- TEMPO mediated electrocatalytic oxidation of pyridyl carbinol using palladium nanoparticles dispersed on biomass derived porous nanoparticles
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Remarkable electrocatalytic property of Pd nanostructures dispersed on CNSareca coated CFP electrode towards TEMPO mediated electrooxidation of pyridyl carbinol was reported for the first time. Carbon nanospheres (CNSs) derived from Areca catechu decorated with Pd nanoparticles were coated on carbon fiber paper (CFP) and was employed for electrooxidation of pyridyl carbinol in aqueous acidic medium. An environmentally benign and economic strategy was utilized for the preparation of CNSs obtained from Areca catechu. The physical characterizations, electronic state and chemical composition of the modified electrode were studied using Fourier transform infrared (FTIR) spectroscopy, X-ray diffraction (XRD) spectroscopy and X-ray photoelectron spectroscopy (XPS). Scanning electron microscopy (SEM), Transmission electron microscopy (TEM) and high resolution transmission electron microscopy (HRTEM) techniques were used for analyzing the morphology of modified electrode. The electrochemical characterizations of the modified electrodes were performed by Cyclic voltammetry (CV) and Electrochemical impedance spectroscopy (EIS). Pd decorated CNSareca dispersed on CFP electrode has exhibited strong electrocatalytic activity towards TEMPO mediated oxidation of pyridyl carbinol.
- B, Akshaya K.,Bhat, Vinay S.,Hegde, Gurumurthy,Mathew, Agnus T.,S, Supriya,T, Maiyalagan,Varghese, Anitha
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- Facile construction of leaf-like WO3 nanoflakes decorated on g-C3N4 towards efficient oxidation of alcohols under mild conditions
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Herein, a well-defined nanostructure with leaf-like WO3 nanoflakes decorated on g-C3N4 was constructed via a facile impregnation and subsequent annealing method. The prepared WO3/g-C3N4 exhibited excellent catalytic activity for the selective oxidation of alcohols under mild conditions, and satisfactory yields to the corresponding carbonyl compounds were achieved without using non-green additives and organic solvents. It was found that the enhanced catalytic activity could be attributed to the enlarged specific surface area, the well-defined nanostructure, and the strong interactions between WO3 and g-C3N4. The distribution of WO3 nanoflakes on the g-C3N4 support increased the number of catalytically active sites for this reaction. XPS analysis suggested that a synergistic electron effect occurred because of the electron transfer from g-C3N4 to WO3. Moreover, the effects of reaction temperature, reaction time, oxidant amount and catalyst dosage on catalytic activity were investigated. Recycle studies showed that the catalyst could be readily recovered and no obvious decrease in catalytic efficiency was observed after seven cycles. The present catalytic system can afford a wide substrate scope for both aryl and alkyl alcohols with superior conversion and selectivity. Also, a plausible reaction mechanism was proposed to better illustrate the catalytic process. This work might provide a facile construction of a well-defined WO3/g-C3N4 catalyst for the selective oxidation of alcohols using a sustainable approach.
- Xu, Cai,Wang, Xiaozhong,Xu, Gang,Chen, Yingqi,Dai, Liyan
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- Zn-doped W/aluminium oxide catalyst: Efficient strategy towards sustainable oxidation of alcohols
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Bifunctional catalysts have been considered to have vital importance in catalytic chemical process, but there is still some developing room for convenient materials with dual active sites. These catalysts have a notorious reputation for inhibiting mutual neutralization and controlling the distribution of active sites in order to perform their functions. We tailor a series of W-Zn-Al2O3 catalysts by modulating the doping density of metal species, which can boost the catalytic process of alcohols into corresponding carbonyl compounds in an additive-free-condition. Test results indicate that the proper content of zinc element can promote the overall activities, and subsequent adjustment of doping zinc can dramatically increase the electronic interaction and change the distribution of chemical active sites. Also, a plausible reaction mechanism was proposed to better understand the acid-base bifunctional catalytic process. Theoretical results confirm this system can provide certain references for similar reactants. Present reaction system is a green procedure and features a broad substrate scope, which reveals a sustainable method to process oxidative dehydrogenation reaction.
- An, Yu,Cai, Menglu,Chen, Yingqi,Dai, Liyan,Fang, Yangyang,Li, Jun,Wang, Xiaozhong,Zhang, Ming
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- Self-promoted vanadium-catalyzed oxidation of pyridinemethanol with molecular oxygen
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Catalytic oxidation of alcohols containing heteroatoms with molecular oxygen is usually rather challenging, as transition metal catalysts are easily deactivated by heteroatoms. In contrast to conventional results, herein facile oxidation of 2-pyridinemethanol with dioxgyen was observed over simple vanadium catalysts including VOSO4 or VO(acac)2, which seemed much easier than that of benzyl alcohol. 2-Pyridinemethanol could coordinate with the vanadium center, which would promote oxidation of 2-pyridinemethanol itself, rather than deactivate vanadium catalysts. This study would provide a new clue to develop efficient catalysts for transformations of heterocyclic compounds.
- Du, Zhongtian,Li, Meijin,Tang, Yangyang,Wang, Wanhui,Xiao, Yonghou
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- An aerobic oxidation of alcohols into carbonyl synthons using bipyridyl-cinchona based palladium catalyst
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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.
- Cheedarala, Ravi Kumar,Chidambaram, Ramasamy R.,Siva, Ayyanar,Song, Jung Il
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p. 32942 - 32954
(2021/12/02)
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- Combining photo-redox and enzyme catalysis for the synthesis of 4H-pyrimido[2,1-b] benzothiazole derivatives in one pot
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A novel strategy combining visible-light and enzyme catalysis in one pot for the synthesis of 4H-pyrimido[2,1-b] benzothiazole derivatives from alcohols is described for the first time. Fourteen 4H-pyrimido[2,1-b] benzothiazole derivatives were prepared with yields of up to 98% under mild reaction conditions by a simple operation. The photoorgano catalyst rose Bengal (rB) was employed to oxyfunctionalise alcohols to aldehydes. Compared with aldehydes, alcohols with more stable properties and lower cost, thus we used photocatalysis to oxidize alcohols into aldehydes. Next, the enzyme was used to further catalyze the reaction of Biginelli to produce the target product of 4H-pyrimidine [2,1-b] benzothiazole. Experimental results show that this method provides a more efficient and eco-friendly strategy for the synthesis of 4H-pyrimido[2,1-b] benzothiazole derivatives.
