An Easy Synthesis of Pyranopyrimidines

Summary.  The one-pot reaction of valerolactone with nitriles in the presence of triflic anhydride affords 2,4-disubstituted pyrano[2,3-d]pyrimidines. Subsequent addition of methyl thiocyanate leads to 2,4-bis(methylthio)pyranopyrimidines which can easily be converted into the corresponding methylsulfonyl derivatives. The reaction of these derivatives with different nucleophiles produces a variety of substituted pyranopyrimidines.     

An Easy Synthesis of Pyranopyrimidines

The one-pot reaction of valerolactone with nitriles in the presence of triflic anhydride affords 2,4-disubstituted pyrano[2,3-d]pyrimidines. Subsequent addition of methyl thiocyanate leads to 2,4-bis(methylthio)pyranopyrimidines which can easily be converted into the corresponding methylsulfonyl derivatives. The reaction of these derivatives with different nucleophiles produces a variety of substituted pyranopyrimidines.     

Short-range-ordering Kinetics of Cu—5 At.% Zn Influenced by Solute—Vacancy Complexes and Cold Rolling

A modified first-order kinetic law which takes into account defect decay during an ordering process was employed to predict the short-range-order kinetics of a quenched and a quenched-deformed Cu—5 at.% Zn alloy, in conjunction with experiments performed by isothermal calorimetry. The effective activation energy of point defect migration and its temperature dependence strongly suggest the contribution of bound vacancies to the ordering process. An estimate of 91.2 kJ mol^–1 was made for the activation energy of solute—vacancy migration by applying an effective rate constant, a value in very good agreement with that obtained from previous non-isothermal experiments. The isothermal curves were utilized to determine the ordering energy: w=–2.90 kJ mol^–1. In conjunction, a parametric study of the defect sink density was performed in order to assess its influence on the calculated isothermal curve profiles.This revised version was published online in November 2005 with corrections to the Cover Date.     

Five bicyclo[3.3.0]octa‐2,6‐dienes

A series of five compounds containing the bicyclo[3.3.0]octa‐2,6‐diene skeleton are described, namely tetramethyl cis,cis‐3,7‐dihydroxybicyclo[3.3.0]octa‐2,6‐diene‐2,4‐exo,6,8‐exo‐tetracarboxylate, C₁₆H₁₈O₁₀, (I), tetramethyl cis,cis‐3,7‐dihydroxy‐1,5‐dimethylbicyclo[3.3.0]octa‐2,6‐diene‐2,4‐exo,6,8‐exo‐tetracarboxylate, C₁₈H₂₂O₁₀, (II), tetramethyl cis,cis‐3,7‐dimethoxybicyclo[3.3.0]octa‐2,6‐diene‐2,4‐exo,6,8‐exo‐tetracarboxylate, C₁₈H₂₂O₁₀, (III), tetramethyl cis,cis‐3,7‐dimethoxy‐1,5‐dimethylbicyclo[3.3.0]octa‐2,6‐diene‐2,4‐exo,6,8‐exo‐tetracarboxylate, C₂₀H₂₆O₁₀, (IV), and tetramethyl cis,cis‐3,7‐diacetoxybicyclo[3.3.0]octa‐2,6‐diene‐2,4‐exo,6,8‐exo‐tetracarboxylate, C₂₀H₂₂O₁₂, (V). The bicyclic core is substituted in all cases at positions 2, 4, 6 and 8 with methoxycarbonyl groups and additionally at positions 3 and 7 with hydroxy [in (I) and (II)], methoxy [in (III) and (IV)] or acetoxy [in (V)] groups. The conformations of the methoxycarbonyl groups at positions 2 and 4 are exo for all five compounds. Each C₅ ring of the bicyclic skeleton is almost planar, but the rings are not coplanar, with dihedral angles of 54.93 (7), 69.85 (5), 64.07 (4), 80.74 (5) and 66.91 (7)° for (I)–(V), respectively, and the bicyclooctadiene system adopts a butterfly‐like conformation. Strong intramolecular hydrogen bonds exist between the –OH and C=O groups in (I) and (II), with O...O distances of 2.660 (2) and 2.672 (2) Å in (I), and 2.653 (2) and 2.635 (2) Å in (II). The molecular packing is stabilized by weaker C—H...O(=C) interactions, leading to dimers in (I)–(III) and to a chain structure in (V). The structure series presented in this article shows how the geometry of the cycloocta‐2,6‐diene skeleton changes upon substitution in different positions and, consequently, how the packing is modified, although the intermolecular interactions are basically the same across the series.     

