Novel five- and six-coordinate zinc (II), cadmium (II) and mercury(II) complexes of macrocyclic ligands

Summary Complexes of 2,6-dipicolinic acid hydrazide, DPH, with Zn^II, Cd^II and Hg^II have been prepared and characterized by elemental analysis, i.r. and electronic spectra and by electrical conductance measurements. The ligand is terdentate, having coordination sites at two deprotonated amide-nitrogen and pyridine-nitrogen atoms. The Zn^II and Hg^II complexes are pentacoordinate whereas the Cd^II complexes are hexacoordinate and have trigonal bipyramidal and pseudooctahedral stereochemistries, respectively. The Zn, Cd and Hg ions induce cyclization of DPH complexes upon reaction with-diketones. The complexes of macrocyclic ligands so formed have the same stereochemistries as those of DPH.     

Zero cycles on conic fibrations and a conjecture of Bloch

Let X be a smooth projective surface over a number field k. Let (CH₀(X)) denote the Chow group of zero-cyles modulo rational equivalence on X. Let CH₀(X) be the subgroup of CH ₀(X) consisting of classes which vanish when going over to an arbitrary completion of k. Bloch put forward a conjecture asserting that this group is isomorphic to the Tate-Shafarevich group of a certain Galois module atttached to X. In this paper, we disprove this general conjecture. We produce a conic bundle X over an elliptic curve, for which the group (CH₀(X) is not zero, but the Galois-theoretic Tate-Shafarevich group vanishes.     

A predictive model for impact response of viscoelastic polymers in drop tests

We show for the first time that a classical Hookean viscoelastic constitutive law for rubbery materials can predict the impact forces and deflections measured with a commercial drop tester when a mass, or tup with a flat impacting surface is dropped onto a flat pad of commercial impact-absorbing rubber. The viscoelastic properties of the rubber, namely the relaxation times and strengths, are obtained by a standard rheological linear-oscillatory test, and the equation of momentum transfer is then solved, using these measured parameters, assuming a uniaxial deflection of the pad during the impact. Good agreement between measured and predicted forces and deflections is obtained for a series of various drop heights, tup masses, impact areas, and pad thicknesses, as long as the deflection of the pad relative to its thickness is small or modest (<50% or so), and as long as the area of the pad is less than or equal to that of the tup. When the pad area is greater than the tup, forces are higher than predicted, unless an empirical factor is introduced to account for the nonuniaxial stretching of the ring of material that extends outside of the impact area. These results imply that the impact-absorbing properties of a rubbery polymeric material can be assessed by simply examining the material's linear viscoelastic spectrum.     

Synthesis of erythrinin A,a naturally occurring pyranoisoflavone

Erythrinin A ($\text{10}$) has been synthesised by the oxidative rearrangement of dihydropyranochalcone $\text{1}$ with thallium(III) nitrate (TTN) in trimethyl orthoformate (TMOF) to the dimethyl acetal $\text{2}$, followed by cyclisation to $\text{3}$, demethylation to $\text{6}$ and dehydrogenation. Compound $\text{10}$ could also be obtained from chalcone $\text{4}$ on similar rearrangement followed by cyclisation, demethoxymethylation and dehydrogenation. In another route, chalcone $\text{7}$ was oxidatively rearranged with TTN in TMOF, to $\text{8}$ which on treatment with HCl yielded $\text{10}$.     

Supramolecular porphyrin-fullerene via 'two-point' binding strategy: axial-coordination and cation-crown ether complexation

A highly stable porphyrin-fullerene conjugate with defined distance and orientation, was formed using a newly developed 'two-point' binding strategy involving axial-coordination and cation-crown ether complexation; photochemical studies performed in benzonitrile revealed efficient charge separation and slow charge-recombination in the supramolecular complex.     