- Yu, Yuan,Lu, Wei-Fan,Yang, Zeng-Jie,Wang, Na,Yu, Xiao-Qi
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supporting information
(2020/12/25)
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- Iodine-imine Synergistic Promoted Povarov-Type Multicomponent Reaction for the Synthesis of 2,2′-Biquinolines and Their Application to a Copper/Ligand Catalytic System
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An efficient iodine-imine synergistic promoted Povarov-type multicomponent reaction was reported for the synthesis of a practical 2,2′-biquinoline scaffold. The tandem annulation has reconciled iodination, Kornblum oxidation, and Povarov aromatization, where the methyl group of the methyl azaarenes represents uniquely reactive input in the Povarov reaction. This method has broad substrate scope and mild conditions. Furthermore, these 2,2′-biquinoline derivatives had been directly used as bidentate ligands in metal-catalyzed reactions.
- Hu, Qi-Qi,Gao, Yan-Ting,Sun, Jia-Chen,Gao, Jing-Jing,Mu, Hong-Xiao,Li, Yi-Ming,Zheng, Ya-Nan,Yang, Kai-Rui,Zhu, Yan-Ping
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supporting information
p. 9000 - 9005
(2021/11/24)
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- Palladium-Catalyzed Reductive Carbonylation of (Hetero) Aryl Halides and Triflates Using Cobalt Carbonyl as CO Source
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An efficient protocol for the reductive carbonylation of (hetero) aryl halides and triflates under CO gas-free conditions using Pd/Co2(CO)8 and triethylsilane has been developed. The mild reaction conditions, enhanced chemoselectivity and, easy access to heterocyclic and vinyl carboxaldehydes highlights its importance in organic synthesis.
- Dogga, Bhushanarao,Joseph, Jayan T.,Kumar, C. S. Ananda
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supporting information
p. 309 - 313
(2020/12/23)
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- Samarium-based Grignard-type addition of organohalides to carbonyl compounds under catalysis of CuI
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Grignard-type additions were readily achieved under the mediation of CuI (10 mol%) and samarium (2 equiv.) by employing various organohalides,e.g.benzyl, aryl, heterocyclic and aliphatic halides (Cl, Br or I), and diverse carbonyl compounds (e.g.carbonic esters, carboxylic esters, acid anhydrides, acyl chlorides, ketones, aldehydes, propylene epoxides and formamides) to afford alcohols, ketones and aldehydes, respectively, with high efficiency and chemoselectivity, in which the organosamarium intermediate might be involved.
- Liu, Chen,Liu, Yongjun,Qi, Yan,Song, Bin,Wang, Liang,Xiao, Shuhuan
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supporting information
p. 6169 - 6172
(2021/06/30)
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- Cyclohexene Promoted Efficient Biomimetic Oxidation of Alcohols to Carbonyl Compounds Catalyzed by Manganese Porphyrin under Mild Conditions?
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Selective oxidation of alcohols to corresponding carbonyl compounds is one of the most important processes both in academic and application research. As a kind of biomimetic catalyst, metalloporphyrins-catalyzed aerobic oxidation of alcohols with aldehyde as hydrogen donator is gathering much attention. However, using olefins as another kind hydrogen donator for aerobic oxidation of alcohols has not been reported. In this study, a system comprising managenese porphyrin and cyclohexene for biomimetic aerobic oxidation of alcohols to carbonyl compounds was developed. The catalytic system exhibited excellent catalytic performance and selectivity towards the corresponding products for most primary and secondary alcohols under mild conditions. Based on the results obtained from experiments as well as in situ EPR (electron paramagnetic resonance) and UV-vis spectroscopy, the role of cyclohexene was demonstrated.
- Ji, Hong-Bing,Liu, Xiao-Hui,Xue, Can,Yu, Hai-Yang,Zhou, Xian-Tai
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- Metal-Organic Framework Based on Heptanuclear Cu-O Clusters and Its Application as a Recyclable Photocatalyst for Stepwise Selective Catalysis
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Visible-light driven photoreactions using metal-organic frameworks (MOFs) as catalysts are promising with regard to their environmental friendly features such as the use of renewable and sustainable energy of visible light and potential catalyst recyclability. To develop potential heterogeneous photocatalysts, a family of three copper(II) coordination polymers bearing different Cu-O assemblies have been synthesized with the ligand 4,4-disulfo-[1,1-biphenyl]-2,2-dicarboxylate acid (H4DSDC), namely, {[Cu7(DSDC)2(OH)6(H2O)10]·xH2O}n (1), {[Cu4(DSDC)(4,4-bpy)2(OH)4]·2H2O}n (2), and {Cu2(DSDC)(phen)2(H2O)2}n (3) (4,4-bpy = 4,4-bipyridine and phen = 1,10-phenanthroline). Complex 1 represents a metal-organic framework featuring a NbO type topology constructed from the infinite linkage of heptanuclear [Cu7(μ3-OH)6(H2O)10]8+ clusters by deprotonated DSDC4- ligands, comprising one-dimensional hexagonal channels of a diameter around 11 ? that are filled with water molecules. The infinite waving {[Cu2(OH)2]2+}n ladderlike chains in complex 2 are bridged by DSDC4- and 4,4-bpy ligands into a three-dimensional framework. A two-dimensional layered structure is formed in complex 3 due to the existence of terminal phenanthroline ligands. All of the coordination polymers 1-3 are able to catalyze the visible-light driven oxidation of alcohols at mild conditions using hydrogen peroxide as an oxidant, in which complex 1 demonstrates satisfactory efficiency. Significantly for this photoreaction catalyzed by 1, the extent of oxidation over aryl primary alcohols is fully controllable with time-resolved product selectivity, giving either corresponding aldehydes or carboxylate acids in good yields. It is also remarkable that the photocatalyst could be recovered almost quantitatively on completion of the catalytic cycle without any structure change, and could be recycled for catalytic use for at least five cycles with constant efficiency. This photocatalyst with time-resolved selectivity for different products may provide new insight into the design and development of novel catalytic systems.
