General Catalytic Methylation of Amines with Formic Acid under Mild Reaction Conditions

2014 ◽  
Vol 20 (26) ◽  
pp. 7878-7883 ◽  
Author(s):  
Iván Sorribes ◽  
Kathrin Junge ◽  
Matthias Beller
Keyword(s):  
Formic Acid ◽  
Reaction Conditions

scholarly journals Prebiotic Route to Thymine from Formamide—A Combined Experimental–Theoretical Study

Molecules ◽  
2021 ◽  
Vol 26 (8) ◽  
pp. 2248
Author(s):  
Lukáš Petera ◽  
Klaudia Mrazikova ◽  
Lukas Nejdl ◽  
Kristyna Zemankova ◽  
Marketa Vaculovicova ◽  
...  
Keyword(s):  
Formic Acid ◽  
Quantum Chemical ◽  
Prebiotic Chemistry ◽  
Theoretical Study ◽  
Reaction Pathway ◽  
Hydrolysis Product ◽  
Current Paper ◽  
Reaction Conditions ◽  
Chemical Modeling ◽  
Chemistry Research

Synthesis of RNA nucleobases from formamide is one of the recurring topics of prebiotic chemistry research. Earlier reports suggest that thymine, the substitute for uracil in DNA, may also be synthesized from formamide in the presence of catalysts enabling conversion of formamide to formaldehyde. In the current paper, we show that to a lesser extent conversion of uracil to thymine may occur even in the absence of catalysts. This is enabled by the presence of formic acid in the reaction mixture that forms as the hydrolysis product of formamide. Under the reaction conditions of our study, the disproportionation of formic acid may produce formaldehyde that hydroxymethylates uracil in the first step of the conversion process. The experiments are supplemented by quantum chemical modeling of the reaction pathway, supporting the plausibility of the mechanism suggested by Saladino and coworkers.

Catalysis by α-cyclodextrin of the reaction of formic acid with bromine

1990 ◽  
Vol 68 (11) ◽  
pp. 2119-2121 ◽  
Author(s):  
Oswald S. Tee ◽  
Bushra Javed ◽  
Susan R. Mikkelsen
Keyword(s):  
Formic Acid ◽  
Dissociation Constant ◽  
Rate Constants ◽  
Reaction Conditions ◽  
Value Analysis ◽  
Potentiometric Measurements

α-Cyclodextrin (CD) modestly increases the rate of oxidation of formic acid by bromine. The variation of rate constants with [Br−] is consistent with dominance of the formation of a CD•Br3− complex in determining the fraction of free Br2 and the CD•Br2 complex, under the reaction conditions. Potentiometric measurements support a dissociation constant of about 0.2 mM for the CD•Br3− complex, in agreement with an earlier spectrophotometric value. Analysis of the rate increases with [CD] implies that CD•Br2 is more reactive (~10 times) than free Br2 towards formate ion, as was found for phenols. These conclusions differ from those of another recent study. Keywords: catalysis, α-cyclodextrin, oxidation, formic acid, bromine.

ChemInform Abstract: General Catalytic Methylation of Amines with Formic Acid under Mild Reaction Conditions.

ChemInform ◽  
2014 ◽  
Vol 46 (2) ◽  
pp. no-no
Author(s):  
Ivan Sorribes ◽  
Kathrin Junge ◽  
Matthias Beller
Keyword(s):  
Formic Acid ◽  
Reaction Conditions

Selective reduction of aromatic alkynes catalyzed by palladium with formic acid as the hydride source

2021 ◽  
Vol 08 ◽  
Author(s):  
Suzanne Chayya ◽  
Mohammad H. El-Dakdouki ◽  
Akram Hijazi ◽  
Ghassan Younes ◽  
Ghassan Ibrahim ◽  
...  
Keyword(s):  
Formic Acid ◽  
Selective Reduction ◽  
Major Product ◽  
Transfer Hydrogenation ◽  
Attractive Alternative ◽  
Unsaturated Ketone ◽  
Partial Reduction ◽  
Reaction Parameters ◽  
Reaction Conditions ◽  
Optimized Conditions

Background: Transfer hydrogenation methods that employ non-H2 hydrogen sources have evolved as an attractive alternative for conventional hydrogenation approaches. Objective: In this study, we aimed at developing optimized conditions to induce the selective transfer hydrogenation reduction of aromatic alkynes catalyzed by PdCl2(PPh3)2 and using formic acid as the hydride source. Methods: The effect of various reaction parameters, such as the nature and amount of the catalyst, the H-donor/base couple, reaction time and temperature, and the nature of the solvent on the outcome of the alkyne reduction were investigated. Results: The reduction of the alkyne can be chemoselectively controlled by adjusting the reaction conditions. Among the tested catalysts, PdCl2(PPh3)2 was the most suitable with 2% of the catalyst being the optimal amount. While the reduction was successful in different solvents of different polarities, THF was selected as the solvent of choice. The reduction of diphenylacetylene yielded the alkene both at 50oC and 80oC. When testing the optimized conditions on the reduction of 4-phenyl-3-butyne-2-one, quantitative partial reduction to the corresponding α,β-unsaturated ketone was obtained at 50oC, while the saturated ketone was produced as the major product at 80oC. Conclusion: The chemoselective reduction of aromatic alkynes was performed successfully with complete conversion using 2% PdCl2(PPh3)2 as a catalyst, formic acid/NEt3 as the H-donor/base couple, THF as the solvent, at 50oC and 80oC.

