cas 552-16-9, 2-Nitrobenzoic acid | Articles data

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Direct C–H Carboxylation Forming Polyfunctionalized Aromatic Carboxylic Acids by Combined Br?nsted Bases
CO2 fixation into electron-deficient aromatic C–H bonds proceeds with the combined Br?nsted bases LiO-t-Bu and LiO-t-Am/CsF/18-crown-6 (t-Am = CEtMe2) under a CO2 atmosphere to afford a variety of polyfunctionalized aromat
Hanasaka, Kazuya,Izumi, Koki,Kondo, Yoshinori,Kwon, Eunsang,Nozawa-Kumada, Kanako,Shigeno, Masanori,Tohara, Itsuki,Yamakoshi, Hiroyuki
supporting information
p. 809 - 814
(2022/02/05)

Continuous production method of benzoic acid derivative
The invention relates to the technical field of preparation of benzoic acid derivatives. The invention particularly relates to a continuous production method of a benzoic acid derivative. The continuous reaction device is characterized by comprising a small-diameter sleeve, wherein the small-diameter sleeve is sleeved with a large-diameter sleeve, and a small pipeline is arranged between the small-diameter sleeve and the large-diameter sleeve, and a plurality of small holes are arranged on the small pipeline. The small-diameter casing is rotated, the large-diameter casing is fixed, and the reaction liquid composed of the nitric acid and the toluene derivative is between a small-diameter casing pipe and a large-diameter casing pipe.
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Paragraph 0032-0034

(2021/11/14)

Bimetallic oxide nanoparticles confined in ZIF-67-derived carbon for highly selective oxidation of saturated C–H bond in alkyl arenes
Zeolite imidazolate frameworks (ZIFs) have recently emerged as an ideal type of carbon precursors with abundant tailorability. In this work, a series of ZIF-derived porous carbon catalysts have been prepared with encapsulation of bimetallic oxide nanoparticles via simple thermal treatment. The composition and structure of these catalysts were confirmed in detail by different characterization methods. The bimetallic oxide (Mn/Co, Fe/Co, and Cu/Co) nanoparticles were encapsulated in the nitrogen-doped graphitized carbon matrix. Moreover, the hierarchically porous structure and carbon defects were successfully constructed in the carbon catalysts. Additionally, in the selective oxidation of saturated C–H bonds in alkyl arenes, the carbon catalysts demonstrate outstanding performance for the oxidation of C–H bonds to corresponding carboxyl groups. This was due to their unique structure can greatly promote mass transfer and molecular oxygen activation, resulting in high conversion and high selectivity. Remarkably, this work here could also provide a novel strategy to the controllable synthesis of metal–organic frameworks (MOFs)-derived carbon catalysts for enhanced performance in heterogeneous catalysis.
Huang, Cheng,Su, Xiaoyan,Gu, Xiangyu,Liu, Rui,Zhu, Hongjun
(2020/10/15)

Acetyl nitrate mediated conversion of methyl ketones to diverse carboxylic acid derivatives
The development of a novel acetyl nitrate mediated oxidative conversion of methyl ketones to carboxylic acid derivatives is described. By analogy to the haloform reaction and supported by experimental and computational investigation we propose a mechanism for this transformation.
Bernard, Josephine,Capilato, Joseph N.,Hoy, Erik P.,Mattiucci, Joseph,Pellegrinelli, Peter J.,Perez, Lark J.,Philippi, Shane,Schnorbus, Logan
p. 5298 - 5302
(2021/06/30)

Nitration of deactivated aromatic compounds via mechanochemical reaction
A variety of deactivated arenes were nitrated to their corresponding nitro derivatives in excellent yields under high-speed ball milling condition using Fe(NO3)3·9H2O/P2O5 as nitrating reagent. A radical involved mechanism was proposed for this facial, eco-friendly, safe, and effective nitration reaction.
Wu, Jian-Wei,Zhang, Pu,Guo, Zhi-Xin
supporting information

(2021/05/05)

Light-induced carboxylation of aryl derivatives with cooperative COF as an active photocatalyst and Ni(ii) co-catalyst
The photocatalytic carboxylation of aryl derivatives was demonstrated under CO2at atmospheric pressure using a mesoporous covalent organic framework (COF) as the active photocatalyst with triethylamine (TEA) as a sacrificial electron source under visible light. A yield of greater than 91% of the isolated product was achieved with 5 mg of catalyst. The reaction cycle is dependent on the use of the Ni(dmg)2co-catalyst and the sacrificial electron donor (TEA). The reaction does not occur in the absence of light (445 nm) even at elevated reaction temperature. We have also demonstrated that a yield of 32% of the isolated product could be obtained with the use of sunlight in the catalytic cycle. Additionally, this heterogeneous catalytic system was recyclable and reusable for several cycles.
Chakrabortty, Pekham,Das, Anjan,Chowdhury, Arpita Hazra,Ghosh, Swarbhanu,Khan, Aslam,Islam, Sk. Manirul
p. 4738 - 4745
(2021/03/22)

Efficiency of lithium cations in hydrolysis reactions of esters in aqueous tetrahydrofuran
Lithium cations were observed to accelerate the hydrolysis of esters with hydroxides (KOH, NaOH, LiOH) in a water/tetrahydrofuran (THF) two-phase system. Yields in the hydrolysis of substituted benzoates and aliphatic esters using the various hydroxides were compared, and the effects of the addition of lithium salt were examined. Moreover, it was presumed that a certain amount of LiOH was dissolved in THF by the coordination of THF with lithium cation and hydrolyzed esters even in the THF layer, as in the reaction by a phase-transfer catalyst.
Harada, Yumi,Hayashi, Kazuhiko,Ichimaru, Yoshimi,Imai, Masanori,Kojima, Yuki,Maeda, Azusa,Nakayama, Kanae,Sugiura, Kirara
p. 581 - 594
(2021/06/06)

