The Absolute Configuration of 1-Methylindane

It is shown unequivocally by chemical correlations (cf. Schemes 1--3) and Raman optical activity spectra (cf. Fig. 1 and 2) that the (R)-configuration has to be attributed to (+)-1-methylindane ((+)- 1 ). This is in contradiction to an earlier assignment of the (R)-configuration to (?)- 1 [2] which was based on the (R)-configuration of (+)-indane-1-carboxylic acid ( 3 ) [11].     

Hydroxybromierung und Methoxybromierung von (Z)-Cycloocten

In addition totrans-2-bromocyclooctanol andtrans-1,2-dibromocyclooctane,cis-4-bromocyclooctanol,cis-1,4-dibromocyclooctane,trans-1,4-dibromocyclooctane, and (Z)-5-bromocyclooctene are obtained, when (Z)-cyclooctene is treated with N-bromosuccinimide in the presence of water. Similarly the methoxybromination of (Z)-cyclooctene gives transanular products.     

Trennung und Bestimmung von Oestron, 17 β-Oestradiol und 16λ, 17β-Oestriol mit Hilfe der Dünnschichtchromatographie

Zusammenfassung Mit Hilfe der Dünnschichtchromatographie wird die Trennung von Oestron, 17-Oestradiol und Oestriol erzielt. Weiter ist es möglich, mit 0,5-n alkoholischer Natronlauge (80%) und Messung der Extinktion bei 242 nm noch 1,67 g/ml der Einzelkomponenten mit einer Genauigkeit von zirka ± 10% zu bestimmen.

---

Summary Oestrone (estrone), 17-oestradiol, and oestriol can be separated by thin layer chromatography. It is also possible to determine as little as 1.67 g/ml of the individual components with an accuracy of around ± 10% by means of 0.5N alcoholic (80%) sodium hydroxide and measurement of the extinction at 242 nm.

---

Résumé On a effectué la séparation de l'oestrone, de l'oestradiol 17 et de l'oestriol, par chromatographie en couche mince. On peut alors doser par la lessive de soude alcoolique 0,5N (80%) et faire la mesure de l'absorption à 242 nm, jusqu'à 1,67 g/ml de chacun des constituants avec une précision d'environ ± 10%.

---

---

Frl. Brigitte Neumann danke ich für die wertvolle Hilfe bei der Durchfiihrung von Vorversuchen.     

HPLC isolation and NMR structure elucidation of the most prominent octabromo isomer in technical octabromo diphenyl ether

The major octabromo isomer of technical octabromo diphenyl ether mixture (technical octaBDE) DE-79 was isolated by RP-HPLC. Three serially coupled columns (each 250 mm long) enabled a good separation of the target compound from other congeners using 100% ACN as eluent. Approximately 100 microg of the target compound was isolated with a purity of >90% and investigated by MS for confirmation of the degree of bromination. 1H-NMR and 2-D 1H-13C correlation NMR spectra unequivocally clarified that the octaBDE in question is 2,2',3,3',4,4',6,6'-octabromodiphenyl ether (BDE 197). Based on annual production rates of technical BDE products (1999/2001), approximately 380 tons of BDE 197 were annually produced which, on the long term, may enter the environment. Compared with other individual BDE congeners, BDE 197 has the seventh highest application rate. Reductive debromination of BDE 197 can lead to four hepta-, 15 hexa-, 23 penta-, and 28 tetra-BDE isomers, respectively. This variety includes all known major BDEs of environmental concern (BDE 47, 85, 99, 100, 153, 154, and 183). The identification of BDE 197 in technical octaBDE DE-79 strongly suggests that research on the environmental fate of BDEs should include this key-BDE congener.     

