502-49-8Relevant articles and documents
Oxidations of secondary alcohols to ketones using easily recyclable bis(trifluoroacetate) adducts of fluorous alkyl iodides, CF3(CF 2)n-1I(OCOCF3)2
Tesevic, Verona,Gladysz
, p. 7433 - 7440 (2006)
Reactions of commercial fluorous alkyl iodides RfnI (1-R fn; Rfn = CF3(CF2)n-1; n = 7, 8, 10, 12) with 80% H2O2 and trifluoroacetic anhydride give RfnI(OCOC
Metal complexes of a tetraazacyclotetradecane bearing highly fluorinated tails: New catalysts for the oxidation of hydrocarbons under fluorous biphasic conditions
Pozzi, Gianluca,Cavazzini, Marco,Quici, Silvio,Fontana, Simonetta
, p. 7605 - 7608 (1997)
The commercially available macrocycle tetraazacyclotetradecane (cyclam) has been converted into the fluorocarbon soluble ligand 1 by N-functionalization with R(F)CH2OCH2CH2OTs 3, wherein R(F) is a (per)fluorooxyalkylenic c
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Friess,Boekelheide
, p. 4145 (1949)
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Novel iron porphyrin-alkanethiolate complex with intramolecular NH···S hydrogen bond: Synthesis, spectroscopy, and reactivity [3]
Suzuki, Noriyuki,Higuchi, Tsunehiko,Urano, Yasuteru,Kikuchi, Kazuya,Uekusa, Hidehiro,Ohashi, Yuji,Uchida, Takeshi,Kitagawa, Teizo,Nagano, Tetsuo
, p. 11571 - 11572 (1999)
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Iron catalysis for in situ regeneration of oxidized cofactors by activation and reduction of molecular oxygen: A synthetic metalloporphyrin as a biomimetic NAD(P)H oxidase
Maid, Harald,Boehm, Philipp,Huber, Stefan M.,Bauer, Walter,Hummel, Werner,Jux, Norbert,Groeger, Harald
, p. 2397 - 2400 (2011)
(Figure Presented) An enzyme substitute: A synthetic FeIII porphyrin was used as a catalyst for the activation and reduction of O 2 into H2O with the cofactor NAD(P)H in aqueous solution. The catalyst is compatible with different preparative enzymatic oxidation reactions. Thus, a new method is provided for the in situ regeneration of the oxidized cofactor NAD(P)+ with help from a nonenzymatic, synthetic catalyst (see scheme).
Reaction of aldehydes with the H5PV2Mo10O40 polyoxometalate and cooxidation of alkanes with molecular oxygen
Khenkin, Alexander M.,Rosenberger, Avi,Neumann, Ronny
, p. 82 - 91 (1999)
The oxidation of alkalies with molecular oxygen using aldehydes as reducing agents (aldehydes are cooxidized) was studied using the α-H5PV2Mo10O40 polyoxometalate as catalyst. Emphasis was placed on the initiation of the radical chain reaction by investigation of the aldehyde-polyoxometalate interaction. Using 31P NMR and ESR spectroscopy one could differentiate between the reactivity of the five inseparable isomers of α-H5PV2Mo10O40. Contrary to previous belief, the 1,11 isomer with vanadium in distal positions is the most abundant. The 31P NMR and ESR spectra supported by UV-vis absorption-time profiles of the reduction of α-H5PV2Mo10O40 indicated that isomers with vanadium in vicinal positions were most kinetically viable in the alkane oxidation. Addition of isobutyraldehyde to α-H5PV2Mo10O40 gave in the 51V NMR spectrum a new downfield peak attributed to the formation of an aldehyde-polyoxometalate intermediate. The alkane/aldehyde/O2 oxidizing system was found to be quite effective and selective for ketone formation. Reaction probes indicated that acyl peroxo radicals were the active oxidizing intermediates. Five pathways for its reaction were identified: chain propagation, alkane oxidation, decomposition to form oxygen, decomposition to acyl oxo radicals leading to CO2 and ketone, and capture and inhibition by the polyoxometalate.
