Preparation of 3-substituted and 2,3-disubstituted-4,4,4-trifluoro-2-butenoic acids—Perkin condensation of activated aromatic ketones

The Perkin reaction of the activated aromatic ketones (2,2,2-trifluoroacetophenone and its 4′-phenyl-derivative) with various condensing agents (acetic anhydride, propionic anhydride, phenylacetic acid/acetic anhydride) gives the title compounds in good or moderate yields, and high E-stereoselectivity. For some derivatives an appreciable amount of the Z isomer was also formed. Several of the resulting butenoic acids and their methyl esters are synthesised and characterised for the first time.     

An Integrated Two Phases Approach to Zn2+ Ions Electroreduction on Hg

The following two numerical models have been applied to zinc cations electroreduction in 1 M NaClO₄ water solution: a classical EE model describing the concentration of involved species in solution (semi infinitive diffusion region), an extended EE model describing both: the concentration of involved species in solution and the concentration of metallic zinc inside mercury drop (in limited area of diffusion). In the latter model the inner part of mercury drop and surrounding solution were treated as dynamic interrelated system. Both models were applied to experimental cyclic voltammetric CV data in 1 M NaClO₄, the results compared and discussed. The concentration profiles of all species including metallic zinc inside mercury drop were performed. The presented integrated model is essential for theoretical and analytical aspects of the electrochemistry of mercury soluble metal cations and amalgams.     

Hankel convolution operators on entire functions and distributions

In this paper we study the Hankel convolution operators on the space of even and entire functions and on Schwartz distribution spaces. We characterize the Hankel convolution operators as those ones that commute with Hankel translations and with a Bessel operator. Also we prove that the Hankel convolution operators are hypercyclic and chaotic on the spaces under consideration.     

A convenient semicarbazide resin for the solid-phase synthesis of peptide ketones and aldehydes

Use of a semicarbazide resin for the solid-phase preparation of peptide ketones and aldehyde led to optimal results in terms of both purity of the final product and overall yield. This resin was prepared without complication by activation of the commercial available aminomethyl polystyrene with CDI at room temperature, followed by treatment with tert-butyl carbazate. Furthermore, the TNBSA colorimetric assay has been adapted for checking the incorporation of the carbonyl moiety onto hydrazine-based resins.     

Conjugate addition of pyrroles to α,β-unsaturated ketones using copper bromide as a catalyst

Copper bromide was used as a catalyst for the addition of pyrroles to enones. When both the reactants were used in equimolar amounts, mono and dialkylated products were obtained. However, the use of excess enone furnished only dialkylated products. Thus, copper bromide was shown to be an efficient catalyst for the dialkylation of pyrroles.     

Structure and electrochemical behaviour of 4,7-diazaheptyl-trimethoxy-silane and vinyl-trialkoxy-silane adsorbed at silver surface

Novel self-assembled monolayers were obtained on silver using 4,7-diazaheptyl-trimethoxy-silane (SiN) and vinyl-trialkoxy-silane (SiVA, where the alkyl group is 3,6,9,12,15,18,21,24,27,30,33,36,39,42,45,48,51,54,57,60-eicozaoxa- hexaheptaconan). It was shown that thus modified metal surface was protected against electrooxidation. A densely packed monolayer remained stable and did not desorb from the Ag electrode on the potential cycling. The structure of SiN and SiVA as well as their complexes with Li⁺ cations were calculated and visualised by the AM1d and PM5 semi-empirical methods.     

Cyclic permutations and evolutionary trees

Given a tree with leaf set X, there are certain ways of arranging the elements of X in a circular order so that can be embedded in the plane and ‘preserve’ this ordering. We investigate some new combinatorial properties of these ‘circular orderings.’ We then use these properties to establish two results concerning dissimilarity maps on X that are induced by edge-weighted trees with leaf set X.     

Selective Propargylation of Carbonyl Compounds and Imines with Barium Reagents

A Barbier‐type regioselective propargylation of aldehydes and ketones with (3‐bromobut‐1‐ynyl)trimethylsilane has been achieved using reactive barium as a low‐valent metal in THF. Especially in the case of ketones, the corresponding homopropargylic alcohols form almost exclusively. In the reaction of α,β‐unsaturated carbonyl compounds, only 1,2‐adducts have been observed. This method is also applicable to propargylation of imines, and the corresponding homopropargylic amines are obtained regiospecifically in good yields with diastereomeric ratios of up to 87:13.     

Synthesis of bioactive indolocarbazoles: synthesis, nucleophilic ring-opening and chiral base desymmetrisation of a cyclic sulfate intermediate

A number of new functionalised bridged indolocarbazole systems have been prepared by ring-opening reactions of a key cyclic sulfate intermediate, prepared from the corresponding diol by the action of sulfuryl diimidazole and DBU. The same cyclic sulfate also undergoes an unprecedented asymmetric rearrangement to a chiral ketone, on treatment with a chiral lithium amide base.     

Stereoselective synthesis of (+)-lauthisan

Stereoselective synthesis of (+)-lauthisan has been accomplished starting from d-glyceraldehyde acetonide by combination of diastereoselective alkylation and ring-closing metathesis. High degree of 1,3-asymmetric induction has been realized in ether system.