Phenyldiazonium Salts Research Articles

A Holistic Review of 3-Dimethylamino-1-Arylpropenones Based Disperse Dyes for Dyeing Polyester Fabrics: Synthesis, Characterization, and Antimicrobial Activities.

The enaminone compounds 3-Dimethylamino-1-arylpropenones produced in this review was synthesized by reacting para-methylacetophenone and para-nitroacetophenone with dimethylformamide dimethyl acetal. In this review article, we discuss how to create novel disperse colors by reacting enaminone derivatives 3a and 3b with phenyldiazonium salt. The highly productive procedure of creating new disperse dyes was followed by the process of dyeing polyester fabrics at temperatures between 70 and 130 °C. As a result, the colours' resistance to light, rubbing, perspiration, and washing fastness was assessed. In an effort to show the additional value of these dyes, the expected biological activity of the synthetic dyes against fungus, yeast, and Gram-positive and Gram-negative bacteria was also assessed. We have applied zinc oxide nanoparticles for polyester fabrics treatment to impact them a self-cleaning quality, increase their light fastness, enhance their antibacterial efficacy, and enhance UV protection as part of our ongoing strategy to obtain polyester fabrics with newly acquired specifications.

Photocatalysis in a multi-capillary assembly microreactor: toward up-scaling the synthesis of 2H-indazoles as drug scaffolds

Visible-light-promoted direct arylation of 2H-indazoles using phenyldiazonium salt enabled a single-step and fast synthesis (<1 min) of C3 arylated products in high yields (>65%) in an eosin Y immobilized capillary microreactor.

Surface modification of graphene-coated carbon steel using aromatic molecules for enhancing corrosion resistance; comparison between type of aryl substitution with different spatial situations

PurposeThe purpose of this paper is study of the type of functional group and its situation on phenyl molecule, in increasing the corrosion protection of modified graphene layers by it. Corrosion protection efficiency of graphene was raised via modifying the surface of graphene-coated carbon steel (CS/G) by using aromatic molecules. Phenyl groups with three different substitutions including COOH, NO2and CH3grafted to graphene via diazonium salt formation route, by using carboxy phenyl, nitro phenyl and methyl phenyl diazonium salts in ortho, meta and para spatial situations.Design/methodology/approachMolecular bindings were characterized by using X-ray diffractometer, fourier-transform infrared spectroscopy (FTIR), Raman and scanning electron microscopy (SEM)/ energy dispersive X-ray analysis (EDXA) methods. Anti-corrosion performance of modified CS/G electrodes was evaluated by weight loss and electrochemical techniques, potentiodynamic polarization (Tafel) and electrochemical impedance spectroscopy, in 3.5 per cent NaCl solution.FindingsThe obtained results confirmed covalently bonding of phenyl groups to the graphene surface. Also, the observed results showed that substitution spatial situations on phenyl groups can affect charge transfer resistance (Rct), corrosion potential (Ecorr), corrosion current density (jcorr) and the slope of the anodic and cathodic reaction (ßa,c), demonstrating that the proposed modification method can hinder the corrosion reactions. The proposed modification led to restoring the graphene surface defects and consequently increasing its corrosion protection efficiency.Originality/valueThe obtained results from electrochemical methods proved that protection efficiency was observed in order COOH < NO2< CH3and MPD in the para spatial situation and showed the maximum protection efficiency of 98.6 per cent in comparison to other substitutions. Finally, the ability of proposed graphene surface modification route was further proofed by using surface methods, i.e. SEM and EDXA, and contact angles measurements.

Impact sensitivity of crystalline phenyl diazonium salts: A first-principles study of solid-state properties determining the phenomenon

Two crystalline salts, phenyl diazonium chloride (PDC) and tetrafluoroborate (PDT), were chosen as probes for theoretical study of solid-state properties responsible for impact sensitivity since these salts differ only in the nature of anion and, hence, in the properties of solid state. In the present report, we have studied the influence of electronic structure, vibrational spectra, mechanical properties, crystal growth morphology, and the stored energy content on impact sensitivity of PDC and PDT to find the most important solid state characteristics governing this phenomenon. The band structure calculations at various external pressures indicate very different response of the band gap. Extremely sensitive PDC crystals acquire the metallic nature at 29 GPa (metallization point), whilst in the PDT crystals the complete closure of band gap occurs only at 200 GPa. Moreover, the stored energy content in PDC is by 1000 kJ mol−1 higher than that of PDT. Only these two properties among the calculated in the present work differ significantly in the studied crystals. The rest solid-state characteristics such as crystal packing, vibratial spectra (phonon-valence vibration energy transfer probability), elastic properties (bulk moduli) demonstrate rather close values. The influence of metallization point (GPa) as well as crystal growth morphology on impact sensitivity is discussed for the first time.