Templating an N-heterocyclic carbene (NHC)-cyclometalated Cp?IrIII-based oxidation precatalyst on a pendant coordination platform: Assessment of the oxidative behavior via electrochemical, spectroscopic and catalytic probes
Gupta, Suraj K.,Choudhury, Joyanta
, p. 1233 - 1239 (2015)
The coordination of metalloligands to derive modified properties of the metal functionality is one of the interesting strategies practiced in materials chemistry and catalysis. In this work, a pendant terpyridine ligand has been utilized for templating a Cp?IrIII(NHC)-based (NHC = N-heterocyclic carbene) oxidation precatalyst to assess its modified oxidative behavior via electrochemical, UV-vis spectroscopic, and catalytic probes. These studies suggested that the coordination-template enhances the electron-deficiency at the IrIII redox center and affects the nature of the oxidized high-valent Ir-oxo species during chemical oxidation. Moreover, both the premodified and postmodified Cp?IrIII(NHC)-based complexes were found to be equally efficient in catalytic sp3 C-H oxidation reactions with NaIO4 as a mild sacrificial oxidant.
Simple soluble Bi(iii) salts as efficient catalysts for the oxidation of alkanes with H2O2
Rocha, Bruno G. M.,Kuznetsov, Maxim L.,Kozlov, Yuriy N.,Pombeiro, Armando J. L.,Shul'Pin, Georgiy B.
, p. 2174 - 2187 (2015)
A simple catalytic system based on a soluble bismuth(iii) salt, Bi(NO3)3/H2O2/HNO3/CH3CN + H2O, exhibits pronounced activity towards the homogeneous oxidation of inert alkanes with the yield of oxygenate products up to 32% and TON up to 112. The experimental selectivity parameters and kinetic data together with theoretical DFT calculations indicate that the reaction occurs via a free radical mechanism involving the formation of the HO radicals which directly react with alkane molecules. The mechanism of the HO generation (which is the rate limiting step of the whole process) includes the substitution of a water ligand for H2O2 in the initial aqua complex [Bi(H2O)8]3+, hydrolysis of the coordinated H2O2, second H2O-for-H2O2 substitution and the homolytic HO-OH bond cleavage in complex [Bi(H2O)4(H2O2)(OOH)]2+ (6). The relatively low overall activation energy for this process (ca. 20 kcal mol-1) is accounted for by the high lability and acidity of the Bi aqua complexes and tremendous activation of coordinated H2O2 in 6 towards homolysis. This journal is
Efficient catalytic cycloalkane oxidation employing a "helmet" phthalocyaninato iron(III) complex
Brown, Elizabeth S.,Robinson, Jerome R.,McCoy, Aaron M.,McGaff, Robert W.
, p. 5921 - 5925 (2011)
We have examined the catalytic activity of an iron(III) complex bearing the 14,28-[1,3-diiminoisoindolinato]phthalocyaninato (diiPc) ligand in oxidation reactions with three substrates (cyclohexane, cyclooctane, and indan). This modified metallophthalocyaninato complex serves as an efficient and selective catalyst for the oxidation of cyclohexane and cyclooctane, and to a far lesser extent indan. In the oxidations of cyclohexane and cyclooctane, in which hydrogen peroxide is employed as the oxidant under inert atmosphere, we have observed turnover numbers of 100.9 and 122.2 for cyclohexanol and cyclooctanol, respectively. The catalyst shows strong selectivity for alcohol (vs. ketone) formation, with alcohol to ketone (A/K) ratios of 6.7 and 21.0 for the cyclohexane and cyclooctane oxidations, respectively. Overall yields (alcohol + ketone) were 73% for cyclohexane and 92% for cyclooctane, based upon the total hydrogen peroxide added. In the catalytic oxidation of indan under similar conditions, the TON for 1-indanol was 10.1, with a yield of 12% based upon hydrogen peroxide. No 1-indanone was observed in the product mixture.
