Arenediazonium Tosylates Research Articles

Iodine/DMF-Mediated Regioselective Sulfenylation Using Arenediazonium Tosylates and Sodium Metabisulfite: An Easy Access to 3-Arylthioindoles.

A practical C3 sulfenylation of indoles has been accomplished using arenediazonium tosylates and sodium metabisulfite, with a key role of iodine/DMF combination in the reaction. The method involves scarce use of sodium metabisulfite as a divalent sulfur source and offers an array of structurally diverse 3-arylthioindoles in high yields under operationally simple transition-metal-free and mild conditions.

Straightforward and Efficient Protocol for the Synthesis of Pyrazolo [4,3-b]pyridines and Indazoles.

An efficient method for the synthesis of pyrazolo [4,3-b]pyridines has been developed on the basis of readily available 2-chloro-3-nitropyridines via a sequence of SNAr and modified Japp-Klingemann reactions. The method offers a number of advantages including utilization of stable arenediazonium tosylates, operational simplicity as well as combining the azo-coupling, deacylation and pyrazole ring annulation steps in a one-pot manner. An unusual rearrangement (C-N-migration of the acetyl group) was observed and a plausible mechanism was proposed based on the isolated intermediates and NMR experiments. In addition, the developed protocol was successfully applied to the synthesis of 1-arylindazoles combining the Japp-Klingemann reaction and cyclization of the resulting hydrazone as a one-pot procedure.

Electrochemical Sensor for Selective Detection of Meldonium in Urine by Voltammetry

AbstractA highly sensitive electrochemical sensor based on arenediazonium tosylates was designed to detect meldonium in urine. The effect of the concentration of ArN2+OTs− arenediazonium tosylate modifier and various substituents was studied. Basic operating parameters for voltammetric meldonium detection were established and the procedure for urine sample preparation was developed. The following values were obtained: limit of detection (LOD) 0.005 mg ⋅ L−1 (P=0.95) and limit of quantification (LOQ) 0.01 mg ⋅ L−1. The relationship between the analytical signal and meldonium concentration in the solution ranging from 0.01 to 400 mg ⋅ L−1 was described by a linear function. The meldonium concentration error did not exceed 18 %. The analysis time for a single urine sample was reduced to 15 minutes.

Arenediazonium sulfonates: synthesis, comparison of structural and physicochemical properties

Aromatic diazonium salts are important building blocks in organic synthesis. The present review is concerned with such aromatic diazonium sulfonates as tosylates, dodecylbenzenesulfonates, triflates, camphorsulfonates, silica sulfates. The first part of the review provides information on the synthesis and application of these diazonium salts. It is shown that these diazonium compounds are easily synthesized by diazotization of anilines with sodium nitrite or alkyl nitrites in the presence of corresponding sulfonic acids with high yields. These diazonium salts have found wide application in the synthesis of aromatic azides, halides, triazenes, azo dyes, stilbenes, biaryls, etc. The second part of the article presents information on the comparison of the results of X-ray analysis, infrared spectroscopy and thermal analysis. The structure of diazonium sulfonate salts corresponds to the structure of classical diazonium salts (chlorides, sulfates, tetrafluoroborates). A significant difference between arenediazonium sulfonates and other diazonium salts is their explosion safety and stability in an individual form. Arenediazonium tosylates, triflates and camphorasulfonates are easily soluble both in water and in polar organic solvents. Arenediazonium dodecylbenzenesulfonates are soluble in nonpolar organic media. These features of sulfonate salts are paramount for distinguishing characteristics of the effect of the acid anion on the stability, solubility and reactivity of diazonium salts.

From Rare Reagents to Rare Products: Regiospecific Silver‐Catalyzed [3+2] Cycloaddition of Aryl‐, Alkyl‐ and Aminosulfonyl Diazomethanes with Arenediazonium Tosylates

The scope of silver nitrate‐catalyzed cycloaddition of arenediazonium salts has been expanded to include aryl‐ and alkylsulfonyl diazomethanes as well as the recently introduced diazomethyl sulfonamides. The reliance on these two classes of diazo compounds led to a new synthetic approach to the rare 2‐aryltetrazol‐5‐yl sulfones as well as to the synthesis of hitherto not described 2‐aryltetrazol‐5‐yl sulfonamides.

Flexible Entry into 3-Arylpent-2-enedioic Acids via Heck–Matsuda Arylation of Dimethyl Glutaconate with Arenediazonium Tosylates

For the preparation of compound libraries of Michael acceptors with tunable reactivity toward nuclophilic selenocysteine residue of thioredoxin reductase, a range of 3-arylglutaconic acids were required. The existing methods at the time had limited scope or involved several steps. A hitherto undescribed protocol for direct palladium(II) acetate-catalyzed arylation of glutaconic acid dimethyl ester at position 3 has been developed with a diverse set of arenediazonium tosylates followed by hydrolysis. This generally good-yielding two-step sequence displayed a propensity to deliver E-configured coupling products while compounds mostly featured in the literature were predominantly Z-configured. The possibility for preparing a library of 4-arylpyridine-2,6(1H,3H)-diones has been exemplified.

