Efficient Baeyer–Villiger Oxidation of Ketones using Molecular Iodine/H2O2 as Heterogeneous Catalytic System

The use of molecular iodine as a catalyst for the oxidation of ketones using hydrogen peroxide in the presence of acetic acid at room temperature is reported.     

Influence of Pretreatment on the Interaction of Oxygen with Silver and the Catalytic Activity of Ag／SiO2 Catalysts for CO Selective Oxidation in H2

The interactions of oxygen with pre~reduced silver catalysts as well as their catalytic propertiesfor CO selective oxidation in H2 after oxygen pre-treatment are studied in this paper. It is found that the pretreatment exerts a strong influence on the activity and selectivity of the silver catalyst. A drop in activity and selectivity is observed after treating a pre-reduced catalyst with oxygen at low temperatures,whereas a converse result is obtained after an oxidizing treatment at high temperatures (T≥350℃). O2-TPD results show that surface oxygen species adsorbs on silver surface after the oxygen treatment at low temperatures. However, penetration of oxygen into the silver is enhanced by a high temperature treatment, meanwhile the surface oxygen species disappear. No other silver species except metallic silver are observed on all the catalysts by XRD, and the size of silver particle is not changed after the treatment with oxygen at low temperatures. The surface oxygen species formed by oxygen treatment can also be removed by hydrogen reduction. The strongly-adsorbed surface oxygen species prohibit the adsorption and diffusion of oxygen species in reaction gas on the surface of silver catalyst, causing the decrease in CO oxidation activity, in other words, it is important to obtain a clean silver surface for increasing the catalyst activity in CO removal from H2-rich feed gas. The differences in activity and selectivity due to the oxygen pretreatment at different temperatures axe discussed in terms of the changes in the surface/subsurface oxygen species of the silver particles.     

Selective Oxidation of CO in Excess H2 over Ru/Al2O3 Catalysts Modified with Metal Oxide

The Ru/Al_2O_3 catalysts modified with metal oxide(K_2O and La_2O_3)were prepared via incipient wetness impregnation method from RuCl_3·nH_2O mixed with nitrate loading on Al_2O3 support. The activity of catalysts was evaluated under simulative conditions for the preferential oxidation of CO (CO-PROX)from the hydrogen-rich gas streams produced by reforming gas,and the performances of catalysts were investigated by XRD and TPR.The results showed that the activity temperature of the modified catalysts Ru-K_2O/Al_2O3 and Ru-La_2O_3/Al_2O_3 were lowered approximately 30℃compared with pure Ru/Al_2O_3,and the activity temperature range was widened.The conversion of CO on Ru-K_2O/Al_2O_3 and Ru-La_2O_3/Al_2O_3 was above 99% at 140-160℃,suitable to remove CO in a hydrogen-rich gas and the selectivity of Ru-La_2O_3/Al_2O_3 was higher than that of Ru-K_2O/Al_2O_3 in the active temperature range. Slight methanation reaction was detected at 220℃and above.     

The Effect of Nb Loading on Catalytic Properties of Ni/Ce0.75Zr0.25O2 Catalyst for Methane Partial Oxidation

In this study,the effect of Nb loading on the catalytic activity of Ce_(0.75)Zr_(0.25)O_2-supported Ni catalysts was studied for methane partial oxidation.The catalysts were characterized by BET,H_2 chemisorption,XRD,TPR,TEM and tested for methane partial oxidation to syngas in the temperature range of 400-800℃at atmospheric pressure.The results showed that the activity of methane partial oxidation on the catalysts was apparently dependent on Nb loading.It seemed that the addition of Nb lowered the catalytic activity for methane partial oxidation and increased the extent of carbon deposition. This might be due to the strong interaction between NiO and Nb-modified support and reduction of surface oxygen reducibility.     

