Spezifisch π→π*-induzierte Reaktionen von γ-Dimethoxymethylcyclohexen-2-onen: 1,3-Umlagerung und Wasserstoffabstraktion durch das α-Kohlenstoffatom

When α,β-unsaturated γ-dimethoxymethyl cyclohexenones are excited to the S₂(π,π*) state, certain unimolecular reactions can be observed to compete with S₂ → S₁ internal conversion. These reactions do not occur from the S₁(n,π*) or the lowest T(π,π* and n,π*) states. They comprise the radical elimination of the formylacetal substituent (cf. 8 , 9 → 32 + 33 ), γ → α formylacetal migration (cf. 6 → 27 , 8 → 30 , 9 → 34 , 12 → 37 ), and a cyclization process involving the transfer of a methoxyl hydrogen to the α carbon and ring closure at the β position (cf. 6 → 28 , 8 → 31 , 12 → 38 , 20 → 40 + 41 ). The quantum yield of the ring closure 20a → 40a + 41a is 0.016 at ≤ 0.05M concentration. It is independent of the excitation wavelength within the π→π* absorption band (238–254 nm), but Φ ( 40a + 41a ) decreases at higher concentrations. According to the experimental data the reactive species of these specifically π→π*-induced transformations is placed energetically higher than the S₁(n,π*) state, and it is either identical with the thermally equilibrated S₂(n,π*) state, or reached via this latter state. The linear dienone 14 undergoes a similar π→π*-induced cyclization (→ 42 ) whereas the benzohomologue 26 proved unreactive, and the dienone 22 at both n → π and π→π* excitation only gives rise to rearrangements generally characteristic of cross-conjugated cyclohexadienones.     

The Enantioselective Synthesis of 3-Methoxy-1, 3, 5 (10)-estratrien-11, 17-dione by a Thermal Intramolecular Cycloaddition Reaction. Preliminary communication

The enantiomerically pure (+)-3-methoxy-1, 3, 5 (10)-estratrien-11, 17-dione 11 (with trans-anti-trans configuration) was synthesized in a highly stereocontrolled fashion from (±)-t-butyl 4-methoxy-1-benzocyclobutene carboxylate (8) and the (+)-carboxylic acid 6 , obtained from 4 in two steps, followed by one crystallization of the (+)-ephedrine salt. The key step 10→11 (Scheme 2) involves a thermal intramolecular cycloaddition reaction.     

The fluorescence of biliverdin dimethyl ester

Freshly prepared solutions of biliverdin dimethyl ester ( 2 ) in ethanol showed fluorescence maxima at 710 and 770 nm [Φ_F = 1.1. 10^?4 (room temperature) and 5.0 10^?4 (77 K)]. The maxima of monoprotonated 2 at 77 K were shifted to 725 and 806 nm and the quantum yield was increased to 2.6. 10^?2. This acid effect was reversible by neutralization with base. When a neutral solution was kept standing in the dark at room temperature, or when an acidic solution was neutralized by base, an additional fluorescence maximum at 500 nm with a mirror image excitation spectrum with λ_max = 470 nm developed, which disappeared on addition of acid and which is attributed to a chemical change of 2 .     

Total Synthesis of (±)-α-Acoradiene via Intramolecular Photoaddition and Reductive Cyclobutane Cleavage

(±)-α-Acoradiene (4) has been synthesized from 3-methoxy-2-cyclohexenone by a sequence of 8 steps. The key steps (Scheme 6) are the regio- and stereoselective photo[2+2]addition 7→6 and the reductive fragmentation 6→5 .     

