Free-electron attachment to coronene and corannulene in the gas phase

Electron attachment to the polyaromatic hydrocarbons coronene and corannulene is studied in the electron energy range of about 0-14 eV using a high-resolution crossed electron-neutral beam setup. The major anions observed are the parent anions peaking at about 0 eV with cross sections of 3.8 x 10(-20) and 1 x 10(-19) m(2), respectively. The only fragment anions formed in coronene and corannulene are the dehydrogenated coronene and corannulene anions. Other anions observed in the negative mass spectra at about 0 eV can be ascribed to impurities of the sample. High-level quantum-mechanical studies are carried out for the determination of electron affinities, hydrogen binding energies, and structures of both molecules. The behavior of coronene and corannulene upon electron attachment is compared with that of other polyaromatic hydrocarbons studied previously.     

Selective liquid adsorption and structural properties of montmorillonite and its hexadecylpyridinium derivatives

Summary An X-ray diffraction method was used to study the structures of montmorillonites, the surfaces of which were covered to a systematically increasing extent with hexadecylpyridinium (HDP) cations. It was found that, depending on the degree of cover of the surface, the HDP cations form a mono- or bimolecular layer in the interlayer space. A detailed investigation was made of the selective sorption of binary mixtures on montmorillonite and on HDP-montmorillonites with different surface coverages. The adsorption excess isotherms were determined, as were the adsorption capacities from analysis of the isotherms, and also the equivalent specific surface areas.It was established that from benzene-n-heptane mixtures the benzene is adsorbed only on the external surface of montmorillonite, while in the case of organocomplexes it causes moderate disaggregation.From benzene, alcohols with different numbers of carbon atoms are also preferentially adsorbed on the internal surfaces of montmorillonite; with the rise in the number of carbon atoms, the extent of interlamellar adsorption decreases. In the case of HDP-montmorillonites in methanol-benzene mixtures, the adsorption capacity exhibits a monotonous increase with the degree of organopbility in the range under consideration. In the event of optimum organophility the disaggregation of the organocomplex is complete, and the equivalent specific surface area is 764-778 m² · g^–1. The swelling of the organocomplex, which can be characterized by X-ray diffraction measurement, is in close correlation with the interlamellar liquid adsorption. The results show modification of the surface of montmorillonite with HDP cations fundamentally determines the nature and extent of the selective liquid adsorption.

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Zusammenfassung Die Struktur von mit Hexadecyl-pyridinium(HDP)-Kationen im systematisch gesteigerten Maße bedeckten Montmorilloniten wurde mit der Röntgendiffraktions-Methode untersucht. Es wurde festgestellt, daß die HDP-Kationen, von der Bedeckung der Oberfläche abhängend, im Schichtzwischenraum eine mono- bzw. bimolekulare Schicht bilden. Die selektive Sorption binärer Gemische wurde an Montmorilloniten und an HDP-Montmorilloniten verschiedener Bedeckung eingehend untersucht. Es wurden die Adsorptionsisothermen von Flüssigkeitsgemischen und aus deren Analyse die Adsorptionskapazitäten und die äquivalenten spezifischen Oberflächen bestimmt.Es wurde festgestellt, daß aus Benzol-n-Heptan-Gemischen das Benzol nur an der äußeren Montmorillonite-Oberfläche adsorbiert wird, während es bei Organokomplexen eine mäßige Desaggregation verursacht. Die Adsorption von Alkoholen verschiedener Kohlenstoffzahl aus Benzol erscheint auch an inneren Montmorillonit-Oberflächen bevorzugt; mit zunehmender Kohlenstoffzahl nimmt das Ausmaß der interlamellaren Adsorption ab. Bei HDP-Montmorilloniten zeigt die Adsorptionskapazität aus Methanol-Benzol-Gemischen mit zunehmender Organophilität im untersuchten Gebiet eine monotone Steigerung. Im Falle optimaler Organophilität ist die Desaggregation vollständig, die äquivalente spezifische Oberfläche beträgt 764-778 m²/g. Die durch Röntgenn-diffraktionsmessung charakterisierbare Quellung des Organokomplexes steht mit der interlamellaren Flüssig-keitsadsorption in engern Zusammenhang. Unsere Ergebnisse zeigen, daß Charakter und Ausmaß der selektiven Flüssigkeitsadsorption durch die Modifizierung der Montmorillonit-Oberfläche mit HDP-Kationen grundlegend verändert wird.

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With 14 figures and 4 tables     

Synthesis of racemic and optically active Δ1- and Δ6-3,4-cis-tetrahydrocannabinols1

Three syntheses of the hitherto unknown (±)-Δ⁶-3,4-cis-THC 4a and the first total synthesis of optically active Δ¹- and Δ⁶-cis-THC's are described. These syntheses utilize a stereospecific intramolecular epoxide opening by phenolate anion; an acid catalyzed equilibration of Δ¹- and Δ⁶-cis-THC acetates; and a kinetically controlled dehydration. The use of HPLC, GLC and NMR for the separation and identification of closely related THC's is discussed.     