Enhancement of Activity of SnO2-doped In2O3/Al2O3 Catalyst for NO Reduction with Propene in the Presence of H2O and SO2

The selective catalytic reduction of nitrogen oxides by hydrocarbons (HC-SCR) has attracted much attention as an efficient way to remove NO in the presence of excess oxygen1-2. The metal oxides are the most promising catalysts for the SCR of NO because of their high activity and selectivity3-5. In the previous work, the metal oxides such as Ag, Sn, In, Co supported on alumina for NO reduction were investigated6-8, however, the HC-SCR is usually suppressed in the presence of H2O and S…     

NaBrO3/NaHSO4 · H2O as a Versatile Reagent System for the Oxidation of Benzylic Alcohols and Aldehydes

The oxidation of benzylic alcohols and aldehydes by NaBrO₃ is efficiently promoted in the presence of NaHSO₄ · H₂O. All reactions were performed under mild and completely heterogeneous conditions in good to high yields.     

Oxidation of Ethers,Alcohols, and Unfunctionalized Hydrocarbons by the Methyltrioxorhenium/H2O2 System: A Computational Study on Catalytic C?H Bond Activation

A concerted mechanism that does not involve an ionic intermediate was revealed by a DFT study on oxidation of ethers, alcohols, and unfunctionalized hydrocarbons by methyltrioxorhenium/H₂O₂. Instead, C? H insertion occurs through hydride transfer and then turns into a hydroxide transfer/rebound in a concerted fashion. The picture shows selected frames from an intrinsic reaction coordinate scan from the transition state to the product for the oxidation of cis‐1,2‐dimethylcyclohexane.

     

An Alternative Method for the Highly Selective Iodination of Alcohols Using a CsI/BF3·Et2O System

Abstract

A variety of allylic and benzylic alcohols have been converted into the corresponding iodides using cesium iodide (CsI) in the presence of boron trifluoride etherate (BF₃·Et₂O) in acetonitrile under mild conditions.     

Effect of a Second γ-Al2O3 Support on the Physico-Chemical Characteristics of Catalysts for CO/NO x /C n H m Three-Way Conversions

We have established that extending the surface of ceramic honeycomb monoliths based on synthetic cordierite, which is achieved by application of a layer of a second support in the form of -Al₂O₃, leads to an increase in the activity of platinum/palladium catalysts in CO/NO/C₆H₁₄ three-way conversions. Introducing modifying additives of rare-earth element oxides (Ce, La, Nb, Pr, Sm) increases the thermal stability of the porous structure of the second support.     

One-Pot Synthesis and Asymmetric Oxidation of 2-Nitro-4-(Trifluoromethyl)Benzene Containing Sulfides

Abstract

An efficient one-pot method for the preparation of 2-nitro-4-(trifluoromethyl)benzene containing sulfides from 1,1′-disulfanediylbis[2-nitro-4-(trifluoromethyl)benzene] is proposed. The corresponding enantiomerically enriched sulfoxides with up to 78% enantiomeric excess are prepared by the asymmetric oxidation of sulfides using a modified Sharpless method. The yield of sulfoxides is shown to decrease with an increase in the bulk of the aliphatic group and with a decrease of the inductive effect of the hydrocarbonic moiety on the sulfur atom.

Supplemental materials are available for this article. Go to the publisher's online edition of Phosphorus, Sulfur, and Silicon and the Related Elements to view the free supplemental file.

GRAPHICAL ABSTRACT      

Selective Oxidation of Sulfides to Sulfoxides/Sulfones by 30% Hydrogen Peroxide

Abstract

A selective and efficient procedure for the oxidation of various sulfides with sodium tungstate dihydrate with 30% hydrogen peroxide in the presence of trioctylmethylammonium dihydrogen phosphate, respectively, to the corresponding sulfoxides and sulfones is reported. The oxidation reaction is carried out at –5 to 0 °C in the presence of hydroxypropyl-β-cyclodextrins for sulfoxides or at 50–60 °C for sulfones. The mild reaction conditions, easy workup, and good yields of the products are the major advantages of this method.     

