A carbon-13 nuclear magnetic resonance study of the 1,4-diene analogues of steroid hormones and related steroids

The ¹³C NMR spectra of sixteen 4-ene-3-keto- and 1,4-diene-3-keto corticosteroids are described. Substituent shifts and the effect of added methanol-d₄ are reported, and conformational distortions and intramolecular hydrogen bonding are analysed based on these data.     

New results on the influence of the nature of the nucleophile in the stereospecific modification of poly(vinyl chloride)

The nucleophilic substitution reactions on poly(vinyl chloride) (PVC) with potassium 4‐acetamidothiophenolate, potassium 2‐naphthalenethiolate, and sodium 2‐mercaptobenzothiazolate have been undertaken in a cyclohexanone solution. The aim was to study, from a comparative point of view, the influence of nucleophile characteristics, in particular bulkiness, reactivity, and nucleophile polarity, on the reaction mechanisms by following the microstructural evolution with the degree of substitution of the same PVC sample with three types of nucleophile under the same experimental conditions. The quantitative microstructural analysis as a function of conversion has been followed by ¹³C NMR spectroscopy. Because of the steric hindrance and moderate reactivity of 2‐mercaptobenzothiazolate, the stereoselective nature of the reaction is enhanced, occurring via the meso‐racemic ( mr ) triad of mmr tetrad, inoperative in practice, unlike the other nucleophiles. This circumstance and the fact that the bulkiness of the nucleophile and interacting effects provide an enhancement of the molecular microstructure‐based mechanisms, such that glass‐transition temperature (T_g) varies with the degree of substitution, in all cases, along with the ratio between the extent to which mmr and rrmr structure intervene in the substitution reaction, thereby providing new and valuable information regarding the T_g–microstructure relationship. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 6052–6060, 2004     

Oxidative Cyclization of Iodo Ketones. Synthesis of 6-Oxa-5alpha-pregnane-3,20-dione

The steroidal delta- and gamma-iodo ketones 1 and 9 were converted to the cyclic hemiketals 3 and 10, by oxidation to the iodoso derivatives with m-CPBA. Spontaneous cyclization of the latter intermediates to the corresponding oxocarbenium ions, followed by stereoselective addition of water, rendered the hemiketals. Depending on the reaction conditions, the five-membered oxocarbenium ion derived from the gamma-iodo ketone 9 may add H(2)O or m-CPBA to give either the hemiketal or a Baeyer-Villiger type product 12, while the oxocarbenium derived from 1 gives exclusively the hemiketal. When the reaction was carried out in dry methanol, methyl ketals were formed. Use of this methodology allowed us to synthesize 6-oxa-5alpha-pregnanes with and without functionalization at C-19.     

Chirality and Crop Protection

The modern agrochemical industry is searching, more intensively than ever, for new substances to combat pests (weeds, deleterious insects, plant pathogens, etc.). In the complex and costly selection and optimization process, state-of-the-art scientific methods are always needed. The aims of the interdisciplinary optimization are mainly the reduction of the rate of application of the new substance, an increase in the selectivity against the target organism, and the optimal ecological profile. If a promising crop protection compound is a racemate or a diastereoisomeric mixture, the chemist has a unique opportunity to contribute to this optimization process through the synthesis of enantiomerically pure isomers for testing purposes. If the single isomer proves to be biologically superior to the racemate, the development of an economical and ecologically sound process for the production of the single isomer presents an even greater challenge. The average price of a crop protection compound is much lower than that for a pharmaceutical product, and this fact imposes a severe limitation upon the flexibility of the chemist who is concerned with the synthesis and production of a stereochemically pure agrochemical. This forces the crop protection chemist to make full use of both his scientific and creative capabilities. Fortunately, parallel to the development of the above optimization aims of a modern and ecologically sound crop protection research, there has been a continuous and worldwide advance in the area of asymmetric synthesis. Due to the interplay of these two parallel efforts there has been a great accumulation of chemical, biological, and agronomical knowledge in recent years, which should have implications beyond merely the synthesis of enantiomerically pure agrochemicals.     

X-ray reflectivity investigations of glass surfaces produced by float and draw techniques

Surfaces of soda-lime glass and borosilicate glass have been investigated by grazing incidence X-ray reflectivity (GIXR). Characteristic differences are obtained in dependence on the fabrication procedure, the composition and the cleaning procedure. Strong variation is recorded between the two soda-lime float glass surfaces while minor differences are analysed between the top and bottom side of borosilicate float glass. This is attributed to the reduced amount of tin diffused into the bottom side of the borosilicate glass surface. Different cleaning procedures generate characteristic changes on the glass surfaces which can be verified by GIXR. The results indicate that borosilicate float glass combines the merits of the good surface quality of float glass with the high chemical resistivity of borosilicate glass.Dedicated to Professor Dr. rer. nat. Dr. h.c. Hubertus Nickel on the occasion of his 65th birthday