Catalytic Transfer Hydrogenolysis of 2-Phenyl-2-Propanol with Pd/C and Formic Acid

2011 ◽  
Vol 287-290 ◽  
pp. 1749-1752 ◽  
Author(s):  
Jian Feng ◽  
Wei Xiong ◽  
Yun Jia ◽  
Jin Bo Wang ◽  
De Rong Liu ◽  
...  
Keyword(s):  
Formic Acid ◽  
Inductively Coupled Plasma ◽  
Molar Ratio ◽  
X Ray Diffraction ◽  
Reaction Conditions ◽  
New Approach ◽  
Inductively Coupled ◽  
Transmission Electron ◽  
Catalytic Transfer ◽  
Adsorption Desorption

The catalytic transfer hydrogenolysis of 2-phenyl-2-propanol was studied over Pd/C catalyst, using formic acid and formate salts as hydrogen donors. The Pd/C catalyst was characterized by powder X-ray diffraction (XRD), inductively coupled plasma (ICP), N2 adsorption/desorption and transmission electron microscopy (TEM). The effects of hydrogen donor, molar ratio of formic acid to 2-phenyl-2-propanol and water content were evaluated. Under mild reaction conditions (80 °C, 2h), 2-phenyl-2-propanol can be hydrogenolyzed to isopropylbenzene with very high selectivity (96.5%) and high conversion (92.8%) in the presence of Pd/C and formic acid. From the viewpoint of environmental friendly principles, this study may open the way to a new approach for the production of propylene oxide.

scholarly journals Solid residue and by-product yields from acid-catalysed conversion of poplar wood to levulinic acid

2019 ◽  
Vol 74 (5) ◽  
pp. 1647-1661
Author(s):  
G. Hurst ◽  
I. Brangeli ◽  
M. Peeters ◽  
S. Tedesco
Keyword(s):  
Formic Acid ◽  
Acid Production ◽  
Levulinic Acid ◽  
Solid Residue ◽  
Poplar Wood ◽  
Reaction Conditions ◽  
Acid Yield ◽  
Renewable Chemicals ◽  
Microwave Assisted ◽  
Hydrolysis Of

AbstractThis study examines the yields of solid residue and by-product from the microwave-assisted acid hydrolysis of lignocellulosic poplar wood for levulinic acid production. The aim of this study was to optimise levulinic acid production via response surface methodology (RSM) and also investigate the effect of reaction conditions on other products such as furfural, solid residue, formic acid and acetic acid yields. A maximum theoretical levulinic acid yield of 62.1% (21.0 wt %) was predicted when reaction conditions were 188 °C, 126 min and 1.93 M sulphuric acid, with a corresponding solid residue yield of 59.2 wt %. Furfural from the hydrolysis of hemicellulose was found to have significantly degraded at the optimum levulinic acid yield conditions. The investigation of formic acid yields revealed lower formic acid yields than stoichiometrically expected, indicating the organic acid reactions under microwave-assisted hydrolysis of lignocellulose. The solid residue yields were found to increase significantly with increasing reaction time and temperature. The solid residue yields under all conditions exceeded that of levulinic acid and, therefore, should be considered a significant product alongside the high-value compounds. The solid residue was further examined using IR spectra, elemental analysis and XRF for potential applications. The overall results show that poplar wood has great potential to produce renewable chemicals, but also highlight all by-products must be considered during optimization.

Reactions of Active Methylene Compounds with Benzhydrol During Solvolysis in Formic Acid

2003 ◽  
Vol 56 (5) ◽  
pp. 385 ◽  
Author(s):  
Glen C. Gullickson ◽  
David E. Lewis
Keyword(s):  
Formic Acid ◽  
Ritter Reaction ◽  
Reaction Products ◽  
Reaction Conditions ◽  
Active Methylene Compounds ◽  
Active Methylene

Formic acid reacts with benzhydrol to give benzhydryl formate, which reacts with active methylene compounds in refluxing formic acid to give either C-alkylation or Ritter reaction products. The product formed is determined by the equilibrium enol content of the active methylene compound. These reaction conditions avoid the use of halogenated reaction solvents, and the pure products are isolated without recourse to chromatography.

scholarly journals The Transfer Hydrogenation Reactions Catalyzed by Rhodium Schiff Base Complexes

2010 ◽  
Vol 2 (3) ◽  
pp. 501
Author(s):  
T. Al-Salim ◽  
J. S. Hadi ◽  
E. A. Al-Nasir ◽  
M. A. Hassen
Keyword(s):  
Schiff Base ◽  
Catalytic Activity ◽  
Formic Acid ◽  
Elemental Analysis ◽  
Mass Spectra ◽  
Transfer Hydrogenation ◽  
Schiff Base Complexes ◽  
Time Range ◽  
Reaction Conditions ◽  
Hydrogenation Reactions

Three new Schiff base rhodium (III) complexes, derived from three ligands, L1, L2 and L3 have been prepared and characterized by IR, 1HNMR, mass spectra and the elemental analysis. These complexes have shown efficient catalytic activity in the transfer hydrogenation of wide variety ketones to the corresponding alcohols in formic acid/triethylamine solution under mild reaction conditions. Depending on the ketone, the percentage of conversion for RhL1 have been found to be (51-92%) compared to RhL2 which had a yield of (42-92%) while for RhL3 (71-94%), within time range of   0.5-12 hrs.  Keywords: Schiff base; Rhodium (III) complex; Transfer hydrogenation; Diamine.                      © 2010 JSR Publications. ISSN: 2070-0237 (Print); 2070-0245 (Online). All rights reserved. DOI: 10.3329/jsr.v2i3.4341                J. Sci. Res. 2 (3), 501-511 (2010) 

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