Photochemische Reaktionen. 68. Mitteilung. Die Photoisomerisierung von α,β-ungesättigten γ,δ-Epoxyketonen: 9α, 10α- und 9β, 10β-Oxido-3-oxo-17β-acetoxy-Δ4-östren

Irradiation in the n→π* absorption band of the α,β-unsaturated γ,δ-epoxyketone 5 in ethanol at ?65° exclusively afforded the rearranged ene-dione 13 , whereas at + 24° under otherwise unchanged reaction conditions or upon triplet sensitization with Michler's ketone and with acetophenone at + 24° essentially identical mixtures of 13 (major product), 14 , and 15 were obtained. Selective π→π* excitation of 5 at ?78° and + 24° led to similar product patterns. The 9β,10β-epimeric epoxyketone 7 selectively isomerized to 14 and 15 at + 24° and n → π* or π → π* excitation. Neither the epoxyketones 5 and 7 nor the photoproducts 13–15 were photochemically interconverted. In separate photolyses each of the latter gave the double bond isomers 16 , 18 , and 19 , respectively. Cleavage of 13 to the dienone aldehyde 17 competed with the double bond shift ( → 16 ) when photolyzed in alcoholic solvents instead of benzene. The selective transformations 5 → 13 (at ?65° and n → π* excitation) and 7 → 14 + 15 are attributed to stereoelectronic factors facilitating the skeletal rearrangements of the diradicals 53 and 55 , the likely primary photoproducts resulting from epoxide cleavage in the triplet-excited compounds 5 and 7 , via the transition states 54 , 56 , and 57 . The loss of selectivity in product formation from 5 at higher temperature and n → π* excitation or triplet sensitization is explicable in terms of radical dissociation into 58 and 59 increasingly participating at the secondary thermal transformations of 53 . The similar effect of π → π* excitation even at ?78° indicates that some of the π,π* singlet energy may become available as thermal activation energy. It is further suggested that the considerably lesser ring strain in 14 and 15 , as compared with 13 , is responsible that selectivity in product formation from 7 is maintained also at +24° and at π → π* excitation.     

Synthesis of non-equilibrium PtxOs1−x Solid solutions. Crystal structure of [Pt(NH3)4][OsCl6]

Several non-equilibrium solid solutions belonging to the platinum-osmium systems Os_0.9Pt_0.1, Os_0.8Pt_0.2, Os_0.5Pt_0.5, Os_0.7Pt_0.3, Os_0.75Pt_0.25 are prepared and studied. The thermal decomposition of [Pt(NH₃)₄][OsCl₆] in the hydrogen and helium atmosphere is investigated. It is found that the Pt_0.5Os_0.5 solid solution develops through the formation of (NH₄)₂[OsCl₆] and a metallic phase based on Pt. The crystal structure of a double complex salt [Pt(NH₃)₄][OsCl₆] is studied (X8-APEX Bruker, 1508 independent reflections, R = 2.04%). Crystal data for PtOsN₄Cl₆H₁₂ are: a = 11.6216(5) Å, b = 11.0016(5) Å, c = 10.3819(5) Å, V = 1327.4(1) ų, space group Cmca, Z = 4, d _x = 3.333 g/cm₃. The coordination polyhedron around Os is octahedral: 〈Os-Cl〉 2.357 Å, ∠Cl-Os-Cl 89.5–90.5°, while around Pt it is square-planar: Pt-N 2.046 Å, ∠ N-Pt-N 89.59° and 90.41°.     

Acid-base interactions and adhesion capacity in the system constituted by an epoxy coating and a metal

Free surface energy and acidity parameter of solid surfaces of polyepoxides used as anticorrosive coatings were measured. Formulations of epoxy resins with various curing agents were studied. The adhesion capacity of epoxy films to various metallic surfaces was evaluated.     

Electrochemical reduction of 4-(nitrophenyl)-1,2- and 4-(nitrophenyl)-1,4-dihydropyridines and the ESR spectra of the obtained free-radical particles

In the course of electrochemical generation the intermediate reaction products (free radicals of the nitro-and nitrosophenyl type, which appear on the cyclic voltammetric curves) were identified by ESR. The N-substituted derivatives are characterized by reduction of the dihydropyridine ring. The 4-nitrophenyl derivatives are characterized by the absence of intramolecular electron transfer during electrochemical reduction. In the case of the corresponding derivatives of 1,2-dihydropyridine intramolecular transfer of electrons and protons is possible under these conditions. Combined schemes of the primary and secondary chemical reactions involved in the electrochemical reduction of the investigated compounds are presented. It was established that the substances investigated with reference to the mechanism of the electrochemical transformations include the antihypertensive nifedipine (corinfar, fenigidine).Latvian Institute of Organic Synthesis, Riga LV-1006. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 2, pp. 219–233, February, 1997.     

