New beta-lactam antibiotics. Cephem derivatives with electron withdrawing substituents at position 3 (author's transl)]

New β-lactam antibiotics. Cephem derivatives with electron withdrawing substituents at position 3 Oxidation of the 3-formyl-2-cephem compound 1 according to Corey [6] gave 2-cephem-3-carboxylic esters 4a, b, c (Scheme 1), which proved to be useful intermediates for the synthesis of cephalosporins bearing in position 3 a methoxycarbonyl group (10a, b, c, d / Scheme 2) or a carboxy group (20, 25, 30/Schemes 3, 4). The 3-formyl-3-cephem compounds 31a, b could be transformed into cyano- (33a) or methoxyiminomethyl- (36a, c, d) cephems (Scheme 5), which represent further examples of cephalosporins with electron withdrawing groups in position 3.     

Homoisoflavonones. IV. New constituents of the eucomin series of Eucomis bicolor (author's transl)]

Homoisoflavanones. IV. New constituents of the Eucomin Series of Eucomis bicolor. Four new homoisoflavanones, (E)-7-O-methyl-eucomin ( 2a ), (—)-7-O-methyleucomol ( 5 ), (+)-3,9-dihydro-eucomin ( 7a ) and 7-O-methyl-3,9-dihydro-eucomin ( 8 ), were isolated from the bulbs of Eucomis bicolor Bak. (Liliaceae). Their structures were determined by spectral data and synthesis. These compounds occur exclusively in the waxy material between the bulb leaves. Furthermore it was shown that only (Z)-eucomin ( 1b ) is genuine, (E)-eucomin ( 1a ) being an artefact. It is likely that 2a is also not genuine. A new method for a selective 7-O-methylation is described.     

Synthesis of a homologous 3beta-hydroxycard-5,22-dienolide (author's transl)]

Synthesis of a homologous 3β-hydroxycard-5,22-dienolide. We describe the synthesis of 4′-[(3β-hydroxy-androst-5-en-17β-yl)methyl]-2′(5′)-furanone ( 22 ) starting from 3β-acetoxy-androst-5-ene-17β-carboxylic acid ( 5 ).     

Lysergic acids. II. Isolation and separation of lysergic acids (author's transl)]

During studies on the isolation of both lysergic acids, D-and D-iso-, from hydrolytic mixtures of ergot alkaloids, it became necessary to find a simple chromatographic system for column isolation of lysergic acids. The column with controlled pore glass is highly effective for these purposes. The separation of both isomeric lysergic acids occurs on the column with silica gel. The assay and the composition of lysergic acid are estimated by thin-layer chromatography on precoated plates.     

Synthesis and absolute configuration of the enantiomers of verapamil (author's transl)]

Synthesis and Absolute Confifguration of the Enantiomers of Verapamil. Starting from the acids IV-(+) and IV-(?), a synthesis of the enantiomers I-(+) and I-(?) of the coronary vasodilator Verapamil is described and their absolute configuration determined through a chemical filiation with the acid XII-(S)-(+).     

Separation of herbicides by high-performance liquid chromatography. Influence of water (author's transl)]

The influence of the amount of water dissolved in dichloromethane on the chromatographic separation of herbicides was studied. The selectivity of the mobile phase was demonstrated and compared to another system, dichloromethane modified with 2-propanol. The high efficiency of microporous packing was also demonstrated.     

