823-19-8

Usage

Synthesis Reference(s)

Tetrahedron, 50, p. 3843, 1994 DOI: 10.1016/S0040-4020(01)90404-1Tetrahedron Letters, 36, p. 3031, 1995 DOI: 10.1016/0040-4039(95)00419-D

Upstream product

• 504-01-8 cyclohexane-1,3-diol 
• 930-68-7 cyclohexenone 
• 50338-46-0 1-Trimethylsiloxy-bicyclo[3.1.0]hexan 
• 108-93-0 cyclohexanol 
• 108-46-3 recorcinol 
• 110-82-7 cyclohexane 
• 302577-72-6 3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)cyclohexan-1-one 
• 73223-83-3 1,4-dioxaspiro[4,5]decan-9-ol 
• 505-03-3 5-oxohexanal 
• 51272-66-3 6,7-dioxa-bicyclo(3.2.1)octane 
• 504-02-9 1,3-cylohexanedione 
• 58564-88-8 7-oxa-bicyclo[2.2.1]heptan-2-one 
• 6705-49-3 7-oxabicyclo[4.1.0]heptan-2-one 

Downstream Products

• 930-68-7 cyclohexenone 
• 505-03-3 5-oxohexanal 
• 60756-95-8 3-phenyl-3-(1-piperidinyl)cyclohexanol 
• 60756-95-8 3-phenyl-3-(1-piperidinyl)cyclohexanol 
• 4746-97-8 cyclohexanedione monoethylene ketal 
• 504-02-9 1,3-cylohexanedione 
• 1132819-57-8 3-[bis(4-hydroxyphenyl)methylene]cyclohexanol 
• 1260250-18-7 (R)-3-oxocyclohexyl acetate 
• 166019-39-2 (S)-(+)-3-hydroxycyclohexanone 
• 165879-90-3 (R)-3-hydroxycyclohexane-1-one 
• 53164-77-5 3-oxocyclohexyl acetate 
• 1419168-58-3 (S)-3-oxocyclohexyl benzoate 

Relevant academic research and scientific papers

Heterogeneous epoxidation of menadione with hydrogen peroxide over the zeolite imidazolate framework ZIF-8

The zeolite imidazolate framework ZIF-8 exhibits superior catalytic performance in the epoxidation of the electron-deficient CC bond in menadione using aqueous hydrogen peroxide as the oxidant. The catalysis has a truly heterogeneous nature and the framework structure remains intact. This is the first example of oxidation catalysis with ZIF-8.

Nucleophilic versus Electrophilic Activation of Hydrogen Peroxide over Zr-Based Metal-Organic Frameworks

Zr-based metal-organic frameworks (Zr-MOF) UiO-66 and UiO-67 catalyze thioether oxidation in nonprotic solvents with unprecedentedly high selectivity toward corresponding sulfones (96-99% at ca. 50% sulfide conversion with only 1 equiv of H2O2). The reaction mechanism has been investigated using test substrates, kinetic, adsorption, isotopic (18O) labeling, and spectroscopic tools. The following facts point out a nucleophilic character of the peroxo species responsible for the superior formation of sulfones: (1) nucleophilic parameter XNu = 0.92 in the oxidation of thianthrene 5-oxide and its decrease upon addition of acid; (2) sulfone to sulfoxide ratio of 24 in the competitive oxidation of methyl phenyl sulfoxide and p-Br-methyl phenyl sulfide; (3) significantly lower initial rates of methyl phenyl sulfide oxidation relative to methyl phenyl sulfoxide (kS/kSO = 0.05); and (4) positive slope ρ = +0.42 of the Hammett plot for competitive oxidation of p-substituted aryl methyl sulfoxides. Nucleophilic activation of H2O2 on Zr-MOF is also manifested by their capability of catalyzing epoxidation of electron-deficient C═C bonds in α,β-unsaturated ketones accompanied by oxidation of acetonitrile solvent. Kinetic modeling on methyl phenyl sulfoxide oxidation coupled with adsorption studies supports a mechanism that involves the interaction of H2O2 with Zr sites with the formation of a nucleophilic oxidizing species and release of water followed by oxygen atom transfer from the nucleophilic oxidant to sulfoxide that competes with water for Zr sites. The nucleophilic peroxo species coexists with an electrophilic one, ZrOOH, capable of oxygen atom transfer to nucleophilic sulfides. The predominance of nucleophilic activation of H2O2 over electrophilic one is, most likely, ensured by the presence of weak basic sites in Zr-MOFs identified by FTIR spectroscopy of adsorbed CDCl3 and quantified by adsorption of isobutyric acid.

