118-90-1Relevant articles and documents
Surfactant-assisted assembly of nanoscale zinc coordination compounds to enhance tandem conversion reactions in water
Huang, Chao,Zhu, Kaifang,Zhang, Yingying,Lu, Guizhen,Shao, Zhichao,Gao, Kuan,Mi, Liwei,Hou, Hongwei
, p. 16008 - 16016 (2019)
Precise control over the morphology and size of coordination polymers (CPs) is crucial for extending these inorganic-organic materials to many advanced applications, in particular for heterogeneous catalysis. In this work, two Zn-based CPs, {[Zn3(idbt)2(4,4′-dmbpy)2]·H2O}n (1) and {[Zn3(idbt)2(H2O)3]·H2O}n (2) (H3idbt = 5,5′-(1H-imidazole-4,5-diyl)-bis-(2H-tetrazole), 4,4′-dmbpy = 4,4′′-dimethyl-2,2′-bipyridine), were synthesized through solvothermal reactions. The morphologies and particle sizes of 1 and 2 could be controlled from large scale to nanoscale by regulating the amount of poly(vinyl alcohol) (PVA). Furthermore, for the conversion reactions of nitromethylbenzenes into benzoic acids, the catalytic properties of nanoscale 1 and 2 were much more efficient than those of large size of 1 and 2, because of the benefit of readily accessible active sites in the nanoscale sized particles, which provide a tunable and functionalizable platform for the conversion reaction by minimizing the diffusion distance but do little for the selectivity.
Experimental and theoretical investigation of the oxidative carbonylation of toluene to toluic acid catalyzed by palladium(II) in the presence of vanadium and molecular oxygen
Behn, Andrew,Zakzeski, Joseph,Head-Gordon, Martin,Bell, Alexis T.
, p. 91 - 97 (2012)
The mechanism and kinetics of the liquid-phase, oxidative carbonylation of toluene to toluic acid over Pd(II) in the presence of trifluoroacetic acid (TFAH), trifluoroacetic anhydride (TFAA), and molecular oxygen were investigated through a combination of experimental and theoretical approaches. The experimental results are consistent with the previously proposed mechanism for the oxidative carbonylation of arenes. The reaction is initiated by coordination of toluene to the Pd(II) complex and activation of a CH bond in the benzene ring. This initial step becomes rate limiting when a sufficiently high (NH 4VO3)/Pd ratio is used for the reoxidation of Pd(0) to Pd(II). Both processes are found to be dependent on the electron withdrawing and donating capability of the anionic ligands. Overall catalyst activity peaks for ligands of intermediate basicity, and diminishes for both more and less basic ligands. Theoretical analysis of the coordination of toluene and activation of the CH bond on the benzene ring reveals that the basicity of the ligands affects the two processes in opposite ways. Weakly basic ligands promote the coordination of toluene but have the opposite effect on the activation of the CH bond. The tradeoff in these two effects leads to a maximum in the apparent rate coefficient with pKa of the conjugate acid of the anionic ligands. The absence of significant product stereoselectivity is due to a lack of steric hindrance in the binding of toluene to the Pd(II) complex.
Cetyltrimethylammonium dichromate: A phase-transferring oxidant
Patel, Sabita,Kuanar, Minati,Nayak, Biswa B.,Banichul,Mishra, Bijay K.
, p. 1033 - 1037 (2005)
A phase-transferring oxidant, cetyltrimethylammonium dichromate (CTADC) has been prepared and characterized from elemental analysis and spectral data. Application of this reagent to oxidize alcohols, aldehyde, and cinnamic acid is reported. Copyright Taylor & Francis, Inc.
Electrochemical reduction of phthalide at carbon cathodes in dimethylformamide: Effects of supporting electrolyte and gas chromatographic injector-port chemistry on the product distribution
Pasciak, Erick M.,Hochstetler, Spencer E.,Mubarak, Mohammad S.,Evans, Dennis H.,Peters, Dennis G.
