617-94-7Relevant articles and documents
Low-temperature oxidation of isopropylbenzene mediated by the system of NHPI, Fe(acac)3 and 1,10-phenanthroline
Babushkin, D. E.,Koscheeva, O. S.,Kuznetsova, L. I.,Kuznetsova, N. I.,Zudin, V. N.
, (2021)
Highly efficient oxidation of isopropylbenzene mediated by the system of NHPI/Fe(acac)3/Phen has been carried out at temperature as low as 60 °C. Significant improvement of catalysis by NHPI was associated with an enhanced oxidizing ability of Fe(III) tandem with Phen, which caused the intense generation of PINO. Furthermore, NMR observations revealed formation of a hydrogen-bonded NHPI-Phen adduct soluble in acetonitrile and isopropylbenzene. Based on this phenomenon, the system was applicable for the oxidation of solvent-free isopropylbenzene. The promise of the system of NHPI/Fe(acac)3/Phen for the selective synthesis of isopropylbenzene hydroperoxide was demonstrated by oxidation at a low content of Fe(acac)3.
EFFECT OF HIGH PRESSURE ON THE KINETIC ISOTOPE EFFECT IN THE ABSTRACTION OF HYDROGEN AND DEUTERIUM ATOMS BY THE CUMYLOXY RADICAL
Zhulin, V. M.,Lipovich, T. V.,Antonovskii, V. L.
, p. 2630 (1985)
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Kinetic regularities of conversion of ozone complexes with arenes
Avzyanova,Kabal'nova,Shereshovets
, p. 356 - 359 (1996)
The kinetic regularities of conversion of ozone complexes with several substituted benzenes (ArX = C6H5Me, C6H5Et, C6H5CHMe2, C6H5CMe3, C6H5F, C6H5Cl, m-BrC6H5Me, and C6H5CH2Cl) were studied by spectrophotometry. The rate of consumption of ArX·O3 in a CH2Cl2-ArX solution obeys the kinetic equation W = k0[ArX·O3]+k1[ArX·O 3][ArX]. The values of the rate constants k0 and k1 for the complexes studied were determined at -60÷0°C.
Phosphonium ionic liquids as reaction media for strong bases
Ramnial, Taramatee,Ino, Daisuke D.,Clyburne, Jason A. C.
, p. 325 - 327 (2005)
Phosphonium ionic liquids are compatible with strong bases; for example, solutions composed of commercially available phenylmagnesium bromide in THF are persistent in tetradecyl(trihexyl)phosphonium chloride for several hours-days: their stability appears to be couched in kinetic terms.
Solvent-dependent catalytic behavior of telluride-containing guest artificial glutathione peroxidase using cumene hydroperoxide and 3-carboxyl-4-nitrobenzenethiol as substrates
Jiao,Yin,Zhang,Zhong,Wang,Zhang,Yang
, p. 2665 - 2668 (2015)
To reveal the solvent-dependent catalytic behaviour of a hydrophobic telluride-containing guest artificial glutathione peroxidase (ADA-Te-OH), the catalytic rates were investigated using cumene hydroperoxide and 4-nitrobenzenethiol as substrates. Herein, ethanol, DMSO, DMF and CH3CN were selected as the co-solvents in the determination of catalytic rates. Significantly, the typical solvent-dependent catalytic behaviour of ADA-Te-OH was observed. Especially, the higher catalytic rate was observed when polar protic solvent (ethanol) was used compared with other co-solvents. It suggested that polar protic solvent was the appropriate co-solvent for the assay of catalytic activity of hydrophobic artificial glutathione peroxidase. This study well for the understanding of the catalytic behaviour of hydrophobic guest artificial glutathione peroxidase.
Autooxidation of hydrocarbons with oxygen in ionic liquids as solvents
Baj, Stefan,Chrobok, Anna
, p. 287 - 293 (2008)
The results of hydrocarbons autooxidation process carried out using several ionic liquids (IL) as solvents are demonstrated. Test studies to check the influence of ILs on this process showed that most ILs can accelerate the initiation rate of autooxidation. The results could be very useful for choosing an IL not only for autooxidation processes but also for catalytic oxidation systems.
