2363-89-5Relevant articles and documents
Radical induced disproportionation of alcohols assisted by iodide under acidic conditions
Huang, Yang,Jiang, Haiwei,Li, Teng,Peng, Yang,Rong, Nianxin,Shi, Hexian,Yang, Weiran
supporting information, p. 8108 - 8115 (2021/10/29)
The disproportionation of alcohols without an additional reductant and oxidant to simultaneously form alkanes and aldehydes/ketones represents an atom-economical transformation. However, only limited methodologies have been reported, and they suffer from a narrow substrate scope or harsh reaction conditions. Herein, we report that alcohol disproportionation can proceed with high efficiency catalyzed by iodide under acidic conditions. This method exhibits high functional group tolerance including aryl alcohol derivatives with both electron-withdrawing and electron-donating groups, furan ring alcohol derivatives, allyl alcohol derivatives, and dihydric alcohols. Under the optimized reaction conditions, a 49% yield of 5-methyl furfural and a 49% yield of 2,5-diformylfuran were obtained simultaneously from 5-hydroxymethylfurfural. An initial mechanistic study suggested that the hydrogen transfer during this redox disproportionation occurred through the inter-transformation of HI and I2. Radical intermediates were involved during this reaction.
Iodine-catalyzed alcohol disproportionation method
-
Paragraph 0034-0035, (2021/06/13)
The invention relates to the technical field of catalysis, in particular to an iodine-catalyzed alcohol disproportionation method which comprises the following steps: sequentially adding alcohol, iodine and a solvent into a high-temperature and high-pressure reaction kettle, introducing a certain amount of nitrogen, conducting reacting for a certain time, collecting an organic phase after the reaction is ended, and conducting fractionating to obtain corresponding alkane and aldehyde/ketone. Alcohol disproportionation is efficient and atom-economical conversion without any additional oxidizing agent and reducing agent, and hydrocarbon and aldehyde/ketone molecules which are easy to separate can be formed at the same time. Meanwhile, the method has wide functional group tolerance, various substrate samples including aryl alcohol derivatives, heterocyclic alcohol derivatives, allyl alcohol derivatives and dihydric alcohol are tested, and the result shows that most of the substrate samples show good or extremely good yield.
Ligand coordination sphere effect of Schiff base cis-dioxomolybdenum(VI) complexes in selective catalytic oxidation of alcohols
Liu, Haiwen,Zhuo, Zihan,Zhang, Yan,Wei, Hang,Zhang, Wenxin,Li, Tong,Mao, Zuodong,Wang, Weili
, p. 1253 - 1261 (2021/08/13)
Several cis-dioxomolybdenum(VI) complexes with Schiff bases-derived ligands were synthesized and fully characterized. The catalytic performances of these complexes were tested in the alcohol oxidation under solvent-free condition using H2O2 as oxidant giving high results. The influence of the oxygen, sulfur, and nitrogen atom within the coordination sphere around the molybdenum center was studied (S?>?N?>?O). From this study, we suggest that there exists a relationship between the electronegativity of the atom and the catalytic performance in alcohol oxidation.
Selective Aerobic Oxidation of Alcohols with NO3? Activated Nitroxyl Radical/Manganese Catalyst System
Lagerblom, Kalle,Keskiv?li, Juha,Parviainen, Arno,Mannisto, Jere,Repo, Timo
, p. 2908 - 2914 (2018/05/03)
A homogeneous Mn(NO3)2/2,2,6,6-tetramethylpiperidin-1-yl)oxyl/2-picolinic acid catalyst system is highly active and versatile for the selective aerobic oxidation of alcohols (2,2,6,6-tetramethylpiperidin-1-yl)oxyl=TEMPO, 2-picolinic acid=PyCOOH). The catalytic method enables near quantitative conversion of various primary alcohols to the respective aldehydes using a very simple reaction setup and workup. This study presents findings on the catalyst stability and mechanisms of deactivation. The results show that NO3? plays a crucial catalytic role in the reaction as a source of oxygen activating NOx species. Yet, disproportionation of NO3? to the volatile NO2 during the reaction leads to catalyst deactivation under open air conditions. Catalyst deactivation through this route can be overcome by adding a catalytic amount of nitrate salt, for example NaNO3 into the reaction. This stabilizes the Mn(NO3)2/TEMPO/PyCOOH catalyst and enables oxidation of various primary alcohols to the respective aldehydes using low catalyst loadings under ambient conditions. Secondary alcohols can be oxidized with a modified catalyst utilizing sterically accessible nitroxyl radical 9-azabicyclo[3.3.1]nonane N-oxyl (ABNO) instead of TEMPO. At the end of the alcohol oxidation, pure carbonyl products and the reusable catalyst can be recovered simply by extracting with organic solvent and dilute aqueous acid, followed by evaporation of both phases.