, p. 557 - 563 (2013)
Cyclic voltammetry and controlled-potential (bulk) electrolysis have been used to investigate the direct reduction of phthalide at carbon electrodes in dimethylformamide (DMF) containing 0.10 M tetramethylammonium perchlorate (TMAP) or tetra-n-butylammonium perchlorate (TBAP). Cyclic voltammograms recorded with a glassy carbon electrode exhibit a single cathodic peak and a corresponding anodic peak that arise, respectively, from one-electron reduction of phthalide to generate a radical-anion intermediate and from reoxidation of the intermediate. At a scan rate of 100 mV s-1, quasi-reversible behavior is observed (due to ring-opening of the radical-anion), whereas fully reversible behavior is seen at 5 V s-1 or higher. Digital simulation of cyclic voltammograms indicates that the lifetime of the radical-anion is 3.5 s. Bulk electrolysis of phthalide at a reticulated vitreous carbon cathode affords products that depend on the procedure used to analyze the catholyte. Direct injection of catholyte into a gas chromatograph shows phthalide and a 2-methylbenzoate ester bearing an alkyl moiety from the supporting-electrolyte cation. However, if the catholyte is partitioned between diethyl ether and aqueous hydrochloric acid before gas chromatographic analysis, phthalide and 2-methylbenzoic acid are observed. Thermally induced reactions that occur in the injector port of the gas chromatograph are responsible for the formation of the 2-methylbenzoate ester as well as for the phthalide found in all electrolyzed solutions.
Pd(OAc)2 promoted bis-N-heterocyclic carbene-catalyzed oxidative transformation of aldehydes
Yu, Ya-Han,Wang, Tsui,Chiu, Chien-Cheng,Lu, Ta-Jung,Lee, Dong-Sheng
, p. 202 - 205 (2020)
The bis-N-heterocyclic carbene-catalyzed (bis-NHC-catalyzed) oxidative transformation of aldehydes was successfully studied in water under air. The reaction rate increased through the use of Pd(OAc)2 as an additive. Notably, the catalytic system exhibited good tolerance toward aliphatic and aromatic aldehydes bearing halide and alkyl functional groups. In addition, gram-scale reaction was also tested in this study. The use of water and operational simplicity make this methodology environmentally benign and cost-effective.
Selective liquid phase oxidation of o-xylene with gaseous oxygen by transition metal containing polysiloxane initiator/catalyst systems
Foerster, Tobias,Schunk, Stephan A.,Jentys, Andreas,Lercher, Johannes A.
, p. 25 - 33 (2011)
The selective liquid phase oxidation of o-xylene over hydrophobic porous Co2+ and Mn3+ containing polysiloxane catalysts showed that both catalysts had higher activity than the homogeneous benchmark system Co naphthenate. The solid catalyst/initiator systems accelerate the radical initiation and the hydroperoxide decomposition. 2-Methylbenzyl hydroperoxide plays a key role in the reaction network as it is the first observed intermediate and is efficiently decomposed by the catalysts. The selectivity of the hydroperoxide decomposition can be controlled to some extent by the choice of transition metal. Co2+ enhances the formation of o-tolualdehyde, while Mn3+ increases the tendency to 2-methylbenzyl alcohol formation. The hydrophobic character, demonstrated by the weak adsorption of water, retards the interaction with the polar reaction products and allows their fast desorption, which in turn is a major cause for the high catalytic activity.
Formation of a Cluster H2V10O 284– under the Action of Br?nsted Acids and Its Catalytic Activity in Oxidation of Alkylbenzenes
Ul’yanova,Pervova,Slepukhin,Aksenova,Pestov
, p. 687 - 690 (2018)
New method was developed for the preparation of vanadium cluster of the composition {Me2NH2}4* H2V10O28 from vanadyl(IV) acetylacetonate in the presence of 2-hydroxy-2-trifluoromethylchroman-4-one or its synthetic precursor, 2′-hydroxyacetophenone. The structure of the cluster was proved by X-ray diffraction (XRD) analysis. The cluster of decavanadate catalyzes oxidation of toluene and o-xylene creating promising situation for developing new catalytic materials.
