Hydroacridines XXV [1]. First Synthesis of (4aα,8aα,9aβ,10aβ)-Tetradecahydroacridine and New Syntheses of (4aα,8aα,9aα,10aβ)- and (4aα,8aβ,9aα,10aβ)-Tetradecahydroacridine

Summary. On heating in dry DMSO, in the presence of potassium t-butoxide, the N-nitrosamine of (4aα,8aβ,9aβ,10aα)-tetradecahydroacridine is completely converted into the N-nitrosamine of (4aα,8aα,9aα,10aβ)-tetradecahydroacridine. Under similar conditions, the N-nitrosamine of (4aα,8aα,9aβ,10aα)-tetradecahydroacridine yields a ternary equilibrium mixture containing itself (19%), and the N-nitrosamines of (4aα,8aβ,9aα,10aβ)-tetradecahydroacridine (46%) and the so far unknown (4aα,8aα,9aβ,10aβ)-tetradecahydroacridine (35%). The resulting N-nitrosamines can be smoothly denitrosated to the corresponding secondary amines.     

Thermal behaviour of <Emphasis Type="Italic">sym</Emphasis>-octahydroacridines and their corresponding N(10)-oxides

We present and discuss results on the thermal behaviour of 1,2,3,4,5,6,7,8-octahydroacridine (OHA), together with six 9-substituted congeners, i.e. R = –Br, –OCH₃, –NH₂, –NO₂, –OH, and furyl (–C₄H₃O), and their corresponding N(10)-oxides, under nitrogen atmosphere and with alumina as reference, at a heating rate of 5 °C min^?1 from room temperature to 300 °C. Chromatography has been carried out on aluminium sheets, with aluminium oxide 60 F254 neutral (Merck). Melting effects are observed for almost all compounds in their corresponding curves, precisely determined by using a Boetius apparatus. Homolysis of the carbon-substituent bond occurs in most cases, a phenomenon which is consistent with the values of the bond dissociation energy. For all compounds, except for hydroxyl congeners, thermal decomposition started with an endothermic peak. Octahydroacridines readily decompose into volatile products, an effect which correlates with their low melting points, while little amounts of residue remain in place of the aromatic amines compared to the N(10)-oxides. The presence of N–O bonds greatly influences the thermal stability of the compound, in the sense of increasing it compared with the parent amine. Quantitative studies of the decomposition products reveal that the melting points, the 9-position substituent, and N–O bond all play an important role upon the thermal behaviour. Mechanistic/kinetic pathways are also proposed as such results are important in further designing laser processing protocols, i.e. matrix-assisted pulsed laser evaporation (MAPLE) or laser-induced forward transfer (LIFT), for thin film deposition and/or device printing.     

Saturated amine oxides: part 10. hydroacridines: part 32. linear 17O/13C and 13C/13C chemical shift correlations between saturated azaheterocyclic N‐methylamine N‐oxides,and the methiodides of their parent amines

Two kinds of good linear correlations were found between the chemical shifts of saturated six‐membered azaheterocyclic N‐methylamine N‐oxides and the chemical shifts of the methiodides of their parent amines. One of the correlations occurs between the ¹⁷O chemical shift of the N⁺―O^– oxygen in the N‐oxides and the ¹³C chemical shift of the N⁺―CH₃ methyl group analogously situated in the appropriate methiodide (r = 0.9778). This correlation enables unambiguous configuration assignment of the N⁺―O^– bond, even if the experimentally observed ¹⁷O chemical shift of only one N‐epimer is available, provided the ¹³C chemical shifts of both N⁺―CH₃ groups in the methiodide are known and assigned; furthermore, it can be used also for the estimation of ¹⁷O chemical shifts of the N⁺―O^– oxygens in N‐epimeric pairs of N‐oxides, for which observed ¹⁷O data hardly become available. The second correlation is observed between the ¹³C chemical shift of the N⁺―CH₃ methyl group in the N‐oxides and the ¹³C chemical shift of the N⁺―CH₃ methyl group analogously situated in the appropriate methiodide (r = 0.9785). It can be used for safe configuration assignment of the N⁺―CH₃ group and, indirectly, also of the N⁺―O^– bond in an amine N‐oxide, even if no ¹⁷O NMR data, and the ¹³C chemical shift of only one N‐epimer is available. Copyright © 2015 John Wiley & Sons, Ltd.     

Fatty acid composition of lipids in pot marigold (Calendula officinalis L.) seed genotypes

Background

The process of thermal decomposition of dichloromethane (DCM) and chlorobenzene (MCB) during the combustion in an inert, bubbling fluidized bed, supported by LPG as auxiliary fuel, have been studied. The concentration profiles of C₆H₅CI, CH₂Cl₂, CO₂, CO, NO_x, COCl₂, CHCl₃, CH₃Cl, C₂H₂, C₆H₆, CH₄ in the flue gases were specified versus mean bed temperature.

Results

The role of preheating of gaseous mixture in fluidized bed prior to its ignition inside bubbles was identified as important factor for increase the degree of conversion of DCM and MCB in low bed temperature, in comparison to similar process in the tubular reactor.

Conclusions

Taking into account possible combustion mechanisms, it was identified that autoignition in bubbles rather than flame propagation between bubbles is needed to achieve complete destruction of DCM and MCB. These condition occurs above 900°C causing the degree of conversion of chlorine compounds of 92-100%.     

Comparative analysis of lipophilic compounds in eggs of organically raised ISA Brown and Araucana hens

Hens?? eggs represent a rich source of important nutrients, including lipids and carotenoids. The lipid composition of hens?? eggs is influenced by genetic factors, age, and diet. The aim of this study was to compare the fatty acids, cholesterol, and carotenoids content of the egg yolk of ISA Brown and Araucana hens grown in free-range housing systems. Fatty acids and cholesterol were analysed by GC-FID and GC-MS and carotenoids were quantified by RP-HPLC-PDA. The Araucana egg yolk has a higher lipid content and higher egg-to-albumen ratio than the ISA Brown yolk, while the total cholesterol, carotenoids content and profile are not significantly different. The lipids of the Araucana egg yolk have a higher content of mono-unsaturated fatty acids (MUFAs), eicosapentaenoic acid (EPA), and docosahexaenoic acid (DHA) and a better n-6/n-3 ratio than the ISA Brown egg yolk lipids. The major carotenoids were lutein and zeaxanthin, which account for more than 83 % in egg yolk. Eggs of both breeds, when raised organically, represent very good sources of highly bio-available lutein and zeaxanthin, pigments which are related to lower risk of age-related macular degeneration. We report for the first time on the fatty acids composition in lipid fractions and the profile and content of carotenoids of the Araucana egg yolk.