- LIQUID-PHASE CATALYTIC OXIDATION OF 2-METHOXYMETHYLTHIOPHENE
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The oxidation of 2-methoxymethylthiophene with molecular oxygen in the presence of a cobalt bromide catalyst in the kinetic region at 65-100 deg C was investigated.It is shown that the principal products are 2-formylthiophene and methylthiophene-2-carboxylate in a ratio of 1:2.The composition of the products does not depend on the oxidation temperature and changes as the starting concentration of 2-methoxymethylthiophene and the amount of cobalt bromide catalyst are changed.
- Leichenko, A. A.,Schedrinskaya, T. V.,Volkov, M. N.
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- The gas-phase elimination kinetics of ethyl 2-furoate and ethyl 2-thiophenecarboxylate
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The gas-phase elimination kinetics of ethyl 2-furoate and 2-ethyl 2-thiophenecarboxylate was carried out in a static reaction system over the temperature range of 623.15-683.15 K (350-410°C) and pressure range of 30-113 Torr. The reactions proved to be ho
- Espitia, Liliany,Meneses, Ruby,Dominguez, Rosa M.,Tosta, Maria,Herize, Armando,Lezama, Jesus,Lafont, Jennifer,Chuchani, Gabriel
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- Facile production of vitamin B3 and other heterocyclic carboxylic acids using an efficient Ag/ZnO/graphene-Si hybrid nanocatalyst
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Abstract: High yield of vitamin B3 is produced using Ag/ZnO/graphene nanocomposite (1?wt%) as a nanocatalyst after its activation by a silicon precursor such as trimethylsilyl chloride(TMSCl) or tert-butyldimethylsilyl chloride (TBSCl) under visible light. TBSCl has been proved as more efficient activating agent than TMSCl in the oxidation of heterocyclic alcohol derivatives to afford their corresponding carboxylic acids. 3-Pyridinemethanol was selected to be a model substrate to test the ability of Ag/ZnO/graphene-Si nanocatalysts. The oxidation reaction of alcohols was completed in short reaction time (30–60?min) at ambient condition to yield vitamin B3 and other heterocyclic carboxylic acids in excellent yields (86–99?%). A catalytic oxidation mechanism that is based on the generation of highly active catalytic oxidation species (oxygen radicals) has been proposed. The utility of this inexpensive and recyclable catalytic system without using molecular oxygen or any oxidants make this procedure interesting from a green chemistry point of view. Graphical Abstract: [Figure not available: see fulltext.]
- Attia, Yasser A.,Vázquez, Carlos Vázquez,Mohamed, Yasser M. A.
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- Photochemistry of diketones: Observation of a triplet state-oxygen adduct
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The presence of triplet state-oxygen adducts (a species previously proposed but never observed in a direct manner) is readily observed following laser flash photolysis studies of 2,2′-thenil. We report on the kinetic and spectroscopic parameters characteristic of this transient adduct. Copyright
- Cosa, Gonzalo,Scaiano, Juan C.
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- Kinetics of the oxidation of heterocyclic aldehydes by quinolinium dichromate
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Quinolinium dichromate in sulfuric acid oxidizes heterocyclic aldehydes (2-furaldehyde, 2-pyrrolecarbaldehyde, 2-thiophenecarbaldehyde) to the corresponding acids in a 50% (v/v) acetic acid-water medium. The kinetic data on the rates of oxidation of the substrates have been discussed with reference to the aldehyde hydration equilibria. The kinetic results support a mechanistic pathway proceeding via a rate-determining oxidative decomposition of the chromate ester of the aldehyde hydrate.
- Chaubey, Girija Shankar,Das, Simi,Mahanti, Mahendra Kumar
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- Palladium-promoted One-step Carboxylation of Aromatic Compounds with Carbon Monoxide
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The one-step carboxylation of aromatic compounds such as benzene, toluene, anisole, chlorobenzene, furan, and thiophen has been carried out using carbon monoxide and palladium acetate; the reaction does not require oxygen and is electrophilic.
- Fujiwara, Yuzo,Kawauchi, Tomio,Taniguchi, Hiroshi
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- Structure and Mechanism of Pseudomonas aeruginosa PA0254/HudA, a prFMN-Dependent Pyrrole-2-carboxylic Acid Decarboxylase Linked to Virulence
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The UbiD family of reversible (de)carboxylases depends on the recently discovered prenylated-FMN (prFMN) cofactor for activity. The model enzyme ferulic acid decarboxylase (Fdc1) decarboxylates unsaturated aliphatic acids via a reversible 1,3-cycloaddition process. Protein engineering has extended the Fdc1 substrate range to include (hetero)aromatic acids, although catalytic rates remain poor. This raises the question how efficient decarboxylation of (hetero)aromatic acids is achieved by other UbiD family members. Here, we show that the Pseudomonas aeruginosa virulence attenuation factor PA0254/HudA is a pyrrole-2-carboxylic acid decarboxylase. The crystal structure of the enzyme in the presence of the reversible inhibitor imidazole reveals a covalent prFMN-imidazole adduct is formed. Substrate screening reveals HudA and selected active site variants can accept a modest range of heteroaromatic compounds, including thiophene-2-carboxylic acid. Together with computational studies, our data suggests prFMN covalent catalysis occurs via electrophilic aromatic substitution and links HudA activity with the inhibitory effects of pyrrole-2-carboxylic acid on P. aeruginosa quorum sensing.
- Payne, Karl A. P.,Marshall, Stephen A.,Fisher, Karl,Rigby, Stephen E. J.,Cliff, Matthew J.,Spiess, Reynard,Cannas, Diego M.,Larrosa, Igor,Hay, Sam,Leys, David
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- Gram-scale synthesis of carboxylic acids via catalytic acceptorless dehydrogenative coupling of alcohols and hydroxides at an ultralow Ru loading
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Acceptorless dehydrogenative coupling (ADC) of alcohols and water/hydroxides is an emergent and graceful approach to produce carboxylic acids. Therefore, it is of high demand to develop active and practical catalysts/catalytic systems for this attractive transformation. Herein, we designed and fabricated a series of cyclometallated N-heterocyclic carbene-Ru (NHC-Ru) complexes via ligand tuning of [Ru-1], the superior complex in our previous work. Gratifyingly, gram-scale synthesis of carboxylic acids was efficiently enabled at an ultralow Ru loading (62.5 ppm) in open air. Moreover, effects of distinct ancillary NHC ligands and other parameters on this catalytic process were thoroughly studied, while further systematic studies were carried out to provide rationales for the activity trend of [Ru-1]-[Ru-7]. Finally, determination of quantitative green metrics illustrated that the present work exhibited superiority over representative literature reports. Hopefully, this study could provide valuable input for researchers who are engaging in metal-catalyzed ADC reactions.