Functionalization of benzylic C(sp3)-H bonds of heteroaryl aldehydes through N-Heterocyclic carbene organocatalysis
Chen, Xingkuan,Yang, Song,Song, Bao-An,Chi, Yonggui Robin
, p. 11134 - 11137 (2013)
Aryl aldehyde activation: Oxidative activation of 2-methylindole-3- carboxaldehyde (I) through N-heterocyclic carbene (NHC) organocatalysis generates heterocyclic ortho-quinodimethane (II) as a key intermediate. This intermediate then undergoes formal [4+2] cycloaddition with trifluoromethyl ketones or isatins to form polycyclic lactones containing a quaternary carbon center. Copyright
Beneficial effect of TMSCl in the Lewis acid-mediated carboxylation of aromatic compounds with carbon dioxide
Nemoto, Koji,Yoshida, Hiroki,Suzuki, Yutaka,Morohashi, Naoya,Hattori, Tetsutaro
, p. 820 - 821 (2006)
The Lewis acid-mediated carboxylation of aromatic compounds with CO 2 is significantly promoted by the addition of a large excess of chlorotrimethylsilane (TMSCl) to give arylcarboxylic acids in good to excellent yields. Copyright
Thermal reactions of benzocyclobutenone with alcohols
Wang, Zhi Yuan,Suzzarini, Laurence,Gao, Jian Ping
, p. 5745 - 5746 (1997)
Thermolysis of benzocyclobutenone alone at 250°C yielded the isocoumarin 3 in 60% yield. In the presence of alcohols at 170-200°C, the corresponding 2-methylbenzoates 4a-e and 5a-c were formed in quantitative yields.
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Fisher,Grant
, p. 718 (1935)
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Photolysis of a series of α-brominated ortho-xylenes in apolar solvents
Rezende, Daisy de B.,Campos, Ivan P. de Arruda,Toscano, Vicente G.,Catalani, Luiz H.
, p. 1857 - 1862 (1995)
The α-brominated ortho-xylenes have been subjected to 254 nm irradiation in deaerated benzene, isooctane and benzene-cyclohexene.The product analysis revealed that homolysis of the C-Br bond is followed by a series of hydrogen abstraction and radical recombination reactions resulting in xylenes more and less brominated than the starting compound.The less brominated products are formed with higher quantum yield when cyclohexene is present, due to hydrogen abstraction by the o-benzyl radical formed initially, together with cyclohexene dimers.Additionally, the formation of 2-bromo-2,4,4-trimethylpentane is observed when isooctane is the solvent.The quantum yields observed for the photolysis of 1 and 2 are higher in benzene than in isooctane, suggesting sensitization by benzene.A biradical intermediate of the type o-quinodimethane was expected in the case of (a) photolysis of the o-benzyl radical formed (biphotonic process) or (b) intramolecular hydrogen abstraction.However, the addition of cyclohexene failed to produce the expected Diels-Alder adduct.The synthesis of the novel α,α-dibromo-o-xylene 3 is reported.
