cas 149-57-5, 2-Ethylhexanoic acid | Articles data

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Preparative microdroplet synthesis of carboxylic acids from aerobic oxidation of aldehydes
Single liquid-phase and liquid-liquid phase reactions in microdroplets have shown much faster kinetics than that in the bulk phase. This work extends the scope of microdroplet reactions to gas-liquid reactions and achieves preparative synthesis. We report highly efficient aerobic oxidation of aldehydes to carboxylic acids in microdroplets. Molecular oxygen plays two roles: (1) as the sheath gas to shear the aldehyde solution into microdroplets, and (2) as the sole oxidant. The dramatic increase of the surface-area-to-volume ratio of microdroplets compared to bulk solution, and the efficient mixing of gas and liquid phases using spray nozzles allow effective mass transfer between aldehydes and molecular oxygen. The addition of catalytic nickel(ii) acetate is shown to accelerate further microdroplet reactions of this kind. We show that aliphatic, aromatic, and heterocyclic aldehydes can be oxidized to the corresponding carboxylic acids in a mixture of water and ethanol using the nickel(ii) acetate catalyst, in moderate to excellent yields (62-91%). The microdroplet synthesis is scaled up to make it preparative. For example, aerobic oxidation of 4-tert-butylbenzaldehyde to 4-tert-butylbenzoic acid was achieved at a rate of 10.5 mg min-1 with an isolated product yield of 66%.
Yan, Xin,Lai, Yin-Hung,Zare, Richard N.
p. 5207 - 5211
(2018)
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The Regiospecific Palladium Catalysed Hydrocarboxylation of Alkenes under Mild Conditions
Alkenes react with carbon monoxide, water, oxygen, hydrochloric acid, and palladium and copper chlorides, to give branched chain acids in good yields.
Alper, Howard,Woell, James B.,Despeyroux, Bertrand,Smith, David J. H.
p. 1270 - 1271
(1983)
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Efficient CuCl-catalyzed selective and direct oxidation of β- And γ-substituted aliphatic primary alcohols to carboxylic acids
A new procedure for the selective and direct oxidation of aliphatic primary alcohols having substitution at - and -positions to corresponding carboxylic acids was developed using a catalytic amount of ligand and additive-free CuCl with anhydrous tBuOOH in acetonitrile solvent under very mild reaction conditions. This procedure is very simple and mild and works efficiently without any additives at room temperature.
Mannam, Sreedevi,Sekar, Govindasamy
p. 2822 - 2829
(2010)
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Physicochemical properties of 2-ethylhexanoic acid N′,N′- dialkylhydrazides
The following characteristics of 2-ethylhexanoic acid N′,N′- dialkyl(C4-C8)hydrazides relevant to their potential application as Cu(II) extractants were studied: solubility, acid-base properties, resistance to hydrolysis, loss with the aqueous phase, and distribution ratio in relation to the composition of the medium and length of alkyl chains. Nauka/Interperiodica 2006.
Radushev,Batueva,Gusev
p. 1196 - 1200
(2006)
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Reinvestigation of the Organocatalyzed Aerobic Oxidation of Aldehydes to Acids
The organocatalyzed aerobic oxidation of aldehydes to acids was reproduced from the original report. In- and ex-situ analysis of the reaction mixture as the function of time reveals that, unlike the claim in the publication, the aerobic oxidation of aromatic and aliphatic aldehydes leads predominantly to the formation of peracids. The latter are transformed into the corresponding carboxylic acids during the workup procedure. The buildup of peracids in solution poses safety problems that should not be overlooked. This finding has also an influence on the way new catalysts are investigated to improve this reaction as well as on aerobic aldehyde-mediated co-oxidation.
Vanoye, Laurent,Abdelaal, Mohamed,Grundhauser, Kacy,Guicheret, Boris,Fongarland, Pascal,De Bellefon, Claude,Favre-Réguillon, Alain
p. 10134 - 10138
(2019)
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Mechanistic Insights into the Aerobic Oxidation of Aldehydes: Evidence of Multiple Reaction Pathways during the Liquid Phase Oxidation of 2-Ethylhexanal
The liquid-phase aldehyde oxidation by molecular oxygen (autoxidation) has been known for about 2 centuries and is a critical organic transformation in both industrial applications and academic research. However, the general reaction pathway proposed for the aerobic oxidation of aldehydes into the corresponding carboxylic acid exhibits some inconstancies, in particular, for β-substituted aliphatic aldehydes. Thus, the liquid-phase aerobic oxidation of 2-ethylhexanal was further studied in acetonitrile at 20 °C with O2 at atmospheric pressure. By precisely monitoring the primary intermediate (peracid), product (carboxylic acid), and byproducts as a function of time and catalysts used, we demonstrated the pivotal role of the acylperoxy radical. The direct formation of peracid and carboxylic acid from the latter was highlighted by analyzing the composition of the reaction mixture at low conversion. Peracid could be converted into carboxylic acid by metal catalysts or through reaction workup. Consequently, the commonly accepted pathway of aerobic oxidation of aldehyde via a Criegee intermediate can be overlooked under these conditions.
Vanoye, Laurent,Favre-Réguillon, Alain
p. 335 - 346
(2022/02/10)

N-Heterocyclic Carbene/Carboxylic Acid Co-Catalysis Enables Oxidative Esterification of Demanding Aldehydes/Enals, at Low Catalyst Loading
We report the discovery that simple carboxylic acids, such as benzoic acid, boost the activity of N-heterocyclic carbene (NHC) catalysts in the oxidative esterification of aldehydes. A simple and efficient protocol for the transformation of a wide range of sterically hindered α- and β-substituted aliphatic aldehydes/enals, catalyzed by a novel and readily accessible N-Mes-/N-2,4,6-trichlorophenyl 1,2,4-triazolium salt, and benzoic acid as co-catalyst, was developed. A whole series of α/β-substituted aliphatic aldehydes/enals hitherto not amenable to NHC-catalyzed esterification could be reacted at typical catalyst loadings of 0.02–1.0 mol %. For benzaldehyde, even 0.005 mol % of NHC catalyst proved sufficient: the lowest value ever achieved in NHC catalysis. Preliminary studies point to carboxylic acid-induced acceleration of acyl transfer from azolium enolate intermediates as the mechanistic basis of the observed effect.
Berkessel, Albrecht,Biswas, Animesh,Harnying, Wacharee,Sudkaow, Panyapon
supporting information
p. 19631 - 19636
(2021/08/09)