- Chen, Cheng,Cheng, Hua,Verpoort, Francis,Wang, Zhi-Qin,Wu, Zhe,Yuan, Ye,Zheng, Zhong-Hui
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- Transformation of Thioacids into Carboxylic Acids via a Visible-Light-Promoted Atomic Substitution Process
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A visible-light-promoted atomic substitution reaction for transforming thiocacids into carboxylic acids with dimethyl sulfoxide (DMSO) as the oxygen source has been developed, affording various alkyl and aryl carboxylic acids in over 90% yields. The atomic substitution process proceeds smoothly through the photochemical reactivity of the formed hydrogen-bonding adduct between thioacids and DMSO. A DMSO-involved proton-coupled electron transfer (PCET) and the simultaneous generation of thiyl and hydroxyl radicals are proposed to be key steps for realizing the transformation.
- Fu, Qiang,Liang, Fu-Shun,Lou, Da-Wei,Pan, Gao-Feng,Wang, Rui,Wu, Min,Xie, Kai-Jun
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supporting information
p. 2020 - 2024
(2022/03/31)
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- Mechanochemical Grignard Reactions with Gaseous CO2 and Sodium Methyl Carbonate**
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A one-pot, three-step protocol for the preparation of Grignard reagents from organobromides in a ball mill and their subsequent reactions with gaseous carbon dioxide (CO2) or sodium methyl carbonate providing aryl and alkyl carboxylic acids in up to 82 % yield is reported. Noteworthy are the short reaction times and the significantly reduced solvent amounts [2.0 equiv. for liquid assisted grinding (LAG) conditions]. Unexpectedly, aryl bromides with methoxy substituents lead to symmetric ketones as major products.
- Pfennig, Victoria S.,Villella, Romina C.,Nikodemus, Julia,Bolm, Carsten
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supporting information
(2022/01/22)
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- Photoinduced FeCl3-Catalyzed Alkyl Aromatics Oxidation toward Degradation of Polystyrene at Room Temperature?
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While polystyrene is widely used in daily life as a synthetic plastic, the subsequently selective degradation is still very challenging and highly required. Herein, we disclose a highly practical and selective reaction for the catalytically efficient oxidation of alkyl aromatics (including 1°, 2°, and 3° alkyl aromatics) to carboxylic acids. While dioxygen was used as the sole terminal oxidant, this protocol was catalyzed by the inexpensive and readily available ferric compound (FeCl3) with irradiation of visible light (blue LEDs) under only 1 atmosphere of O2 at room temperature. This system could further facilitate the selective degradation of polystyrene to benzoic acid, providing an important and practical tool to generate high-value chemical from abundant polystyrene wastes.
- Zhang, Guoxiang,Zhang, Zongnan,Zeng, Rong
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supporting information
p. 3225 - 3230
(2021/09/28)
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- An efficient chromium(iii)-catalyzed aerobic oxidation of methylarenes in water for the green preparation of corresponding acids
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A highly efficient method to oxidize methylarenes to their corresponding acids with a reusable Cr catalyst was developed. The reaction can be carried out in water with 1 atm oxygen and K2S2O8as cooxidants, proceeds under green and mild conditions, and is suitable for the oxidation of both electron-deficient and electron-rich methylarenes, including heteroaryl methylarenes, even at the gram level. The excellent result, together with its simplicity of operation and the ability to continuously reuse the catalyst, makes this new methodology environmentally benign and cost-effective. The generality of this methodology gives it the potential for use on an industrial scale. Differing from the accepted oxidation mechanism of toluene, GC-MS studies and DFT calculations have revealed that the key benzyl alcohol intermediate is formed under the synergetic effect of the chromium and molybdenum in the Cr catalyst, which can be further oxidized to afford benzaldehyde and finally benzoic acid.
- Jiang, Feng,Liu, Shanshan,Wei, Yongge,Yan, Likai,Yu, Han,Zhao, Wenshu
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supporting information
p. 12413 - 12418
(2021/09/28)
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- Photo-induced deep aerobic oxidation of alkyl aromatics
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Oxidation is a major chemical process to produce oxygenated chemicals in both nature and the chemical industry. Presently, the industrial manufacture of benzoic acids and benzene polycarboxylic acids (BPCAs) is mainly based on the deep oxidation of polyalkyl benzene, which is somewhat suffering from environmental and economical disadvantage due to the formation of ozone-depleting MeBr and corrosion hazards of production equipment. In this report, photo-induced deep aerobic oxidation of (poly)alkyl benzene to benzene (poly)carboxylic acids was developed. CeCl3 was proved to be an efficient HAT (hydrogen atom transfer) catalyst in the presence of alcohol as both hydrogen and electron shuttle. Dioxygen (O2) was found as a sole terminal oxidant. In most cases, pure products were easily isolated by simple filtration, implying large-scale implementation advantages. The reaction provides an ideal protocol to produce valuable fine chemicals from naturally abundant petroleum feedstocks. [Figure not available: see fulltext.].
- Wang, Chang-Cheng,Zhang, Guo-Xiang,Zuo, Zhi-Wei,Zeng, Rong,Zhai, Dan-Dan,Liu, Feng,Shi, Zhang-Jie
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p. 1487 - 1492
(2021/07/10)
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- Hydrolysis of amides to carboxylic acids catalyzed by Nb2O5
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Hydrolysis of amides to carboxylic acids is an industrially important reaction but is challenging due to the difficulty of cleaving the resonance stabilized amidic C-N bond. Twenty-three heterogeneous and homogenous catalysts were examined in the hydrolysis of acetamide. Results showed that Nb2O5was the most effective heterogeneous catalyst with the greatest yield of acetic acid. A series of Nb2O5catalysts calcined at various temperatures were characterized and tested in the hydrolysis of acetamide to determine the effects of crystal phase and surface properties of Nb2O5on catalytic performance. The high catalytic performance observed was attributed mainly to the facile activation of the carbonyl bond by Lewis acid sites that function even in the presence of basic inhibitors (NH3and H2O). The catalytic studies showed the synthetic advantages of the present method, such as simple operation, catalyst recyclability, additive free, solvent free, and wide substrate scope (>40 examples; up to 95% isolated yield).