A new highly active La2O3-CuO-MgO catalyst for the synthesis of cumyl peroxide by catalytic oxidation
Liu, HanShuang,Wang, KaiJun,Cao, XiaoYan,Su, JiaXin,Gu, Zhenggui
, p. 12532 - 12542 (2021)
In this study, different magnesium, copper, lanthanide single metal, and composite multimetal oxide catalysts were preparedviathe coprecipitation route for the aerobic oxidation of cumene into cumene hydroperoxide. All catalysts were characterized using several analytical techniques, including XRD, SEM, EDS, FT-IR, BET, CO2-TPD, XPS, and TG-DTG. La2O3-CuO-MgO shows higher oxidation activity and yield than other catalysts. The results of XRD and SEM studies show that the copper and magnesium particles in the catalyst are smaller in size and have a distribution over a larger area due to the introduction of the lanthanum element. The CO2-TPD results confirmed that the catalyst has more alkali density and alkali strength, which can excite active sites and prevent the decomposition of cumene hydroperoxide. XPS results show that due to the promotional effect of La2O3, there are more lattice and active oxygen species in the catalyst, which can effectively utilize the lattice defects under the strong interaction between metal oxides for rapid adsorption and activation, thus improving the oxidation performance. Besides, La2O3-CuO-MgO exhibits good stability and crystalline structure due to its high oxygen mobility inhibiting coking during the cycle stability test. Finally, the possible reaction pathway and promotional mechanism on La2O3-CuO-MgO in cumene oxidation are proposed. We expect this study to shed more light on the nature of the surface-active site(s) of La2O3-CuO-MgO catalyst for cumene oxidation and the development of heterogeneous catalysts with high activity in a wide range of applications.
Heterolytic alkyl hydroperoxide O-O bond cleavage by copper(I) complexes
Tano, Tetsuro,Sugimoto, Hideki,Fujieda, Nobutaka,Itoh, Shinobu
, p. 4099 - 4103 (2012)
The reaction of copper(I) complexes and cumene hydroperoxides was examined to demonstrate that heterolytic O-O bond cleavage of the peroxides proceeds predominantly to give the corresponding alcohols (cumyl alcohols) as the major product, when the stoichiometry of CuI/peroxide is 2:1. The result is in sharp contrast to the 1:1 reaction between the copper(II) complexes and cumene hydroperoxide, which provides the ketone (acetophenone) as the major product through homolytic O-O bond cleavage.
Reactivity of copper nanopowders in a model reaction of isopropylbenzene oxidation
Skorokhodova,Kobotaeva,Sirotkina
, p. 753 - 757 (2005)
The reactivity of copper nanopowders produced by an electric explosion of a conductor or mechanochemically was studied. Oxidation of isopropylbenzene was used as a model reaction. The dependence of the oxygen uptake rate on the specific surface area of a copper nanopowder and on the method used for its production is discussed. A possible mechanism of isopropylbenzene oxidation in the presence of copper nanopowders is suggested.
N-Hydroxyphthalimide in combination with Cu(II), Co(II) or Mn(II) salts as catalytic systems for the oxidation of isopropyl-aromatic hydrocarbons with oxygen
Orlińska, Beata
, p. 4100 - 4102 (2010)
Catalytic systems consisting of N-hydroxyphthalimide in combination with copper(II), cobalt(II) and manganese(II) acetylacetonate, acetate or chloride were applied to the oxidation of cumene with oxygen. The use of these catalytic systems decreases cumyl hydroperoxide selectivity as a result of the decomposition reaction of hydroperoxide to 2-phenyl-2-propanol and acetophenone. It has been demonstrated that the use of N-hydroxyphthalimide in combination with copper salts at 60 °C results in high alcohol content whereas ketone is the major product at 90 °C. The results can be used to develop a method for alcohol or ketone synthesis from other isopropyl-aromatic hydrocarbons.
Copper salt-crown ether systems as catalysts for the oxidation of cumene with 1-methyl-1-phenylethylhydroperoxide to bis(1-methyl-1- phenylethyl)peroxide
Zawadiak, Jan,Gilner, Danuta,Mazurkiewicz, Roman
, p. 4059 - 4062 (1999)
Evidence for phase transfer catalysis in the oxidation of cumene with 1- methyl-1-phenylethylhydroperoxide to bis-(1-methyl-1-phenylethyl)peroxide in the presence of copper salt - crown ether catalysts is given.
A copper complex supported by an N2S-tridentate ligand inducing efficient heterolytic O-O bond cleavage of alkylhydroperoxide
Tano, Tetsuro,Mieda, Kaoru,Sugimoto, Hideki,Ogura, Takashi,Itoh, Shinobu
, p. 4871 - 4877 (2014)
We have recently reported a copper(ii)-superoxide complex supported by an N3-tridentate ligand (LN3), which exhibits a similar structure and reactivity to those of a putative reactive intermediate involved in the catalytic reactions of copper monooxygenases such as peptidylglycine α-hydroxylating monooxygenase (PHM) and dopamine β-monooxygenase (DβM). In this study, we have synthesised and characterised copper complexes supported by a related sulphur-containing ligand (LN2S) to get insight into the notable electronic effect of the sulphur donor atom in the reaction with cumene hydroperoxide, inducing efficient heterolytic O-O bond cleavage.
