Efficient and Environmentally Benign Oxidative Cleavage of Pyrrolidine-2-methanols to γ-Lactams Using 2-Iodobenzamide as a Catalyst and Oxone.

The oxidative cleavage reaction of pyrrolidine-2-methanols to γ-lactams has been described. In this reaction, [4-iodo-3-(isopropylcarbamoyl)phenoxy]acetic acid and powdered Oxone (2KHSO5·KHSO4·K2SO4) were employed as the catalyst and co-oxidant, respectively. The reaction is efficient and environmentally benign because it produces various lactams from readily available substrates in moderate to excellent yields using organocatalyst and inorganic non-toxic co-oxidant.

8-Iodoisoquinolinone, a Conformationally Rigid Highly Reactive 2-Iodobenzamide Catalyst for the Oxidation of Alcohols by Hypervalent Iodine.

The first lactam-type 2-iodobenzamide catalysts, 8-iodoisoquinolinones 8 (IB-lactam) and 9 (MeO-IB-lactam), were developed. These catalysts have a conformationally rigid 6/6 bicyclic lactam structure and are more reactive than the previously reported catalysts 2-iodobenzamides 4 (IBamide) and 5 (MeO-IBamide) for the oxidation of alcohols. The lactam structure could form an efficient intramolecular I---O interaction, depending on the size of the lactam ring.

Influence of amino acid and N-terminal protection residue structures on peptide p-nitroanilide adsorption on polystyrene-based support.

Polystyrene-based support Bio-Beads® SM-2 was employed for desalting peptide-p-nitroanilides from Oxone®. Neither tosyl, 9-fluorenyl(methoxycarbonyl), p-nitroanilide groups nor indolyl or p-hydroxyphenyl side-chains of Trp and Tyr ensured an efficient adsorption of peptide-p-nitroanilides onto Bio-Beads® SM-2. Only unsubstituted phenyl-containing protection groups (carbobenzoxy or benzoyl) and Phe residues provided the adsorption of peptides on Bio-Beads® SM-2 and their efficient desalting. This support is well suitable for multiple parallel phenyl group-containing peptide derivative separations and high-throughput screenings.

Decolouration of azo dyes by radicals generated from K2S2O8 automatically in homogeneous aqueous solutions.

In this work, at 15 °C and 25 °C, authors study the decolouration reactions (or degradation reactions or oxidation reactions) of 0.10 mM azo dyes (methyl orange and congo red) by (1) K2S2O8 and (2) Co2+/K2S2O8, expounding the roles of K2S2O8 and Co2+: K2S2O8 can oxidize azo dyes automatically in water by radicals; Co2+ has catalysis for oxidation of K2S2O8, whether Co2+ is from CoSO4 or Co(NO3)2, CoCl2, CoAc2. The decolouration degree of azo dyes in all systems quickens with the increase of the initial concentration of K2S2O8 and the reaction temperature. In the presence and absence of Co2+, comparative experiments are done between the oxidation of K2S2O8 and oxone, K2S2O8 shows weaker oxidation than oxone. The decolouration reaction of methyl orange (MO) in the system of (0.10 mM MO + 2.00 mM K2S2O8) accords with the second order reaction, the reaction rate constants are 4.789 M-1 min-1 at 15 °C and 5.894 M-1 min-1 at 25 °C respectively, the activation energy Ea is 14813 J/mol, and Arrhenius equation is k = 2.328 exp[-14813/(RT)].

Recent Advances in the Oxone-Mediated Synthesis of Heterocyclic Compounds.

Oxone is a commercially available oxidant, composed of a mixture of three inorganic species, being the potassium peroxymonosulfate (KHSO5) the reactive one. Over the past few decades, this cheap and environmentally friendly oxidant has become a powerful tool in organic synthesis, being extensively employed to mediate the construction of a plethora of important compounds. This review summarizes the recent advances in the Oxone-mediated synthesis of N-, O- and chalcogen-containing heterocyclic compounds, through a wide diversity of reactions, starting from several kinds of substrate, highlighting the main synthetic differences, advantages, the scope and limitations.

Selective Oxidation of Clopidogrel by Peroxymonosulfate (PMS) and Sodium Halide (NaX) System: An NMR Study.