- Siddiki,Rashed, Md. Nurnobi,Touchy, Abeda Sultana,Jamil, Md. A. R.,Jing, Yuan,Toyao, Takashi,Maeno, Zen,Shimizu, Ken-Ichi
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p. 1949 - 1960
(2021/03/26)
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- Oxidation of Primary Alcohols and Aldehydes to Carboxylic Acids via Hydrogen Atom Transfer
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The oxidation of primary alcohols and aldehydes to the corresponding carboxylic acids is a fundamental reaction in organic synthesis. In this paper, we report a new chemoselective process for the oxidation of primary alcohols and aldehydes. This metal-free reaction features a new oxidant, an easy to handle procedure, high isolated yields, and good to excellent functional group tolerance even in the presence of vulnerable secondary alcohols and tert-butanesulfinamides.
- Tan, Wen-Yun,Lu, Yi,Zhao, Jing-Feng,Chen, Wen,Zhang, Hongbin
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supporting information
p. 6648 - 6653
(2021/09/08)
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- One-Pot Direct Oxidation of Primary Amines to Carboxylic Acids through Tandem ortho-Naphthoquinone-Catalyzed and TBHP-Promoted Oxidation Sequence
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Biomimetic oxidation of primary amines to carboxylic acids has been developed where the copper-containing amine oxidase (CuAO)-like o-NQ-catalyzed aerobic oxidation was combined with the aldehyde dehydrogenase (ALDH)-like TBHP-mediated imine oxidation protocol. Notably, the current tandem oxidation strategy provides a new mechanistic insight into the imine intermediate and the seemingly simple TBHP-mediated oxidation pathways of imines. The developed metal-free amine oxidation protocol allows the use of molecular oxygen and TBHP, safe forms of oxidant that may appeal to the industrial application.
- Kim, Hun Young,Oh, Kyungsoo,Si, Tengda
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supporting information
p. 18150 - 18155
(2021/12/09)
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- Heterogeneous Cobalt-Catalyzed C?C Bond Cleavage in Alcohols to Carbonyl Compounds
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Cobalt oxide hydrate (Co(OH)x) supported on metal oxides were prepared. The oxidative cleavage of C(OH)?C bond in alcohol was catalyzed by Co(OH)x/metal oxides using molecular oxygen as the oxidant, and the corresponding product was obtained with high selectivity. The composition and characteristics of the catalysts were analyzed by X-ray diffraction (XRD), high resolution transmission electron microscopy (HRTEM), high-angle ring dark-field scanning TEM (HAADF-STEM), N2 physico-adsorption characterization, inductively coupled plasma optical emission spectrometry (ICP-OES), Fourier transform infrared spectrum (FTIR), X-ray photoelectron spectroscopy (XPS) and NH3-temperature-programmed desorption (NH3-TPD). Additionally, a reasonable reaction mechanism was proposed based on the characterization results and a series of controlled experiments. Notably, this heterogeneous catalytic system did not require any additives and had good recycling performance.
- Teng, Jia-nan,Zhu, Rui,Li, Xinglong,Fu, Yao
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p. 4355 - 4363
(2021/09/14)
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- Merging N-Hydroxyphthalimide into Metal-Organic Frameworks for Highly Efficient and Environmentally Benign Aerobic Oxidation
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Two highly efficient metal-organic framework catalysts TJU-68-NHPI and TJU-68-NDHPI have been successfully synthesized through solvothermal reactions of which the frameworks are merged with N-hydroxyphthalimide (NHPI) units, resulting in the decoration of pore surfaces with highly active nitroxyl catalytic sites. When t-butyl nitrite (TBN) is used as co-catalyst, the as-synthesized MOFs are demonstrated to be highly efficient and recyclable catalysts for a novel three-phase heterogeneous oxidation of activated C?H bond of primary and secondary alcohols, and benzyl compounds under mild conditions. Based on the high efficiency and selectivity, an environmentally benign system with good sustainability, mild conditions, simple work-up procedure has been established for practical oxidation of a wide range of substrates.
- Wang, Man,Liang, Gan,Wang, Yunhao,Fan, Tao,Yuan, Baoling,Liu, Mingxian,Yin, Ying,Li, Liangchun
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supporting information
p. 9674 - 9685
(2021/06/09)
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- Cobalt-Catalyzed Deprotection of Allyl Carboxylic Esters Induced by Hydrogen Atom Transfer
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A brief, efficient method has been developed for the removal of the allyl protecting group from allyl carboxylic esters using a Co(II)/TBHP/(Me2SiH)2O catalytic system. This facile strategy displays excellent chemoselectivity, functional group tolerance, and high yields. This transformation probably occurs through the hydrogen atom transfer process, and a Co(III)-six-membered cyclic intermediate is recommended.
- Li, Nan,Gui, Yizhen,Chu, Mengqi,You, Mengdi,Qiu, Xiaohan,Liu, Hejia,Wang, Shiang,Deng, Meng,Ji, Baoming
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supporting information
p. 8460 - 8464
(2021/11/13)
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- 1,2-Dibutoxyethane-Promoted Oxidative Cleavage of Olefins into Carboxylic Acids Using O2 under Clean Conditions
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Herein, we report the first example of an effective and green approach for the oxidative cleavage of olefins to carboxylic acids using a 1,2-dibutoxyethane/O2 system under clean conditions. This novel oxidation system also has excellent functional-group tolerance and is applicable for large-scale synthesis. The target products were prepared in good to excellent yields by a one-pot sequential transformation without an external initiator, catalyst, and additive.
- Ou, Jinhua,Tan, Hong,He, Saiyu,Wang, Wei,Hu, Bonian,Yu, Gang,Liu, Kaijian
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p. 14974 - 14982
(2021/10/25)
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- Pd-Catalysed Decarbonylation Free Approach to Carbonylative Esterification of 5-HMF to Its Aryl Esters Synthesis Using Aryl Halides and Oxalic Acid as C1 Source
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A decarbonylation free, polystyrene-supported, Pd (Pd@PS)-catalysed carbonylative esterification of the hydroxy group of 5-hydroxymethyl furfural (5-HMF) to its corresponding aryl esters has been developed. The use of Pd@PS, oxalic acid as CO source, and aryl halides was first explored for the aryl ester of 5-HMF synthesis. Here, we investigated the vital role of a polystyrene support to avoid the commonly known decarbonylation of 5-HMF. The reaction exhibits vast substrate scope with comparably good yield and catalyst recyclability.
