Reaction Of Aryldiazonium Salts Research Articles

Host-aided pH-controlled substitution reaction of aryl diazonium salts and sodium azide

Host-aided pH-controlled substitution reaction of aryl diazonium salts and sodium azide

Effect of Surface Modification on the Fundamental Electrical Characteristics of Solution-Gated Indium Tin Oxide-Based Thin-Film Transistor Fabricated by One-Step Sputtering.

Our solution-gated indium tin oxide (ITO)-based thin-film transistor (TFT) produced by single-step sputtering has great future potential in bioelectronics. In particular, chemical modifications of the ITO channel surface are expected to contribute to biomolecular recognition with ultrahigh sensitivity owing to a remarkably steep subthreshold slope (SS). In this study, we investigate the effect of a chemical modification of an aptamer as a receptor molecule at the ITO channel surface on the electrical characteristics of the solution-gated TFT. In this case, a SARS-CoV-2 aptamer is immobilized using a spacer molecule on an aryl diazonium monolayer that is electrochemically deposited with a radical scavenger. The monolayer is expected to not only passivate the ITO channel surface but also change the electron density in the ITO channel owing to the reduction reaction of aryl diazonium salts. Indeed, the electrochemical deposition of aryl diazonium salts decreases the leakage current through the ITO channel surface and provides a steep SS, which is near the thermal limit at 300 K, owing to the decrease in depletion layer capacitance. After the aptamer immobilization, the leakage current and SS unexpectedly return close to their original values before the surface modifications. This finding indicates that aptamer molecules should be carefully used because their negative charges would attract cations around the detection interface. Eventually, the solution-gated ITO-based TFT with the SARS-CoV-2 aptamer clearly responds to inactivated SARS-CoV-2 particles owing to the successful surface modification.

Transition metal-free, photocatalytic arylation and dioxygenation for vicinal diketone synthesis using alkynes and arene diazonium salts

A metal-free dioxygenative reaction of aryl diazonium salts with aryl alkynes for vicinal diketone synthesis is developed.

A Fruitful Decade of Organofluorine Chemistry: New Reagents and Reactions

A Fruitful Decade of Organofluorine Chemistry: New Reagents and Reactions

One-Pot Synthesis of Pentafluorophenyl Sulfonic Esters via Copper-Catalyzed Reaction of Aryl Diazonium Salts, DABSO, and Pentafluorophenol.

Pentafluorophenyl (PFP) sulfonic esters were synthesized via a copper-catalyzed one-pot multicomponent reaction of aryl diazonium tetrafluoroborate, DABSO (DABCO·(SO2)2), and pentafluorophenol. The reaction system provided the desired pentafluorophenyl sulfonic esters in good yields and exhibited excellent functional group tolerance. In addition, the generated PFP sulfonic esters were successfully applied in Sonogashira, Suzuki, Chan-Evans-Lam, and decarboxylative coupling reactions.

Base‐Free Cross‐Couplings of Aryl Diazonium Salts in Methanol: PdII–Alkoxy as Reactivity‐Controlling Intermediate

AbstractPd‐catalyzed cross‐coupling reactions of aryl diazonium salts are generally assumed to proceed via cationic PdII intermediates which in turn would be highly reactive in the subsequent transmetalation step. Contrary to this belief, we herein report our observation and rationalization of opposing reactivities of ArN2+ in Suzuki (=effective) and Stille (=ineffective) cross‐couplings in MeOH. Our systematic experimental and computational studies on the roles of transmetalating agent, solvent, base and the likely involvement of in situ formed diazoether derivatives challenge the currently accepted mechanism. Our data suggest that the observed solvent dichotomy is primarily due to PdII‐methoxy intermediates being formed, which are unreactive with arylstannanes, but highly reactive with arylboronic acids, complementing the Suzuki “Pd‐oxy” mechanism with the direct demonstration of transmetalation of a PdII‐alkoxy complex. Lewis acids were found to circumvent this reactivity divergence, promoting efficient couplings regardless of the employed conditions or coupling partners.

Base-Free Cross-Couplings of Aryl Diazonium Salts in Methanol: PdII -Alkoxy as Reactivity-Controlling Intermediate.