A selective transformation of clopidogrel hydrogen sulfate (CLP) by reactive halogen species (HOX) generated from peroxymonosulfate (PMS) and sodium halide (NaX) is described. Other sustainable oxidants as well as different solvents have also been investigated. As result of this study, for each sodium salt the reaction conditions were optimized, and four different degradation products were formed. Three products were halogenated at C-2 on the thiophene ring and have concomitant functional transformation, such as N-oxide in the piperidine group. A halogenated endo-iminium product was also observed. With this condition, a fast preparation of known endo-iminium clopidogrel impurity (new counterion) was reported as well. The progress of the reaction was monitored using nuclear magnetic resonance spectroscopy as an analytical tool and all the products were characterized by 1D-, 2D-NMR and HRMS.

Advances in the Synthesis of Ring-Fused Benzimidazoles and Imidazobenzimidazoles.

This review article provides a perspective on the synthesis of alicyclic and heterocyclic ring-fused benzimidazoles, imidazo[4,5-f]benzimidazoles, and imidazo[5,4-f]benzimidazoles. These heterocycles have a plethora of biological activities with the iminoquinone and quinone derivatives displaying potent bioreductive antitumor activity. Synthesis is categorized according to the cyclization reaction and mechanisms are detailed. Nitrobenzene reduction, cyclization of aryl amidines, lactams and isothiocyanates are described. Protocols include condensation, cross-dehydrogenative coupling with transition metal catalysis, annulation onto benzimidazole, often using CuI-catalysis, and radical cyclization with homolytic aromatic substitution. Many oxidative transformations are under metal-free conditions, including using thermal, photochemical, and electrochemical methods. Syntheses of diazole analogues of mitomycin C derivatives are described. Traditional oxidations of o-(cycloamino)anilines using peroxides in acid via the t-amino effect remain popular.

Practical Synthesis of 2-Iodosobenzoic Acid (IBA) without Contamination by Hazardous 2-Iodoxybenzoic Acid (IBX) under Mild Conditions.

We report a convenient and practical method for the preparation of nonexplosive cyclic hypervalent iodine(III) oxidants as efficient organocatalysts and reagents for various reactions using Oxone® in aqueous solution under mild conditions at room temperature. The thus obtained 2-iodosobenzoic acids (IBAs) could be used as precursors of other cyclic organoiodine(III) derivatives by the solvolytic derivatization of the hydroxy group under mild conditions of 80 °C or lower temperature. These sequential procedures are highly reliable to selectively afford cyclic hypervalent iodine compounds in excellent yields without contamination by hazardous pentavalent iodine(III) compound.

Oxone®-Mediated TEMPO-Oxidized Cellulose Nanomaterials form I and form II.

The 2,2,6,6-tetramethylpiperidin-1-oxyl (TEMPO) oxidation of cellulose, when mediated with Oxone® (KHSO5), can be performed simply and under mild conditions. Furthermore, the products of the reaction can be isolated into two major components: Oxone®-mediated TEMPO-oxidized cellulose nanomaterials Form I and Form II (OTO-CNM Form I and Form II). This study focuses on the characterization of the properties of OTO-CNMs. Nanoparticle-sized cellulose fibers of 5 and 16 nm, respectively, were confirmed through electron microscopy. Infrared spectroscopy showed that the most carboxylation presented in Form II. Conductometric titration showed a two-fold increase in carboxylation from Form I (800 mmol/kg) to Form II (1600 mmol/kg). OTO-CNMs showed cellulose crystallinity in the range of 64-68% and crystallite sizes of 1.4-3.3 nm, as shown through XRD. OTO-CNMs show controlled variability in hydrophilicity with contact angles ranging from 16 to 32°, within or below the 26-47° reported in the literature for TEMPO-oxidized CNMs. Newly discovered OTO-CNM Form II shows enhanced hydrophilic properties as well as unique crystallinity and chemical functionalization in the field of bio-sourced material and nanocomposites.

Reaction of Aldoximes with Sodium Chloride and Oxone under Ball-Milling Conditions.

The solvent-free mechanochemical reaction has aroused increasing interest among scientists. Mechanical ball-milling can implement reactions under mild conditions, shorten the reaction time, and improve the reaction efficiency. Particularly, the most attractive characteristic of mechanochemistry is that it can alter the reaction pathway. However, few such examples have been reported so far. In this paper, we report the reaction of aldoximes with NaCl and Oxone under ball-milling conditions to afford N-acyloxyimidoyl chlorides, which are different from those of the liquid-phase counterpart.

