The two diastereomers of [3] (2,5) (7,7,8,8-tetracyanoquinodimethano) - [3] (2,5-dimethoxyparacyclophane)

As the first set of stereomeric donor-acceptor cyclophanes with TCNQ as an acceptor, $\text{1}$ and $\text{2}$ were synthesized; their charge-transfer absorptions differ strongly as a consequence of the different donor-acceptor orientation.     

Mass spectrometric fragmentation of S-(1-aryltetrazol-5-yl)-monothiocarbonic acid esters

The mass spectra of S-(1-aryltetrazol-5-yl)-monothiocarbonic acid esters have been studied. The stability of the ester molecular ions is lower than the stability of the corresponding 1-aryl-5-mercaptotetrazoles. Substituents at the phenyl group increase the stability, whereas the influence of the ester alkyl groups is very small. The esters undergo fragmentation via four different fragmentation pathways. The elimination of carbon dioxide is influenced by an ‘ortho effect’ of the substituents.     

Photoisomerisierung und Relaxation symmetrischer Triazacarbocyanine in einem Alkoholgemisch

Photoisomerization and Relaxation of Symmetrical Triazacarbocyanine Dyes in an Alcoholic Mixture at Low Temperature The partial photobleaching of a series of symmetrical triazacarbocyanine dyes with different heterocycles in EtOH/MeOH/i-PrOH at low temperature (110 to 250 K) was investigated by UV/VIS spectra. Kinetic data of the dark reaction of photobleached compounds are given. The effect of electron-donating or -accepting substituents, respectively, and of protonation of the photobleached compound on kinetic data and on UV/VIS spectra was studied. Products of photobleaching and mechanisms of the dark reaction are discussed.     

Die Cope-Umlagerung als Prinzip einer repetierbaren Ringerweiterung

The Cope Rearrangement, a Reaction for Repeatable Ring Expansions Starting with the unsaturated β-ketoesters of type I, a vinyl group is introduced into the β-position by 1,4-addition of vinyl magnesium chloride to give II (Scheme 3). Treatment of the β-ketoester II with phenyl vinyl sulfoxide in the presence of sodium hydride yields the sulfoxides III, which on thermolysis lead to the α, β-divinyl ketoesters of type IV via elimination of sulfinic acid (Scheme 3). The Cope-System IV undergoes rearrangement to V, which is again an unsaturated β-ketoester. The latter is suitable for a further ring expansion sequence. These reaction steps were carried out with the nine-, twelve- and fifteen-membered ketoesters 32, 33 and 34 , as well as with the open-chain compound 35 (Table 1). With the cyclohexane derivative 31 , ring expansion could not be achieved with the described sequence.     

Zum Mechanismus massenspektrometrischer Fragmentierungsreaktionen: XII-Einfluß einer sterischen Hinderung der Mesomerie bei der Fragmentierung von N,N-Dimethyl-N′-4-Biphenylformamidinen

The formation of cyclic [M ? H]⁺ ions (a) in the mass spectra of N,N-dimethyl-N′-arylformamidines is suppressed by electron donating groups in the aryl group para to the formamidine group, due to the participation of resonance structures of type c. This effect is also observed in the mass spectra of N,N-dimethyl-N′-4-biphenylformamidines (III) substituted in the 4′-position. By substitution in the 2-, 2′-, 6- and 6′- positions of III, the formation of resonance structure c′ in the molecular ions is so difficult that these derivatives show the normal fragmentations. This is observed with two methyl groups in the 2- and 2′- positions of III.     

Connected and alternating vectors: Polyhedra and algorithms

Given a graphG = (V, E), leta ^S, S L, be the edge set incidence vectors of its nontrivial connected subgraphs.The extreme points of = {x R ^E: a^sx |V(S)| - |S|, S L} are shown to be integer 0/± 1 and characterized. They are the alternating vectorsb ^k, k K, ofG. WhenG is a tree, the extreme points ofB 0,b ^kx 1,k K} are shown to be the connected vectors ofG together with the origin. For the four LP's associated with andA, good algorithms are given and total dual integrality of andA proven.On leave from Swiss Federal Institute of Technology, Zurich.     

