Gas chromatographic analysis of chlorophenylmercapturic acid lindane metabolites

An analytical method for phenols has been adapted for the analysis of chlorophenylmercapturic acids in rat urine. Chlorothiophenols were produced from the mercapturic acids by hydrolytic cleavage with sodium hydroxide. Acetate esters of the chlorothiophenols were formed by addition of acetic anhydride to the aqueous alkaline solution. After acylation, the acetate derivatives were extracted into hexane. Forming the acetate esters of the chlorothiophenols prevented their oxidation to disulfides and significantly improved their chromatographic properties. Electron-capture gas chromatographic analysis of the stable acetate esters was performed on a mixed phase column, 4% SE-30 + 6% OV-210. Recoveries of four chlorothiophenols ranged from 82 to 93%. This method required no sample transfer steps; therefore, sample loss and analysis time were minimized.     

An investigation of the reaction of primary nitroalkanes with acetic anhydride/sodium acetate

Oxidation of primary nitroalkanes by acetic anhydride/sodium acetate has been found to be more complex than previously suspected. Phenylnitromethane, with acetic anhydride/sodium acetate at 60–80°, for example, gives a mixture of benzoic anhydride, triacethylhydroxylamine and acetanilide, through the mixed anhydride

as a key intermediate. Evidence in support of this latter species has been obtained by carrying out the oxidation in the presence of dimethyl acetylenedicarboxylate as a 1,3-dipolarophile, when 3-phenyl-4,5-dicarbomethoxyisoxazole is formed in 82% yield. A number of other 3-alkyl- and 3-aryl-4,5-dicarbomethoxyisoxazoles have been prepared in a similar manner.     

Gas-chromatographic determination of formic acid in the oxidation products of organic substances

Procedures for the gas-chromatographic determination of formic acid in oxidation produts of organic substances after its conversion to benzyl formate were developed. In determining formic acid in an organic phase, free formic acid was esterified with benzyl alcohol in a pyridine solution while adding acetic anhydride under mild conditions. The conversion of formic acid was complete even in the presence of other mono-and dicarboxylic acids in considerable amounts. It was found that the formation of benzyl formate occurred via a mixed aldehyde formed in situ from formic acid and acetic anhydride. The determination of formic acid in aqueous solutions involves the synthesis of its sodium or potassium salt and the successive treatment of this salt with acetyl chloride and benzyl alcohol in a pyridine solution.     

Synthesis of mixed acid anhydrides from methane and carbon dioxide in acid solvents

[reaction: see text] The reaction of CH(4) with CO(2) has been performed in anhydrous acids using VO(acac)(2) and K(2)S(2)O(8) as promoters. NMR analysis establishes that the primary product is a mixed anhydride of acetic acid and the acid solvent. In sulfuric acid, the overall reaction is CH(4) + CO(2) + SO(3) --> CH(3)C(O)-O-SO(3)H. Hydrolysis of the mixed anhydride produces acetic acid and the solvent acid. When trifluoroacetic acid is the solvent, acetic acid is primarily formed via the reaction CH(4) + CF(3)COOH --> CH(3)COOH + CHF(3).     

Corrected structure of the reaction product of gibberellin A3 with acetic anhydride and zinc and its crystalline structure. Rare case of the diels-alder reaction

The correct structure has been established for the compound obtained on the treatment of the methyl ester of gibberellin A₃ with zinc in boiling acetic anhydride, to which the erroneous structure (II) was previously assigned. A mechanism of the formation of compound (II) is suggested which includes an intramolecular diene condensation between an acetate carbonyl group and the conjugated diene system in the intermediate mixed anhydride (V).     

The DMAP-catalyzed acetylation of alcohols--a mechanistic study (DMAP = 4-(dimethylamino)pyridine)

The acetylation of tert-butanol with acetic anhydride catalyzed by 4-(dimethylamino)pyridine (DMAP) has been studied at the Becke3 LYP/6-311 + G(d,p)//Becke3 LYP/6-31G(d) level of theory. Solvent effects have been estimated through single-point calculations with the PCM/UAHF solvation model. The energetically most favorable pathway proceeds through nucleophilic attack of DMAP at the anhydride carbonyl group and subsequent formation of the corresponding acetylpyridinium/acetate ion pair. Reaction of this ion pair with the alcohol substrate yields the final product, tert-butylacetate. The competing base-catalyzed reaction pathway can either proceed in a concerted or in a stepwise manner. In both cases the reaction barrier far exceeds that of the nucleophilic catalysis mechanism. The reaction mechanism has also been studied experimentally in dichloromethane through analysis of the reaction kinetics for the acetylation of cyclohexanol with acetic anhydride, in the presence of DMAP as catalyst and triethylamine as the auxiliary base. The reaction is found to be first-order with respect to acetic anhydride, cyclohexanol, and DMAP, and zero-order with respect to triethyl amine. Both the theoretical as well as the experimental studies strongly support the nucleophilic catalysis pathway.     

