Dihydroxybenzene Derivatives Research Articles

The Coupling of Dihydroxybenzene Derivatives to MWCNT and Electrochemical NADH Oxidation

3,4 and 2,5- dihydroxybenzene compounds were separately and covalently coupled to the multiwalled carbon nanotube (MWCNT) deposited on the surface of glassy carbon electrode through electrochemical reduction of diazonium compound of benzylamine bearing Boc protecting group (tert-butyloxycarbonyl). Following the removal of the Boc group, an amide bond was formed between the amine-terminated surface and the acyl group of the dihydroxybenzene derivatives. The electrochemical properties of dihydroxybenzene-modified MWCNT and the influence of the sweep rate on the voltammogram were elucidated by cyclic voltammetry (CV). Electron transfer kinetics of modified MWCNT by dihydroxybenzene derivatives was also studied using Laviron’s theory. As evidenced by an improvement in the anodic peak current and a negative shift in the overpotential of NADH oxidation when compared to the bare MWCNT, 3,4 and 2,5- dihydroxybenzene modified MWCNT electrodes were shown to possess catalytic activity toward NADH oxidation.

Allosteric Guest Binding in Chiral Zirconium(IV) Double Decker Porphyrin Cages.

Chiral zirconium(IV) double cage sandwich complex Zr(1)2 has been synthesized in one step from porphyrin cage H21. Zr(1)2 was obtained as a racemate, which was resolved by HPLC and the enantiomers were isolated in >99.5 % ee. Their absolute configurations were assigned on the basis of X‐ray crystallography and circular dichroism spectroscopy. Vibrational circular dichroism (VCD) experiments on the enantiomers of Zr(1)2 revealed that the chirality around the zirconium center is propagated throughout the whole cage structure. The axial conformational chirality of the double cage complex displayed a VCD fingerprint similar to the one observed previously for a related chiral cage compound with planar and point chirality. Zr(1)2 shows fluorescence, which is quenched when viologen guests bind in its cavities. The binding of viologen and dihydroxybenzene derivatives in the two cavities of Zr(1)2 occurs with negative allostery, the cooperativity factors α (=4 K2/K1) being as low as 0.0076 for the binding of N,N’‐dimethylviologen. These allosteric effects are attributed to a pinching of the second cavity as a result of guest binding in the first cavity.

Thermodynamic dependence of the electrochemical oxidation of dihydroxybenzenes in the presence of some Meldrum's acids

Electrochemical oxidation of some dihydroxybenzene derivatives in the presence of methyl-Meldrum's acid (MMA) and phenyl-Meldrum's acid (PMA) as nucleophiles were investigated both experimentally and theoretically. Using recorded E-pH diagrams of some catechol derivatives, Ep0 of the studied species were obtained. Also, ∆Gtot of the electrochemical oxidation of the catechols have been calculated using different computational methods. Then, by the use of Ep0 vs. ∆Gtot graphs, it was found that BP86/6-31G(d,p) is the best method and it was selected for other computational studies. Electrolysis of the catechols in the presence of MMA and PMA was performed, and the results indicate that the final products are produced via an EC mechanism. The electrochemical oxidation of hydroquinone species in the presence of the nucleophiles was studied too. It was found that unlike what was observed for catechols, the electrochemical oxidation of hydroquinones in the presence of MMA and PMA is ECE. Also, the mechanism of the electrochemical oxidation of hydroquinone in the presence of MMA changed to ECECE due to the changing condition of the electrolysis. Different electrochemical behaviors of the studied dihydroxybenzenes in the presence of the nucleophiles were analyzed by the computational study, and the results indicate that although the mechanisms are not the same, all of them proceed in the thermodynamically favored directions.

ChemInform Abstract: Microwave‐Assisted Methylation of Dihydroxybenzene Derivatives with Dimethyl Carbonate.

Abstract1,2‐ and 1,4‐dihydroxybenzene undergo microwave assisted O‐methylation to give bis‐methyl ethers in excellent yields.