V(iv), Fe(ii), Ni(ii) and Cu(ii) complexes bearing 2,2,2-tris(pyrazol-1-yl)ethyl methanesulfonate: Application as catalysts for the cyclooctane oxidation
Silva, Telma F. S.,Rocha, Bruno G. M.,Guedes Da Silva, M. Fátima C.,Martins, Luísa M. D. R. S.,Pombeiro, Armando J. L.
, p. 528 - 537 (2016)
Water-soluble compounds [VOCl2{CH3SO2OCH2C(pz)3}] (pz = pyrazol-1-yl) 1, [FeCl2{CH3SO2OCH2C(pz)3}] 2, [NiCl2{CH3SO2OCH2C(pz)3}] 3 and [Cu{CH3SO2OCH2C(pz)3}2](OTf)24 were obtained by reactions between the corresponding metal salts and 2,2,2-tris(pyrazol-1-yl)ethyl methanesulfonate, CH3SO2OCH2C(pz)3. They were isolated as air-stable solids and fully characterized by IR, FTIR, NMR (for 2), EPR (for 1), ESI-MS(+/-), elemental analysis and (for 4) single-crystal X-ray diffraction. In all, half- (1-3) or full-sandwich (4), compounds the C-scorpionate ligand shows the N,N,N-coordination mode. 3 and 4 appear to provide the first examples of a Ni(ii) and a full-sandwich Cu(ii) compound respectively, bearing that scorpionate ligand. Compound 3 is the first Ni(ii) tris(pyrazol-1-yl)methane type complex to be applied as catalyst for the oxidation of alkanes. Compounds 1-4 exhibit catalytic activity for the peroxidative (with aq. H2O2) oxidation, in water/acetonitrile medium and under mild homogeneous conditions, of cyclooctane to the corresponding alcohol and ketone (yields up to ca. 27%). The effect of the presence of additives, such as nitric acid or pyridine, was studied.
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Stoll,Rouve
, p. 1570,1578, 1579, 1582 (1944)
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Hydrogen Peroxide Oxygenation of Alkanes catalysed by Manganese(III)-tetraarylporphyrins: the Remarkable Co-catalytic Effect of Lipophilic Carboxylic Acids and Heterocyclic Bases
Banfi, Stefano,Maiocchi, Alessandro,Moggi, Alberto,Montanari, Fernando,Quici, Silvio
, p. 1794 - 1796 (1990)
Oxygenation of alkanes promoted by 30percent H2O2 and catalysed by chemically robust manganese(III)-tetraaryl porphyrins 2-4 is strongly accelerated by addition of small amounts of lipophilic carboxylic acids and lipophilic heterocyclic bases; cycloalkanes are converted into mixtures of alcohols and ketones at a rate of up to 125 turnovers min-1 in CH2Cl2-H2O solution at 0 deg C.
Oxidation of alkanes catalyzed by manganese(III) porphyrin in anionic liquid at room temprature
Li, Zhen,Xia, Chun-Gu,Xu, Chuan-Zhi
, p. 9229 - 9232 (2003)
Efficient oxidation of alkanes is achieved by using an electron-deficient manganese(III) porphyrin catalyst in combination with iodobenzene diacetate in an ionic liquid at room temperature; a high-valent manganese-oxo porphyrin complex (MnV=O) was considered as the reactive oxidation intermediate.