Influence of the side chain on the stability of Schiff-bases formed between pyridoxal 5′-phosphate and amino acids

The stability of some Schiff-bases formed between PLP and different amino acids has been investigated in a wide range of pH. The kinetic constants of formation of these compounds and their hydrolysis rate constants have been determined. Results show that the α-position of the carboxyl group of amino acid plays an important role on the mechanism of water attack upon the C?N? bond. The absence of ionic groups in the surroundings of that bond must be an important factor of stability. Bulky hydrophobic substituents in the amino acid, near the amine part, protect the imine bond against hydrolysis.     

ESR of Nd+3 in type II superconductors

The resonance properties of the Γ₆ ground state of Nd⁺³ in the type II Superconductors CeRu₂, ThRu₂ and LaRu₂ are reported. A significant change of the g value and lineshape were observed for CeRu₂:Nd upon going from the normal state to the superconducting state. The data in the superconducting state is discussed in terms of conduction electron's pairing mechanism and inhomogeneous field distribution mechanism in the superconducting state. A preliminary lineshape analysis is not completely consistent with previous theoretical predictions and experiments.     

Spin uncoupling in free Nb clusters: support for nascent superconductivity

Molecular beam Stern-Gerlach deflection measurements on Nb clusters (Nb(N), N<100) show that at very low temperatures the odd-N clusters deflect due to a single unpaired spin that is uncoupled from the cluster. At higher temperatures the spin is coupled and no deflections are observed. Spin uncoupling occurs concurrently with the transition to the recently found ferroelectric state, which has superconductor characteristics [Science 300, 1265 (2003)]]. Spin uncoupling (also seen in V, Ta, and Al clusters) is analogous to the reduction of spin-relaxation rates observed in bulk superconductors below T(c).     

Holes drilling in gold and silver decahedral nanoparticles by the convergent beam electron diffraction electron beam

The 200?kV focused electron beam in the convergent beam electron diffraction patterns mode in a transmission electron microscope (TEM) with field emission gun is able to drill holes in gold and silver decahedral nanoparticles. However, although they are done under the same circumstances, the holes are shapeless in the silver and faceted in gold nanoparticles. In addition to this, the holes are closed during their high-resolution TEM observation in both materials. To comment their differences, displacement energy considerations are taken into account as function of the sputtering energy in order to modify the displacement cross-section of the processes.     

Remote regio- and stereocontrol by the sulfinyl group: Diels–Alder reaction of sulfinyl dienols and 8,8-dimethylnaphthalene-1,4,5(8H)-trione

Diels–Alder cycloaddition of 8,8-dimethylnaphthalene-1,4,5(8H)-trione with diastereomeric hydroxysulfinyldienes proceeded with high yields and good π-facial and regioselectivities. The hydroxysulfoxide moiety controls the regio- and stereoselectivities, through hydrogen bonds in the suggested transition state.     

Constructions of Large Graphs on Surfaces

We consider the degree/diameter problem for graphs embedded in a surface, namely, given a surface Σ and integers Δ and k, determine the maximum order N(Δ,k,Σ) of a graph embeddable in Σ with maximum degree Δ and diameter k. We introduce a number of constructions which produce many new largest known planar and toroidal graphs. We record all these graphs in the available tables of largest known graphs. Given a surface Σ of Euler genus g and an odd diameter k, the current best asymptotic lower bound for N(Δ,k,Σ) is given by $$\sqrt{\frac{3}{8}}g \Delta^{\lfloor k/2 \rfloor}.$$ Our constructions produce new graphs of order $$\left\{\begin{array}{ll}6 \Delta^{\lfloor k/2 \rfloor} \qquad \qquad \qquad \qquad {\rm if \Sigma\;is\;the\;Klein\;bottle} \\ \left(\frac{7}{2} + \sqrt{6g + \frac{1}{4}}\right) \Delta^{\lfloor k/2 \rfloor} \quad {\rm otherwise},\end{array}\right.$$ thus improving the former value.