- Singh Chauhan, Arvind,Kumar, Ajay,Kumar Sharma, Ajay,Das, Pralay
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supporting information
p. 12971 - 12975
(2021/08/06)
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- Method for preparing organic acid by oxidative cleavage of aromatic secondary alcohol
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The invention relates to a method for preparing organic acids by oxidation of aromatic secondary alcohols. With air or oxygen as an oxygen source, a copper salt and an organic ligand as catalysts, aninorganic alkali is added, and aromatic secondary alcohols are subjected to carbon-carbon bond oxidative cracking to obtain the organic acids. The method has the advantages of high oxidation efficiency and high product yield; with the use of air or oxygen as the oxygen source, the method is economical and environmentally friendly and has good application prospects.
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Paragraph 0043-0046; 0051
(2020/09/16)
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- Light and oxygen-enabled sodium trifluoromethanesulfinate-mediated selective oxidation of C-H bonds
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Visible light-induced organic reactions are important chemical transformations in organic chemistry, and their efficiency highly depends on suitable photocatalysts. However, the commonly used photocatalysts are precious transition-metal complexes and elaborate organic dyes, which hamper large-scale production due to high cost. Here, for the first time, we report a novel strategy: light and oxygen-enabled sodium trifluoromethanesulfinate-mediated selective oxidation of C-H bonds, allowing high-value-added aromatic ketones and carboxylic acids to be easily prepared in high-to-excellent yields using readily available alkyl arenes, methyl arenes and aldehydes as materials. The mechanistic investigations showed that the treatment of inexpensive and readily available sodium trifluoromethanesulfinate with oxygen under irradiation of light could in situ form a pentacoordinate sulfide intermediate as an efficient photosensitizer. The method represents a highly efficient, economical and environmentally friendly strategy, and the light and oxygen-enabled sodium trifluoromethanesulfinate photocatalytic system represents a breakthrough in photochemistry. This journal is
- Fu, Hua,Liu, Can,Liu, Yong,Yang, Haijun,Zhu, Xianjin
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supporting information
p. 4357 - 4363
(2020/07/14)
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- 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
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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.
- Kim, Seongwoo,Lee, Ha-Eun,Suh, Jong-Min,Lim, Mi Hee,Kim, Min
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supporting information
p. 17573 - 17582
(2020/12/22)
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- Cobalt-Catalyzed Reductive Carboxylation of Aryl Bromides with Carbon Dioxide
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Cobalt-catalyzed reductive carboxylation of aryl bromides with carbon dioxide has been developed. The reaction proceeded under one atm pressure of CO2 at 40 °C in the presence of cobalt iodide/2,2′-bipyridine catalysts and zinc dust as a reducing reagent. Various aryl bromides could be converted to the corresponding carboxylic acids in good to high yields. Preliminary mechanistic experiments ruled out intervention of intermediate organozinc species for carboxylation with CO2, thus suggesting a direct CO2 insertion into the corresponding ArCoBr species. (Figure presented.).
- Hang, Wei,Yi, Yaping,Xi, Chanjuan
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supporting information
p. 2337 - 2341
(2020/04/30)
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- Cobalt-catalyzed carboxylation of aryl and vinyl chlorides with CO2
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The transition-metal-catalyzed carboxylation of aryl and vinyl chlorides with CO2 is rarely studied, and has been achieved only with a Ni catalyst or combination of palladium and photoredox. In this work, the cobalt-catalyzed carboxylation of aryl and vinyl chlorides and bromides with CO2 has been developed. These transformations proceed under mild conditions and exhibit a broad substrate scope, affording the corresponding carboxylic acids in good to high yields.
- Wang, Yanwei,Jiang, Xiaomei,Wang, Baiquan
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supporting information
p. 14416 - 14419
(2020/12/01)
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- Cp2TiCl2-Catalyzed Carboxylation of Aryl Chlorides with Carbon Dioxide in the Presence of n-BuMgCl
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Cp2TiCl2-catalyzed carboxylation of aryl chlorides with carbon dioxide to afford benzoic acids in good yields has been achieved in the presence of n-BuMgCl. The reaction proceeds by a sequential magnesium halide exchange reaction and carboxylation with CO2 in a wide variety of aryl chlorides under mild conditions.
- Hang, Wei,Yi, Yaping,Xi, Chanjuan
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supporting information
p. 1476 - 1479
(2020/01/21)
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- Highly efficient oxidation of alcohols to carboxylic acids using a polyoxometalate-supported chromium(iii) catalyst and CO2
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Direct catalytic oxidation of alcohols to carboxylic acids is very attractive, but economical catalysis systems have not yet been well established. Here, we show that a pure inorganic ligand-supported chromium compound, (NH4)3[CrMo6O18(OH)6] (simplified as CrMo6), could be used to effectively promote this type of reaction in the presence of CO2. In almost all cases, oxidation of various alcohols (aromatic and aliphatic) could be achieved under mild conditions, and the corresponding carboxylic acids can be achieved in high yield. The chromium catalyst 1 can be reused several times with little loss of activity. Mechanism study and control reactions demonstrate that the acidification proceeds via the key oxidative immediate of aldehydes.
- Han, Sheng,Wang, Ying,Wei, Yongge,Wu, Zhikang,Yu, Han
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p. 3150 - 3154
(2020/06/19)
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- A sodium trifluoromethanesulfinate-mediated photocatalytic strategy for aerobic oxidation of alcohols
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A sodium trifluoromethanesulfinate-mediated photocatalytic strategy for the aerobic oxidation of alcohols has been developed for the first time, and the photoredox aerobic oxidation of secondary and primary alcohols provided the corresponding ketones and carboxylic acids, respectively, in high to excellent yields.