Direct Oxidation of Csp3 -H bonds using in Situ Generated Trifluoromethylated Dioxirane in Flow.

A fast, scalable, and safer Csp 3 -H oxidation of activated and un-activated aliphatic chains can be enabled by methyl(trifluoromethyl)dioxirane (TFDO). The continuous flow platform allows the in situ generation of TFDO gas and its rapid reactivity toward tertiary and benzylic Csp3 -H bonds. The process exhibits a broad scope and good functional group compatibility (28 examples, 8-99 %). The scalability of this methodology is demonstrated on 2.5 g scale oxidation of adamantane.

Oxidation of azo and anthraquinonic dyes by peroxymonosulphate activated by UV light.

The photochemical degradation of two azo and two anthraquinonic dyes was performed using potassium peroxymonosulphate (Oxone®) activated by UV radiation. The fast decolourization of all dyes was observed within 6 min of UV irradiation, with corresponding dye decays higher than 80%. The kinetic rate constants of the dyes' decay were determined, along with the energetic efficiency of the photochemical treatment, taking into account the influence of a few anions commonly present in real wastewaters (i.e., chloride, nitrate, carbonate/bicarbonate and phosphate ions). Chloride and carbonate/bicarbonate ions enhanced dye degradation, whereas phosphate ions exerted an inhibitory effect, and nitrates did not have a predictable influence. The dye decolourization was not associated with efficient mineralization, as suggested by the lack of a significant total organic carbon (TOC) decrease, as well as by the low concentrations of a few detected low molecular weight by-products, including nitrate ions, formaldehyde and organic acids. High molecular weight by-products were also detected by mass spectrometry analysis. The investigated process may be proposed as a convenient pre-treatment to help dye degradation in wastewater during combined treatment methods.

One-pot synthesis of diaryliodonium salts from arenes and aryl iodides with Oxone-sulfuric acid.

A facile synthesis of diaryliodonium salts utilizing Oxone as versatile and cheap oxidant has been developed. This method shows wide applicability and can be used for the preparation of iodonium salts containing electron-donating or electron-withdrawing groups in good yields. In addition, this procedure can be applied to the preparation of symmetric iodonium salts directly from arenes via a one-pot iodination-oxidation sequence.

2-Iodo-N-isopropyl-5-methoxybenzamide as a highly reactive and environmentally benign catalyst for alcohol oxidation.

Several N-isopropyliodobenzamides were evaluated as catalysts for the oxidation of benzhydrol to benzophenone in the presence of Oxone® (2KHSO5·KHSO4·K2SO4) as a co-oxidant at room temperature. A study on the substituent effect of the benzene ring of N-isopropyl-2-iodobenzamide on the oxidation revealed that its reactivity increased in the following order of substitution: 5-NO2 < 5-CO2Me, 3-OMe < 5-OAc < 5-Cl < H, 4-OMe < 5-Me < 5-OMe. The oxidation of various benzylic and aliphatic alcohols using a catalytic amount of the most reactive 5-methoxy derivative successfully resulted in moderate to excellent yields of the corresponding carbonyl compounds. The high reactivity of the 5-methoxy derivative at room temperature is a result of the rapid generation of the pentavalent species from the trivalent species during the reaction. 5-Methoxy-2-iodobenzamide would be an efficient and environmentally benign catalyst for the oxidation of alcohols, especially benzylic alcohols.

Cellulose Nanofibers Prepared via Pretreatment Based on Oxone® Oxidation.

Softwood sulfite bleached cellulose pulp was oxidized with Oxone® and cellulose nanofibers (CNF) were produced after mechanical treatment with a high-shear homogenizer. UV-vis transmittance of dispersions of oxidized cellulose with different degrees of mechanical treatment was recorded. Scanning electron microscopy (SEM) micrographs and atomic force microscopy (AFM) images of samples prepared from the translucent dispersions showed individualized cellulose nanofibers with a width of about 10 nm and lengths of a few hundred nm. All results demonstrated that more translucent CNF dispersions could be obtained after the pretreatment of cellulose pulp by Oxone® oxidation compared with the samples produced without pretreatment. The intrinsic viscosity of the cellulose decreased after oxidation and was further reduced after mechanical treatment. Almost translucent cellulose films were prepared from the dispersions of individualized cellulose nanofibers. The procedure described herein constitutes a green, novel, and efficient route to access CNF.

