Photoreactions of aromatic compounds—XXXV: Nucleophilic photosubstitution of methoxy substituted aromatic compounds. Monophotonic ionization of the triplet

Methoxy groups exert an activating and ortho/para directing influence in light induced nucleophilic substitution reactions (cyanation, hydroxylation, etc) of aromatic compounds in aqueous media. The first chemical step in these processes is monophotonic ionization of the aromatic compound in its lowest triplet state, followed by reaction of the radical cation with the nucleophile Quantum yields of photocyanation of 4-fluoro- and 4-chloroanisole indicate that in 99% (mole fraction) water virtually all triplets formed undergo electron ejection.This hypothesis is in agreement with the results of charge density calculations for the radical cations. It is directly supported by the similarity of the product composition of these photochemical substitutions with that of anodic substitutions, where the intermediacy of an aromatic cation is generally accepted. The presence of an oxidizing agent (oxygen, or persulphate) is required only when a hydrogen is replaced. The nucleophilic photosubstitution at electron rich aromatic systems in solvents as water can therefore be classified as an S_r⁺n¹(³Ar^*) process.     

Photometrische Bestimmung von Titan in molybd?nhaltigen St?hlen mit Tetrahydroxyphenazin

Zusammenfassung Tetrahydroxyphenazin (THP) bildet mit Titan im sauren Medium Komplexe mit sehr hohen Werten des Extinktionskoeffizienten. Es wird ein Bestimmungsverfahren für Titan in molybdänhaltigen Stählen beschrieben, bei dem die störenden Elemente mit einem Gemisch aus Tri-n-butylphosphat und Chloroform extrahiert werden. Das in der wäßrigen Phase verbleibende Titan wird mit THP photometrisch bestimmt. Die hochempfindliche Methode erlaubt Titanbestimmungen im Nanomol-Bereich. Bei Stahlproben mit 0,2–0,7% Ti (in Gegenwart von 0–2% Mo) ergab sich ein Variationskoeffizient von 0,4 bis 2,4%.

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Photometric determination of titanium in molybdenum steels with tetrahydroxyphenazine

Complexes with very high molar extinction coefficients are produced in the reaction of tetrahydroxyphenazine (THP) with titanium in acid solution. In the method described titanium is determined photometrically by complexing with THP in the aqueous phase after extracting the interfering elements with a mixture of tri-n-butyl-phosphate and chloroform. This highly sensitive method is applicable for determination of titanium in the nanomolar region. With steel samples containing 0.2–0.7% of Ti (in presence of 0–2% of Mo) variation coefficients of 0.4 to 2.4% have been obtained.

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Für die Durchführung dieser Arbeit wurden dankenswerterweise Forschungsmittel aus dem ERP-Sondervermögen bereitgestellt.Dem Verbande der Chemischen Industrie und der Deutschen Forschungsgemeinschaft, die diese Arbeit unterstützt haben, danken wir bestens.     

Hemmung der aktiven Bromidaufnahme durch Pflanzenzellen durch Glucose

Zusammenfassung Die Aufnahme von Bromid-Ion durch Chlorella pyrenoidosa, die durch aktiven Transport erfolgt, wird durch Glucose gehemmt, obwohl die Atmung stimuliert wird. Die Hemmung tritt bei Energielieferung durch Belüftung oder Belichtung ein. Galactose und Mannit wirken nicht wie Glucose. Offenbar hemmt die Glucose die Nutzbarmachung des Elektronenflusses bei dem System der Atmung oder Photophosphorylierung für die Bromid-Aufnahme.

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The absorption of bromide ion by chlorella pyrenoidosa, which is due to active transport, is inhibited by glucose though respiration is stimulated. Inhibition is observed when energy is supplied either by aeration or by illumination. Galactose or mannitol do not act like glucose. Apparently glucose interferes with the utilization of electron flow in the respiration or photophosphorylation systems for the absorption of bromide.

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Mit 3 Abbildungen.

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Herrn Prof. Dr.F. Wessely zum 70. Geburtstag in Verehrung gewidmet.     

Inhibition by protease inhibitors of binding of adrenal and sex steroid hormones.

Binding of steroid hormones is inhibited by protease inhibitors and substrates. The protease inhibitors phenylmethyl sulphonylfluoride, tosyl-lysine chloromethyl ketone, and tosylamide-phenylethyl-chloromethyl ketone and the protease substrates tosyl arginine methyl ester and tryptophan methyl ester eliminate specific binding of aldosterone, dexamethasone, dihydrotestosterone, estrogen, and progesterone to their respective receptors. These protease inhibitors and substrates also inhibit binding of progesterone to the 20,000 molecular weight mero-receptor formed from the progesterone receptor in chick oviduct. The binding of estradiol to rat alpha-fetoprotein is inhibited by the protease inhibitors and substrates but not by tryptophan or tryptophan amide, indicating the importance of an ester structure in the inhibition of steroid binding. Our results suggest that all steroid hormone receptors have a site with both common structural features and a role in the regulation of steroid hormone binding.     

