Oxidation of N-benzyl groups

The oxidative reactivity of 2,6,8,12-tetraacetyl-4,10-dibenzy1-2,4,6,8,10,12-hexaazatetracydot[5,5.0,05.9.03.11] dodecane (3) in several conditions was studied.It was found that the N-benzyl groups in compound 3 could be oxidized to benzoyi groups byCr(Ⅵ) reagents,and could be removed by cerium ammonium nitrate (CAN),meanwhile nitroamine products were given.     

Visualizing Redox Chemistry: Probing Environmental Oxidation–Reduction Reactions with Indicator Dyes

One of the important questions in the chemistry of pollutant degradation is the identity and distribution of chemical agents that are responsible for reduction reactions in the environment. Reduction occurs primarily in water-saturated environments, such as sediments, soils, and sludges. Redox indicators can be used (i) as chemical probes to obtain fundamental insights into biogeochemical processes and (ii) as the basis for demonstrations suitable for teaching aspects of environmental chemistry. This paper explores the latter with examples that involve a variety of indicators (indigo sulfonates, resazurin, etc.), environmental media (anaerobic sediments and granular iron metal), and physico-chemical processes (oxidation-reduction, adsorption, and diffusion). The results show that reduction by either media (sediments or iron metal) is primarily, although not always entirely, a surface reaction. This situation results in indicator behavior that is interesting and challenging for students with a wide range of backgrounds.     

N-Confused Phlorin-Prodigiosin Chimera: meso-Aryl Oxidation and π-Extension Triggered by Peripheral Coordination

An N-confused phlorin isomer bearing a dipyrrin moiety at the α-position of the confused pyrrole ring ( 1 ) was synthesized. Pd^II and B^III coordination at the peripheral prodigiosin-like moiety of 1 afforded the corresponding complexes 2 and 3 . Reflux of 2 in triethylamine (TEA) converted the meso-phenyl into the Pd^II-coordinating phenoxy group to afford 4 . Under the same reaction conditions, TEA was linked to the α-position of the dipyrrin unit in 3 as an N,N-diethylaminovinyl group to afford 5 . Furthermore, peripheral coordination of B^III in 3 and 5 improved the planarity of the phlorin macrocycle and thus facilitated the coordination of Ag^III at the inner cavity to afford 3-Ag and 5-Ag , respectively. These results provide an effective approach for developing unique porphyrinoids through peripheral coordination.     

Syntheses of DL-threo-Thiamphenicol via Green Oxidation

IntroductionAqueous hydrogen peroxide is considered to be a“green”oxidant with a high oxidation efficiency due toits low molecular weight,cleanness in the oxidationprocess in which only harmless water is produced,lowcost of production and safe transport…     

Oxidation of fluoroalkyl-substituted allylic alcohols: a synthesis of fluorinated α,β-epoxyketones

Fluoroalkyl-substituted allylic alcohols are readily and selectively oxidized at the hydroxyl group with the Swern or Dess-Martin reagents to give ,-unsaturated ketones, and on treatment withm-chloroperbenzoic acid ortert-butyl hydroperoxide they are oxidized to the corresponding epoxyalcohols. The latter are oxidized by Swern or Dess-Martin reagents at the hydroxyl group to ,-epoxyketones, which form hydrates stable under the conditions of isolation.Translated fromIzvestiya Akadernii Nauk. Seriya Khimicheskaya, No. 3, pp. 680–683, March, 1996.     