Reactivity of secondary N-alkyl acrylamides in Morita–Baylis–Hillman reactions
The Morita–Baylis–Hillman (MBH) reaction of secondary N-alkyl acrylamides, discarded up to now from investigations of the scope of activated alkenes, was studied. Optimization of the reaction conditions revealed that a balance must be found between activation of the MBH coupling reaction and that of the undesired competitive aldehyde Cannizzaro reaction. Using 3-Hydroxyquinuclidine (3-HQD) in a 1:1 water-2-MeTHF mixture provides the appropriate conditions that were applicable to a wide range of diversely substituted secondary N-alkyl acrylamides and aromatic aldehydes, giving rise to novel amide-containing MBH adducts under mild and clean conditions.
Ahmar, Mohammed,Queneau, Yves,Verrier, Charlie,Yue, Xiaoyang
p. 319 - 330
(2021/10/29)

A tunable synthesis of either benzaldehyde or benzoic acid through blue-violet LED irradiation using TBATB
In this paper, a highly efficient, metal-free, and homogeneous method for the selective aerobic photooxidation of alcohols and photooxidative-desilylation of tert-butyldimethylsilyl ethers (TBDMS) in the presence of tetrabutylammonium tribromide (TBATB) under irradiation of visible light was reported. The light source: blue (460 nm) and violet (400 nm) LED, can control selective oxidation to aldehyde or carboxylic acid.
Mardani, Atefeh,Heshami, Marouf,Shariati, Yadollah,Kazemi, Foad,Abdollahi Kakroudi, Mazaher,Kaboudin, Babak
(2019/11/29)

Pd(II) porphyrins: Synthesis, singlet oxygen generation and photoassisted oxidation of aldehydes to carboxilic acids
The synthesis and spectral studies of A3B and A2B2 type porphyrins and their Pd(II) complexes are reported. The meso-positions on porphyrin macrocycle are substituted with pentafluorophenyl and N-butylcarbazole or triphenylamine groups. Pd(II) porphyrins displayed decent phosphorescence ～670 nm and are able to produce singlet oxygen by type II pathway, after photoirradiation. The calculated singlet oxygen quantum yields for Pd(II) porphyrins are (ΦΔ = 30%–63%). The catalytic application of Pd(II) porphyrins towards photoassisted aerobic oxidation of aromatic aldehydes to carboxylic acids is demonstrated.
Pandey, Vijayalakshmi,Jain, Drishti,Pareek, Nitesh,Gupta, Iti
(2020/01/08)

Method for directly oxidizing benzylic C-H bond to ketone or acid
The invention discloses a method for directly oxidizing benzylic C-H bonds into ketone or acid. A target product is obtained through an oxidation reaction with a compound containing benzylic C-H bondsas a substrate, trichloroisocyanuric acid as an oxidizing agent and sodium bromide and tetramethyl piperidine nitrogen oxide as catalysts. The oxidizing agent and the catalysts are cheap and easy toobtain, transport and store; the oxidative catalysis effect is good; the reaction condition is mild, the requirement and effect of harsh reaction conditions on equipment are avoided, and the method issuitable for industrial mass production. The use of a large quantity of heavy metal salts is avoided, and environmental pollution is further avoided.
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Paragraph 0026-0029

(2020/12/14)

Conversions of aryl carboxylic acids into aryl nitriles using multiple types of Cu-mediated decarboxylative cyanation under aerobic conditions
Here, we used malononitrile or AMBN as a cyanating agent to develop efficient and practical protocols for Cu-mediated decarboxylative cyanations, under aerobic conditions, of aryl carboxylic acids bearing nitro and methoxyl substituents at the ortho position as well as of heteroaromatic carboxylic acids. These protocols involved economical methods to synthesize value-added aryl nitriles from simple and inexpensive raw materials. Further diversification of the 2-nitrobenzonitrile product was performed to highlight the practicality of the protocols. This journal is
Cai, Hu,Cao, Xihan,Fu, Zhengjiang,Guo, Shengmei,Wang, Shuiliang
supporting information
p. 8381 - 8385
(2020/11/05)

Divergent Syntheses of Indoles and Quinolines Involving N1-C2-C3 Bond Formation through Two Distinct Pd Catalyses
Pd-catalyzed annulative couplings of 2-alkenylanilines with aldehydes using alcohols as both the solvent and hydrogen source have been developed. These domino processes allow divergent syntheses of two significant N-heterocycles, indoles and quinolines, from the same substrate by tuning reaction parameters, which seems to invoke two distinct mechanisms. The nature of the ligand and alcoholic solvent had a profound influence on the selectivity and efficiency of these protocols. Particularly noteworthy is that indole formation was achieved by overcoming two significant challenges, regioselective hydropalladation of alkenes and subsequent reactions between the resulting Csp3-Pd species and less reactive imines.
San Jang, Su,Kim, Young Ho,Youn, So Won
supporting information
p. 9151 - 9157
(2020/11/03)