Microwave-assisted methylation of dihydroxybenzene derivatives with dimethyl carbonate

Dihydroxybenzene derivatives were methylated with dimethyl carbonate to generate useful synthetic intermediates for wide range of applications.

ELECTROCHEMICAL PREPARATION OF NEW ORGANOSILICONE COMPOUNDS FOR FUNCTIONALIZING OF MESOPOROUS SILICA

Electrochemistry has been introduced as a powerful tool in order to prepare new organometallic reagents for functionalizing of mesoporous silica. Preparation of the reagents was based on electrochemical oxidation of dihydroxybenzene derivatives in the presence of 3-(trimethoxysilyl)-1-propanethiol as a nucleophile. The mechanisms of electrochemical reactions were studied by voltammetric studies. Mesoporous silica SBA-15 was also synthesized in this work through sol-gel hydrothermal method using Genapol PF-10 as structure directing compound. The prepared mesoporous silica was characterized by FT-IR analysis and Barrett–Joiner–Halenda (BJH) pore size and Brunauer–Emmett–Teller (BET) surface area measurement methods using N2adsorption–desorption isotherm. Finally, the organometallic reagent was covalently grafted on the surface of mesoporous silica. Functionalizing of this material with the new reagent was confirmed by Fourier transform infrared (FT-IR) spectroscopy. The functionalized mesoporous silica by new reagent can be utilized in biological applications.

Synthesis and characterization of redox-active charge-transfer complexes with 2,3,5,6-tetracyanopyridine (TCNPy) for the photogeneration of pyridinium radicals.

The heteroaromatic polynitrile compound tetracyanopyridine (TCNPy) is introduced as a new electron acceptor for the formation of deeply colored charge-transfer complexes. In MeCN, TCNPy is characterized by a quasireversible one-electron-reduction process at −0.51 V (versus SCE). The tetracyanopyridine radical anion undergoes a secondary chemical reaction, which is assigned to a protonation step. TCNPy has been demonstrated to generate 1:1 complexes with various electron donors, including tetrathiafulvalene (TTF) and dihydroxybenzene derivatives, such as p-hydroquinone and catechol. Visible- or NIR-light-induced excitation of the intense charge-transfer bands of these compounds leads to a direct optical electron-transfer process for the formation of the corresponding radical-ion pairs. The presence of available electron donors that contain protic groups in close proximity to the TCNPy acceptor site opens up a new strategy for the photocontrolled generation of pyridinium radicals in a stepwise proton-coupled electron-transfer (PCET) sequence.

Synthesis, computational study and binding properties of some structurally rigid glycoluril-derived molecular clips

Several new clip-shaped molecules, with different degrees of steric hindrance around their cavities as well as more rigidity on their glycoluril scaffold, have been synthesized and the molecular geometry of their most stable structures has been investigated and optimized with density functional theory (DFT) at the B3LYP level of theory using 6-311G basis set. The affinity of these molecular clips for some dihydroxybenzene derivatives (guests) has been computationally and experimentally studied. The clips having dimethyl-substituted aromatic side walls, showed the best interaction energies towards the mentioned guests. Also, the computational results revealed that the more electron-deficient guest interacts more strongly with the clips (hosts).

Anchoring of Fe(III)salicylamide onto MCM-41 for Catalytic Hydroxylation of Phenol in Aqueous Medium Using Hydrogen Peroxide as Oxidant

Fe(III)salicylamide immobilized on MCM-41 has been developed for hydroxylation of phenol in water medium using hydrogen peroxide as the oxidant. In the first step, the amine group containing 3-aminopropyltrimethoxy silane has been immobilized on the surface of MCM-41 via co-condensation. The amine group upon condensed with methyl salicylate afford a bidentate ligand in the mesoporous matrix for anchoring Fe(III) ions in the second step. Small angle XRD, N2 adsorption–desorption isotherms, 13C and 29Si cross-polarization magic angle spinning NMR spectroscopy, Fourier transform infrared spectroscopy (FT-IR) and diffuse reflectance UV–vis spectra were employed for the characterization of the catalysts. The heterogeneous iron salicylamide complex shows excellent catalytic activity in phenol hydroxylation using hydrogen peroxide as the oxidant and water as the solvent. Notably, phenol shows high conversion (64.6%) with very high selectivity for dihydroxybenzene compounds. The heterogeneous catalyst shows a successive slight decrease in catalytic activity when reused for three more times. Fe(III)salicylamide–MCM-41 has been synthesized successfully through an easy co-condensation route. XRD and N2 adsorption–desorption showed mesoporosity is retained even after complexation and FT-IR and diffuse reflectance UV–vis spectra confirmed the formation of complex. The heterogeneous catalyst exhibit excellent catalytic performance and stability in phenol hydroxylation reaction for the formation of dihydroxybenzene derivatives using H2O2.