Pd-catalyzed cross-coupling reactions of aryl diazonium salts are generally assumed to proceed via cationic PdII intermediates which in turn would be highly reactive in the subsequent transmetalation step. Contrary to this belief, we herein report our observation and rationalization of opposing reactivities of ArN2+ in Suzuki (=effective) and Stille (=ineffective) cross-couplings in MeOH. Our systematic experimental and computational studies on the roles of transmetalating agent, solvent, base and the likely involvement of in situ formed diazoether derivatives challenge the currently accepted mechanism. Our data suggest that the observed solvent dichotomy is primarily due to PdII -methoxy intermediates being formed, which are unreactive with arylstannanes, but highly reactive with arylboronic acids, complementing the Suzuki "Pd-oxy" mechanism with the direct demonstration of transmetalation of a PdII -alkoxy complex. Lewis acids were found to circumvent this reactivity divergence, promoting efficient couplings regardless of the employed conditions or coupling partners.

Synthesis of heterobicyclic tetrakis- and bis-triazenes: Reaction between 3,3′-ethane-1,2-diylbis(1,3,5-triazabicyclo[3.2.1]octane) (ETABOC) with diazonium salts bearing electron donating groups

In this work, a coupling reaction of aryl diazonium salts with a poly-N-nucleophile is developed for the synthesis of a variety of heterobicyclic tetrakis- and bistriazene compounds. The transformation proceeds smoothly in basic medium with good and moderate yields. In addition to the expected 3,3′-methanediylbis{1,5-bis[(E)-aryldiazenyl]-1,3,5-triazepanes}, two classes of heterobicyclic bis-triazenes were obtained by two ring rearrangement reactions. Using this method, an unknown class of organic compounds containing the saturated bis(imidazolidinyl)-methane unit can be accessed efficiently.

Cu‐Catalysed Three‐Component Reaction of Aryldiazonium Salts with Fluorinated Diazo Reagents and Nitriles: Access to Difluoro‐ and Trifluoromethylated N1‐Aryl‐1,2,4‐triazoles

AbstractA copper‐catalysed three‐component reaction of aryldiazonium salts with fluorinated diazo reagents and nitriles is described. This formal [1+2+2] annulation protocol provides rapid access to a diverse array of difluoro‐ and trifluoromethylated N1‐aryl‐1,2,4‐triazoles under simple conditions. The synthetic applicability to divergent drug‐like 1,2,4‐triazoles is also demonstrated.magnified image

Base-Promoted Radical Azofluoromethylation of Unactivated Alkenes.

The base-induced reaction of aryl diazonium salts with commercially available CF3SO2Na/CF2HSO2Na allows for the generation of the corresponding diazene radicals along with fluoromethyl radicals. The addition of fluoromethyl radicals to alkenes with subsequent diazene trapping provides the azofluoromethylation products in good to excellent yields. This metal-free method under mild reaction conditions has broad functional group compatibility and is applicable in the late-stage modification of various natural products and bioactive molecules.

Preparation of N-Arylquinazolinium Salts via a Cascade Approach.

An easy manipulation method for the preparation of N-arylquinazolinium salts is described from readily available aryldiazonium salts, nitriles, and 2-aminoarylketones in a one-pot operation. This method relies on the in situ generation of the N-arylnitrilium intermediate from the reaction of aryldiazonium salt with nitrile, which undergoes amination/cascade cyclization/aromatization, leading to N-arylquinazolinium salts in excellent yields. Nucleophilic addition of alkoxide to these N-arylquinazolinium salts provides functionalized dihydro- N-arylquinazoline.

Surface modulation of single-walled carbon nanotubes for selective bacterial cell agglutination.

BackgroundBacterial resistance to antibiotics is one of the biggest challenges facing medicine today. Anti-adhesive therapy, using inhibitors of bacterial adhesion to epithelial cells, one of the first stages of infection, is a promising approximation in this area. The size, shape, number of sugar and their placement are variables that have to be taken into account in order to develop multivalent systems able to inhibit the bacterial adhesion based on sugar-lectin interaction.Materials and methodsIn the present work we report a modular approach for the synthesis of water-soluble 1D-carbon nanotube-sugar nanoconstructs, with the necessary flexibility to allow an efficient sugar-lectin interaction. The method is based on the reaction of aryl diazonium salts generated in situ from aniline-substituted mannose and lactose derivatives with single wall carbon nanotubes (SWCNTs) sidewalls.ResultsTwo hybrid nanosystems, I-II, exposing mannose or lactose and having a tetraethylene glycol spacer between the sugar and the nanotube sidewall were rapidly assembled and adequately characterized. The sweet nano-objects were then tested for their ability to agglutinate and selectively inhibit the growth of uropathogenic Escherichia coli. These studies have shown that nanosystem I, exposing mannose on the nanotube surface is able to agglutinate and to inhibit the bacterial growth unlike nano-objects II exposing lactose.ConclusionThe results reported constitute a proof of principle in using mannose-coated 1D-carbon nanotubes as antiadhesive drugs that compete for FimH binding and prevent the uropathogenic bacteria from adhering to the urothelial surface.

