Phenols, electrolytic oxidation

Direct Electron Transfer. We have already met some reactions in which the reduction is a direct gain of electrons or the oxidation a direct loss of them. An example is the Birch reduction (15-14), where sodium directly transfers an electron to an aromatic ring. An example from this chapter is found in the bimolecular reduction of ketones (19-55), where again it is a metal that supplies the electrons. This kind of mechanism is found largely in three types of reaction, (a) the oxidation or reduction of a free radical (oxidation to a positive or reduction to a negative ion), (b) the oxidation of a negative ion or the reduction of a positive ion to a comparatively stable free radical, and (c) electrolytic oxidations or reductions (an example is the Kolbe reaction, 14-36). An important example of (b) is oxidation of amines and phenolate ions ... 

Both inter- and intramolecular [5 + 2] cycloaddition modes have been utilized in the synthesis of natural products. Successful intermolecular cycloaddition depends on making an appropriate selection of solvent, supporting electrolyte, oxidation potential, and current density. This is nicely illustrated in Schemes 23 to 25. For example, in methanol the controlled potential oxidation of phenol (101) affords a high yield (87%) of (102), the adduct wherein methanol has intercepted the reactive intermediate [51]. In contrast, a constant current electrolysis conducted in acetonitrile rather than methanol, led to an 83% yield of quinone (103). 

The nitrosodisulfonate salts, particularly the dipotassium salt called Fremy s salt, are useful reagents for the selective oxidation of phenols and aromatic amines to quinones (the Teuber reaction). - Dipotassium nitrosodisulfonate has been prepared by the oxidation of a hydroxylaminedisulfonate salt with potassium permanganate, " with lead dioxide, or by electrolysis. This salt is also available commercially. The present procedure illustrates the electrolytic oxidation to form an alkaline aqueous solution of the relatively soluble disodium nitrosodisulfonate. This procedure avoids a preliminary filtration which is required to remove manganese dioxide formed when potassium permanganate is used as the oxidant. " ... 

The anodic oxidation of phenol (dissolved in sodium sulfate) was studied by De Sucre and Watkinson using two types of lead dioxide anodes [26]. The first was made of 2 mm lead shot that was oxidized for 12 h at 526mA/cm in 20% sulfuric acid while the second anode, electrodeposited lead dioxide flakes, was supplied by a commercial manufacturer. The phenol oxidized faster on the electrodeposited Pb02, which also turned out to be more corrosion-resistant than the oxidized lead shot. While all of the phenol oxidized rapidly (1.5 h) on the electrodeposited anode, not all of it formed CO2. It was found that 80% of the total organic carbon remained in solution after the phenol was completely oxidized. Phenol destruction increased with an increase in current density, and decreased as electrolyte flowrate, pH, and anode particle size were increased. 

The Ebonex ceramic anode has been used to study the electrolytic oxidation of trichloroethylene to CO2, CO, Cl , and ClOa [19]. Ebonex and Pb02-coated Ebonex electrodes were used for the electrochemical treatment of phenolic pollutants in water [20]. 

This section covers the union of two aryl moieties, one of which is a fully alkylated phenol, and the other is either a free phenol or a phenol ether. Clearly, radical dimerization is not operative in such reactions. An early example is to be found in the work of Pitcher and Dietrich (1924) ° who showed that 3,3, 4,4 -tetramethoxybiphenyl was among the products of electrolytic oxidation of veratrole in sulfuric acid using a lead dioxide anode the biaryl was formed in about 20% yield based on reacted veratrole. 

There remain some problems to be solved for this electrolytic oxidation of phenols. (i) Considerable magnitude of overvoltage and low current efficiency. (ii) Poly(phenylene oxide) formed deposits on the electrode surface as a thin, insulating film passivating of the electrode. (iii) The side reaction which forms b iphenoquinone. 

The further oxidation of phenol may also result in the formation of catechol, C,iH4(OH) (1 2). The transformation may be effected by fusion with sodinm hydroxide.85 The snbstance may also be obtained by oxidizing benzene with hydrogen peroxide in the presence of ferrous sulfate88 and by reducing o-benzoquinone with aqueous sulfurous acid in the cold.81 Quinol may be prepared from phenol by oxidation with potassium persulfate in alkaline solution.38 It can also be obtained directly from benzene by the electrolytic oxidation of an alcohol solution to which... 

The electrolytic oxidation of the sodium salt of (+ )-N-ethoxycarbonyl-Al-norarmepavine (46) led to the dimeric mixtures (47) and (48). The latter mixture was converted into a mixture of dauricine analogues (49) via O-benzylation, reduction with lithium aluminium hydride, and hydrogenolytic debenzylation. This transformation represents the first preparation of an analogue of a natural bis-benzylisoquinoline by oxidation of a phenolic monomeric benzylisoquinoline. Detailed studies on the mass-spectral cleavage patterns of bisbenzylisoquinolines have appeared. 