A study of 1,2,3,4-tetrahydro-4-azafluorene-3,9-diones

Intramolecular cyclization of the diamides and N,N-dimethylamides of -[indan-1,3-dion-2-yl]benzylmalonic acids (I) has given 1-aryl-2-carbamoyl-1,2,3,4-tetrahydro-4-azafluorene-3, 9-diones and 1-aryl-4-methyl-2-methylcarbamoyl-1,2,3,4-tetrahydro-4-azafluorene-3,9-diones (II). The structure of compounds II was shown by chemical methods: bromination, xanthylation, and hydrolysis in alkaline and acid media, and also by a study of IR and UV spectra.     

Peak distortion in the column liquid chromatographic determination of omeprazole dissolved in borax buffer.

Injection of a sample containing omeprazole dissolved in borax buffer (pH 9.2) into a reversed-phase liquid chromatographic system consisting of a mixture of acetonitrile and phosphate buffer (pH 7.6) as the mobile phase and a C18 surface-modified silica as the solid phase resulted under special conditions in split peaks of omeprazole. The degree of peak split and the retention time of omeprazole varied with the concentration of borax in the sample solution and the ionic strength of the mobile phase buffer as well as with the column used. Borax is eluted from the column in a broad zone starting from the void volume of the column. The retention is probably due to the presence of polyborate ions. The size of the zone varies with the concentration of borax in the sample injected. In the borax zone the pH is increased compared with the pH of the mobile phase, and when omeprazole (a weak acid) is co-eluting in the borax zone its retention is affected. In the front part and in the back part of the borax zone, pH gradients are formed, and these gradients can induce the peak splitting. When the dissolving medium is changed to a phosphate buffer or an ammonium buffer at pH 9 no peak distortion of omeprazole is observed.     

Effect of the specific activity of the tracer on rat luteinizing hormone radioimmunoassay

Rat luteinizing hormone /LH/ was labelled with¹²⁵I by the Chloramine T method.¹²⁵I-LH, used as tracer in radioimmunoassay, was separated from the labelling reaction mixture by gel filtration. By using the proper protein/radioiodine ratio in the labelling reaction mixture the specific activity of¹²⁵I-LH was adjusted to 2.5–20.5 MBq g^–1. The influence of the specific activity on the assay parameters as well as on the tracer stability was investigated.     

New catalytic method for the synthesis of vitamins K

A new catalytic method for the synthesis of vitamins of the K family is suggested. In this method 2-methyl-1-naphthol is oxidized by dioxygen in the presence of Mo-V-P heteropoly acids or their salts in a two-phase system (organic solvent + water) to 2-methyl-1,4-naphthoquinone or vitamin K3, which is the precursor of all K family vitamins.     

An investigation of mononuclear and binuclear palladium(II) complexes of egta (egta = glycine,N,N′-(1,2-ethanediylbis(oxy-2,1-ethanediyl)bis[N-carboxymethyl]) by 1H-, 13C- and 15N-n.m.r. methods

1:1 and 2:1 palladium(II) complexes of egta^4– (egta^4– = glycine, N,N-(1,2-ethanediylbis)(oxy-2,1-ethanediyl)bis[N-carboxymethyl]) were prepared by 1:1 and 2:1 addition of K₂PdCl₄ to K₄egta, and examined by ¹H-, ¹³C- and ¹⁵N-n.m.r. methods. The 1:1 complex, [Pd(egta)]^2– in solution, utilizes a square-planar coordination comprised of two nitrogen and two glycinato carboxylate donors of egta^4–, leaving two glycinato carboxylates pendant. The complex has a cis-(R,S) stereochemistry which places both pendant carboxylates below the PdN₂O₂ square plane and the tether backbone of egta^4– in the up, up sense above the same plane. The cis-(R,S) assignment was assisted by computer simulations of the ¹³C-n.m.r. spectrum for four possible isomers. Only cis-(R,S) and trans-(R,R) calculated ¹³C-spectra were compatible with the observed ¹³C-n.m.r. pattern. The HH NOESY spectrum of [Pd(egta)]^2– detects long range coupling of the backbone –OCH₂CH₂O– linkage with both coordinated and pendant glycinato CH₂ moieties. The cis-(R,S) isomer's tortional movements allow such contacts whereas a trans-(R,R) isomer does not. The 2:1 complex, [Pd₂(egta)(H₂O)₂] in solution has an extended-chain structure with each palladium(II) center coordinated in the mer-iminodiacetate-like coordination with two bound glycinato-functionalities.