Synthesis of nonactin (author's transl)]

Synthesis of Nonactin. The macrotetrolide antibiotic nonactin (I), containing four units of a C₁₀ hydroxy acid, has been synthesized starting from two adequately protected derivatives (III and IV) of nonactic acid (II). The 32-membered ring of the macrotetrolide is built up by a sequence of condensation and deprotection steps leading first to a product with two, and subsequently to one with four nonactic acid residues (VIII) which is then cyclized in the presence of Ag⁺-ions. Two reactions forming ester bonds have been developed to condense the hydroxy acids and to effect the final cyclization. In one the activation of the carboxyl group is achieved by conversion into the mixed anhydride with 2,4,6-trimethylbenzene sulfonyl chloride in pyridine. In the other the Ag⁺-ion induced reaction of a S-(2-pyridyl) hydroxy carbothioate is used to form the corresponding macrocyclic lactone. In the case of nonactin the ring closure is promoted by the coordinating effect of Ag⁺-ions present in the reaction mixture.     

The synthesis of 2,2'-Dinor-carotenoids (author's transl)]

The Synthesis of 2,2′-Dinor-carotenoids. 2,2′-Dinor-carotenoids which include the naturally occurring actinioerythrol ( 1 ) and the blue carotenoid violerythrin ( 2 ) have been obtained by total synthesis. The synthesis starts with acetone and acetylene and yields compounds 1 and 2 as well as other carotenoids of the same type.     

Synthesis of racemic proferrorosamin and ferrorosamin A (author's transl)]

Synthesis of Racemic Proferrorosamin and Ferrorosamin A. The synthesis of proferrorosamin starting from methyl 2-phenylacetamido-acrylate and ethyl 3-oxo-3-(2-pyridyl)-propionate is described. Proferrorosamin A is complexed with Fe²⁺ and isolated as pure ferrorosamin A.     

Urine steroid profiles of hirsute women (author's transl)]

Steroid profiles of women suffering from idiopathic hirsutism show in more than 50% of the cases of 10--100 fold increase in the excretion of dehydroepiandrosterone (DHEA) compared with normal values. The excretion of DHEA was reduced much more than that of other 17-ketosteroids if the adrenals (NNR) were suppressed by dexamethasone (DXM). Within one week they reached values at the compound noise level of the gas chromatograms. If the ovaries were stimulated with human chorionic gonadotropin during continued suppression of the NNR with DXM no increase of DHEA could be detected.     

Determination of indolalkylamines after selective derivatisation (author's transl)]

The 1N-TMS-omegan-TFA-derivatives of indolalkylamines are suitable for estimation by combined gas chromatography and mass spectrometry for two reasons, viz. (1) Under electron impact charge stabilisation at the indole nucleus is favoured, so structure-specific ions form the base peak. For unsubstituted indoles m/e values of 202 are found and for hydroxyl-substituted indoles m/e values of 290. (2) The calibration curves of the derivatives are linear, even in the femtomole range. The 1N-TMS-omegan-derivatives can easily be obtained by trimethylsilylation with N-methyl-N-trimethylsilyltrifluoroacetamide containing catalytic amounts of N-trimethylsilylimidazole followed by acylation with N-methyl bis(trifluoroacetamide). The serotonin concentrations in different rat tissues are determined by this method of selective omegaN-trifluoroacylation-1N-trimethylsilylation and compared with the values obtained by pertrimethylsilylation.     

Radiolytic decontamination of Di-n-butyl phthalate from water (author's transl)]

Recently, a considerable amount of phthalic acid esters (PAE), the most widely utilized plasticizer, has been released into and polluted the environment. Since their toxicity and teratogenicity, although fairly low, to experimental animals have recently been shown, the removal of them from the environment, especially from the drinking water, is desirable. As an attempt for the removal, the radiolytic degradation of 7-14C-di-n-butyl phthalate (14C-DBP) in water was investigated at several pHs. Approximately 50% of 14C-DBP (1 ppm aqueous solution) was decomposed by 60Co gamma-irradiation to a dose of 3 X 10(4) rad at pH 7 and the main product was mono-n-butyl phthalate (MBP). At pHs 3 and 11 14C-DBP was more easily radiolyzed and converted to ether-soluble compounds other than MBP or phthalic acid (PA). By irradiation to 10(6) rad 14C-DBP as well as 14C-MBP and 14C-PA, at pH value tested, was almost completely decomposed to volatile or water-soluble substances of possibly low molecular weight. These findings suggest that the gamma-irradiation is effective to make the PAE-polluted water clean.     