Electrophoretic Approach for the Simultaneous Deposition and Functionalization of Reduced Graphene Oxide Nanosheets with Diazonium Compounds: Application for Lysozyme Sensing in Serum.

Electrophoretic deposition (EPD) of reduced graphene oxide nanosheets (rGO) offers several advantages over other surface coating approaches, including process simplicity, uniformity of the deposited films, and good control of the film thickness. The EPD conditions might also be of interest for the reduction of diazonium salts, which upon the release of N2 molecules and generation of radicals, can form covalent bonds with the sp2 hybridized carbon lattice atoms of rGO films. In this work, we report on the coating of gold electrodes in one step with rGO/polyethylenimine (PEI) thin films and their simultaneous modification using different phenyl (Ph) diazonium salt precursors bearing various functionalities such as -B(OH)2, -COOH, and -C≡CH. We show further the interest of such interfaces for designing highly sensitive sensing platforms. Azide-terminated lysozyme aptamers were clicked onto the rGO/PEI/Ph-alkynyl matrix and used for the sensing of lysozyme levels in patients suffering from inflammatory bowel disease (IBD), where lysozyme levels are up-regulated. The approach attained the required demand for the determination of lysozyme level in patients suffering from IBD with a 200 fM detection limit and a linear range up to 20 pM without signal amplification.

Electroreduction of Viologen Phenyl Diazonium Salts as a Strategy To Control Viologen Coverage on Electrodes.

A majority of the reported electrografting of aryldiazonium salts result in the formation of covalently attached films with a limited surface coverage of below 5 nmol·cm-2. Herein, we report the preparation of higher-thickness redox-active viologen-grafted electrodes from the electroreduction of viologen phenyl diazonium salts, by either cyclic voltammetric (CV) sweeps or electrolysis using a fixed potential. Both of the methodologies were successfully applied for various conductive surfaces, including glassy carbon (GC), gold disc, indium tin oxide glass, mesoporous TiO2 electrodes, and 3D compacted carbon fibers. A robust maximal viologen coverage, Γviologen = 9.5 nmol·cm-2, was achieved on a GC electrode by CV electroreduction. Electroreduction held at a fixed potential at Eappl. = -0.3 V can fabricate viologen-grafted electrodes with Γviologen in the range of 0-37 nmol·cm-2 in a controllable way, by simply adjusting the electrodeposition time tappl.. Time-dependent Γviologen were found to be 10 nmol·cm-2@2 min, 20 nmol·cm-2@4.2 min, and 30 nmol·cm-2@7 min. Furthermore, a TiO2 electrode coupled with Γviologen of 140 nmol·cm-2 exhibited electrochromic performance, with the color changing from pale yellow to blue and red brown.

The Conjugated Phenylene Polymer-Modified Photoanodes for Quantum Dot-Sensitized Solar Cells

Five types of conjugated phenylene polymer-modified photoanodes for quantum dot-sensitized solar cells (QDSSCs) were prepared by immobilization of CdSe QDs after electrochemical polymerization of functionalized phenyldiazonium salts onto ITO glass electrodes. The successful preparation of the conjugated phenylene polymer-modified photoanodes for QDSSCs was confirmed by scanning electron microscopy (SEM), X-ray photoelectron spectroscopy (XPS), FT-IR spectroscopy, UV-visible spectroscopy, contact angles, and electrochemical impedance spectroscopy. The open-circuit voltage and fill factor in QDSSCs with the conjugated phenylene polymer with -COOH photoanodes were achieved at 0.52 V and 76.8%, respectively, and the energy conversion efficiency was improved to 2.73% using the conjugated phenylene polymer with -COOH photoanodes.

Regioselective Radical Arylation of 3-Hydroxypyridines.