Solid state aldol reactions of solvated and unsolvated lithium pinacolone enolate aggregates
We reported the first systematic study of the solid-state aldol reactions of solvated and unsolvated lithium pinacolone enolate with a variety of solid aromatic aldehydes utilizing a mortar and pestle condition in comparison with the simple ball milling condition or tetrahydrofuran (THF) solution condition. In solution, the reactions are highly-selective with the aldol condensation product at room temperature. Under the condition of mortar and pestle, the reactions with unsolvated lithium pinacolone enolate showed the mixture of aldol condensation product and aldol addition product at room temperature. With the usage of solvated lithium pinacolone enolate, higher yields for most substrates were obtained. Furthermore, repeating the reactions under a simple ball billing condition with no other precautions at room temperature, we achieved high selectivity and yield of products for all substrates, indicating the powerful ability and the utility of solid-state, mechanochemical aldol reaction conditions.
Pang, Huan,Williard, Paul G.
(2020/01/13)

Studies on Iron-Catalyzed Aerobic Oxidation of Benzylic Alcohols to Carboxylic Acids
A comprehensive study on aerobic oxidation of benzylic alcohols to carboxylic acids with a catalytic amount each of Fe(NO 3) 3 ·9H 2 O, TEMPO, and KCl is conducted. Various synthetically useful functional groups are well tolerated in the reaction. Distinct electronic and steric effects are observed in the reaction: electron-withdrawing groups accelerate the reaction while electron-donating groups make the reaction slower, and ortho -substituted substrates react slower than meta -substituted substrates. Several large-scale reactions (100 mmol) are conducted using a slow air flow of 30 mL/min to demonstrate the practicality of this method in an academic laboratory.
Jiang, Xingguo,Ma, Shengming
p. 1629 - 1639
(2018/02/26)

Metal-Free Aerobic Oxidation of Nitro-Substituted Alkylarenes to Carboxylic Acids or Benzyl Alcohols Promoted by NaOH
Efficient and selective aerobic oxidation of nitro-substituted alkylarenes to functional compounds is a fundamental process that remains a challenge. Here, we report a metal-free, efficient, and practical approach for the direct and selective aerobic oxidation of nitro-substituted alkylarenes to carboxylic acids or benzyl alcohols. This sustainable system uses O2 as clean oxidant in a cheap and green NaOH/EtOH mixture. The position and type of substituent critically affect the products. In addition, this sustainable protocol enabled gram-scale preparation of carboxylic acid and benzyl alcohol derivatives with high chemoselectivities. Finally, the reactions can be conducted in a pressure reactor, which can conserve oxygen and prevent solvent loss. The approach was conducive to environmental protection and potential industrial application.
Fang, Kun,Li, Guijie,She, Yuanbin
p. 8092 - 8103
(2018/06/25)

Method for preparing 2-amino-4'-fluorobenzophenone
The invention discloses a method for preparing 2-amino-4'-fluorobenzophenone. The method comprises the following steps: o-nitrotoluene, trichloroisocyanuric acid, tetramethylpiperidine nitrogen oxideand sodium bromide undergo an oxidation reaction to obtain o-nitrobenzoic acid; the o-nitrobenzoic acid and trichloromethyl carbonate undergo an acylating chlorination to obtain o-nitrobenzoyl chloride; the o-nitrobenzoyl chloride, fluorobenzene and aluminum trichloride undergo a Friedel-Crafts reaction to obtain 2-nitro-4'-fluorobenzophenone; and the 2-nitro-4'-fluorobenzophenone is reduced by hydrogen to the 2-amino-4'-fluorobenzophenone. The method has the advantages of green and environmentally-friendly synthesis route, cheap and easily available initial raw materials, low cost, convenience in operation, suitableness for industrial production, and high yield, and the prepared 2-amino-4'-fluorobenzophenone has a good purity.
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Paragraph 0050; 0056; 0062; 0068; 0072-0074

(2018/03/26)

Method for preparing o-nitrobenzoic acid through oxygen oxidation of ortho-nitrotoluene in absence of catalyst
The invention discloses a method for preparing o-nitrobenzoic acid through oxygen oxidation of ortho-nitrotoluene in absence of a catalyst and relates to a preparation method of o-nitrobenzoic acid. The method comprises the following steps: under a condition that any catalyst is not added, by taking ortho-nitrotoluene as a raw material, taking oxygen as an oxidizing agent and taking sodium hydroxide as base, reacting in alcohol or an aqueous solution thereof at a reaction temperature of 25-85 DEG C for 5-72 hours; and performing after-treatment, separating and purifying, thereby obtaining theo-nitrobenzoic acid. According to the method, any catalyst is not needed; the price of the raw material and solvent is low; the reaction temperature is moderate; and the product is easy for productioncontrol, has the yield of 90% or higher, is suitable for large-scale preparation and industrialization and has wide application prospects.
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Paragraph 0021-0044

(2018/07/30)

The Cu(I)- and HNO3-catalyzed oxidation of substituted toluenes to the benzoic acid based on NOx recycling
Based on the recycling of NOx, the Cu(I)- and HNO3-catalyzed oxidation of 2-chloro-4-(methylsulfonyl)toluene to 2-chloro-4-(methylsulfonyl)benzoic acid has been developed with an excellent yield of 84.2% and a purity of 99.7%. The optimized reaction conditions (160?°C, oxygen pressure 1.5?MPa, HNO3 concentration 25?wt%, HNO3: substrate 0.5:1) use 1.0?mol% CuI as catalyst. The dosage of HNO3 in the new process is only 25% of the stoichiometric amount and 12.5% of the amount of the traditional process. The NOx emission is 5% amount of the traditional process. The oxidation of several additional toluene derivatives with comparable yields demonstrates the generality to these reaction conditions.
Wei, Mengyi,Qian, Chao,Chen, Xinzhi
p. 51 - 56
(2018/01/17)