Synthesis and absolute configuration of clemastine and its isomers (author's transl)]

Synthesis and Absolute Configuration of Clemastine and its Isomers. Condensation of 4-chloro-α-methylbenzhydrylalkohol ( 1 ) with 2-(2-chloroethyl)-1-methylpyrrolidine ( 2 ) gave an isomeric mixture of 2-[2-(p-chloro-α-methyl-=-phenylbenzyloxy)ethyl]-1-methylpyrrolidine ( 3 ) and 4-(p-chloro-=-phenylbenzyloxy)-1-methyl-hexahydroazepin ( 4 ). The separation of the four possible optically active isomers of 3 is described and their absolute configuration established by degradation to (R)- and (S)-1-methyl-2-pyrrolidineethanol ( 6 ), respectively, and by an X-ray cristallographic analysis of the quarternary methiodide of the isomer 3-A . Clemastine (3-A) is (+)-(2R)-2-[2-((αR)-(p-chloro-α-methyl-α-phenylbenzyloxy)ethyl)]-1-methylpyrrolidine.     

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 ).     

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)-(+).     

High-pressure liquid chromatography of free and conjugated 17-ketosteroids (author's transl)]

High-pressure liquid chromatography (HPLC) should be used more frequently in biomedical research because heavy molecules can be analysed at ambient temperature without derivatisation to volatile compounds. In this paper the separation of four free 17-ketosteroids, their ester sulfates and glucuronides by reversed-phase HPLC on a Micropak CH column is described. In order to improve the separation several parameters have been studied. Retention data allow comparison of the hydrophilic behaviour of free and conjugated steroids.     

Accumulation mechanism of 111In in malignant tumor (author's transl)]

In order to clarify the accumulation mechanism of 111In in maligant tumor, subcellular distribution of 111In was quantitatively determined. Buffalo rats bearing Morris hepatoma 7316A were injected intraperitoneally 111In-chloride and tumor tissues were removed 24 hours later. Subcellular fractionation of tumor tissues were carried out according to the method of C. de Duve, et al. and radioactivity of each fraction was counted. Most of the total radioactivity was distributed among the soluble, nuclear and lysosomal fractions. On account of its low protein content, the relative specific radioactivity was the highest in the lysosomal fraction. The lysosomal fraction was solubilized gradually and the resultant stepwise release of 111In and acid phosphatase activity were measured. There was a close relationship between them. From these results it was concluded that 111In accumulated especially in the lysosomes. In the electron micrography the tumor lysosomes had already engulfed many foreign materials, so that the lysosomal function would be depressed.     

13C-NMR. Studies on ion-selective liquid membranes (author's transl)]

¹³C-NMR. Studies on Ion-Selective Liquid Membranes. A method for the ¹³C-NMR. study of solvent polymeric membranes in equilibrium with aqueous salt solutions is described. Neutral ion carriers incorporated in these membranes maintain a high degree of rotational mobility. The complexation by group IA and IIA cations of macrotetrolide antibiotics as well as of carriers of the type 3,6-dioxa-octanedioic diamides in the membrane phase was followed by ¹³C-NMR. chemical shift and spin-lattice relaxation studies.     

Determination of radioactive and stable cobalt in marine biological materials (author's transl)]

Studies were made to develop the method for rapid determination of radioactive and stable cobalt in a single specimen of marine biological materials. The sample was dried, ashed, and dissolved in acid. The cobalt was extracted with 1-nitroso-2-naphthol benzene and determined by absorptiometry on the benzene phase. Then, the organic solution was evaporated to dryness, and the residue was treated with nitric-perchloric acid mixture to decompose any organic matter, and taken up with hydrochloric acid. The cobolt was extracted from the solution with TIO A-toluene, and the radioactive cobalt was determined by liquid scintillation counting on the toluene phase. Examinations were made on the chemical yield and on the decontamination factor of the fission product nuclides. Analysis were made on the marine biological samples of Urazoko Bay, Fukui prefecture. Agreement of the radioactive cobalt data between that by the present method and that by Ge(Li) gamma ray spectometry was good. Also, the stable cobalt value by the present method agreed well with that by neutron activation analysis method.     

A general method for synthesis of folic acid, its conjugates and analogues (author's transl)]

A general method for synthesis of folic acid, its conjugates and analogues . A new and general method for the synthesis of folic acid, folic acid conjugates and folic acid analogues is described. The key step, i.e. the condensation of N(2′)-acetyl-6-formyl-pterine (I: R¹ ? COCH₃) with aminoaryl derivatives II, is achieved by refluxing in absolute ethanol to afford the azomethines III. NaBH₄-reduction followed by basic hydrolysis gives pure V products in high yield, free from 7-isomers.     

Isolation and identification of two beta-carbolins in roasted chicory root (author's transl)]

Isolation and identification of two β-carbolins in roasted chicory roet. Two β-carbolines, harman and norharman, have been isolated from roasted chicory roots by solvent extraction and chromatography on alumina. They have been identified by chromatographic and spectroscopic techniques in comparison with reference compounds.