Hydrogenation of Phenol to Cyclohexanone over Bifunctional Pd/C-Heteropoly Acid Catalyst in the Liquid Phase

Abstract: Cyclohexanone is an important intermediate in the manufacture of polyamides in chemical industry, but direct selective hydrogenation of phenol to cyclohexanone under mild conditions is a challenge. Hydrogenation of phenol to cyclohexanone has been investigated in the presence of the composite catalytic system of Pd/C-heteropoly acid. 100% conversion of phenol and 93.6% selectivity of cyclohexanone were achieved within 3?h under 80?°C and 1.0?MPa hydrogen pressure. It has been found that a synergetic effect of Pd/C and heteropoly acid enhanced the catalytic performance of the composite catalytic system which suppressed the hydrogenation of cyclohexanone to cyclohexanol. Graphic Abstract: [Figure not available: see fulltext.].

High-Cluster (Cu9) Cage Silsesquioxanes: Synthesis, Structure, and Catalytic Activity

Unusual high-cluster (Cu9) cage phenylsilsesquioxanes were obtained via complexation of in situ CuII,Na-silsesquioxane species formed with phenanthroline and neocuproine. In the first case, phenanthroline, acting as "a silent ligand" (not participating in the composition of the final product), favors the formation of an unprecedented cagelike phenylsilsesquioxane of Cu9Na6 nuclearity, 1. In the second case, neocuproine ligands withdraws two Cu ions from the metallasilsesquioxane matrix, producing two cationic fragments Cu+(neocuproine)2. The remaining metallasilsesquioxane is rearranged into an anionic cage of Cu9Na4 nuclearity, finalizing the formation of a specific ionic complex, 2. The impressive molecular architecture of both types of complexes, e.g., the presence of different (cyclic/acyclic) types of silsesquioxane ligands, was established by single-crystal X-ray diffraction studies. Compound 1 was revealed to be highly active in the oxidative amidation of benzylic alcohol and the catalyst loading could be reduced down to 100 ppm of Cu. Catalytic studies of compound 1 demonstrated its high activity in hydroperoxidation of alkanes with H2O2 and oxidation of alcohols to ketones with tert-BuOOH.

Amorphous Cr/SiO2 Materials Hydrothermally Treated: Liquid Phase Cyclohexanol Oxidation

Abstract: Amorphous Cr–SiO2 materials were synthesized by the sol–gel method and hydrothermally treated at temperatures between 150 and 220?°C. These materials were used as catalysts for cyclohexanol oxidation with H2O2 as oxidant and CH3CN as a solvent. They were responsible for the decomposition of H2O2, which triggers, by a free?radical mechanism in the homogeneous phase, the oxidation or degradation of the hydrocarbon chain. Metal leaching causes a drop in catalytic activity when the material is recycled. Studies on the hydrothermal treatment effect on the leaching process have demonstrated that the higher the hydrothermal treatment temperature, the higher the metal/support interaction, leading to a diminution of the leaching process. Under mild reaction conditions, and using TBHP as oxidant, leaching was reduced, and improvements were obtained on the selectivity towards the formation of cyclohexanone. The use of these catalysts in the oxidation of verbenol, an allylic alcohol, showed a significant increase in the substrate conversion and in the selectivity to carbonyl derivative formation. Graphical Abstract: [Figure not available: see fulltext.].

