76-93-7Relevant articles and documents
Photocatalytic Carbinol Cation/Anion Umpolung: Direct Addition of Aromatic Aldehydes and Ketones to Carbon Dioxide
Okumura, Shintaro,Uozumi, Yasuhiro
supporting information, p. 7194 - 7198 (2021/09/22)
We have developed a new photocatalytic umpolung reaction of carbonyl compounds to generate anionic carbinol synthons. Aromatic aldehydes or ketones reacted with carbon dioxide in the presence of an iridium photocatalyst and 1,3-dimethyl-2-phenyl-2,3-dihydro-1H-benzimidazole (DMBI) as a reductant under visible-light irradiation to furnish the corresponding α-hydroxycarboxylic acids through nucleophilic addition of the resulting carbinol anions to electrophilic carbon dioxide.
Synthesis of α-hydroxycarboxylic acids from various aldehydes and ketones by direct electrocarboxylation: A facile, efficient and atom economy protocol
Singh, Kishanpal,Sohal, Harvinder Singh,Singh, Baljit
, p. 839 - 845 (2021/04/09)
In present work, the formation of α-hydroxycarboxylic acids have been described from various aromatic aldehydes and ketones via direct electrocarboxylation method with 80-92% of yield without any side product and can be purified by simple recrystallization using sacrificial Mg anode and Pt cathode in an undivided cell, CO2at (1 atm) was continuously bubbled in the cell throughout the reaction using tetrapropylammonium chloride as a supporting electrolyte in acetonitrile. The synthesized compounds obtained in fair to excellent yield with a high level of purity. The characterization of electrocarboxylated compounds was done with spectroscopic techniques like IR, NMR (1H & 13C), mass and elemental analysis.
Hydrodebromination of Aromatic Bromides Catalyzed by Unsupported Nanoporous Gold: Heterolytic Cleavage of Hydrogen Molecule
Bao, Ming,Feng, Xiujuan,Yamamoto, Yoshinori,Zhang, Sheng,Zhao, Yuhui
, p. 4951 - 4957 (2020/09/09)
Unsupported nanoporous gold (AuNPore) is a highly efficient, practically applicable, and recyclable catalyst for hydrodebromination of aromatic bromides. The AuNPore-catalyzed hydrodebromination of aromatic bromides proceeded smoothly at relatively low hydrogen pressure and temperature to achieve good to excellent yields of the corresponding non-bromine variants. The selective hydrodebromination reaction occurred exclusively in the coexistence of chlorine atom. For the first time, a mechanistic study revealed that the H?H bond splits in a heterolysis manner on the surface of AuNPore to generate Au?H hydride species.
Visible light-induced aerobic oxidation of diarylalkynes to α-diketones catalyzed by copper-superoxo at room temperature
Charpe, Vaibhav Pramod,Hwang, Kuo Chu,Sagadevan, Arunachalam
, p. 4426 - 4432 (2020/08/10)
We have developed the visible light induced simple copper(ii) chloride catalyzed oxidation of diarylacetylenes to α-diketones by molecular oxygen at room temperature. The in situ generated copper(ii)-superoxo complex is a light-absorbing species that oxidizes inert diarylacetylenes to α-diketones. In contrast to reported photochemical processes, the current oxidation protocol does not require any exogenous photocatalyst or radical initiator. The green chemistry metrics evaluation signifies that the E-factor for the current oxidation process is ～2.3 times better than that of reported photochemical processes. The current reaction scores 63 on the EcoScale of 0-100, indicating an adequate synthesis process. Thus, the overall oxidation process is simple, environmentally benign, and economically feasible. This journal is
A Bifunctional Iron Nanocomposite Catalyst for Efficient Oxidation of Alkenes to Ketones and 1,2-Diketones
Ma, Zhiming,Ren, Peng,Song, Tao,Xiao, Jianliang,Yang, Yong,Yuan, Youzhu
, p. 4617 - 4629 (2020/05/19)
We herein report the fabrication of a bifunctional iron nanocomposite catalyst, in which two catalytically active sites of Fe-Nx and Fe phosphate, as oxidation and Lewis acid sites, were simultaneously integrated into a hierarchical N,P-dual doped porous carbon. As a bifunctional catalyst, it exhibited high efficiency for direct oxidative cleavage of alkenes into ketones or their oxidation into 1,2-diketones with a broad substrate scope and high functional group tolerance using TBHP as the oxidant in water under mild reaction conditions. Furthermore, it could be easily recovered for successive recycling without appreciable loss of activity. Mechanistic studies disclose that the direct oxidation of alkenes proceeds via the formation of an epoxide as intermediate followed by either acid-catalyzed Meinwald rearrangement to give ketones with one carbon shorter or nucleophilic ring-opening to generate 1,2-diketones in a cascade manner. This study not only opens up a fancy pathway in the rational design of Fe-N-C catalysts but also offers a simple and efficient method for accessing industrially important ketones and 1,2-diketones from alkenes in a cost-effective and environmentally benign fashion.
Room Temperature Coupling of Aryldiazoacetates with Boronic Acids Enhanced by Blue Light Irradiation
da Silva, Amanda F.,Afonso, Marco A. S.,Cormanich, Rodrigo A.,Jurberg, Igor D.
