The effects of isotopic substitution and competitive adsorption on the oxidation of aldehydes and alcohols at gold electrodes

The nature of the mechanism of the anodic oxidation of aldehydes in aqueous base on gold electrodes has been probed using isotopic substitution and competitive adsorption studies. A primary kinetic isotope effect of k_H/k_D=3?4 was observed upon substitution of deuterium for protium on the formyl group of benzaldehyde and cyclohexanecarboxaldehyde on gold in aqueous base using the techniques of cyclic voltammetry, rotating disc electrode voltammetry and chronoamperometry. Similar results are reported for the same aldehydes on a silver electrode, and also for the anodic oxidation of 2-propanol and 2-propanol-2-d on gold under similar conditions. Inhibition of the anodic cyclic voltammetric peak for benzaldehyde on gold by a variety of adsorbed species including CN^?, I^?, Br^?, (C₂H₅)₄N⁺ and diethylenetriamine is also described. These observations are used to propose a mechanism for the low potential oxidations of aldehydes and alcohols on gold involving a rate limiting dissociative adsorption step with cleavage of the α-carbon-hydrogen bond.     

Electrode processes in the oxidation of tetrahydroisoquinoline derivatives

The electrochemical oxidation of the alkaloid laudanosine (Ia) to O-methylflavinantine (II) has been studied in acetonitrile solvent. Using cyclic voltammetry, rotating disc voltammetry and preparative electrolyses on several alkaloids, simple aliphatic amines and aromatic compounds, some aspects of the mechanism of this coupling reaction are elucidated. The first anodic wave for laudanosine at platinum has E_p=0.55 V vs. Ag/Ag⁺. The electrode rapidly becomes partially passivated at potentials above 0.5 V. This is due to a film which “dissolves” below 0.5 V, at a rate independent of the potential. It is shown that the reaction (Ia)→(II) proceeds at 0.5 V by initial oxidation of the amine moiety. If acids such as sodium bicarbonate are added to the anolyte the amine is protonated causing the first wave to disappear. Oxidation at 1.1 V under these acidic conditions produces the same product, but more rapidly and in significantly higher yield because electrode filming and side reactions resulting from the amine oxidation are abrogated.     

Electrochemical oxidation of tetramethylhydrazine, 1,1-dimethyl-2,2-dibenzylhydrazine and tetrabenzyl-hydrazine

Cyclic voltammetric studies of the title hydrazines have shown that the first step of oxidation yields stable radical cations. Though the electron transfer reaction is somewhat slow and very dependent on surface condition when solid electrodes are used, the process is quite reversible at mercury electrodes. Chemical analyses of electrolysis solutions were used to supplement rotating ring-disk voltammetric studies of the second stage of oxidation. The initially formed dication undergoes rapid deprotonation and the protons so formed can react with incoming starting material reducing the currents observed below the two-electron level. Deprotonation of the dication at an α-carbon gives a postulated cationic intermediate which can undergo two reactions whose products were observed: dealkylation to form a hydrazone and deprotonation with N-N cleavage giving an imine.     

Comportement polarographique et solvatation de quelques cations dans le mélange binaire diméthylsulfoxyde-carbonate de propylène

The electrochemical oxidation of 2,4,6-tri-tert-butylphenol as well as the phenoxide and phenoxy radical derived from it has been investigated in acetonitrile and ethanol+water. The ease of oxidation decreases in the order phenoxide, phenoxy radical, phenol with the separation between potentials for phenoxide oxidation and phenoxy radical oxidation being 1.2 V in acetonitrile. The phenoxide is oxidized to the stable phenoxy radical in a highly reversible reaction in acetonitrile and alkaline ethanol+water. Oxidation of the radical produces a phenoxonium ion which is attacked by water giving 2,4,6-tri-tert-butyl-4-hydroxy-2,5-cyclohexadienone. This two electron product is also formed upon oxidation of the phenol in either solvent. However, in acidic media the hydroxydienone dealkylates give 2,6-di-tert-butylhydroquinone which is oxidized to the final product 2,6-di-tert-butyl-1,4-benzoquinone. The dealkylation is quite rapid in anhydrous acetonitrile but the rate is depressed by the addition of water.A novel double potential step experiment was used to characterize the oxidation of the phenoxy radical. A step to a potential where the phenoxide is oxidized to the phenoxy radical is followed by a step to a potential where the phenoxy radical is oxidized. The current during the second step is unusually small because protons produced by the oxidation of the radical deactivate the phenoxide. The current-time curve was found to agree with that predicted by digital simulation.     

