Novel Synthesis of Pyrazolyloxothiazolidine Derivatives

1‐Substituted 3‐[3‐(methyl/phenyl)‐1H‐pyrazol‐5‐yl]thioureas react with the triple bond of dimethyl acetylenedicarboxylate forming (Z)‐methyl 2‐[(Z)‐3‐substituted‐2‐(3‐(methyl/phenyl‐1H‐pyrazol‐5‐ylimino)‐4‐oxothiazolidin‐5‐ylidene)acetates. Rational for these conversations are presented.     

Piperazine Functionalization of C70 for Incorporation into Supramolecular Assemblies

The photochemical reaction of piperazine with C₇₀ produces a mono‐adduct (N(CH₂CH₂)₂NC₇₀) in high yield (67 %) along with three bis‐adducts. These piperazine adducts can combine with various Lewis acids to form crystalline supramolecular aggregates suitable for X‐ray diffraction. The structure of the mono‐adduct was determined from examination of the adduct I₂N(CH₂CH₂)₂NI₂C₇₀ that was formed by reaction of N(CH₂CH₂)₂NC₇₀ with I₂. Crystals of polymeric {Rh₂(O₂CCF₃)₄N(CH₂CH₂)₂NC₇₀}_n?nC₆H₆ that formed from reaction of the mono‐adduct with Rh₂(O₂CCF₃)₄ contain a sinusoidal strand of alternating molecules of N(CH₂CH₂)₂NC₇₀ and Rh₂(O₂CCF₃)₄ connected through Rh?N bonds. Silver nitrate reacts with N(CH₂CH₂)₂NC₇₀ to form black crystals of {(Ag(NO₃))₄(N(CH₂CH₂)₂NC₇₀)₄}_n?7nCH₂Cl₂ that contain parallel, nearly linear chains of alternating (N(CH₂CH₂)₂NC₇₀ molecules and silver ions. Four of these {Ag(NO₃)N(CH₂CH₂)₂NC₇₀}_n chains adopt a structure that resembles a columnar micelle with the ionic silver nitrate portion in the center and the nearly non‐polar C₇₀ cages encircling that core. Of the three bis‐adducts, one was definitively identified through crystallization in the presence of I₂ as ¹²{N(CH₂CH₂)₂N}₂C₇₀ with addends on opposite poles of the C₇₀ cage and a structure with C_2v symmetry. In ¹²{I₂N(CH₂CH₂)₂N}₂C₇₀, individual ¹²{I₂N(CH₂CH₂)₂N}₂C₇₀ units are further connected by secondary I2???N2 interactions to form chains that occur in layers within the crystal. Halogen bond formation between a Lewis base such as a tertiary amine and I₂ is suggested as a method to produce ordered crystals with complex supramolecular structures from substances that are otherwise difficult to crystallize.     

A scaling limit for the length of the longest cycle in a sparse random digraph

We discuss the length of the longest directed cycle in the sparse random digraph , constant. We show that for large there exists a function such that a.s. The function where is a polynomial in . We are only able to explicitly give the values , although we could in principle compute any .     

Simplification and analysis of a model of social interaction in voting

A recently proposed model of social interaction in voting is investigated by simplifyingit down into a version that is more analytically tractable and which allows a mathematicalanalysis to be performed. This analysis clarifies the interplay of the different elementspresent in the system – social influence, heterogeneity and noise – and leads to a betterunderstanding of its properties. The origin of a regime of bistability is identified. Theinsight gained in this way gives further intuition into the behaviour of the originalmodel.     

A new force field for simulating phosphatidylcholine bilayers

A new force field for the simulation of dipalmitoylphosphatidylcholine (DPPC) in the liquid‐crystalline, fluid phase at zero surface tension is presented. The structure of the bilayer with the area per lipid (0.629 nm²; experiment 0.629–0.64 nm²), the volume per lipid (1.226 nm³; experiment 1.229–1.232 nm³), and the ordering of the palmitoyl chains (order parameters) are all in very good agreement with experiment. Experimental electron density profiles are well reproduced in particular with regard to the penetration of water into the bilayer. The force field was further validated by simulating the spontaneous assembly of DPPC into a bilayer in water. Notably, the timescale on which membrane sealing was observed using this model appears closer to the timescales for membrane resealing suggested by electroporation experiments than previous simulations using existing models. © 2009 Wiley Periodicals, Inc. J Comput Chem, 2010     

A μ4‐oxide‐containing a dimeric variant of a sodium dialkyl(amido)zincate reagent