Method for producing aliphatic carboxylic acid compound and pyridine compound adduct of aliphatic ketone compound
Provided are: a method for producing an aliphatic carboxylic acid compound safely and easily from a starting material that can be obtained or produced industrially without generating a harmful substance such as haloform; and a pyridine compound adduct of an aliphatic ketone compound. The method for producing an aliphatic carboxylic acid compound is a method for producing an aliphatic carboxylic acid compound represented by Formula (I), and comprises: a first step for obtaining a pyridine compound adduct by adding a pyridine compound to an aliphatic ketone compound having an alpha-methyl groupin the presence of an oxidizing agent; and a second step of hydrolyzing the pyridine compound adduct in the presence of a base. In the Formula, R1 represents a substituted or unsubstituted linear alkyl group having 4-8 carbon atoms or a substituted or unsubstituted branched alkyl group having 4-8 carbon atoms; M represents hydrogen, a metal belonging to Group 1 or Group 2 of the periodic table, amethyl group, an ethyl group, an n-propyl group or an isopropyl group.
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Paragraph 0172; 0175-0176; 0182; 0185-0186; 0192; 0195-0196

(2020/05/02)

Preparation method of bimetallic catalyst oxidation aldehyde synthetic carboxylic acid (by machine translation)
The method is, in a reaction solvent: under normal pressure oxygen condition, under the action of a bimetallic catalyst under the action of a bimetallic catalyst under the action of a bimetallic catalyst under the action of a bimetallic catalyst, at, DEG, under stirring . under a stirring condition with an aldehyde compound as a substrate 10-90 °C in a reaction solvent under, a stirring condition under the action of a bimetallic catalyst . The reaction solution is stirred, for. 1-12h, hours at; room temperature, under, the action, of a bimetallic 1:1 catalyst Cu(OAc) under the action of a bimetallic catalyst under the action of a bimetallic catalyst under the action of a double-metal catalyst. 2 · H2 O And Co(OAc)2 · 44H2 O As the bimetallic catalyst, can achieve the highest yield of the carboxylic acid product, in high yield, by adjusting the reaction temperature, solvent, catalyst amount, for different types of the raw material aldehyde 98%. (by machine translation)
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Paragraph 0050-0051

(2020/05/30)

Oxidation of aromatic and aliphatic aldehydes to carboxylic acids by Geotrichum candidum aldehyde dehydrogenase
Oxidation reaction is one of the most important and indispensable organic reactions, so that green and sustainable catalysts for oxidation are necessary to be developed. Herein, biocatalytic oxidation of aldehydes was investigated, resulted in the synthesis of both aromatic and aliphatic carboxylic acids using a Geotrichum candidum aldehyde dehydrogenase (GcALDH). Moreover, selective oxidation of dialdehydes to aldehydic acids by GcALDH was also successful.
Hoshino, Tomoyasu,Yamabe, Emi,Hawari, Muhammad Arisyi,Tamura, Mayumi,Kanamaru, Shuji,Yoshida, Keisuke,Koesoema, Afifa Ayu,Matsuda, Tomoko
(2020/07/20)

PROCESSES FOR PRODUCING CARBOXYLIC ACIDS
Processes are disclosed for preparing carboxylic acids from organic esters, the processes comprising contacting an ester with water in the presence of an acid catalyst and a homogenizing solvent at conditions effective to form a carboxylic acid. The homogenizing solvent is present in an amount sufficient to form a single-phase reaction mixture comprising the ester, water, and homogenizing solvent. The homogenizing solvent may be selected from acetonitrile, dimethyl sulfoxide, and 1,4-dioxane.
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Page/Page column 0043

(2020/10/20)

Practical catalytic nitration directly with commercial nitric acid for the preparation of aliphatic nitroesters
To pursue a sustainable and efficient approach for aliphatic nitroester preparation from alcohol, europium-triflate-catalyzed nitration, which directly uses commercial nitric acid, has been successfully developed. Gram scalability with operational ease showed its practicability.
An, Jichao,He, Pan,Li, Wenhao,Liu, Peipei,Si, Mengyuan,Yang, Bo,Yang, Guanyu
p. 6612 - 6616
(2020/09/21)

ESTER SYNTHESIS USING HETEROGENEOUS AU/TIO2 CATALYST
A process for direct esterification of an alkyl aldehyde with an alkyl alcohol to produce an alkyl ester is disclosed. The process comprises reacting an alkyl aldehyde with an alkyl alcohol in the presence of an Au/TiOa catalyst, a base and an enal or oxygen to form an ester and an aldehyde. The process avoids liberation of water and avoids the step of oxidation of the alkyl aldehyde to an alkyl acid.
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Paragraph 0034; 0035

(2020/06/05)

Iodine phosphine oxide ligand, preparation method and complex thereof, catalyst system comprising complex and application
The invention relates to an iodine phosphine oxide ligand, a preparation method and a complex thereof, a catalyst system comprising the complex, a method for preparing isooctanoic acid from 2-ethylhexanal by oxidizing in the presence of the catalyst system and an application of the catalyst system. In the catalyst system, isooctanoic acid is prepared from 2-ethylhexanal by oxidizing on the basis of the iodine phosphine oxide ligand and a cesium complex taken as catalysts and potassium salt taken as a catalyst aid. The defect of poor selectivity in the prior art can be overcome, the process ismild, and the ligand is convenient to prepare and has high activity and small dosage.
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Paragraph 0091-0104

(2019/01/23)

Organocatalyzed Aerobic Oxidation of Aldehydes to Acids
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
supporting information
p. 1393 - 1396
(2019/02/26)

