Reaction of K[(π-C5H5)Fe(CO)(CN)2] with boranes and AlCl3: Preparation and investigation of iron(II) complexes containing isocyanoborate ligands

Iron(II) complexes containing CNBX^?₃ or CNBX₂NC^? ligands were prepared from the reaction of K[(π-C₅H₅)Fe(CO)(CN)₂] with boranes (BX₃; X = F, Cl, Br H, Ph). Stable, twelve-membered ring compounds containing Fe, C, N, and B atoms were formed involving CNBF₂NC^? and CNBBr₂NC^? ligands. The reaction of K[(π-C₅H₅)Fe(CO)(CN)₂] with AlCl₃ gave a four-center complex with two Fe and two Al atoms. The compounds were studied by infrared and mass spectroscopic methods.     

Ring Enlargement of Phospholenes to Phosphorin Derivatives Through Dichlorocarbene Adducts

Abstract

The ring enlargement of ready available phospholenes by dichlorocarbene addition to the double bond and subsequent opening of the cyclopropane ring is discussed. Adductcs of phospholene wih dichlorocarbene (2)can be synthetised under liquid-liquid phase transfer circumstances. The simplest bray to open the cyclopropane ring in the adducts is thermal transformation giving the two regioisomers of the appropriate dihydrophosphorin (3). Electrophilic reagents can also be used for -the opening of the cyclopropane ring. On heating with silver nitrate in water or in alcohols the adducts are transformed to the -two rcgioisomers of the hydroxy- or the alkoxy -tetrahydrophosphorins, respectively (4, Y=H, CH₃ C₂H₅) In the reaction of adducts with mercury acetate-acetic acid the corresponding acetoxy-derivatives (4, Y=CH₃CO) are formed. The Friedl Crofts reaction of the adducts with benzene iii the presence of aluminium trichloride yields diarylated product.     

DIHALOCARBENE ADDITION TO ARYLSUBSTTTUTED VINYL PHOSPHATES UNDER PHASE TRANSFER CATALYTIC CONDITIONS

Abstract

Dihalocarbene addition to aryl-substituted vinyl phosphates was carried out both in solid-liquid and in liquid-liquid two phase systems. The dihalocyclopropane adducts of vinyl phosphates could be obtained in better yield using dihalocarbenes generated by the latter method and no hydrolysis of the vinyl phosphate and of the adduct occurred under these circumstances. Eighteen new vinyl phosphate-dihalocarbene adducts were synthetized and characterized.     

Simple,Safe, Large Scale Synthesis of 5-Arylmethyl-2,2-dimethyl-1,3-dioxane-4,6-diones and 3-Arylpropanoic Acids

Reaction of aryl aldehydes with Meldrum's acid 2 in the presence of formic acid and triethylamine gives 5-arylmethyl Meldrum's acid derivatives 4 at room temperature, whereas at 80–100°C 3-arylpropanoic acids 5 are formed.     

Effect of fullerene C60 branching center on the conformational properties of arms and the structure of star-shaped polystyrenes in solutions

The effect of the fullerene C₆₀ branching center on the structure and conformation of star-shaped polystyrenes with different arm lengths at equal concentrations in deuterotoluene (c = 1 g/dL) is studied by the method of small-angle neutron scattering. The analysis of neutron scattering for linear PS precursors and stars (the molecular masses of arms are ～7 × 10³ and ～4 × 10⁴) shows that the stars have ～6 arms that form a dense excluded-volume zone around a core inaccessible to other macromolecules. In low-molecular-mass stars (the molecular mass of the arm is ～7 × 10³), strengthening of the static rigidity of arms is observed; as a result, the size of arms increases relative to the size of free PS chains in a good solvent. At a greater length of arms (M ～ 4 × 10⁴), their individual properties are weakly pronounced in the correlation spectrum of the arm because of the interpenetration of arms, thereby demonstrating similarity in the structures of stars and their linear analogs. The mechanism controlling the effect of fullerene C₆₀ on the conformations of stars via solvent structuring by fullerene is discussed.     

Quality-by-Design-Based Development of n-Propyl-Gallate-Loaded Hyaluronic-Acid-Coated Liposomes for Intranasal Administration

The present study aimed to develop n-propyl gallate (PG)-encapsulated liposomes through a novel direct pouring method using the quality-by-design (QbD) approach. A further aim was to coat liposomes with hyaluronic acid (HA) to improve the stability of the formulation in nasal mucosa. The QbD method was used for the determination of critical quality attributes in the formulation of PG-loaded liposomes coated with HA. The optimized formulation was determined by applying the Box–Behnken design to investigate the effect of composition and process variables on particle size, polydispersity index (PDI), and zeta potential. Physiochemical characterization, in vitro release, and permeability tests, as well as accelerated stability studies, were performed with the optimized liposomal formulation. The optimized formulation resulted in 90 ± 3.6% encapsulation efficiency, 167.9 ± 3.5 nm average hydrodynamic diameter, 0.129 ± 0.002 PDI, and −33.9 ± 4.5 zeta potential. Coated liposomes showed significantly improved properties in 24 h in an in vitro release test (>60%), in vitro permeability measurement (420 μg/cm²) within 60 min, and also in accelerated stability studies compared to uncoated liposomes. A hydrogen-peroxide-scavenging assay showed improved stability of PG-containing liposomes. It can be concluded that the optimization of PG-encapsulated liposomes coated with HA has great potential for targeting several brain diseases.     

Measures of inset information on the open domain — I: Inset entropies and information functions of all degrees

This is one in a series of papers studying measures of information in the so-called mixed theory of information (i.e. considering the events as well as their probabilities) on the open domain (i.e. without empty sets and zero probabilities). In this paper we find all-recursive, 3-semisymmetric inset entropies on the open domain. We do this by solving the fundamental equation of inset information of degree () on the open domain.Dedicated to Professor János Aczél on his 60th birthday.     

Periodic decomposition of integer valued functions

We study those functions that can be written as a finite sum of periodic integer valued functions. On ℤ we give three different characterizations of these functions. For this we prove that the existence of a real valued periodic decomposition of a ℤ → ℤ function implies the existence of an integer valued periodic decomposition with the same periods. This result depends on the representation of the greatest common divisor of certain polynomials with integer coefficients as a linear combination of the given polynomials where the coefficients also belong to ℤ[x]. We give an example of an ℤ → {0, 1} function that has a bounded real valued periodic decomposition but does not have a bounded integer valued periodic decomposition with the same periods. It follows that the class of bounded ℤ → ℤ functions has the decomposition property as opposed to the class of bounded ℝ → ℤ functions. If the periods are pairwise commensurable or not prescribed, then we get more general results. Supported by OTKA grants T 43623 and K 61908.     

Large antipodal families

A family {A _i | i ∈ I} of sets in ℝ ^d is antipodal if for any distinct i, j ∈ I and any p ∈ A _i , q ∈ A _j , there is a linear functional ϕ:ℝ ^d → ℝ such that ϕ(p) ≠ ϕ(q) and ϕ(p) ≤ ϕ(r) ≤ ϕ(q) for all r ∈ ∪ _i∈I A _i . We study the existence of antipodal families of large finite or infinite sets in ℝ³. The research was supported by the Hungarian-South African Intergovernmental Scientific and Technological Cooperation Programme, NKTH Grant no. ZA-21/2006 and South African National Research Foundation Grant no. UID 61853, as well as Hungarian National Foundation for Scientific Research Grants no. NK 67867, no. T47102, and no. K72537.