- Zhu, Xianjin,Liu, Can,Liu, Yong,Yang, Haijun,Fu, Hua
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p. 12443 - 12446
(2020/10/30)
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- Exploration of New Biomass-Derived Solvents: Application to Carboxylation Reactions
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A range of hitherto unexplored biomass-derived chemicals have been evaluated as new sustainable solvents for a large variety of CO2-based carboxylation reactions. Known biomass-derived solvents (biosolvents) are also included in the study and the results are compared with commonly used solvents for the reactions. Biosolvents can be efficiently applied in a variety of carboxylation reactions, such as Cu-catalyzed carboxylation of organoboranes and organoboronates, metal-catalyzed hydrocarboxylation, borocarboxylation, and other related reactions. For many of these reactions, the use of biosolvents provides comparable or better yields than the commonly used solvents. The best biosolvents identified are the so far unexplored candidates isosorbide dimethyl ether, acetaldehyde diethyl acetal, rose oxide, and eucalyptol, alongside the known biosolvent 2-methyltetrahydrofuran. This strategy was used for the synthesis of the commercial drugs Fenoprofen and Flurbiprofen.
- Gevorgyan, Ashot,Hopmann, Kathrin H.,Bayer, Annette
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p. 2080 - 2088
(2020/02/20)
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- Transformations of N-arylpropiolamides to indoline-2,3-diones and acids via C≡C triple bond oxidative cleavage and C(sp2)–H functionalization
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A new palladium-catalyzed oxidative conversion of N-arylpropiolamides and H2O to various indoline-2,3-diones and acids through the C≡C triple bond cleavage and C(sp2)–H functionalization is described, which is promoted by a cooperative action of catalytic CuBr2, 2,2,6,6-tetramethyl-1-piperidinyloxy (TEMPO) and O2. The method provides a practical tool for transformations of alkynes by means of a C–H functionalization strategy, which enables the formation of one C–C bond and multiple C–O bonds in a single reaction with high substrates compatibility and excellent functional group tolerance.
- Zhou, Ming-Bo,Li, Yang,Ouyang, Xuan-Hui,Li, Jin-Heng
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p. 222 - 227
(2019/11/13)
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- METHOD FOR PRODUCING 3-METHYL-2-THIOPHENECARBOXYLIC ACID
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To provide a method for producing 3-methyl-2-thiophenecarboxylic acid. A method for producing 3-methyl-2-thiophenecarboxylic acid, which comprises reacting 3-methylthiophene with chlorosulfonyl isocyanate, and hydrolyzing the obtained reaction product.
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- Microwave-assisted Cannizzaro reaction—Optimisation of reaction conditions
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The microwave-assisted Cannizzaro reaction was studied in order to develop fully reproducible synthetic protocols for transformation of aldehydes to carboxylic acid and alcohols. Optimised were the following process parameters: power, temperature, and time. Aromatic, heteroaromatic and aliphatic aldehydes were used in the studies. It was found that furfural, thiophene-2-carbaldehyde, pyridinecarboxaldehyde and aromatic aldehydes react under mild conditions, while 1-methyl-pyrrole-2-carboxaldehyde derivatives and aliphatic aldehydes require more drastic reaction conditions and a longer exposure time to microwave radiation.
- Janczewski, ?ukasz,Walczak, Ma?gorzata,Fr?czyk, Justyna,Kamiński, Zbigniew J.,Kolesińska, Beata
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supporting information
p. 3290 - 3300
(2019/11/05)
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- Three step, one-pot process to prepare thiophene-2-carbonyl chloride (TCC), a key raw material in the manufacture of tioxazafen (Nemastrike)
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Nematodes are parasitic organisms that cause significant damage to crops. Tioxazafen (Nemastrike), is a proprietary seed treatment being developed by Bayer AG as a broad-spectrum nematicide. Thiophene-2-carbonyl chloride (TCC) is the key raw material in the manufacture of tioxazafen. Current manufacturing routes to TCC suffer from byproduct formation and significant waste generation, which leads to high manufacturing cost. A potentially more cost-effective process for preparing TCC from commercial thiophene has been developed. The advantages of this new chemical approach are illustrated in the processing details described in this Letter.
- Walker, Daniel P.,Graham, Charles R.,Miller, William H.,Koeller, Kevin J.
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supporting information
p. 834 - 838
(2019/02/25)
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- Organocatalyzed Aerobic Oxidation of Aldehydes to Acids
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The first example organocatalyzed aerobic oxidation of aldehydes to carboxylic acids in both organic solvent and water under mild conditions is developed. As low as 5 mol % N-hydroxyphthalimide was used as the organocatalyst, and molecular O2 was used as the sole oxidant. No transition metals or hazardous oxidants or cocatalysts were involved. A wide range of carboxylic acids bearing diverse functional groups were obtained from aldehydes, even from alcohols, in high yields.
- Dai, Peng-Fei,Qu, Jian-Ping,Kang, Yan-Biao
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supporting information
p. 1393 - 1396
(2019/02/26)
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- RhI-Catalyzed PIII-Directed C?H Bond Alkylation: Design of Multifunctional Phosphines for Carboxylation of Aryl Bromides with Carbon Dioxide
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We report the C?H alkylation of biarylphosphines at the ortho′ position(s) with alkenes by using rhodium(I) catalysis, which provides straightforward access to a large library of multifunctionalized phosphines. Some of these modified ligands outperformed commercially available phosphines in the Pd-catalyzed carboxylation of aryl bromides with carbon dioxide in the presence of a photoredox catalyst.
- Zhang, Zhuan,Roisnel, Thierry,Dixneuf, Pierre H.,Soulé, Jean-Fran?ois
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supporting information
p. 14110 - 14114
(2019/08/30)
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- Preparation of large-size, superparamagnetic, and highly magnetic Fe3O4@PDA core-shell submicrosphere-supported nano-palladium catalyst and its application to aldehyde preparation through oxidative dehydrogenation of benzyl alcohols
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Large-size, superparamagnetic, and highly magnetic Fe3O4@PDA core-shell submicrospheresupported nano-palladium catalysts were prepared in this study. Dopamine was encapsulated on the surface of Fe3O4 particles via self-polymerization and then protonated to positively charge the microspheres. PdCl42- was dispersed on the surface of the microspheres by positive and negative charge attraction and then reduced to nano-palladium. With air as oxidant, the catalyst can successfully catalyze the dehydrogenation of benzyl alcohols to produce the corresponding aldehydes at 120 °C.
