Spectrophotometric determination of thiourea in microgram quantities

Summary Copper(II) forms a stable colourless complex with thiourea. This property has been utilized to develop a Spectrophotometric method for the determination ofg quantities of thiourea. The complex absorbs in ultraviolet region and the determinations are carried out at 250 nm. The method permits the determination of thiourea from 10–60g with error not exceeding ± 1.0%.

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Zusammenfassung Kupfer(II) bildet mit Thioharnstoff eine farblosa Komplexverbindung, die sich auf Grund ihrer Absorption bei 250 nm zur spektrophotometrischen Bestimmung von Mikrogrammengen Thioharnstoff eignet. 10 bis 60g Thioharnstoff lassen sieh mit einem Fehler von höchstens ± 1,0% bestimmen.

     

One-Pot Convenient and High Yielding Synthesis of Dithiocarbamates

Summary. A convenient and high yielding method for the synthesis of diverse dithiocarbamates having various substituents including alkyl, aryl, heteroaryl, and alkylaryl at the thiol chain or at the amine chain or at both thiol and amine chains were developed by the one-pot reaction of mercaptans, amines, and bis(benzotriazolyl)methanethione in presence of amidine base under mild reaction conditions.     

Novel solid-phase extraction and preconcentration technique coupled with ICP-AES for the determination of Cr(III), Ni(II), and Zn(II) in various water samples

Newly synthesized 2-propylpiperidine-1-carbodithioate (2-PPC) was used for the extraction of Cr(III), Ni(II), and Zn(II) from various water samples. In the present investigation, the use of a syringe loaded with sorbent for the separation and enrichment of Cr(III), Ni(II), and Zn(II) prior to their determination by inductively coupled plasma-atomic emission spectrometry (ICP-AES) was proposed to substitute the batch and column techniques. The described method was compared with the column technique with respect to fastness, simplicity, recovery, and risk of contamination. The syringe was loaded with 1.0 g of sorbent in order to retain the analyte elements. Next, 7.0 mL of sample solution (pH 5.0 ± 0.2) was drawn into the syringe in 15 s and discharged over 15 s. Then, an eluent (3.0 M HCl) was drawn into the syringe and ejected back to desorb the analyte elements. At the optimum conditions, the percentage recoveries of Cr(III), Ni(II), and Zn(II) were in the range of 94.50 to 99.62% with a standard deviation (S.D.) of 0.03%. The elements could be concentrated by drawing and discharging several portions of sample successively and eluting only one time. The detailed study of various interferences proved the method to be highly selective. The risk of contamination is less than that with the column technique. The method was successfully applied to the determination of Cr(III), Ni(II), and Zn(II) in spiked and natural water samples. The results obtained are in good agreement with those obtained by the reported methods at the 95% confidence level. The text was submitted by the authors in English.     

Dispersion characteristics of broadside coupled dielectric image guide at millimeter wave frequencies

Dispersion characteristics and wave impedance for the even and odd modes of the broad side coupled dielectric image guides are computed by using mode matching techniques. Dispersion curves for broadside image guide are plotted for various dielectric materials and dimensional parameters as a function of frequency. Normalized electric field for dominant electric field component E of TM even and odd modes for various half spacings between two dielectric slabs of broadside coupled image guide have been plotted. Polysterene ( r=2.56) and Stycast ( r=3.4) have been used as dielectric materials in fabricating broadside coupled image guide. This broadside coupled dielectric guide is very convenient as compared to the other dielectric guides. Since in case of broadside coupled image guide the dielectric slab can be bonded to the side metallic walls using some low loss adhesive material, while in other coupled dielectric guides the dielectric slab have to be supported by some low dielectric constant material (Eccofoam with r=1.02) to maintain the proper distance of side metallic walls from the dielectric slab. Since this structure is symmetrical, this configuration can be analysed in terms of even and odd mode phase velocities. The difference in these even and off mode phase velocities can be used to determine the coupling between coupled dielectric slab. Various couplers in this configuration can be realised.     

Molecular constants of substituted ethylene-type molecules: IV. Inertia defects and rotational constants of vinyl halides and their deuterated derivatives

The inertia defects of some vinyl halides and their deuterated derivatives have been calculated on the basis of the general formulation developed by Oka and Morino. The initial sets of Urey-Bradley force constants, based on published data, were adjusted by a least squares procedure until they reproduced the fundamental vibrational frequencies satisfactorily. The Coriolis coupling constants which satisfy the sum rules derived were evaluated and used to calculate the inertia defect in the ground vibrational state. The theoretical values of the inertia defect are used to determine the rotational constant A which cannot otherwise be accurately determined from an “a” type transition.     