The titanium(III)-mediated radical arylation of 3-hydroxypyridines was found to proceed with high regioselectivity for the 2-position. Using aryldiazonium chlorides, which were prepared from the corresponding anilines, as aryl radical sources, a range of 3-hydroxy-2-phenylpyridines were obtained in moderate to good yields under simple reaction conditions. Reactions of ortho-carboxylic ester substituted phenyldiazonium salts directly provided tricyclic benzopyranopyridinones.

Polyelectrolyte Multilayers Deposition on Nitinol Modified by In Situ Generated Diazonium in Gentle Conditions

This work is an investigation of the electrografting of in situ generated 4-sulfonic acid phenyldiazonium salt (PD-SO3H) on Nitinol followed by layer-by-layer (LBL) deposition of polyelectrolyte (chitosan and alginate) multilayers (PEM). Nitinol is interesting for many biomedical applications. A great deal of attention has thus been paid to its surface modification in order to impart and/or improve its surface properties. This can be achieved using PEM deposition which requires an adhesion promoter i.e. PD-SO3H in this work. Results show the successful electrografting of PD-SO3H and the preservation of the TiO2 surface layer (which provides its biocompatibility to Nitinol) allowed by the gentle conditions used for the in situ generation. Nitinol corrosion resistance has been shown to be preserved. Based on XPS analysis, PD-SO3H has been shown to be grafted in its deprotonated form and hypothesis of C-O-M and C-N=N-O-M covalent bonds formation between the grafted layer and the Nitinol surface could be made. It can therefore act effectively as adhesion promoter for PEM deposition as confirmed by the deposition, accumulation and alternation of the deposited chitosan and alginate layers. PEM further improve Nitinol corrosion resistance and its resulting hydrophilicity has been shown to be controlled by the last deposited layer.

Post-Polymerization Electrochemical Functionalization of a Conducting Polymer: Diazonium Salt Electroreduction at Polypyrrole Electrodes

In this paper we report the functionalization of conductive polypyrrole (PPY) films via electrochemical reduction of the aryl diazonium salts in a manner that is similar to the one employed for other conductive surfaces. To understand the general trends of the grafting behavior of diazonium salts and to establish the optimal conditions for the covalent functionalization of the PPY films, we have compared the grafting behavior of four p-substituted phenyldiazonium salts: p-nitrophenyl diazonium tetrafluoroborate (PNBDBF4−), p-tolyl diazonium tetrafluoroborate (TDBF4−), p-fluorophenyl diazonium tetrafluoroborate (FPDBF4−) and 4-diazo-N,N-dimethylaniline tetrafluoroborate (DDMABF4−). The selection of the molecules to be grafted was done both for their electroactivity after grafting and the contrasted electronegativityof the substituents at the benzene ring. For all investigated diazonium salts, a linear relationship between their reduction potential at the PPY electrodes and Hammett substituent constants was obtained, suggesting a similar electrochemical reaction mechanism. The functionalization of the polypyrrole films has been evaluated using electrochemical methods like EQCM, CV and EIS. The presence at the polymeric films surface of the functional groups introduced by the electrochemical reduction of diazonium salts was evidenced also by XPS. This approach enables new functionalities on PPY that could otherwise not withstand the polymerization conditions.

Formation of a Bifunctional Redox System Using Electrochemical Reduction of Platinum in Ferrocene Based Ionic Liquid and Its Reactivity with Aryldiazonium

The electrochemical reduction of platinum in ferrocene based ionic liquid, 1-ferrocenylethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide ([FcEMIM][TFSI]), has been investigated on both macro and micro platinum electrodes. The electrochemical and X-ray photoelectron spectroscopy (XPS) analyses of the reduced platinum evidence the presence and the intercalation of the ferrocene imidazolium into the platinum surface. The resulting metal-organic phase was anticipated to be of the general formula [Ptn(δ-), FcEMIM(δ+)]. Next, the spontaneous reaction of the electrogenerated Pt phases as reducing agent with phenyl diazonium salts was performed. The "reduced platinum phase" reacts with nitrophenyl diazonium salts, without applying any external potential, and conduces to the attachment of nitrophenyl groups onto the surface. Detailed experiments based on cyclic voltammetry and XPS were carried out to follow the occurrence of the grafting. Indeed, both experiments evidence the presence of ferrocene and nitrophenyl groups on the Pt surface. As a result, a bifunctional active surface containing two redox systems has been obtained.

