Isolation,Structure Determination and Synthesis of New Acetylenic Steroids from the Sponge Calyx nicaaensis

Two acetylenic steroids, cholest-5-en-23-yn-3β-ol ( 5 ) and 26,27-dinorcholest-5-en-23-yn-3β-ol ( 3 ), and another unsaturated steroidalcohol, stigmasta-5,23-dien-3β-ol ( 7 ), were isolated from the sponge Calyx nicaaensis. The structures of these two acetylenic steroids were established by synthesis. Several attempts to synthesize the marine steroids alcohol calysterol ( 1 ), with a cyclopropene-containing side chain, starting from cholest-5-en-23-yn-3β-ol are also recorded. Addition of ethyl-diazo-acetate to the triple bond was performed, but the reduction to the methyl derivative yielded decomposition products.     

Syntheses, structures, and surface aromaticity of the new carbaalane [(AlH)(6)(AlNMe(3))(2)(CCH(2)R)(6)] (R = Ph, CH(2)SiMe(3)) and a stepwise functionalization of the inner and outer sphere of the cluster

The reaction of the acetylene RC triple bond CH (R = Ph, CH(2)SiMe(3)) with an excess of AlH(3).NMe(3) in boiling toluene leads to the carbaalane [(AlH)(6)(AlNMe(3))(2)(CCH(2)R)(6)] (R = Ph 1, CH(2)SiMe(3) 2) in good yield. Treatment of 2 with BCl(3) under varying conditions gives the chlorinated products [(AlCl)(6)(AlNMe(3))(2)(CCH(2)CH(2)SiMe(3))(6)] 3 and [(AlCl)(6)(AlNMe(3))(2)(CCH(2)CH(2)SiMe(2)Cl)(6)] 4, respectively. The latter clearly demonstrates that the cluster can be stepwise functionalized within the inner and outer sphere. The X-ray single-crystal structures of 1, 2, and 4 have been determined. All compounds have in common that the central core consists of a cluster having eight aluminum and six carbon atoms. The bonding properties in this cluster are described as a new manifestation of three-dimensional surface aromaticity. Each Al(4)C fragment of the cube is formed by four bonds with three electron pairs, thus leading to a strong delocalization of the electrons. A phenomenological modeling using a three-dimensional Hückel scheme with fitted parameters to reproduce the energies from ab initio calculations revealed that the orbital scheme localized at one Al(4)C fragment possesses an orbital sextet with a large HOMO-LUMO gap. This is in line with the criteria of aromaticity. The idea of aromaticity was sustained also by qualitative valence bond reasons enumerating the different resonance structures by means of graph theoretical methods.     

Coupled liquid chromatography-gas chromatography for the rapid analysis of gamma-oryzanol in rice lipids

An approach based on on-line coupled liquid chromatography-gas chromatography (LC-GC) was developed for the rapid analysis of gamma-oryzanol in rice. Total lipids were extracted from rice and subjected to LC-GC without any prior purification. gamma-Oryzanol was pre-separated by HPLC from rice lipids and transferred on-line to GC analysis in order to separate its major constituents. 24-methylenecycloartanyl ferulate, cycloartenyl ferulate, campesteryl ferulate, beta-sitosteryl ferulate and campestanyl ferulate. The identities of the compounds were confirmed by off-line GC-MS analysis. Total gamma-oryzanol content could be quantified by HPLC-UV detection and the distribution of gamma-oryzanol constituents could be determined by on-line coupled GC analysis. The proposed methodology paves the way for high-throughput investigations providing information on natural variations in gamma-oryzanol content and its composition in different rice varieties.     

Die Berechnung von Einelektronen-Integralen in der SCF-Xα-SW-Methode: I. Die Normierung

A normalization of the wave functions by means of the theoretical exact Multiple-Scattering-(MS)-formalism is discussed within the framework of the SCF-X-SW-method. For the atomic and extramolecular regions the integrals of normalization can be easily determined and the results can be described by the corresponding electronic charges. The calculation of the integral of the interatomic region is problematic. The needful volume integration is only necessary to theGreen's functions of the wave functions and can be solved by means of the residual theory. The further analytical calculation of the surface integrals leads to a complicated formalism which can be numerically evaluated.

     

A spirocyclic system comprising both phosphazane and phosphazene rings

The reaction of hexakis(cyclohexylamino) cyclotriphosphazene [NP(CyNH)(2)](3), 1, with phosphorus trichloride yields [NP(CyN)(2)PCl](3), 2, which contains three four-membered phosphazane rings fused in spirocyclic fashion to a central six-membered phosphazene ring and constitutes the first structurally characterized compound that comprises both phosphazene and phosphazane rings. The peripheral P atoms feature stereoactive lone pairs, and, thus, 2 exists in isomeric C(3h) and C(s) forms. The spirocyclic phosphazene-phosphazane derivative 2 carries three reactive PCl functions in peripheral positions, promising an interesting precursor molecule for the synthesis of extended phosphorus nitrogen structures of high rigidity. Extension of the PN moiety can be achieved by reaction of 2 with a primary amine yielding [NP(CyN)(2)PN(H)(t)Bu](3), 3, which features a central scaffold of 6 phosphorus and 12 nitrogen centers and aggregates via N-H...P hydrogen bonds in the solid state. On the contrary, the reaction of 1 with SbCl(3) undergoes incomplete proton abstraction, resulting in the formation of the tricyclic compound N(3)P(3)(CyNH)(4)(CyNSbCl(2))(2), 4, which contains two four-coordinate Sb centers chelated by N(exo)-N(ring) sites of the phosphazene.     

Charge neutralization of ions from benzene

Cross-sections have been measured for the charge neutrilization if ions from benzene in kiloelectron-volt collisions with benezene target molecules. Measured values range from 65 Ų for the symmetric [C₆H₆]⁺? C₆H₆ resonant reactions to 8 Ų for [C₃H₃]⁺? C₆H₆ reactions. Cross-sections computed using a simple resonance charge transfer model compare favourably with experimental data for the symmetric reactions. The cross-sections for asymmetric reactions are smaller that those for they symmetric system and magnitudes of the asymmetric cross-sections are correlated with recombination energies of the respective ions.     

Azobridges from azines, XVII. Intra- and intermolecular [3+2] cycloaddition between nonstabilized azomethineimines and alkenes

Azo compounds 1 and 3 containing a CC-double bond in a parallel but distant position are quatemized by Me₃OBF₄ to 1,MeBF₄ and 3,MeBF₄, whereas MeI produces the cage compounds 2,HX and 4,HX. These [3+2] cycloadducts also are quantitatively formed from 1,MeBF₄ and 3,MeBF₄ with catalytic amounts of azo compounds. Intermolecular [3+2] cycloadditions occur with a mixture of DBH (5) or DBO (8), MeI and a variety of alkenes (→ HI) salts of (6, 7, 9 — 12). The intermediate azomethineimines, if stabilized by a fluorenylidene group, can be isolated (20, 22,24), but not, however, in the presence of a close parallel CC-bond (25 → 26).     

Position dependent heavy atom effect in physical triplet quenching by electron donors

The radical yields and rate constants in the quenching reaction of thionine triplet with the complete series of monohalogen substituted anilines as electron donors were determined by flash spectroscopy. Whereas the quenching rate constants show little and unsystematic variation, the radical yields decrease with increasing spin—orbit coupling constant of the halogen substituent. This effect is very sensitive to the position of the halogen in the donor. The results are explained in terms of a heavy atom effect on the intersystem crossing rate constant in a triplet exciplex.