Robustly supported rhodium nanoclusters: Synthesis and application in selective hydrogenation of lignin derived phenolic compounds

The stabilization of small rhodium nanoclusters (NCs) in a polymer derived silicon carbonitride (SiCN) matrix has been reported to generate highly robust and active solid catalysts for the selective hydrogenation of phenolic compounds. An aminopyridinato Rh complex was used to modify a preceramic polymer (HTT 1800) followed by its pyrolysis at 1100 °C to afford small Rh NCs nicely dispersed over dense SiCN ceramic. For the synthesis of porous catalysts containing Rh NCs, microphase separation (followed by pyrolysis) of a diblock copolymer of HTT 1800 with hydroxy-polyethylene (PE-OH) was used. Both catalysts exhibit high activity in the hydrogenation of substituted phenols at room temperature and under low hydrogen pressure. The catalysts remained highly active and selective for six consecutive catalytic runs.

Enantioselective Michael addition of water

The enantioselective Michael addition using water as both nucleophile and solvent has to date proved beyond the ability of synthetic chemists. Herein, the direct, enantioselective Michael addition of water in water to prepare important β-hydroxy carbonyl compounds using whole cells of Rhodococcus strains is described. Good yields and excellent enantioselectivities were achieved with this method. Deuterium labeling studies demonstrate that a Michael hydratase catalyzes the water addition exclusively with anti-stereochemistry.

Synthesis of 2-nickela(II)oxetanes from nickel(0) and epoxides: Structure, reactivity, and a new mechanism of formation

2-Nickelaoxetanes have been frequently invoked as reactive intermediates in catalytic reactions of epoxides using nickel, but have never been isolated or experimentally observed in these transformations. Herein, we report the preparation of a series of well-defined nickelaoxetanes formed via the oxidative addition of nickel(0) with epoxides featuring ketones. The stereochemistry of the products is retained, which has not yet been reported for nickelaoxetanes. Theoretical calculations support a bimetallic ring-opening/closing pathway over a concerted oxidative addition. Initial reactivity studies of a nickelaoxetane demonstrated protonolysis, oxidatively induced reductive elimination, deoxygenation, and elimination reactions when treated with the appropriate reagents.

Efficient room-temperature aqueous-phase hydrogenation of phenol to cyclohexanone catalyzed by Pd nanoparticles supported on mesoporous MMT-1 silica with unevenly distributed functionalities

Efficient and selective aqueous-phase hydrogenation of phenol by a novel Pd catalyst supported on dually and selectively functionalized mesoporous MMT-1 silica nanoparticles has been developed. The catalyst features small (～1.1 nm) Pd nanoparticles surrounded by unevenly distributed nitrogen- or heteroatom-free organic groups in the helical mesopores and the presence of non-hydrogen-bonded isolated silanol groups on the mesopore surface. The catalyst exhibited superior conversion of phenol and high selectivity of cyclohexanone at room temperature under atmospheric pressure of hydrogen and remained highly active after ten catalytic runs. The catalyst was active for the aqueous-phase hydrogenation of a variety of mono- and dihydroxylated aromatic compounds. The green protocol with the designed catalyst would be practical for the hydrogenation of phenol and other derivatives.

Pt nanoparticle supported on nanocrystalline CeO2: Highly selective catalyst for upgradation of phenolic derivatives present in bio-oil

Pt nanoparticle supported on nanocrystalline CeO2 was prepared, and it was found that the catalyst can selectively hydrogenate phenolic derivatives present in bio-oil. The catalyst was characterized by XRD, XPS, ICP-AES, EXAFS, SEM and TEM. TEM micrograms confirm the presence of very small Pt nanoparticles supported on nanocrystalline CeO2. The catalyst was found to be very effective in liquid phase hydrogenation of phenol and phenolic compounds present in bio-oil in the presence of molecular H2. The synergy between the surface and very small Pt particles on the nanocrystalline CeO2 plays the most vital role towards the extremely high catalytic activity of the catalyst. The reusability of the catalyst was tested, and it was found that the catalyst does not exhibit any significant change in its catalytic activity even after five reuses. The catalyst showed ～100% conversion with very high selectivity after 3 h in phenol conversions of 100% with >98% cyclohexanol selectivity achieved after 3 h of reaction at 100 °C in aqueous medium.