Investigation of electrochemically induced Michael addition reactions. Oxidation of some dihydroxybenzene derivatives in the presence of azide ion

In aqueous solution containing azide ion as a nucleophile, electrochemical oxidation of hydroquinone and some dihydroxybenzoic acids have been studied using cyclic voltammetry and controlled-potential coulometry. The voltammetric data show that electrochemically generated para and ortho-benzoquinones participate in Michael addition reactions with azide ions to form the corresponding diazido or diaminobenzoquinones. In this work, we have proposed various mechanisms for the electrode process and we report an efficient and one-pot method for the synthesis of 2,5-diazido-1,4-benzoquinone, 2,5-diamino-1,4-benzoquinone, 4,5-diamino-1,2-benzoquinone, and 2,3-diamino-5,6-dioxocyclohexa-1,3-dienecarboxylic acid based on the Michael reaction of electrochemically generated ortho and para-benzoquinones with azide ion in an undivided cell using an environmentally friendly reagent-less method in ambient conditions. An estimation of the observed homogeneous rate constant ( k obs) of the reaction of electrochemically generated para-benzoquinone with azide ion by the digital simulation method is also presented.

Electrochemical and solid-phase synthetic modification of glassy carbon electrodes with dihydroxybenzene compounds and the electrocatalytic oxidation of NADH

We report the preparation, using electrochemical and solid-phase synthesis, and characterisation of a 26 member library of 13 dihydroxybenzene derivatives covalently attached to glassy carbon through ethylenediamine (EDA) and C 6H 4CH 2NH linkers. First, Boc-protected EDA or Boc–NHCH 2C 6H 4 were electrochemically attached to the GC surface. After Boc-deprotection, dimethoxybenzoyl chlorides were coupled to the EDA and C 6H 4CH 2NH linkers using solid-phase synthesis followed by deprotection of the methoxy groups to give the corresponding dihydroxybenzene compounds. Surface coverage and electrochemical parameters of the dihydroxybenzene modified electrodes were evaluated in parallel using cyclic voltammetry. The mid-peak potentials, E mp, and surface coverages for the 13 dihydroxybenzene derivatives were found to be independent of the choice of linker. The mid-peak potentials of the immobilised dihydroxybenzene derivatives varied between 0.0 and 260 mV vs. SCE and their surface coverages varied between 0.07 and 1.1 nmol cm − 2 , depending on the pattern of substitution of the dihydroxybenzene ring. The electrocatalytic activities of the library were evaluated for mediation of NADH oxidation, and the ortho-dihydroxybenzene derivatives were found to have higher catalytic activity.

Investigation of solvent effects on UV–vis absorption spectra of dihydroxybenzene derivatives by solvatochromic parameters

The solvatochromism of dihydroxybenzene derivatives as probes in 18 solvents were investigated in the UV–vis spectra. The position, intensity and shape of absorption bands change with various solvent nature. These changes were rationalized by solvatochromic parameters such as α, β, E T(30), DN and AN using multiple linear regression (MLR) method. The studied dihydroxibenzene derivatives show negative solvatochromism and the correlation coefficients of derived equations by MLR method were obtained in the range 0.974–0.996. The linear solvation energy relationship parameters of the backward regression were applied to the Kamlet and Taft equation for the interaction of these three probes and solvents. The best LSER equation for these three probes, and the LSER parameters of backward regression with their mean effects and the regression coefficient have been calculated.

