeneous, and the catalyst could be reused for the conversion of cyclohexanone oxime to Aniline at least five times with keeping its high catalytic performance. Kinetic studies and several control experiments showed that the high activity and selectivity of the present catalyst system were attributed to the concerted catalysis of the basic LDH support and the active Pd species on LDH. The present transformation of cyclohexanone oximes to primary Anilines proceeds through a dehydration/dehydrogenation sequence, and herein the plausible reaction mechanism is proposed on the basis of several pieces of experimental evidence

Ziad El Rassi - One of the best experts on this subject based on the ideXlab platform.

  • electrically driven microseparation methods for pesticides and metabolites vi surfactant mediated electrokinetic capillary chromatography of Aniline pesticidic metabolites derivatized with 9 fluoroenylmethyl chloroformate and their detection by laser
    Electrophoresis, 2001
    Co-Authors: William Wall, King C Chan, Ziad El Rassi
    Abstract:

    In this report, we describe a surfactant-mediated electrokinetic capillary chromatography (SM-EKC) system for the separation of 9-fluoroenylmethyl chloroformate (FMOC)-derivatized Anilines by capillary electrophoresis (CE). The SM-EKC system consisted of dioctyl sulfosuccinate (DOSS)/acetonitrile mixtures and was suited for the CE separation of the relatively hydrophobic FMOC-Aniline analytes and other neutral compounds, e.g. alkylphenyl ketones. While the organic modifier acetonitrile (ACN) allowed the solubilization of the hydrophobic solutes and maintained the DOSS surfactant in its monomeric form by inhibiting micellization, the DOSS surfactant associated with the FMOC Anilines to a varying degree thus leading to their differential migration and separation. Under these conditions, the FMOC-Anilines were readily detected at the 10(-6) M level by UV at 214 nm and at the 10(-8) M level by laser-induced fluorescence (LIF) using a solid-state UV laser operating at 266 nm line as the excitation wavelength. The FMOC precolumn derivatization was also readily performed in lake water spiked with Anilines at near the limit of detection (LOD) level. The lake water matrix showed no significant effects on the extent of derivatization at the LOD level as well as on the detection of the analytes due to the selectivity of the FMOC derivatization. The derivatization and detection of spiked lake water necessitated only the removal of microparticles by microfiltration prior to derivatization and detection.

  • electrically driven microseparation methods for pesticides and metabolites v micellar electrokinetic capillary chromatography of Aniline pesticidic metabolites derivatized with fluorescein isothiocyanate and their detection in real water at low level
    Electrophoresis, 2001
    Co-Authors: William Wall, Ziad El Rassi
    Abstract:

    Anilines are important pollutants occurring in the environment as industrial discharges as well as the transformation products (i.e.,metabolites) of a wide variety of commonly used pesticides. In this report, we describe the precolumn derivatization of Anilines with fluorescein isothiocyanate (FITC) and their subsequent separation and detection by capillary electrophoresis-laser induced fluorescence (CE-LIF) detection. The FITC-Aniline derivatives were readily detected at the 10–10M level. This limit of detection (LOD) was achieved in the presence of glycosidic surfactants complexed with borate at alkaline pH yielding the so-called in situ charged micelles. The glycosidic surfactants evaluated were n-octyl- and n-nonylglucopyranoside. Furthermore, and under optimum conditions, the FITC precolumn derivatization of the Anilines was performed in real water (e.g., tap and lake water) spiked with Anilines at the LOD level. The water matrices showed marginal effects on the extent of derivatization at the LOD level, and the possible interferents in the water samples did not affect the FITC-solute signal due to the selectivity of the derivatization and detection schemes. Besides filtration from microparticles, the real water samples did not necessitate extensive sample cleanup prior to derivatization.

Kyoko Nozaki - One of the best experts on this subject based on the ideXlab platform.

  • selective synthesis of primary Anilines from nh3 and cyclohexanones by utilizing preferential adsorption of styrene on the pd nanoparticle surface
    Angewandte Chemie, 2019
    Co-Authors: Yu Koizumi, Xiongjie Jin, Kyoko Nozaki, Noritaka Mizuno, Takafumi Yatabe, Ray Miyazaki, Junya Hasegawa, Kazuya Yamaguchi
    Abstract:

    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.