Mild C-H functionalization of alkanes catalyzed by bioinspired copper(ii) cores
Three new copper(ii) coordination compounds formulated as [Cu(H1.5bdea)2](hba)·2H2O (1), [Cu2(μ-Hbdea)2(aca)2]·4H2O (2), and [Cu2(μ-Hbdea)2(μ-bdca)]n (3) were generated by aqueous medium self-assembly synthesis from Cu(NO3)2, N-butyldiethanolamine (H2bdea) as a main N,O-chelating building block and different carboxylic acids [4-hydroxybenzoic (Hhba), 9-anthracenecarboxylic (Haca), or 4,4′-biphenyldicarboxylic (H2bdca) acid] as supporting carboxylate ligands. The structures of products range from discrete mono- (1) or dicopper(ii) (2) cores to a 1D coordination polymer (3), and widen a family of copper(ii) coordination compounds derived from H2bdea. The obtained compounds were applied as bioinspired homogeneous catalysts for the mild C-H functionalization of saturated hydrocarbons (cyclic and linear C5-C8 alkanes). Two model catalytic reactions were explored, namely the oxidation of hydrocarbons with H2O2 to a mixture of alcohols and ketones, and the carboxylation of alkanes with CO/S2O82- to carboxylic acids. Both processes proceed under mild conditions with a high efficiency and the effects of different parameters (e.g., reaction time and presence of acid promoter, amount of catalyst and solvent composition, substrate scope and selectivity features) were studied and discussed in detail. In particular, an interesting promoting effect of water was unveiled in the oxidation of cyclohexane that is especially remarkable in the reaction catalyzed by 3, thus allowing a potential use of diluted, in situ generated solutions of hydrogen peroxide. Moreover, the obtained values of product yields (up to 41% based on alkane substrate) are very high when dealing with the C-H functionalization of saturated hydrocarbons and the mild conditions of these catalytic reactions (50-60 °C, H2O/CH3CN medium). This study thus contributes to an important field of alkane functionalization and provides a notable example of new Cu-based catalytic systems that can be easily generated by self-assembly from simple and low-cost chemicals.
Kirillova, Marina V.,Fernandes, Tiago A.,André, Vania,Kirillov, Alexander M.
supporting information
p. 7706 - 7714
(2019/08/30)

A aldehyde or mellow directly converted into the carboxylic acid (by machine translation)
The invention discloses a aldehyde or mellow oxidation can be directly transformed into carboxylic acid, is characterized in that the pure oxygen environment, in N - hydroxy imide compound under the catalysis of the imide compound or N - hydroxy and nitrous acid ester compound common under the catalysis, the CH2 OH and CHO oxidation directly converted into the carboxylic acid compounds. The invention using oxygen as the oxidizing agent, does not add any metal catalyst, environment-friendly, high catalytic efficiency, simple and convenient operation. With the previous metal catalytic system complex and different catalytic system, has some metal catalytic system in the process, the use of transition metal will cause the transition metal of the residual, the invention adopts the non-metallic catalytic system, environmental protection, preventing the metal residue problem, this to the solution of the drug in the synthesis of transition metal residue problem and provides a new method of thinking. (by machine translation)
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Paragraph 0027; 0028

(2018/08/03)

Pharmaceutical intermediate 2-ethylhexanoic acid synthesis method
The invention relates to a pharmaceutical intermediate 2-ethylhexanoic acid synthesis method, which mainly comprises: (1) adding 3 mol 1-amino-2-bromo-3-ethylheptene and 4-5 mol dimethyl fumarate solution into a reaction container, controlling the stirring speed at 130-160 rpm, increasing the solution temperature to 40-48 DEG C, carrying out a reaction for 2-3 h, washing 4-6 times with a potassiumnitrate solution, adjusting the pH value to 3-4 with a potassium hydrogen sulfate solution, layering the solution, extracting 5-7 times with a 1,3-propylenediamine solution, extracting 6-9 times witha propylene glycol methyl ether solution, and re-crystallizing in a N-propyl aniline solution to obtain the finished product 2-ethylhexanoic acid.
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Paragraph 0006; 0009-0014

(2018/07/30)

Regioselectivity inversion tuned by iron(iii) salts in palladium-catalyzed carbonylations
Impactful regioselectivity control is crucial for cost-effective chemical synthesis. By using cheap and abundant iron(iii) salts, the hydroxycarbonylations of both aromatic and aliphatic alkenes were significantly enhanced in both reactivity and selectivity (iso/n or n/iso up to >99:1). Moreover, Pd-catalyzed carbonylation selectivity can be switched from branched to linear by using different Fe(iii) salts. In addition, similar results were obtained for the carbonylation of secondary alcohols.
Huang, Zijun,Cheng, Yazhe,Chen, Xipeng,Wang, Hui-Fang,Du, Chen-Xia,Li, Yuehui
supporting information
p. 3967 - 3970
(2018/04/23)

Transfer-hydrogenation process
A transfer-hydrogenation process for preparing a carbonyl compound and an alcohol compound comprises the steps of (a) contacting a first carbonyl compound with a first alcohol compound in the presence of a transfer-hydrogenation catalyst in a first reaction zone at conditions effective to form a second carbonyl compound from the first alcohol compound and a second alcohol compound from the first carbonyl compound, and (b) removing the second carbonyl compound from the first reaction zone during step (a). The first carbonyl compound is a saturated aldehyde or ketone, or an α,β-unsaturated aldehyde or ketone. The first alcohol compound is a primary or secondary alcohol. The second alcohol compound is α,β-saturated. The transfer-hydrogenation catalyst includes a Group 8 to 11 metal. This process is useful for preparing and higher value alcohols, such as butanol or 2-ethylhexanol, from the corresponding carbonyl compounds by engaging lower alcohol (C2-C4) feedstocks instead of hydrogen (H2).
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Page/Page column 15; 16

(2018/06/19)

Three-component 1D and 2D metal phosphonates: structural variability, topological analysis and catalytic hydrocarboxylation of alkanes
Herein, we report the use of diphosphonate building blocks and chelating auxiliary N,N-ligands to generate novel polymeric architectures. Specifically, we report new 1D and 2D coordination polymers incorporating three components: transition metal ions (Co2+, Cu2+, Mn2+ or Zn2+), diphosphonate ligands (methane-diphosphonate, MDPA, or 1,2-ethanediphosphonate, EDPA) and N,N-heterocyclic chelators (1,10-phenanthroline, phen, or 2,2′-bipyridine, bpy). Six compounds were isolated under mild synthesis (ambient temperature) conditions: [Cu2(phen)2(EDPA)2(H2O)4]∞ (1), [Co(phen)(EDPA)(H2O)2]∞ (1a), {[Cu(phen)(MDPA)]·H2O]}∞ (2), [Mn(bpy)(EDPA)(H2O)2]∞ (3), [Zn(bpy)(EDPA)]∞ (4), and, lastly, a discrete Ni2+ molecular derivative [Ni(phen)(H2O)4](EDPA) (5). Synthetic details, crystal structures, and intermolecular interactions (π-π stacking and hydrogen bonding) in 1-5 are discussed. Topological analyses and classification of the underlying metal-organic networks in 1-4 were performed, revealing the uninodal 1D chains with the 2C1 topology in 1-3 and the binodal 2D layers with the 3,4L13 topology in 4. In 1-3 and 5, multiple hydrogen bonds lead to the extension of the structures to give 3D H-bonded nets with the seh-4,6-C2/c topology in 1 and 3, 2D H-bonded layers with the 3,5L52 topology in 2, and a 3D H-bonded net with the 6,6T1 topology in 5. The catalytic activity of compounds 1 and 1a was evaluated in a single-step hydrocarboxylation of cyclic and linear C5-C8 alkanes to furnish the carboxylic acids with one more carbon atom. These reactions proceed in the presence of CO, K2S2O8, and H2O at 60 °C in MeCN/H2O medium. Compound 1 showed higher activity than 1a and was studied in detail. Substrate scope was investigated, revealing that cyclohexane and n-pentane are the most reactive among the cyclic and linear C5-C8 alkanes, and resulting in the total yields of carboxylic acids (based on substrate) of up to 43 and 36%, respectively. In the case of cycloalkane substrates, only one cycloalkanecarboxylic acid is produced, whereas a series of isomeric monocarboxylic acids is generated when using linear alkanes; an increased regioselectivity at the C(2) position of the hydrocarbon chain was also observed.
Demadis, Konstantinos D.,Anagnostou, Zafeiria,Panera, Aggeliki,Mezei, Gellert,Kirillova, Marina V.,Kirillov, Alexander M.
p. 17788 - 17799
(2017/03/30)