The Mechanism of Low-Temperature Ammonia Oxidation on Metal Oxides According to the Data of Spectrokinetic Measurements

Low temperature ammonia oxidation on MoO₃, Fe₂O₃, Cr₂O₃, and ZnO is studied by the spectrokinetic method. It is shown that the following adsorbed species are intermediates in this reaction: NH₃ and N₂O on Fe₂O₃ and ZnO; NH₃, N₂O, and NO on Cr₂O₃. All of the detected intermediates are used to construct the mechanism of the process. In the framework of the proposed mechanism, stationary and nonstationary spectral and kinetic data are quantitatively processed. The dependence of the rate constants of the same steps on different oxides on their physicochemical properties is discussed.     

Photo- and Thermochromic Spirans. New Metal Chelates Based on Azomethines and Hydrazones Containing a Spiropyran Fragment

Imine- and hydrazone-based metal chelates containing a spiropyran fragment derived from 3-methyl-4-oxo[2H]-1,3-benzoxazinone were prepared. Attempts are made to monitor the photochromic activity of spiropyran using nontraditional -acceptor substituents (products of condensation of the formyl group in 6"-dimethyl-8"-formylspiro-(4-oxo-3,4-dihydro-2H-1,3-benzoxazine-2,2"-[2H]chromene) with o- aminophenol and aromatic acid hydrazides) and using transition metal ions.     

Crystal Structures and Magnetic Properties of the Two Misfit Layer Compounds: [SrGd0.5S1.5]1.16 NbS2 and [Sr(Fe,Nb)0.5S1.5]1.13 NbS2

Crystal structures of two new misfit compounds, [SrGd_0.5S_1.5]_1.16NbS₂ and [Sr(Fe,Nb)_0.5S_1.5]_1.13NbS₂, were determined through the composite approach, i.e., by refining each subpart (Q, H-parts, and the common part) of these composite materials, separately. The Q-part is a three-atom-thick layer, with the NaCl-type structure, where external SrS planes enclose the inner GdS or (Fe,Nb)S plane; the structural difference between these two compounds lies in the central layer within the Q-part: Gd and S atoms are in special positions (octahedral coordination), while Fe and S atoms are statistically distributed on split (×4) positions (tetrahedral coordination) around a central unique site (=special position occupied by Nb). The H-part is a sandwich of sulfur planes enclosing the inner Nb plane as observed for the structure of the binary compound NbS₂ itself. The Sr-Gd derivative shows a paramagnetic behavior in the whole studied temperature range (2-300 K). On the other hand, antiferromagnetic interactions occur in the Sr-Fe derivative; the complex magnetic behavior of this compound is related to the statistical distribution of Fe atoms which leads to frustration of the magnetic interactions. At room temperature, experimental values obtained from Mössbauer spectrum correspond to Fe³⁺ in tetrahedral sulfur environment: isomer shift δ=0.32 mm s⁻¹, and quadrupole splitting ΔE=0.48 mm s⁻¹.     

Features of complexing of molecular NMR relaxation probes with cellulose acetates in solutions

The method of active and inert NMR relaxation probes can be used for determining the degree of substitution of cellulose acetates. The formation of hydrogen bonds between the hydroxyl and acetate groups of cellulose acetate is more probable than between the hydroxyl groups, which results in relative large shielding of the free OH groups in the polymer in samples with high degrees of substitution.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 8, pp. 1761–1765, August, 1989.We would like to thank N. I. Naimark for providing the samples of the cellulose acetates.     

Mechanism and products of electrochemical reduction of 4-nitrophenyl-2,6-dimethyl-3,5-dicyano-1,4-dihydropyridines in dimethylformamide

Free anion radicals of the nitrobenzene and nitrosobenzene type, which were identified by EPR spectroscopy, are formed in the electrochemical reduction of isomeric 4-(nitrophenyl)-2,6-dimethyl-3,5-dicyano-1,4-dihydropyridines on mercury and solid electrodes. Reduction of the dihydropyridine ring is observed only for N-substituted p- and m-nitrophenyl derivatives of 1,4-dihydropyridine. An intermediate with a 2-pyridonemethide structure was identified; a set of primary and secondary chemical reactions that are associated with the electrolytic reduction of the investigated compounds is presented.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 11, pp. 1494–1505, November, 1988.     

2-Benzopyrylium salts. 27. Some transformations of 6-oxodibenzo[a,g]-quinolizinium salts

The synthesis of 6-oxodibenzo[a,g]quinolizinium perchlorate — an analog of the alkaloid berberine — and a number of its derivatives, including mesoionic compounds, was accomplished on the basis of a 1-unsubstituted 3-(2-methylenecarboxyaryl)-2-benzopyrylium salt. The interconversions of the compounds obtained in this research were studied.See [1] for communication 26.Deceased.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 10, pp. 1381–1387, October, 1982.