Zur katalytischen Bestimmung von Kupferspuren

Zusammenfassung Das Verfahren beruht auf der Mitfällung der Kupferspuren an Quecksilbersulfid mit Natriumthiosulfat, Entfernung des Hg und katalytischer Bestimmung des Cu mit Hilfe der rhodanidindizierten Eisen(III)-Thiosulfatreaktion nach der Simultankomparationsmethode [2]. Es gestattet die Bestimmung von Kupferspuren bis 5 · 10^–6% (gegebenenfalls 0,01 ppm) in beispielsweise Alkali-, Mg-, Ca-, Sr-, Zn-, Mn-, Co-, Ni-, Al-, Cr-, Cd-Salzen, Borsäure, Salzsäure und anderen Substanzen. Die Verbindungen dürfen nicht als Nitrate vorliegen oder andere Oxydationsmittel sowie stark komplexbildende Anionen enthalten. Mitgeteilte Modelluntersuchungen an AlCl₃ und ZnCl₂ (Cu-Gehalt 0,1 ppm) ergaben in letzterem Falle eine Varianz S von rund 3%.

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On the catalytic determination of traces of copperII. Isolation of traces of copper by coprecipitation with mercury sulphide and their catalytic determination according to the simultaneous-comparison method

The procedure is based on the coprecipitation of traces of copper with mercury sulphide by means of sodium thiosulphate, removal of the mercury and catalytic copper determination by means of the simultaneous-comparison method using the reaction between iron(III) thiocyanate and thiosulphate [2]. Traces of copper down to 5×10^–6% (0.01 ppm) can be determined in alkali, Mg, Ca, Sr, Zn, Mn, Co, Ni, Al, Cr and Cd salts, in boric acid, hydrochloric acid and other substances. Nitrates and other oxidizing agents and also strongly complexing anions must be absent. Results with AlCl₃ and ZnCl₂ (Cu content 0.1 ppm) are given. In the latter case the variation was about 3%.

     

Die konformationsenergie des ferroc̄enylrestes

From equilibration experiments with ferrocenyl cyclohexanes substituted at position 4, an average conformational free enthalpy of 2.9±0.1 kcal/mole was established for the ferrocenyl group. The spatial requirement of ferrocenyl at the equilibrium equatorial ? axial is approximately equivalent to that of the phenyl residue (3.0±0.1 kcal/mole).     

On the correlation of implantation defects and implanted species

Using high-sensitive deep level transient spectroscopy (DLTS), we have determined ion-related defects in monocrystalline silicon in the asimplanted state. In comparison with secondary ion mass spectrometry (SIMS) data and neutron depth profiling (NDP) results it is demonstrated that the defect profiles and the chemical distributions have nearly identical shape. From these experimental facts it can be concluded that this electrical spectroscopy can be applied for the detection of very low concentrations (down to 10¹⁰ cm^–3) of implanted ion species.     

Photochemical Z-->E isomerization of a hemithioindigo/hemistilbene omega-amino acid.

The molecule HTI, which combines hemithioindigo and hemistilbene molecular parts, allows reversible switching between two isomeric states. Photochromic behaviour of the HTI molecule is observed by irradiation with UV/Vis light. The photochemical reaction, a Z/E isomerization around the central double bond connecting the two molecular parts, is investigated by transient absorption and emission spectroscopy. For a special HTI molecule, namely, an omega-amino acid, the Z-->E isomerization process occurs on a timescale of 30 ps. In the course of the reaction fast processes on the 1-10 ps timescale are observed which point to motions of the molecule on the potential-energy surface of the excited state. The combination of transient absorption experiments in the visible spectral range with time-resolved fluorescence and infrared measurements reveal a photochemical pathway with three intermediate states. Together with a theoretical modelling procedure the experiments point to a sequential reaction scheme and give indications of the nature of the involved intermediates.