Coulometric generation of protons by oxidation of hydrogen dissolved in palladium, in non-aqueous media

Coulometric generation of H(+) ions by the oxidation of hydrogen dissolved in palladium, in media such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, acetic anhydride and acetic acid-acetic anhydride mixture, for use in titration of bases, has been investigated. The hydrogen is oxidized at potentials which are much more negative than those of the bases and other components present in the solution. Titrations of numerous bases have established that the oxidation is quantitative and proceeds with 100% current efficiency.     

Kinetics and mechanism of the liquid-phase reaction of 2,4-dinitrotoluene with ozone in the presence of manganese(II) acetate

The kinetics and the mechanism of the liquid-phase oxidation of 2,4-dinitrotoluene with ozone in the presence of manganese(II) acetate have been investigated. The major products of 2,4-dinitrotoluene oxidation with ozone in acetic anhydride are 2,4-dinitrobenzyl acetate (65.8%) and 2,4-dinitrobenzylidene diacetate (18.8%). The effect of the manganese(II) acetate concentration on the selectivity of substrate oxidation at the methyl group is reported. A redox catalysis mechanism providing an explanation to experimental data is considered.     

1,2- and 1,4-Diacetoxylation of 1,3-butadiene via 2,5-dihydrothiophene 1,1-dioxide as a probable intermediate

Sulphur dioxide has been found to promote a novel liquid-phase oxidation of 1,3-butadiene in acetic anhydride with oxygen gas and catalytic amounts of concentrated protic acids (e.g. hydrobromic acid). 1,2-Diacetoxy-3-butene and 1,4-diacetoxy-2-butene together with small amounts of 1-hydroxy-2-acetoxy-3-butene and 1-hydroxy-4-acetoxy-2-butene are formed in the reaction.     

Oxidation of 4-Nitrotoluene by Ozone in Acetic Anhydride in the Presence of Manganese Sulfate

The reaction of 4-nitrotoluene oxidation with ozone in acetic anhydride in the presence of MnSO₄and sulfuric acid was studied. The main reaction product is 4-nitrobenzyl acetate, the yield of which is 63.2%. Based on an analysis of the experimental data, a mechanism of the catalytic ozonation of 4-nitrotoluene in acetic anhydride was proposed.     

Liquid-phase reactions of isomeric methylphenols with ozone

Ozonation of isomeric methylphenols in acetic anhydride was studied. Here, acetic anhydride acts simultaneously as solvent and acylating agent. In the presence of a mineral acid methylphenols were converted into methylphenyl acetates during preparation of solutions for ozonation. The major products in the oxidation of isomeric methylphenyl acetates with ozone were aliphatic peroxides (80–90%); oxidation of the methyl group gave rise to the corresponding acetoxybenzyl acetates (7–14%) and acetoxybenzylidene diacetates (3–6%). A probable scheme for the liquid-phase oxidation of methylphenyl acetates with ozone in acetic anhydride was proposed.     

A stable intermediate: a new insight into the mechanism of Lewis acids-promoted formation of acylals from aldehydes

Treatment of m-nitrobenzaldehyde with acetic anhydride in the presence of Lewis acids, such as InBr₃, ZnBr₂, Cu(OTf)₂, gives a stable intermediate at the initial stage of reaction. Based on this new organic compound characterized by X-ray single crystal diffraction, a new mechanism for Lewis acids-promoted formation of acylals from aldehydes is proposed. Exchange reaction with different ratio of acetic anhydride to propionic anhydride, in the presence of Lewis acids, is studied.     

Determination of aliphatic anhydrides and acids by reversed-phase liquid chromatography

Few chromatography methods have been reported for the determination of anhydrides in mixtures or as mixed anhydrides. The potential reactivity of anhydrides with water and other common eluent components complicates possible schemes for separation and analysis. By optimizing variables that affect hydrolysis, including the stationary phase, conditions can be found to successfully analyze anhydrides as reactive as acetic anhydride. The corresponding acids can be determined at the same time. The effect of the stationary phase on anhydride hydrolysis rates may prove to be a sensitive means of probing stationary phase chemistry.     