Fabrication and electrochemical behavior of single-walled carbon nanotube/graphite-based electrode

An electrochemical method for determining the dihydroxybenzene derivatives on glassy carbon (GC) has been developed. In this method, the performance of a single-walled carbon nanotube (SWCNT)/graphite-based electrode, prepared by mixing SWCNTs and graphite powder, was described. The resulting electrode shows an excellent behavior for redox of 3,4-dihydroxybenzoic acid (DBA). SWCNT/graphite-based electrode presents a significant decrease in the overvoltage for DBA oxidation as well as a dramatic improvement in the reversibility of DBA redox behavior in comparison with graphite-based and glassy carbon (GC) electrodes. In addition, scanning electron microscopy (SEM) and atomic force microscopy (AFM) procedures performed for used SWCNTs.

Electrochemical oxidation of some dihydroxybenzene derivatives in the presence of indole

The present work explains electrochemical behavior of some dihydroxybenzoic acid and catechol derivatives (1a–d) in the presence of indole (3) a as nucleophile using cyclic voltammetry and controlled-potential coulometry methods and describes a new electrochemical strategy for the synthesis of some new indolyl derivatives of quinones and catechols. In this work, we derive these products with good yields based on electrochemical oxidation under controlled potential conditions in aqueous solutions, without toxic reagents and solvents at a carbon electrode, using an environmentally friendly method.

Spectrophotometric determination of certain vicinal dihydroxybenzene derivatives in pharmaceutical preparations.

A simple, rapid and sensitive spectrophotometric method for the assay of certain adrenergic drugs, [pyrocatechol (PC), levodopa (LD), methyldopa (MD) and dopamine (DP)] is described. The method involves the oxidation of o-dihydroxybenzene derivatives by K2CrO4 followed by oxidative coupling with sulfanilic acid (SPA), leading to the formation of a red or violet colored product having maximum absorbance at 490-495 nm for LD, MD and DP or at 560 nm for PC. This method has been successfully applied to the determination of LD, MD and DP in tablets and injections of pharmaceutical preparation. The common excipients do not interfere with the proposed method. A statistical comparison of these results with those of a reported method shows good agreement and indicates no significant difference in precision.

Molecular clips based on propanediurea: exceptionally high binding affinities for resorcinol guests.

A series of new receptor molecules derived from 2,4,6,8-tetraazabicyclo[3.3.1]nonane-3,7-dione (propanediurea) is described. These molecules possess a cavity which is defined by two nearly parallel aromatic side walls positioned on top of a bis-urea framework. The resulting "U-shaped" clip molecules are ideal hosts for the complexation of flat aromatic guest molecules. The affinity of these new propanediurea based molecular clips for dihydroxybenzene derivatives is exceptionally high, with association constants up to K(a) = 2 400 000 L mol(-)(1). Comparison of the binding mechanism of a variety of clip and half clip hosts, in conjunction with NMR, IR, and X-ray studies, has enabled the reason for this high binding to be elucidated. It is shown that subtle sub-angstrom changes in the geometry of the clip molecules have a great impact on their binding properties.

Spectrophotometric Determination of Certain Vicinal Dihydroxybenzene Derivatives with Sodium Bismuthate

A simple and accurate spectrophotometric method is developed for the determination of certain vicinal dihydroxybenzene derivatives, namely, dopamine (DPH), levodopa (LD), methyldopa (MD) and pyrocatechol (PC) using sodium bismuthate in an acid medium. The method is based on the formation of a yellow colored product by the oxidation of vicinal dihydroxybenzene derivatives using sodium bismuthate. Beer's law was obeyed over the concentration range of 8–130 μg/mL with the maximum absorption at 422–429 nm. The molar absorptivity and Sandell's sensitivity as evaluated from Beer's law data were found to be in the range of 1.02–1.34 × 10–3L mol–1cm–2and 108–185 ng/cm2respectively. The proposed method has been successfully applied for the determination of DPH, LD and MD in injections and tablets of pharmaceutical preparations. The reliability of the methods was established by replicate determinations with the reported and official method.