Monopersulfate photocatalysis under 365 nm radiation. Direct oxidation and monopersulfate promoted photocatalysis of the herbicide tembotrione.

Oxone(®) (potassium monopersulfate, MPS) has been used to oxidize the herbicide tembotrione in aqueous solution. Tembotrione elimination kinetics by MPS direct oxidation has been studied. The influence of the main operating variables affecting the process (MPS concentration, temperature and pH) has been evaluated. The process follows 2/3 and first orders in MPS and tembotrione concentrations, respectively. Optimal pH is located around circumneutral conditions. MPS decomposition in the presence of 365 nm UVA radiation and titanium dioxide has also been studied. A kinetic mechanism that simulates MPS decomposition has been proposed, showing the positive effect of titania load and MPS concentration. The system MPS/UVA/TiO2 significantly improves tembotrione and mineralization rate abatement if compared to runs conducted in the absence of MPS. Tembotrione total abatement was achieved in 20 min when 0.05 g L(-1) of titania and 10(-4) M of Oxone(®) were used. TOC conversion was roughly 70% in 90 min under similar operating conditions. An experimental design (Plackett-Burman) has been considered to study the influence of the main variables affecting tembotrione photocatalytic oxidation promoted by MPS.

Guanosine in a single stranded region of anticodon stem-loop tRNA models is prone to oxidatively generated damage resulting in dehydroguanidinohydantoin and spiroiminodihydantoin lesions.

Oxidation of RNA hairpin models corresponding to anticodon stem-loop (ASL) of transfer RNA led to RNA damage consisting solely of a unique loop guanine oxidation. Manganese porphyrin/oxone treatment of RNA resulted in dehydroguanidinohydantoin (DGh; major) and/or spiroiminodihydantoin (Sp) lesions. Ribose damage was not observed. This two-electron transfer oxidation reaction allowed the identification of guanine oxidation products for further study of RNA species carrying a unique lesion at a single G to investigate their biological impact.

An efficient approach for conversion of 5-substituted 2-thiouridines built in RNA oligomers into corresponding desulfured 4-pyrimidinone products.

An efficient approach for the desulfuration of C5-substituted 2-thiouridines (R5S2U) bound in the RNA chain exclusively to 4-pyrimidinone nucleoside (R5H2U)-containing RNA products is proposed. This post-synthetic transformation avoids the preparation of a suitably protected H2U phosphoramidite, which otherwise would be necessary for solid-phase synthesis of the modified RNA. Optimization of the desulfuration, which included reaction stoichiometry, time and temperature, allowed to transform a set of ten R5S2U-RNAs into their R5H2U-RNA congeners in ca. 90% yield.

C-H oxygenation and N-trifluoroacylation of arylamines under metal-free conditions: a convenient approach to 2-aminophenols and N-trifluoroacyl-ortho-aminophenols.

Direct ortho-hydroxylation through C-H oxygenation and N-trifluoroacylation of anilines was achieved in a single step under metal-free conditions by using a combination of TFA and oxone. The method allowed the formation of functionalised amino phenolic compounds such as ortho-hydroxy-N-trifluoroacetanilides in good yields with broad substrate scope.

Formation of the carboxamidine precursor of cyanuric acid from guanine oxidative lesion dehydro-guanidinohydantoin.

DNA damage under oxidative stress leads to oxidation of guanine base. The identification of the resulting guanine lesions in cellular DNA is difficult due to the sensitivity of the primary oxidation products to hydrolysis and/or further oxidation. We isolated dehydroguanidino-hydantoin (DGh) (or oxidized guanidinohydantoin), a secondary oxidation product of guanine, and showed that this lesion reacts readily with nucleophiles such as asymmetric peroxides and transforms to 2,4,6-trioxo-1,3,5-triazinane-1-carboxamidine residue. Further hydrolysis of this intermediate leads to cyanuric acid and finally to urea residue. This work demonstrates a new possible pathway for the formation of the well-known carboxamidine precursor of cyanuric acid lesion.