Continuous Platform to Generate Nitroalkanes On-Demand (in Situ) Using Peracetic Acid-Mediated Oxidation in a PFA Pipes-in-Series Reactor
The synthetic utility of the aza-Henry reaction can be diminished on scale by potential hazards associated with the use of peracid to prepare nitroalkane substrates and the nitroalkanes themselves. In response, a continuous and scalable chemistry platform to prepare aliphatic nitroalkanes on-demand using the oxidation of oximes with peracetic acid and direct reaction of the nitroalkane intermediate in an aza-Henry reaction is reported. A uniquely designed pipes-in-series plug-flow tube reactor addresses a range of process challenges, including stability and safe handling of peroxides and nitroalkanes. The subsequent continuous extraction generates a solution of purified nitroalkane, which can be directly used in the following enantioselective aza-Henry chemistry to furnish valuable chiral diamine precursors with high selectivity, thus completely avoiding isolation of the potentially unsafe low-molecular-weight nitroalkane intermediate. A continuous campaign (16 h) established that these conditions were effective in processing 100 g of the oxime and furnishing 1.4 L of nitroalkane solution.
Tsukanov, Sergey V.,Johnson, Martin D.,May, Scott A.,Kolis, Stanley P.,Yates, Matthew H.,Johnston, Jeffrey N.
supporting information
p. 971 - 977
(2018/08/28)

Synthesis method of antagonist medicine intermediate o-nitrobenzoic acid
The invention provides a synthesis method of an antagonist medicine intermediate o-nitrobenzoic acid. The method mainly comprises the following steps of adding 3mol of 2-ethyl-3-nitrophenol and 4 to 5mol of ethylene glycol monopropyl ether solution into a reaction container; raising the solution temperature to 30 to 35 DEG C; controlling the stirring speed being 150 to 170 rpm; maintaining the state for 30 to 50min; then, adding 6 to 7mol of triphenylphosphine powder; continuously performing reaction for 60 to 90min; lowering the solution temperature to 5 to 8 DEG C; separating out solid; performing filtering; sequentially using propionic anhydride solution for washing and triethylamine solution for washing; then, performing recrystallization in the 2-methyl pentane solution; performing dewatering by a dewatering agent; obtaining crystal o-nitrobenzoic acid.
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Paragraph 0006; 0009-0014

(2018/10/19)

Reductive Cleavage of Aromatic and Heteroaromatic Ester Functions via Copper-Catalyzed Proto-Decarbomethoxylation
An unprecedented catalytic reductive cleavage of aromatic and heteroaromatic methyl ester functions was successfully achieved with a cheap, nontoxic, and air-stable Cu(OAc)2 catalyst. This reaction is fast, features good functional group tolerance, does not require inert atmosphere or anhydrous solvent, and can be scaled up to 1 g. Moreover, carboxylic acids and t-butyl esters also reacted smoothly under these conditions.
Fichez, Jeanne,Prestat, Guillaume,Busca, Patricia
supporting information
p. 2724 - 2727
(2018/05/22)

Stereodivergent trifluoromethylation of: N -sulfinylimines by fluoroform with either organic-superbase or organometallic-base
Here we have successfully demonstrated the first stereodivergent direct nucleophilic trifluoromethylation of N-sulfinylimines using the potent greenhouse gas "HFC-23, fluoroform" with an organic-superbase or an organometallic-base in high yields and selectivity.
Punna, Nagender,Saito, Takuya,Kosobokov, Mikhail,Tokunaga, Etsuko,Sumii, Yuji,Shibata, Norio
supporting information
p. 4294 - 4297
(2018/05/07)

Iodine catalyzed oxidation of alcohols and aldehydes to carboxylic acids in water: A metal-free route to the synthesis of furandicarboxylic acid and terephthalic acid
A metal-free iodine/NaOH-catalyzed oxidation of alcohols and aldehydes has been developed for the practical synthesis of a wide range of carboxylic acids using water as the solvent. This transformation involves dehydrogenation of an alcohol, followed by a fast attack of water on an aldehyde. This method is mostly free from chromatographic purification, which makes it suitable for large-scale synthesis. The iodine species formed during the reaction as the active oxidation catalyst has been deduced as IO2- by control experiments. We also demonstrate a 10 gram scale synthesis of furandicarboxylic acid (FDCA) from HMF in good yield using our method.
Hazra, Susanta,Deb, Mayukh,Elias, Anil J.
supporting information
p. 5548 - 5552
(2017/12/06)

Iron(II) and copper(II) phthalocyanine-catalyzed synthesis of 2-nitro-4-methylsulfonylbenzoic acid under mild conditions
Abstract : A novel method was?developed?to produce 2-nitro-4-methylsulfonylbenzoic acid (NMSBA) from the oxidation of 2-nitro-4-methylsulfonyltoluene (NMST) by oxygen catalyzed by iron(II) phthalocyanine (FePc) and copper(II) phthalocyanine (CuPc). The order of activity for oxidation of NMST was found to be: FePc > CuPc. Meanwhile, major reaction parameters such as concentrations of catalyst and NaOH, reaction temperature and oxygen pressure have been investigated. Through optimization of the reaction parameters, the highest yield of NMSBA and conversion of NMST (up to 53%, 89.3%, respectively) were achieved with oxygen (2.0 MPa), FePc (1.0×10-4molL-1), NaOH (0.6molL-1), in methanol at 55°C for 8 h. A plausible mechanism for this catalytic process is proposed which involved deprotonation and radical pathways. Graphical Abstract: A novel method to produce 2-nitro-4-methylsulfonylbenzoic acid (NMSBA) from the oxidation of 2-nitro-4-methylsulfonyltoluene (NMST) by oxygen catalyzed by iron(II) phthalocyanine (FePc) and copper(II) phthalocyanine (CuPc) has been developed. The reaction parameters and mechanism were studied. The catalytic system will be readily applicable to large-scale production of NMSBA. [Figure not available: see fulltext.].
Huang, Cheng,Liu, Rui,Zhang, Caiting,Cheng, Qipeng,Zhu, Hongjun
p. 1587 - 1594
(2017/11/03)