  • selective synthesis of primary Anilines from cyclohexanone oximes by the concerted catalysis of a mg al layered double hydroxide supported pd catalyst
    Journal of the American Chemical Society, 2017
    Co-Authors: Xiongjie Jin, Yu Koizumi, Kazuya Yamaguchi, Kyoko Nozaki, Noritaka Mizuno
    Abstract:

    Although the selective conversion of cyclohexanone oximes to primary Anilines would be a good complement to the classical synthetic methods for primary Anilines, which utilize arenes as the starting materials, there have been no general and efficient methods for the conversion of cyclohexanone oximes to primary Anilines until now. In this study, we have successfully realized the efficient conversion of cyclohexanone oximes to primary Anilines by utilizing a Mg-Al layered double hydroxide supported Pd catalyst (Pd(OH)x/LDH) under ligand-, additive-, and hydrogen-acceptor-free conditions. The substrate scope was very broad with respect to both cyclohexanone oximes and cyclohexenone oximes, which gave the corresponding primary Anilines in high yields with high selectivities (17 examples, 75% to >99% yields). The reaction could be scaled up (gram-scale) with a reduced amount of the catalyst (0.2 mol %). Furthermore, the one-pot synthesis of primary Anilines directly from cyclohexanones and hydroxylamine was also successful (five examples, 66-99% yields). The catalysis was intrinsically heterogeneous, and the catalyst could be reused for the conversion of cyclohexanone oxime to Aniline at least five times with keeping its high catalytic performance. Kinetic studies and several control experiments showed that the high activity and selectivity of the present catalyst system were attributed to the concerted catalysis of the basic LDH support and the active Pd species on LDH. The present transformation of cyclohexanone oximes to primary Anilines proceeds through a dehydration/dehydrogenation sequence, and herein the plausible reaction mechanism is proposed on the basis of several pieces of experimental evidence.

  • Selective Synthesis of Primary Anilines from Cyclohexanone Oximes by the Concerted Catalysis of a Mg–Al Layered Double Hydroxide Supported Pd Catalyst
    2017
    Co-Authors: Xiongjie Jin, Yu Koizumi, Kazuya Yamaguchi, Kyoko Nozaki, Noritaka Mizuno
    Abstract:

    Although the selective conversion of cyclohexanone oximes to primary Anilines would be a good complement to the classical synthetic methods for primary Anilines, which utilize arenes as the starting materials, there have been no general and efficient methods for the conversion of cyclohexanone oximes to primary Anilines until now. In this study, we have successfully realized the efficient conversion of cyclohexanone oximes to primary Anilines by utilizing a Mg–Al layered double hydroxide supported Pd catalyst (Pd­(OH)x/LDH) under ligand-, additive-, and hydrogen-acceptor-free conditions. The substrate scope was very broad with respect to both cyclohexanone oximes and cyclohexenone oximes, which gave the corresponding primary Anilines in high yields with high selectivities (17 examples, 75% to >99% yields). The reaction could be scaled up (gram-scale) with a reduced amount of the catalyst (0.2 mol %). Furthermore, the one-pot synthesis of primary Anilines directly from cyclohexanones and hydroxylamine was also successful (five examples, 66–99% yields). The catalysis was intrinsically heterogeneous, and the catalyst could be reused for the conversion of cyclohexanone oxime to Aniline at least five times with keeping its high catalytic performance. Kinetic studies and several control experiments showed that the high activity and selectivity of the present catalyst system were attributed to the concerted catalysis of the basic LDH support and the active Pd species on LDH. The present transformation of cyclohexanone oximes to primary Anilines proceeds through a dehydration/dehydrogenation sequence, and herein the plausible reaction mechanism is proposed on the basis of several pieces of experimental evidence

Yu Koizumi - One of the best experts on this subject based on the ideXlab platform.