wo3催化h2o2氧化环己酮合成己二酸

以WO3为催化剂,在无有机溶剂和相转移催化剂的情况下,用H2O2氧化环己酮合成己二酸。探讨了催化剂用量、H2O2用量、反应温度和时间等条件对反应的影响。在优化条件下:n(环己酮)∶n(H2O2)∶n(WO3)=100∶500∶2,反应温度为120℃,反应6 h,己二酸分离收率可达80.3%,纯度为99.8%;催化剂重复使用5次后己二酸收率仍可达70.2%。     

Metal-Free Highly Efficient Aerobic Oxidation of Sulfides to Sulfoxides Catalyzed by DBDMH/TBN/H2O

A highly efficient metal-free catalytic system, 1,3-dibromo-5,5-dimethylhydantoin (DBDMH)–tert-butylnitrite (TBN)–H₂O, has been developed for an environmentally friendly and economical aerobic acid-free oxidation of sulfides. TBN was identified as an efficient NO equivalent for the activation of molecular oxygen. Under optimal conditions, a variety of sulfides substrates were converted into their corresponding sulfoxides in good yields by molecular oxygen.     

Catalytic Asymmetric Bromination of Unfunctionalized Olefins with H2O as a Nucleophile

The dimeric cinchona alkaloid (DHQD)₂PHAL is used to catalyze an effective asymmetric bromohydroxylation of unfunctionalized olefins with H₂O as nucleophile an N‐bromobenzamide as a bromine source. A variety of optically active bromohydrins are formed with up to 88 % ee.     

Asymmetric Sulfoxidation of Thioether Catalyzed by Soybean Pod Shell Peroxidase to Form Enantiopure Sulfoxide in Water-in-Oil Microemulsions: A Kinetic Model

Esomeprazole with chiral sulfoxides structure is used to treat gastric ulcer disease. Soybean pod shell peroxidase (SPSP) is a peroxidase extracted from soybean pods shells which are one of the most abundant natural resources in the world. In the production of chiral sulfoxides catalyzed by SPSP, it is very important to establish the reaction kinetic model and explore the reaction mechanism for the development of the process, however, there is no report on the establishment of the model. Asymmetric sulfoxidation reactions catalyzed by SPSP in water-in-oil microemulsions were carried out, and the King-Altman approach was used to establish a kinetic model. A yield of 91% and e.e. value of 96% for esomeprazole were obtained at the activity of SPSP of 3200 U ml⁻¹ and 50 °C for 5 h. The mechanism with a two-electron reduction of SPSP-I is accompanied with a single-electron transfer to SPSP-I and nonenzymatic reactions, indicating that three concomitant sub-mechanisms contribute to the asymmetric oxidation involving five enzymatic and two nonenzymatic reactions, which can represent the asymmetric sulfoxidation of organic sulfides to form enantiopure sulfoxides. With 5.44% of the average relative deviation, a kinetic model fitting experimental data was developed. The enzymatic reactions may follow ping-pong mechanism with substrate inhibition of H₂O₂ and product inhibition of esomeprazole, while nonenzymatic reactions follow a power law. Those results indicate that SPSP with a lower cost and higher thermal stability may be used as an effective substitute for horseradish peroxidase.     

DBDMH/NaNO2 Catalyst: Transition-Metal-Free Approach to Highly Efficient Aerobic Oxidation of Sulfides to Sulfoxides

DBDMH/NaNO₂/O₂ in water is a very efficient nonmetal transition system for catalytic oxidation of a variety of sulfides to the corresponding sulfoxides. The present catalytic system utilizes cheap and readily available agents as the catalysts and has the advantages of simple operations, easy separation of products, and high yields.     

An Efficient Catalytic Procedure for the Selective Oxidation of Sulfides to Sulfoxides by Citric Acid/Al(NO3)3.9H2O/MBr Under Mild and Heterogeneous Conditions

A wide range of aliphatic or aromatic sulfides are selectively oxidized to the corresponding sulfoxides using Al(NO₃)₃.9H₂O, citric acid and a catalytic amount of KBr or NaBr in the presence of wet SiO₂ (50% w/w)in CH₂Cl₂ under mild and heterogeneous conditions in good to high yields.