On the Use of Polyelectrolytes and Polymediators in Organic Electrosynthesis
Schille, Benjamin,Giltzau, Niels Ole,Francke, Robert
supporting information, p. 422 - 426 (2018/02/21)
Although organic electrosynthesis is generally considered to be a green method, the necessity for excess amounts of supporting electrolyte constitutes a severe drawback. Furthermore, the employment of redox mediators results in an additional separation problem. In this context, we have explored the applicability of soluble polyelectrolytes and polymediators with the TEMPO-mediated transformation of alcohols into carbonyl compounds as a test reaction. Catalyst benchmarking based on cyclic voltammetry studies indicated that the redox-active polymer can compete with molecularly defined TEMPO species. Alcohol oxidation was also highly efficient on a preparative scale, and our polymer-based approach allowed for the separation of both mediator and supporting electrolyte in a single membrane filtration step. Moreover, we have shown that both components can be reused multiple times.
Chemoenzymatic one-pot reaction of noncompatible catalysts: Combining enzymatic ester hydrolysis with Cu(i)/bipyridine catalyzed oxidation in aqueous medium
Sand, Henning,Weberskirch, Ralf
, p. 33614 - 33626 (2017/07/12)
The combination of chemical catalysts and biocatalysts in a one-pot reaction has attracted considerable interest in the past years. However, since each catalyst requires very different reaction conditions, chemoenzymatic one-pot reactions in aqueous media remain challenging and are limited today to metal-catalysts that display high activity in aqueous media. Here, we report the first combination of two incompatible catalytic systems, a lipase based ester hydrolysis with a water-sensitive Cu/bipyridine catalyzed oxidation reaction, in a one-pot reaction in aqueous medium (PBS buffer). Key to the solution was the compartmentalization of the Cu/bipyridine catalyst in a core-shell like nanoparticle. We show the synthesis and characterization of the Cu/bipyridine functionalized nanoparticles and the application in the oxidation of allylic and benzylic alcohols in aqueous media. Furthermore, the work demonstrates the implementation of a one-pot reaction process with optimized reaction conditions involving a lipase (CAL-B) to hydrolyze various acetate ester substrates in the first step, followed by oxidation of the resulting alcohols to the corresponding aldehydes under aerobic conditions in aqueous media.
Selective oxidation of styrene catalyzed by cerium-doped cobalt ferrite nanocrystals with greatly enhanced catalytic performance
Tong, Jinhui,Li, Wenyan,Bo, Lili,Wang, Huan,Hu, Yusen,Zhang, Zhixia,Mahboob, Abdulla
, p. 474 - 481 (2016/11/18)
The rare earth metal Ce-doped cobalt ferrite samples CexCo1?xFe2O4 (x?=?0.1, 0.3, 0.5) were prepared by the sol–gel autocombustion route. The as-prepared samples were characterized by X-ray diffractometry, scanning electron microscopy, transmission electron microscopy, ICP–atomic emission spectroscopy, and N2 physisorption. Their catalytic performance was evaluated in oxidation of styrene using hydrogen peroxide (30%) as oxidant. Compared with pristine CoFe2O4, the Ce-doped samples were found to be more efficient catalysts for the oxidation of styrene to benzaldehyde, with greatly enhanced catalytic performance. Especially, when Ce0.3Co0.7Fe2O4 was used as catalyst, 90.3% styrene conversion and 91.5% selectivity for benzaldehyde were obtained at 90?°C for 9?h reaction. The catalyst can be magnetically separated easily for reuse, and no obvious loss of activity was observed when it was reused in five consecutive runs.