  • selective synthesis of primary Anilines from nh3 and cyclohexanones by utilizing preferential adsorption of styrene on the pd nanoparticle surface
    Angewandte Chemie, 2019
    Co-Authors: Yu Koizumi, Xiongjie Jin, Kyoko Nozaki, Noritaka Mizuno, Takafumi Yatabe, Ray Miyazaki, Junya Hasegawa, Kazuya Yamaguchi
    Abstract:

    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.

  • selective synthesis of primary Anilines from cyclohexanone oximes by the concerted catalysis of a mg al layered double hydroxide supported pd catalyst
    Journal of the American Chemical Society, 2017
    Co-Authors: Xiongjie Jin, Yu Koizumi, Kazuya Yamaguchi, Kyoko Nozaki, Noritaka Mizuno
    Abstract:

    Although the selective conversion of cyclohexanone oximes to primary Anilines would be a good complement to the classical synthetic methods for primary Anilines, which utilize arenes as the starting materials, there have been no general and efficient methods for the conversion of cyclohexanone oximes to primary Anilines until now. In this study, we have successfully realized the efficient conversion of cyclohexanone oximes to primary Anilines by utilizing a Mg-Al layered double hydroxide supported Pd catalyst (Pd(OH)x/LDH) under ligand-, additive-, and hydrogen-acceptor-free conditions. The substrate scope was very broad with respect to both cyclohexanone oximes and cyclohexenone oximes, which gave the corresponding primary Anilines in high yields with high selectivities (17 examples, 75% to >99% yields). The reaction could be scaled up (gram-scale) with a reduced amount of the catalyst (0.2 mol %). Furthermore, the one-pot synthesis of primary Anilines directly from cyclohexanones and hydroxylamine was also successful (five examples, 66-99% yields). The catalysis was intrinsically heterogeneous, and the catalyst could be reused for the conversion of cyclohexanone oxime to Aniline at least five times with keeping its high catalytic performance. Kinetic studies and several control experiments showed that the high activity and selectivity of the present catalyst system were attributed to the concerted catalysis of the basic LDH support and the active Pd species on LDH. The present transformation of cyclohexanone oximes to primary Anilines proceeds through a dehydration/dehydrogenation sequence, and herein the plausible reaction mechanism is proposed on the basis of several pieces of experimental evidence.

  • Selective Synthesis of Primary Anilines from Cyclohexanone Oximes by the Concerted Catalysis of a Mg–Al Layered Double Hydroxide Supported Pd Catalyst
    2017
    Co-Authors: Xiongjie Jin, Yu Koizumi, Kazuya Yamaguchi, Kyoko Nozaki, Noritaka Mizuno
    Abstract:

    Although the selective conversion of cyclohexanone oximes to primary Anilines would be a good complement to the classical synthetic methods for primary Anilines, which utilize arenes as the starting materials, there have been no general and efficient methods for the conversion of cyclohexanone oximes to primary Anilines until now. In this study, we have successfully realized the efficient conversion of cyclohexanone oximes to primary Anilines by utilizing a Mg–Al layered double hydroxide supported Pd catalyst (Pd­(OH)x/LDH) under ligand-, additive-, and hydrogen-acceptor-free conditions. The substrate scope was very broad with respect to both cyclohexanone oximes and cyclohexenone oximes, which gave the corresponding primary Anilines in high yields with high selectivities (17 examples, 75% to >99% yields). The reaction could be scaled up (gram-scale) with a reduced amount of the catalyst (0.2 mol %). Furthermore, the one-pot synthesis of primary Anilines directly from cyclohexanones and hydroxylamine was also successful (five examples, 66–99% yields). The catalysis was intrinsically heterogeneous, and the catalyst could be reused for the conversion of cyclohexanone oxime to Aniline at least five times with keeping its high catalytic performance. Kinetic studies and several control experiments showed that the high activity and selectivity of the present catalyst system were attributed to the concerted catalysis of the basic LDH support and the active Pd species on LDH. The present transformation of cyclohexanone oximes to primary Anilines proceeds through a dehydration/dehydrogenation sequence, and herein the plausible reaction mechanism is proposed on the basis of several pieces of experimental evidence