Search results for "AROMATICITY"

Zirconocene-Based Methods for the Preparation of BN-Indenes : Application to the Synthesis of 1,5-Dibora-4a,8a-diaza-1,2,3,5,6,7-hexaaryl-4,8-dimethy…

2017

A method for the preparation of 3-bora-9aza-indene heterocycles based on zirconocene mediated functionalization of the ortho-CH bonds of pyridines has been developed and used to make two such compounds. Unlike other methods, the boron center in these heterocycles remains functionalized with a chloride ligand and so the compounds can be further elaborated through halide abstraction and reduction. The utility of the method was further demonstrated by applying it towards the preparation of 1,5- dibora-4a,8a-diaza BN analogues of the intriguing hydrocarbon s-indacene starting from 2,5-dimethylpyrazine. Gram quantities of one such compound was prepared and fully characterized, and both experimen…

UHPLC-Orbitrap mass spectrometric characterization of organic aerosol from a central European city (Mainz, Germany) and a Chinese megacity (Beijing)

2018

Abstract Fine urban aerosol particles with aerodynamic equivalent dimeter ≤2.5 μm (PM2.5) were collected in Mainz (a city within the Rhine-Main area, the third largest metropolitan region in Germany) and Beijing (Chinese megacity). A solvent mixture of acetonitrile-water was used to extract the organic aerosol fraction (OA) from the particle samples. The extracts were analyzed by an ultrahigh resolution mass spectrometer (UHRMS) Orbitrap coupled with ultra-high-performance liquid chromatography (UHPLC) both in the negative and positive ion mode. The number of compounds observed in Beijing is a factor of 2–10 higher compared to Mainz. The clear differences on chemical composition of OA in th…

Geometric and electronic structure of dithiapyranylidine: evolution upon oxidation

1993

Abstract We present a theoretical investigation of the modifications that successive oxidation induces on the geometric and electronic structures of the π-electron donor dithiapyranylidene. The lengthening of the double bonds and the shortening of the single bonds calculated as the molecular charge increases indicate a gain of aromaticity with oxidation. Both the geometricand the electronic structure of dithiapyranylidene show a clear evolution towards those of biphenyl as oxidation takes place.

Untersuchungen von polymeren im massenspektrometer, 3. Fragmentierungsreaktionen oligomerer benzyle

1974

Beim thermischen Abbau von Polybenzylen im Massenspektrometer werden oligomere Benzylbruchstucke mit gesattigten (Phenyl-, Alkyl-) und ungesattigten (Chinonmethid)-Endgruppen gebildet. Zur Differenzierung der thermischen und elektronenstosinduzierten Abbaureaktionen wurden die Fragmentierungsreaktionen oligomere Benzyle vom Typ 1a, b im Massenspektrometer untersucht. Bei Anwendung niedriger Elektronenstosenergien wurden als Hauptfragmentierungsreaktionen Alkyl-, α-Benzyl- und β-Benzylspaltung sowie die fur 1,2-disubstituierte Benzyle strukturspezifische ortho-Umalgerung gefunden, die eine Differenzierung stellungsisomerer Oligobenzyle ermoglicht. Die genannten Reaktionen wurden durch Hochau…

N-[3-(5-Oxo-10,11-dihydro-5H-dibenzo[a,d]cyclohepten-2-ylamino)phenyl]furan-3-carboxamide

2010

In the title compound, C26H20N2O3, the two aromatic rings of the tricyclic unit are oriented at a dihedral angle of 54.53 (9)°. The crystal structure displays intermolecular N—H...O hydrogen bonding.

Chemical characterization of peat fulvic acid fractions

1993

Abstract Milled peat fulvic acid (FA) preparation was fractionated by XAD-8 and conventional extraction methods. The fractions were further analyzed by IR and NMR and subjected to cupric oxide (CuO) oxidation. Carbohydrates of polydisperse FA were mostly not retained in the XAD-8 fractionation. The intensity of the signals due to double bonded carbons was much greater in the 13 C and proton NMR spectrum of the XAD-8 retained fraction than in the spectra of the XAD-8 non-retained or XAD-8 non-treated fractions. In CuO oxidation the main products of all FA fractions were 4-hydroxybenzaldehyde and 4-hydroxyacetophenone, both indicators of 4-hydroxyphenylpropane building blocks. Their concentra…

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…

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…

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…