Post‐metallation derivatives of the sodium dialkyl(amido)zincate reagent (TMEDA)Na(μ‐TMP)Zn(^tBu)₂ (TMEDA is N,N,N′,N′‐tetramethylethylenediamine and TMP is 2,2,6,6‐tetramethylpiperidide) have been of structural interest due to the insight they give into aromatic metallation mechanisms. Here, the aromatic substrate is formally replaced with [ZnO]₂ to give tetra‐tert‐butyldi‐μ₄‐oxido‐bis(tetramethylethylenediamine‐κ²N,N′)bis(μ₂‐2,2,6,6‐tetramethylpiperidin‐1‐ido‐κ²N:N)disodiumtetrazinc hexane 0.59‐solvate, [Na₂Zn₄(C₄H₉)₄(C₉H₁₈N)₂O₂(C₆H₁₆N₂)₂]·0.59C₆H₁₄. The crystallographically centrosymmetric complex retains many of the structural features of its parent monomer but has an unusual dimeric structure, with a central planar Zn–O–Zn–O ring joined to two orthogonal near‐planar Zn–O–Na–N rings through the distorted tetrahedral geometries of the oxide ions.     

Crystalline Behavior and Structure of a Liquid Crystal Compound, 5‐{[4′‐(((Pentyl)oxy)‐4‐biphenylyl)carbonyl]oxy}‐1‐pentyne

Single crystals of two liquid crystal compounds, 5‐{[4′‐(((pentyl)oxy)‐4‐biphenylyl)carbonyl]oxy}‐1‐pentyne (A3EO5) and 5‐{[(4′‐nonyloxy‐4‐biphenylyl)carbonyl]oxy}‐1‐pentyne (A3EO9), have been prepared by solution growth technique. The morphologies and structures of A3EO5 and A3EO9 crystals were investigated by wide angle X‐ray diffraction (WXRD), atom force microscope (AFM) and transmission electron microscope (TEM). In contrast to the same series of compounds which have a longer alkyl tail, 5‐{[(4′‐heptoxy‐4‐biphenylyl)carbonyl]oxy}‐1‐pentyne (A3EO7), 5‐{[(4′‐heptoxy‐4‐biphenylyl)oxy]carbonyl}‐1‐pentyne (A3E′O7) and A3EO9, A3EO5 shows strikingly different crystalline behavior. The former three compounds have only one crystal form, whereas A3EO5 exhibits polymorphism. Specifically, A3EO5 crystals grown from toluene solution show two crystal forms. The first one is crystal I which adopts a monoclinic P112/m space group with unit cell parameters of a?5.79 Å, b?8.34 Å, c?43.92 Å, γ?96°, and the other one is crystal II which adopts a monoclinic P112 space group with unit cell parameters of a?5.55 Å, b?7.38 Å, c?31.75 Å, γ?94°. When using dioxane as the solvent to grow A3EO5 crystal, we can selectively obtain crystal I. A3EO5 melt‐grown crystals also have two crystal forms which derive from crystal I and crystal II, respectively. The different crystalline behavior of the compounds should correlate with their different electron dipole moment resulting from the different length of alkyl tail.     

Coherence transfer delay optimisation in PSYCOSY experiments

PSYCOSY is an f1 broadband homonuclear decoupled version of the COSY nuclear magnetic resonance pulse sequence. Here, we investigate by a combination of experimental measurements, spatially distributed spin dynamics simulations, and analytical predictions the coherence evolution delay necessary in PSYCOSY experiments to ensure intensity discrimination in favour of the correlations typically arising from short range (ⁿJ, n ≤ 3) ¹H–¹H couplings and show that, in general, a coherence evolution delay of around 35 ms is optimum.     

Organozinc Pivalate Reagents: Segregation,Solubility, Stabilization,and Structural Insights

The pivalates RZnOPiv?Mg(OPiv)X?n LiCl (OPiv=pivalate; R=aryl; X=Cl, Br, I) stand out amongst salt‐supported organometallic reagents, because apart from their effectiveness in Negishi cross‐coupling reactions, they show more resistance to attack by moist air than conventional organometallic compounds. Herein a combination of synthesis, coupling applications, X‐ray crystallographic studies, NMR (including DOSY) studies, and ESI mass spectrometric studies provide details of these pivalate reagents in their own right. A p‐tolyl case system shows that in [D₈]THF solution these reagents exist as separated Me(p‐C₆H₄)ZnCl and Mg(OPiv)₂ species. Air exposure tests and X‐ray crystallographic studies indicate that Mg(OPiv)₂ enhances the air stability of aryl zinc species by sequestering H₂O contaminants. Coupling reactions of Me(p‐C₆H₄)ZnX (where X=different salts) with 4‐bromoanisole highlight the importance of the presence of Mg(OPiv)₂. Insight into the role of LiCl in these multicomponent mixtures is provided by the molecular structure of [(THF)₂Li₂(Cl)₂(OPiv)₂Zn].