Acetic electrochemical methods

Although an inherently more efficient process, the direct chemical oxidation of 3-methylpyridine does not have the same commercial significance as the oxidation of 2-methyl-5-ethylpyridine. Liquid-phase oxidation procedures are typically used (5). A Japanese patent describes a procedure that uses no solvent and avoids the use of acetic acid (6). In this procedure, 3-methylpyridine is combined with cobalt acetate, manganese acetate and aqueous hydrobromic acid in an autoclave. The mixture is pressurized to 101.3 kPa (100 atm) with air and allowed to react at 210°C. At a 32% conversion of the picoline, 19% of the acid was obtained. Electrochemical methods have also been described (7). 

The procedure described is essentially that of Belleau and Weinberg and represents the only known way of obtaining the title compound. One other quinone acetal, 1,4,9,12-t6traoxadispiro[4.2.4.2]tetradeea-6,13-diene, has been synthesized by a conventional method (reaction of 1,4-cyclohexanedione with ethylene glycol followed by bromination and dehydrobromination ) as well as by an electrochemical method (anodic oxidation of 2,2-(l,4-phenylenedioxy)diethanol ). Quinone acetals have been used as intermediates in the synthesis of 4,4-dimethoxy-2,5-cyclohexadienone,. syw-bishomoquinone, - and compounds related to natural products. ... 

Preparation of Memfield resin-bound nitro acetates, which is a suitable bndding block for the development of combinatorial solid phase synthesis, is repotted. The anion of ethyl nitro acetate is generated in DMF by an electrochemical method using Pt cathode, magnesium rod anode, and tetrabutylairunonium bromide as an electrolyte. Alkylaton of this anion with alkyl hahdes gives mono-alkylated products in 80% yield." ... 

Only few applications have been reported to determine antioxidants in rubbers or polymers by using electrochemical methods [927,928]. Sawada et al. [929] reported successful separations by coupling the antioxidants with p-diazobenzene sulfonic acid before electrophoresis. Amine AOs were coupled in acetic acid and phenolic AOs in NaOH-ethanol were analysed by CE methods. MEKC separation of the four major food grade antioxidants (PG, BHA, BHT, TBHQ) was completed within 6 min with pmole amount detection using UV absorption [930]. RPLC was not as efficient and required larger sample amounts and longer separation times. 

The value of X found here appears to agree well with the values 5.0 and 2.3mequiv dm 3 absorbed water found by Oemisch and Pusch (4) by analytical and electro-chemical measurements respectively in cellulose acetate from a different manufacturer. The agreement is deceptive however because their value is based on the total water held in an asymmetric membrane. A value of M estimated from their data is almost ten times our M. It may be noted that their electrochemical method and their assumptions are quite different from ours. 

A more recent oxidation of hexafluoropropene (29) with oxygen over silica gel gives epoxide 30 in 79% yield.49 Among oxidations of 29 in solution, a highly selective continuous electrochemical method for the industrial production of 30 has been reported.50 This process is carried out in aqueous acetic acid/nitric acid/hydrogen fluoride on a lead(IV) oxide anode. 

Both 2- and 3-nitrothiophenes are reduced by tin and hydrochloric acid to the corresponding aminothiophenes. Reduction of 2,5-dibromo-3,4-dinitrothiophene gives 3,4-diaminothiophene as a stable crystalline solid. 2-Acetamido-furans are prepared by the reduction of 2-nitrofurans in the presence of acetic anhydride. 2-Substituted 5-nitrofurans can be reduced to the S-aminofurans by an electrochemical method. Although catalytic reduction gives 2-aminofurans only in low yields, they can be trapped using ethyl ethoxymethylenecyanoacetate or ethoxymethylenemalononitrile. Benzofuranone 412 and not 2-aminobenzofuran is obtained from tin and hydrochloric acid treatment of 2-nitrobenzo[ ] furan 411. 

Plesch showed by electrochemical methods that at the sufficiently low concentrations, the components exist in the 2-to-2 equilibrium with unpaired ions These salts were used to initiate polymerization of cyclic ethers and acetals but the structure of the tirst addition products has not yet been determined. Nevertheiess, several authors observed the corresponding end groups in oligomers (at the early stages of polymerization) or in high polymers . These observations indicate that the oxocarbenium salts initiate by simple addition, for instance ... 

The heavy end products of acetic anhydride processes are separated from catalyst streams and distillation residues. The high affinity of the heavy ends for rhodium components affords specified procedures to separate rhodium and recycle it to the reaction stage of the process. Different methods for rhodium recovery were tested during the process development, including extraction methods [65], precipitation [66], complexing, and electrochemical methods [67]. 

Aizawa and Wang have reported123 that the copper-containing enzyme, bilirubin oxidase (BOX), catalyzes the oxidative polymerization of pyrrole to give thin films of PPy on substrates such as glass, plastic, or platinum plates. The BOX was first adsorbed onto the matrix support from an aqueous acetate buffer solution (pH 5.5), followed by incubation with the pyrrole monomer (0.2 M) in acetate buffer (pH 6) for several hours at room temperature. The deposited PPy film was reported to have similar properties to PPy made by conventional chemical or electrochemical methods. 

An interesting electrochemical method for the determination of bound sialic acid has been developed, making use of a potentiometric four-channel thick-film sensor [236]. The sialidase sensor consists of a bilayer of a membrane containing Clostridium perfringens sialidase immobilized in a poly(vinyl acetate)-polyethylene copolymer, which is placed on top of an fT -selective poly(vinyl chloride)-poly(vinyl acetate) indicator membrane. The enzyme-induced release of bound sialic acid leads to a concomitant decrease in pA a of the carboxyl function of sialic acid. This decrease affords a local pH change inside the sialidase-containing sensor membrane, which is monitored by the H -selective indicator membrane. The pH optimum of the sialidase sensor was pH 4 for sialyllactose, mucin and colominic acid. 

We shall now consider how far the rates of simple proton-transfer reactions fulfil these predictions. It should first be noted that velocity constants of the magnitude with which we are concerned are not known with any accuracy, and that the discrepancies between the results obtained by different methods are frequently far outside the limits of error estimated by the investigators. This is illustrated by Table 16 which collects rate constants reported for the reaction between hydrogen ions and acetate ions in aqueous solution. Although some of the discrepancies may be due to differences in experimental conditions (e.g., electrochemical methods often involve the use of high concentrations of inert electrolyte ), there are certainly considerable differences which must stem from experimental or theoretical uncertainties in the techniques used. Caution is therefore necessary in interpreting minor variations in velocity constants of this magnitude, especially if they have been obtained by different methods. 

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