- Zhou, Jie,Huang-Fu, Xu,Huang, Yang-Ying,Cao, Chu-Ning,Han, Jie,Zhao, Xiao-Li,Chen, Xu-Dong
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p. 254 - 263
(2019/12/04)
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- Efficient selective oxidation of alcohols to carbonyl compounds catalyzed by Ru-terpyridine complexes with molecular oxygen
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The oxidation of alcohols with molecular oxygen is a promising approach to produce corresponding carbonyl compounds. In this work, efficient aerobic oxidation of alcohols to carbonyl compounds catalyzed by ruthenium-terpyridine [(tpy-PhCH3)RuCl3] with isobutyraldehyde as co-substrate was developed. Various alcohols including primary and secondary alcohols are smoothly converted to corresponding carbonyl compounds in good yield. In a 100 times large-scale oxidation of benzyl alcohol, benzaldehyde was obtained with 92% isolated yield. Moreover, a plausible mechanism involving high-valence ruthenium species was proposed based on in situ UV–vis spectroscopy.
- Han, Qi,Guo, Xiao-Xuan,Zhou, Xian-Tai,Ji, Hong-Bing
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- A Remote ‘Imidazole’-Based Ruthenium(II) Para-Cymene Pre-catalyst for the Selective Oxidation Reaction of Alkyl Arenes and Alcohols
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Herein we disclosed the use of a remote ‘imidazole’-based precatalyst [(para-cymene)RuII(L)Cl]+, C-1 where L=2-(4-substituted-phenyl)-1H-imidazo[4,5-f][1,10] phenanthroline) for the selective oxidation of a variety of alkyl arenes/heteroarenes and alcohols to their corresponding aldehydes or ketones in presence of tert-butyl hydroperoxide (TBHP). The remote ‘imidazole’ moiety present in the complex facilitates the activation of oxidant and subsequent generation of active species via the release of para-cymene from C-1, which in-turn was less effective without the ‘imidazole’ moiety. The mechanistic features of C-1 promoted oxidation of alkyl arenes were also assessed from spectroscopic, kinetic, and few control experiments. The substrate scope for C-1 promoted oxidation reaction was assessed based on the selective oxidation of 27-different alkyl arenes/heteroarenes and 25 different alcohols to their corresponding aldehydes/ketones in moderate to good yields.
- Dutta, Manali,Bania, Kusum K.,Pratihar, Sanjay
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p. 926 - 932
(2020/03/05)
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- Effective Control of Particle Size and Electron Density of Pd/C and Sn-Pd/C Nanocatalysts for Vanillin Production via Base-Free Oxidation
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The effective control of particle size and electron density of metal active sites is challenging yet important for supported nanoparticles, as size effects and promoter effects play vital roles in heterogeneous catalysis on the nanoscale. In this work, we report Pd/C and Sn-Pd/C nanocatalysts for the base-free aerobic oxidation of vanillyl alcohol to vanillin, a challenging reaction not only in the fundamental research of selective oxidation of alcohols but also for the practical transformation of bio-based alcohols to value-added chemicals. We effectively tuned the mean size of Pd nanoparticles from 1.8 to 6.7 nm by varying the temperature used for catalyst preparation and further modified the electron density of the Pd/C catalyst by adding a SnO2 promoter with different loadings. TEM, HAADF-STEM, XPS, CO chemisorption, and in situ DRIFT-IR of CO adsorption characterizations allowed us to get insight into the unique catalytic properties of Pd nanocatalysts. It was conjectured that the base-free aerobic oxidation of vanillyl alcohol to vanillin over the Pd/C catalyst can be a structure-sensitive reaction and the Pd particle size was decisive for the dispersion of Pd, the proportion of catalytically active Pd0 sites, and the intrinsic turnover frequency (iTOF). The 1 wt % Pd/C (1.8 nm) catalyst showed an iTOF value of 268 h-1 and 100% yield to vanillin at 120 °C, 5 bar of O2, and 20 mg of the catalyst within 9 h. We further demonstrated that Sn4+ ions in SnO2 as an electronic promoter can promote Pd/C activity by the formation of highly active, electron-sufficient Pd0 sites which significantly lowered the apparent activation energy of reaction. The 0.1Sn-Pd/C catalyst showed a higher iTOF value of 458 h-1 and a yield of 100% to vanillin at 120 °C, 3 bar of O2 and 15 mg of the catalyst within 6 h. Moreover, we verified a satisfying reusability and an adequate substrate scope over the 0.1Sn-Pd/C catalyst.
- Cao, Qiue,Fang, Wenhao,Lu, Yaowei,Sun, Weixiao,Wang, Yongxing,Wu, Shipeng
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p. 7699 - 7709
(2020/08/21)
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- Visible-light assisted of nano Ni/g-C3N4 with efficient photocatalytic activity and stability for selective aerobic C?H activation and epoxidation
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A selective, economical, and ecological protocol has been described for the oxidation of methyl arenes and their analogs to the corresponding carbonyl compounds and epoxidation reactions of alkenes with molecular oxygen (O2) or air as a green oxygen source, under mild reaction conditions. The nano Ni/g-C3N4 exhibited high photocatalytic activity, stability, and selectivity in the C?H activation of methyl arenes, methylene arenes, and epoxidation of various alkenes under visible- light irradiation without the use of an oxidizing agent and under base free conditions.
- Akrami, Zahra,Hosseini-Sarvari, Mona
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supporting information
(2020/10/13)
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- Facile synthesis of 1,3,4-oxadiazoles via iodine promoted oxidative annulation of methyl-azaheteroarenes and hydrazides
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An oxidative sp3 C–H bond of methyl-azaheteroarenes protocol was reported for the synthesis of 1,3,4-oxadiazoles via [4 + 1] annulation with hydrazides. This protocol enables 1,3,4-oxadiazole and quinoline linked diheterocycles via selective oxidation of sp3 C–H bond of methyl-azaheteroarenes in the presence of I2-DMSO. The reaction has a broad substrate scope and good functional group tolerance for methyl-azaheteroarenes and hydrazides.
- Shang, Zhi-Hao,Sun, Ji-Na,Guo, Jiang-Shan,Sun, Yuan-Yuan,Weng, Wei-Zhao,Zhang, Zhen-Xiao,Li, Zeng-Jing,Zhu, Yan-Ping
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supporting information
(2020/01/08)
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- The Synergy Effect in Tio2 Supported Bi-Mo Catalysts for Facile and Environmentally-Friendly Synthesis of Pyridylaldehydes from Oxidation of Picolines
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Abstract: The oxidation of picolines to pyridlaldehydes was studied over bismuth molybdate catalysts supported on TiO2. The research results showed that α-Bi2Mo3O12 was superior to β-Bi2Mo2O9 and γ-Bi2MoO6 in terms of reactivity. Further doping MoO3 to α-Bi2Mo3O12/TiO2 gave rise to increased catalytic performance, which was due to the synergy effect of α-Bi2Mo3O12 and MoO3. The effect was on one hand manifested in the intimate relationship between α-Bi2Mo3O12 and MoO3 in stabilizing the crystallographic structure of catalysts and thereafter maintaining the surface area of the catalyst, as indicated by the BET surface area and XRD analysis. Moreover, NH3-TPD analysis demonstrated the effect in modifying the surface acidity of the catalysts, and thus facilitating the substrate adsorption as the picolines are alkaline substances. Additionally, the effect between α-Bi2Mo3O12 and MoO3 rendered the modification of the electronic properties and thereafter the oxygen desorption properties and reducible properties of the catalysts, as evidenced in the H2-TPR and O2-TPD analysis.