Vapor Annealing and Colloid Lithography: An Effective Tool To Control Spatial Resolution of Surface Modification.

Colloid lithography represents a simple and efficient method for creation of a large-scale template for subsequent surface patterning, deposition of regular metal nanostructures, or periodical surface structures. However, this method is significantly restricted by its ability to create only a limited number of structures with confined geometry and symmetry features. To overcome this limitation, different techniques, such as plasma treatment or tilting angle metal deposition, have been proposed. In this paper, an alternative method based on the vapor annealing of ordered single polystyrene (PS) microspheres layer, followed by the surface grafting with arenediazonium tosylates is proposed. Application of vapor treatment before surface grafting allows effective control of the area screened by PS microspheres. Pristine and vapor-annealed microsphere arrays on the gold substrate were electrochemically modified using ADTs. Subsequent removal of the PS microsphere mask enabled to prepare well-defined nanostructures with controllable surface features. In particular, prepared periodic arrangements were achieved by the grafting of OFGs to the empty interspaces between nanopore arrays. The process of sample preparation was controlled, and the properties of prepared structures were characterized by various techniques, including atomic force microscopy (AFM), conductive AFM, scanning electron microscopy energy-dispersive X-ray spectrometry, Raman spectroscopy, and voltammetry.

Telescopic Synthesis of Azo Compounds via Stable Arenediazonium Tosylates by Using n-Butyl Nitrite as Diazotization Reagent

ABSTRACTA multi-step catalyst-free synthesis of azo compounds by using n-butyl nitrite as a diazotization reagent and p-toluene sulfonic acid as a mild acidic agent in ethanol/water mixed solvent was investigated. In the combined one-pot synthesis process, no nitrous acid was produced during the diazotization. By controlling the conditions in a continuous process, a 62–88% yield was obtained. The current method has the following advantages: reduce waste by avoiding solvent for the purification of products in the diazotization step; save energy, time, and cost; work under environmentally benign conditions, and produce a good amount of products with potential use as azo-dyes, pigments, and therapeutic agents.

Tuning of PEDOT:PSS Properties Through Covalent Surface Modification

ABSTRACTConductive polymer (poly(3,4‐ethylenedioxythiophene)‐poly(styrenesulfonate) (PEDOT:PSS) is an attractive platform for the design of flexible electronic, optoelectronic, and (bio)sensor devices. Practical application of PEDOT:PSS often requires an incorporation of specific molecules or moieties for tailoring of its physical–chemical properties. In this article, a method for covalent modification of PEDOT:PSS using arenediazonium tosylates was proposed. The procedure includes two steps: chemisorption of diazo‐cations on the PEDOT:PSS surface followed by thermal decomposition of the diazonium salt and the covalent bond formation. Structural and surface properties of the samples were evaluated by XPS, SEM‐EDX, AFM, goniometry, and a range of electric and optical measurements. The developed modification procedure enables tuning of the PEDOT:PSS surface properties such as conductivity and optical absorption. The possibility to introduce various organic functional groups (from hydrophilic to hydrophobic) and to create new groups for further functionalization makes the developed procedure multipurpose. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2017, 55, 378–387

Surface modification of Au and Ag plasmonic thin films via diazonium chemistry: Evaluation of structure and properties

Plasmon-active noble metals nanostructures based on Ag and Au thin films become widely applied in the field of plasmonics and related sensing technologies. For improvement of the metal interaction with different media, metals surface can be functionalized in order to increase/decrease hydrophilicity, lipophilicity or introduce/change the surface charge. In this paper, the surface functionalization of plasmon-active Au and Ag films using arenediazonium tosylates was described. The surface functionalization was performed in the aqueous medium by the spontaneous and electrically induced mechanisms. Functionalized surfaces were characterized by the Raman and UV–vis spectroscopies, AFM nanomechanical mapping, SEM (EDX), XPS, CVA, zeta- potential, and water contact angle measurement techniques. It was founded that the key difference between reactivity of gold and silver films is distributional behavior of grafted organic functional groups: silver has higher tendency to form clustered, island-like structure while gold is covered more homogeneously. Spontaneous modification forms approximately monomolecular thick films of organic compounds and can be used in the field of SPR or SERS sensors. Electrochemically induced activation produces thick polyphenylene layer on the metal surface and can find application in the field of tunable plasmonic devices or plasmon-based lasers.