Catalytic Fehling's Reaction: An Efficient Aerobic Oxidation of Aldehyde Catalyzed by Copper in Water
The first example of homogeneous copper-catalyzed aerobic oxidation of aldehydes is reported. This method utilizes atmospheric oxygen as the sole oxidant, proceeds under extremely mild aqueous conditions, and covers a wide range of various functionalized aldehydes. Chromatography is generally not necessary for product purification.
Liu, Mingxin,Li, Chao-Jun
supporting information
p. 10806 - 10810
(2016/09/03)

Additional nucleophile-free FeCl3-catalyzed green deprotection of 2,4-dimethoxyphenylmethyl-protected alcohols and carboxylic acids
The deprotection of the methoxyphenylmethyl (MPM) ether and ester derivatives can be generally achieved by the combinatorial use of a catalytic Lewis acid and stoichiometric nucleophile. The deprotections of 2,4-dimethoxyphenylmethyl (DMPM)-protected alcohols and carboxylic acids were found to be effectively catalyzed by iron(III) chloride without any additional nucleophile to form the deprotected mother alcohols and carboxylic acids in excellent yields. Since the present deprotection proceeds via the self-assembling mechanism of the 2,4-DMPM protective group itself to give the hardly-soluble resorcinarene derivative as a precipitate, the rigorous purification process by silica-gel column chromatography was unnecessary and the sufficiently-pure alcohols and carboxylic acids were easily obtained in satisfactory yields after simple filtration.
Sawama, Yoshinari,Masuda, Masahiro,Honda, Akie,Yokoyama, Hiroki,Park, Kwihwan,Yasukawa, Naoki,Monguchi, Yasunari,Sajiki, Hironao
p. 778 - 784
(2016/07/16)

Structurally well-characterized new multinuclear Cu(II) and Zn(II) clusters: X-ray crystallography, theoretical studies, and applications in catalysis
Two new trinuclear Cu(ii) and dinuclear Zn(ii) clusters are crystallized out by reacting the metal salts with the triethanolamine (H3tea) ligand in the presence of benzoic acid (Hba). The complexes are characterized by elemental, thermal, magnetic, spectral (FTIR, UV-Visible, EPR, and photoluminescence) and single crystal X-ray studies. Single crystal X-ray crystallography reveals the composition of the complexes to be [Cu3(H2tea)2(ba)2(NO3)2] (1) and [Zn2(H2tea)(ba)3]H2O (2). FTIR ascertains the binding modes of H2tea-, ba- and NO3-. Triethanolamine binds in both the complexes in the monoanionic (H2tea-) mode. ba- is present as an anchoring auxiliary to generate di- and trinuclear clusters. The Cu(ii) ion is present as a distorted octahedral center in the Cu3 cluster (1), while the two Zn(ii) ions in 2 have been reported for the first time to possess distorted octahedral as well as tetrahedral geometry in the same molecule. The intriguing features of the non-covalent supramolecular interactions have been investigated and supported theoretically by using Hirshfeld surface analysis and ab initio methods. The solid state photoluminescence (PL) spectra of 1 and 2 disclose the luminescence property of the complexes. Due to the closed or nearly closed shell configuration (d9 or d10), the present complexes are screened for catalytic properties in the hydrocarboxylation of alkanes and cycloalkanes. The catalytic activity data are indicative of the potential catalytic properties of 1 and 2.
Ansari, Istikhar A.,Sama, Farasha,Raizada, Mukul,Shahid,Ahmad, Musheer,Siddiqi, Zafar A.
supporting information
p. 9840 - 9852
(2016/11/11)

Aerobic oxidation of aldehydes: Selectivity improvement using sequential pulse experimentation in continuous flow microreactor
The aerobic oxidation of aldehydewas investigated using a continuous flow microreactor under 5 bar of oxygen at room temperature. High-throughput screening of experimental conditions resulted in the development of an improved protocol. The synergistic use of a large range of salts and Mn(II) catalyst was found to be a very efficient catalytic system for selective aldehyde oxidation. Indeed for short residence time (i.e. 6min.), a quantitative conversion of 2-ethylhexanal was obtained with a selectivity toward carboxylic acid of 98%.
Vanoye, Laurent,Pablos, Mertxe,Smith, Neil,De Bellefon, Claude,Favre-Rguillon, Alain
p. 57159 - 57163
(2015/01/09)

How to force a classical chelating ligand to a metal non-chelating bridge: The observation of a rare coordination mode of diethanolamine in the 1D complex {[Cu2(Piv)4(H3tBuDea)](Piv)}n
The novel chain coordination polymer {[Cu2(Piv) 4(H3tBuDea)](Piv)}n (1) has been prepared through the self-assembly reaction of copper(ii) nitrate with pivalic acid (HPiv) and N-tert-butyldiethanolamine (H2tBuDea) in acetonitrile solution. Crystallographic analysis revealed the extremely rare non-chelating bridging coordination mode of diethanolamine ligand in 1, observed for the first time in transition metal complexes, as well as in complexes of diethanolamine having a non-coordinating aliphatic group at the N atom. Possible reasons for such a coordination and analysis of the main coordination modes of diethanolamine-based ligands are discussed. Variableerature (1.8-300 K) magnetic susceptibility measurements showed that 1 represents a rare example of dicopper(ii) tetracarboxylate that is a diamagnetic solid at room temperature. This behaviour is compared with literature examples and discussed on the basis of DFT calculations. Furthermore, 1 acts as an efficient catalyst for the mild hydrocarboxylation of linear and cyclic C5-C8 alkanes into the corresponding carboxylic acids.
Nesterova, Oksana V.,Kirillova, Marina V.,Guedes Da Silva, M. Fatima C.,Boca, Roman,Pombeiro, Armando J. L.
p. 775 - 783
(2014/01/17)