Kinetics and mechanism of 4-acetoxytoluene oxidation by ozone in an acetic anhydride solution in the presence of manganese bromide catalysts

The kinetics of the reaction of ozone with 4-acetoxytoluene in an acetic anhydride solution in the presence of a manganese bromide catalyst is reported. Under these conditions, the major reaction products are 4-acetoxybenzylidenediacetate (68.0%), 4-acetoxybenzyl acetate (18.5%), and 4-acetoxybenzyl bromide (1.6%). The effect of manganese(II) acetate and potassium bromide on the selectivity of oxidation at the methyl group has been investigated. A probable redox catalysis mechanism explaining the experimental data is considered.     

Potentiometric titration of peptides and the starting materials and intermediates of their synthesis. I. Acidimetric determination of N-acetylamino acids

The potentiometric titration of N-acetylamino acids and their sodium salts in nitromethane-acetic anhydride (2:1) with a nitromethane solution of perchloric acid has been investigated. A procedure has been developed for the quantitative determination of N-acetylamino acids in the presence of acetic acid in aqueous solutions. A differentiation determination of N-acetylamino acids and their salts in the presence of sodium acetate has been carried out.All-Union Scientific-Research Institute of Applied Biochemistry, Biolar Scientific-Industrial Association, Olaine. Translated from Khimiya Prirodnykh Soedinenii, Vol. 6, pp. 830–834, November–December, 1989.     

Coulometric generation of H+ ions by oxidation of thiols at a platinum anode and by oxidation of mercury in acetic acid—acetic anhydride

The coulometric generation of hydrogen ions by anodic oxidation of propane-1-thiol, butane-1-thiol, 2-mercaptopropionic acid, heptane-1-thiol, 2-mercaptoethanol, methyl and ethyl thioglycollate and p-thiocresol in acetic acid—acetic anhydride (1 + 6 v/v) is described, together with the possibility of coulometric generation of protons by mercury oxidation in the presence of p-thiocresol in the same solvent system.Current-potential curves for the solvent, indicator, titrated bases, mercury and the investigated thiols showed that in acetic acid—acetic anhydride (5 + 95, v/v), mercury and the investigated thiols are oxidized at potentials which are much more negative than those of the titrated bases and other components present in the solution.Titration of potassium hydrogenphthalate and sodium acetate with protons generated by the oxidation of thiols, and of sodium acetate, lithium acetate and pyridine with protons generated by the oxidation of mercury, demonstrated that the oxidation of both thiols and mercury proceeds quantitatively with 100% current efficiency.     

Potentiometric titration of peptides and the starting materials and intermediates of their synthesis. I. Acidimetric determination of N-acetylamino acids

The potentiometric titration of N-acetylamino acids and their sodium salts in nitromethane-acetic anhydride (2:1) with a nitromethane solution of perchloric acid has been investigated. A procedure has been developed for the quantitative determination of N-acetylamino acids in the presence of acetic acid in aqueous solutions. A differentiation determination of N-acetylamino acids and their salts in the presence of sodium acetate has been carried out.     

Coulometric generation of acetylions by oxidation of mercury in acetic anhydride and in acetic acid/acetic anhydride mixture

Coulometric generation of acetyl (CH₃CO⁺) ions by oxidation of mercury in acetic anhydride and in acetic acid/acetic anhydride (5:95, v/v) is described. Current/potential curves for solvents, titrated bases, indicator and mercury showed that in both these solvents mercury is oxidized at potentials which are much more negative than those for the titrated bases and other components present in the solution. Quinoline, triethanolamine, triethylamine, pyridine and quinolin-8-ol in acetic anhydride, as well as triethylamine, 2,2′-bipyridine, 2,4,6-collidine, pyridine and sodium acetate in acetic acid/acetic anhydride were titrated with acetyl ions generated by the oxidation of mercury. In this way, it was established that the oxidation of mercury to mercury (I) ions proceeds quantitatively with 100% current efficiency.     

Study of reaction of isomeric acetoxytoluenes with ozone in liquid phase in the presence of manganese bromide catalyst

The kinetics of the ozone reaction with isomeric acetoxytoluenes in acetic anhydride in the presence of sulfuric acid and mixed manganese bromide catalyst was studied. Under these conditions it is possible to stop the oxidation process at the stage of formation of hydroxybenzaldehydes in the form of the respective acetoxybenzylidendiacetates (63–70%). The reaction products contain also acetoxybenzyl acetate (16–18%) and a small amount of acetoxybenzyl bromide (2%). The mechanism of oxidation-reduction catalysis with manganese bromide complex explaining the experimental data was considered.