Alkylation of carbonyl compounds through their conversion into the corresponding oxycyclopropane intermediates followed by a three-carbon atom ring cleavage is reviewed.

Temperature-dependent magnetic properties (4.2-300 K) of a series of pseudohalide metal complexes with organic nitrogen ligands of the type ML₂X₂, where M = Cu, Ni, Co; L = pyrazole, imidazole or pyridine type ligand; X = [C(CN)₃]^-, [N(CN)₂]^- , [C(CN)₂,NO]^- are reviewed. Three types of µ_eff vs. T functions were ascertained and discussed in terms of both ferro- and antiferromagnetic interactions, which operate between the Cu(II) atoms through orbitals of the bridging pseudohalides. The theory of Kahn et. al. is applied to understand the complex magnetic behaviour of these compounds.

Three new manganese(II) binuclear complexes: [Mn₂(BTPHA)(Phen)₄](ClO₄)₂ (1), [Mn₂(BTPHA)(Nphen)₄](ClO₄)₂ ·H₂O (2), [Mn₂(BTPHA(Bpy)₄](ClO₄)₂·H₂O (3), (BTPHA = 2-bromoterephthalate, Phen = 1,10-phenanthroline, Nphen = 5-nitro-1,10-phenanthroline, Bpy = 2,2-bipirydyl), have been synthesized with 2-bromoterephthalato as the bridged ligand, and were characterized by elemental analysis, IR, molar conductance and electronic reflection spectra. They are proposed to have an extended 2-bromoterephthalato-bridged structure and to consist of two manganese(II) atoms. The variable-temperature magnetic susceptibility of complex 1 was measured over 4.2-300 K. The magnetic coupling parameter is consistent with an antiferromagnetic exchange between the two manganese(II) centers and fits the data with binuclear magnetic exchange model based on the Hamiltonian operator (H=- 2JS₁S₂, S₁ = S₂ = 5/2), giving the antiferromagnetic coupling parameter of 2J = -2.3 cm^-1.

The interaction of copper selenogalate with cadmium selenide was investigated using differential thermal, microstructural and X-ray analyses. Polythermal CuGaSe₂-CdSe section of the quasiternary Cu₂Se-CdSe-Ga₂Se₃ system has been constructed. The existence of an intermediate delta-phase and solid solutions has been established.

Using DTA and X-ray phase diffraction methods, a diagram of phase equilibria in V₂O₅-Fe₂WO₆ system has been constructed. This system is not a real binary system, even below the solidus line.

The usefulness of N,N'-dicyclopentylcarbodiimide as a coupling reagent for solid phase peptide synthesis was demonstrated by the synthesis of sequences comprising the 65-74 residues of acyl carrier protein. The result was compared with that obtained using N,N'-dicyclohexylcarbodiimide and N-cyclohexyl-N'- isopropylcarbodiimide. The title compound was also used for synthesis of [Nle²⁷]GH-RH(1- 29)NH₂. All coupling steps were monitored with quantitative ninhydrin test. It is concluded that this new reagent can be successfully used for solid phase peptide synthesis.

Friedlaender reaction was investigated, starting from 3'-alkyl-derivatives of phenolphthalein 1- 3 (alkyl = Me, Et and i-Pr) and hydroxylamine in strongly alkaline medium. The process was found to give, after acidic hydrolysis of primarily formed anil-type semi-products, a mixture of two 2-aroylbenzoic acids (2-ABAs) in each case. Identification and quantification of 2-ABAs were carried out within RP-HPLC on ODS column. Based on quantitative results, migratory aptitude (MA) parameter values of ionized 4-hydroxy-3- alkylphenyl nuclei were calculated, taking an unsubstituted ionized 4-hydroxyphenyl ring as a standard.