Oxidative degradation of fragrant aldehydes. Autoxidation by molecular oxygen
The oxidative degradation of fragrant aldehydes by molecular oxygen has been investigated. The oxygen consumption was monitored and the bond dissociation energy (BDE) of the aldehyde C(O)-H bond were calculated by DFT method. The oxidation products were identified by GC/MS. The different pathways accounting for the oxidative degradation are discussed. The main product is the acid, beside the formate ester. Both oxidation products result from the Baeyer-Villiger reaction involving a peracid R(CO)OOH whereas minor products arise from the hydroperoxide ROOH intermediate derived either from the acyl peroxy radical, R(CO)OO or from the decarboxylation of the peracid RC(O)OOH.
Marteau,Ruyffelaere,Aubry,Penverne,Favier,Nardello-Rataj
p. 2268 - 2275
(2013/04/10)

Insights in the aerobic oxidation of aldehydes
The hydroformylation of olefins (oxo synthesis) is the most important process for the production of higher aldehydes (>C4). The liquid phase oxidation of the latter to carboxylic acids by molecular oxygen or air has been known for more than 150 years and is an industrially important process. However, in the recent literature, several different oxidizing reagents and catalytic processes have been reported for this oxidation but most of them have limitations as they use environmentally unacceptable reagents or unnecessarily sophisticated conditions. Herein, we re-evaluated the air oxidation of aldehydes. We show that under mild conditions (air or oxygen and non-optimized stirring), reactions are transfer limited and thus catalyst has no effect on reaction rate. Using efficient stirring (self-suction turbine), uncatalysed air oxidation of 0.8 M aldehyde is possible in 50 min at room temperature whereas less than 10 min was necessary with 10 ppm Mn(ii). Thus, recommendations for avoiding common pitfalls that may rise during the evaluation of new catalysts are made. The Royal Society of Chemistry 2013.
Vanoye, Laurent,Favre-Reguillon, Alain,Aloui, Asma,Philippe, Regis,De Bellefon, Claude
p. 18931 - 18937
(2013/10/22)

Metal-free, hydroacylation of CC and NN bonds via aerobic C-H activation of aldehydes, and reaction of the products thereof
In this report, a thorough evaluation of the use of aerobically initiated, metal-free hydroacylation of various CC and NN acceptor molecules with a wide range of aldehydes is presented. The aerobic-activation conditions that have been developed are in sharp contrast to previous conditions for hydroacylation, which tend to use transition metals, peroxides that require thermal or photochemical degradation, or N-heterocyclic carbenes. The mildness of the conditions enables a number of reactions involving sensitive reaction partners and, perhaps most significantly, allows for α-functionalised chiral aldehydes to undergo radical-based hydroacylation with complete retention of optical purity. We also demonstrate how the resulting hydroacylation products can be transformed into other useful intermediates, such as γ-keto- sulfonamides, sultams, sultones, cyclic N-sulfonyl imines and amides.
Chudasama, Vijay,Akhbar, Ahmed R.,Bahou, Karim A.,Fitzmaurice, Richard J.,Caddick, Stephen
p. 7301 - 7317
(2013/10/22)

A safe and efficient flow oxidation of aldehydes with O2
A safe, straightforward, and atom economic approach for the oxidation of aliphatic aldehydes to the corresponding carboxylic acids within a continuous flow reactor is reported. Typically, the reaction is performed at room temperature using 5 bar of oxygen in PFA tubing and does require neither additional catalysts nor radical initiators except for those already contained in the starting materials. In some cases, a catalytic amount of a Mn(II) catalyst is added. Such a flow process may prove to be a valuable alternative to traditionally catalyzed aerobic processes.
Vanoye, Laurent,Aloui, Asma,Pablos, Mertxe,Philippe, Regis,Percheron, Aurelien,Favre-Reguillon, Alain,De Bellefon, Claude
supporting information
p. 5978 - 5981
(2014/01/06)

Metal-free reductive cleavage of benzylic esters and ethers: Fragmentations result from single and double electron transfers
The mechanisms for the reductive cleavage of benzylic esters and ethers by neutral organic electron donor 1 are different (see scheme). Products isolated from the cleavage of benzylic ethers result from the transfer of two electrons, without the intermediacy of benzyl radicals, which are believed to be intermediates in the reductive cleavage of benzylic esters. Copyright
Doni, Eswararao,O'Sullivan, Steven,Murphy, John A.
p. 2239 - 2242
(2013/03/28)

Tautomeric effect of hydrazone Schiff bases in tetranuclear Cu(ii) complexes: Magnetism and catalytic activity towards mild hydrocarboxylation of alkanes
Three new tetranuclear copper(ii) complexes [Cu(HL1)] 4·4EtOH (1·4EtOH), [Cu(HL2)]4 (2) and [Cu(H2L3)]4(NO3) 4·2H2O (3·2H2O) have been synthesized using three different hydrazone Schiff base ligands derived from the condensation of the aromatic acid hydrazides 2-hydroxybenzo-, 2-aminobenzo- or benzo-hydrazide, with 2,3-dihydroxybenzaldehyde. Complexes 1 and 3 have been characterized by single crystal X-ray diffraction analysis. The coordinating behaviour of the ligand depends on the nature of the ortho substituent present in the hydrazide moiety. The ligands bearing a strong electron donating group (by resonance) in the ortho position undergo complexation via enolization and deprotonation, whereas the absence of such an effect leads to complexation via the keto form, and two different types of tetranuclear Cu(ii) clusters, viz. open-cubane and cubane, are obtained. Variable temperature magnetic susceptibility measurements of complexes 1 and 3 have been carried out to examine the nature of magnetic interaction between the Cu(ii) centres. All the three complexes (1-3) act as good catalyst precursors towards mild hydrocarboxylation of linear and cyclic alkanes into carboxylic acids in water-acetonitrile medium.
Sutradhar, Manas,Kirillova, Marina V.,Guedes Da Silva, M. Fatima C.,Liu, Cai-Ming,Pombeiro, Armando J. L.
p. 16578 - 16587
(2013/12/04)