Direct Comparison of Photoefficiencies of C-C Bond Scission in Radical Cations generated by Photosensitized Electron-Transfer and by Irradiation of Charge-transfer Complexes
Maslak, Przemyslaw,Chapman, Jr. William H.
, p. 1809 - 1811 (1989)
Quantum yields for C-C bond scission are at least 50 times larger in radical cations of methoxybicumenes (1.*) generated by quenching of the p-tetrachlorobenzoquinone (TCBQ) excited state (a process that results in triplet solvent-separeted ion pairs) than in those obtained by the irradiation of charge-transfer complexes (a reaction that yields singlet contact ion pairs).
Role of electron transfer processes in the oxidation of aryl sulfides catalyzed by nonheme iron complexes
Barbieri, Alessia,Di Stefano, Stefano,Lanzalunga, Osvaldo,Lapi, Andrea,Mazzonna, Marco,Olivo, Giorgio
, p. 241 - 244 (2017)
The oxidation of a series of aryl 1-methyl-1-phenylethyl sulfides with H2O2catalyzed by the two tetradentate nonheme-iron complexes [(PDP)FeII(SbF6)2] and [(BPMCN)FeII(OTf)2] occurs by an electron transfer-oxygen transfer (ET/OT) mechanism as supported by the observation of products deriving from fragmentation of the corresponding radical cations in association with S-oxidation products (sulfoxides).
Inverse axial-ligand effects in the activation of H2O 2 and ROOH by an MnIII corrolazine
Lansky, David E.,Narducci Sarjeant, Amy A.,Goldberg, David P.
, p. 8214 - 8217 (2006)
(Chemical Equation Presented) Upside-down push: Reaction of an Mn III corrolazine complex with H2O2 or ROOH leads to O-O-bond cleavage to give an MnV≡O complex (see scheme). Dramatic and unexpected axial-ligand (or "push") effects are observed, namely, the more electron-poor the axial ligand L, the faster and more heterolytic the cleavage.
Investigation of solvent-dependent catalytic behaviour of hydrophobic guest artificial glutathione peroxidase
Yin,Wei,Shi,Shi,Hu,Jiao,Chen
, p. 2311 - 2314 (2014)
To reveal the relation between the catalytic rate of artificial glutathione peroxidase (GPx) and the property of solvent used in the determination of catalytic behaviour of glutathione peroxidase (ADA-Te-ADA) was investigated. Ethanol, DMSO, DMF and CHsu
Synthesis and characterization of N3Py2 ligand-based cobalt(II), nickel(II) and copper(II) catalysts for efficient conversion of hydrocarbons to alcohols
Narulkar, Dattaprasad D.,Srivastava, Anant Kumar,Butcher, Raymond J.,Ansy, Kanakappan M.,Dhuri, Sunder N.
, p. 405 - 414 (2017)
Three new complexes [Co(N3Py2)(H2O)](ClO4)2 1, [Ni(N3Py2)(H2O)](ClO4)2 2 and [Cu(N3Py2)](ClO4)2 3 (N3Py2 is N,N′-dimethyl-N-(2-(methyl(pyridin-2-ylmethyl)amino)ethyl)-N′-(pyridin-2-ylmethyl)ethane-1,2-diamine) have been synthesized and characterized. Non-heme ligand N3Py2 have been prepared by Eschweiler-Clarke method and reported for the first time. Compounds 1 and 2 were characterized by single crystal X-ray structure analysis. The structure of 1 and 2 revealed that Co(II) cation in 1 and Ni(II) cation in 2 are bonded to the five nitrogen atoms of N3Py2 and a water molecule thus forming an octahedral motif [M(N3Py2)(H2O)]2+. For compound 3, a square pyramidal geometry has been proposed based on the spectroscopic, elemental analysis and ESI-MS data. Compounds 1–3 were tested as catalysts in the oxidation of cumene and adamantane using m-CPBA. Comparative effect of counter anions on the product yields was observed when the perchlorates anions of 1–3 were replaced with tetraphenylborates to give compounds 1a–3a. The turnover numbers of alcohol over ketone product increased in order of catalysts, 1(1a) > 2(2a) > 3(3a).