- Guo, Haichang,Zheng, Renhua,Jiang, Huajiang,Xu, Zhenyuan,Xia, Aibao
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- Table salt as a catalyst for the oxidation of aromatic alcohols and amines to acids and imines in aqueous medium: Effectively carrying out oxidation reactions in sea water
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A simple, efficient, sustainable and economical method for the oxidation of alcohols and amines has been developed based on chloride, a sea abundant anionic catalyst for the practical synthesis of a wide range of carboxylic acids, ketones and imines. Oxidation of aromatic alcohols was carried out using NaCl (20 mol%) as the catalyst, NaOH (50 mol%) and aq. TBHP (4 equiv.) as the oxidant in 55-92% isolated yields. Oxidation of aromatic amines to imines was achieved by using only 20 mol% of NaCl and aq. TBHP (4 equiv.) in 32-93% isolated yields. The chlorine species formed during the reaction as the active oxidation catalyst has been identified as ClO2- for alcohols and ClO-/ClO2- for amines by control experiments. This method is mostly free from chromatographic purification, which makes it suitable for large-scale synthesis. We have scaled up to 30 gram scale the synthesis of carboxylic acids and imines in good yields and have also carried out efficiently this new method using filtered sea water as the solvent and catalyst.
- Hazra, Susanta,Kushawaha, Ajay Kishor,Yadav, Deepak,Dolui, Pritam,Deb, Mayukh,Elias, Anil J.
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supporting information
p. 1929 - 1934
(2019/04/29)
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- Silver-catalyzed decarboxylative homocoupling reaction for the construction of tetrafluoroethylene-bridging aromatic compounds
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The Ag(I)-catalyzed decarboxylative homocoupling from the difluoroacetate has been developed to the synthesis of symmetric CF2–CF2 containing dimers. This radical dimerization overpasses the prefunctionalization of the substrate and provides a direct and efficient method for construction of tetrafluoroethylene bridge-linked homodimers.
- Wang, Yong,Zhao, Huaxin,Xie, Xiaojuan,Jiang, Haizhen,Deng, Hongmei,Hao, Jian,Wan, Wen
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supporting information
p. 2961 - 2970
(2019/08/22)
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- Picolinamide Assisted Oxidation of CH2 Groups Bound to Organic and Organometallic Compounds Using Ferrocene as a Catalyst
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Picolinamide group assisted sp3 C-H bond oxidation of methylene groups to the corresponding carbonyl compounds has been achieved by using simple bottle ferrocene as catalyst and Cu(OAc)2 or tert-butyl peroxybenzoate (TBPB) as oxidant under mild conditions. This method is applicable for picolinamide bound organic as well as organometallic compounds with yields in the range of 46-82%. Control experiments and mechanistic studies indicate that a radical mechanism is responsible for these oxidative transformations in which ferrocene acts as a catalyst.
- Dolui, Pritam,Hazra, Susanta,Deb, Mayukh,Elias, Anil J.
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p. 2015 - 2021
(2019/05/16)
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- Metal-Free Aerobic Oxidative Selective C-C Bond Cleavage in Heteroaryl-Containing Primary and Secondary Alcohols
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A transition-metal-free aerobic oxidative selective C-C bond-cleavage reaction in primary and secondary heteroaryl alcohols is reported. This reaction was highly efficient and tolerated various heteroaryl alcohols, generating a carboxylic acid derivative and a neutral heteroaromatic compound. Experimental studies combined with density functional theory calculations revealed the mechanism underlying the selective C-C bond cleavage. This strategy also provides an alternative simple approach to carboxylation reaction.
- Xia, Anjie,Qi, Xueyu,Mao, Xin,Wu, Xiaoai,Yang, Xin,Zhang, Rong,Xiang, Zhiyu,Lian, Zhong,Chen, Yingchun,Yang, Shengyong
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supporting information
(2019/05/07)
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- Copper Catalyzed Oxidative C-C Bond Cleavage of 1,2-Diketones: A Divergent Approach to 1,8-Naphthalimides, Biphenyl-2,2′-dicarboxamides, and N-Heterocyclic Amides
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We report here a simple and efficient copper catalyzed oxidative C-C bond cleavage of stable aromatic cyclic-fused and acyclic 1,2-diketones to deliver amides and imides in high yields. This newly developed protocol provides an excellent tool to transform structurally different 1,2-diketones into different products under the same reaction conditions. The key synthetic features of this methodology are the formation of 1,8-naphthalimides and biphenyl-2,2′-dicarboxamide motifs in high yields. The fluorescent studies of 1,8-naphthalimide derivatives were also carried out in order to show the potential application of these scaffolds.
- Sakhare, Priyanka R.,Subramanian, Parthasarathi,Kaliappan, Krishna P.
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p. 2112 - 2125
(2019/02/14)
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- Efficient and Recyclable RuCl3 ? 3H2O Catalyst Modified with Ionic Diphosphine for the Alkoxycarbonylation of Aryl Halides
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A series of ionic (mono-/di-)phosphines (L2, L4, and L6) with structural similarity and their corresponding neutral counterparts (L1, L3, and L5) were applied to modulate the catalytic performance of RuCl3 ? 3H2O. With the involvement of the ionic diphosphine (L4), in which the two phosphino-fragments were linked by butylene group, RuCl3 ? 3H2O with advantages of low cost, robustness, and good availability was found to be an efficient and recyclable catalyst for the alkoxycarbonylation of aryl halides. The L4-based RuCl3 ? 3H2O system corresponded to the best conversion of PhI (96 %) along with 99 % selectivity to the target product of methyl benzoate as well as the good generality to alkoxycarbonylation of different aryl halides (ArX, X=I and Br) with alcohols MeOH, EtOH, i-PrOH and n-BuOH. The electronic and steric effects of the applied phosphines, which were analyzed by the 31P NMR for 1J31P-77Se1J measurement and single-crystal X-ray diffraction, were carefully co-related to the performance RuCl3 ? 3H2O catalyst. In addition, the L4-based RuCl3 ? 3H2O system could be recycled successfully for at least eight runs in the ionic liquid [Bmim]PF6.
