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Solvent effects were investigated for selective hydrogenation of acetophenone (AP) with commercial 5% Pd/Al2O3 and 5% Pd/C catalysts using polar and nonpolar solvents. The rate of AP hydrogenation varied with the solvents used in different ways depending on the catalysts used. The highest AP conversion was achieved with water for the two catalysts and the AP conversion was correlated with hydrogen-bond-acceptance (HBA) capability (β) for Pd/Al2O3 and hydrogen-bond-donation (HBD) capability (α) for Pd/C. These trends were the same as the corresponding solvent effects obtained previously with Rh/Al2O3 and Rh/C catalysts, respectively (Green Chem., 2015, 17, 1877–1883). The influence of solvents on the rate of AP hydrogenation depends on the support materials and not on the metal species. Furthermore, AP hydrogenation was conducted with the four supported noble metal catalysts in different solvents pressurized by CO2 (CO2-dissolved expanded solvents). The influence of CO2 pressurization on the rate of reaction, the product selectivity, and the catalyst life was investigated to know whether or not CO2 molecules could function as a reaction promoter in heterogeneous AP hydrogenation reactions with supported Pd and Rh catalysts in different solvents. [ABSTRACT FROM AUTHOR]

The hydrogenation of levulinic acid (LA) to γ-valerolactone (GVL) was studied with a homogeneous RuCl2(PPh3)3 catalyst in supercritical CO2 (scCO2). The conversion of LA was observed to increase with CO2 pressure and the possible reasons for this rate acceleration were discussed, including the molecular interactions of CO2 with the reacting and catalytic species as well as the acidity and phase behavior of the reaction mixture. The interaction between CO2 and RuCl2(PPh3)3 was significant, which resulted in the production of an active RuHCl(CO)(PPh3)3 complex and thus enhanced the rate of hydrogenation in the presence of CO2. [ABSTRACT FROM AUTHOR]

Selective hydrogenation of acetophenone (AP) to 1-phenylethanol (PhE) was investigated over Rh/Al2O3 and Rh/C catalysts in 13 solvents including water and conventional organic solvents. Strong solvent effects on the overall rate of AP conversion were observed in different manners depending on the catalysts used. The conversion obtained is correlated with hydrogen-bond-donation (HBD) capability for Rh/C but with hydrogen-bond-acceptance (HBA) capacity for Rh/Al2O3. The solvent effects should result from interactions between the carbonyl group of AP and the solvent molecules through hydrogen bonding for Rh/C and from those between the solvent molecules and the catalyst surface for Rh/Al2O3 having HBD hydroxyl groups on its surface. Water is the most effective functional solvent in the selective hydrogenation of AP for C and Al2O3-supported Rh catalysts due to its high HBD capability (α) and low HBA capability (β), respectively. For the hydrogenation with Rh/Al2O3 in water, its large polarity/polarizability index (π*) may contribute to the high selectivity to PhE. [ABSTRACT FROM AUTHOR]

The selective hydrogenation of benzyl cyanide (BC) to the primary amine of 2-phenylethylamine (PEA) was investigated with a Pd/Al2O3 catalyst in different multiphase reaction media including n-hexane, water, and/or CO2. In neat n-hexane, the hydrogenation of BC occurs at a large rate but no PEA was formed and the secondary amine of N,N-bis(2-phenylethyl)amine (BPEA) was produced as the main product. The pressurization of n-hexane with CO2 decreased the rate of hydrogenation and the main product was BPEA. In this n-hexane–CO2 medium, the catalyst lost its activity during the reaction. When a similar volume of water was added to n-hexane, the rate of hydrogenation did not change so much but a small amount of the primary amine was detected to form in addition to the main product of BPEA. In contrast to these reaction media, a high PEA selectivity of ＞90% was obtained and no catalyst deactivation occurred in an n-hexane–water–CO2 medium. The rate of hydrogenation was smaller than that in neat n-hexane but comparable to those in n-hexane–water and n-hexane–CO2 media. Those results show that synergistic effects appear on the selective hydrogenation of BC to PEA when both water and CO2 are included in the reaction medium. Possible roles and actions of water and CO2 have been discussed on the basis of the results of hydrogenation runs under different conditions and in situ ambient and high pressure Fourier transform infrared spectroscopy measurements that give insights into molecular interactions of CO2 with reacting species. [ABSTRACT FROM AUTHOR]

Chemoselective hydrogenation of water-insoluble aromatic nitro compounds can be achieved over Ni catalysts in a H2O–compressed CO2system at 35–50 °C without using any environmentally harmful solvent. The effective CO2pressure is much lower than the critical pressure of CO2. The hydrogenation of nitro group should be the rate-determining step. [ABSTRACT FROM AUTHOR]

Chemoselective hydrogenation of water-insoluble aromatic nitro compounds can be achieved over Ni catalysts in a H2O–compressed CO2 system at 35–50 °C without using any environmentally harmful solvent. The effective CO2 pressure is much lower than the critical pressure of CO2. The hydrogenation of nitro group should be the rate-determining step. [ABSTRACT FROM AUTHOR]

The hydrogenation of levulinic acid (LA) to γ-valerolactone (GVL) was studied with a homogeneous RuCl2(PPh3)3 catalyst in supercritical CO2 (scCO2). The conversion of LA was observed to increase with CO2 pressure and the possible reasons for this rate acceleration were discussed, including the molecular interactions of CO2 with the reacting and catalytic species as well as the acidity and phase behavior of the reaction mixture. The interaction between CO2 and RuCl2(PPh3)3 was significant, which resulted in the production of an active RuHCl(CO)(PPh3)3 complex and thus enhanced the rate of hydrogenation in the presence of CO2. [ABSTRACT FROM AUTHOR]