- Dai, Liyan,Jie, Yu,Zhylko, Viachaslau
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p. 181 - 186
(2020/03/30)
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- Rhodium-catalyzed reductive carbonylation of aryl iodides to arylaldehydes with syngas
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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.
- Chen, Suqing,Liu, Zhenghui,Mu, Tiancheng,Wang, Peng,Yan, Zhenzhong,Yu, Dongkun,Zhao, Xinhui
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p. 645 - 656
(2020/05/14)
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- Photo-Difunctionalization and Photo-Oxidative Cleavage of the C–C Double Bond of Styrenes in the Presence of Nanosized Cadmium Sulfide (CdS) as a Highly Efficient Photo-Induced Reusable Nanocatalyst
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The synthesis of cyclic dithiocarbonates via photo-difunctionalization of the C–C double bond of styrene and aryl aldehydes via photo-oxidative cleavage of the C–C double bond of styrene was accomplished in the presence of CdS NPs at room temperature in air atmosphere under visible light irradiation without using any external oxidant. Some of the special advantages of these processes are the use of CdS NPs as a simple, accessible, safe, and visible-light-induced reusable catalyst, as well as the use of air as an easily attainable, inexpensive, and harmless oxidant, styrene as a readily accessible substrate, and visible-light as a renewable and safe energy source.
- Firoozi, Somayeh,Hosseini-Sarvari, Mona
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p. 3834 - 3843
(2020/07/06)
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- Visible-light-driven photochemical activity of ternary Ag/AgBr/TiO2nanotubes for oxidation C(sp3)-H and C(sp2)-H bonds
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The Ag/AgBr/TiO2 ternary component nanotube as a heterogeneous photocatalyst was used for the solvent-free oxidation of the benzylic C(sp3)-H bond to the corresponding carbonyl compound or the solvent-controlled selective oxidative cleavage of the CC double bond of styrene to benzaldehyde under visible light at room temperature. A wide variety of carbonyl compounds were successfully synthesized through the developed photocatalytic process. Several advantages such as solvent-free conditions, sans additional oxidant, simple reaction, short reaction time, and easy separation of the product promote the reaction to be green. Moreover, the Ag/AgBr/TiO2 nanotubes could be used several times without reduction in their photocatalytic activity. This journal is
- Hosseini-Sarvari, Mona,Dehghani, Abdulhamid
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p. 16776 - 16785
(2020/10/27)
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- Kinetics of the Reaction between Cobinamide and Isoniazid in Aqueous Solutions
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Abstract: The kinetics and mechanism of the reaction of diaquacobinamide (Cbi(III)) with isoniazid (iso-nicotinoyl hydrazide (INH)) are studied. It is determined that the composition of the products depends on the ratio between the concentrations of the reactants. Adding excess INH to cobinamide results in the rapid formation of a stable complex of Cbi(III) with two isoniazid molecules. If the concentrations of isoniazid and cobinamide are close, or cobinamide is in excess, then a complex of Cbi(III) with one isoniazid molecule initially forms. There is then a fast inner-sphere electron transfer to yield an unstable complex of reduced Cbi(II) with hydrazyl radical (RN2H2)(Cbi(II)) that decomposes to form reduced cobinamide and the products of the oxidation of isoniazid: isonicotinamide, pyridine-4-carboxaldehyde, and isonicotinic acid (INA). It is concluded that with a 1000% excess of cobinamide, the main product of the oxidation of INH is INA.
- Tumakov,Dereven’kov,Sal’nikov,Makarov
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p. 265 - 270
(2019/06/03)
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- Metal-free nitrogen -doped carbon nanosheets: A catalyst for the direct synthesis of imines under mild conditions
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Herein, a highly stable, porous, multifunctional and metal-free catalyst was developed, which exhibited significant catalytic performance in the oxidation of amines and transfer hydrogenation of nitriles under mild conditions; this could be attributed to the presence of numerous active sites and their outstanding BET surface area. The obtained results showed that most of the yields of imines exceeded 90%, and the cycling performance of the catalyst could be at least seven runs without any decay in the reaction activity, which could be comparable to those of metal catalysts. Subsequently, a kinetic study has demonstrated that the apparent activation energy for the direct synthesis of imines from amines is 67.39 kJ mol-1, which has been performed to testify that the catalytic performances are rational. Via catalyst characterizations and experimental data, graphitic-N has been proven to be the active site of the catalyst. Hence, this study is beneficial to comprehend the mechanism of action of a metal-free N-doped carbon catalyst in the formation of imines.
- Wang, Kaizhi,Jiang, Pengbo,Yang, Ming,Ma, Ping,Qin, Jiaheng,Huang, Xiaokang,Ma, Lei,Li, Rong
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p. 2448 - 2461
(2019/05/17)
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- Production of [...] (by machine translation)
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[A] can be obtained in a high yield production of cheap material and [...][...] of. (1) According to the reaction scheme represented by formula [a], (a)- (e) step without purification of intermediate products isolated formyl pyridine produced through a method. (A) a cyanopyridine, formyl pyridine (b) present in the acid and a metal catalyst under hydrogen added in the reaction liquid after hydrogenation steps (25 °C converted value) or more by neutralizing the formyl pyridine to produce free pH4 step (c) (d) was obtained by the extraction process of extracting the formyl pyridine in an organic solvent to produce formyl pyridine (e) concentrating the solution to a process for concentrating a formyl pyridine, methylpyridine using acid halide or acid anhydride with a condensation process[R′ and R " is H, an alkyl group, an aryl group, a heterocyclic group or a halogen atom][Drawing] no (by machine translation)
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Paragraph 0045; 0046
(2019/06/07)
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- Efficient Chemoselective Reduction of N-Oxides and Sulfoxides Using a Carbon-Supported Molybdenum-Dioxo Catalyst and Alcohol
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The chemoselective reduction of a wide range of N-oxides and sulfoxides with alcohols is achieved using a carbon-supported dioxo-molybdenum (Mo@C) catalyst. Of the 10 alcohols screened, benzyl alcohol exhibits the highest reduction efficiency. A variety of N-oxide and both aromatic and aliphatic sulfoxide substrates bearing halogens as well as additional reducible functionalities are efficiently and chemoselectively reduced with benzyl alcohol. Chemoselective N-oxide reduction is effected even in the presence of potentially competing sulfoxide moieties. In addition, the Mo@C catalyst is air- and moisture-stable, and is easily separated from the reaction mixture and then re-subjected to reaction conditions over multiple cycles without significant reactivity or selectivity degradation. The high stability and recyclability of the catalyst, paired with its low toxicity and use of earth-abundant elements makes it an environmentally friendly catalytic system.
