Isolierung,Konstitution und Synthese der (R)-(−)-Eucominsäure

From the bulbs of Eucomis punctata L'Hérit. (Liliaceae) and of a hitherto undefined species of Eucomis a new optically active phenolic carboxylic acid, eucomic acid, was isolated. Structure 1 was assigned on the basis of chemical and spectral evidence. The absolute configuration of eucomic acid was determined by its correlation with piscidic acid ((2 R, 3 S)-2-(4′-hydroxybenzyl)-tartaric acid) ( 8 ). Consequently, eucomic acid is (R)-(?)-2-(4′-hydroxybenzyl)-malic acid ( 1 ). For the stereospecific synthesis, methyl cis-p-methoxybenzylidene-succinic acid ( 22 ) was transformed into the γ-lactone 24 which, by catalytic hydrogenolysis, yielded (±)-2-(4′-hydroxybenzyl)-malic acid 1-methyl ester ( 27 ). Resolution with (?)-quinine led to the enantiomeric acids 29 and 30 . The methyl ester of the levorotatory enantiomer 30 was identical with the dimethyl ester 3 of 4′-O-methyl-eucomic acid.     

Silylanions: inversion barriers and NMR chemical shifts

Alpha-substituent effects on inversion barriers and NMR chemical shifts have been studied on a set of silyl anions, [X(3-n)Y(n)Si](-) (X, Y=H, CH(3), and SiH(3)). The MP2/6-31+G* optimized structures show a pattern of increasing inversion barriers with augmenting numbers of methyl substituents. The highest barrier of 48.5 kcalmol(-1) is obtained for the (CH(3))(3)Si(-) ion. The silyl group displays the opposite effect by decreasing the inversion barrier to a minimum of 16.3 kcalmol(-1) in (SiH(3))(3)Si(-). The influence of counterions on these barriers is probed by addition of a lithium or potassium cation. In most cases, a decrease of the energy barriers with respect to the bare anions is observed. The (29)Si NMR chemical shifts calculated at the IGLO-DFT and GIAO-MP2 level of theory are also analyzed in view of the substituents and counterions.     

Substituent control of hydrogen bonding in palladium(II)-pyrazole complexes

Inter- and intramolecular hydrogen bonding of an N-H group in pyrazole complexes was studied using ligands with two different groups at pyrazole C-3 and C-5. At C-5, groups such as methyl, i-propyl, phenyl, or tert-butyl were present. At C-3, side chains L-CH(2)- and L-CH(2)CH(2)- (L = thioether or phosphine) ensured formation of chelates to a cis-dichloropalladium(II) fragment through side-chain atom L and the pyrazole nitrogen closest to the side chain. The significance of the ligands is that by placing a ligating side chain on a ring carbon (C-3), rather than on a ring nitrogen, the ring nitrogen not bound to the metal and its attached proton are available for hydrogen bonding. As desired, seven chelate complexes examined by X-ray diffraction all showed intramolecular hydrogen bonding between the pyrazole N-H and a chloride ligand in the cis position. In addition, however, intermolecular hydrogen bonding could be controlled by the substituent at C-5: complexes with either a methyl at C-5 or no substituent there showed significant intermolecular hydrogen bonding interactions, which were completely avoided by placing a tert-butyl group at C-5. The acidity of two complexes in acetonitrile solutions was estimated to be closer to that of pyridinium ion than those of imidazolium or triethylammonium ions.     

Structural phase transitions in ‘hcp’ C70 single-crystals

The thermal expansion of vapor-grownC ₇₀ single crystals ahs been investigated using high-resolution capacitance dilatometry from 5–380 K. Measurements were made both parallel and perpendicular to the hexagonalc-axis. Three first-order phase transitions which we associate with the consecutive disordering of theC ₇₀ molecules are observed upon heating at 280 K (long-axis spinning), 300 K (long-axis precession) and 355 K (quasi-free rotation), respectively. The highest-temperature transition exhibits a very large (50 K) thermal hysteresis. Powder and single-crystal X-ray diffraction show that the crystals are predominantly hexagonal-close-packed (HCP) with an idealc/a1.63 above 360 K andc/a1.84 at 295 K.     

A bound for minimal graphs with a normal at infinity

It is shown that a minimal graph with a normal at infinity is in a-priori bounded vertical distance from its approximating halfcatenoid. This is used to show that the exterior contact angle problem is wellposed under natural geometric conditions on the domain, while the exterior Dirichlet problem can be solvable only for data which satisfy an oscillation bound.This paper was written under the support of the Deutsche Forschungsgemeinschaft while the author was visiting the department of mathematics at Stanford University.This article was processed by the author using the LaT_EX style filepljour1 from Springer-Verlag.     

Structure and reactivity of xanthocorrinoids. Part V. Formation of trans-diol derivatives of 5,6-dihydrocobyrinic acid from xanthocorrinoids under acidic conditions

On treatment with H₂SO₄/MeOH, epimerization of hexamethyl cis-5,6-dihydroxycobyrinate c,8-lactam ( 3 ) takes place quantitatively at C(6), yielding the corresponding trans-diol 4 . The corresponding lactone 7 , whose structure has been established by X-ray analysis, is obtained from xanthocorrinoids 5 and 6 under similar conditions.     

A liquid chromatography-mass spectrometry method for the quantification of both etoricoxib and valdecoxib in human plasma

A practicable and selective liquid chromatography-mass spectrometry assay for the determination of two cyclooxygenase-2 inhibitors, etoricoxib and valdecoxib, in human plasma is presented. The analytical technique is based on reversed-phase high-performance liquid chromatography (HPLC) coupled to atmospheric pressure chemical ionisation (APCI) mass spectrometry (Finnigan Mat LCQ ion trap). Mass analysis was performed in the positive ion mode. The ion trap was operated in the tandem MS mode (MS2) and the transitions of etoricoxib (m/z 359.2 --> 280.3) and valdecoxib (m/z 315.1 --> 235.1) were followed by selected reaction monitoring. Retention times of etoricoxib and valdecoxib were 1.05 and 1.08 min, respectively. The method was validated over a linear range 10-2500 and 5-1000 microg/L using the other substrate as internal standard. After validation, the method was used to study the pharmacokinetic pro fi le of etoricoxib or valdecoxib in a healthy volunteer after administration of a single oral dose (valdecoxib, 20 mg; etoricoxib, 90 mg). The presented method was suf fi cient to cover more than 90% of the area under the plasma concentration time curve.     

On the Chemistry of a Dibenzohypericin Derivative

Summary.  A hypericin derivative was synthesized in which instead of the methyl groups two benzene rings were condensed to the chromophoric system in order to extend its conjugation. This derivative showed lowered fluorescence and concomitantly enhanced sensitized production of active oxygen species as compared to hypericin. However, in contrast to intuition its long wavelength band remained unshifted in comparison to its parent compound hypericin. Geometry and absorption properties were also investigated by means of semiempirical calculations. Received July 27, 2001. Accepted August 9, 2001