122-85-0Relevant academic research and scientific papers
Oxidation of Substituted Benzyl Alcohols by Pyridinium Fluorochromate: A Kinetic Study
Banerji, Kalyan K.
, p. 2154 - 2159 (1988)
The kinetics of the oxidation of 30 monosubstituted benzyl alcohols to the corresponding benzaldehydes by pyridinium fluorochromate (PFC) have been studied.The reaction is first order with respect to PFC.A Michaelis-Menten type kinetics was observed with respect to the substrate, indicating the formation of a PFC-alcohol complex in the preequilibrium.The formation constants and the rates of disproportionation of the complexes were determined.The oxidation of benzyl alcohol indicated the presence of a substantial primary kinetic isotope effect.The ratesof the decomposition of the complexes of the meta-and para-substituted alcohols were analyzed in terms of Taft's and Swain's dual substituent parameter equations.The meta compounds showed an excellent correlation with Taft's ?I and ?R0 values while the para-substituted compounds correlate with ?1 and ?RBA constants.The rates of the ortho-substituted alcohols correlate with Charton's equation of inductive, resonance, and steric paramaters.The reaction was studied in 19 solvents.The correlation analysis of the solvent effect indicated the greater importance of the cation-solvating power of the solvent.The reaction involves a hydride ion transfer in the rate-determining step.
Kinetic Study of the Oxidation of Substituted Benzyl Alcohols by Ethyl Chlorocarbamate
Jain, Suman,Banerji, Kalyan K.
, p. 1767 - 1772 (1988)
The kinetics of the oxidation of twenty-four monosubstituted benzyl alcohols by ethyl chlorocarbamate (ECC) have been studied in aqueous acetic acid solution, in the presence of perchloric acid.The main product of the oxidation is the corresponding benzaldehyde.The reaction is first order with respect to the alcohol, ECC, and hydrogen ion.The oxidation of 2>benzyl alcohol indicated a primary kinetic isotope effect, kH/kD=5.40 at 298 K.The value of solvent isotope effect, k(H2O)/k(D2O), is 1.85 at 298 K.Addition of ethyl carbamate does not affect the reaction rate. + has been postulated as the reactive oxidizing species.The rates of oxidation of para- and meta-substituted benzyl alcohols show excellent correlation in Taft's dual substituent parameter equation, with negative reaction constants.The rates of the ortho-substituted compounds correlate well in Charton's equation of inductive, resonance and steric substituent parameters.A mechanism involving simultaneous transfer of a hydride ion from the C-H bond and of a proton from O-H bond to the oxidant is proposed.
An aerobic oxidation of alcohols into carbonyl synthons using bipyridyl-cinchona based palladium catalyst
Cheedarala, Ravi Kumar,Chidambaram, Ramasamy R.,Siva, Ayyanar,Song, Jung Il
, p. 32942 - 32954 (2021/12/02)
We have reported an aerobic oxidation of primary and secondary alcohols to respective aldehydes and ketones using a bipyridyl-cinchona alkaloid based palladium catalytic system (PdAc-5) using oxygen at moderate pressure. ThePdAc-5catalyst was analysed using SEM, EDAX, and XPS analysis. The above catalytic system is used in experiments for different oxidation systems which include different solvents, additives, and bases which are cheap, robust, non-toxic, and commercially available on the industrial bench. The obtained products are quite appreciable in both yield and selectivity (70-85%). In addition, numerous important studies, such as comparisons with various commercial catalysts, solvent systems, mixture of solvents, and catalyst mole%, were conducted usingPdAc-5. The synthetic strategy of oxidation of alcohol into carbonyl compounds was well established and all the products were analysed using1H NMR,13CNMR and GC-mass analyses.