A patent for the electrochemical treatment of various industrial wastes, prior to discharge, was obtained by Carey et al. and represented one of the first demonstrations of diamond in electrochemistry [100]. Various chemical contaminants (e.g., phenols) from a Kodak industrial film-making process were oxidatively treated with diamond anodes. Up to 90% of the effluent was oxidized in their electrolytic approach. Hagans and coworkers used diamond anodes to oxidize phenol all the way to CO2 in acidic media [104]. The total organic content was effectively reduced from... 

A general synthesis of polysubstituted phenols from aliphatic precursors has been described. The phenols have been converted toquinones by a novel indirect electrolytic oxidation involving Fremy s radical . ... 

Films of a pentaerythritol alkyd, a tung oil phenolic and an epoxypolyamide pigmented with iron oxide in the range 5-7% p.v.c. were exposed to solutions of potassium chloride in the range 0.0001-2.0 m. It was found that in all cases the resistance of the films steadily decreased as the concentration of the electrolyte increased. Since the resistances of the films were at no time independent of the concentration of the electrolyte, it was concluded that the Donnan equilibrium was not operative and that the resistance of the films were controlled by the penetration of electrolyte moving under a concentration gradient. 

Electropolymerization is also an attractive method for the preparation of modified electrodes. In this case it is necessary that the forming film is conductive or permeable for supporting electrolyte and substrates. Film formation of nonelectroactive polymers can proceed until diffusion of electroactive species to the electrode surface becomes negligible. Thus, a variety of nonconducting thin films have been obtained by electrochemical oxidation of aromatic phenols and amines Some of these polymers have ligand properties and can be made electroactive by subsequent inincorporation of transition metal ions... 

Another point of importance about the film structure is the degree to which it can be permeated by various ions and molecules. It is of course essential that supporting electrolyte ions be able to penetrate the film, else the electrical double layer at the electrode/polymer interface could not be charged to potentials that drive electron transfers between the polymer and the electrode. The electroneutrality requirements of porphyrin sites as their electrical charges are changed by oxidation or reduction also could not be satisfied without electrolyte permeation. With the possible exception of the phenolic structure in Fig. 1, this level of permeability seems to be met by the ECP porphyrins. 

The third application is the oligomerization of phenol. By selecting solvent and supporting electrolyte, phenol is electro-oxidatively polymerized to yield poly (phenyleneoxide) as a tan-colored powder. 

The anodic coupling of aryl ethers is reviewed in Ref. [180]. Aryl ethers are more selectively coupled than phenols for the following reasons The carbon-oxygen coupling is made impossible and the ortho-coupling and the oxidation to quinones become more difficult. A mixture of triflu-oroacetic acid (TFA) and dichloromethane proved to be the most suitable electrolyte [181]. TFA enhances the radical cation stability and suppresses the nucle-ophilicity of water. Of further advantage is the addition of alumina or trifluo-roacetic anhydride [182]. Table 12 compiles representative examples of the aryl ether coupling. 

Although the literature on electrodeposited electroactive and passivating polymers is vast, surprisingly few studies exist on the solid-state electrical properties of such films, with a focus on systems derived from phenolic monomers, - and apparently none exist on the use of such films as solid polymer electrolytes. To characterize the nature of ultrathin electrodeposited polymers as dielectrics and electrolytes, solid-state electrical measurements are made by electrodeposition of pofy(phenylene oxide) and related polymers onto planar ITO or Au substrates and then using a two-electrode configuration with a soft ohmic contact as the top electrode (see Figure 27). Both dc and ac measurements are taken to determine the electrical and ionic conductivities and the breakdown voltage of the film. 

Numerous methods for the synthesis of salicyl alcohol exist. These involve the reduction of salicylaldehyde or of salicylic acid and its derivatives. The alcohol can be prepared in almost theoretical yield by the reduction of salicylaldehyde with sodium amalgam, sodium borohydride, or lithium aluminum hydride by catalytic hydrogenation over platinum black or Raney nickel or by hydrogenation over platinum and ferrous chloride in alcohol. The electrolytic reduction of salicylaldehyde in sodium bicarbonate solution at a mercury cathode with carbon dioxide passed into the mixture also yields saligenin. It is formed by the electrolytic reduction at lead electrodes of salicylic acids in aqueous alcoholic solution or sodium salicylate in the presence of boric acid and sodium sulfate. Salicylamide in aqueous alcohol solution acidified with acetic acid is reduced to salicyl alcohol by sodium amalgam in 63% yield. Salicyl alcohol forms along with -hydroxybenzyl alcohol by the action of formaldehyde on phenol in the presence of sodium hydroxide or calcium oxide. High yields of salicyl alcohol from phenol and formaldehyde in the presence of a molar equivalent of ether additives have been reported (60). Phenyl metaborate prepared from phenol and boric acid yields salicyl alcohol after treatment with formaldehyde and hydrolysis (61). 

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