, p. 5648 - 5653 (2020/04/22)
A visible-light-promoted photochemical protocol is reported for the coupling of aryldiazoacetates with boronic acids. This photochemical reaction shows great enhancement compared to the same protocol performed in the absence of light. Except for a few cases, the room temperature coupling in the dark (thermal process) generally does not work. When it does, it is likely to also involve free carbenes as key intermediates. Alternatively, photochemical reactions show a broad scope, can be performed under air and tolerate a wide variety of functional groups. Reaction-evolution monitoring, DFT calculations and control experiments have been used to evaluate the main aspects of this intricate mechanistic scenario. Biologically active molecules Adiphenine, Benactyzine and Aprophen have been prepared as examples of synthetic applications.
Synthesis of diphenyl glycolic acid
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Paragraph 0007; 0008, (2018/10/11)
The invention relates to synthesis of diphenyl glycolic acid. The synthesis comprises the following process steps: adding 2.5-3.6 g of diphenylethylenedione and 15mL of ethanol with the concentrationof 95% to a round bottom flask with the volume of 50mL, dissolving by heating, dropwise adding a solution obtained by dissolving 2.7g of potassium hydroxide in 5-10mL of water, and performing a reaction while stirring magnetically, refluxing for 30-60min, then transferring a reaction mixture to a small beaker, placing in an ice water bath to separate out crystals of potassium diphenylglycolate, performing suction filtration, washing the crystals by using a small amount of cold ethanol, dissolving the filtered potassium salt in 70-90mL of water, dropwise adding 2-5 drops of concentrated hydrochloric acid, keeping a small amount of unreacted diphenylethylenedione to be in a state of a colloidal suspension, decolorizing by adding about two flat spoons of activated carbon, filtering in a hot state, cooling a filtrate to a room temperature, acidifying by using hydrochloric acid with the concentration of 5% until Congo red test paper turns blue, keeping stirring to guarantee that a product is loose, cooling in an ice water bath to achieve complete crystallization, performing suction filtration, washing for several times by using cold water to remove inorganic salt and the hydrochloric acid in the crystals, and drying the product in a drying oven with the temperature of 85 DEG C till the constant weight.
Magnetic magnetite nanoparticals catalyzed selective oxidation of Α-hydroxy ketones with air and one-pot synthesis of benzilic acid and phenytoin derivatives
Li, Xiaona,Xia, Dandan,Wen, Zhiyong,Gong, Bowen,Sun, Maolin,Wu, Yue,Zhang, Jie,Sun, Jun,Wu, Yang,Bao, Kai,Zhang, Weige
, p. 63 - 69 (2018/06/26)
A clean and efficient protocol for selective oxidation of α-hydroxy ketones using magnetic magnetite nanoparticals (Fe3O4·MNPs) as catalyst with air as green oxidant has been developed. Application of Fe3O4·MNPs was also proved to be successful in one-pot synthesis of benzilic acid and phenytoin derivatives. The facile one-pot procedure enhanced the production efficiency, shortened the reaction time and minimized the chemical waste. Notably, the catalyst can be reused at least for five times without any appreciable loss of its activity.
Enhanced solvent-free selective oxidation of cyclohexene to 1,2-cyclohexanediol by polyaniline@halloysite nanotubes
Zhou, Tianzhu,Zhao, Yue,Han, Wenmei,Xie, Huazhong,Li, Cuiping,Yuan, Mingquan
supporting information, p. 18230 - 18241 (2017/09/08)
One-dimensional polyaniline@halloysite (PANI@HA) nanotubes with enhanced selective oxidation activity of cyclohexene are fabricated by employing aniline (ANI) chemical polymerization on halloysite nanotubes in situ. By facilely controlling the doping acid, acidity, and ANI/HA weight ratio during the fabrication, PANI with a controllable doping degree, redox state, and content is grown on halloysite nanotubes. The cyclohexene selective oxidation result shows that PANI@HA nanotubes are effective catalysts in a solvent-free reaction system with H2O2 as the oxidant, and their catalytic activity relies on the doping acid, acidity, and ANI/HA weight ratio in the fabrication. PANI@HA synthesized with HCl as a doping acid to condition the acidity at 1 M and 2.04 ANI/HA weight ratio (PANI@HA/1 M/2.04-HCl) demonstrates highest catalytic activity (98.17% conversion and 99.50% selectivity to 1,2-cyclohexanediol). The cyclohexene selective catalytic activity matches well with the PANI doping degree in PANI@HA. In addition, the optimal reaction condition is 20 mg catalyst, 2.5 mL H2O2, 70 °C, and 24 h. Furthermore, PANI@HA/1 M/2.04-HCl exhibits superior dihydroxylation activity toward 2,3-dimethyl-2-butene and cycling performance with 99.11% conversion and 96.92% selectivity to 1,2-cyclohexanediol after five cycles. The CV of PANI@HA indicates that the cyclohexene selective oxidation is attributed to a reversible redox reaction of PANI in PANI@HA for catalytic decomposition of H2O2.