Method for catalyzing one-pot hydrogenation and amidation of nitroaromatic hydrocarbon and carboxylic acid by visible light
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Paragraph 0030, (2021/06/09)
The invention discloses a method for catalyzing one-pot hydrogenation and amidation reaction of nitroaromatic hydrocarbon and carboxylic acid by visible light. The method comprises the following steps: preparing Pt nanoparticles uniformly dispersed on an N-doped titanium dioxide/titanium carbide (MXene) heterojunction as a photocatalyst (3% Pt/N-TiO2/Ti3C2), and applying the catalyst to a cascade reaction of an aromatic nitro compound and carboxylic acid to prepare an amide product. The 3% Pt/N-TiO2/Ti3C2 has excellent tandem hydrogenation and amidation activity and chemical selectivity of an aromatic nitro compound and carboxylic acid under the irradiation of visible light. The excellent catalytic performance of 3% Pt/N-TiO2/Ti3C2 is attributed to the close contact of TiO2 and conductive Ti3C2, and the separation efficiency of photo-induced electrons and holes is improved through charge short-range directional transmission. The preparation method of the catalyst is simple and easy to operate, the catalyst can be used for photocatalytic efficient one-pot hydrogenation and amidation reactions, the reaction conditions are mild, and the catalyst is easy to recycle.
Chlorination Reaction of Aromatic Compounds and Unsaturated Carbon-Carbon Bonds with Chlorine on Demand
Liu, Feng,Wu, Na,Cheng, Xu
supporting information, p. 3015 - 3020 (2021/05/05)
Chlorination with chlorine is straightforward, highly reactive, and versatile, but it has significant limitations. In this Letter, we introduce a protocol that could combine the efficiency of electrochemical transformation and the high reactivity of chlorine. By utilizing Cl3CCN as the chloride source, donating up to all three chloride atom, the reaction could generate and consume the chlorine in situ on demand to achieve the chlorination of aromatic compounds and electrodeficient alkenes.
Cu(OTf)2-Mediated Cross-Coupling of Nitriles and N-Heterocycles with Arylboronic Acids to Generate Nitrilium and Pyridinium Products**
Bell, Nicola L.,Xu, Chao,Fyfe, James W. B.,Vantourout, Julien C.,Brals, Jeremy,Chabbra, Sonia,Bode, Bela E.,Cordes, David B.,Slawin, Alexandra M. Z.,McGuire, Thomas M.,Watson, Allan J. B.
supporting information, p. 7935 - 7940 (2021/03/03)
Metal-catalyzed C–N cross-coupling generally forms C?N bonds by reductive elimination from metal complexes bearing covalent C- and N-ligands. We have identified a Cu-mediated C–N cross-coupling that uses a dative N-ligand in the bond-forming event, which, in contrast to conventional methods, generates reactive cationic products. Mechanistic studies suggest the process operates via transmetalation of an aryl organoboron to a CuII complex bearing neutral N-ligands, such as nitriles or N-heterocycles. Subsequent generation of a putative CuIII complex enables the oxidative C–N coupling to take place, delivering nitrilium intermediates and pyridinium products. The reaction is general for a range of N(sp) and N(sp2) precursors and can be applied to drug synthesis and late-stage N-arylation, and the limitations in the methodology are mechanistically evidenced.
Visible-light induced one-pot hydrogenation and amidation of nitroaromatics with carboxylic acids over 2D MXene-derived Pt/N-TiO2/Ti3C2
Jiang, Heyan,Hu, Zujie,Gan, Chuan,Sun, Bin,Kong, Shuzhen,Bian, Fengxia
, (2021/03/03)
Pt nanoparticles supported on N doped titanium dioxide/titanium carbide (MXene) heterojunctions were employed as photocatalysts for the tandem reactions between aromatic nitro compounds and carboxylic acids to produce amide products. The 3%Pt/N-TiO2/Ti3C2 heterojunction was prepared by in situ grew TiO2 on Ti3C2 nanosheets and then N doped TiO2 with melamine, Pt nanoparticles with 3.3 nm mean diameter well dispersed on N-TiO2/Ti3C2. 3%Pt/N-TiO2/Ti3C2 had excellent amidation activity and chemoselectivity under visible-light irradiation. The elevated catalytic performance of 3%Pt/N-TiO2/Ti3C2 was owing to the improvement in photogenerated electron and hole separation efficiency through charge short-range directional transmission caused by the intimate contact between the TiO2 and the conductive Ti3C2. This direct hydrogenation along with amidation between nitroaromatics and carboxylic acids own actual merits in the amides produce with no harmful byproducts. In situ DRIFTS spectra verified that the amidation activation with visible light irradiation at 25 °C was much faster than heating.
