Because a flame ionization detector (FID) is based on the combustion of analytes, we have previously shown that a good correlation exists between the relative response factors (RRFs) and the combustion enthalpies. The latter can themselves be predicted by ab initio calculation, or directly from the molecular formula. As a consequence, the RRFs can be simulated with good accuracy for all volatile constituents of flavours and fragrances. The technique is exemplified here with several applications in the field of flavours and fragrances. The composition of complex mixtures by full internal standardization is very time consuming. This task can be greatly shortened with satisfactory accuracy if predicted RRFs are used instead of the inaccurate semi‐quantification (all RRFs = 1). Non‐commercially available compounds normally require re‐synthesis to determine their RRFs. This time‐consuming step can be avoided and the compounds well quantified by using predicted RRFs. In addition, with unstable standards, measuring their RRFs or purities is impossible, whereas this issue is overcome with the present technique. We herein report the successful testing of the predicted RRFs in comprehensive GC×GC‐FID. Copyright © 2012 John Wiley & Sons, Ltd.

Alkyl or aryl a-keto esters of primary or secondary alcohols decompose upon irradiation at 350 ± 370 nm from the intermediate triplet state into aldehydes or ketones in polar, as well as apolar solvents. The use of these keto esters as delivery systems for the controlled release of perfumery aldehydes and ketones was investigated by photoirradiation in the presence of oxygen with a Xe or UV lamp, as well as outdoor sunlight. Systematic GC/ MS analysis of the irradiated solutions showed that, under these conditions, the desired Norrish type-II fragmentation of the ester side chain is the predominant reaction pathway in most of the cases. g-H Abstraction from the alkyl side chain of alkyl keto esters, as well as an intramolecular PaternoÁ-Büchi reaction or epoxidation of the alkene function in different citronellyl a-keto esters were identified as the most important side reactions. Some of the experimental findings have been rationalized on the basis of ab initio and density-functional calculations. (Cyclohexyl)oxoacetates and oxo(phenyl)acetates were found to be the most suitable precursors for the desired perfumery applications.1. Introduction. ± Aldehydes and ketones are important classes of fragrances that are present in all kinds of perfumes. However, many of them are very volatile and can, after application, only be perceived over a relatively short period of time. Furthermore, as constituents of perfumes for a variety of different bodycare or household applications, such as shampoos, soaps, all purpose cleaners, fabric softeners, or detergent powders, they are often too hydrophilic and thus easily carried away by water during various rinsing processes instead of staying on substrates like hair, skin, or fabrics.To prolong the desired odor perception of this class of compounds, we have prepared a series of photolabile, hydrophobic, non-volatile fragrance precursors as potential delivery systems for the controlled release of perfumery aldehydes and ketones in typical bodycare and household applications. In this publication, we describe the fragrance release from a-keto esters upon irradiation with artificial light sources, as well as natural sunlight in the presence of O 2 [1]. Some interesting fragrances for release in functional perfumery are depicted in Fig. 1 [2].The photolysis of alkyl or aryl a-keto esters of primary or secondary alcohols has been intensively studied since the early sixties [3 ± 7]. It was found that these esters decompose from their intermediate triplet state into aldehydes or ketones upon irradiation at 350 ± 370 nm in polar, as well as apolar solvents [7 ± 11]. Most of the photoirradiations described in the literature were carried out in degassed solutions in the absence of O 2 . The relatively good yields of the fragmentation process have allowed the use of a-keto esters as intermediates for the transformation of primary or secondary alcohols to aldehydes and ketones, respectively [12].

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Among the few papers related to the gas chromatography (GC)-olfactometric determination of important odorants in cooked beef aroma, only one uses roasting conditions, but none of them investigates the appealing aroma during the cooking of the piece of meat. The present paper investigates this top note as perceived from the oven, by analyzing the oven headspace using GC-"SNIF", a GC-olfactometric technique. From the different functional classes of odorants participating in overall in-oven aroma, this first paper focuses only on the role of aldehydes and ketones, as they represent the majority of aroma compounds formed during cooking. To ascertain the identification of these odorants, a microderivatization technique was used, based on (2,3,4,5,6-pentafluorophenyl)hydrazine. The resulting hydrazones exhibit very specific mass spectrometric fragments, leading to a sensitive and specific detection. A total of 23 carbonyl compounds were shown to contribute to the roast beef top note.