Observations on the formation of spark discharge and its influence by an external magnetic field

Described are a series of experiments executed to characterize the physical and chemical nature of spark discharge in argon at atmospheric pressure. Results are reported concerning the expansion properties of the spark and the distribution and longevity of cathode material in and around the spark channel following cessation of the discharge current. The nature of a previously reported symmetrical post-discharge torus is studied at high spark repetition rates. The interaction of residual vapor on following sparks is investigated. Basic features of the spark process are generalized with a set of Schlieren photographs that show bulk motion of the spark plasma. Time-resolved and space-resolved emission and absorption experiments on magnesium electrodes suggest a charged nature to the post-discharge environment. The bulk plasma character is probed further with external magnetic fields to determine the existence of charged species within the post-discharge torus, and the effects of magnetic forces on its formation.     

Properties of low-capacity macroporous anion-exchangers and their use with high-pH eluents for the determination of weak acids in urine

Low-capacity anion-exchangers have been synthesized from the macroporous styrene-divinylbenzene co-polymer Hamilton PRP-1. These anion-exchangers have non-polar adsorbent properties for neutral sample molecules. The dependence of the capacity factor for a polar weak-acid metabolite of the drug polythiazide on the type and concentration of electrolyte, the organic solvent concentration, and pH of aqueous eluents has been studied to characterize the exchangers. As an application, a method has been developed to determine the metabolite in urine at levels as low as 10 ng ml . The method employs the exchangers in both a precolumn, which is used to preconcentrate and clean-up the metabolite from urine, and an analytical column. Eluents containing 0.001-0.01M sodium hydroxide are used to ionize the weak-acid metabolite.     

The electrochemical stripping determination of bismuth in aqueous and nonaqueous media after its extraction

The cyclic voltammetry of bismuth in aqueous media and electrochemical stripping determination of bismuth in aqueous and nonaqueous media after its extraction using a rotating disc electrode of glassy carbon was studied. To raise the conductivity of the organic medium and for the preparation of a convenients medium for the determination of bismuth, an alcoholic (methanol) solution of NH₄SCN+HClO₄ was employed. In non-aqueous medium bismuth can be determined down to concentrations 10^?8M by anodic stripping voltammetry and to 5×10^?8M by anodic stripping chronopotentiometry. The selectivity of the determination of bismuth after its extraction was studied. Electrochemical determination of 10^?6M Bi³⁺ with error ±3–4% was not interfered with by these elements: Co²⁺, Ni²⁺, Zn²⁺, Cd²⁺, As³⁺ in the concentration 8×10^?3M, Fe³⁺, In³⁺, Sn²⁺ and Sn⁴⁺ (5× 10^?3M), Cu²⁺ (10^?3M), Sb³⁺ (1.5×10^?4M) and Hg²⁺ (2×10^?5M). The reproducibility of the electrochemical determination of bismuth according to the recommended procedure is very good.     

Stereochemistry at tin and mechanism of three cleavage reactions of carbontin bonds

The cleavages of the trityltin bond by NaFe(CO)₂Cp, LiBHEt₃ and Ph₃-SnLi are not stereoselective. This is explained in terms of a one-electron transfer mechanism leading to a triorganostannyl radical which can undergo inversion before reacting with another radical to give the product.     

A study of aldehyde oxidation at glassy carbon,mercury, copper,silver, gold and nickel anodes

The rate, potential and mechanism of the anodic oxidation of aliphatic aldehydes have been found to be highly dependent on solution conditions and electrode material. Aldehyde oxidations in neutral acetonitrile on glassy carbon occur at very positive potentials (ca. +3 V vs. SCE) and the peak potentials correlate with the ionization potentials of the aldehydes. In aqueous base, aldehyde oxidation is assisted by reversible addition of hydroxide to the carbonyl group to form electroactive gem-diolate (II). Oxidations of aldehydes in aqueous base on Hg, Ni, Ag and Au all yield the corresponding carboxylate via two-electron oxidation plus aldol and Cannizzaro byproducts and the oxidations occur at potentials far negative of the unassisted oxidation in neutral acetonitrile. On Ni, Cu and possibly Hg the oxidation involves the formation of a metal oxide which acts as a chemical oxidizing agent. On Ag and Au the oxidations take place on a surface which is not covered by a phase oxide. A mechanism involving a direct electrochemical process with oxidation of gem-diolate adsorbed on an oxide-free metal surface is proposed. A pulsed electrolysis technique was utilized to circumvent deactivation of Ag and Au electrodes during electrolysis and preparation of an “aurized” gold surface with a much slower deactivation rate is described.     

Design of a large,rigid, modular optical bed for versatile optical and spectroscopic experimentation

Described is a mechanically-rigid and referenceable, vibrationally-isolated, modular optical support bed which has demonstrated significant utility in recent research on the physical—chemical nature of the atmospheric pressure spark discharge. By interconnecting an assembly of pre-aligned, truss-like sub-structures, a complete instrumental complex has been fabricated which exhibits high mechanical stability. This stability is sufficient to allow alignment of, for example, a 5 m focal length, high-dispersion optical spectrometer, to be maintained for months without detectable degradation. The approach is versatile and can be easily extended to include a wide variety of optical and other research applications. Supporting mechanical, vibration, and optical data are included as well as documentation of fabrication details.     