Laboratory evolution of enantiocomplementary Candida antarctica lipase B mutants with broad substrate scope
Candida antarctica lipase B (CALB) is a robust and easily expressed enzyme used widely in academic and industrial laboratories with many different kinds of applications. In fine chemicals production, examples include acylating kinetic resolution of racemic secondary alcohols and amines as well as desymmetrization of prochiral diols (or the reverse hydrolytic reactions). However, in the case of hydrolytic kinetic resolution of esters or esterifying kinetic resolution of acids in which chirality resides in the carboxylic acid part of the substrate, rate and stereoselectivity are generally poor. In the present study, directed evolution based on iterative saturation mutagenesis was applied to solve the latter problem. Mutants with highly improved activity and enantioselectivity relative to wild-type CALB were evolved for the hydrolytic kinetic resolution of p-nitrophenyl 2-phenylpropanoate, with the selectivity factor increasing from E = 1.2 (S) to E = 72 (S) or reverting to E = 42 (R) on an optional basis. Surprisingly, point mutations both in the acyl and alcohol pockets of CALB proved to be necessary. Some of the evolved CALB mutants are also efficient biocatalysts in the kinetic resolution of other chiral esters without performing new mutagenesis experiments. Another noteworthy result concerns the finding that enantiocomplementary CALB mutants for α-substituted carboxylic acid esters also show stereocomplementarity in the hydrolytic kinetic resolution of esters derived from chiral secondary alcohols. Insight into the source of stereoselectivity was gained by molecular dynamics simulations and docking experiments.
Wu, Qi,Soni, Pankaj,Reetz, Manfred T.
supporting information
p. 1872 - 1881
(2013/08/24)

Topologically unique 2D heterometallic CuII/Mg coordination polymer: Synthesis, structural features, and catalytic use in alkane hydrocarboxylation
The new two-dimensional (2D) heterometallic CuII/Mg coordination polymer [Cu2Mg2(μ-Htea)2(μ6- pma)(H2O)6]n?6nH2O (1) with an unprecedented [Cu2Mg(μ-O)2(μ-COO)2] - core has been easily generated by aqueous medium self-assembly from copper(II) nitrate, triethanolamine (H3tea), magnesium hydroxide, and pyromellitic acid (H4pma). The crystal structure of 1 is composed of infinite interdigitated 2D metal-organic layers that extend via H-bonds into an intricate 3D supramolecular framework. The topological analysis of 1 discloses a binodal 2,4-connected underlying 2D net with the unique topology described by the point symbol of (64?8?10)(6), further simplification of which leads to an uninodal 4-connected net with the sql topology. Apart from representing a very rare example of the heterometallic Cu/Mg coordination network, compound 1 also acts as an efficient catalyst precursor for the mild single-pot hydrocarboxylation of linear and cyclic C n (n = 5-9) alkanes into the corresponding Cn+1 carboxylic acids.
Kirillov, Alexander M.,Karabach, Yauhen Y.,Kirillova, Marina V.,Haukka, Matti,Pombeiro, Armando J. L.
scheme or table
p. 1069 - 1074
(2012/06/18)

Rapid aerobic oxidation of alcohols to carbonyl compounds with dioxygen using metallodeuteroporphyrin dimethyl esters as catalysts in the presence of isobutylaldehyde
A facile biomimetic method for rapid oxidation of alcohols to carbonyl compounds using dioxygen as the primary oxidant catalyzed by metallodeuteroporphyrin dimethyl ester [M(DPDME)] in acetonitrile as the reaction solvent and isobutylaldehyde as cocatalyst has been investigated. Among the M(DPDME) catalysts, where M = Fe(III), Co(II), Mn(III), Ni(II), Cu(II), and Zn(II), cobalt porphyrin was found to be the most active and effective catalyst. The catalytic system was widely used in the oxidation of various alcohols and especially exhibited excellent activity for oxidation of aromatic alcohols under mild conditions. Moreover, M(DPDME) was prepared from an improved facile method by chemical modification of natural hemin and an alternative mechanism for the aerobic oxidation of alcohols has been proposed and discussed.
Sun, Chengguo,Hu, Bingcheng,Liu, Zuliang
experimental part
p. 295 - 303
(2012/07/28)

Green and chemoselective oxidation of alcohols with hydrogen peroxide: A comparative study on Co(II) and Co(III) activity toward oxidation of alcohols
Two new cobalt (II) and cobalt (III) complexes of a terpyridine based ligand, (4′-(2-thienyl)-2,2′;6′,2″-terpyridine (L)), were synthesized. Each complex has two units of the tridentate ligand. The complexes were fully characterized by spectroscopic methods as well as CHN analysis. Moreover, their solid state structures were determined by single crystal X-ray diffraction. The cobaltous complex has the formula [Co(L) 2](NO3)2·2CH3OH·H 2O (1), whereas the cobaltic complex shows the formula [Co(L) 2](NO3)3·2CH3OH (2). Both complexes were tested as homogenous catalysts for the oxidation of a variety of aliphatic and aromatic alcohols utilizing aqueous hydrogen peroxide in water media. The Co(II) complex showed more activity in comparison with its isostructural Co(III) species. The results show that the aromatic alcohols were oxidized with higher conversions and selectivity compared to the aliphatic substrates, possibly due to their conjugation systems which thermodynamically stabilized the carbonyl products.
Nemati Kharat, Ali,Bakhoda, Abolghasem,Tamaddoni Jahromi, Bahareh
scheme or table
p. 2768 - 2775
(2011/12/13)

Optimization of enzymatic synthesis of cetyl 2-ethylhexanoate by Novozym 435
Waxes are esters obtained from long-chain fatty acids and long-chain alcohols which are biodegradable, biocompatible and nontoxic. Seafowl feather oil is a natural wax ester that exists on seafowl feathers. Cetyl 2-ethylhexanoate is the major ingredient of seafowl feather oil. Cetyl 2-ethylhexanoate is widely used in cosmetics as a base oil because of its lubricity, moisture retention and non-toxic properties. An optimal production of cetyl 2-ethylhexanoate by direct esterification of cetyl alcohol with 2-ethylhexanoic acid was developed using an immobilized lipase (Novozym 435) as a catalyst in n-hexane. Response surface methodology (RSM) and 5-level-4-factor central composite rotatable design (CCRD) were employed to evaluate the effects of reaction time, reaction temperature, substrate molar ratio, and enzyme amount on the yield of cetyl 2-ethylhexanoate. The results show that reaction time, reaction temperature, substrate molar ratio, and enzyme amount have significant effects on the yield of the esterification reaction. On the basis of ridge-max analysis, the optimum conditions were as follows: a reaction time of 2.65 days, a reaction temperature of 56.18 °C, a substrate molar ratio of 2.55:1, and an enzyme amount of 251.39%. The predicted and experimental values of molar conversion were 91.95 and 89.75 ± 1.06%, respectively. AOCS 2011.
Chen, Hsiao Ching,Kuo, Chia-Hung,Chen, Hsin Hung,Liu, Yung-Chuan,Shieh, Chwen Jen
scheme or table
p. 1917 - 1923
(2012/04/10)