- Zhou, Qing,Liu, Lei,Guo, Wen-Di,Liang, Wen-Yu,Lu, Yong,Liu, Ye
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p. 166 - 172
(2019/02/01)
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- Solvent-free mechanochemical oxidation and reduction of biomass-derived 5-hydroxymethyl furfural
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The simultaneous synthesis of 5-hydroxymethyl-2-furoic acid and 2,5-hydroxymethylfuran from biomass-derived 5-hydroxymethyl furan was developed using a solvent-free mechanochemical approach. The results obtained for the Cannizzaro disproportionation reaction show quantitative conversions of the starting materials with reaction times of only 5 min. Employing solvent-free conditions allows for a more sustainable synthetic approach that is reflected in an Efactor 7 times smaller than that in previous reports. Additionally, initial results of the use of a sacrificial reagent, with the same solvent-free mechanochemical approach, for the selective reduction and oxidation of HMF are presented.
- Chacón-Huete,Messina,Chen,Cuccia,Ottenwaelder,Forgione
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p. 5261 - 5265
(2018/12/05)
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- Preparation method of thiophene carboxyl-substituted derivative
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The invention provides a preparation method of a thiophene carboxyl-substituted derivative. The preparation method comprises that glyoxal and a compound A undergo a cyclization reaction to produce a 2, 2'-thiophene diester compound, and the 2, 2'-thiophene diester compound undergoes a hydrolysis reaction to produce 2-thiophenecarboxylic acid or 2, 2'-thiophene dicarboxylic acid. The preparation method has simple processes. Compared with the existing complex production method used under harsh production conditions, the one-pot method can realize the synthesis of a desired product. Compared withthe existing multiple-step synthesis method, the one-pot method improves a yield by at least 50%. Through optimizing the production processes and the synthesis route, the method has few side reactions in production, is free of a selective reaction, produces less impurities, is easy to post-process, needs mild production conditions and is suitable for an industrial production mode .
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Paragraph 0080; 0082; 0085
(2018/05/07)
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- Method for preparing 2-thiophenecarboxylic acid
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The invention provides a method for preparing 2-thiophenecarboxylic acid. The method comprises that thiophene and a compound A undergo a reaction to produce a 2-thiophene ester and the 2-thiophene ester is hydrolyzed into 2-thiophenecarboxylic acid. The method is simple. Compared with the prior art with a complicated production method and harsh production conditions, the method using a one-pot method can realize the synthesis of the target product. Compared with the existing multi-step synthesis process, the method improves a yield by at least 50%. The method optimizes the production process and the synthesis route. In the production process, side reactions are few, a selective reaction is avoided, impurities are few, post-treatment is convenient, production conditions are mild and methodis suitable for an industrialized production mode.
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Paragraph 0046-0050
(2018/05/07)
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- An Efficient Aerobic Oxidation Protocol of Aldehydes to Carboxylic Acids in Water Catalyzed by an Inorganic-Ligand-Supported Copper Catalyst
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A method for the aerobic oxidation of aldehydes to carboxylic acids in water by using an inorganic-ligand-supported copper catalyst was developed. This method was performed with the use of atmospheric oxygen as the sole oxidant under extremely mild aqueous conditions, and furthermore, a wide range of aldehydes with various functional groups were tolerated. The copper catalyst could be recycled and used in successive reactions at least six times without any appreciable degradation in performance. This method is operationally simple and avoids the use of high-costing, toxic, air/moisture-sensitive, and commercially unavailable organic ligands. The generality of this method gives it potential to be used on the industrial scale.
- Yu, Han,Ru, Shi,Zhai, Yongyan,Dai, Guoyong,Han, Sheng,Wei, Yongge
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p. 1253 - 1257
(2018/02/16)
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- A Highly Efficient NHC-Catalyzed Aerobic Oxidation of Aldehydes to Carboxylic Acids
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An N-heterocyclic carbene (NHC) organocatalytic aerobic oxidation of aldehydes to the corresponding carboxylic acids is explored. Remarkably, this method allows for efficient conversion of different classes of aldehydes including highly challenging electron-rich aryl aldehydes, ortho -substituted aryl aldehydes, various heteroaromatic aldehydes and α,β-unsaturated aldehydes under mild reaction conditions. These substrates, under previously reported NHC-catalyzed methods, are typically unreactive or give poor yields, require high reaction temperatures and reaction times of several days.
- Khatana, Anil Kumar,Singh, Vikram,Gupta, Manoj Kumar,Tiwari, Bhoopendra
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p. 4290 - 4294
(2018/11/23)
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- Effect of alkyl chain and linking units on mesophase transitions and molecular order of rod-like thiophene mesogens: 13C NMR investigation
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Thermotropic liquid crystals with π-conjugated cores are increasingly witnessed due to their promising optoelectronic and optophotonic properties. As π-conjugated mesogens are often realized by direct linking of the rings of the core, the mesophase transitions are usually modulated by inserting the required alkyl/alkoxy chains either at a terminal or lateral location. In this work, five mesogens in which thiophene and two phenyl rings are common in the core unit with terminal alkyl/alkoxy chains are investigated to probe the influence of (a) a terminal alkyl chain on the mesophase characteristics, (b) the linking units on the mesophase range and (c) the disparity of thiophene orientational constraints. The mesophase properties reveal that whenever the alkyl chain is located at one end of the molecule, polymesomorphism is observed. The XRD studies reveal layer ordering typical of smectic mesophases with lower temperature and higher order phases, namely SmB and CrE phases. A detailed 13C NMR study of the mesogens in the liquid crystalline phase indicates that the order parameters are governed by the nature of the substitution of thiophene and its linkage with two phenyl rings. Importantly, the 13C NMR data of the terminal chains in the liquid crystalline phase are compared with the recently reported thiophene mesogen in which the n-hexyl chain is located at the lateral position and completely different orientation characteristics were found for the terminal versus lateral chains.