Oxalic acid as the: In situ carbon monoxide generator in palladium-catalyzed hydroxycarbonylation of arylhalides
An efficient palladium-catalyzed hydroxycarbonylation reaction of arylhalides using oxalic acid as a CO source has been developed. The reaction features high safety, low catalyst loading, and a broad substrate scope, and provides a safe and tractable approach to access a variety of aromatic carboxylic acid compounds. Mechanistic studies revealed the decomposition pattern of oxalic acid.
Shao, Changdong,Lu, Ailan,Wang, Xiaoling,Zhou, Bo,Guan, Xiaohong,Zhang, Yanghui
supporting information
p. 5033 - 5040
(2017/07/10)

K-10 and KSF clays as green and recyclable heterogeneous catalysts for the Cannizzaro reaction using DABCO under MWI and solvent-free conditions
Montmorillonite K-10 and KSF clays as recyclable and heterogeneous catalysts are used to catalyze the Cannizzaro reaction by 1,4-diazabicyclo [2.2.2]octane (DABCO) under microwave irradiation (MWI) and solvent-free conditions in excellent yields within seconds. The solid clays applied in the first cycle are recovered and reused in the subsequent reactions.
Marvi, Omid,Talakoubi, Maryam
p. 359 - 365
(2016/05/09)

Dual inhibitors of epidermal growth factor receptor and topoisomerase IIα derived from a quinoline scaffold
Based on the quinazoline bearing EGFR inhibitors, a series of thirty four compounds having a quinoline scaffold were synthesised and evaluated in vitro for EGFR kinase inhibitory activity. A structure-activity relationship study revealed that 2,4-bis(arylamino) substituted quinolines possessed better anti-EGFR kinase activity. Compounds 3f and 3m emerged as potent EGFR kinase inhibitors (200 and 210 nM, respectively) and showed excellent anticancer activity at the micromolar level against a panel of cancer cell lines comparable to erlotinib. Furthermore, representative compounds inhibited the human topoisomerase IIα selectively and catalytically, did not intercalate with DNA, increased intracellular ROS concentration (except 3m) and altered the mitochondrial membrane potential of the cancer cells. Cell cycle analysis and annexin-V staining in a lung cancer cell line showed that the compounds delayed cell cycle progression by inducing cell cycle arrest and subsequent apoptosis at the G1 phase. The facts were further corroborated through molecular modeling studies.
Chauhan, Monika,Joshi, Gaurav,Kler, Harveen,Kashyap, Archana,Amrutkar, Suyog M.,Sharma, Praveen,Bhilare, Kiran D.,Chand Banerjee, Uttam,Singh, Sandeep,Kumar, Raj
p. 77717 - 77734
(2018/06/22)

Preparation and characterization of nanosized copper (II) oxide embedded in hyper-cross-linked polystyrene: Highly efficient catalyst for aqueous-phase oxidation of aldehydes to carboxylic acids
Preparation and catalytic properties of nanosized copper (II) oxide embedded in hypercrosslinked polystyrene (HPS) were investigated in this article. The CuO@HPS nanocomposite was characterized by inductively coupled plasma optical emission spectrometry (ICP-OES), Fourier transform infrared spectroscopy (FT-IR), N2-sorption analysis, X-ray powder diffraction (XRD), energy dispersive X-ray spectroscopy analysis (EDS), and transmission electron microscopy (TEM). The TEM analysis showed that the mean diameter of the resulted particles is ~ 4 nm. The nanocomposite was found to be efficient and durable catalyst in the oxidation of aldehydes to the corresponding carboxylic acids in water. The catalyst can be recycled and reused in 4 reaction runs.
Saadati, Fariba,Khani, Neda,Rahmani, Mohammad,Piri, Farideh
p. 26 - 30
(2016/04/04)

Iodine-catalyzed oxidative C-C bond cleavage for benzoic acids and benzamides from alkyl aryl ketones
Iodine-catalyzed oxidative C-C bond cleavage has been performed for the facile synthesis of both benzoic acids and benzamides from readily available alkyl aryl ketones. Additionally benzylidene acetones and phenylacetylenes were also converted to the corresponding aromatic acids under the same conditions. This approach features the use of inexpensive iodine as a catalyst, broad substrate scope and open air conditions.
Sathyanarayana, Pochampalli,Upare, Atul,Ravi, Owk,Muktapuram, Prathap Reddy,Bathula, Surendar Reddy
p. 22749 - 22753
(2016/03/15)