New diamondoid-like [Cu3B(μ-O)6] core self-assembled from Bis-Tris biobuffer for mild hydrocarboxylation of alkanes to carboxylic acids
The new tricopper(ii) complex [Cu3(μ3-BO)(H 3L)3][BF4]·2H2O (1) with an unprecedented diamondoid-like [Cu3B(μ-O)6] core has been easily generated by self-assembly in an aqueous medium from Cu(NO 3)2, NaBF4, NaOH and Bis-Tris (H5L) biobuffer, (HOCH2)3CN(CH2CH2OH) 2. Compound 1 efficiently promotes the mild single-pot hydrocarboxylation, by CO and H2O, of various linear and cyclic Cn (n = 2-8) alkanes into the corresponding Cn+1 carboxylic acids.
Kirillov, Alexander M.,Karabach, Yauhen Y.,Kirillova, Marina V.,Haukka, Matti,Pombeiro, Armando J. L.
supporting information; experimental part
p. 6378 - 6381
(2011/08/06)

Mild oxidative functionalization of alkanes and alcohols catalyzed by new mono- and dicopper(II) aminopolyalcoholates
The new mono- and dicopper(II) complexes [Cu(H3L 1)(NCS)] (1) and [Cu2(μ-HL2) 2(NCS)2] (2) were easily self-assembled from Cu(CH 3COO)2·H2O, NaNCS, NaOH and N,N,N′,N′-tetrakis(2-hydroxyethyl)ethylenediamine (H 4L1) or N-ethyldiethanolamine (H2L 2), respectively. They were fully characterized by IR spectroscopy, ESI-MS(±), elemental and single-crystal X-ray diffraction analyses, and applied as homogeneous catalysts for (i) the oxidation of alkanes by t-BuOOH in air to alkyl peroxides, alcohols and ketones, and in turn the oxidation of alcohols to ketones, and (ii) the single-pot aqueous medium hydrocarboxylation, by CO, H2O and K2S2O8, of various linear and cyclic Cn (n = 5-8) alkanes into the corresponding C n+1 carboxylic acids. Compound 1 was significantly more active in the oxygenation of alkanes and oxidation of alcohols, allowing to achieve 18% yield (TON = 800) of oxygenates in the oxidation of cyclohexane, and 78% yield (TON = 780) of cyclohexanone in the oxidation of cyclohexanol. In alkane hydrocarboxylations, 1 and 2 exhibited comparable activities with the total yields (based on alkane) of carboxylic acids attaining 39%. The selectivity parameters for oxidative transformations were measured and discussed, supporting free-radical mechanisms.
Kirillov, Alexander M.,Kirillova, Marina V.,Shul'Pina, Lidia S.,Figiel, Pawe? J.,Gruenwald, Katrin R.,Guedes Da Silva, M. Fátima C.,Haukka, Matti,Pombeiro, Armando J.L.,Shul'Pin, Georgiy B.
experimental part
p. 26 - 34
(2012/01/14)

Mild, single-pot hydrocarboxylation of linear C5-C9 alkanes into branched monocarboxylic C6-C10 acids in copper-catalyzed aqueous systems
A single-pot method has been developed for the hydrocarboxylation of the liquid C5-C9 alkanes (n-pentane, n-hexane, n-heptane, n-octane, n-nonane and 3-methylhexane) into the branched monocarboxylic C 6-C10 acids bearing one more carbon atom. This method is characterized by a direct, selective and low-temperature (60 °C) hydrocarboxylation reaction of the alkane with carbon monoxide, water (which acts as a reagent besides being a solvent component) and potassium peroxodisulfate, in H2O/MeCN medium. The hydrocarboxylations are markedly enhanced in the presence of a tetracopper(II) triethanolaminate complex as a homogeneous catalyst precursor. Total yields (based on alkane) of carboxylic acids up to 46% (with 97-99% overall selectivity) have been achieved, which are remarkable in the field of alkane functionalization under mild conditions, especially for a C-C bond formation reaction in aqueous acid-solvent-free medium. The regio- and bond selectivity parameters have been determined and a free radical mechanism has been proposed.
Kirillova, Marina V.,Kirillov, Alexander M.,Pombeiro, Armando J.L.
experimental part
p. 106 - 113
(2012/04/04)

Alternative selective oxidation pathways for aldehyde oxidation and alkene epoxidation on a SiO2-supported Ru-monomer complex catalyst
We have prepared a novel Ru-mononer complex supported on a SiO2 surface by using a Rumonomer complex precursor with a p-cymene ligand, which was found to be highly active for the selective oxidation of aldehydes and the epoxidation of alkenes using O2. The structure of the supported Ru catalyst was characterized by means of FT-IR, solid-state NMR, diffuse-reflectance UV/vis, XPS, Ru K-edge EXAFS, and DFT calculations, which demonstrated the formation of isolatedly located, unsaturated Ru centers behind a p-cymene ligand of the Ru-complex precursor. The site-isolated Ru-monomer complex on SiO2 achieved tremendous TONs (turnover numbers) for the selective oxidation of aldehydes and alkenes; e.g. TONs of 38,800,000 for selective isobutyraldehyde (IBA) oxidation and 2,100,000 for trans-stilbene epoxidation at ambient temperature, which are among the highest TONs in metal-complex catalyzes to our knowledge. We also found that the IBA sole oxidation with an activation energy of 48 kJ mol-1 much more facile than the trans-stilbene epoxidation with an activation energy of 99 kJ mol -1 was completely suppressed by the coexistence of trans-stilbene. The switchover of the selective oxidation pathways from the IBA oxidation to the trans-stilbene epoxidation was explained in terms of energy profiles for the alternative selective oxidation pathways, resulting in the preferential coordination of trans-stilbene to the Ru-complex at the surface. This aspect gives an insight into the origin of the efficient catalysis for selective epoxidation of alkenes with IBA/O2.
Tada, Mizuki,Muratsugu, Satoshi,Kinoshita, Mutsuo,Sasaki, Takehiko,Iwasawa, Yasuhiro
experimental part
p. 713 - 724
(2010/04/01)