Nakayama
, p. 1124 (1969)
Direct carboxylation of arenes and halobenzenes with CO2 by the combined use of AlBr3 and R3SiCl
Nemoto, Koji,Yoshida, Hiroki,Egusa, Naoki,Morohashi, Naoya,Hattori, Tetsutaro
, p. 7855 - 7862 (2010)
The Lewis acid-mediated direct carboxylation of aromatic compounds with CO2 is efficiently promoted by the addition of silyl chlorides bearing three alkyl and/or aryl substituents in total on the silicon atom. Thus, toluene, xylenes, mesitylene, and some other alkylbenzenes are treated with a 1:1 mixture of AlBr3 and Ph3SiCl in neat substrates under CO2 pressure (3.0 MPa) at room temperature, to give the corresponding carboxylic acids in 60-97% yields, based on AlBr3. Polycyclic arenes, including naphthalene, phenanthrene, and biphenyl, are regioselectively carboxylated in 91-98% yields with the aid of 1 molar equiv of AlBr3 and Ph3SiCl in an appropriate solvent, chosen from benzene, chlorobenzene, and fluorobenzene. These solvents, as well as bromobenzene, resist carboxylation; however, they are also carboxylated in moderate yields when treated with a 1:5 mixture of AlBr3 and iPrSiCl at elevated temperatures. The FT-IR spectrum of a mixture prepared by exposing a suspension of AlBr3 and Ph3SiCl in cyclohexane to CO 2 exhibits an absorption band around 1650 cm-1, assigned to the C=O stretching vibration of a species consisting of CO2, AlBr3, and Ph3SiCl, which suggests that the silyl chlorides activate CO2 in cooperation with AlBr3. 1H NMR analysis of unworked-up reaction mixtures reveals that the products merge as aluminum carboxylates. The mass balance concerning silicon indicates that the silyl chlorides are recycled during the reaction sequence. On the basis of these observations, a feasible mechanism is proposed for the present carboxylation.
Nanosheet-assembled microflower-like coordination polymers by surfactant-assisted assembly with enhanced catalytic activity
Han, Suzhen,Hu, Mingjun,Huang, Chao,Lu, Guizhen,Mi, Liwei,Qin, Na,Zhang, Ying-Ying,Zhu, Kaifang
, p. 7858 - 7863 (2020)
Tuning the morphology and size of coordination polymers (CPs) is an effective strategy to enable crystalline materials for desired applications. Herein, two CPs, named [Cd2(DBTP)(H2O)2]n (1) and {[Zn2(DBTP)(H2O)]·2.5H2O}n (2), were prepared by employing a rigid V-shaped and multidentate N-heterocyclic ligand 2,6-di(1H,2′H-[3,3′-bi(1,2,4-triazol)]-5′-yl)pyridine (H4DBTP) under solvothermal conditions. Their crystal morphologies and sizes were controlled by varying the type and the amount of surfactants. The morphology can be changed from bulk blocks to microflower-like hierarchical spheres assembled by nanosheets and the mean size of the microflowers is approximately 2 μm. Nanoscale 1a and 2a were further evaluated as heterogeneous catalysts for the conversion reactions of nitromethylbenzenes into benzoic acids. The results showed that nanoscale 2a is a more efficient catalyst than nanoscale 1a and their corresponding bulk counterparts.
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Brill
, p. 837,838 (1960)
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The Carboxylic Acid Group as an Effective Director of Ortho-Lithiation
Mortier, Jacques,Moyroud, Joeel,Bennetau, Bernard,Cain, Paul A.
, p. 4042 - 4044 (1994)
Treatment of PhCO2H in tetrahydrofuran with 2.2 equiv of a 1:1 sec-butyllithium/N,N,N',N'-tetramethyl-1,2-ethylenediamine complex at -90 deg C gave o-LiC6H4CO2Li, which was treated with electrophiles to give o-RC6H4CO2H (R = Me, SMe, Cl, Br) in good yields.
Ultrasmall Platinum Nanoparticles Supported Inside the Nanospaces of Periodic Mesoporous Organosilica with an Imidazolium Network: An Efficient Catalyst for the Aerobic Oxidation of Unactivated Alcohols in Water
Karimi, Babak,Naderi, Zahra,Khorasani, Mojtaba,Mirzaei, Hamid M.,Vali, Hojatollah
, p. 906 - 910 (2016)
The imidazolium group inside the wall of a periodic mesoporous organosilica provides an excellent environment for the stabilization of ultrasmall Pt nanoparticles ((NP)@PMO-IL) with significant activity and recyclability in the selective aerobic oxidation of various alcohols in water at ambient pressure of oxygen. In particular, the catalyst exhibited high activity in the oxidation of unactivated primary alcohols and sterically encumbered secondary aliphatic alcohols, which remain challenging substrates for many catalytic aerobic protocols.
