Search results for "AROMA"

CO2 as a C1-organic building block: Electrocarboxylation of aromatic ketones. A quantitative study of the effect of the concentration of substrate an…

2006

The purpose of this work is to establish and discuss quantitative relationships between the selectivity in preparative scale electrolysis and intrinsic and operational parameters for the electrocarboxylation of aromatic ketones. For the investigated ketones, under appopriate experimental conditions the selectivity of the process is mainly determined by the competition between carboxylation and protonation, de-halogenation reactions (when an halogenated ketone is involved), and possibly dimerizations involving the electrogenerated radical anion. A simple model was proposed to account for these unwanted side paths which allows to predict the dependence of the selectivity as a function of the …

On the relations between aromaticity and substituent effect

2019

Aromaticity/aromatic and substituent/substituent effects belong to the most commonly used terms in organic chemistry and related fields. The quantitative description of aromaticity is based on energetic, geometric (e.g., HOMA), magnetic (e.g., NICS) and reactivity criteria, as well as the properties of the electronic structure (e.g., FLU). The substituent effect can be described using either traditional Hammett-type substituent constants or characteristics based on quantum-chemistry. For this purpose, the energies of properly designed homodesmotic reactions and electron density distribution are used. In the first case, a descriptor named SESE (energy stabilizing the substituent effect) is o…

1978

The thermal degradation mechanism of three aromatic polymers containing double bridged phenylether units was investigated by direct pyrolysis in the ion source of a mass spectrometer. Thermal degradation reactions were followed directly by this method detecting the thermal and electron impact induced fragments. The results obtained have provided evidence that the double bridge between the aromatic rings is the preferred fragmentation site in these polymers. Furthermore in the double sulfur bridged polymer III, extrusion of S2 from the polymer backbone takes place above 400°C. The synthesis of polymers studied is reported in the text. Der Mechanismus des thermischen Abbaus von drei aromatisc…

Saturated vapour pressure of aroma compounds at various temperatures

2004

Abstract The aim of this study was to determine experimentally the vapour pressures of aroma compounds at various temperatures, especially at negative ones. The aroma compounds were: acetone, 2-butanone, 2-hexanone, 2-octanone, ethyl acetate, ethyl butanoate, ethyl hexanoate, n-hexanal, n-hexanol and γ-hexalactone. The technique used was a static device where vapour pressure was measured at equilibrium. The temperatures of analysis varied from −40 to 25 °C. Volatility of a pure compound depends on characteristics such as length of the aliphatic chain, the functional group and temperature. Among an homologous series, volatility increases when the aliphatic chain decreases and when temperatur…

Lauroyl peroxide as thermal initiator of lauryl methacrylate monolithic columns for CEC

2008

The preparation of lauryl methacrylate (LMA)-based monolithic columns for CEC using lauroyl peroxide (LPO) as thermal initiator of polymerization has been investigated. The influence of initiator amount and composition of porogenic solvent on the physical and electrochromatographic properties of the resulting LMA-based monoliths was evaluated. A comparison with LMA-based columns thermally polymerized with AIBN was performed. At a given porogenic solvent composition, LMA stationary phases initiated with LPO showed higher permeabilities and better efficiency values than those prepared using AIBN as initiator. The optimum polymerization mixture found for LPO initiator provided a minimum plate …

Fluidity of liposome membranes doped with organic tin compounds: ESR study.

2008

The kinetics of change in the fluidity of liposome membranes, obtained in the process of sonication of Egg Yolk Lecithin (EYL), with the admixture of organic tin compounds, was investigated. Five compounds were selected for the research: three differed in the length of hydrocarbon chains, (CH(3))(4)Sn, (C(2)H(5))(4)Sn, and (C(3)H(7))(3)SnCl, whereas two differed in the number of aromatic rings, (C(6)H(5))(2)SnCl(2) and (C(6)H(5))(3)SnCl. The concentration of the compounds in proportion to EYL was 2 mol-%. Electron Spin (paramagnetic) Resonance (ESR) was applied using two spin probes TEMPO (2,2,6,6-tetramethylpiperidine-1-oxyl) and 16-DOXYL-stearic acid methyl ester (2-ethyl-2-(15-methoxy-15…

Interactions between aroma and edible films. 1. Permeability Of methylcellulose and low-density polyethylene films to methyl ketones.

1998

This work contributes to the study of aroma transfers through edible and plastic packaging films. Permeability, sorption, and diffusivity of three methyl ketones (2-heptanone, 2-octanone, and 2-nonanone) in and through low-density polyethylene and methylcellulose-based edible films have been determined. Permeability was measured using a dynamic method coupled with a gas chromatograph. The methyl ketone permeability of polyethylene films mainly depends on diffusivity of the penetrant in the polymer. In the case of 2-heptanone, a saturation of the polymer network is observed at high vapor concentrations. The formation of clusters could take place when concentrations are higher in the vapor ph…

Salt and fat contents influence the microstructure of model cheeses, chewing/swallowing andin vivoaroma release

2013

The effects of the lipid/protein ratio (20/28, 24/24, 28/20) and salt content of model cheeses were investigated simultaneously with respect to chewing behaviour, swallowing events and in vivo aroma release. Chewing parameters were measured by electromyography. Swallowing events were recorded manually. In vivo aroma release was investigated using nose-space on-line atmospheric pressure chemical ionisation-mass spectrometry. The values for chewing activity and time before swallowing were higher with lower lipid/protein ratios and lower salt contents, due to the greater mechanical resistance of the model cheeses. The corresponding microstructure was made up of smaller and more circular fat dr…

Five-to-Six Membered Ring-rearrangements in the Reaction of 5-Perfluoroalkyl-1,2,4-oxadiazoles with Hydrazine and Methylhydrazine

2006

The hydrazinolysis reaction of 5-perfluoroalkyl-1,2,4-oxadiazoles with hydrazine or methylhydrazine as bidentate nucleophiles has been investigated. The reaction occurred through the addition of the bidentate nucleophile to the C(5)-N(4) double bond of the 1,2,4-oxadiazole followed by ring-opening and ring-closure (ANRORC) involving the second nucleophilic site of the reagent. This ring-closure step could involve either the original C(3) of the 1,2,4-oxadiazole (giving a five-to-five membered ring rearrangement) or an additional electrophilic center linked to it (exploiting a five-to-six membered ring rearrangement). An alternative initial nucleophilic attack may involve the additional elec…

On the aromaticity of uracil and its 5-halogeno derivatives as revealed by theoretically derived geometric and magnetic indexes

2020

AbstractThe problem of aromaticity in heterocyclic rings of uracil and its 5-halogenoderivatives (5XU) was analyzed theoretically by calculating modified harmonic oscillator model of aromaticity (HOMA) for Heterocycle Electron Delocalization (HOMHED), nucleus-independent chemical shift parameters (NICS) and the so-called scan experiments, using helium-3 atom as a magnetic probe. The impact of halogen electronegativity on C5 atom’s NBO charges was also investigated. Water, as a polar environment, has a negligible impact on 5XU aromaticity. The most stable diketo tautomer shows a very low aromaticity while the “rare” dihydroxy form (tautomer No 6) is aromatic and resembles benzene. This is in…