Method to oxidize alcohols selectively to aldehydes and ketones with heterogeneous supported ruthenium catalyst at room temperature in air and catalyst thereof
-
Paragraph 0021; 0022, (2016/10/07)
The present invention relates to a method for selectively oxidizing alcohol by using a heterogeneous catalyst for producing aldehyde and ketone in an organic synthesis process used in the laboratory and chemical industries, and a catalytic system thereof. The method can be used as an intermediate product for synthesizing medicine, scent, fragrance, and precise chemical products, and can use a heterogeneous catalyst at room temperature in air by using the catalytic system and producing alcohol and ketone.COPYRIGHT KIPO 2016
Iron-Catalysed Selective Aerobic Oxidation of Alcohols to Carbonyl and Carboxylic Compounds
Lagerblom, Kalle,Wrigstedt, Pauli,Keskiv?li, Juha,Parviainen, Arno,Repo, Timo
, p. 1160 - 1165 (2016/11/23)
A method for aerobic alcohol oxidation catalysed by Fe(NO3)3/2,2’-bipyridine/TEMPO has allowed highly selective conversion of primary alcohols into either aldehydes or carboxylic acids in one-step. The oxidation of primary alcohols proceeded selectively to aldehydes, as TEMPO was present in the reaction. Nevertheless, the aldehydes were further oxidized into carboxylic acids as the reaction time was extended. Detailed investigation of the reaction suggested, that the deoxygenation of TEMPO into TMP enabled the auto-oxidation of aldehydes to carboxylic acids, which was initially inhibited in the presence of TEMPO. The procedure was also efficient in oxidation of secondary alcohols when TEMPO was replaced by the less sterically hindered ABNO.
Crystal Structure and Catalytic Behavior in Olefin Epoxidation of a One-Dimensional Tungsten Oxide/Bipyridine Hybrid
Amarante, Tatiana R.,Antunes, Margarida M.,Valente, Anabela A.,Paz, Filipe A. Almeida,Pillinger, Martyn,Gon?alves, Isabel S.
, p. 9690 - 9703 (2015/11/03)
The tungsten oxide/2,2′-bipyridine hybrid material [WO3(2,2′-bpy)]·nH2O (n = 1-2) (1) has been prepared in near quantitative yield by the reaction of H2WO4, 2,2′-bpy, and H2O in the mole ratio of ca. 1:2:700 at 160°C for 98 h in a rotating Teflon-lined digestion bomb. The solid-state structure of 1 was solved and refined through Rietveld analysis of high-resolution synchrotron X-ray diffraction data collected for the microcrystalline powder. The material, crystallizing in the orthorhombic space group Iba2, is composed of a one-dimensional organic-inorganic hybrid polymer, ∞1[WO3(2,2′-bpy)], topologically identical to that found in the previously reported anhydrous phases [MO3(2,2′-bpy)] (M = Mo, W). While in the latter the N,N′-chelated 2,2′-bpy ligands of adjacent corner-shared {MO4N2} octahedra are positioned on the same side of the 1D chain, in 1 the 2,2′-bpy ligands alternate above and below the chain. The catalytic behavior of compound 1 for the epoxidation of cis-cyclooctene was compared with that for several other tungsten- or molybdenum-based (pre)catalysts, including the hybrid polymer [MoO3(2,2′-bpy)]. While the latter exhibits superior performance when tert-butyl hydroperoxide (TBHP) is used as the oxidant, compound 1 is superior when aqueous hydrogen peroxide is used, allowing near-quantitative conversion of the olefin to the epoxide. With H2O2, compounds 1 and [MoO3(2,2′-bpy)] act as sources of soluble active species, namely, the oxodiperoxo complex [MO(O2)2(2,2′-bpy)], which is formed in situ. Compounds 1 and [WO(O2)2(2,2′-bpy)] (2) were further tested in the epoxidation of cyclododecene, trans-2-octene, 1-octene, (R)-limonene, and styrene. The structure of 2 was determined by single-crystal X-ray diffraction and found to be isotypical with the molybdenum analogue.