Dioxygen mediated hydroacylation of vinyl sulfonates and sulfones on water
Herein we report a mild, facile method for the preparation of 1,4-keto-sulfonates and sulfones on water. Further synthetic manipulations can result in products that are not readily accessed by hydroacylation of electron rich alkenes.
Chudasama, Vijay,Fitzmaurice, Richard J.,Ahern, Jenna M.,Caddick, Stephen
scheme or table
p. 133 - 135
(2010/04/01)

Straightforward radical organic chemistry in neat conditions and "on water"
Radicals generated during aldehyde oxidation to carboxylic acids can be efficiently trapped under environmentally friendly conditions, either in neat conditions or "on water".
Shapiro, Nelly,Kramer, Maria,Goldberg, Israel,Vigalok, Arkadi
supporting information; experimental part
p. 582 - 584
(2010/09/05)

Syntheses and evaluation of anticonvulsant profile and teratogenicity of novel amide derivatives of branched aliphatic carboxylic acids with 4-aminobenzensulfonamide
Despite the availability of 14 new antiepileptic drugs (AEDs), about 30% of epileptic patients are not seizure-free. Consequently there is substantial need to develop new effective AEDs. A novel class of aromatic amides composed of phenylacetic acid or branched aliphatic carboxylic acids, with five to nine carbons in their carboxylic moiety, and aminobenzenesulfonamide were synthesized and evaluated in the anticonvulsant rat-maximal electroshock (MES) and subcutaneous metrazol seizure (scMet) tests. Fourteen of the synthesized amides had an anticonvulsant ED50 of 50 values of 7.6, 9.9, and 9.4 mg/kg and remarkable protective index (PI = TD 50/ED50) values of 65.7, 50.5, and 53.2, respectively. These potent sulfanylamides caused neural tube defects only at doses markedly exceeding their effective dose. The anticonvulsant properties of these compounds make them potential candidates for further development as new, potent, and safe AEDs.
Hen, Naama,Bialer, Meir,Wlodarczyk, Bogdan,Finnell, Richard H.,Yagen, Boris
experimental part
p. 4177 - 4186
(2010/09/04)

Synthesis and evaluation of antiallodynic and anticonvulsant activity of novel amide and urea derivatives of valproic acid analogues
Valproic acid (VPA, 1) is a major broad spectrum antiepileptic and central nervous system drug widely used to treat epilepsy, bipolar disorder, and migraine. VPA's clinical use is limited by two severe and lifethreatening side effects, teratogenicity and hepatotoxicity. A number of VPA analogues and their amide, N-methylamide and urea derivatives, were synthesized and evaluated in animal models of neuropathic pain and epilepsy. Among these, two amide and two urea derivatives of 1 showed the highest potency as antineuropathic pain compounds, with ED50 values of 49 and 51 mg/kg for the amides (19 and 20) and 49 and 74 mg/kg for the urea derivatives (29 and 33), respectively. 19, 20, and 29 were equipotent to gabapentin, a leading drug for the treatment of neuropathic pain. These data indicate strong potential for the above-mentioned novel compounds as candidates for future drug development for the treatment of neuropathic pain. 2009 American Chemical Society.
Kaufmann, Dan,Bialer, Meir,Shimshoni, Jakob Avi,Devor, Marshall,Yagen, Boris
experimental part
p. 7236 - 7248
(2010/07/04)

OXIDATION OF ALDEHYDES AND ALKENES
A general method is disclosed for the conversion of aldehydes and alkenes to the corresponding carboxylic acids and 1,2-diols. The method is carried out in a catalyst-free aqueous medium under an atmosphere of oxygen or oxygen containing gas.
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Page/Page column 14-15

(2009/01/24)

Highly efficient organic reactions "on water", "in water", and both
(Chemical Equation Presented) Wet, wet, wet: Hydrophobic aldehydes are cleanly oxidized upon stirring with water in air. Addition of hydrophobic isocyanides to aqueous suspensions of such aldehydes results in the formation of Passerini reaction products, with the aldehyde being the source of both carbonyl and ester functions. Partially watersoluble reagents reacted slower than water-insoluble ones. Isotope labeling studies show that water participates in these "on water" reactions.
Shapiro, Nelly,Vigalok, Arkadi
p. 2849 - 2852
(2008/12/23)

Preparation or organic acids from aldehyde compounds by means of liquid phase oxidation reaction
The present invention provides a method of preparing organic acids from aldehyde compounds by means of liquid phase oxidation which converts an aldehyde group of a compound harboring one or more aldehyde groups into a carboxyl group by using an ionic liquid as a reaction solvent or a reaction catalyst. According to the present invention, the ionic liquid is less volatile even at high temperature and stable against heat, enhancing conversion rate and selectivity and further increasing yield. In addition, the ionic liquid can be easily separated and recycled from the reactant and product.
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Page/Page column 3-4

(2008/06/13)

METHOD OF PREPARING ORGANIC ACIDS FROM ALDEHYDE COMPOUNDS BY MEANS OF LIQUID PHASE OXIDATION REACTION
The present invention provides a method of preparing organic acids from aldehyde compounds by means of liquid phase oxidation which converts an aldehyde group of a compound harboring one or more aldehyde groups into a carboxyl group by using an ionic liquid as a reaction solvent or a reaction catalyst. According to the present invention, the ionic liquid is less volatile even at high temperature and stable against heat, enhancing conversion rate and selectivity and further increasing yield. In addition, the ionic liquid can be easily separated and recycled from the reactant and product.
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Page/Page column 7; 8

(2008/06/13)

Method for producing carboxylic acid
An aldehyde-containing oily solution and an aqueous hydrogen peroxide solution are reacted in the presence of a catalyst comprising a polymer compound having a sulfonic acid group in a side chain thereof in a heterogeneous solution system. According to such a reaction process, carboxylic acid can be efficiently produced under mild conditions having very little influence and toxicity on the environment and a human body, with simple operations, without requiring the operation for removing a solvent after the completion of the reaction.
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Page/Page column 4

(2008/06/13)

METHOD FOR PREPARING ORGANIC ACID
Provided is a method for producing an organic acid, which includes: mixing a compound containing one or two aldehyde groups and a solvent to obtain a reaction mixture; and maintaining the reaction mixture in a liquid phase in the presence of pure oxygen or O2-enriched air containing 25-90 % oxygen at a temperature of a 0-70 °C, under a pressure condition of an atmospheric pressure to 10kg/cm2, and for 2-10 hours. The method can enhance the selectivity of the organic acid, thereby increasing the yield of the organic acid.
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Page 10; 11

(2008/06/13)