Volumetric studies and thermodynamics of viscous flow of hydroxamic acids in acetone + water solvent at temperatures 303.15 and 313.15 K

Densities ρ and viscosities η of two hydroxamic acids, N-phenyl-2-chlorobenzo- and N-o-tolyl-4-chlorobenzo-, have been determined as a function of their concentration in aqueous acetone solution at temperatures 303.15 and 313.15 K. Apparent molar volumes, standard-state partial molar volumes and relative viscosities have been calculated. The viscosity data have been analyzed using Jones-Dole equation. The activation thermodynamic parameters of viscous flow have been evaluated using Feakins equation. These were obtained to throw light on the mechanism of viscous flow. Thermodynamic interactions in solutions have been studied in terms of a number of excess functions calculated from the experimental data. The effect of hydroxamic acid concentration and temperature on these parameters has been discussed. The results were interpreted in the light of solute-solvent interactions in aquo-organic media.     

On a new partitioning of the Hamiltonian in many-body calculation of pair-correlation energies in closed-shell systems

We introduce here a new partitioning of the Hamiltonian in calculating pair-correlation energies using many-body perturbation theory, by which we are able to eliminate the off-diagonal particle–hole (p–h) ladders exactly to all orders in the perturbation expansion. In this formulation, the particle states turn out to be different for each distinct pair of hole states in the correlation energy calculation. We have also included the contributions of the diagonal particle–particle (p–p) and hole–hole ladders exactly to all orders. The effect of the off-diagonal p–p ladders has been estimated for each pair by computing the third-, foruth- and fifth-order energies. For highly symmetric systems the present partitioning yields in general symmetry-broken orbitals. Here one may use an average kind of partitioning for all the partners of the degenerate sets, which restores the symmetry and at the same time ensures cancellation of the p–h ladders exactly at the lowest order and approximately at the higher orders. Results are presented for a selection of 6π-electron conjugated systems. The correlation energy for each pair is in excellent agreement with that obtained from a partial CI calculation involving all double excitations from this pair. The advantages of implementing the present scheme in larger systems has been discussed.     

Synthetische Versuche in der Gruppe hypotensiv wirksamer Alkaloide, 13. Mitt.: Synthese vondl-10-Methyldeserpidin,dl-10-Äthoxydeserpidin unddl-10-Methylmercapto-deserpidin

Zusammenfassung Die durch Umsetzung von 5-Methyltryptamin, 5-Äthoxytryptamin und 5-Methylmercapto-tryptamin (I, R=CH₃, OC₂H₅ bzw. SCH₃) mit dem racemischen Aldehyd-Ester II entstandenenSchiffschen Basen wurden durch Natriumborhydrid-Reduktion in Methanol unter gleichzeitiger Cyclisierung und Desacetylierung in die entsprechenden 10-substituiertendl-Methyl-2,3-seco-3-oxodeserpidate (IV) übergeführt. Die bei der Einwirkung von 3,4,5-Trimethoxybenzoylchlorid in Pyridin erhaltenen Ester V wurden weiter mit Phosphoroxychlorid cyclisiert und die Produkte als Perchlorate (VI) mit Zink in sauerer Lösung zu den entsprechenden 10-substituiertendl-Deserpidinen (VII, R=CH₃, OC₂H₅ bzw. SCH₃) reduziert. Mit Hilfe der Chromatographie gelang es in zwei Fällen, aus den Rohprodukten auch die entsprechendendl-3-Isodeserpidine (VIII, R=CH₃ bzw. OC₂H₅) zu isolieren. Zum Unterscheiden der Produkte der normalen Reihe (VII) und der 3-Iso-Reihe (VIII) wurden IR-Spektren und die Papierchromatographie angewendet.Mit 2 Abbildungen     

Kinetics and mechanism of oxidation of cyclopentanone by N-bromosuccinimide

N-bromosuccinimide oxidation of cyclopentanone in acidic media in presence of mercuric acetate has been made. A zero order dependance to N-bromosuccinimide and a first order dependence to cyclopentanone and hydrogen ion concentration has been observed. Ionic strength, mercuric acetate and succinimide has negligible effect while methanol addition has a positive effect. Various rate parameters have been computed and 1,2-cyclopentanedione identified as the end product. A suitable mechanism in confirmity with the above observations has been proposed.With 2 Figures     

Origin of the stereo- and regioselectivities in the Diels-Alder reactions of azaphospholes: a DFT investigation

Computations of the Diels-Alder (DA) reactions of azaphosphole representative namely, thiazolo[3,2-d][1,4,2]diazaphosphole with 1,3-butadiene and isoprene at the density functional theory level reveal concerted mechanisms via asynchronous transition states. The activation energies (B3LYP/6-311++G**// B3LYP/6-311G**), 16-19 kcal mol⁻¹, are much smaller than the value (32.57 kcal mol⁻¹) calculated for the DA reaction of the non-phosphorus analogue, imidazo[2,1-b]thiazole with 1,3-butadiene. An electron-withdrawing group at the 3-position of the dienophile enhances both stereo- and regioselectivities, which agree nicely with the experimental values. Inclusion of solvent effect (PCM model) reveals that the stereo- and regioselectivities are not affected appreciably. The relative stabilities of the transition structures corresponding to the endo/exo stereoisomers and meta (P/Me, 1:3)/para (P/Me, 1:4) regioisomers have been rationalized on the basis of the secondary molecular orbital interactions.