A new cytotoxic limonoid from Odontadenia macrantha from the Suriname rainforest

Bioassay‐guided fractionation of the methanol extract of Odontadenia macrantha afforded a new limonoid, odontadenin A (1) and two known triterpenoids, lupeol (2) and α‐amyrin (3). The structure of 1 was established on the basis of 1D and 2D NMR and high‐resolution fast atom bombardment mass spectrometric data. The new compound was found to possess moderate cytotoxicity against A2780, the ovarian cancer cell line. Copyright © 2003 John Wiley & Sons, Ltd.     

Assignment of chemical shifts in benzohydroxamic acid and structure of its silylated derivatives by 15N enrichment

¹⁵N isotopic enrichment was necessary for the unequivocal assignment of the ¹H NMR lines to the protons in the NH–OH fragment of benzohydroxamic acid, BHXA, C₆H₅CONHOH, in dry dimethyl sulfoxide solutions. The assignment [δ(NH) = 11.21, δ(OH) = 9.01, ¹J(¹⁵N,¹H) = 102.2 Hz, ²J(¹⁵N,¹H) <1.5 Hz], which is opposite to that used by other authors, confirms the assignment extended to BHXA by Brown and co‐workers from the spectra of acetohydroxamic acid. The enrichment allowed also assignment of the ²⁹Si lines in the spectra of disilylated benzohydroxamic acid, (Z)‐tert‐butyldimethylsilyl N‐tert‐butyldimethylsilyloxybenzoimidate (2) and (Z)‐tert‐butyldiphenylsilyl N‐tert‐butyldiphenylsilyloxybenzoimidate (3), and confirmed structure of the monosilylated products, N‐tert‐butyldiphenylsilyloxybenzamide (4) and N‐tert‐butyldiphenylsilyloxy benzoimidic acid (5). Copyright © 2003 John Wiley & Sons, Ltd.     

A two dimensional, experimental study on the evolution of the detachment and its time-behavior in filled rubber

Summary The detachment of a rubber matrix from a rigid inclusion under monotonic loading and at subsequent relaxation is investigated within two dimensional analysis. Examined are stress–strain experimental data acquired with the help of a test bed equipped with a digital image-acquisition device. The influence of the interfacial bonding strength and the particle size on the detachment process is analyzed. The influence of the interfacial bonding strength is visible in the stress–strain diagram of loading and in the recorded images. The relaxation test reveals no influence of the bonding strength on the stress-relaxation. However, the image analysis indicates a secondary transient creep of the contour of detachment, which depends on the interfacial bonding.     

Tetraphenylantimony carboxylates in the cascade Pd-catalyzed C-phenylation reaction of methyl acrylate in the presence of peroxide

Tetraphenylantimony(V) carboxylates have been used in the palladium-catalyzed C-phenylation reaction of methyl acrylate in the presence of (PhCO₂)₂ or t-BuOOH under mild conditions (50 °C). The peroxides promote a cascade participation of the organoantimony compound and result in the transfer of three phenyl groups. Organoantimony intermediates have been isolated from the reaction.     

SCDA for 3D lattice gases with repulsive interaction

The selfconsistent diagram approximation (SCDA) is generalized for three-dimensional lattice gases with nearest neighbor repulsive interactions. The free energy is represented in a closed form through elementary functions. Thermodynamical (phase diagrams, chemical potential and mean square fluctuations), structural (order parameter, distribution functions) as well as diffusional characteristics are investigated. The calculation results are compared with the Monte Carlo simulation data to demonstrate high precision of the SCDA in reproducing the equilibrium lattice gas characteristics. It is shown that similarly to two-dimensional systems the specific statistical memory effects strongly influence the lattice gas diffusion in the ordered states. Received 7 August 2002 / Received in final form 22 January 2003 Published online 24 April 2003     

Bundles, Handcuffs, and Local Freedom

We answer a question of J. Anderson's by producing infinitely many commensurability classes of fibered hyperbolic 3-manifolds whose fundamental groups contain subgroups that are locally free and not free. These manifolds are obtained by performing 0–surgery on a collection of knots with the same properties.     

Magnetotransport and magnetic properties of InAs/Mn digital alloys

We have investigated the magnetic and magneto-transport properties of a systematic sequence of five InAs/Mn digital alloys grown by a combination of molecular beam epitaxy and atomic layer epitaxy. The samples consist of 30 periods of Mn fractional monolayers (ML) (0.17–0.5 ML) separated by 14 ML thick InAs spacer layers in a superlattice configuration. Four samples show n-type electrical conduction while the fifth (0.25 ML Mn) is p-type. Squid magnetization measurements performed on these samples show remnant magnetization above room temperature, which is apparently related to a second phase.     

NMR studies on a palladium(II) complex containing an incompletely coordinated facultative pentadentate Schiff base ligand

Palladium(II) dichloride reacts with 1,10‐bis(2‐pyrrolyl)‐2,5,9‐triaza‐1,9‐decadiene to give a [Pd(C₁₅H₂₀N₅)]Cl complex in which the ligand is four‐coordinated, leaving one pyrrole group dangling. By using COSY, gHSQC, gHMBC connectivities and NOE experiments it has been concluded that one linkage isomer exists in DMSO solution, in spite of the fact that different sets of N atoms of potentially pentadentate ligand might be involved in coordination, and that the three chelate rings in the complex cation are arranged in a sequence: five‐membered, six‐membered, five‐membered which is different from that (5–5–6) found by x‐ray studies on the related [Ni(C₁₅H₂₀N₅)]Cl compound. NMR studies allowed an unambiguous assignment of all ¹H and ¹³C NMR resonances for the complex. Results of x‐ray structural analysis of [Pd(C₁₅H₂₀N₅)](CH₃COO)H₂O supported the five‐membered, six‐membered, five‐membered ring sequence in the [Pd(C₁₅H₂₀N₅)]⁺ complex cation and show an E (trans) orientation of the dangling pyrrole group with respect to the metal center. Copyright © 2002 John Wiley & Sons, Ltd.     

Ca(NO3)2•4H2O-catalysed Biginelli Reaction: One-pot Synthesis of 1,2,3,4-Tetrahydropyrimidin-2-ones/pyrimidine-2-thiones under Solvent-free Conditions

The synthesis of 1,2,3,4-dihydropyrimidinone/thione derivatives was achieved in good to excellent yields using calcium(II) nitrate as catalyst to promote the Biginelli three-component condensation reaction from a diversity of aromatic aldehydes, β-keto compounds and urea or thiourea. The reaction was carried out under solvent-free conditions.     

Studies on the blends of cardanol-based epoxidized novolac resin and CTPB

Cardanol-based novolac-type phenolic resins were synthesized with different mole ratios of cardanol-to-formaldehyde, viz., 1:0.6, 1:0.7, and 1:0.8. These novolac resins were epoxidized with molar excess of epichlorohydrin at 120 °C in basic medium. The epoxidized novolac resins were, separately, blended with different weight ratios of carboxyl-terminated polybutadiene liquid rubber ranging between 0-25 wt% with an interval of 5 wt%. All the blends were cured at 150 °C with 40 wt% polyamide. The formation of various products during the curing of blend samples has been studied by Fourier-transform infra-red spectroscopic analysis. The tensile strength and elongation-at-break of the cured samples increased up to 15 wt% in the blend and decreased thereafter. This blend sample was also found to be most thermally stable system. The blend morphology, studied by scanning electron microscopy analysis, was finally correlated with the structural and property changes in the blends.