Disorder Imposed Limits of Mono- and Bilayer Graphene Electronic Modification Using Covalent Chemistry

A central question in graphene chemistry is to what extent chemical modification can control an electronically accessible band gap in monolayer and bilayer graphene (MLG and BLG). Density functional theory predicts gaps in covalently functionalized graphene as high as 2 eV, while this approach neglects the fact that lattice symmetry breaking occurs over only a prescribed radius of nanometer dimension, which we label the S-region. Therefore, high chemical conversion is central to observing this band gap in transport. We use an electrochemical approach involving phenyl-diazonium salts to systematically probe electronic modification in MLG and BLG with increasing functionalization for the first time, obtaining the highest conversion values to date. We find that both MLG and BLG retain their relatively high conductivity after functionalization even at high conversion, as mobility losses are offset by increases in carrier concentration. For MLG, we find that band gap opening as measured during transport is linearly increased with respect to the I(D)/I(G) ratio but remains below 0.1 meV in magnitude for SiO(2) supported graphene. The largest transport band gap obtained in a suspended, highly functionalized (I(D)/I(G) = 4.5) graphene is about 1 meV, lower than our theoretical predictions considering the quantum interference effect between two neighboring S-regions and attributed to its population with midgap states. On the other hand, heavily functionalized BLG (I(D)/I(G) = 1.8) still retains its signature dual-gated band gap opening due to electric-field symmetry breaking. We find a notable asymmetric deflection of the charge neutrality point (CNP) under positive bias which increases the apparent on/off current ratio by 50%, suggesting that synergy between symmetry breaking, disorder, and quantum interference may allow the observation of new transistor phenomena. These important observations set definitive limits on the extent to which chemical modification can control graphene electronically.

Iodo-Bodipys as visible-light-absorbing dual-functional photoredox catalysts for preparation of highly functionalized organic compounds by formation of C–C bonds via reductive and oxidative quenching catalytic mechanisms

Iodo-Bodipys were used as organic catalysts for three different photoredox catalytic organic reactions, i.e. the aza-Henry reaction of tetrahydroisoquinoline, oxidation/[3 + 2] cycloaddition/oxidative aromatization tandem reaction between tetrahydroisoquinolines and maleimides, and C–H arylation of heteroarenes with diazonium salts. The organic photocatalysts act as either electron acceptors (reductive quenching) or electron donors (oxidative quenching) in the single electron transfer (SET) of the catalytic cycles. Different from the widely used Ru(bpy)3[PF6]2, Ir(ppy)3, or halo-xanthane photocatalysts (Eosin Y or Rose Bengal), the new organic photocatalysts show strong absorption of visible light and long-lived triplet excited states, which are beneficial for SET, a crucial step for photoredox catalytic organic reactions. Moreover, the molecular structures of the new photocatalysts can be easily modified, as a result the absorption wavelength of the photocatalysts was readily tuned from 529 nm to 630 nm. The three different types of organic reactions are accelerated with the new organic photocatalysts (typical reaction times 1–2 h) compared to that catalyzed by Ru(bpy)3[PF6]2 or Ir(ppy)3 (reaction time: 12–72 h). The C–H arylation of thiophene with phenyl diazonium salts was used to prepare new Bodipy derivatives that show large Stokes shift. Our results are useful for designing of new organic catalysts for photoredox catalytic organic reactions to prepare highly functionalize organic compounds.

Synthesis, pharmacological activity evaluation and molecular modeling of new polynuclear heterocyclic compounds containing benzimidazole derivatives