Photobiological effects of UVA and UVB light in zebrafish embryos: evidence for a competent photorepair system

The consequences of UVB and UVA irradiation on hatch rate, mortality, and malformation were studied in embryonic zebrafish (Danio rerio). The use of zebrafish embryos has expanded from traditional developmental models to diverse studies, including many techniques utilizing light exposure. To characterize useful indicators of photodamage, the responses and threshold limits of UV radiation as a function of embryonic stage and fish source were evaluated. Significant differences in UVB susceptibility were observed in embryos at 3, 6-7, 12, and 24h post-fertilization (hpf), with the 1000-cell stage (3 hpf) having greatest tolerance to UVB. Embryos derived from zebrafish raised in outdoor ponds were more tolerant to UVB than were embryos from laboratory-raised fish. Combinations of UVB and UVA exposure were used to confirm the presence of a competent photorepair system in zebrafish that could return otherwise malformed embryos to a normal phenotype. Overall, embryonic zebrafish had large tolerances (LD(50) of 850 J/cm(2)) to UVA, confirming their suitability for photoactivation and photorepair studies.     

[Cl3PNPCl3][MoNCl4], eine Verbindung mit strangartig assoziierten Anionen

[Cl₃PNPCl₃][MoNCl₄], a Compound having Columns of Stacked Anions The title compound is formed by the reaction of [Cl₃PNPCl₃]Cl with MoNCl₃ in CH₂Cl₂ and subsequent precipitation with CCl₄ in from of orange-red crystals. According to the ³¹P-NMR spectrum, the compound exists as its isomer phosphaneiminate [Cl₅Mo(NPCl₂NPCl₃)] in CD₂Cl₂/CH₃CN solution. The crystal structure of [Cl₃PNPCl₃][MoNCl₄] is isotypic with that of [Cl₃PNPCl₃][MoOCl₄] and shows the same kind of two-dimensional disorder. X-ray diffraction patterns show planes of diffuse scattering as well as Bragg reflexions. The latter correspond to an averaged structure with a = 1590.0, b = 1141.6, c = 418.0 pm, space group Pba2, Z = 2. In the averaged structure (606 reflexions, R = 0.071) the atom sites have fractional occupation. The real structure consists of square-pyramidal [MoNCl₄]^? ions stacked to form columns with alternating MoN distances of 175 and 243 pm. The packing of the columns is disordered in that the [MoNCl₄]^? pyramids point either in the +c or ?c direction. The [Cl₃PNPCl₃]⁺ ions are stacked in the c direction and show two types of disorder, namely a displacement parallel to c and a rotation by 120° about the P? P axis.     

Phosphaniminate von Alkalimetallen: Die Kristallstrukturen von [KNPCy3]4, [KNPCy3]4·2OPCy3, [CsNPCy3]4·4OPCy3 und [Li4(NPPh3)(OSiMe2NPPh3)3(DME)]

The alkalimetal phosphoraneiminates [KNPCy₃]₄, ( 1 ) [KNPCy₃]₄·2OPCy₃ ( 2 ) and [CsNPCy₃]₄·4OPCy₃ ( 3 ) (Cy = cyclohexyl) which are obtainable by the reaction of pottassium amide or cesium amide with Cy₃PI₂ or Cy₃PBr₂ in liquid ammonia, as well as the lithium derivative [Li₄(NPPh₃)(OSiMe₂NPPh₃)₃(DME)] ( 4 ) have been characterized by crystal structure determinations. 4 has been formed by the insertion reaction of silicon greaze (‐OSiMe₂)n into the LiN bonds of [LiNPPh₃]₆ in DME solution (DME = 1, 2‐dimethoxyethane). 1 : Space group P&1macr;, Z = 2, lattice dimensions at 193 K: a = 1389.8(1); b = 1408.1(1); c = 2205.2(2) pm; α = 78.952(10)?; β = 81.215(10)?; γ = 66.232(8)?; R1 = 0.0418. 2 : Space group Pbcn, Z = 4, lattice constants at 193 K: a = 2943.6(2); b = 2048.2(1); c = 1893.8(1) pm; R1 = 0.0428. 3 : Space group Cmc2₁, Z = 4, lattice dimensions at 193 K: a = 2881.6(2); b = 2990.2(2); c = 1883.7(2) pm; R1 = 0.0586. 4 ·1/2DME: Space group R&3macr;c, Z = 12, lattice dimensions at 193 K: a = b = 1583.5(1); c = 11755.3(5) pm; R1 = 0.0495. All complexes have heterocubane structures. In 1‐3 they are formed by four alkali metal atoms and by the nitrogen atoms of the (μ₃‐NPCy₃^‐) groups, whereas 4 forms a "heteroleptic" Li₄NO₃ heterocubane.     