Synthesis and some pharmacological properties of eight new analogues of bradykinin are described. Five peptides were designed to gain more information about features of N-terminal bulky acyl groups suitable for improvement of B₂-antagonistic properties. Two other compounds were synthesized in order to learn how removal of N-terminal D-Arg residue or replacement of D-Arg-Arg with a Lys-Lys fragment would influence B₂-antagonism. The last peptide was obtained in order to check whether inversion of configuration of C-terminal Arg residue in the molecule of potent B₂-blocker will decrease its antagonistic activity. The B₂-antagonistic potency of analogues was evaluated by their ability to inhibit vasodepressor response to exogenous bradykinin in conscious rats. Thus it appears that not only the size of an acyl group attached to the N-terminus of peptide, but also chemical features of the substituent are important for B₂-antagonism.

6-Bromo-2-bromomethyl-1-butyl-3-ethoxycarbonyl-5-methoxy-indole (2) was prepared from 2- methylindole derivative 1 using NBS as regioselective brominating agent. Compound 2 was then reacted with different nucleophiles: phenols, thiophenols and amines to yield the corresponding phenoxy, phenylthio and aminomethylindole derivatives. All new compounds were screened for antibacterial activity.

Four new analogues of bradykinin (BK) were designed, synthesized and bioassayed. The analogues were designed by introduction of the conformationally restricted dipeptide fragment D-Phe-D-Phe into positions 6, 7 or 7, 8 of an previously synthesized antago-nist. The antagonistic potency of peptides was assessed by their ability to inhibit vasodepressor response to exogenous bradykinin in conscious rats. We proved the importance of appropriate localization of the modification used in the molecule for the value of antagonistic activity. We also demonstrated that acylation of the N-terminus of the new analogues with 1-adamantaneacetic acid did not increase, as previously considered, antagonistic potencies of the resulting peptides. Our study, besides providing new information about the structure-activity relationship of bradykinin antagonists, resulted in compounds, which may be useful for clarifying the role of BK in various physiological effects.

Radical cyclization of unsaturated aldehyde: 2,3,4-tri-O-benzyl-5,6,7,8-tetradeoxy- -5(E),6-dieno-oct-D- xylose (2) afforded 1(R)-hydroxy-2(S),3(S),4(R)-tri-O-benzyloxy-5(R)-[prop-1(E)-enyl]-cyclopentane (5); similar reaction of xanthate 7 derived from 2 led to 2(S),3(R),4(R)-tri-O- benzyloxy-5(R)-methyl-cyclopentane (8). The cyclization of other sugar-derived unsaturated aldehydes and xanthates was also studied.

Glycidonitriles 1a-e, when treated with acetyl chloride in the presence of catalytic amounts of zinc chloride, afforded mixtures of chloroacetoxynitriles 2 and acetoxycyanoalkenes 4. Isolated nitriles 2 treated with triethylamine transform into substituted acetoxyacrylonitriles 3.

The carbonyl signal of the 100 MHz ¹³C NMR spectrum of methacrylate/acrylate copolymers provides sufficient resolution for detailed analysis of sequence distribution up to configurational-compositional pentads. It has been shown for the investigated methyl methacrylate/ethyl acrylate copolymer, MMA/EA, that the spectrum of carbonyl region can be positively simulated by applying Bernoulli/1st order Markov statistics to calculate the sequence intensities and a method of incremental calculation of chemical shift to determine the line positions. The method may be readily adopted for other acrylate/methacrylate copolymer systems.

The polymerization of propylene oxide on the surface of thermoactivated anatase has been studied by infrared spectroscopy, thermal gravimetry, field ionization mass spectrometry, and quantum-chemical simulation. Data are given upon the dependence of the grafted oligomer mass on the temperature of the preliminary treatment of anatase surface. The coordination mechanism of the propylene oxide polymerization with the participation of Ti⁴⁺ ions of the TiO₂ matrix is discussed.

Results concerning the influence of calcination conditions and Na⁺ ions addition on the specific surface area of MgO using BET and XRD techniques are presented. Na⁺ ions cause the sintering process of MgO - a considerable loss of surface area and structural changes in MgO lattice. Na⁺/MgO doped catalysts were active and selective for C₂ hydrocarbons formation, especially above 950 K.

