108-94-1Relevant articles and documents
Chemiluminescence-promoted oxidation of alkyl enol ethers by NHPI under mild conditions and in the dark
Anderson,Andia, Alexander A.,Woerpel
, (2021)
The hydroperoxidation of alkyl enol ethers using N-hydroxyphthalimide and molecular oxygen occurred in the absence of catalyst, initiator, or light. The reaction proceeds through a radical mechanism that is initiated by N-hydroxyphthalimide-promoted autoxidation of the enol ether substrate. The resulting dioxetane products decompose in a chemiluminescent reaction that allows for photochemical activation of N-hydroxyphthalimide in the absence of other light sources.
One-step hydroxylation of benzene to phenol via a Pd capillary membrane microreactor
Wang, Xiaobin,Tan, Xiaoyao,Meng, Bo,Zhang, Xiongfu,Liang, Qi,Pan, Hui,Liu, Shaomin
, p. 2380 - 2391 (2013)
A novel Pd capillary membrane microreactor for one-step hydroxylation of benzene to phenol was synthesized and investigated to showcase the effectiveness of 'Niwa concept'. Reaction parameters including H2/O2 ratio and temperature were systematically studied for their effects on benzene conversion and phenol yield. A detailed examination of different membrane reactors, feed mode and long-term reaction stability was also conducted. Pd capillary membrane displayed good stability for low temperature separation and reaction due to the excellent anchorage of Pd layer into the porous α-alumina support. An optimum H2/O2 ratio was identified at 473 K with the benzene conversion of 19.6% and phenol yield of 18.1%. An increase in reaction temperature caused not only an increase in benzene conversion but also a decrease in phenol selectivity. A comparison between our work and the literature results was also made to discuss the feasibility of the membrane reactor concept. Experimental results proved that narrow flow channels and larger Pd membrane surface area-to-volume ratios provided more effective area of Pd interface and promoted the radial diffusion of reactants, enabling the reactive species more opportunities to react directly with benzene resulting in high benzene conversion. The Royal Society of Chemistry 2013.
Synthesis of 1,1′-bishydroperoxydi(cycloalkyl) peroxides by homocoupling of 11-15-membered gem-bis(hydroperoxy)cycloalkanes in the presence of boron trifluoride
Terent'ev,Kutkin,Platonov,Starikova,Ogibin,Nikishin
, p. 1214 - 1218 (2005)
A procedure was developed for the synthesis of 1,1′- bishydroperoxydi(C11-C15-cycloalkyl) peroxides based on homocoupling of geminal 11-15-membered bis(hydroperoxy)cycloalkanes in the presence of BF3·OEt2.
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Brooks,D.W.,Gettler,J.D.
, p. 4469 - 4475 (1962)
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Shono et al.
, p. 165 (1979)
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Catalytic Activity of a Polymerizable tris(β-ketoesterate)Iron(III) Complex towards the Oxidation of Organic Substrates
Mastrorilli, Piero,Nobile, Cosimo Francesco
, p. 4193 - 4196 (1994)
The facile oxidation of alkenes, aldehydes, cyclic ketones, alkanes, sulfides and alcohols is achieved by a polymerizable b-ketoesterato complex under Mukaiyama's conditions (atmospheric pressure of molecular oxygen in the presence of a sacrificial aldehyde at room temperature).
Cubberley,Mueller
, p. 1535 (1947)
Reduction of Aromatic Nitro Compounds by Secondary Alcohols Using Rhodium Complexes as Catalysts
Liou, K. F.,Cheng, C. H.
, p. 3018 - 3021 (1982)
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Effect of Zirconia Morphology on Hydrodeoxygenation of Phenol over Pd/ZrO2
De Souza, Priscilla M.,Rabelo-Neto, Raimundo C.,Borges, Luiz E. P.,Jacobs, Gary,Davis, Burtron H.,Graham, Uschi M.,Resasco, Daniel E.,Noronha, Fabio B.