- Li, Jiaqi,Liu, Shengsi,Lohr, Tracy L.,Marks, Tobin J.
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p. 4139 - 4146
(2019/05/27)
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- Efficient and selective oxidation of alcohols to carbonyl compounds at room temperature by a ruthenium complex catalyst and hydrogen peroxide
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In this study, convenient and selective oxidation of alcohols using aqueous hydrogen peroxide to yield carbonyl compounds was studied. Using the ruthenium-(4-methylphenyl-2,6-bispydinyl) pyridinedicarboxylate complex [Ru(mpbp)(pydic)] as a catalyst, primary and secondary alcohols were oxidized to aldehydes and ketones at room temperature with a satisfactory yield and excellent selectivity. The influence of various reaction parameters, such as solvent, catalyst and oxidant amount on both the activity and selectivity was also evaluated. Kinetic studies showed that the oxidation of alcohol was first order in terms of the substrate and hydrogen peroxide, and was second order in terms of the catalyst. A plausible mechanism involving ruthenium-oxo species with electrophilic character was proposed based on the in situ UV-vis spectroscopy studies and Hammett plots.
- Wang, Jie-Xiang,Zhou, Xian-Tai,Han, Qi,Guo, Xiao-Xuan,Liu, Xiao-Hui,Xue, Can,Ji, Hong-Bing
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p. 19415 - 19421
(2019/12/24)
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- Catalytic oxidation of alcohols using Fe-bTAML and NaClO: Comparing the reactivity of Fe(V)O and Fe(IV)O intermediates
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We demonstrate the selective oxidation of secondary alcohols and activated primary alcohols to their corresponding aldehydes or ketones using Fe-bTAML as the catalyst and sodium hypochlorite (NaClO) as the oxidant. Good to excellent yields of 80%–99% for the carbonyl compounds and turnover numbers up to ～500 was obtained with this catalytic system. The reactions are clean, performed under mild conditions (air, room temperature) and yielded sodium chloride as the only by-product. The yield and turnover number were dependent on the pH of the reaction and this difference was attributed to the different reactive intermediates that was formed at pH 7 and pH 12 (FeV(O) and FeIV(O) respectively). Reactions involving the FeV(O) intermediate oxidize secondary alcohols more efficiently than its FeIV(O) analog. This trend was reversed for the oxidation of activated primary alcohols where reactions involving FeIV(O) afforded much higher TON's. This reactivity trend can be explained from the differences in bond dissociation energy (BDE) of their corresponding one electron reduced species ([FeIV-OH], ～99 kcal/mol; [FeIII-OH], ～83 kcal/mol) as well as their relative stabilities in the solvent during reaction. This catalytic system was found to be unsuitable for nonconjugated primary alcohol due to the formation of the inactive FeIV(OMe) intermediate after one catalytic cycle.
- Jana, Sandipan,Thomas, Jithin,Sen Gupta, Sayam
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p. 476 - 482
(2018/11/23)
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- An Engineered Alcohol Oxidase for the Oxidation of Primary Alcohols
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Structure-guided directed evolution of choline oxidase has been carried out by using the oxidation of hexan-1-ol to hexanal as the target reaction. A six-amino-acid variant was identified with a 20-fold increased kcat compared to that of the wild-type enzyme. This variant enabled the oxidation of 10 mm hexanol to hexanal in less than 24 h with 100 % conversion. Furthermore, this variant showed a marked increase in thermostability with a corresponding increase in Tm of 20 °C. Improved solvent tolerance was demonstrated with organic solvents including ethyl acetate, heptane and cyclohexane, thereby enabling improved conversions to the aldehyde by up to 30 % above conversion for the solvent-free system. Despite the evolution of choline oxidase towards hexan-1-ol, this new variant also showed increased specific activities (by up to 100-fold) for around 50 primary aliphatic, unsaturated, branched, cyclic, benzylic and halogenated alcohols.
- Heath, Rachel S.,Birmingham, William R.,Thompson, Matthew P.,Taglieber, Andreas,Daviet, Laurent,Turner, Nicholas J.
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p. 276 - 281
(2019/01/04)
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- A catalytic oxidation heterocyclic aromatic primary alcohol for the preparation of heterocyclic aromatic aldehyde
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The invention provides a method for preparing heterocyclic aromatic aldehyde by catalytically oxidizing heterocyclic aromatic primary alcohol. The method takes dioxovanadium nitrate as a catalyst and air as an oxidant; under a normal pressure condition, the heterocyclic aromatic primary alcohol is high-selectively oxidized into the heterocyclic aromatic aldehyde. The method provided by the invention has a high oxidization yield and a byproduct is water, so that the method is green, economical and environment-friendly; reaction conditions are moderate and the operation is simple. A catalysis system takes the air as the oxidant and non-metal metal as a catalyst, reaction conditions are moderate and the oxidization efficiency is high; the catalysis system is green and economical and can be used for efficiently catalyzing the heterocyclic aromatic primary alcohol into the corresponding heterocyclic aromatic aldehyde. Compared with a noble metal catalysis system and a catalysis system containing nitrogen-oxygen free radicals, the catalysis system has low oxidization reaction cost and has very high application value.
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Paragraph 0015-0018
(2019/05/04)
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- Transition-Metal-Free Oxidation of Benzylic C-H Bonds of Six-Membered N-Heteroaromatic Compounds
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A novel oxidation of benzylic C-H bonds for the synthesis of diverse six-membered N-heteroaromatic aldehydes and ketones has been developed. The obvious advantages of this approach are the simple operation, mild reaction conditions, and without use of toxic reagent and transition metal. The present method should provide a useful access for the synthesis and modification of N-heterocycles.
