Synthesis of Tricyclic (λ5)-Phosphoranes; unusual N-demethylation/N-alkylation reactions during the oxidative addition of hexafluoroacetone and tetrachloro-ortho-benzoquinone to benzodiaza-λ3-phosphorinones. Single crystal X-ray diffraction studies of various products

The reaction of methylisatoic acid anhydride 1 with benzylamines led to the N-benzyl-N′-methylanthranilamide derivatives 2 – 4 . Their reaction with phosphorus trichloride furnished the 2-chloro-1-halobenzyl/benzyl-3-methyl-4(1 H)-1,3,2-benzodiazaphosphorin-4-ones 5 – 7 which, upon reaction with bis-(2-chloroethyl)ammonium chloride/triethylamine, were converted into the P-bis-(2-chloroethyl)amino-1-halobenzyl/benzyl-3-methyl-4(1 H)-1,3,2-benzodiazaphosphorin-4-ones 8 – 10 and 12 . With 2-chloroethylammonium chloride/triethyl-amine the P? NHCH₂CH₂Cl-substituted compound 11 was obtained from the P^IIICl-species 6 . The reaction of 8 – 10 and 12 with hexafluoroacetone (HFA) took an unusual course: apart from the oxidative addition of HFA and formation of the perfluoropinacolyl ring system, one of the two CH₂CH₂Cl groups was found to alkylate the CH₃N atom with formation of a five-membered (diazaphospholane) ring in the tricyclic phosphoranes 13 – 16 . The reaction of 11 with HFA also produced a spirophosphorane 17 which involved a λ⁵-oxazaphosphetidine ring system. In the reaction of 8, 10 and 12 with tetrachloro-o-benzoquinone, an oxidative addition reaction with concomitant N-alkylation and formation of the tricyclic phosphoranes 18 – 20 was found to take place. Single crystal X-ray structure determinations are described for the phosphoranes 13, 14 and 16 , and for the precursor compound 9 . The following features are common to the isostructural compounds 13 and 16 and the diethyl ether hemisolvate of 14 : the (λ⁵)-spiro phosphorus atom lies out of the plane of the other atoms of the rings to which it is common, and the dioxaphospholane rings display a twist conformation. In the λ³P-compound 9 the phosphorus atom also lies out of the plane of the other ring atoms.     

Absorption Spectra and Termination Kinetics of Transient Free Radicals in Solution Observed by UV./VIS. Spectroscopy with modulated excitation

Free radicals are generated in liquid solutions by harmonically modulated photolysis of suitable substrates. Harmonic analysis of the absorbance as functions of wavelength and modulation frequency yields the optical spectra and the decay kinetics of the transient species. The experimental technique and the analysis are described in detail. Results on t-butyl, 2-propyl and benzyl radicals generated by photolysis of the corresponding dialkyl resp. dibenzyl ketones are reported. They confirm previous spectral assignments and show that the termination reactions are diffusion controlled.     

Positive muons as probes in liquid phase free radical chemistry: Radical structures and reaction rates

Muonium-substituted organic free radicals are observed by muon spin rotation when positive muons are stopped in liquid unsaturated compounds. From muon precession frequencies in high external magnetic fields the isotropic muon-electron hyperfine coupling constants are determined. They lead to radical structure assignments. Results of a variety of projects are described which show thatSR can successfully complement conventional physical methods of free radical chemistry: A study of the temperature dependence of the coupling constants of isotopically substituted ethyl radicals yields information on structure and barriers to internal rotation. Rate constants for several radical reactions are extracted from the damping of theSR signals, in particular for unimolecular rearrangements and cis-trans-isomerizations. The theory for the analysis for the case of reversible site exchange is outlined.All results described here were obtained by E. Roduner, P. Burkhard and W. Strub of this laboratory, and B. Webster, M. Ramos and D. McKenna of the University of Glasgow. We all appreciate support from the Swiss National Foundation for Scientific Research, the National Institut for Scientific Investigations of Portugal, the Carnegie Trust for the Universities of Scotland, the Royal Society London and SIN.     

Determination of the average lifetime of bottom hadrons

We have determined the average lifetime of hadrons containing b quarks produced in e⁺e^? annihilation to be

$\text{τ}\text{B}\text{=}\text{1.83}\text{+0.83}\text{+0.37}\text{?}\text{?0.34}\text{×10}{}^{\mathrm{?12}}\text{s}$

. Our method uses charged decay products from both non-leptonic and semileptonic decay modes.     

Dynamics of vector spin glasses: The Gabay-Toulouse line

The dynamics of ann-component vector spin glass with infinite range interactions are investigated near and above the Gabay-Toulouse (GT) line. The local transverse susceptibility _T for 0 varies along the whole GT lineT _c1 (H) as ^v , with a field and temperature independent critical exponentv=1/2. The longitudinal susceptibility _L () remains analytic for all (T, H)T _c1 (H), except for a cross-over fromv=1 tov=1/2 forH0 at the freezing temperatureT=T _f . The dynamic susceptibilities _T () and _L () are already coupled above the GT line via self-energy terms. BelowT _c1 (H), this coupling is strongly enhanced by other mechanisms.     