Cobalt(II) Bipyrazolate Metal-Organic Frameworks as Heterogeneous Catalysts in Cumene Aerobic Oxidation: A Tag-Dependent Selectivity
Nowacka, Anna,Vismara, Rebecca,Mercuri, Giorgio,Moroni, Marco,Palomino, Miguel,Domasevitch, Kostiantyn V.,Di Nicola, Corrado,Pettinari, Claudio,Giambastiani, Giuliano,Llabrés I Xamena, Francesc X.,Galli, Simona,Rossin, Andrea
, p. 8161 - 8172 (2020)
Three metal-organic frameworks with the general formula Co(BPZX) (BPZX2- = 3-X-4,4′-bipyrazolate, X = H, NH2, NO2) constructed with ligands having different functional groups on the same skeleton have been employed as heterogeneous catalysts for aerobic liquid-phase oxidation of cumene with O2 as oxidant. O2 adsorption isotherms collected at pO2 = 1 atm and T = 195 and 273 K have cast light on the relative affinity of these catalysts for dioxygen. The highest gas uptake at 195 K is found for Co(BPZ) (3.2 mmol/g (10.1 wt % O2)), in line with its highest BET specific surface area (926 m2/g) in comparison with those of Co(BPZNH2) (317 m2/g) and Co(BPZNO2) (645 m2/g). The O2 isosteric heat of adsorption (Qst) trend follows the order Co(BPZ) > Co(BPZNH2) > Co(BPZNO2). Interestingly, the selectivity in the cumene oxidation products was found to be dependent on the tag present in the catalyst linker: while cumene hydroperoxide (CHP) is the main product obtained with Co(BPZ) (84% selectivity to CHP after 7 h, pO2 = 4 bar, and T = 363 K), further oxidation to 2-phenyl-2-propanol (PP) is observed in the presence of Co(BPZNH2) as the catalyst (69% selectivity to PP under the same experimental conditions).
Study by methods of electron spin resonance and model oxidation reaction of nanosize metal powders obtained in electric explosion of conductors
Fedushchak,Il'ln
, p. 345 - 350 (2002)
Paramagnetic properties of nanopowders obtained by electric explosion of copper, aluminum, cobalt, and platinum conductors have been studied. The possibility of using ESR and model reaction of isopropylbenzene for testing the electric-explosion powders as
Green method for catalyzing deprotection of tetrahydropyrane ether into hydroxyl compound
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Paragraph 0035-0037, (2022/03/17)
The invention provides a green method for catalyzing deprotection of tetrahydropyrane ether into hydroxyl compound, and belongs to the field of green organic chemistry. According to the method, under neutral, open and room-temperature conditions, acetonitrile is used as a reaction solvent, FeBr2 or FeBr3 is used as a catalyst, H2O2 is used as an oxidizing agent, and a tetrahydropyrane ether derivative is converted into a hydroxyl compound within a short time. According to the invention, the catalyst FeBr2 and FeBr3, the oxidizing agent H2O2 and the solvent acetonitrile used in the method are cheap and easy to obtain, the reaction time is short, the condition is mild, the method has wide functional group compatibility, post-treatment is simple, operation is easy, and the method is a current green, environment-friendly and safe method for deprotecting the tetrahydropyrane ether derivative into the hydroxyl compound and has wide application prospects.
Efficient oxidation of cumene to cumene hydroperoxide with ambient O2 catalyzed by metalloporphyrins
Shen, Hai M.,Ye, Hong L.,Wang, Qin,Hu, Meng Y.,Liu, Lei,She, Yuan B.
, p. 314 - 322 (2021/04/09)
A novel and efficient protocol for oxidation of cumene to cumene hydroperoxide was presented using ambient O2 catalyzed by very simple metalloporphyrins. The selectivity toward cumene hydroperoxide reached 98.3% in the cumene conversion of 28.1% with T(4-COOH)PPCu as a catalyst at 80°C. The origin of the higher performance of T(4-COOH)PPCu was mainly ascribed to the low catalytic performance of copper(II) in the cumene hydroperoxide decomposition, and the ability of T(4-COOH)PP in stabilizing cumene hydroperoxide through hydrogen-bond interactions between them. Compared with current industrial processes and academic research in oxidation of cumene to cumene hydroperoxide with O2, the main superiorities of this protocol were the high selectivity, high conversion, simple catalysts, solvent-free, additive-free and mild conditions which made this work an appealing reference for the industrial oxidation of cumene to cumene hydroperoxide, as well as the oxidative functionalization of other C-H bonds in various hydrocarbons. 2021 World Scientific Publishing Company.