Combined production method for substituted benzaldehyde, substituted benzyl alcohol and substituted benzoic acid
The invention discloses a combined production method for substituted benzaldehyde, substituted benzyl alcohol and substituted benzoic acid. The method comprises the following steps: (1) oxidation: a step of continuously introducing substituted toluene, a catalyst and oxygen-contained gas into an oxidation reactor and carrying out reaction so as to obtain oxidation reaction liquid; (2) hydrolyzation: a step of allowing the oxidation reaction liquid to continuously enter a hydrolysis reactor, and continuously adding water into the hydrolysis reactor and carrying out reaction so as to obtain a hydrolysis reaction mixture; (3) liquid-liquid layering: a step of layering the hydrolysis reaction mixture so as to obtain an oil phase and an aqueous phase; and (4) separation of products: a step of subjecting the oil phase to distillation so as to respectively obtain incompletely-reacted substituted toluene, substituted benzyl alcohol and substituted benzaldehyde, and subjecting the aqueous phase to cooling, crystallizing and filtering so as to obtain filtrate and substituted benzoic acid. The combined production method provided by the invention has the advantages of high raw material conversion rate, few by-products, good selectivity of target products, greenness and environmental protection.
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Paragraph 0089; 0090

(2017/01/31)

Iron oxalate capped iron-copper nanomaterial for oxidative transformation of aldehydes
An efficient, sustainable and green procedure for the synthesis of selective orthorhombic iron(oxalate) capped Fe-Cu bimetallic oxide nanomaterial [Fe(ox)Fe-CuOx] was developed using a sodium borohydride reduction of iron(ii) salt in the presence of oxalic acid at room temperature followed by addition of copper sulfate in water. The reported method is a cost-effective chemical route for producing [Fe(ox)Fe-CuOx] nano material at the gram level with a surface area of 78.4 m2 g-1 and a pore volume of 0.141 cm3 g-1. The [Fe(ox)Fe-CuOx] nanomaterials were found to be useful as a recoverable catalyst for the oxidative transformation of an aldehyde to its corresponding ester and acid in presence of hydrogen peroxide.
Kashyap, Rajarshi,Talukdar, Dhruba Joyti,Pratihar, Sanjay
p. 1430 - 1437
(2015/02/19)

Copper catalyzed oxygen assisted C(CNOH)-C(alkyl) bond cleavage: A facile conversion of aryl/aralkyl/vinyl ketones to aromatic acids
A novel copper-catalyzed aerobic oxidative C(NOH)-C(alkyl) bond cleavage reaction of aryl/aralkyl/vinyl ketones for the synthesis of aromatic/acrylic acids is described. A series of ketones having aryl/aralkyl/vinyl at the one end and methyl to any higher alkyl at the other end can be selectively cleaved and converted into the corresponding acids via oxime intermediates.
Sathyanarayana, Pochampalli,Ravi, Owk,Muktapuram, Prathap Reddy,Bathula, Surendar Reddy
supporting information
p. 9681 - 9685
(2015/09/28)

Amyl nitrite-mediated conversion of aromatic and heteroaromatic primary amides to carboxylic acids
A series of aromatic and heteroaromatic primary amides were converted directly to carboxylic acids by heating with amyl nitrite in acetic acid. Most conversions proceeded to give reasonable to excellent yields on a range of substrates containing various functional groups. This reagent system is thus applicable for the direct hydrolysis of a range of different primary carboxamides. The reaction with a phenolic aromatic substrate afforded two alternative nitration products as major outcomes, evidencing alternative reaction pathways resulting from the free phenolic OH.
Potter, Garrett T.,Jayson, Gordon C.,Miller, Gavin J.,Gardiner, John M.
supporting information
p. 5153 - 5156
(2015/08/19)

Manganese dioxide and N,N′,N″-trihydroxyisocyanuric acid: A novel and recyclable catalytic system for aerobic oxidation of toluene derivatives in PEG-1000-based dicationic acidic ionic liquid
N,N′,N″-trihydroxyisocyanuric acid (THICA) with MnO2 promotes the aerobic oxidation of toluene derivatives to corresponding acids in PEG-1000-based dicationic acidic ionic liquid (PEG1000-DAIL). It is demonstrated that THICA/MnO2 is very active and selective and several toluene derivatives are efficiently oxidized to corresponding acids under mild conditions. Both the catalyst and PEG1000-DAIL can be reused after simple separation. A plausible mechanism is also proposed based on the experimental observations.
Lu, Tingting,Zhang, Lijie,Ge, Zhongxue,Ji, Yueping,Lu, Ming
p. 276 - 279
(2015/04/27)

Copper-mediated ortho-nitration of arene and heteroarene c-h bonds assisted by an 8-aminoquinoline directing group
A copper-mediated, chelation-assisted ortho C-H bond nitration of benzoic acid derivatives using sodium nitrite as the source of the nitro group has been achieved with the aid of an 8-aminoquinoline directing group. Selective mono- or dinitration can be achieved by simply changing the reaction conditions. The method shows excellent functional group tolerance and provides a novel and straightforward route for the preparation of ortho-nitrated benzoic acids.
Liu, Jidan,Zhuang, Shaobo,Gui, Qingwen,Chen, Xiang,Yang, Zhiyong,Tan, Ze
p. 732 - 738
(2015/03/18)

Oxidative cleavage of olefins by in situ-generated catalytic 3,4,5,6-tetramethyl-2-iodoxybenzoic acid/oxone
Oxidative cleavage of a variety of olefins to the corresponding ketones/carboxylic acids is shown to occur in a facile manner with 3,4,5,6-tetramethyl-2-iodobenzoic acid (TetMe-IA)/oxone. The simple methodology involves mere stirring of the olefin and catalytic amount (10 mol %) of TetMe-IA and oxone in acetonitrile-water mixture (1:1, v/v) at rt. The reaction mechanism involves initial dihydroxylation of the olefin with oxone, oxidative cleavage by the in situ-generated 3,4,5,6-tetramethyl-2-iodoxybenzoic acid (TetMe-IBX), and oxidation of the aldehyde functionality to the corresponding acid with oxone. Differences in the reactivities of electron-rich and electron-poor double bonds have been exploited to demonstrate chemoselective oxidative cleavage in substrates containing two double bonds.
Moorthy, Jarugu Narasimha,Parida, Keshaba Nanda
p. 11431 - 11439
(2015/02/05)