Indirect Electrochemical Oxidation of 4-Amino-dimethyl-aniline Hydrochloride

Introduction4Amino dimethyl anilinehydrochlorideisoneof themaincomponentsofthewastewaterresultedfrom vanillinproduction[1]whichinhibitsthenormalactivity ofthemicroorganismsofmicrobialpopulation,thereby affectingthebiologicaltreatmentprocessofvanillin.Comm…     

Electroanalytical Oxidation of p‐Coumaric Acid

Abstract

The mechanism of the electrochemical oxidation of p‐coumaric acid on a glassy carbon electrode was investigated using cyclic, differential pulse, and square wave voltammetry at different pHs. The oxidation of p‐coumaric acid is irreversible over the whole pH range. After successive scans, the p‐coumaric acid oxidation product deposits on the electrode surface, forming a polymeric film that undergoes reversible oxidation at a lower potential than p‐coumaric acid. This polymeric film increases in thickness with the number of scans, covering the electrode surface, and impeding the diffusion of the p‐coumaric acid and its oxidation on the electrode. The oxidation of p‐coumaric acid is pH dependent up until values close to the pK_a. For pHs higher than pK_a, the p‐coumaric acid oxidation process is pH independent. An electroanalytical determination procedure of p‐coumaric in pH 8.7 0.2 M ammonium buffer was developed, and a detection limit, LOD=83 nM, and the limit of quantification, LOQ=250 nM, were obtained.     

Sodium Bismuthate–Induced Oxidation of Baccatin

Sodium bismuthate in acetic acid has proven very effective in the oxidation of allyic alcohols. An extension of this oxidation method using baccatin as the substrate has provided keto‐baccatin, an important compound for the semisynthesis of Taxol and Taxotere.     

Improved Solvent‐Free Dakin Oxidation Protocol

A solvent‐free Dakin reaction with mCPBA was accomplished with various aromatic aldehydes, resulting in an easy and improved methodology for the preparation of corresponding phenols. 3,4‐Methylenedioxyphenol, 3,4‐dimethoxyphenol, 4‐methoxyphenol, 4‐chlorophenol, and other functionalized phenols were obtained in high yields from the corresponding aromatic aldehydes in a few minutes. This new methodology represents an efficient alternative for this important synthetic conversion.     

Advances of PtRu-Based Electrocatalysts for Methanol Oxidation

Platinum-Ruthenium(PtRu)-based materials are considered the “holy grail” of electrocatalysts for methanol oxidation reaction(MOR) in the fuel cells technique. However,to the best of our knowledge, the exhaustive review report on the advance of PtRu materials for methanol oxidation is rarely summarized for the recent novel achievements. Herein,we summarize and discuss the latest progress of PtRu-based catalysts in MOR. The reaction mechanism of MOR is firstly introduced, and the promotion mechani...     

Regiospecific Baeyer-Villiger Oxidation of α,α-Dichlorocyclobutanones: A Norbisabolide γ-lactone Analogue1

Details and methodological comparisons are presented on the preparation of a norbisabolide γ-lactone analogue (4) via dichloroketene cycloaddition to limonene followed by regioselective Baeyer-Villiger oxidation (CH₃CO₃H) of the α,α-dichlorocyclobutanones 3 and C-Cl reduction (Zn/HOAc). The sequence of reduction followed by oxidation (HOCI) applied to 3 produced 4 in much better yield.     

N‐Bromosuccinimide: A Facile Reagent for the Oxidation of Benzylic Alcohols to Aldehydes

The oxidation of benzylic alcohols to aldehydes using N‐bromosuccinimide (NBS) under ambient conditions without use of a transition‐metal catalyst has been described.     

Improving Physical Properties via C?H Oxidation: Chemical and Enzymatic Approaches

Physicochemical properties constitute a key factor for the success of a drug candidate. Whereas many strategies to improve the physicochemical properties of small heterocycle‐type leads exist, complex hydrocarbon skeletons are more challenging to derivatize because of the absence of functional groups. A variety of C H oxidation methods have been explored on the betulin skeleton to improve the solubility of this very bioactive, yet poorly water‐soluble, natural product. Capitalizing on the innate reactivity of the molecule, as well as the few molecular handles present on the core, allowed oxidations at different positions across the pentacyclic structure. Enzymatic oxidations afforded several orthogonal oxidations to chemical methods. Solubility measurements showed an enhancement for many of the synthesized compounds.     