- Gao, Xianying,Han, Shuaijun,Zheng, Maolin,Liang, Apeng,Zou, Dapeng,Wu, Yusheng,Wu, Yangjie,Li, Jingya
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p. 4040 - 4049
(2019/04/30)
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- On/Off O2 Switchable Photocatalytic Oxidative and Protodecarboxylation of Carboxylic Acids
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Photoredox catalysis in recent years has manifested a powerful branch of science in organic synthesis. Although merging photoredox and metal catalysts has been a widely used method, switchable heterogeneous photoredox catalysis has rarely been considered. Herein, we open a new window to use a switchable heterogeneous photoredox catalyst which could be turned on/off by changing a simple stimulus (O2) for two opponent reactions, namely, oxidative and protodecarboxylation. Using this strategy, we demonstrate that Au@ZnO core-shell nanoparticles could be used as a switchable photocatalyst which has good catalytic activity to absorb visible light due to the localized surface plasmon resonance effect of gold, can decarboxylate a wide range of aromatic and aliphatic carboxylic acids, have multiple reusability, and are a reasonable candidate for synthesizing both aldehydes/ketones and alkane/arenes in a large-scale set up. Some biologically active molecules are also shown via examples of the direct oxidative and protodecarboxylation which widely provided pharmaceutical agents.
- Bazyar, Zahra,Hosseini-Sarvari, Mona
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p. 13503 - 13515
(2019/10/11)
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- Method for synthesizing aromatic aldehyde through iron catalyzed oxidation allyl aromatic compound
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The invention discloses a method for synthesizing aromatic aldehyde through an iron catalyzed oxidation allyl aromatic compound. According to the specific method, under the promotion effect of hydrogen silane, with air or oxygen as the oxidant, the aromatic aldehyde compound is synthesized through the iron catalyzed oxidation allyl aromatic compound, the reaction temperature is 20-150 DEG C, and the time is 0.25-60 h. The method has the advantages that a catalyst source is wide, the price is low and the environment is protected; an oxidant source is wide, the price is low and no waste is generated; the reaction conditions are mild, selectivity is high and the yield is high; a substrate source is wide and stable; a substrate functional group is high in compatibility and a substrate is widein application range; complicated small molecules are compatible and can be well converted into aldehyde. The target product separation yield can reach up to 96% under the optimized reaction conditions.
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Paragraph 0048-0050; 0149
(2019/06/27)
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- new synthesis method of 4-pyridine formaldehyde
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The invention belongs to the field of organic matter matter synthesis, and particularly relates to a new synthesis method of 4-pyridine formaldehyde, wherein isonicotinic acid is used as a starting raw material, and is subjected to esterifying and hydrazinolysis to synthesize isoniazid, and the isoniazid is oxidized into 4-pyridine formaldehyde by using recyclable K3[Fe(CN)]6 as an oxidant. According to the present invention, the new synthesis method is used so as to achieve advantages of economical raw material, few step, no environment pollution, simple operation and yield improving.
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Paragraph 0010; 0011
(2019/05/16)
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- Rhodium-Catalyzed Formylation of Aryl Halides with CO2 and H2
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The reductive formylation of aryl iodides/bromides to aryl aldehydes using CO2/H2 is presented for the first time. It was realized over a catalytic system composed of RhI3 or RhI3/Pd(dppp)Cl2 (dppp = 1,3-bis(diphenyphosphino)propane) and PPh3 in the presence of Ac2O/Et3N at 100 °C, affording aromatic aldehydes in good to excellent yields, together with good functional-group tolerance and broad substrate scope. The reaction proceeds through three cascade steps, involving HCOOH formation, CO release, and formylation of aryl halides.
- Liu, Zhenghui,Yang, Zhenzhen,Yu, Bo,Yu, Xiaoxiao,Zhang, Hongye,Zhao, Yanfei,Yang, Peng,Liu, Zhimin
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supporting information
p. 5130 - 5134
(2018/09/13)
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- Promotional synergistic effect of Sn doping into a novel bimetallic Sn-W oxides/graphene catalyst for selective oxidation of alcohols using aqueous H2O2 without additives
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A series of novel catalysts with bimetallic Sn-W oxides uniformly dispersed on reduced graphene oxide (denoted as Sn-W/RGO) were successfully prepared via a conventional one-pot hydrothermal method. Interestingly, it was found that the introduction of Sn could significantly improve the catalytic activities compared with single WO3/graphene catalyst for selective oxidation of alcohols using H2O2 without organic solvents and additives. Subsequently, the catalysts were characterized by FT-IR, XRD, Raman, FESEM, EDS, HRTEM, XPS and N2 adsorption-desorption to investigate the promotional synergistic effect of Sn among catalyst structure, surface properties and catalytic performance. The results revealed that the incorporation of Sn had induced the formation of hexagonal WO3 with dominant exposed (001) and (200) planes, meanwhile, doping Sn could dramatically increase the specific surface area, change the structural properties and enhance the interactions between Sn-W oxides and graphene, which were beneficial to the improvement of catalytic performance. Additionally, reaction parameters (temperature, time, oxidant dosage and catalyst amount) were also explored. Both aryl and alkyl alcohols exhibited high conversion and selectivity to corresponding target products over the catalyst. And delightedly, the robust catalyst could be reused for five times without significant loss in catalytic efficiency. This work demonstrates the promotional synergistic effect of Sn in a novel Sn-doped WO3/RGO catalyst and makes it a promising candidate in green oxidation of alcohols under mild reaction conditions.
- Xu, Cai,Zhang, Lingling,An, Yu,Wang, Xiaozhong,Xu, Gang,Chen, Yingqi,Dai, Liyan
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- Controlled Aerobic Oxidation of Primary Benzylic Alcohols to Aldehydes Catalyzed by Polymer-Supported Triazine-Based Dendrimer-Copper Composites
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A controlled aerobic oxidation of primary benzylic alcohols to the corresponding benzaldehydes by using polystyrene-poly(ethylene glycol) (PS-PEG) resin-supported triazine-based polyethyleneamine dendrimer-copper complexes [PS-PEG-TD2-Cu(II)] was developed. In particular, PS-PEG-TD2-Cu(OAc) 2 efficiently catalyzed the aerobic oxidation of benzylic alcohols in the presence of a catalytic amount of TEMPO under atmospheric conditions to give the corresponding aldehydes in up to quantitative yield. The catalyst was readily recovered by simple filtration and reused four times without significant loss of its catalytic activity.