Lipase catalyzed Cannizzaro-type reaction with substituted benzaldehydes in water
Lipases were found to catalyze Cannizzaro-type reaction of substituted benzaldehydes in aqueous medium at 30 °C without the addition of any external redox reagent. The ratio of alcohol product to acid product varied with nature of the substituted benzaldehyde, enzyme, and the presence of organic co-solvent.
Arora, Benu,Pandey, Pramod S.,Gupta, Munishwar N.
supporting information
p. 3920 - 3922
(2014/07/08)

An insight into the mechanism of the aerobic oxidation of aldehydes catalyzed by N-heterocyclic carbenes
N-Heterocyclic carbene catalysis for the aerobic oxidation and esterification of aromatic aldehydes was monitored by ESI-MS (MS/MS) and the key intermediates were intercepted and characterized using the charge-tag strategy.
Bortolini,Chiappe,Fogagnolo,Giovannini,Massi,Pomelli,Ragno
supporting information
p. 2008 - 2011
(2014/03/21)

Electrophilicity and nucleophilicity of commonly used aldehydes
The present approach for determining the electrophilicity (E) and nucleophilicity (N) of aldehydes includes a kinetic study of KMNO4 oxidation and NaBH4 reduction of aldehydes. A transition state analysis of the KMNO4 promoted aldehyde oxidation reaction has been performed, which shows a very good correlation with experimental results. The validity of the experimental method has been tested using the experimental activation parameters of the two reactions. The utility of the present approach is further demonstrated by the theoretical versus experimental relationship, which provides easy access to E and N values for various aldehydes and offers an at-a-glance assessment of the chemical reactivity of aldehydes in various reactions. the Partner Organisations 2014.
Pratihar, Sanjay
p. 5781 - 5788
(2014/07/22)

Lanthano-phosphotungstate: A water soluble and reusable catalyst for oxidation of alcohols using H2O2 as an oxidant
A series of water soluble lanthano-phosphotungstate K 11[Ln(PW11O39)2]·xH 2O [Ln = Pr(iii), Nd(iii), Eu(iii), Gd(iii), Tb(iii), Dy(iii), Ho(iii), Er(iii), Tm(iii) and Yb(iii)] catalysts were synthesized. These catalysts (0.24 mol%) were screened for oxidation of primary and secondary alcohols using H2O2 as an oxidant in water. The Pr-POM catalyst retained its activity after being recycled and reused upto five cycles. the Partner Organisations 2014.
Saini, Mukesh Kumar,Gupta, Rakesh,Parbhakar, Swati,Singh, Surendra,Hussain, Firasat
p. 38446 - 38449
(2014/11/08)

Palladium(0)-catalyzed intramolecular decarboxylative allylation of ortho nitrobenzoic esters
A Pd/Ag bimetallic system has been developed for the decarboxylative allylation of ortho-nitrobenzoic esters in an intramolecular fashion. In contrast to the typical sp2-sp3 cross-coupling approach which requires air and moisture sensitive preformed organometallic reagents, we provide an alternative route to the synthesis of ortho-allyl nitroarenes from the corresponding ortho-nitrobenzoic acid derivatives. The reaction proceeds through a mechanistically distinct decarboxylative metalation pathway. A cooperative reactivity of palladium and silver is crucial for the reaction outcome.
Hossian, Asik,Singha, Shantanu,Jana, Ranjan
p. 3934 - 3937
(2014/08/18)

Extremely fast gas/liquid reactions in flow microreactors: Carboxylation of short-lived organolithiums
Carboxylation of short-lived organolithiums bearing electrophilic functional groups such as nitro, cyano, and alkoxycarbonyl groups with CO 2 to give carboxylic acids and active esters was accomplished in a flow microreactor system. The successful reactions indicate that gas/liquid mass transfer and the subsequent chemical reaction with CO2 are extremely fast. Carboxylation of short-lived organolithiums bearing electrophilic functional groups such as nitro, cyano, and alkoxycarbonyl groups with CO 2 to give carboxylic acids and active esters was accomplished in a flow microreactor system. The successful reactions indicate that gas/liquid mass transfer and the subsequent chemical reaction with CO2 are extremely fast (see scheme).
Nagaki, Aiichiro,Takahashi, Yusuke,Yoshida, Jun-Ichi
p. 7931 - 7934
(2014/07/07)

Ruthenium-catalyzed c-h silylation of 1-arylpyrazole derivatives and fluoride-mediated carboxylation: Use of two nitrogen atoms of the pyrazole Group
Carboxylation of 1-arylpyrazole derivatives was developed using a ruthenium-catalyzed ortho silylation in conjunction with fluoride-mediated carboxylation with carbon dioxide. The two nitrogen atoms of pyrazole play crucial roles in promoting ortho silylation via the formation of a five-membered ruthenacycle and in accelerating aryl anion formation by lowering the electron density of the aromatic ring. Georg Thieme Verlag Stuttgart New York.
Mita, Tsuyoshi,Tanaka, Hiroyuki,Michigami, Kenichi,Sato, Yoshihiro
supporting information
p. 1291 - 1294
(2014/06/10)