Preparation of 4(3H)-quinazolinones from aryldiazonium salt, nitriles and 2-aminobenzoate via a cascade annulation

One-pot synthesis of 3-aryl-4(3H)-quinazolinones has been realized through a cascade annulation. Reaction of aryldiazonium salt with a nitrile provides in situ generation of a reactive nitrilium ion, which is attacked by the amino group of 2-aminobenzoate followed by cyclization to deliver the desired product. This strategy offers a convenient and easy access to a wide range of functionalized quinazolinone.

Three component reaction of aryl diazonium salt with sulfonamide & actonitrile to synthesize N-sulfonyl amidine

A new method was developed to prepare N-sulfonyl amidine compounds through three-component reaction of aryl diazonium salts with sulfonamides and acetonitrile, in which, nitrilium ion intermediate, generated from the reaction of aryldiazonium salt with nitrile, was subsequently trapped by sulfonamides. A series of N-sulfonyl amidine derivatives were synthesized by using various types of aryl diazonium salts, sulfonamides and nitriles. In addition, indolyl imine products could also be prepared by using indole as the nucleophile to trap nitrilium ion intermediate.

ChemInform Abstract: Tunable Cascade Reaction of Aryl Diazonium Salts and Trialkylamine: Synthesis of Monofluorinated Arylhydrazones and gem‐Difluorinated Azo Compounds.

AbstractUsing H2O, monofluorinated arylhydrazones are obtained.

The copper-catalyzed cross-coupling reactions of aryl diazonium salts and isocyanides

The copper-catalyzed cross-coupling reaction of aryl diazonium salts and isocyanides has been performed. This is a successful example of preparation of arylcarboxyamides with moderate to good yield under mild conditions.

Tunable Cascade Reaction of Aryl Diazonium Salts and Trialkylamine: Synthesis of Monofluorinated Arylhydrazones and gem-Difluorinated Azo Compounds.

The first example of a mild and tunable cascade reaction of aryl diazonium salts and trialkylamine in the presence of Selectfluor to prepare monofluorinated arylhydrazones and gem-difluorinated azo compounds without metal has been explored. In the presence of H2O, the monofluorinated arylhydrazones were observed in moderate to good yield. In the absence of H2O, the gem-difluorinated azo compounds were obtained. The fluorinated arylhydrazones were utilized to synthesize fluorinated pyrazoles and other nitrogen-containing compounds.

Nano-CuFe2O4-supported sulfonic acid as a novel and recyclable nanomagnetic acid for diazotization of aromatic amines: efficient synthesis of various azo dyes

A novel heterogeneous sulfonic acid functionalized nanomagnetic CuFe2O4 was successfully prepared and characterized by analyzing different obtained data including Fourier transform infrared spectroscopy, X-ray powder diffraction, field emission scanning electron microscopy, energy-dispersive X-ray spectroscopy, thermogravimetric analysis, dynamic light scattering and vibrating sample magnetometer. Then the novel acidic reagent was examined in synthesis of various azo-containing compounds from coupling of aryl diazonium ferrite sulfate salts with aromatic and non-aromatic compounds. The procedure starts by diazotization of aromatic amines with NaNO2 and wet CuFe2O4–SO3H and then coupling reaction of aryl diazonium ferrite sulfate salts with appropriate reagent. The prepared nano-solid acid showed high activity in synthesis of variety of aryl diazonium salts. In addition the as-prepared aryl diazonium ferrite sulfate salts are stable at room temperature for many hours and reacted efficiently in coupling reactions of aryl diazonium salts. All the azo dyes are synthesized in high yields and simple reaction conditions at room temperature. Moreover, the nanomagnetic solid acid was easily recovered from the reaction mixture and reused five runs without significant loss of activity.

ChemInform Abstract: Cross‐Coupling Reaction of Aryl Diazonium Salts with Azodicarboxylate Using FeCl2.

AbstractVarious N‐aryl hydrazides are easily and completely selectively obtained.

Cross-coupling reaction of aryl diazonium salts with azodicarboxylate using FeCl2

Arene diazonium salts have been employed as the aryl source in reaction with dialkyl azodicarboxylates to form N-aryl hydrazide derivatives.