A facile synthesis of pyrrolo[3,2‐d]pyrimidines from 6‐azidouracils and ylide phosphoranes

A series of the title compounds, 9‐deazaxanthines, was regioselectively prepared in reasonable yields as major products from the reactions of 6‐azidouracils 1a,b with stabilized ester‐ 2a,b or keto‐ 2c ylide phosphoranes and a moderated phosphorus ylide 3 , instead of the expected triazoles. Side products were also observed wherein pyrimido[5,4‐g]pteridine‐2,4,5,7‐tetrone ( 15 ) and other fused ring systems or acyclic‐substituted uracil derivatives were isolated. A comparative study on the reactivity of 1a in analogy to 1b toward phosphoranes is also described. © 2002 Wiley Periodicals, Inc. Heteroatom Chem 13:357–365, 2002; Published online in Wiley Interscience (www.interscience.wiley.com). DOI 10.1002/hc.10048     

Synthesis of fused ring heterocycles from aromatic amines with hydroximoyl chlorides

Substituted 2-arylbenzimidazoles, 2-arylbenzoxazoles and 2-arylbenzothiazoles were obtained in good yield by the reaction of hydroximoyl chlorides with ortho-substituted aromatic amines. The benzo moiety of the benzimidazoles was shown by nmr to be symmetrical, indicating that the N-H group proton of the imidazole ring is exchanging with the water protons in the DMSO-d₆ solvent.     

Magnetic exchange coupling in imido bimetallic uranium(V) complexes. A relativistic DFT study

Magnetic exchange coupling between uranium U(V) ions, in the case of the two para- and meta-imido diuranium complexes, respectively [(C₅H₅)₃U]₂(μ-1,4-N₂C₆H₄) and [(C₅H₅)₃U]₂(μ-1,3-N₂C₆H₄) exhibiting the 5f¹-5f¹ configuration, have been investigated using relativistic DFT calculations, combined with the broken symmetry (BS) approach. Using the B3LYP functional, the singlet BS state of the para complex has been found of lower energy than the high spin (HS) triplet one, in agreement with the observed antiferromagnetic character of the complex. On the contrary the BP86 functional fails to predict this magnetic property. The spin density distributions and MO analysis explain well the antiferromagnetic character of the para complex and clarify the failure of the BP86 functional. The effective participation of the 5f metal orbitals in bonding with the imido ligand plays a key role for electronic and magnetic communication between the two active U(V) 5f¹ electrons. The same technique led us to explain the ferromagnetic character of the meta isomer in agreement with experiment. For both isomers the spin polarization mechanism explains well their observed magnetic behaviour.     

High-performance liquid chromatography quantification of principal antioxidants in black seed (Nigella sativa L.) phytopharmaceuticals

A new, simple, sensitive, rapid, and accurate isocratic RP-HPLC method was developed and validated for simultaneous analysis of the principal antioxidants of Nigella sativa, i.e., thymoquinone (TQ), carvacrol (CR), and its isomer thymol (THY), in different phytopharmaceuticals. The mobile phase was water-methanol (40 + 60, v/v) at a flow rate of 1.5 mL/min. Quantification was achieved with UV detection at 254 nm, based on peak area. The method was validated for linearity, accuracy, precision, selectivity, and robustness. The proposed method is stability-indicating for determination of TQ in the presence of its degradants. The LOD and LOQ (microg/mL) were, respectively, 0.006 and 0.021 for TQ, 0.002 and 0.006 for CR, and 0.027 and 0.090 for THY. The mean recoveries measured at three concentrations were higher than 99%, with RSD <2%. This analytical method is suitable for quality control of the marker substances in this widely used natural protective and curative remedy.     

Synthesis of Fused Thioxo-Pyran Systems From α-Methylene Carbonyl Compounds and Bismethylene-1,3-dithietane

A number of [2, 1-b] fused phosphono substituted-thioxo-pyrans 7,10,13 and 18 have been regioselectively synthesised from the reaction of the corresponding α-methylene carbonyl compound with phosphenato-substituted 1,3-dithietane 1. Conversely, 2-thiohydantoin 14 reacts with 1 to afford the respective 4-substituted derivative 15.     

KN Scattering in 3D Formulation

KN scattering is formulated in three-dimensional (3D) momentum space. A direct product of the relative-momentum state and the spin state is used as the basis state. The spin quantization axis is chosen along the z-axis. The interaction for the KN system is assumed to take the Yukawa-type. It consists of two terms, the central and the spin-orbit one. Calculations for the cross section based on this technique are shown, as well as comparison with the standard partial-wave calculations.     

Studies on arylhydrazonoisoxazolinethiones. Behaviour of 4-arylhydrazono-3-phenyl-2-isoxazoline-5-thiones toward hydrazines,grignard reagents and alkylating agents

The 4-arylhydrazono-3-phenyl-2-isoxazoline-5-thiones 2 react with hydrazines to yield the 5-hydrazones 3 and 5 . The reaction of 2 with Grignard reagent resulted in addition of the reagent to the thiocarbonyl group to yield 7 . Treatment of 2 with diazomethane effected S - and N -methylation beside 1,2,3-triazole derivative 11 obtained through isomerisation. The potassium salt of 2 react with alkyl halides to yield the S-alkyl derivatives 12 .     

Polarographic reduction and tautomeric structure of 2-amino-5-arylazothiazoles

The polarographic behaviour of a series of 2-amino-4-phenyl-5-arylazothiazoles has been investigated at a dropping mercury electrode. Each of the compounds studied exhibits one wave which was shown to correspond to the reductive cleavage of the azo linkage by a 4e irreversible step. On the basis of the polarographic data, it was concluded that the compounds exist only in one tautomeric form, namely the aminoazo structure 1 . The results of E_1/2 — σ_X correlations and HMO calculations of bonding energies of the various possible tautomeric forms 1–3 indicate that the aminoazo form 1 is the most stable structure of the compounds examined.     

On the strong convergence of a general-type Krasnosel’skii–Mann’s algorithm depending on the coefficients

Let H be a Hilbert space, \({(W_n)_{n \in \mathbb{N}}}\) a suitable family of mappings, S a nonexpansive mapping and D a strongly monotone operator. We are interested in the strong convergence of the general scheme

$$x_{n + 1} = \gamma x_{n} + (1 - \gamma)W_{n} (\alpha_{n}S_{x_{n}} + (1 - \alpha_{n})(I - \mu_{n}D)x_{n}),\quad \gamma \in [0, 1),$$

in dependence of the coefficients \({(\alpha_{n})_{n \in \mathbb{N}}}\) and \({(\mu_{n})_{n \in \mathbb{N}}}\) .