Fused pyrazolopyrimidines. I. Pyrazolo[4,3-e]-v-triazolo[1,5-a]pyrimidine. A new heterocyclic system

5-Azido-4-cyano-1-phenylpyrazole reacts with benzylcyanide in the presence of sodium methoxide to give the title ring system.     

Anodic oxidation mechanism of 3-arylaminoindoles at a rotating and at a (new type of) pulsing platinum electrode in dipolar aprotic solvents

The oxidation of 2-phenyl-3-arylaminoindoles (1a–e) has been studied in acetonitrile, dimethylformamide and propylene carbonate at a new type of platinum electrode with periodical renewal of the diffusion layer and at a rotating platinum electrode by cyclic voltammetry, d.c. and a.c. voltammetry, controlled potential coulometry and spectrometry (e.s.r. and u.v.). In the examined aprotic solvents and in the presence of a base (like water or diphenylguanidine) amines 1a–e undergo a two-electron oxidation to the corresponding imines. In a protophobic medium (acetonitrile or propylene carbonate) 1a–e are oxidized in two one-electron steps, the first of which leads to the formation of a cation radical (identified by e.s.r. spectrum), oxidizable at more positive potentials (second step). The second electron transfer, however, must be simultaneous with, or be immediately followed by, a very fast deprotonation reaction. The same e.e.c. sequence explains the observed bielectronic step of 1a–e in a protophilic aprotic solvent, like dimethylformamide.     

Structure and Dynamics of Methyl-substituted Beryllocene: [Be(C5Me5)2]

In this paper we study theoretically the molecular structure of [Be(C₅Me₅)₂], with special interest in similarities and differences found in the computed geometric parameters, depending on the treatment of the electron correlation used. Given the low energy differences found between the different configurations studied (less than 4 kcal mol⁻¹), and the high fluxionality found in experimental studies for this compound, we analyzed the dynamics of the system by means of first principles molecular dynamics calculations. A complex dynamics is found and analyzed in terms of two molecular rearrangement processes: 1,2-sigmatropic intraring rearrangement and a ring inversion mechanism that interchanges the roles (with regard to their coordination to the central Be atom) of the two rings.Dedicated to Dr. Jeal Paul Malrieu on occasion of his 65th birthday.     

Photochemical reactivity of α,β-unsaturated δ-lactams: Synthesis of seco-steroids. Photochemical reactions. XIII [1]

The UV. irradiation of 17 β-hydroxy-2-aza-4-androsten-3-one (1) , N-methyl-17 β-hydroxy-2-aza-4-androsten-3-one (3) , 17 β-hydroxy-4-aza-5 β-androst-1-en-3-one (2) and N-methyl-17 β-hydroxy-4-aza-5 β-androst-1-en-3-one (4) , gives rise to 1,10-seco (from 1 and 3 ) and 5, 10-seco (from 2 and 4 ) steroids.     

Molecular imprinting technology in capillary electrochromatography

Molecularly imprinted polymers (MIPs) are tailor-made synthetic polymers with a predetermined selectivity for a given analyte, or group of structurally related compounds, that make them ideal materials for use as stationary phases in affinity chromatography. However, extensive peak broadening and tailing, especially of the more retained compound (normally the template) are often observed. Thus, huge efforts have been made during recent years to use MIPs in capillary electrochromatography, which is inherently a more efficient chromatographic technique than conventional HPLC. Accordingly, this paper gives an overview of the attempts carried out in the recent past to improve the chromatographic performance of MIPs in capillary electrochromatography as well as more recent applications. It is concluded that MIPs are very promising materials for use as selective stationary phases in CEC.     

Characterizing projective bundles by means of ample divisors

Let X be a complex projective manifold and AX a non-singular hypersurface which is an ample divisor having characteristic cycles A_i non-singular in every dimension i0. The pairs (X,A) such that g(A₁)=h^1,0 (X) are characterized.     

Small carbon clusters doped with early transition metals: a theoretical study of ScCn, ScCn+, and ScCn- (n = 1-8) open-chain clusters

A theoretical study of the ScCn, ScCn+, and ScCn- (n = 1-8) open-chain clusters has been carried out. Predictions for their electronic energies, rotational constants, dipole moments and vibrational frequencies have been made using the B3LYP method with different basis set including effective core potentials, ECPs. For the ScCn open-chain clusters the lowest-lying states correspond to quartet states for n-odd members, whereas for n-even species the ground state is found to be a doublet. In the cationic and anionic species, the electronic ground state is found to be a singlet for even n and a triplet for odd n. An even-odd parity effect (n-even clusters being more stable than n-odd ones) is observed in neutral and charged clusters. Ionization energies and electron affinities also exhibit a clear parity alternation trend, with n-even clusters having higher values than n-odd ones.