Chemistry of thienopyridines. VII. Mechanistic studies on the synthesis of thieno[2,3-c] pyridine by thermolytic cyclization

A study was made of the formation of thieno[2,3-c]pyridine (1) from hydrogen sulfide and 4-vinylpyridine in a flow system at 630°. 2-(4-Pyridyl)ethanethiol and bis-2-(4-pyridyl)ethyl sulfide were found to be likely intermediates. Based on these studies, there was devised a two-step practical preparative method for I (optimum overall yield 58%) which consists of preliminary conversion of 4-vinylpyridine to benzyl 2-(4-pyridyl)ethyl sulfide and subsequent thermolysis (at 605°) of this substance.     

Studies on antianaphylactic agents—I : A facile synthesis of 4-oxo-4H-1-benzopyran-3-carboxaldehydes by Vilsmeier reagents

By the application of the Vilsmeier-Haack reaction to various o-hydroxyacetophenone derivatives, 4-oxo-4H-1-benzopyran-3-carboxaldehydes were synthesized in one step. Their IR, NMR and mass spectra were studied. In the mass spectra characteristic fragmentation pathways were observed.     

Translational energy disposal in molecular collisions: The transfer of momentum constraint

A Franck—Condon type argument, which requires the least transfer of momenta to the nuclei during a collision is outlined and applied to the analysis of translational energy disposal and its dependence on the initial translational energy. Using the maximal entropy procedure of information theory we are able to proceed directly from the assumed (model) constraint to the product state distribution.     

A thermochemical study of acid-base interactions in aqueous solutions of citric acid

The heat effects of interaction of a solution of citric acid with HNO₃ and KOH were measured calorimetrically at 298.15 K and ionic strengths of 0.5, 1.0, and 1.5 (KNO₃). The heat effects of acid dissociation were calculated using the universal HEAT program. The standard thermodynamic characteristics of step dissociation of citric acid were determined.     

The synthesis of diene and of vinyl copolymers containing predetermined quantities of polynuclear hydrocarbon or heterocyclic adducts—IV. Copolymers of butadiene or isoprene,anthracene and a linking agent

Evidence is given that, when solutions of diene monomers and anthracene in tetrahydrofuran are reacted with alkali metal and subsequently titrated with linking agents such as alkyl dihalides, copolymers are formed; they contain the 9,10-dihydroanthracene adduct and the diene in the same proportion as in the original solution. The structures of these copolymers have been elucidated by NMR spectroscopy and the mechanism of formation is discussed.     

Qy-excitation resonance Raman spectra of chlorophyll a and bacteriochlorophyll c/d aggregates. Effects of peripheral substituents on the low-frequency vibrational characteristics

Low-frequency (80-700 cm-1) Qy-excitation resonance Raman (RR) spectra are reported for thin-solid-film aggregates of several chlorophyll (Chl) a and bacteriochlorophyll (BChl) c/d pigments. The pigments include Chl a, pyrochlorophyll a (PChl a), methylpyrochloropyllide a (MPChl a), methylbacteriochloropyllide d (MBChl d), [E,M] BChl cS, [E,E] BChl cF, and [P,E] BChl cF. The BChl c/d's are the principal constituents of the chlorosomal light-harvesting apparatus of green photosynthetic bacteria. Together, the various Chl a's and BChl c/d's represent a series in which the peripheral substituent groups on the chlorin macrocycle are varied in systematic fashion. All of the Chl a and BChl c/d aggregates exhibit rich low-frequency vibrational patterns. In the case of the BChl c/d's, certain modes in the very low-frequency region (100-200 cm-1) experience exceptionally strong Raman intensity enhancements. The frequencies of these modes are qualitatively similar to those of oscillations observed in femtosecond optical experiments on chlorosomes. The RR data indicate that the low-frequency vibrations are best characterized as intramolecular out-of-plane deformations of the chlorin macrocycle rather than intermolecular modes. The coupling of the out-of-plane modes in turn implies that the Qy electronic transition(s) of the aggregate have out-of-plane character. The RR spectra of the BChl c/d's also reveal that the nature of the alkyl substituents at the 8 and 12 positions of the macrocycle plays an important role in determining the detailed features of the low-frequency vibrational patterns. The frequencies of the modes are particularly sensitive to larger substituent groups whose conformations may be more easily perturbed in the tightly packed aggregates. These factors also make aggregates of pigments containing larger substituents more susceptible to structural, electronic, and vibrational inhomgeneities. Collectively, the RR studies of the various pigments delineate the factors which influence the low-frequency vibrational characteristics of chlorosomal aggregates.