Catalytic Ketonization over Oxide Catalysts (Part XIV): The Ketonization and Cross-Ketonization of Anhydrides, Substituted Acids and Esters

A series of 20 wt.% MO2/S catalysts (where M = Ce, Mn or Zr and S = SiO2 or Al2O3) were prepared using various precursors of the active phases. The resulting catalysts were characterized using different methods (XRD, TPR and SBET). For the first time, anhydrides were used as potential starting materials for ketone synthesis. This novel reaction was performed on various aliphatic anhydrides in the presence of catalysts within a temperature range of 523–723 K. For all anhydrides, except for pivalic anhydride, the appropriate ketones were obtained with good or very good yields. The vapor-phase catalytic ketonization of esters of benzene-1,x-dicarboxylic acids (x = 2, 3 or 4) with acetic acid were studied in the range of 673–723 K in order to obtain 1,x-diacetylbenzenes. Their yields strongly increased with an increase in the x value (0, 8 and 43% for x = 2, 3 and 4, respectively). The presence of acetophenone as a side product was always noted. In the case of ω-phenylalkanoic acids, their vapor-phase ketonization with acetic acid led to the formation of appropriate ketones with 47–49% yields. Much lower yields of ketones (3–19%) were obtained for acids and ethyl esters containing heterocycle substituents (with O or S atoms) and/or vinyl groups. In the reaction between ethyl 4-nitrophenylacetate and acetic acid, only the products of ester decomposition (p-toluidine and p-nitrotoluene) were determined.

[1]  Zhong-Wen Liu,et al.  Rhodium-Catalyzed Alkylation of Aromatic Ketones with Allylic Alcohols and α,β-Unsaturated Ketones , 2023, Catalysts.

[2]  M. Engelhard,et al.  Single Ru(II) Ions on Ceria as a Highly Active Catalyst for Abatement of NO. , 2023, Journal of the American Chemical Society.

[3]  I. Fatimah,et al.  ZrO2-based catalysts for biodiesel production: a Review , 2022, Inorganic Chemistry Communications.

[4]  G. Hutchings,et al.  A Perspective on Heterogeneous Catalysts for the Selective Oxidation of Alcohols , 2021, Chemistry.

[5]  Kenichi Kato,et al.  An active, selective, and stable manganese oxide-supported atomic Pd catalyst for aerobic oxidation of 5-hydroxymethylfurfural , 2019, Green Chemistry.

[6]  T. Ioannides,et al.  Intrinsic Activity of MnOx-CeO2 Catalysts in Ethanol Oxidation , 2017 .

[7]  J. Llorca,et al.  Ceria Catalysts at Nanoscale: How Do Crystal Shapes Shape Catalysis? , 2017 .

[8]  D. Fino,et al.  Nanostructured Ceria-Based Materials: Effect of the Hydrothermal Synthesis Conditions on the Structural Properties and Catalytic Activity , 2017 .

[9]  M. Rueping,et al.  Continuous-flow hydration–condensation reaction: Synthesis of α,β-unsaturated ketones from alkynes and aldehydes by using a heterogeneous solid acid catalyst , 2011, Beilstein journal of organic chemistry.

[10]  W. Shim,et al.  Catalytic combustion of VOCs over a series of manganese oxide catalysts , 2010 .

[11]  Ji Man Kim,et al.  Manganese oxide catalysts for NOx reduction with NH3 at low temperatures , 2007 .

[12]  W. Szymański,et al.  Catalytic ketonization over oxide catalysts: X. Transformations of various alkyl heptanoates , 2005 .

[13]  M. Renz Ketonization of Carboxylic Acids by Decarboxylation: Mechanism and Scope , 2005 .

[14]  W. Nicol,et al.  One-step methyl isobutyl ketone synthesis from acetone and hydrogen using Amberlyst® CH28 , 2004 .

[15]  Kerry M. Dooley,et al.  Kinetics of catalyzed acid/acid and acid/aldehyde condensation reactions to non-symmetric ketones , 2003 .

[16]  N. Mizuno,et al.  Supported ruthenium catalyst for the heterogeneous oxidation of alcohols with molecular oxygen. , 2002, Angewandte Chemie.

[17]  K. Yamaguchi,et al.  Creation of a Monomeric Ru Species on the Surface of Hydroxyapatite as an Efficient Heterogeneous Catalyst for Aerobic Alcohol Oxidation , 2000 .

[18]  J. Kijeński,et al.  Decarboxylative coupling of heptanoic acid. Manganese, cerium and zirconium oxides as catalysts , 2000 .

[19]  V. Chikán,et al.  One-Step Synthesis of Methyl Isobutyl Ketone from Acetone and Hydrogen over Cu-on-MgO Catalysts , 1999 .

[20]  D. Boocock,et al.  Pathway for the Catalytic Conversion of Carboxylic Acids to Hydrocarbons over Activated Alumina , 1995 .

[21]  A. Baiker,et al.  Oxidation of alcohols with molecular oxygen on platinum metal catalysts in aqueous solutions , 1994 .

[22]  R. Fréty,et al.  Temperature-programmed reduction: limitation of the technique for determining the extent of reduction of either pure ceria or ceria modified by additiv , 1993 .

[23]  Erwin Müller‐Erlwein Heterogen katalysierte Ketonisierung von Laurin‐ und Stearinsäure in der Gasphase , 1990 .

[24]  K. Tanabe Surface and catalytic properties of ZrO2 , 1985 .

[25]  H. Hattori,et al.  Surface and catalytic properties of cerium oxide , 1981 .

[26]  O. Neunhoeffer,et al.  Über den Mechanismus der Ketonbildung aus Carbonsäuren , 1939 .

[27]  S. Kistler,et al.  Thoria Aërogel Catalyst: Aliphatic Esters to Ketones , 1934 .

[28]  E. Bamberger Notiz ber das Verhalten von Essigsureanhydrid bei hoher Temperatur , 1910 .

[29]  E. R. Squibb IMPROVEMENT IN THE MANUFACTURE OF ACETONE.1 , 1895 .

[30]  M. Gliński,et al.  Catalytic Ketonisation Over Oxide Catalysts. Part IX*. Single Step Synthesis of Aliphatic Saturated and Undsaturated C11-C13 Ketones from Carboxylic Acids , 2004 .

[31]  V. Perrichon,et al.  Reduction of CeO2 by hydrogen. Magnetic susceptibility and Fourier-transform infrared, ultraviolet and X-ray photoelectron spectroscopy measurements , 1991 .

[32]  Antonio J. Hernández,et al.  Molecular orbital study of cobalt-oxygen interaction , 1987 .

[33]  S. Patai The chemistry of carboxylic acids and esters , 1969 .

[34]  L. Ruzicka,et al.  Zur Kenntnis des Kohlenstoffringes IV. Über die Gewinnung des Cyclo-nonanons aus Sebacinsäure , 1926 .