, p. 7385 - 7398 (2015)
This work studies the effect of zirconia structure on the performance of Pd/ZrO2 catalysts for hydrodeoxygenation of phenol at 300 °C and 1 atm using a fixed bed reactor. Benzene was the major product over Pd/t-ZrO2, while significant formation of cyclohexanone was observed over Pd/m-ZrO2. On the other hand, Pd/m,t-ZrO2 exhibited intermediary behavior. DRIFTS of adsorbed pyridine, NH3-TPD, and the dehydration of the cyclohexanol reaction revealed that the Pd/t-ZrO2 catalyst exhibits a higher density of oxophilic sites than Pd/m-ZrO2 and Pd/m,t-ZrO2. This promoted the formation of deoxygenated products. However, a mechanism involving dehydration of cyclohexanol to cyclohexene, followed by dehydrogenation to benzene, may not be ruled out. Pd/ZrO2 catalysts significantly deactivated as a function of time on stream. Results of dehydrogenation of cyclohexane and dehydration of cyclohexanol indicate that the Pd particle size increased and the density of oxophilic sites decreased during the hydrodeoxygenation of the phenol reaction. In addition, the DRIFTS spectra under reaction conditions demonstrated that the coverage of oxophilic sites by phenoxy and intermediate species increased during the reaction. The growth of Pd particles is likely responsible for the losses in the metal-support interface that gradually inhibits the ability of the adsorbed species to turnover at the metal-support boundary.
Epoxidation of cyclohexene with tert-butyl hydroperoxide catalyzed by mixed oxide V2O5–TiO2
Lahcene, Driss,Choukchou-Braham, Abderrahim
, p. 1529 - 1535 (2018)
TiO2 and 20 wt% V2O5–TiO2 catalysts were prepared by the sol–gel route and calcined at 500 °C. The mixed oxide presented the crystalline structures of TiO2 anatase and V2O5 Shcherbinaite phases, with a BET (Brunauer–Emmett–Teller) surface area of 19 m2/g. The catalytic material was tested for the epoxidation of cyclohexene by tert-butyl hydroperoxide at 80 °C. The activity and selectivity were investigated as a function of the reaction time as well as the amounts of the catalyst and solvent. The reaction followed second-order kinetics, and the best catalytic performance was observed after 6 hr of reaction time, with 150 mg of catalyst in n-heptane solvent. The epoxidation selectivity reached 76% at 48% conversion. The catalyst remained stable after two cycles.
o-Nitrobenzyl Alcohol, a Simple and Efficient Reagent for the Photoreversible Protection of Aldehydes and Ketones
Gravel, Denis,Murray, Stevens,Ladouceur, Gaetan
, p. 1828 - 1829 (1985)
Two independent procedures are described for the preparation of bis-o-nitrobenzyl acetal derivatives of aldehydes and ketones which are shown to be photoremovable in high yield by simple irradiation at 350 nm in an aprotic solvent.
Mild oxidative conversion of nitroalkanes into carbonyl compounds in ionic liquids
Bortolini, Olga,Nino, Antonio De,Garofalo, Angelo,Maiuolo, Loredana,Russo, Beatrice
, p. 2483 - 2487 (2010)
Basic hydrogen peroxide and sodium perborate were found to be cheap and efficient alternatives for the conversion of primary and secondary nitro to carbonyl compounds (Nef reaction) in ionic liquids. Copyright Taylor & Francis Group, LLC.
Rhodium(iii) complexes with a bidentate N-heterocyclic carbene ligand bearing flexible dendritic frameworks
Fujihara, Tetsuaki,Obora, Yasushi,Tokunaga, Makoto,Tsuji, Yasushi
, p. 1567 - 1569 (2007)
Rh(iii) complexes with a bidentate N-heterocyclic carbene ligand bearing flexible dendritic frameworks have been synthesized and fully characterized by X-ray crystallographic analysis, NMR measurements and theoretical calculations. The Royal Society of Chemistry.