Efficient and selective oxidation of hydrocarbons with tert-butyl hydroperoxide catalyzed by oxidovanadium(IV) unsymmetrical Schiff base complex supported on γ-Fe2O3 magnetic nanoparticles
Samani, Mahnaz,Ardakani, Mehdi Hatefi,Sabet, Mohammad
, p. 1481 - 1494 (2022/01/22)
The catalytic activity of an oxidovanadium(IV) unsymmetrical Schiff base complex supported on γ-Fe2O3 magnetic nanoparticles, γ-Fe2O3@[VO(salenac-OH)] in which salenac-OH = [9-(2′,4′-dihydroxyphenyl)-5,8-diaza-4
Cu6- And Cu8-Cage Sil- And Germsesquioxanes: Synthetic and Structural Features, Oxidative Rearrangements, and Catalytic Activity
Astakhov, Grigorii S.,Levitsky, Mikhail M.,Zubavichus, Yan V.,Khrustalev, Victor N.,Titov, Aleksei A.,Dorovatovskii, Pavel V.,Smol'Yakov, Alexander F.,Shubina, Elena S.,Kirillova, Marina V.,Kirillov, Alexander M.,Bilyachenko, Alexey N.
, p. 8062 - 8074 (2021/05/26)
This study reports intriguing features in the self-assembly of cage copper(II) silsesquioxanes in the presence of air. Despite the wide variation of solvates used, a series of prismatic hexanuclear Cu6 cages (1-5) were assembled under mild conditions. In turn, syntheses at higher temperatures are accompanied by side reactions, leading to the oxidation of solvates (methanol, 1-butanol, and tetrahydrofuran). The oxidized solvent derivatives then specifically participate in the formation of copper silsesquioxane cages, allowing the isolation of several unusual Cu8-based (6 and 7) and Cu6-based (8) complexes. When 1,4-dioxane was applied as a reaction medium, deep rearrangements occurred (with a total elimination of silsesquioxane ligands), causing the formation of mononuclear copper(II) compounds bearing oxidized dioxane fragments (9 and 11) or a formate-driven 1D coordination polymer (10). Finally, a "directed"self-assembly of sil- and germsesquioxanes from copper acetate (or formate) resulted in the corresponding acetate (or formate) containing Cu6 cages (12 and 13) that were isolated in high yields. The structures of all of the products 1-13 were established by single-crystal X-ray diffraction, mainly based on the use of synchrotron radiation. Moreover, the catalytic activity of compounds 12 and 13 was evaluated toward the mild homogeneous oxidation of C5-C8 cycloalkanes with hydrogen peroxide to form a mixture of the corresponding cyclic alcohols and ketones.
Three metal centers (Co _AOMARKENCODEAMPX0AOA) Cu _AOMARKENCODEAMPX0AOA Method using Zn) 2D MOFs/ultraviolet light to catalyze oxidation of cycloalkane
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Paragraph 0028; 0079-0080, (2021/11/06)
The invention relates to a three-metal center (Co _AOMARKENCODEAMPX0AOA). Cu _AOMARKENCODEAMPX0AOA The method comprises Zn) 2D MOFs/ultraviolet light catalytic oxidation of cycloalkane to synthesize cycloalkyl alcohol and cycloalkanone, and belongs to the field of industrial catalysis and fine organic synthesis. To the application method, metalloporphyrin three-metal center (Co _AOMARKENCODEAMPX0AOA) is used. Cu _AOMARKENCODEAMPX0AOA Zn) 2D MOFs dispersed in cycloalkane, wherein metalloporphyrin three-metal center (Co _AOMARKENCODEAMPX0AOA) Cu _AOMARKENCODEAMPX0AOA Zn) 2D MOFs mass is 0.01% - 20%, g / mol of the substance of the cycloalkane, and the reaction system is sealed. An oxidant is introduced, the ultraviolet lamp is a light source, and the reaction liquid of the stirring reaction 2.0-24 . 0h. is subjected to post-treatment to obtain the product cycloalkyl alcohol and cycloalkyl ketone. The method provided by the invention has the advantages of low reaction temperature, mild reaction conditions, high reaction efficiency, high selectivity of cycloalkyl alcohol and cycloalkyl ketone, less byproducts and small environmental impact. The invention provides a high efficiency. Available, safe cycloalkanes selectively catalyze the oxidative synthesis of cycloalkyl alcohols and cycloalkyl ketones.