Fast and Reproducible Wettability Switching on Functionalized PVDF/PMMA Surface Controlled by External Electric Field

In this paper, the novel material with controllable wettability switching triggered by external electric field is developed. The material is based on the piezopolymer blend of poly(methyl methacrylate) (PMMA) and polyvinylidene difluoride (PVDF), grafted with various hydrophobic and hydrophilic molecules to alter the initial wettability of polymer films. Organic functional groups are grafted on the blend surface via formation of covalent bonds between PMMA and arenediazonium tosylates. The surface chemical structure and morphology of prepared samples are studied by X‐ray photoelectron spectroscopy, UV–vis, and attenuated total reflection infra red (ATR‐IR) spectroscopies, atomic force microscopy (AFM), and confocal microscopy. Attachment of gold nanoparticles to grafted thiol chemical groups is additionally used to confirm the modification procedure. Application of external stimuli in the form of the electric field leads to dramatic changes in water contact angle. Wettability switching is found to be extremely fast and completely repeatable without the destructions of the polymer film. Mechanism of switching is attributed to the morphological smoothening of piezoelectric responsible composite PVDF–PMMA under the application of external stimuli.

Arenediazonium Tosylates (ADTs) as Efficient Reagents for Suzuki–Miyaura Cross-Coupling in Neat Water

A simple, convenient, and environment-friendly procedure for the preparation of substituted biaryls via Suzuki–Miyaura cross-coupling­ was developed. The use of arenediazonium tosylates and corresponding boron compounds allows a conversion in neat water in the presence of commercially available Pd(OAc)₂ under mild conditions with tolerance to a wide range of functional groups. A procedure particularly useful for the synthesis of di-<i>ortho</i>-substituted biaryls was developed.

ChemInform Abstract: Matsuda—Heck Reaction with Arenediazonium Tosylates in Water.

AbstractThe reaction is conducted under environmentally benign conditions.

The convenient preparation of stable aryl-coated zerovalent iron nanoparticles.

A novel approach for the in situ synthesis of zerovalent aryl-coated iron nanoparticles (NPs) based on diazonium salt chemistry is proposed. Surface-modified zerovalent iron NPs (ZVI NPs) were prepared by simple chemical reduction of iron(III) chloride aqueous solution followed by in situ modification using water soluble arenediazonium tosylate. The resulting NPs, with average iron core diameter of 21 nm, were coated with a 10 nm thick organic layer to provide long-term protection in air for the highly reactive zerovalent iron core up to 180 °C. The surface-modified iron NPs possess a high grafting density of the aryl group on the NPs surface of 1.23 mmol/g. FTIR spectroscopy, XRD, HRTEM, TGA/DTA, and elemental analysis were performed in order to characterize the resulting material.

Grafting of the Organic Functional Groups to the Iron Nanoparticles Surface via Arenediazonium Tosylates

The nanoscale materials and their application have received considerable attention for the last few years owing to its potential use in biomedical fields of science and technology. Recent studies have demonstrated the ability of arenediazoniumtosylates (ADTs) to modify nanoscale materials. An efficient method of modifying zero-valent iron nanoparticles using ADT with different functional organic groups in a water suspension at the room temperature has been developed. Particle composition, size, stability and possible functionalization with ADT have been characterised by using the FT-IR and X-ray diffraction methods, the low-temperature nitrogen adsorption analysis (BET), TGA/DSC/DTA analyses in the air and the elemental analysis. The obtained methods and results are to foster better understanding of nanoparticles modification process and contribute to its further research and development due to the ability of changing functional groups in the ADT molecule for medical and other applications. Variation of the functional groups in the ADT molecule can change the properties of Fe-NPs and predetermine the field of their use.

ChemInform Abstract: A Simple and Effective Synthesis of Aryl Azides via Arenediazonium Tosylates.

Aromatic azides are formed in high yield from arenediazonium tosylates and sodium azide in water at room temperature or from aromatic amines via diazotization in the presence of p-TsOH. Besides being experimentally simple, these methods do not require any metal catalysis and provide clean products without purification.

A Simple and Effective Synthesis of Aryl Azides via Arenediazonium Tosylates

Aromatic azides are formed in high yield from arenediazonium tosylates and sodium azide in water at room temperature or from aromatic amines via diazotization in the presence of p-TsOH. Besides being experimentally simple, these methods do not require any metal catalysis and provide clean products without purification.

One-Pot Homo- and Cross-Coupling Reactions of Arenediazonium Tosylate Salts for the Synthesis of Biaryls and Polyaryls

One-pot homo- and cross-coupling reactions of arenediazonium tosylate salts bearing a halogen group have been exploited for the synthesis of biaryls and polyaryls under mild conditions. <TEX>$Pd(OAc)_2$</TEX> has proven to be an efficient catalyst for the successful dual transformation of diazonium salts into p-quaterphenyl (3).

ChemInform Abstract: An Expeditious and Environmentally Benign Preparation of Aryl Halides from Aryl Amines by Solvent‐Free Grinding.

AbstractVarious substituted aryl halides are synthesized via arenediazonium tosylate salt intermediates in an environmentally friendly manner.

ChemInform Abstract: Efficient and Economic Halogenation of Aryl Amines via Arenediazonium Tosylate Salts.

AbstractBromination and chlorination of various aniline substrates is carried out under optimized conditions A) and proceeds via formation of arenediazonium tosylates.