Backbone cleavages of [M - H](-) anions of peptides. Cyclisation of citropin 1 peptides involving reactions between the C-terminal [CONH](-) residue and backbone amide carbonyl groups. A new type of beta cleavage: a joint experimental and theoretical study

This paper reports the study of backbone cleavages in the collision-induced negative-ion mass spectra of the [M - H](-) anions of some synthetic modifications of the bioactive amphibian peptide citropin 1 (GLFDVIKKVASVIGGL-NH(2)). The peptides chosen for study contain no amino acid residues which could effect facile side-chain cleavage, i.e. Ser (-CH(2)O, side-chain cleavage) and Asp (-H(2)O) are replaced by Ala or Lys. We expected that such peptides should exhibit standard and pronounced peaks due to alpha cleavage ions (and to a lesser extent beta cleavage ions) in their collision-induced negative-ion spectra. This expectation was realised, but the spectra also contained peaks formed by a new series of cleavage anions. These are produced following cyclisation of the C-terminal CONH(-) moiety at carbonyl functions of amide groups along the peptide backbone; effectively transferring the NH of the C-terminal CONH(-) group to other amino acid residues. We have called the product anions of these processes beta' ions, in order to distinguish them from standard beta ions. Some beta' ions also fragment directly to some other beta' ions of smaller mass. The reaction coordinates of alpha,beta and beta' backbone processes have been calculated at the HF/6-31G*//AM1 level theory for simple model systems. The initial cyclisation step of the beta' sequence is barrierless and exothermic. Subsequent steps have a maximum barrier of +40 kcal mol(-1), with the overall reaction being endothermic by some 30 kcal mol(-1) at the level of theory used. These calculations take no account of the complexity of the conformationally flexible peptide system, and it is surprising that each of the two reacting centres can 'find' each other in such a large system.     

Electron depleted bis(methylene)cyclobutenes: sulfinyl and sulfonyl substitution

Double [2,3] sigmatropic rearrangements of bis(propargyl sulfenates) to bis(allenic sulfoxides) and of bis(propargyl sulfinates) to bis(allenic sulfones) are shown to be a convenient and effective method for the preparation of conjugated diallene systems bearing two electron withdrawing trihalomethyl sulfoxide or sulfone substituents either on C-1 and C-6, or on C-3 and C-4. Such substituents are further shown to facilitate cyclization to bis(methylene)cyclobutenes, and to stabilize the latter. The electron withdrawing group substitution on the exocyclic methylene extremities proved more effective than similar substitution on the endocyclic double bond.     

Dithiane additions to vinyl epoxides: steric control over the SN2 and SN2' manifolds

High chemoselectivity can be achieved in the addition of lithium dithiane anions to vinyl epoxides exploiting the steric nature of the dithiane substituent. Unencumbered dithiane anions afford SN2 adducts, whereas sterically encumbered anions lead primarily to SN2' adducts. Furthermore, the SN2' addition occurs syn to the vinyl epoxide.     

Simultaneous Determination of Olanzapine and Fluoxetine by HPLC

A rapid, specific reversed phase HPLC method has been developed for simultaneous determination of olanzapine and fluoxetine in their formulations. Chromatographic separation of these two pharmaceuticals was carried out on an Inertsil C₁₈ reversed phase column (150 mm × 4.6 mm, 5 μm) with a 40:30:30 (v/v/v) mixture of 9.5 mM sodium dihydrogen phosphate (pH adjusted to 6.8 ± 0.1 with triethylamine), acetonitrile and methanol as mobile phase. The flow rate 1.2 mL min⁻¹ and the analytes are monitored at 225 nm. Paroxetine was used as internal standard. The assay results were linear from 25 to 75 μg mL⁻¹ for olanzapine (r ² ≥ 0.995) and 100–300 μg mL⁻¹ for fluoxetine (r ² ≥ 0.995), showed intra- and inter-day precision less than 1.0%, and accuracy of 97.7–99.1% and 97.9–99.0%. LOQ was 0.005 and 0.001 μg mL⁻¹ for olanzapine and fluoxetine, respectively. Separation was complete in less than 10 min. Validation of the method showed it to be robust, precise, accurate and linear over the range of analysis.     

Regioselective nucleophilic addition to carbonyl ylide intermediates: a novel diastereoselective synthesis of cycloalkyl fused furan-3-ones

[structures: see text] A range of cis-fused hexahydro-1-benzofuran-3(2H)-one or tetrahydro-2H-cyclopenta[b]furan-3(3aH)-one ring systems was synthesized by the rhodium(II) acetate catalyzed reaction of alpha-diazo carbonyl compounds in the presence of various oxygen, nitrogen, and sulfur nucleophiles. A double-nucleophilic addition was possible by using an excess of alpha-diazo ketone. These reactions proceeded with complete diastereoselectivity, and the stereochemistry was confirmed by the single-crystal X-ray analysis. This process discloses the first example of tandem cyclization-nucleophilic addition reaction.