On the efficiency of phenol and cyclohexanone electrocatalytic hydrogenation - Effect of conditioning and working pH in acetic acid solution on palladium/fluorine-doped tin dioxide supported catalyst
Tountian, Dihourahouni,Brisach-Wittmeyer, Anne,Nkeng, Paul,Poillerat, Gerard,Menard, Hugues
, p. 463 - 471 (2010)
The electrocatalytic hydrogenation (ECH) of phenol and cyclohexanone was performed on a conductive Pd/SnO2:F catalyst. The catalyst was obtained by the impregnation method. We studied the influence of the pH of the supporting electrolyte, the conditioning pH, and the quantity of the conditioning charge passed before hydrogenation. Fourier transform infrared spectroscopy analysis showed that the functionalization of the catalyst surface by the acetic acid electrolyte depends on the pH. A direct correlation was observed between the efficiency of the hydrogenation, the pH of the electrolyte, and the electrode conditioning charge. Phenol hydrogenation was favored in acidic media, whereas cyclohexanone hydrogenation needed an acidic medium for conditioning and a basic medium for hydrogenation. The ECH rate appeared to depend on the functionalization of the catalyst surface, the adsorption of the target organic molecule on the catalyst, and its structural modification with the pH.
Dehydrogenation of cyclohexanol on copper containing catalysts: The role of the support and the preparation method
Popova,Dimitrov,Santo, V. Dal,Ravasio,Scotti
, p. 150 - 153 (2012)
SiO2 and Al2O3 supported copper catalysts were prepared by "chemisorption-hydrolysis" or incipient wetness impregnation methods and investigated by XRD, TG-TPR, UV-vis diffuse reflectance and FTIR spectroscopy. Formation of finely dispersed copper oxide species was registered for the samples prepared by "chemisorption-hydrolysis" method, while a significant amount of XRD detectable copper oxide phase is registered for the SiO2 impregnated one. The latter materials possess higher catalytic selectivity in cyclohexanol dehydrogenation to cyclohexanone.
Comparison of three enoate reductases and their potential use for biotransformations
Chaparro-Riggers, Javier F.,Rogers, Thomas A.,Vazquez-Figueroa, Eduardo,Polizzi, Karen M.,Bommarius, Andreas S.
, p. 1521 - 1531 (2007)
Enoate reductases (ERs) selectively reduce carbon-carbon double bonds in α,β-unsaturated carbonyl compounds and thus can be employed to prepare enantiomerically pure aldehydes, ketones, and esters. Most known ERs, most notably Old Yellow Enzyme (OYE), are biochemically very well characterized. Some ERs have only been used in whole-cell systems, with endogenous ketoreductases often interfering with the ER activity. Not many ERs are biocatalytically characterized as to specificity and stability. Here, we cloned the genes and expressed three non-related ERs, two of them novel, in E. coli: XenA from Pseudomonas putida, KYE1 from Kluyveromyces lactis, and Yers-ER from Yersinia bercovieri. All three proteins showed broad ER specificity and broad temperature and pH optima but different specificity patterns. All three proteins prefer NADPH as cofactor over NADH and are stable up to 40°C. By coupling Yers-ER with glucose dehydrogenase (GDH) to recycle NADP(H), conversion of > 99 % within one hour was obtained for the reduction of 2-cyclohexenone. Upon lowering the loadings of Yers-ER and GDH, we discovered rapid deactivation of either enzyme, especially of the thermostable GDH. We found that the presence of enone substrate, rather than oxygen or elevated temperature, is responsible for deactivation. In summary, we successfully demonstrate the wide specificity of enoate reductases for a range of α,β- unsaturated carbonyl compounds as well as coupling to glucose dehydrogenase for recycling of NAD(P)(H); however, the stability limitations we found need to be overcome to envision large-scale use of ERs in synthesis.
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Me'rour et al.
