A novel mild methodology for the preparation of o-hydroxybenzyl ketones is described starting from o-alkenyl phenols and based on the VO(acac)(2)/TBHP (2 mol %/1.2 equiv) system. VO(acac)(2) first catalyzes the epoxidation of o-alkenyl phenols and then the rearrangement of the epoxyphenols to ketones via the selective benzylic C-O cleavage and 1,2 hydride migration. The protocol has also been applied to set up a useful and easy one-pot conversion of o-alkenyl phenols to benzo[b]furans by means of the sequential addition of TFA, after the generation of the intermediate o-hydroxybenzyl ketones.

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Vinegar is produced from the fermentation of agricultural materials and diluted acetic acid (diluted with water to 4–30% by volume) via sequential ethanol and acetic acid fermentation. The concentration of acetic acid must be measured during vinegar production. A Community method for analyzing acetic acid in vinegar is a non-specific method based on the assumption that the total acid concentration of the vinegar is attributable to the acetic acid. It consists of titration with a strong base in the presence of an indicator. This test is laborious and has a time-consuming character. In this work, a highly specific automated enzymatic method was validated, for the first time, to quantify the acetic acid in the wine vinegar, in terms of linearity, precision, repeatability, and uncertainty measurement. The results were compared to the Community method of analysis. Regression coefficient ≅ 1 and the normal distribution of residuals in the ANOVA test confirmed the method’s linearity. LLOD (0.946 ppm) and LLOQ (2.00 ppm) defined the method’s sensitivity. The results of the tested and the Community methods, linearly distributed in the Shapiro–Wilk test, confirmed the method’s repeatability. The few anomalous data in the Huber test were due to random errors. The high selectivity of the enzymatic method, which exclusively measures acetic acid concentration, determined the significant differences between the two tests, examined in the accuracy determination. The enzymatic method can be considered applicable since its precision and uncertainty were lower than the Community method values (relative percentage deviations = 10%). The enzymatic method compared to the Community method reduces the analysis time and the risk of errors due to operators (avoid pipetting errors and wrong calculations), minimizes solvent and the sample consumption and guarantees assay quality through method standardization.

KetonesKetones Q 0350 Novel Highly Regioselective VO(acac) 2 /TBHP Mediated Oxidation of o-Alkenyl Phenols to o-Hydroxybenzyl Ketones. -In addition to the title reaction of phenols (I) yielding ketones (II), a one-pot conversion of these phenols to benzofurans (V) is reported involving the oxidation and subsequent treatment with TFA. In the case of phenols (III), epoxides (IV) are isolated from the oxidation reaction. Probably, steric factors prevent further rearrangement of the epoxides to the desired ketones. -(LATTANZI*, A.; SENATORE, A.; MASSA, A.; SCETTRI, A.; J. Org. Chem. 68 (2003) 9, 3691-3694; Dip. Chim., Univ. Salerno, I-84081 Baronissi, Salerno, Italy; Eng.) -Klein 35-077

The determination of alcohol, SO2, and total acids in wine through conventional laboratory techniques have some limitations related to the amount of the samples, analytical preparation of laboratory staff, and time to carry out the analysis. In recent years, spectroscopic and chromatographic methods have been proposed to determinate simultaneously multiple analytical parameters. The new methods claim the speed of analysis and easy execution. However, they need a validation process that guarantees the reliability of the results to be used in official determinations. This study aimed to evaluate the usefulness of FT-infrared reflectance (FT-IR) to quantify total acid, alcohol, and SO2 concentration in the wines. For this purpose, 156 DOC Italian wines were tested with IR technology, and results were compared to those obtained by official analysis methods. The comparison was performed using two non-parametric statistical methods: the Bland & Altman test and Passing & Bablok regression. Our results showed that the spectrophotometric methods make errors due to interfering contaminants in the sample that can be corrected by blank determination. Therefore, the spectrophotometric methods that use the infrared region of the electromagnetic spectrum can be used by the wine industry and regulators for the wine routine as an alternative to official methodologies.