Calculations of van der Waals forces in thin liquid films using Lifshitz' theory

For the study of thin, free liquid films (soap films) van der Waals dispersion forces were calculated from Lifshitz' theory for some three-layer models with film thicknesses between 5 and 150 nm. The complete expression as given by [2.] was used to calculate the force, the energy, and the second derivative of the energy after the thickness, as a function of film thickness. The second derivative of the energy after the thickness is needed in light scattering of soap films. The calculations are based on the dielectric data of [14.]. Some effects of the hydrocarbon layers on and electrolyte in the aqueous layer are considered. In order to make the results readily usable, the calculations are presented in the form of accurate empirical equations.     

Synthesis of phenethylamines from phenylacetonitriles obtained by alkylation of cyanide ion with mannich bases from phenols and other benzylamines

Benzylamines, obtained by the Mannich reaction on phenols or by reductive alkylation of aldehydes, have been used in place of benzyl chlorides to alkylate cyanide ion to obtain nitriles which may be reduced to phenethylamines. Yields of 4-hydroxy-3-methoxyphenylacetonitrile were about the same from the primary, secondary, and tertiary amines. Benzylamines not having either an ortho or para OH group did not function as alkylating agents. With such compounds it was necessary to prepare the quaternary salts before alkylation could be achieved. 6-Hydroxydopamine was prepared from 2,4,5-trimethoxybenzaldehyde utilizing the latter approach. 3,5-Dimethoxy-4-hydroxyphenethylamine was cyclized to the corresponding dihydroisoquinoline. The isoquinoline and tetrahydroisoquinoline analogs were also prepared. 4-Hydroxy-3-methoxyphenylacetonitrile was hydrolysed to homovanillic acid, the naturally occurring metabolite of dopamine.     

Redox reactions in nonaqueous media determination of amines via dithiocarbamate formation and iodine monobromide titrations

A simple and accurate nonaqueous oxidimetric method of wide applicability has been developed for the determination of primary and secondary amines after their quantitative conversion with carbon disulphide in acetonitrile to the alkylammonium alkyldithiocarbamates, which are titrated with iodine monobromide solution also in acetonitrile at room temperature. The endpoint is detected visually by the yellow tint imparted to the solution by the first drop of oxidant solution in excess; and potentiometrically by using a bright platinum wire indicator electrode, and antimony or modified calomel reference electrode. The method is simple, rapid, accurate, and widely applicable.     

Brillouin scattering in liquid mixtures: CCl4/CHCl3

The Brillouin light scattering spectra of mixtures of liquid CCl₄ and CHCl₃ have been obtained. The resulting relaxation rates and the relaxing energy reservoir were studied as a function of the mole fraction over the entire concentration range. The energy exchange between the pertinent degrees of freedom are discussed in terms of the relaxation rates of homomolecular and heteromolecular collisions. We came to the conclusion that the resonance energy transfer between vibrational levels play a significant role in determining the vibration—translation energy migration observed by Brillouin scattering'     

Experimental characterization of straight spectrometer slits

A technique for calibrating slit width for straight spectrometer slits based on the diffraction of laser radiation is described. Related slit properties and calibration apparatus are discussed.     

A phosphorimetric investigation of the external heavy-atom effect in aqueous solution and its correlation with phosphorescence intensity and quantum yield

Excitation and emission phosphorescence spectra, lifetimes, and relative quantum yields of benzene and ten monosubstituted benzenes were determined at 77 K in methanol/water 10/90 v/v and in sodium iodide/methanol/water solutions. Substituents CHO, COCH(3), COC(2)H(5), OH, OCH(3), H(3), C(2)H(5), CH(2)OH and N(CH(3))(2) were investigated. Aqueous sodium iodide solutions were found to be a suitable heavy-atom solvent for phosophorimetry. Heavy-atom enhancement factors ranged from 1.2 to 8.3 according to the molecular structure and a marked decrease of the lifetime was observed for nine compounds in aqueous sodium iodide solution. A linear log-log correlation was obtained between the relative corrected phosphorescence signal and the heavy-atom enhancement factor of the monosubstituted benzenes. A similar correlation was found between the quantum yields and the heavy-atom enhancement factors. The analytical usefulness of these correlations is evident for the prediction of the magnitude of the heavy-atom effect.     

The preparation of 4-alkylated derivatives of apopinene

Grignard reagents coupling with bromo-apopinene, which was prepared by NBS treatment of apopinene, leads to 4-alkylated derivatives of apopinene in high yields. Of particular interest is the convenient preparation of trans δ-pinene. The stereochemistry of these new compounds was established on the basis of NMR considerations.