, p. 337,348 (1979)
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Copper nanoparticle/carbon quantum dots hybrid as green photocatalyst for high-efficiency oxidation of cyclohexane
Qiao, Shi,Fan, Baohu,Yang, Yanmei,Liu, Naiyun,Huang, Hui,Liu, Yang
, p. 43058 - 43064 (2015)
To develop green catalysts for cyclohexane oxidation with high efficiency and high selectivity is a trend in nanotechnology and nanocatalysis. In this work, we demonstrate that copper nanoparticles/carbon quantum dots (Cu/CQDs) hybrid as photocatalyst exh
Highly Effective Dehydrogenation of Cyclohexanol to Cyclohexanone over Carbon-Supported Cobalt Catalyst
Uemichi, Yoshio,Shouji, Kiyoshi,Sugioka, Masatoshi,Kanazuka, Takaji
, p. 385 - 387 (1995)
The dehydrogenation of cyclohexanol to cyclohexanone has been studied over activated carbon-supported transition metals as catalysts.The Co/carbon catalyst was found to be highly effective for the reaction.Its catalytic behaviors strongly depended on the temperature of hydrogen reduction.Highly dispersed and well-reduced cobalt catalyst showed pronounced activity and stability.
MECHANISM OF THE SELECTIVE FORMATION OF CYCLOHEXANONE IN THE DECOMPOSITION OF CYCLOHEXYL HYDROPEROXIDE BY CHROMIUM STEARATE
Petrov, L. V.,Solyanikov, V. M.
, p. 1958 - 1960 (1991)
From a comparison of the rates of formation of cyclohexanone and 2-decanone in cyclohexane solutions of cyclohexyl hydroperoxide or tert-butyl-hydroperoxide in the presence of chromium(III) stearate and a mixture of cyclohexanol and 2-decanol in an atmosphere of argon at 350 K, it is concluded that the direct breakdown of cyclohexyl hydroperoxide by chromium stearate leads to selective formation of cyclohexanone.The contribution of the oxidation of cyclohexanol to ketone formation at a cyclohexanol concentration comparable with the hydroperoxide concentration (ca. 0.1 M) is ca. 10percent.
Study of the deactivation of copper-based catalysts for dehydrogenation of cyclohexanol to cyclohexanone
Simón, Ernesto,Rosas, Juana María,Santos, Aurora,Romero, Arturo
, p. 150 - 158 (2012)
Catalytic dehydrogenation of cyclohexanol was carried out in the gas phase in a continuous fixed bed reactor under atmospheric pressure. Two commercial catalysts composed by copper chromite and copper zinc oxide were tested. The activity of the catalysts
CYCLOKETONIZATION AND LINEAR POLYKETONIZATION OF α,ω-DICARBOXYLIC ACIDS. COMMUNICATION 7. PREPARATION AND REACTIONS OF ZINC SALTS OF UNBRANCHED DICARBOXYLIC ACIDS
Vasina, T. V.,Chelmakova, S. A.,Lutovinova, V. N.,Liberman, A. L.
, (1982)
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Highly efficient and metal-free aerobic hydrocarbons oxidation process by an o-phenanthroline-mediated organocatalytic system
Tong, Xinli,Xu, Jie,Miao, Hong
, p. 1953 - 1957 (2005)
A highly efficient o-phenanthroline-mediated, metal-free catalytic system has been developed for oxidation of hydrocarbons with dioxygen in the presence of N-hydroxyphthalimide; various hydrocarbons were efficiently and high selectively oxidized, e.g., ethylbenzene to acetophenone in 97% selectivity and 76% conversion, under mild conditions.
Catalytic synergism in a C;inf;60;/inf;IL;inf;10;/inf;TEMPO;inf;2;/inf; hybrid in the efficient oxidation of alcohols
Beejapur, Hazi Ahmad,Campisciano, Vincenzo,Giacalone, Francesco,Gruttadauria, Michelangelo
, p. 51 - 58 (2015)
A novel fullerene [5:1]hexakisadduct bearing two 2,2,6,6-tetramethylpiperidine 1-oxyl (TEMPO) radicals and ten 1-propyl-3-methylimidazolium bromide moieties has been synthesized and characterized. Such an C;inf;60;/inf;IL;inf;10;/inf;TEMPO;inf;2;/inf; hybrid has been successfully employed as a catalyst in the selective oxidation of a wide series of alcohols and is highly active at just 0.1 mol% loading. Moreover, it can be easily recovered by adsorption onto a multilayered covalently-linked SILP phase (mlc-SILP) through a "release and catch" approach and reused for up to 12 cycles without loss in efficiency. Interestingly, a catalytic synergistic effect of TEMPO and imidazolium bromide moieties combined in the same hybrid has been clearly shown.