Photoluminescence of AlxGa1−xAs/GaAs quantum well heterostructures grown by molecular beam epitaxy

Low-temperature photoluminescence measurements on nominally undoped Al_xGa_1–xAs/GaAs quantum well heterostructures (QWHs) grown by molecular beam epitaxy (MBE) exemplified the exclusivelyintrinsic free-exciton nature of the luminescence under moderate excitation conditions. Neither any spectroscopic evidence for alloy clustering in the Al_xGa_1–xAs barriers nor any extrinsic luminescence due to recombination with residual acceptors has been detected in single and double QWHs when grown at 670 °C under optimized MBE growth conditions. Carrier confinement in Al_xGa_1–xAs/GaAs QWHs starts at a well width ofL _z30 nm when x0.25. The minor average well thickness fluctuation ofL _z=4×10^–2nm as determined from the excitonic halfwidth allowed the realization of well widths as low asL _z=1 nm and thus a shift of the free-exciton line as high as 2.01 eV which is close to the conduction band edge of the employed Al_0.43Ga_0.57As confinement layer. The measurements further revealed a strongly enhanced luminescence efficiency of the quantum wells as compared to bulk material which is caused by the modified exciton transition probabilities due to carrier localization.     

Photoluminescence of Al x Ga1−x As/GaAs quantum well heterostructures grown by molecular beam epitaxy

Nominally undoped Al_xGa_1–xAs grown by molecular beam epitaxy from As₄ species at elevated substrate temperatures of 670°C exhibits well-resolved excitonic fine structure in the low-temperature photoluminescence spectra, if the effective As-to-(Al+Ga) flux ratio on the growth surface is kept within a rather narrow range of clearly As-stabilized conditions. In contrast to previous results on Al_xGa_1–xAs of composition 0.15not to shift in energy by changing the excitation intensity. This implies a simple freeelectron carbon-acceptor recombination mechanism for the line without any participation of a donor. In Al_xGa_1–xAs of composition close to the direct-to-indirect cross-over point, two distinct LO-phonons separated by 34 and 48 meV from the (D ⁰,C ⁰) peak position at x=0.43 were observed which were before only detectable by Raman scattering experiments. The intensity of the carbon-impurity related luminescence lines in bulk-type Al_xGa_1–xAs and GaAs layers was found to be strongly reduced, as compared to the excitonic recombination lines, if the respective active layer was covered by a very thin confinement layer of either GaAs on top of Al_xGa_1–xAs or vice versa grown in the same growth cycle.     

Chromatographie von Carbamat- und Phenylharnstoff-Pesticiden auf Dünnschichten von basischem Zinkcarbonat

Thin layers of basic zinc carbonate can be used with good results for separation and multiple identification of carbamate and phenylurea pesticides. Five important substances could be separated by one-dimension TLC. The best results were obtained by the following developing solvents: a) benzene, b) a mixture of benzene/petroleum ether/chloroform (6∶1∶1). The substances are either recognisable in short-wave UV-light, when a fluorescence indicator (F 254 nm) is added, or in day-light, after spraying a solution of 0.1 N AgNO₃ in 3 N HNO₃, followed by an UV-exposure for about 4 min.     

Electrophilic Aromatic Substitution of Groups other than Hydrogen. Part I: Ipso Factors and Rate-Limiting Steps in Dehalogenations by Diazonium Ions. 26th communication on diazo coupling reactions

The rates of substitution of the group X in 1-X-2-naphthol-6-sulfonic acids (X = H, Cl, Br, and I) by p-chlorobenzenediazonium ions in aqueous solution have been measured. The rates of the halogenated naphthols relative to that of the parent compound (X = H) are 0.0070:0.0089:0.149 for X = Cl, Br, and I respectively. The reaction of 1-bromo-2-naphthol-6-sulfonic acid is catalysed by thiosulfate ions; the relative rate observed for this compound does not, therefore, represent the ipso factor. It is postulated that in its substitution the release of the electrofugal leaving group (Br^⊕) is rate-limiting.     

A novel spectroscopy using ultrafast two-pulse excitation of large polyatomic molecules

A first infrared pulse at frequency ν₁ interacts with vibrational states in S₀ and a second visible pulse at ν₂ promotes the excited molecules to the S₁ state from where they fluoresce. Tuning the frequency ν₂ over 600 cm^?1 allows the observation of a detailed spectrum which gives information on vibrational states in S₀ and on vibronic states in S₁ together with corresponding Franck—Condon factors. The spectra differ drastically from the common broad and featureless absorption and fluorescence bands.