Dipole moments of some diphenyl thioethers: Absolute conformation of bis(o-nitrophenyl) sulphide

The electric dipole moments of three diphenyl thioethers have been measured in benzene solution at 25· and the conformational analysis of bis(o-nitrophenyl) sulphide has been carried out by vector addition. The results show that this compound exists in a twisted conformation with the phenyl rings considerably rotated from coplanarity with respect to the C-S-C plane and indicate that in o,o′-disubstituted derivatives of diphenyl sulphide steric rather than conjugative effects operate in determining the conformational preference.     

Conversions of 2-thioxo-1,3-dithiol-4,5-dicarboxylic acid dimethyl ester — The path to a new heterocyclic system, (4H,6H)-1,3-dithiolo[4,5-d]pyrimidine-2,5,7-trione and 5,6-dimercaptouracil derivatives

The conversions of 2-thioxo-1,3-dithiol-4,5-dicarboxylic acid methyl ester into anhydride, mono- and diamide, and monoamide methyl ester were demonstrated. The new heterocyclic system, (4H,6H)-1,3-dithiolo[4,5-d]pyrimidine-2,5,7-trione, was obtained by oxidative rearrangement-cyclization of 2-oxo-1,3-dithiol-4,5-dicarboxylic acid diamide with phenyliodosyl(hydroxy)tosylate and used to synthesize previously unknown 5,6-dimercaptouracil derivatives, including nickel dithiolene complex.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 9, pp. 1270–1275, September, 1992.     

Reaction of some sympathomimetic amines with sodium 1,2-naphthoquinone-4-sulphonate

Summary The condensation products of 4 sympathomimetic amines with 1,2-naphthoquinone-4-sulphonic acid have been prepared and examined. A spectrophotometric procedure based on the chloroform-soluble orange-red condensation product is described. The same products were investigated fluorimetrically after reduction with sodium borohydride. The results obtained are satisfactory.

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Zusammenfassung Die Kondensationsprodukte vier sympathicomimetischer Amine mit 1,2-Naphthochinon-4-sulfonsäure wurden dargestellt und untersucht. Ein spektralphotometrisches Verfahren auf der Grundlage des chloroformlöslichen, orangeroten Kondensationsproduktes wurde beschrieben. Die gleichen Produkte wurden auch fluoreszenzanalytisch nach ihrer Reduktion mit Natriumborhydrid untersucht. Die Ergebnisse sind befriedigend.

     

Preparation of high purity labelled Rose-Bengal with radioiodine

The exchange of Rose-Bengal in the mono-sodium salt with elementary¹³¹I in an organic medium allows for the preparation of a labelled product substantially higher in radiochemical purity than that produced by other methods. Purification of the starting material before the labelling process has been done by adsorption chromatography. Under the conditions described a radiochemical yield more than 97% can be obtained within 30–60 minutes. The product was stable during sterilization and storage for 10 days and was found to be free of¹³¹I.     

On the alkaloids of strychnos—xxxvi: The alkaloids of strychnos hirsuta spruce exbentham; two new β-carbolinic alkaloids,strychnohirsutine and tetradehydrostrychnohirsutine

The structures and configurations of two new β-carbolinic alkaloids, strychnohirsutine 1 and tetra-dehydrostrychnohirsutine 2, isolated from stem and root bark of Strychnos hirsuta, were reported. ¹H NMR data of N,O-diacetylstrychnohirsutine 5 and ¹H and ¹³C NMR data of O-acetyltetradehydrostrychnohirsutine 4 were listed. Alkaloid 1 was converted into 2 by catalytic dehydrogenation.     

Special features in the chemical structure of phosphorus isocyanates

The UV and IR absorption spectra and the NMR and NQR spectra of certain isocyanates of three- and four-coordinated phosphorus have been investigated. The reciprocal effect of the phosphorus atom and the NCO group is discussed on the basis of spectral analysis, quantum chemical calculations of the electron systems, and calculations of the normal vibrational forms. Comparison of the (PO) frequencies in the IR spectra of the phosphorus isocyanates with the Taft gives a linear relationship which testifies to the predominant inductive effect of the NCO group on the P(O)R₁R₂ grouping. A similar relationship is observed between the resonance frequency _res in the NMR spectra and for C1P(O)R₁R₂ compounds. The effect of the phosphorus atom on the electronic system in the NCO group is shown by the hypsochromic shift of the absorption band in the210-m region and an appreciable increase in its intensity, compared with alkyl isocyanates. This fact, which agrees with the NMR spectral data and the quantum chemical calculations, indicates the presence of conjugation in the P-N bond. We found the order of the P-N bond to be approximately 1.2. This partial double-bond nature of the P-N bond results from the interaction of the p electrons of nitrogen in the NCO group with the d orbitals of the phosphorus atom.We are grateful to our colleagues at the Kazan Physicotechnical Institute AS USSR A. I. Rivkind, S. G. Salikhov, and I. A. Safin for recording the spectra.     

Phenol Degradation Features in Aqueous Solutions upon Dielectric-Barrier Discharge Treatment

The formation kinetics and mechanism were studied for the intermediate and final products of degradation of aqueous phenol solutions in air and oxygen low-temperature dielectric-barrier discharge plasmas in a reactor with different geometric arrangements of electrodes. It was shown that the plasma-enhanced oxidation of phenol could be described in the general form by the well-known mechanism of enzymatic oxidation of toxic pollutants (-mechanism). The estimated effective rate constant of phenol degradation in an aqueous solution in an ₂ plasma in reactors with the parallel-plate and coaxial arrangement of electrodes was 2.2 × 10^–3 s^–1 and 5.8 × 10^–2 s^–1, respectively. It was found that the potential toxicity of solutions after treatment was 7.5 times lower than that of the untreated solutions.     

Colorimetric method for the determination of vanadium with tannic acid in water and oils

A new spectrophotometric method was developed to determine vanadium using tannic acid as a complexing reagent to form a coloured reaction product which can easily be extracted by 1-pentanol in the presence of cetylpyridinium. The developed method can successfully be applied to determine trace levels of 10 ng/ml of vanadium in natural waters without any preconcentration step. It can also determine less than 1 mg/kg of vanadium in edible oils and petroleum products.     

Photosensitized processes in vivo: proposed phototherapeutic applications

The use of photosensitizing dyes having intense absorption bands in the 600-900 nm spectral interval opens up new prospects in the field of photochemotherapy, because it allows the illumination of relatively large tissue volumes with no significant damage to photosensitizer-free tissues. Special interest is currently focused on the photodynamic therapy of solid tumors, because of the property of several dyes with a macrocyclic chemical structure (porphyrins, chlorins, phthalocyanines, xanthenes) to accumulate in significant amounts and be retained for prolonged periods of time by neoplastic lesions. Strategies are being developed for enhancing the selectivity of tumor targeting by photosensitizers through the exploitation of functional or biochemical differences between normal and malignant cells.