The aromatic amino acid constituent of echinocandin B: 3, 4-dihydroxyhomotyrosine (author's transl)]

The aromatic amino acid constituent of Echinocandin B: 3,4-Dihydroxyhomotyrosine. The antifungal antibiotic echinocandin B gave upon treatment of its tetrahydroderivative with anhydrous trifluoroacetic acid and subsequent methanolysis the tripeptide threonyl-(4-hydroxyprolyl)-(4-oxohomotyrosine) methyl ester ( 8 ), which could be hydrolysed to 4-oxohomotyrosine ( 11 ). These facts together with the earlier described hydrolysis of the antibiotic to 1-amino-3-p-hydroxyphenyl-2-propanone ( 6 ) and the reductive hydrolysis to homotyrosine suggested the presence of 3,4-dihydroxyhomotyrosine ( 14 ) as a constituent amino acid of echinocandin B. This was confirmed by a degradation of the intact tetrahydro-polypeptide with perjodate yielding p-hydroxybenzaldehyde and by the isolation of free 3,4-dihydroxyhomotyrosine upon mild acidic treatment of the tetrahydro-polypeptide.     

On renal excretion of sodium 4-iodo-5-methylpyrazole-3-carboxylate-131I (author's transl)]

Sodium 4-iodo-5-methylpyrazole-3-carboxylate-131I(IMPC-131I) was synthesized by isotope exchange with Na 131I in the molten state to evaluate its potential usefulness as a renal function and/or imaging agent. Tissue distribution and clearance characteristics of IMPC-131I are described. Tissue distribution experiments in rats indicated a very high renal concentration of radioactivity following intravenous administration. At 5 min the kidney took up 27.8% of the injected dose (16.1% dose per gram) and the total activity in the kidney still accounted for 9.8% of the injected dose at 30 min, with only 1.2% localizing in the liver. The ratios for kidney-to-liver in the concentration of IMPC-131I were always higher than those of hippuran -131I throughout the period of the experiment. Within 24 hr, 78.6% of the injected dose were excreted in the urine. The autoradiographic and the scannographic studies were also performed. The present results suggest that IMPC-131I has potential as a new agent for both funciton and imaging studies of the kidney.     

257. New beta-lactam antibiotics. The preparation of 8-beta-phenylacetamidohomoceph-4-em-5-carboxylic acid (1). Modifications of antibiotics. 7

The thiazolidine β-lactam 3 adds acrolein in a Michael type reaction. The resulting 'carbinolamide 4 is converted to 8-β-phenylacetamido-homoceph-4-em-5-carboxylic acid ( 1 ) by previously described methods.     

A synthesis of vitamin A according to the sulfone method (author's transl)]

A Synthesis of Vitamin A According to the Sulfone Method. Starting from β-ionyl phenyl sulfone 7 and an appropriate allylic chloride 10 retinol 14 has been prepared by a direct procedure. Subsequent acetylation and isomerization led to crystalline all-E-vitamin A acetate 16 .     

Profiles in chronic diseases. I. Investigations of steroid profiles in uremia (author's transl)]

Steroid profiles of hemofiltrates of uremic patients contain as main steroids the sulfates of 11beta-hydroxyetiocholanolone, 11-ketoetiocholanolone, 11beta-hydroxyandrosterone and 11-ketoandrosterone. In blood of uremic patients androstenediol is the main steroid of the sulfate fraction, while in blood of healthy persons dehydroepiandrosterone sulfate is the main steroid. The gradual decrease of the kidney function is characterized by an increase of 11-oxigenated androstane conjugates in urine.     

Vinylogous acyl compounds. XV. Thin-layer chromatographic detection of 2-halovinyl ketones with toxicological relevance (author's transl)]

The basic ring-opening of 1-(2-acylvinyl)-pyridinium salts yielding azaoxonol dyes and the spontaneous dehydrohalogenation of 1-(2-acylvinyl)-4-(4-nitrobenzyl)-pyridinium salts to deeply coloured anhydrous bases underlie two sensitive thin-layer chromatographic detection procedures for 2-halovinyl ketones (R-CO-CH=CH-X). The detection limits are 0.06 mug on successive use of methanolic solutions of pyridine and potassium hydroxide as spray reagents and 0.02 mug on spraying with an acetonic solution of 4-(4-nitrobenzyl)-pyridine. RF values of twenty-five trans- and twelve cis-configurated 1-halovinyl ketones for three solvent systems are given.