625-45-6Relevant academic research and scientific papers
Ruthenium Catalyzed Dehydrogenation of Alcohols and Mechanistic Study
Awasthi, Mahendra K.,Singh, Sanjay K.
supporting information, p. 14912 - 14923 (2019/11/03)
We synthesized pyridylamine ligated arene-Ru(II) complexes and employed these complexes for the catalytic acceptorless dehydrogenation of primary alcohols to carboxylic acids. All the synthesized complexes [Ru]-1-[Ru]-10 are characterized using several spectro-analytical techniques, and the structures of complexes [Ru]-1, [Ru]-2, and [Ru]-5 are determined using single crystal X-ray crystallography. Efficient catalytic conversion of primary alcohols to potassium carboxylates or carboxylic acids is achieved in toluene with the quantitative release of hydrogen gas. The studied protocol for carboxylic acid synthesis with hydrogen generation is also employed for a wide range of substrates, including aliphatic alcohols, aromatic alcohols, and heteroaromatic alcohols, to obtain respective carboxylic acids in good yields (up to 86%). The studied arene-Ru catalysts also exhibit superior catalytic activity for the bulk reaction to achieve a turnover number of 1378. Moreover, extensive mass investigations are also performed to elucidate the mechanistic pathway by identifying the crucial catalytic intermediates, including aldehyde and diol coordinated Ru species under the catalytic and controlled reaction conditions.
Dehydrogenative Synthesis of Carboxylic Acids from Primary Alcohols and Hydroxide Catalyzed by a Ruthenium N-Heterocyclic Carbene Complex
Santilli, Carola,Makarov, Ilya S.,Fristrup, Peter,Madsen, Robert
, p. 9931 - 9938 (2016/11/02)
Primary alcohols have been reacted with hydroxide and the ruthenium complex [RuCl2(IiPr)(p-cymene)] to afford carboxylic acids and dihydrogen. The dehydrogenative reaction is performed in toluene, which allows for a simple isolation of the products by precipitation and extraction. The transformation can be applied to a range of benzylic and saturated aliphatic alcohols containing halide and (thio)ether substituents, while olefins and ester groups are not compatible with the reaction conditions. Benzylic alcohols undergo faster conversion than other substrates, and a competing Cannizzaro reaction is most likely involved in this case. The kinetic isotope effect was determined to be 0.67 using 1-butanol as the substrate. A plausible catalytic cycle was characterized by DFT/B3LYP-D3 and involved coordination of the alcohol to the metal, β-hydride elimination, hydroxide attack on the coordinated aldehyde, and a second β-hydride elimination to furnish the carboxylate.
Synthesis, molecular modeling, and DNA binding of new schiff base ruthenium(II) complex and its catalytic oxidation
El-Shobaky, Amira R.
, p. 1481 - 1488 (2015/06/08)
A new ruthenium(II) complex was derived from 4-aminoantipyrine Schiff base (L). The structural feature has been confirmed through elemental, magnetic susceptibility, and molar conductivity analysis. IR, UV-Vis, and 1H NMR spectral studies show that the complex has composition of [Ru LCl2] type, suggesting an octahedral geometry around the central metal ion. DNA interaction studies throw spectroscopic and viscosity measurement confirmed that complex bind through intercalative mode, which confirmed by computational data throw the calculation of thermodynamic parameter. Also, catalytic oxidation of the Ru(II) complex was carried out showing that the complex is efficient catalyst for the oxidation.
Larvicidal activity and click synthesis of 2-alkoxyl-2-(1,2,3-triazole-1- yl)acetamide library
Su, Na-Na,Xiong, Li-Xia,Yu, Shu-Jing,Zhang, Xiao,Cui, Can,Li, Zheng-Ming,Zhao, Wei-Guang
, p. 484 - 493 (2013/07/28)
Heterogeneous copper-in-charcoal-catalyzed click synthesis in 96-well polypropylene filter plates is an efficient method for the rapid generation of sufficient pure 2-alkoxyl-2-(1,2,3-triazole-1-yl) acetamide derivatives library by simple filtration, which directly assay the products for larvicidal activity against mosquitoes. In this procedure, copper nanoparticles on charcoal were arrayed into each well on a 96-well plate, reagents were delivered using a pipette gun, and a constant temperature shaker bath was used to complete the click reaction in 24-72 hours under temperature-controlled conditions. The results of bioassays indicated that the target compounds possessed excellent larvacidal activities against mosquitoes. In particular, the larvacidal activities against mosquitoes of compounds 8[2,3] and 8[7,1] at 2g.mL-1 were 100% and 73%, respectively.