Novel heterocyclic compounds containing benzimidazole derivatives were synthesized from 2-(1H-benzimidazol-2-yl) acetonitrile (1) and arylhydrazononitrile derivative 2 was obtained via coupling of 1 with 4-methyl phenyldiazonium salt, which was then reacted with hydroxylamine hydrochloride to give amidooxime derivative 3. This product was cyclized into the corresponding oxadiazole derivative 4 upon reflux in acetic anhydride. Compound 4 was refluxed in DMF in the presence of triethylamine to give the corresponding 5-(1H-benzimidazol-2-yl)-2-p-tolyl-2H-1,2,3-triazol-4-amine 6. Treatment of compound 6 with ethyl chloroformate afforded 2,6-dihydro-2-(4-methylphenyl)-1,2,3-triazolo[4",5"-4',5']pyrimido[1,6-a]benzimidazole-5(4H)-one (8). 1,2-bis(2-cyanomethyl-1H-benzimidazol-1-yl)ethane-1,2-dione (10) was synthesized via the condensation reaction of 2-(1H-benzimidazol-2-yl) acetonitrile (1) and diethyloxalate. The reactivity of compound 10 towards some diamine reagents was studied. The in vitro antimicrobial activity of the synthesized compounds was investigated against several pathogenic bacterial strains such as Escherichia coli O157, Salmonella typhimurium, E. coli O119, S. paratyphi, Pseudomonas aeruginosa, Staphylococcus aureus, Listeria monocytogenes and Bacillus cereus. The results of MIC revealed that compounds 12a-c showed the most effective antimicrobial activity against tested strains. On the other hand, compounds 12a, b exhibited high activity against rotavirus Wa strain while compounds 12b, c exhibited high activity against adenovirus type 7. In silico target prediction, docking and validation of the compounds 12a-c were performed. The dialkylglycine decarboxylase bacterial enzyme was predicted as a potential bacterial target receptor using pharmacophore-based correspondence with previous leads; giving the highest normalized scores and a high correlation docking score with mean inhibition concentrations. A novel binding mechanism was predicted after docking using the MOE software and its validation.

Formation of Intermediate Layers for Immobilization of Biomacromolecules by Self‐Assembling and Reduction of Phenyldiazonium Salts. A Comparative Study

AbstractTwo types of biomolecules were tested in the comparison of usefulness of two ways of formation of the intermediate layers at electrodes: a 20‐nucleotide DNA sequence and glucose oxidase. Chronocoulometric, amperometric, electrochemical impedance and PM‐IRRAS experiments proved that the layers obtained by electroreduction of diazonium salts are much more stable and more efficient in the accumulation of biomolecules compared to layers obtained by self‐assembling of appropriate thiols.

SYNTHESIS AND PHOTO- IRRADIATION OF SOME PYRIMIDINE AND PURINE DERIVATIVES

The current study included the synthesis of a series of azo compounds. These compounds were prepared by coupling nitrogen bases with phenyl diazonium salts. While the azo Schiff compounds were prepared by direct condensation of the prepared azoaldehydes with the nitrogen bases (2-amino pyrimidine & guanine ). The Schiff base derivatives were prepared by direct condensation of nitrogen bases (2-amino pyrimidine & adenine) with substituted benzaldehyde and chloral.The structures of the prepared compounds were confirmed by spectral analysis including ultra-violet visible and infra red spectra. Also photo irradiation of these compounds at (=356nm) has been done to study the stability of these compounds. The results revealed complete disappearance of the (OH) and (NH) bands in a number of compounds and partial disappearance in others which reflects the photo-oxidation or hydrogen bonding for the groups of (OH) or (NH).The disappearance of the (NH2) and (C=O) bands conforms the successful of prepared compounds.

Formation of Mixed Organic Layers by Stepwise Electrochemical Reduction of Diazonium Compounds

This work describes the formation of a mixed organic layer covalently attached to a carbon electrode. The strategy adopted is based on two successive electrochemical reductions of diazonium salts. First, bithiophene phenyl (BTB) diazonium salt is reduced using host/guest complexation in a water/cyclodextrin (β-CD) solution. The resulting layer consists of grafted BTB oligomers and cyclodextrin that can be removed from the surface. The electrochemical response of several outer-sphere redox probes on such BTB/CD electrodes is close to that of a diode, thanks to the easily p-dopable oligo(BTB) moieties. When CD is removed from the surface, pinholes are created and this diode like behavior is lost. Following this, nitrophenyl (NP) diazonium is reduced to graft a second component. Electrochemical study shows that upon grafting NP insulating moieties, the diode-like behavior of the layer is restored which demonstrates that NP is grafted predominately in the empty spaces generated by β-CD desorption. As a result, a mixed BTB/NP organic layer covalently attached to a carbon electrode is obtained using a stepwise electrochemical reduction of two diazonium compounds.