Sequential Connection of Mutually Exclusive Catalytic Reactions by a Method Controlling the Presence of an MOF Catalyst: One-Pot Oxidation of Alcohols to Carboxylic Acids
Kim, Seongwoo,Lee, Ha-Eun,Suh, Jong-Min,Lim, Mi Hee,Kim, Min
supporting information, p. 17573 - 17582 (2020/12/22)
A functionalized metal-organic framework (MOF) catalyst applied to the sequential one-pot oxidation of alcohols to carboxylic acids controls the presence of a heterogeneous catalyst. The conversion of alcohols to aldehydes was acquired through aerobic oxidation using a well-known amino-oxy radical-functionalized MOF. In the same flask, a simple filtration of the radical MOF with mild heating of the solution completely altered the reaction media, providing radical scavenger-free conditions suitable for the autoxidation of the aldehydes formed in the first step to carboxylic acids. The mutually exclusive radical-catalyzed aerobic oxidation (the first step with MOF) and radical-inhibited autoxidation (the second step without MOF) are sequentially achieved in a one-pot manner. Overall, we demonstrate a powerful and efficient method for the sequential oxidation of alcohols to carboxylic acids by employing a readily functionalizable heterogeneous MOF. In addition, our MOF in-and-out method can be utilized in an environmentally friendly way for the oxidation of alcohols to carboxylic acids of industrial and economic value with broad functional group tolerance, including 2,5-furandicarboxylic acid and 1,4-benzenedicarboxylic acid, with good yield and reusability. Furthermore, MOF-TEMPO, as an antioxidative stabilizer, prevents the undesired oxidation of aldehydes, and the perfect "recoverability"of such a reactive MOF requires a re-evaluation of the advantages of MOFs from heterogeneity in catalytic and related applications.
Rhodium-catalyzed reductive carbonylation of aryl iodides to arylaldehydes with syngas
Chen, Suqing,Liu, Zhenghui,Mu, Tiancheng,Wang, Peng,Yan, Zhenzhong,Yu, Dongkun,Zhao, Xinhui
, p. 645 - 656 (2020/05/14)
The reductive carbonylation of aryl iodides to aryl aldehydes possesses broad application prospects. We present an efficient and facile Rh-based catalytic system composed of the commercially available Rh salt RhCl3·3H2O, PPh3 as phosphine ligand, and Et3N as the base, for the synthesis of arylaldehydes via the reductive carbonylation of aryl iodides with CO and H2 under relatively mild conditions with a broad substrate range affording the products in good to excellent yields. Systematic investigations were carried out to study the experimental parameters. We explored the optimal ratio of Rh salt and PPh3 ligand, substrate scope, carbonyl source and hydrogen source, and the reaction mechanism. Particularly, a scaled-up experiment indicated that the catalytic method could find valuable applications in industrial productions. The low gas pressure, cheap ligand and low metal dosage could significantly improve the practicability in both chemical researches and industrial applications.
1,1,1,3,3,3-Hexafluoroisopropanol as an efficient medium for the room temperature oxidation of styrenes to benzaldehydes
Zhang, Zhuyong,Chen, Weidong,Luo, Junfei
supporting information, (2020/10/23)
A room temperature N-hydroxyphthalimide-catalyzed oxidation of styrene derivatives to the corresponding aldehydes has been developed. The use of 1,1,1,3,3,3-hexafluoroisopropanol as the solvent was determined as being key for efficient oxidation. The incorporated oxygen atom originates from molecular dioxygen.