An efficient Pd(II)-based catalyst system for carboxylation of aromatic C-H bond by addition of a phosphenium salt
Sakakibara, Ken,Yamashita, Makoto,Nozaki, Kyoko
, p. 959 - 962 (2005)
Addition of a phosphenium dramatically improved the reaction yields in the carboxylation of arenes by formic acid catalyzed by Pd(II). Control experiments revealed that the majority of the phosphenium triflate was converted to a mixed anhydride of phosphonic acid and formic acid (7), which however did not substitute for the phosphenium to improve the reaction yield.
Gram-scale synthesis of carboxylic acids via catalytic acceptorless dehydrogenative coupling of alcohols and hydroxides at an ultralow Ru loading
Chen, Cheng,Cheng, Hua,Verpoort, Francis,Wang, Zhi-Qin,Wu, Zhe,Yuan, Ye,Zheng, Zhong-Hui
, (2021/12/13)
Acceptorless dehydrogenative coupling (ADC) of alcohols and water/hydroxides is an emergent and graceful approach to produce carboxylic acids. Therefore, it is of high demand to develop active and practical catalysts/catalytic systems for this attractive transformation. Herein, we designed and fabricated a series of cyclometallated N-heterocyclic carbene-Ru (NHC-Ru) complexes via ligand tuning of [Ru-1], the superior complex in our previous work. Gratifyingly, gram-scale synthesis of carboxylic acids was efficiently enabled at an ultralow Ru loading (62.5 ppm) in open air. Moreover, effects of distinct ancillary NHC ligands and other parameters on this catalytic process were thoroughly studied, while further systematic studies were carried out to provide rationales for the activity trend of [Ru-1]-[Ru-7]. Finally, determination of quantitative green metrics illustrated that the present work exhibited superiority over representative literature reports. Hopefully, this study could provide valuable input for researchers who are engaging in metal-catalyzed ADC reactions.
Oxidative carbon-carbon bond cleavage of 1,2-diols to carboxylic acids/ketones by an inorganic-ligand supported iron catalyst
Chen, Weiming,Xie, Xin,Zhang, Jian,Qu, Jian,Luo, Can,Lai, Yaozhu,Jiang, Feng,Yu, Han,Wei, Yongge
supporting information, p. 9140 - 9146 (2021/11/23)
The carbon-carbon bond cleavage of 1,2-diols is an important chemical transformation. Although traditional stoichiometric and catalytic oxidation methods have been widely used for this transformation, an efficient and valuable method should be further explored from the views of reusable catalysts, less waste, and convenient procedures. Herein an inorganic-ligand supported iron catalyst (NH4)3[FeMo6O18(OH)6]·7H2O was described as a heterogeneous molecular catalyst in acetic acid for this transformation in which hydrogen peroxide was used as the terminal oxidant. Under the optimized reaction conditions, carbon-carbon bond cleavage of 1,2-diols could be achieved in almost all cases and carboxylic acids or ketones could be afforded with a high conversion rate and high selectivity. Furthermore, the catalytic system was used efficiently to degrade renewable biomass oleic acid. Mechanistic insights based on the observation of the possible intermediates and control experiments are presented.
Isotruxene-based porous polymers as efficient and recyclable photocatalysts for visible-light induced metal-free oxidative organic transformations
Zhang, Haowen,Zhang, Xiao,Zheng, Ying,Zhou, Cen
supporting information, p. 8878 - 8885 (2021/11/27)
Two new isotruxene-based porous polymers were prepared and demonstrated to be highly efficient, metal-free heterogeneous photocatalysts for oxidative transformations using air as the mild oxidant under visible-light irradiation. Both catalysts show excellent recyclability. In addition, the reactions can be performed in water, further indicating the greenness of this method. This journal is