Oxidation cascade with oxone: Cleavage of olefins to carboxylic acids
A variety of olefins is shown to be cleaved oxidatively to the corresponding acids with oxone as the reagent. The simple methodology that works well for a range of alkenes, i.e., styrenes, nitrostyrenes, stilbenes, cinnamic acids, chalcones, etc., involves heating of the reactant with oxone in acetonitrile-water mixture (1:1, v/v) at reflux. The oxidation cascade involves initial dihydroxylation followed by oxidative cleavage and oxidation of the resultant aldehydes to acids.
Parida, Keshaba Nanda,Moorthy, Jarugu Narasimha
p. 2280 - 2285
(2014/03/21)

V-doped titanium mixed oxides as efficient catalysts for oxidation of alcohols and olefins
V/TiO2 nanoparticles were synthesized by a one-pot solution combustion method using ammonium metavanadate and titanyl nitrate as a source of vanadium and titanium, respectively. Atomic absorption spectroscopy (AAS), FT-IR, X-ray diffraction (XRD), scanning electron microscopy (SEM) and transmission electron microscopy (TEM) were employed to characterize the physicochemical properties of this compound. This compound shows efficient catalytic reactivity for epoxidation of olefins and oxidation of alcohols in the presence of H2O2 as an oxidant.
Amini, Mojtaba,Naslhajian, Hadi,Farnia, S. Morteza F.
p. 1581 - 1586
(2014/05/06)

Nanoparticle-supported and magnetically recoverable organic-inorganic hybrid copper(ii) nanocatalyst: A selective and sustainable oxidation protocol with a high turnover number
A magnetically recoverable copper-based nanocatalyst was prepared from inexpensive starting materials. With a particle size between 20 to 30 nm, it was shown to catalyze the oxidation of benzylic alcohols. The catalyst exhibited a high turnover number (TON) and excellent selectivity. The catalyst was characterized by several techniques, such as XRD, HR-TEM, SAED, EDS, FT-IR, VSM, and BET surface area. Factors affecting the reaction parameters, such as the substrate to oxidant molar ratio, weight of the catalyst, reaction time, etc., were investigated in detail. The reusability of the catalyst was examined by conducting repeat experiments with the same catalyst; it was observed that the catalyst displayed no significant changes in its activity even after seven cycles for the aerobic, as well as for the peroxide, oxidation of benzyl alcohol. Furthermore, the heterogeneous nature, easy recovery, and reusability, makes the present protocol highly beneficial for addressing environmental concerns and industrial requirements. This journal is
Rathore, Puran Singh,Patidar, Rajesh,Thakore, Sonal
p. 41111 - 41121
(2014/12/10)

Inclusion complex containing epoxy resin composition for semiconductor encapsulation
The invention is an epoxy resin composition for sealing a semiconductor, including (A) an epoxy resin and (B) a clathrate complex. The clathrate complex is one of (b1) an aromatic carboxylic acid compound, and (b2) at least one imidazole compound represented by formula (II): wherein R2 represents a hydrogen atom, C1-C10 alkyl group, phenyl group, benzyl group or cyanoethyl group, and R3 to R5 represent a hydrogen atom, nitro group, halogen atom, C1-C20 alkyl group, phenyl group, benzyl group, hydroxymethyl group or C1-C20 acyl group. The composition has improved storage stability, retains flowability when sealing, and achieves an effective curing rate applicable for sealing delicate semiconductors.
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(2014/03/21)

SnO 2 nanoparticles: Preparation and evaluation of their catalytic activity in the oxidation of aldehyde derivatives to their carboxylic acid and sulfides to sulfoxide analogs
A variety of aromatic and aliphatic aldehydes were converted to the corresponding carboxylic acid derivatives with 30% H2O2 and tert-butyl hydroperoxide as the oxidant in the presence of a catalytic amount of SnO2 nanoparticles as a precursor. These nanoparticles were also used for the efficient catalytic oxidation of sulfides to sulfoxides using 30% H2O2. The present methodology offers several advantages such as applicability to a wide range of aldehydes/sulfides, convenient work-up, mild reaction conditions as well as good yields and reasonable time of the reactions. Supplemental materials are available for this article. Go to the publisher's online edition of Phosphorus, Sulfur, and Silicon and the Related Elements to view the free supplemental file.
Dehbashi, Mohsen,Aliahmad, Mousa,Shafiee, Mohammad Reza Mohammad,Ghashang, Majid
p. 864 - 872
(2013/08/23)

Nickel(II) catalyzed oxidation of aldehyde derivatives to their carboxylic acid or ester analogs
Diverse aromatic, aliphatic and conjugated aldehydes were converted to the corresponding carboxylic acid or methyl ester derivatives with 30 % H 2O2 as the oxidant in the presence of a catalytic amount of nickel(II) complex as precursor. Ni(II) complex was prepared from the reaction of methyl 2-{3-[(E)-4-oxopent-2-en-2-ylamino]propylamino}cyclopent-1- enecarbodithioate as a tetra-dentate ligand with Ni(II) acetate in 60 % yield and was tested for its catalytic activity in the oxidation reaction. The prepared complex was characterized on the basis of 1H NMR, FT-IR, MASS, and CHN analysis. Aldehydes were oxidized to their corresponding carboxylic acid in acetonitrile as solvent and were converted to methyl esters in methanol as solvent. For all substrates, a considerable rate enhancement was observed. The present methodology offers several advantages such as applicability to a wide range of aldehydes, convenient work-up, mild reaction conditions, and good yields and reasonable time of the reactions. Graphical Abstract: [Figure not available: see fulltext.]
Esfandiari, Hadi,Jameh-Bozorghi, Saeed,Esmaielzadeh, Sheida,Shafiee, Mohammad Reza Mohammad,Ghashang, Majid
p. 3319 - 3325
(2013/09/23)