Protonic electrolytes from the PEO-H₃PO₄ system are studied by impedance and Fourier transform infrared spectroscopies and differential scanning calorimetry. Different conduction mechanisms are found depending on the concentration of H₃PO₄ and are discussed on the basis of the experimental data.

The addition of LiCl causes a decrease in reaction rate and even inhibition of dehydrocoupling of organic hydrosilanes (Et₃SiH and Me₂PhSiH) with Ph₃SiOH, Ph₂Si(OH)₂, MeOH, and PhCOOH, when carried out in DMF in the presence of ZnCl₂. The rate constants are proportional to the difference in the catalyst and LiCl concentrations, due to the effect of addition of a common anion on the dissociation equilibria. The driving force for the reaction is an electrophilic assistance of the active form(s) of the catalyst (most likely Zn²⁺) to the cleavage of the Si—H bond in the rate determining step, while the interaction of chloride anion Cl^- with silicon in H-silanes does not play any role in the reaction mechanism. This is a new example of the mechanism of the nucleophilic substitution of hydrosilanes with reagents containing a hydroxyl group, because of zero order of the reaction with respect to OH group.

The osmium(VIII) catalyzed oxidation af allyl alcohol by N-bromosuccinimide in alkaline medium is first order each in [N-bromosuccinimide] and [osmium(VIII)], whereas fractional order each in [allyl alcohol] and [alkali]. Increase in [alkali] increases the rate, while added succinimide retards the reaction. Negligible effect of dielectric constant and ionic strength on the reaction medium has been observed. A mechanism involving hypobromite ion, as the reactive species of the oxidant has been proposed. The reaction constants of individual steps of the reaction mechanism have been evaluated.

The chemical diffusion coefficient in non-stoichiometric manganous sulphide, Mn_1-yS, has been measured as a function of temperature (1073-1373 K) and sulphur activity (10^-2- 10³ Pa) using electrical conductivity reequilibration method. It has been shown that the mobility of doubly ionized cation vacancies, constituting the predominant point defects in Mn_1-yS, is independent of their concentration and characterized by the following empirical relationship: D_v = 1.3· 10^-2exp((76.4+/-0.5 kJ mol^-1)/(RT)).
Using these data and those of non-stoichiometry the self-diffusion coefficient of cations in metal deficient manganous sulphide has been calculated: D_Mn = 6.5^. 10^-4p_S2^1/6 exp((119.0+/-0.7 kJ mol^-1)/(RT)). This relationship is in agreement with that calculated from manganese sulphidation kinetics. It may be then concluded, that the growth process of alfa-MnS scale on manganese at high temperatures (> 1000 K) is governed by the volume diffusion of cations.

The crystal structure of 3-[4-(4-phenylpiperazine)butyl]-5,5-diisopropylhydantoin has been determined by X- ray diffraction methods. Compound crystallizes in a monoclinic system, space group P2₁/n with a = 12.943(2), b = 8.514(2), c = 21.746(2) Å, ß = 103.96(1)^o, V = 2325.6(7) ų. The piperazine ring adopts a chair conformation. The phenyl ring and the mean piperazine plane are close to coplanarity. The molecules form centrosymmetric dimers by means of the intermolecular hydrogen bonds N-H···O.

The structure of O-benzyl-7,8-dihydro-8-phenyl-3-trifluoromethyl-
-triazolo[4,3-b]pyridazine- 6(5H)-one has been solved. Two independent molecules found in the unit cell differ in the rotational position of the benzoyl substituent on the C6-O10 and O10-C10 bonds by 6^o and 15^o respectively. The differences result from the unit cell packing requirements.

The crystal lattice of the title red-brown compound contains dimeric [Ni₂(tu)₈Br₂]²⁺ cations and NO₃^- anions. The cations consist of symmetrically bridged S atoms of thiourea with Ni-S bridging distance of 2.47 Å, the Ni-Ni distance of 4.04 Å, and the bridging angle of 104^o. Each nickel(II) atom has a distorted octahedral S₅Br coordination sphere. The susceptibility data for powder, determined betwen 4.2 and 295 K, show the existence of antiferromagnetic intradimer interaction between the nickel(II) centers.