- Santhosh Kumar Reddy,Lobo, Nitin P.,Narasimhaswamy
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supporting information
p. 598 - 612
(2017/12/28)
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- A biocatalytic method for the chemoselective aerobic oxidation of aldehydes to carboxylic acids
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Herein, we present a study on the oxidation of aldehydes to carboxylic acids using three recombinant aldehyde dehydrogenases (ALDHs). The ALDHs were used in purified form with a nicotinamide oxidase (NOx), which recycles the catalytic NAD+ at the expense of dioxygen (air at atmospheric pressure). The reaction was studied also with lyophilised whole cell as well as resting cell biocatalysts for more convenient practical application. The optimised biocatalytic oxidation runs in phosphate buffer at pH 8.5 and at 40 °C. From a set of sixty-one aliphatic, aryl-Aliphatic, benzylic, hetero-Aromatic and bicyclic aldehydes, fifty were converted with elevated yield (up to >99%). The exceptions were a few ortho-substituted benzaldehydes, bicyclic heteroaromatic aldehydes and 2-phenylpropanal. In all cases, the expected carboxylic acid was shown to be the only product (>99% chemoselectivity). Other oxidisable functionalities within the same molecule (e.g. hydroxyl, alkene, and heteroaromatic nitrogen or sulphur atoms) remained untouched. The reaction was scaled for the oxidation of 5-(hydroxymethyl)furfural (2 g), a bio-based starting material, to afford 5-(hydroxymethyl)furoic acid in 61% isolated yield. The new biocatalytic method avoids the use of toxic or unsafe oxidants, strong acids or bases, or undesired solvents. It shows applicability across a wide range of substrates, and retains perfect chemoselectivity. Alternative oxidisable groups were not converted, and other classical side-reactions (e.g. halogenation of unsaturated functionalities, Dakin-Type oxidation) did not occur. In comparison to other established enzymatic methods such as the use of oxidases (where the concomitant oxidation of alcohols and aldehydes is common), ALDHs offer greatly improved selectivity.
- Knaus, Tanja,Tseliou, Vasilis,Humphreys, Luke D.,Scrutton, Nigel S.,Mutti, Francesco G.
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supporting information
p. 3931 - 3943
(2018/09/11)
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- A mild method for synthesizing carboxylic acids by oxidation of aldoximes using hypervalent iodine reagents
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A mild oxidation method for the conversion of aldoximes to carboxylic acids was developed mediated by hypervalent iodine reagents. This method covers a wide range of functionalized aldoximes and proceeds under mild conditions, utilizing PhI(OH)OTs as an oxidant.
- Nakamura, Akira,Kanou, Hodaka,Tanaka, Junki,Imamiya, Akira,Maegawa, Tomohiro,Miki, Yasuyoshi
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supporting information
p. 541 - 544
(2018/02/07)
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- Bis(methoxypropyl) ether-promoted oxidation of aromatic alcohols into aromatic carboxylic acids and aromatic ketones with O2 under metal- and base-free conditions
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We describe an eco-friendly, practical and operationally simple procedure for the bis(methoxypropyl) ether-promoted oxidation of aromatic alcohols into aromatic carboxylic acids and aromatic ketones with atmospheric dioxygen as the sole oxidant. This chemical process is clean with high conversion and good selectivity, and an external initiator, catalyst, additive and base are not required. The virtue of this reaction is highlighted by its easily available and economical raw materials and excellent functional group tolerance (acid-, base- and oxidant-labile groups).
- Liu, Kai-Jian,Jiang, Si,Lu, Ling-Hui,Tang, Ling-Li,Tang, Shan-Shan,Tang, Hai-Shan,Tang, Zilong,He, Wei-Min,Xu, Xinhua
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supporting information
p. 3038 - 3043
(2018/07/13)
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- Method for preparing 2-thiophenecarboxylic acid
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The invention provides a method for preparing 2-thiophenecarboxylic acid. The method comprises that 1, 3-malonaldehyde and a compound A undergo a ring-closure reaction to produce a 2-thiophene ester compound and the 2-thiophene ester compound is hydrolyzed into 2-thiophenecarboxylic acid. The method is simple. Compared with the prior art with a complicated production method and harsh production conditions, the method using a one-pot method can realize the synthesis of the target product. Compared with the existing multi-step synthesis process, the method improves a yield by at least 50%. The method optimizes the production process and the synthesis route. In the production process, side reactions are few, a selective reaction is avoided, impurities are few, post-treatment is convenient, production conditions are mild and method is suitable for an industrialized production mode.
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Paragraph 0061-0066
(2018/05/07)
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- Catalytic oxidation synthesis method of aryl formic acid
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The invention discloses a catalytic oxidation synthesis method of aryl formic acid. According to the method, aryl alkyl ketone is used as a reaction substrate, iodine is used as a catalyst, and dimethyl sulfoxide (DMSO) is taken as an oxidizing agent; the method comprises the steps of adding the reaction substrate into chlorobenzene, and carrying out a reaction for 2-4h at the temperature of 110-135 DEG C; after that, cooling reaction liquid to the room temperature, adding another oxidizing agent, i.e., t-butylhydroperoxide (TBHP), continuously carrying out a reaction at the temperature of 110-135 DEG C, and separating after the reaction is finished so as to obtain the aryl formic acid. The method provided by the invention avoids the use of a transition metal catalyst, thus reducing the consumption of toxic and harmful additives; the reaction substrate is wide in application scope.
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Paragraph 0092; 0093
(2018/07/30)
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- I2/Fe(NO3)3·9H2O-catalyzed oxidative synthesis of aryl carboxylic acids from aryl alkyl ketones and secondary benzylic alcohols
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An interesting and convenient procedure for the oxidative transformation of aryl alkyl ketones and secondary benzylic alcohols to aryl carboxylic acids has been developed. By using iodine and Fe(NO3)3·9H2O as the catalysts, DMSO and oxygen as the oxidants, the desired aryl carboxylic acids were synthesized in moderate to excellent yields (up to 91%).
- Xu, Liang,Chen, Yingying,Shen, Zhenlu,Wang, Yuru,Li, Meichao
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supporting information
p. 4349 - 4354
(2018/11/03)
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- Method for preparing aryl formic acid by adopting aryl alkyl ketone as raw material
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The invention discloses a method for preparing aryl formic acid by adopting aryl alkyl ketone as a raw material. The method is characterized in that: aryl alkyl ketone is used as a reaction substrate,iodine and Fe(NO3)3.9H2O are used catalysts to react for 8 to 16 hours in dimethyl sulfoxide at the temperature 110 to 140 DEG C in an oxygen atmosphere of one barometric pressure, and after the reaction is ended, the reactant is separated to obtain the aryl formic acid. According to the synthetic method of the invention, the environment-friendly iron catalyst is used; the environment-friendly green oxidant oxygen is used; the reaction is performed at the normal pressure, and no pressurizing device is needed; and the application range of the reaction substrate is wide.
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Paragraph 0089; 0090
(2019/01/08)
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