Catalytic transformation of alcohols to carboxylic acid salts and H 2 using water as the oxygen atom source
Balaraman, Ekambaram,Khaskin, Eugene,Leitus, Gregory,Milstein, David
, p. 122 - 125 (2013/08/24)
The oxidation of alcohols to carboxylic acids is an important industrial reaction used in the synthesis of bulk and fine chemicals. Most current processes are performed by making use of either stoichiometric amounts of toxic oxidizing agents or the use of pressurized dioxygen. Here, we describe an alternative dehydrogenative pathway effected by water and base with the concomitant generation of hydrogen gas. A homogeneous ruthenium complex catalyses the transformation of primary alcohols to carboxylic acid salts at low catalyst loadings (0.2 mol%) in basic aqueous solution. A consequence of this finding could be a safer and cleaner process for the synthesis of carboxylic acids and their derivatives at both laboratory and industrial scales.
HYDROCARBOXYLATION OF FORMALDEHYDE IN THE PRESENCE OF A HIGHER ORDER CARBOXYLIC ACID AND A HOMOGENEOUS CATALYST
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Paragraph 0153; 0154, (2013/10/08)
Disclosed is a process for the production and purification of glycolic acid or glycolic acid derivatives by the carbonylation of formaldehyde in the presence of a homogeneous acid catalyst and a carboxylic acid. This invention discloses hydrocarboxylations and corresponding homogeneous acid catalyst and glycolic acid separations. The homogeneous acid catalyst is readily separated from the hydrocarboxylation reaction effluent and recycled and the carboxylic acid is readily removed from the glycolic acid and the carboxylic acid is recycled.
HYDROCARBOXYLATION OF METHYLENE DIPROPIONATE IN THE PRESENCE OF PROPIONIC ACID AND A HETEROGENEOUS CATALYST
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Paragraph 0142; 0143, (2013/10/08)
Disclosed is a process for the production and purification of glycolic acid or glycolic acid derivatives by the carbonylation of methylene dipropionate in the presence of a solid acid catalyst and propionic acid. This invention discloses hydrocarboxylations and corresponding glycolic acid separations wherein the propionic acid stream is readily removed from the glycolic acid and the propionic acid is recycled.
HYDROCARBOXYLATION OF FORMALDEHYDE IN THE PRESENCE OF A HIGHER ORDER CARBOXYLIC ACID AND HETEROGENEOUS CATALYST
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Paragraph 0148; 0149, (2013/10/08)
Disclosed is a process for the production and purification of glycolic acid or glycolic acid derivatives by the carbonylation of formaldehyde in the presence of a solid acid catalyst and a carboxylic acid. This invention discloses hydrocarboxylations and corresponding glycolic acid separations wherein the glycolic acid stream is readily removed from the carboxylic acid and the carboxylic acid is recycled.
HYDROCARBOXYLATION OF METHYLENE DIPROPIONATE IN THE PRESENCE OF A PROPIONIC ACID AND A HOMOGENEOUS CATALYST
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Paragraph 0162; 0163, (2013/10/08)
Disclosed is a process for the production and purification of glycolic acid or glycolic acid derivatives by the carbonylation of methylene dipropionate in the presence of a homogeneous acid catalyst and propionic acid. This invention discloses hydrocarboxylations and corresponding homogeneous acid catalyst and glycolic acid separations. The homogeneous acid catalyst is readily separated from the hydrocarboxylation reaction effluent and recycled and the propionic acid is readily removed from the glycolic acid and the propionic acid is recycled
Asymmetric hydrogenation of α- Or β-acyloxy α,β- unsaturated phosphonates catalyzed by a Rh(i) complex of monodentate phosphoramidite
Zhang, Jinzhu,Dong, Kaiwu,Wang, Zheng,Ding, Kuiling
supporting information; scheme or table, p. 1598 - 1601 (2012/03/22)
The Rh(i) complex of a monodentate phosphoramidite bearing a primary amine moiety (DpenPhos) has been disclosed to be highly efficient for the asymmetric hydrogenation of a variety of α- or β-acyloxy α,β- unsaturated phosphonates, providing the corresponding biologically important chiral α- or β-hydroxy phosphonic acid derivatives with excellent enantioselectivities (90->99% ee).