1-Alkoxy-2-azaallenyl-komplexe von chrom und wolfram

The successive reaction of (CO)₆M with Na[NCR₂¹] and [Et₃O]BF₄ yields (CO)₅M[C(NCR₂¹)OEt] (II: M = Cr; III: M = W; CR₂¹ = C(C₆H₄Br-p)₂ (a), CPh₂ (b), C(C₆H₄OMe-p)₂ (c), C(C₆H₄)₂O (d), CBu₂^tt (e)). Hexacarbonyltungsten, (CO)₆W, reacts with Na[NCPh₂] and MeOSO₂F to give (CO)₅W[C(NCPh₂) OMe] (IV). X-Ray analysis of IIe shows that: (1) the CNC fragment is almost linear (171.7°); (2) the two NC bond lengths are equal within experimental error; and (3) the O,C,Cr,N plane is perpendicular to the C(Me₃),C,N,C(Me₃) plane (90.0°). Therefore compounds II–IV are best described as 1-alkoxy-2-azaallenyl complexes.     

Direct optical detection of singlet oxygen from a single cell

Singlet oxygen has been detected in single nerve cells by its weak 1270 nm phosphorescence (a1deltag --> X3sigmag-) upon irradiation of a photosensitizer incorporated in the cell. Thus, one can now consider the application of direct optical imaging techniques to mechanistic studies of singlet oxygen at the single-cell level.     

Investigation on anodized aluminium

Results of examinations with TEM, SEM, EDX, ISS, SIMS and AES on sulphuric acid anodized films on aluminium are reported. Important technical information about the 20-μm thick coatings were obtained by monolayer and depth analysis. The fine structure of the oxide film and its modifications during a sealing process are discussed. Possibilities to prevent sealing smut on the surface are shown. The metal distribution inside the films which are coloured electrolytically with metal salts, is investigated.     

Photochemistry of Isothiocoumarin (= 1H-[2]benzothiopyran-1-one)

Irradiation (λ = 350 nm) of 1H-[2]benzothiopyran-1-one ( 2 ) in the solid state affords selectively and in good yield 6aα, 6bα, 12bα, 12cα -tetrahydrocyclobuta[1, 2-c:4, 3-c′]bis([2]benzothiopyran)-5, 8-dione ( 3 ), the head-to-head (HH) cis-cisoid-cis-cyclodimer of 2 , X-Ray analysis of 2 confirms that this reaction proceeds according to the well-established topochemical principles. The same dimer 3 is obtained in low yields on irradiation of 10⁻¹ M solutions of 2 in either MeOH or MeCN, while no conversion at all is observed in benzene. On irradiation of 2 in MeCN in the presence of tetrachloroethene, the [2 + 2] photocycloadduct 4 is formed in good yield, the conversion 2 → 4 being efficiently quenched by naphthalene. In contrast, no reaction is observed -on irradiation of 2 in the presence of 2, 3-dimethylbut-2-ene, neither in polar nor in apolar solvents.     

Comparison between capillary electrophoresis and ion-chromatography for analysis of inorganic anions

Separation and detection of some selected inorganic anions with capillary electrophoresis are shown. The anions are separated in microbore capillaries (25 m* 0.2 m) and detected with a UV-detector. Results are compared with the method of ion exchange chromatography. In consideration of the most important physical and chemical parameters an easy kind of computer simulation for such electropherograms was developed.To get optimal results of separation and UV-detection in capillary electrophoresis some parameters of the device HPE 100, i.e. loading time in the electrokinetic sample injection mode and the running voltage are varied. The behaviour of absorption in the UV region of the chosen anions as well as the influence of pH values in retention behaviour are investigated. There is a simple way to calculate the electrophoretic mobilities from known retention times. Approximate limits of detection for all anions and for each technique are given.     

Organische Schwefelverbindungen—IV: Elektronenstossinduzierte Redoxreaktion von ortho-Nitrothiobenzoesäure-S-p-tolylester

The electron-impact fragmentation of S-p-tolylester of nitrothiobenzoic acid leads to a previously unknown rearrangement in the case of the ortho compound. This consists of an intra molecular redoxreaction with oxygen transfer from the o-nitro group onto the sulphur of the thiol ester group. The position of the nitro group is not only an essential influence on the fragmentation pattern, but also of dramatic importance in determining the lifetime of the molecular ion.