TRANSFORMATION OF ORGANOIRON COMPLEXES OF SYNTHETIC AND CHEMICAL INTEREST.
Rosenblum,Bucheister,Chang,Cohen,Marsi,Samuels,Scheck,Sofen,Watkins
, p. 129 - 136 (1983)
Cationic organometallic complexes derived by complexation of vinyl ethers with the dicarbonyl cyclopentadienyliron cation (F//p** plus ) are readily prepared, highly reactive reagents. These substances have been shown to function as vinyl cation equivalents for the vinylation of ketones, and for the synthesis of alpha -methylene- gamma -lactones and dihydrofurans. Similar complexation of propiolic esters gives a reactive species, which functions as a beta -acrylic ester cation equivalent and yields cyclobutenes, 1,3-dienes and dihydro- alpha -pyrones with olefins and cinnamic esters with aromatic systems.
Efficient and selective oxidation of hydrocarbons with tert-butyl hydroperoxide catalyzed by oxidovanadium(IV) unsymmetrical Schiff base complex supported on γ-Fe2O3 magnetic nanoparticles
Ardakani, Mehdi Hatefi,Sabet, Mohammad,Samani, Mahnaz
, (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
An alternative route for the preparation of phenol: Decomposition of cyclohexylbenzene-1-hydroperoxide
Yang, Yufei,Zhang, Yadong
, p. 71 - 80 (2021/09/28)
In this work, a HPW/ZSM-5 catalyst was prepared by impregnating phosphotungstic acid (HPW) with carrier ZSM-5 zeolite and characterized by XRD, SEM, N2 adsorption/desorption isotherm, NH3-TPD, and FT-IR techniques. The catalytic performance of HPW/ZSM-5 was investigated by using the decomposition reaction of cyclohexylbenzene-1-hydroperoxide (CHBHP) to phenol and cyclohexanone. The conversion rate of CHBHP was up to 97.28%. In addition, the reusability test exhibited that the high durability HPW/ZSM-5 as the conversion rate of CHBHP only decreased by 3.11% after five runs. The kinetic study of the decomposition reaction indicated it was a primary reaction. The apparent activation energy of the decomposition reaction was 102.39?kJ·mol–1 in the temperature range of 45–60℃. All results indicate that the HPW/ZSM-5 catalyst has good performance and promising applications in acid catalyzed organic chemistry.
From Ring-Expansion to Ring-Contraction: Synthesis of γ-Lactones from Cyclobutanols and Relative Stability of Five- and Six-Membered Endoperoxides toward Organic Bases
Ferrié, Laurent,Jamey, Nicolas
, (2022/04/07)
Cyclobutanols undergo ring expansion with molecular oxygen in the presence of Co(acac)2 to afford 1,2-dioxane-hemiperoxyketals. In the course of acylation, we observed that endoperoxides rearranged into ?-lactone in the presence of triethylamine. Thus, a generalization of this ring contraction through a Kornblum DeLaMare rearrangement is here reported. Application of this transformation to monosubstituted 1,2-dioxane derivatives also led to 1,4-ketoaldehydes, in proportions depending on the nature of the substituent. These same conditions applied to five-membered dioxolane analogues led to fragmentation instead, through a retro-aldol type process. This study emphasizes the difference of stability of 1,2-dioxane and 1,2-dioxolane against organic bases, 1,2-dioxolanes having proved to be particularly reactive whereas 1,2-dioxanes showed a relative tolerance under these conditions.