- Pan, Shiguang,Yan, Shuo,Osako, Takao,Uozumi, Yasuhiro
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supporting information
p. 1152 - 1156
(2018/04/16)
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- Pseudohalide assisted aerobic oxidation of alcohols in the presence of visible-light
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Pseudohalides are well known to do similar chemistry like halides. Thiocyanate, a pseudohalide acts like halides in many ways. Thiocyanate radicals ([rad]SCN) are generated from readily available thiocyanate salts using Rose Bengal through single electron transfer (SET) in the presence of visible light. Thiocyanate radicals abstract hydrogen like other halide radicals, so this aspect of chemistry was used for the oxidation of alcohols to their corresponding aldehydes using oxygen as the terminal oxidant. This method shows a broad scope and well tolerance towards various functional groups.
- Sheriff Shah, Sk,Pradeep Singh
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supporting information
p. 247 - 251
(2018/01/03)
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- Synthesis and characterization of Co3O4 immobilized on dipeptide-functionalized silica-coated magnetite nanoparticles as a catalyst for the selective aerobic oxidation of alcohols
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Synthesis and characterization of a new silica-coated magnetite nanocatalyst are described. This catalyst was prepared through a multistep procedure consisting of surface modification, functionalization with the product of an Ugi multicomponent reaction, and immobilization of Co3O4 on silica-coated magnetite nanoparticles. The prepared nanocatalyst was characterized using various techniques such as Fourier-transform infrared and energy-dispersive X-ray spectroscopies, thermal and elemental analyses, X-ray diffraction, and field-emission scanning and transmission electron microscopies. The catalyst showed high catalytic activity for the aerobic oxidation of alcohols in acetonitrile as the solvent at mild temperatures and reusability for five repeated runs without loss of its activity.
- Khodaei, Mohammad Mehdi,Dehghan, Mahsa
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p. 11381 - 11389
(2018/07/24)
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- Synthesis and characterization of a Ni nanoparticle stabilized on Ionic liquid-functionalized magnetic Silica nanoparticles for tandem oxidative reaction of primary alcohols
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In this research, preparation of the magnetic nanoparticle, coating by a silica shell using (3-aminopropyl) triethoxysilane and synthesis of a novel sulfonic acid-substituted imidazolium-based ionic liquid onto the surface of these particles via a multi-component reaction, is described. The functionalized nanoparticles was loaded by Ni nanoparticles and characterized by means of techniques such as XRD, FTIR, SEM, EDX, TEM, TGA and ICP-OES. The nanostructures have spherical shapes that ranged in size from 80 to 100?nm. The catalytic activity of these nanoparticles was tested in aerobic oxidation of primary alcohols that showed good performance in the wide range of primary alcohols in water at mild reaction conditions. As a second step of this work, the tandem oxidative synthesis of alkylacrylonitriles and bisindolylmethanes were investigated using primary alcohols under oxidation conditions. This catalyst system can be recovered using external magnet and reused for five consecutive cycles without significantly less of its activity.
- Hosseinzadeh-Khanmiri, Rahim,Kamel, Yaser,Keshvari, Zahra,Mobaraki, Ahmad,Shahverdizadeh, Gholam Hossein,Vessally, Esmail,Babazadeh, Mirzaagha
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- Polydentate 4-Pyridyl-terpyridine Containing Discrete Cobalt Phosphonate and Polymeric Cobalt Phosphate as Catalysts for Alcohol Oxidation
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Mononuclear discrete cobalt phosphonate [Co(pytpy)(tBuPO3H)2(H2O)]·H2O (1) and 1D zigzag polymeric cobalt phosphate [Co(pytpy)2(dipp)(MeOH)·2MeOH]n (2) were prepared from the reactions of tert-butyl phosphonic acid (tBuPO3H2) and organic-soluble 2,6-diisopropylphenyl phosphate (dippH2) ligands with Co(OAc)2·4H2O in the presence of 4′-pyridyl 2,2′:6′,2′′-terpyridine in MeOH/CHCl3(1:1 v/v) solvent mixture at 25 °C. The new compounds were characterized by analytical, thermo-analytical, and spectroscopic techniques. Further, the molecular structures were established by single-crystal X-ray diffraction studies. Mass spectrometry analysis reveal that both the compounds exist in the solution phase as dimers. Compound 1 was employed as homogeneous catalysts for alcohol oxidation reactions using tert-butyl hydroperoxide (TBHP) as the oxidant.
- Bhat, Gulzar A.,Rajendran, Antony,Murugavel, Ramaswamy
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p. 692 - 699
(2018/08/06)
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- Combined Iron/Hydroxytriazole Dual Catalytic System for Site Selective Oxidation Adjacent to Azaheterocycles
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This report details a new method for site-selective methylene oxidation adjacent to azaheterocycles. A dual catalysis approach, utilizing both an iron Lewis acid and an organic hydroxylamine catalyst, proved highly effective. We demonstrate that this method provides complementary selectivity to other known catalytic approaches and represents an improvement over current heterocycle-selective reactions that rely on stoichiometric activation.
- Cooper, Julian C.,Luo, Chaosheng,Kameyama, Ryohei,Van Humbeck, Jeffrey F.
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supporting information
p. 1243 - 1246
(2018/02/09)
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- Carbazole-triazine based donor-acceptor porous organic frameworks for efficient visible-light photocatalytic aerobic oxidation reactions
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We report the synthesis of a series of carbazole-triazine based donor-acceptor (D-A) POFs and their photocatalytic activities for aerobic oxidation reactions. The simultaneous introduction of a carbazole-based electron donor and a triazine-based electron acceptor in D-A POFs stabilizes the charge transfer state and enables an efficient triplet-triplet energy transfer to generate 1O2. Meanwhile, systematic variation of the D-A distance results in the tunable photoredox properties and consequently the efficiency for generation of reactive oxygen species (ROSs). Upon visible light excitation, all three D-A POFs exhibit excellent capability to promote three aerobic oxidations: sulfide oxidation, oxidative amine coupling, and Mannich reactions. This systematic study validates the design principle of D-A POFs as high-performance photo-oxidation catalysts with wide substrate scope and excellent stability and recyclability.
