Structure (x-ray analysis) of Manicoline B,a mixture of two diastereoisomers of a new alkaloid from dulacia guianensis (olacaceae)

Manicoline B, isolated from the root bark of $\text{Dulacia guianensis}$ (Olacaceae), was shown by X-ray analysis to be an equimolecular mixture of two diastereoisomers of a new alkaloid and to have structure (3).     

Synthesis and some properties of titanium-containing silica gels

Microporous silica gels containing small amounts of titanium ions have been synthesized. Porous structure and surface active sites of silica gels have been studied. It has been found that the titanium ions are distributed uniformly in silica gel matrix, substituting silicon ions isomorphically.     

New intra-intermolecular criss-cross cycloaddition of unsymmetrical allenylazines with alkynes leading to three fused five-membered heterocycles

This report describes a new type of intra-intermolecular criss-cross cycloadditions. Thermal reactions of unsymmetrical allenylazines in the presence of alkynes led to three fused five-membered heterocycles in some cases. In the case of unsymmetrical substituted alkynes, a regioselectivity was observed. The molecular structures of all products are discussed. One X-ray crystal structure is also reported.     

Laser studies of vibrational energy transfer and relaxation of CO trapped in solid neon and argon

The infrared emission of CO trapped in solid Ne and Ar is observed at low temperature. The first vibrational level of ¹²C¹⁶O is excited by a Q-switched frequency doubled CO₂ laser. The emission spectrum consists of several lines arising from upper vibrational levels of ¹²C¹⁶O and also of ¹³C¹⁶O and ¹²C¹⁸O which are present in natural abundance. An interpretation is proposed which is based on the assumption that long range dipole—dipole interaction is the main physical process involved in these experiments. Resonance energy transfer produces an energy migration among ¹²C¹⁶O molecules without any change in vibrational populations. Phonon assisted energy transfer takes place between vibrational levels of the various isotopic species present in the solution. In order to satisfy the resonance condition a phonon is emitted or absorbed whose energy compensates for the energy mismatch between the transitions in each interacting molecule due to isotopic effect and or vibrational anharmonicity. The range of this process is greatly extended by energy migration. At the low phonon bath temperature phonon emission is much more probable than phonon absorption. So a strong excitation of upper vibrational levels with in some cases population inversions is observed.Molecular impurities act as efficient quenching centers even at very low concentration. When highly purified samples are used, the fluorescence decay time is found to be 20.6 ms in Ne and 14.5 ms in Ar and does not significantly depend upon concentration and temperature. It is concluded that radiationless relaxation is unimportant.     

Synthesis of light-sensitive arenesulfonylazido polycarboxylic acids

Several light-sensitive arenesulfonylazido polycarboxylic acids were synthesized by a one-step reaction of a polymeric anhydride with a light-sensitive monofunctional alcohol, or by the reverse reaction, i.e., reaction of a polymeric alcohol with a light-sensitive monofunctional anhydride. The polycarboxylic acids are soluble in polar organic solvents and in aqueous base. Neutralization of part of the carboxyl groups gives rise to the formation of water-soluble polymers. Coreaction of poly(maleic anhydride-co-methyl vinyl ether) with 2-hydroxyethyl 4-sulfonylazidocarbanilate and 2-hydroxyethyl trans-2,5-dimethoxystilbene-4′-carbamate produces a light-sensitive polycarboxylic acid with “built-in” sensitizer.     

Optisch aktive übergangsmetall-komplexe : XXV. Substituenteneinflüsse auf die intramolekulare epimerisierung von tetragonal-pyramidalen molybdanund wolfram-komplexen

The synthesis, IR, ¹H NMR and UV spectra of optically active square pyramidal cyclopentadienyldicarbonyl-molybdenum and -tungsten complexes with Schiff bases, derived from methyl-substituted pyridine carbaldehyde(2) and S-(—)-α-methylbenzylamine, are described. The epimerisation of these complexes, measured polarimetrically at 75–97°C in DMF, follows a 1^st order rate law and represents a regular pentatopal skeletal rearrangement. The inductive effect of a methyl group in the para position of a pyridine ring leads to a retardation of the epimerisation compared to unsubstituted complexes. The rate constants decrease even more if an ortho methyl group is introduced into the pyridine system, since additional steric effects are introduced. If the metal complex contains a 4,6-dimethyl-substituted Schiff base as a chelating ligand, the contributions of a 4- and a 6-methyl group are additive. A benzene ring fused to the 5,6-positions of the pyridine system also leads to stabilisation of the configuration.     

Oligomérisation anionique de l'ethylène. I. Etude cinétique

A kinetic study of ethylene oligomerization in hexane, in the presence of n-BuLi–TMEDA complexes, allowed us to suggest a new mechanism for anionic ethylene oligomerization. n-BuLi and n-Bu(CH₂CH₂)Li species have the same reactivity. The RLi–TMEDA complex in a 1-to-1 stoichiometry is the active species. The following kinetic equation has been established: It reflects the intervention of associated species (n-BuLi–TMEDA)₂ as well as the influence of the concentration of the complexing agent on the kinetics of oligomerization.     

Structural materials: metal-silicon-Boron. The Nb-rich corner of the Nb-Si-B system

Phase equilibria in the Nb-Nb₅Si₃-NbB region were studied in the melting (crystallization) range by means of light microscopy, XRD, SEM and EMPA on alloys after arc-melting and annealing at 1800°C and at subsolidus temperatures. Phase transition and melting temperatures were determined by DTA and pyrometric Pirani-Alterthum technique resulting in a solidus projection and two isopleths, Nb₇₇Si₂₃-Nb₇₇B₂₃ and Nb₉₉Si₁-Nb₅Si₂B. The T₂-phase Nb₅Si_3−xB_x (0?x?2, Cr₅B₃-type) was found to form equilibria with (Nb), NbB, Nb₃Si, and with the T₁-phase (Mn₅Si₃ derivative type). The T₂-phase melts incongruently (Nb₅Si_1.8B_1.2 at 2245°C) and forms a quasibinary eutectic with the niobium solid solution on a minimum tie-line at ∼1880°C.     

The cellulose system in viscin from mistletoe berries

The cellulose system of the viscous fibrous cellulosic polysaccharide (viscan) in the viscin tissue of the European mistletoe, Viscum album L., was analyzed by chemical and physicochemical techniques including sugar analysis, optical and transmission electron microscopy, X-ray and electron diffraction together with solid state CP/MAS ¹³C-NMR spectroscopy. The results confirmed that in the elongated thin viscin cells, the cellulose microfibrils (having a diameter of around 3 nm) were tightly coiled with their axes perpendicular to the long axis of the cell. Upon stretching these cells became deformed by more than a hundred fold. In such a deformation, the cellulose microfibrils became unwound to be perfectly aligned along the stretching direction. Based on solid-state CP/MAS ¹³C-NMR spectroscopic analysis of the viscin tissue, it was found that its cellulose consisted of I and I polymorphs in the ratio 1:1.     

Phenylselenolactonisation des acides homogeranique et homonerique

The reaction of PhSeCl and N-PSP with homogeranic acid ($\text{1}$) or homoneric acid ($\text{2}$) affords butanolides in a stereospecific way. Despite the large number of cyclic cases studied in the literature such acyclic systems were remained largely unexplored. PhSe⁺ was unable to realize polycyclization.