Oxidation of Hecogenin and Diosgenin Derivatives with Dimethyldioxirane

Diacetyl derivative of hecogenin 1 was oxidized to unsaturated ketone 5 via allylic alcohol 3 when it reacted with dimethyldioxirane (DMDO). The structure of 3 was confirmed by X-ray crystal analysis and the highly regioselectivity of DMDO to different olefin bonds was also observed when diosgenin derivative 6 was treated with DMDO.     

Aqueous Media Oxidation of Alcohols with Ammonium Persulfate

Oxidation of series of various primary and secondary alcohols to corresponding carbonyl compounds with ammonium persulfate in aqueous media was described. No over oxidation of primary alcohols to carboxylic acids and secondary alcohols to esters was observed. Under such conditions benzoin was converted to benzoic acid.     

Microreactor for the Catalytic Partial Oxidation of Methane

Fixed-bed reactors for the partial oxidation of methane to produce synthetic gas still pose hot-spot problems. An alternative reactor, which is known as the shell-and-tube-typed microreactor, has been developed to resolve these problems. The microreactor consists of a 1 cm outside-diameter, 0.8 cm inside-diameter and 11 cm length tube, and a 1.8 cm inside-diameter shell. The tube is made of dense alumina and the shell is made of quartz. Two different methods dip and spray coating were performed to line the tube side with the LaNixOy catalyst. Combustion and reforming reactions take place simultaneously in this reactor. Methane is oxidized in the tube side to produce flue gases (CO2 and H2O) which flow counter-currently and react with the remaining methane in the shell side to yield synthesis gas. The methane conversion using the higher-loading catalyst spray-coated tube reaches 97% at 700℃, whereas that using the lower-loading catalyst dip-coated tube reaches only 7.78% because of poor adhesion between the catalyst film and the alumina support. The turnover frequencies (TOFs) using the catalyst spray-and dip-coated tubes are 5.75×10-5 and 2.24×10-5 mol/gcat·s, respectively. The catalyst spray-coated at 900℃provides better performance than that at 1250℃because sintering reduces the surface-area. The hydrogen to carbon monoxide ratio produced by the spray-coated catalyst is greater than the stoichiometric ratio, which is caused by carbon deposition through methane cracking or the Boudouard reaction.     

Electrocatalytic Oxidation of Ethanol on Electrodcposited Palladium Electrode

Therearemanyinvestigationsabouttheelectrocatalyticoxldationofethanolontheelectrodeofplatinunlelectrode'-'.whicharemainlyinacidmedium.However.tothebestknowledgeoftheauthor.therearenoinvestigationsabouttheoxidatiollofethanolonpalladiumelectrode.letaloneonPd/GCelectrodepreparedbyelectrodeposition.Accordingtotheexperimentalresultsinthispaper,Pd/GCelectrodeismoreelectroactivetotheoxidationofethanolthantothatofmethanolinalkalinemedium(e.g.inI.0mol/LNaOH).basedontheiroxidationpeakpotentialswhicha…     

Silica‐Supported bis (Trimethylsilyl) Chromate: Oxidation of Thiols to Their Corresponding Disulfides

An efficient and convenient method for the oxidation of thiols mediated by silica‐supported bis (trimethylsilyl) chromate (BTSC) in acetonitrile is reported.     

Predictable Selectivity in Remote C−H Oxidation of Steroids: Analysis of Substrate Binding Mode

Predictability is a key requirement to encompass late-stage C−H functionalization in synthetic routes. However, prediction (and control) of reaction selectivity is usually challenging, especially for complex substrate structures and elusive transformations such as remote C(sp³)−H oxidation, as it requires distinguishing a specific C−H bond from many others with similar reactivity. Developed here is a strategy for predictable, remote C−H oxidation that entails substrate binding to a supramolecular Mn or Fe catalyst followed by elucidation of the conformation of the host-guest adduct by NMR analysis. These analyses indicate which remote C−H bonds are suitably oriented for the oxidation before carrying out the reaction, enabling prediction of site selectivity. This strategy was applied to late-stage C(sp³)−H oxidation of amino-steroids at C15 (or C16) positions, with a selectivity tunable by modification of catalyst chirality and metal.