Experimental investigation of the parameter dependency of the removal rate of thermochemically polished CVD diamond films

Parameters controlling the removal rate of chemical vapor deposition (CVD) diamond films thermochemically polished on transition metals in a mixed argon-hydrogen atmosphere were investigated. The ambient temperature, the pressure exerted on the diamond film, the angular velocity of the polishing plate, the frequency and the amplitude of the transverse vibrations were among the parameters used in the experiments. Temperature measurements showed that the removal rate was increased exponentially with increasing magnitude of the parameter. An exponential increase in the removal rate was also observed with increasing pressure and hence with increasing contact between the diamond film and the polishing plate. However, an exponential decrease in the removal rate was observed with increasing angular velocity of the polishing plate. The removal rate obtained with the application of transverse vibrations was more than three times that obtained without transverse vibrations. Moreover, the removal rate was seen to be higher at resonant frequencies. An increase in the removal rate with increasing amplitude of the transverse vibrations was also observed. Raman measurements carried out on the films to determine the presence of the non-diamond carbon layer after thermochemical polishing revealed non-diamond Raman lines only for films polished at 1000 °C and 1050 °C for the temperature range 750–1050 °C. Received: 27 October 1999 / Accepted: 2 February 2000     

Chiral recognition by CD-sensitive dimeric zinc porphyrin host. 2. Structural studies of host-guest complexes with chiral alcohol and monoamine conjugates.

A structural study of complexes formed between a dimeric zinc porphyrin tweezer (host) and chiral monoalcohols and monoamines derivatized by a bidentate carrier molecule (guest) confirmed that their CD couplets arise from the preferred porphyrin helicity of 1:1 host-guest complexes. NMR experiments and molecular modeling of selected tweezer complexes revealed that the preferred conformation is the one in which the L (larger) group protrudes from the porphyrin sandwich; this preferred helicity of the complex determines the CD of the complexes. It was found that the porphyrin ring-current induced (1)H chemical shifts and molecular modeling studies of the complex lead to the assignments of relative steric size of the L (large)/M (medium) substituents attached to the stereogenic center. The assignments, in turn, are correlated with the sign of the CD exciton couplet that establishes the absolute configuration at the stereogenic center. Variable-temperature NMR experiments proved that the observed increase in CD amplitude at lower temperatures derives from conformational changes in the preferred offset geometry between two porphyrin rings.     

Induced secondary metabolites from the endophytic fungus Aspergillus versicolor through bacterial co-culture and OSMAC approaches

Two new cryptic 3,4-dihydronaphthalen-(2H)-1-one (1-tetralone) derivatives, aspvanicin A (1) and its epimer aspvanicin B (2), as well as several known cryptic metabolites (3–8), were obtained from the ethyl acetate extract of the co-culture of the endophytic fungus Aspergillus versicolor KU258497 with the bacterium Bacillus subtilis 168 trpC2 on solid rice medium. When A. versicolor was cultured axenically in liquid Wickerham medium supplemented with 3.5% DMSO, an additional three known secondary metabolites (9–11) were isolated that were lacking when the fungus was fermented on rice medium. The structures of the new compounds were elucidated using one- and two-dimensional NMR spectroscopy as well as HRESIMS. The relative and absolute configurations of 1 and 2 were determined by the combination of NMR and electronic circular dichroism (ECD) analysis aided by DFT conformational analysis and TDDFT-ECD calculations. The ECD calculations revealed that although the sign of the blue-shifted overlapping n-π¹ ECD transition follows the helicity rule of cyclic aryl ketones, the calculation of low-energy conformers and ECD spectra was necessary to determine the stereochemistry. All metabolites were assessed for their antibacterial and cytotoxic activities; one of the new diastereomers, compound 2, showed moderate cytotoxic activity against the mouse lymphoma cell line L5178Y.