Synthesis and Evaluation of Some New Thiazoles as Antioxidant Additives for Egyptian Lubricating Oils

4-(2-Aminothiazol-4-yl)-phenol (1) reacted with 2-(4-methoxy-benzylidene)-malononitrile or 1,3-diphenyl-1H- pyrazole-4-carbaldehyde to afford enaminonitrile, pyrazolo derivatives 2 and 3, respectively. On the other hand, methylation of 1 afforded the acetyl derivative 4 which reacted with phenyl isothiocyanate, diazonium salt, acetic anhydride, cyclic anhydride, ethyl acetoacetate, benzaldehyde or phosphorous oxychloride to afford compounds 5-9, 11 and 12, respectively. Moreover, the compound 12 reacted with ethyl cyanoacetate to afford compound 13. A one-pot reaction of compound 1 with ethyl acetoacetate and benzaldehyde afforded compound 10. The synthesized compounds were evaluated as antioxidant additives for lube oil. Key words: Key words: Aminothiazole; Condensation; Antioxidant Additives

Synthesis, spectroscopy, and quantum-chemical calculations on 1-substituted phenyl-3,5-diphenylformazans

In this study 1-substituted phenyl-3,5-diphenylformazans were synthesized from benzaldehyde-N-phenylhydrazone and appropriate phenyldiazonium salts having CH 3, Br, and Cl at the o-, m-, and p-positions of 1-phenyl ring. Their structures were determined by infrared and ultraviolet–visible spectra. Bathochromic effect in accordance with the electron-donating effect of CH 3, Br, and Cl group and its magnitude were dependent upon type and position of substituent on the ring. The ground-state geometries and absorption wavelengths for 1-phenyl substituted formazans were studied with density functional theory and time-dependent density functional theory. The calculations were carried out by using PBE1PBE functional with 6-311G(2d,2p) basis set for λ max of the UV–vis spectra for the studied formazans. A good agreement was obtained between the experimental and computed values.

Near-Infrared Absorbing Azo Dyes: Synthesis and X-ray Crystallographic and Spectral Characterization of Monoazopyrroles, Bisazopyrroles, and a Boron−Azopyrrole Complex

Symmetric 2,5-bisazopyrroles 2(a-d) were synthesized by a one-step reaction of substituted phenyl diazonium salts [R'(Ph)N2(+)Cl-] [a, R' = 4-N(CH3)2; b, R' = 2-OH; c, R' = 2-CO2H; d, R' = 4-NO2] with pyrrole under basic conditions. Asymmetric 2,5-bisazopyrroles 3(a-d) were synthesized by reacting substituted phenyl diazonium salts [R''(Ph)N2(+)Cl-] (a, R'' = 4-OCH(3); b, R'' = H; c, R'' = 4-Br; d, R'' = 4-NO2) with 2-(4-dimethylaminophenylazo)-1H-pyrrole (1a) under the same conditions. The reactions of 2a with boron trifluoride and iodomethane provided a BF2-azopyrrole complex of 1H-pyrrolo[2,1-c]-1,2,4,5-boratriazole (4) and 2,5-bisazo-1-methylpyrrole 5. X-ray crystallographic and spectral analysis of 1a, 2a, 2b, and 4 showed that 1a has three crystal forms: 1a(I), 1a(II), and 1a(III), the latter two bearing a bicyclic ring system formed via intermolecular hydrogen bonding. Complex 4 was found to be the most planar due to a rigid trans-azo configuration and has the longest N horizontal lineN bond distances (1.322 and 1.300 Angstrom) and wavelength of maximum absorption (754 nm). The N horizontal lineN bond distances increase in the sequence of monoazopyrrole [1a(I): 1.253 Angstrom], bisazopyrrole (2a: 1.283 Angstrom), bisazopyrrole with intramolecular hydrogen bonding (2b: 1.293 and 1.293 Angstrom), and the BF2-azopyrrole complex. Their maximum absorptions shift bathochromically in the sequence of monoazopyrrole (1a: 443 nm), bisazopyrroles [2(a-d), 3(a-d), 5: 486-615 nm], and the BF2-azopyrrole complex. These results are important for the design of near-infrared absorbing azo dyes and suggest an efficient path for the preparation of near-infrared absorbing azo dyes by effectively enhancing pi-electron delocalization.