- Luo, Jian,Lu, Jingzhi,Zhang, Jian
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supporting information
p. 15154 - 15161
(2018/08/17)
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- Visible-light-responsive catalysis of a zinc-introduced lacunary disilicoicosatungstate for the deoxygenation of pyridine N-oxides
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We herein report the synthesis and photoredox catalysis of a mononuclear zinc-introduced lacunary disilicoicosatungstate TBA7[{Zn(CH3CN)}(γ-SiW10O34){γ-SiW10O32(CH3CONH)}(μ-O)2] (II, TBA = tetra-n-butylammonium). POM II showed efficient photocatalytic activity in the selective deoxygenation of pyridine N-oxides under visible light irradiation (λ > 400 nm).
- Jeong, Jinu,Suzuki, Kosuke,Yamaguchi, Kazuya,Mizuno, Noritaka
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supporting information
p. 13226 - 13229
(2017/11/27)
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- Chemoselective hydrogen peroxide oxidation of primary alcohols to aldehydes by a water-soluble and reusable iron(iii) catalyst in pure water at room temperature
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Hydrogen peroxide oxidation of primary alcohols to aldehydes is described, which is catalyzed by a novel, reusable and water-soluble FeCl3 complex in situ-formed with quaternary ammonium salt-functionalized 8-aminoquinoline. This reaction exhibits unique chemoselectivity and broad functional-group tolerance, and it can operate efficiently in pure water at room temperature.
- Yan, Qi,Fang, Ye Chen,Jia, Yun Xue,Duan, Xin Hong
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p. 2372 - 2377
(2017/03/21)
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- Synthesis of smart bimetallic nano-Cu/Ag@SiO2 for clean oxidation of alcohols
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Here, we have demonstrated the synthesis and characterization of silica supported bimetallic copper/silver nanoparticles (Cu/Ag@SiO2 NPs) and their application in the clean oxidation of benzoins/benzyl alcohols in the presence of tert-butyl hydroperoxide as a mild oxidant. All the reactions were very fast (4 h) and high yielding (95-99%), and the Cu/Ag@SiO2 NPs were very stable under the reaction conditions. The catalyst was recovered simply by filtration and reused eight times without loss of its catalytic performance.
- Saha, Arijit,Payra, Soumen,Banerjee, Subhash
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supporting information
p. 13377 - 13381
(2017/11/27)
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- Nitrogen dioxide-catalyzed aerobic oxidation of benzyl alcohols under cocatalyst and acid-free conditions
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Nitrogen dioxide is usually considered as a mediator between dioxygen and the catalysts for the aerobic oxidation of alcohols. Here, we report that nitrogen dioxide has an ability to catalyze this reaction, which not only avoids the use of the cocatalysts or the acids in traditional approaches, but also reveals a method for the present transformation with a single component catalyst. A series of primary and secondary benzyl alcohols underwent this transformation to give the targeted products in low to high yields.
- Ren, Fangping,Tian, Xinzhe,Ren, Yun-Lai,Zhao, Shuang,Wang, Jianji,Zhao, Bo
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- Highly selective aerobic oxidation of alcohols to aldehydes over a new Cu(II)-based metal-organic framework with mixed linkers
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A new Cu(II)-based metal-organic framework {[Cu2(1,2-BDC)2(Fbtx)2]·3H2O}n (denoted as Cu-FMOF, CCDC-1519440, 1,2-BDC?=?1,2-benzenedicarboxylate, Fbtx?=?1,4-bis(1,2,4-triazole-1-ylmethyl)-2,3,5,6-tetrafluorobenenze) was hydrothermally synthesized and structurally characterized. The Cu-FMOF exhibits a 3D 4-connected coordination framework with the extremely rare (65·8)-hxg-d-4-P2/c topology. Using air as the oxidant, the crystalline Cu-FMOF could be used as a highly efficient heterogeneous catalyst for the TEMPO-assisted oxidation of alcohols to aldehydes. Furthermore, the Cu-FMOF catalyst could be easily recovered and reused for several times without a significant loss of catalytic activity or structural deterioration.
- Chen, Sheng-Chun,Lu, Sheng-Nan,Tian, Feng,Li, Nan,Qian, Han-Yu,Cui, Ai-Jun,He, Ming-Yang,Chen, Qun
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- Synthetic method of 4-pyridylaldehyde
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The invention relates to the field of organic chemistry, in particular to a synthetic method of 4-pyridylaldehyde. The synthetic method comprises the following steps: 1, taking 4-methyl pyridine as a raw material and obtaining 4-pyridine nitrogen oxide through oxidation reaction under an acidic condition; 2, synthesizing the 4-pyridine nitrogen oxide into acetic acid-4-pyridine methyl ester through acetic anhydride rearrangement; 3, hydrolyzing the acetic acid-4-pyridine methyl ester to obtain 4-pyridine methanol; 4, performing oxidation reaction on the 4-pyridine methanol to obtain the 4-pyridylaldehyde. After the synthetic method is adopted, the 4-methyl pyridine is used as the raw material, and the 4-pyridine methanol is obtained through N-oxidation, rearrangement and hydrolyzation and is further oxidized to obtain the 4-pyridylaldehyde. The synthetic method provided by the invention is high in total yield, low in raw material price, short in reaction time, mild in condition, and simple in process operation.
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Paragraph 0032; 0036; 0041; 0046
(2017/11/18)
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- METHOD FOR PRODUCING FORMYLPYRIDINE
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PROBLEM TO BE SOLVED: To provide a method for producing a formylpyridine directly from a picoline with excellent environmental harmony. SOLUTION: A formylpyridine is produced by oxidizing a picoline in a polar organic solvent, with a copper salt as a catalyst, in an atmosphere of the air under 1 atm. SELECTED DRAWING: None COPYRIGHT: (C)2018,JPOandINPIT
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Paragraph 0036; 0039; 0043
(2018/01/09)
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- Copper-catalyzed selective oxygenation of methyl and benzyl substituents in pyridine with O2
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A selective oxygenation of picolines and their derivatives has been achieved by usingasimple copper salt as a catalyst and molecular oxygen as an oxidant, where the α-position of the alkyl substituent is selectively oxidized to give the corresponding aldehydes or ketones. Addition of a catalytic amount of water enhances the catalytic activity, which could be attributed to the role of the proton donor to activate the substrates.
- Abe, Tsukasa,Tanaka, Shinji,Ogawa, Atsuko,Tamura, Masanori,Sato, Kazuhiko,Itoh, Shinobu
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supporting information
p. 348 - 350
(2017/02/23)
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