Spectrophotometric methods for the determination of certain catecholamine derivatives in pharmaceutical preparations

Two simple, rapid and sensitive spectrophotometric methods for the determination of catecholamine derivatives (pyrocatechol, dopamine, levodopa and methyldopa) are developed. The first method involves the oxidation of o-dihydroxybenzene derivatives by N-bromosuccinimide followed by oxidative coupling with isoniazid leading to the formation of a red-coloured products of maximum absorbance ( λ max=480–490 nm). The second method is based on the formation of green to blue complex ( λ max=635–660 nm) between o- dihydroxybenzene derivatives and sodium nitroprusside in the presence of hydroxylamine hydrochloride. All measurements of the two procedures are carried out in an alkaline medium at room temperature. The two methods are successfully applied for the determination of dopamine hydrochloride, levodopa and methyldopa in injections and tablets of pharmaceutical preparation. The common excipients used as additives in pharmaceuticals do not interfere in the proposed methods. The reliability of these methods are established by parallel determination with the reported and official methods.

Rose Bengal‐sensitized photooxygenation of chlorohydroxyaromatic contaminants in water: A kinetic study

Abstract A kinetic study of the RB‐sensitized photooxygenation of a series of chlorohydroxyaromatic (ClArOH) water contaminants (phenolic and dihydroxybenzene derivatives) has been carried out. In addition, an exhaustive study on the possible interactions of RB electronically excited triplet and singlet states with ClArOH was also developed. The determination of relative rates of oxygen uptake upon sensitized irradiation, employing auxiliar selective quenchers of oxygen active species, indicate the contribution of both singlet molecular oxygen (ca. 71%) and Superoxide ion (ca. 26%) as the reactive pathways for ClArOH degradation. The substitution by chlorine atoms in position meta greatly decrease the photooxygenation rate of the phenolic derivatives. For the dihydroxybenzene series, increase in nuclear chlorination parallels a decrease in the photodegradation rate. Outdoors sensitized solar irradiation experiments on different ClArOH mixtures leads to measurable levels of oxygen after a few minutes expos...

In vivo depigmentation by hydroxybenzene derivatives.

Certain mono- and dihydroxybenzene derivatives are selectively cytotoxic for melanocytes in vivo, and can cause depigmentation of skin and hair. We produced selective melanocytotoxicity/hair depigmentation in C57Bl mice by injection of 0.032-1.0% p-t-butylcatechol (tBC) or p-hydroxyanisole (MMEH) in physiological saline. No depigmentation occurred on injection of 3,4-dihydroxyphenylalanine (DOPA) or 3,4-dihydroxyphenylacetic acid (DOPAC). Light- and electron-microscopic examination of biopsy specimens taken from depigmented areas indicates selective melanocyte damage as early as 2 h post-injection. Melanocytes from anagen hair are most susceptible to depigmentation. All four compounds are substrates for tyrosinase, but only tBC and MMEH generate their respective isolable 1,2-benzoquinones, tBCQ and MMEHQ. These caused depigmentation in C57Bl mice to a comparable degree to the parent compounds. DOPA- and DOPAC-quinones (DOPAQ and DOPACQ) are not spectroscopically detectable in solution, suggesting extremely low steady-state levels of these compounds. The net observed rate of reaction of the respective 1,2-quinone with 300 microM bovine serum albumin (BSA) in vitro varies widely, with tBCQ >> MMEHQ = DOPACQ >> DOPAQ. The results are consistent with a mechanism involving attack of -SH on melanosomal proteins and/or enzymes by tyrosinase-generated 1,2-quinones. This mechanism evidently differs from that involved in in vitro hydroxybenzene melanocytotoxicity of melanoma cells, in which active oxygen intermediates generated by hydroxybenzene autoxidation play a significant role. The most reliable prognosticator of in vivo depigmentation appears to be the ability of the depigmenter to form a spectroscopically stable 1,2-quinone which is capable of reacting with protein -SH.