Изменеяин агрегатны х состояний на электр одах нри конденсированных ра зрядах

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New approaches to side-chain fluorinated bioimidazoles: 4-alkynylimidazoles as substrates for fluorination

4-Alkynylimidazoles have been prepared and their behavior as substrates for “FBr” addition (NBS+Et₃N·3HF) have been studied. Facile Markownikov addition to ethylnylimidazole 2 gave fluorobromoolefin 9a, a potential synthon for the 2-imidazolyl-2-fluoro-1-ethenyl moiety. Reaction of the lithium salt of 2 with diethyl oxalate produced imidazolylpropynoic ester 3b. However, because of the deactivating effect of the ester functionality, all attempts to carry out addition of “FBr” to 3b met with failure. Reduction of the ester gave the hydroxymethyl-substituted acetylene 4. Addition of “FBr” to this substrate and reductive removal of bromine from the product produced fluoroolefins 12, precursors to E- and Z-β-fluorourocanic acids. The same fluoroolefins can be used as intermediates in the synthesis of β-fluorohistidinols.     

The perminvar effect and magnetic after-effect in magnesium manganese ferrite

An unstable perminvar effect was found in magnesium manganese ferrite at a temperature of –195°C and its connection with the magnetic after-effect was investigated. The analysis carried out on the basis of Néel's theory showed that both effects are a result of the same diffusion process. The experimental results also show that 180° Bloch walls are displaced when the sample is magnetized.

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- – 195° C qe, , . , - . , 180- .

     

Cyclosporins of Symmetry P21 – a Series of Clathrates

A series of isomorphous clathrates(cyclosporin A: solvent = 1 : 1) is reported. Thestructure of the tetrahydrofuran (1) anddibutylether (2) clathrates have been determinedby X-ray single crystal diffraction. The cyclosporinmolecules in both structures are associated via vander Waals interactions forming cavities occupied bysolvent molecules. The structure refinement based onroom-temperature data sets show significant disorderof the side chains of the cyclosporin A molecule withno adequate model of the solvent molecule in bothstructures. In contrast, the position of dibutyletherwas successfully localised using a low-temperaturedata set for 2.     

Unusual interaction of alkynes with nine-vertex arachno-monocarbaboranes 4-CB8H14 and [4-CB8H13]-

Alkynes R(1)R(2)C(2) react with the neutral monocarbaborane arachno-4-CB(8)H(14) (1) at elevated temperatures (115-120 degrees C) under the formation of the derivatives of the ten-vertex dicarbaborane nido-5,6-C(2)B(8)H(12) (2) of general formula 9-Me-5,6-R1,R2-nido-5,6-C(2)B(8)H(9) (where R1,R2 = H,H 2a; Me,Me 2b; Et,Et 2c, H,Ph 2d, and Ph,Ph 2e) in moderate yields (26-52%). Side reaction with PhC(2)H also yields 1-Ph-6-Me-closo-1,2-C(2)B(8)H(8) (3d). In contrast, the reaction between [arachno-4-CB(8)H(13)](-) anion ((-)) and PhC(2)H produces a mixture of the closo anions [1-CB7H8]- (4-) and [1-CB6H7]- (5-) (yields 32 and 24%, respectively). Individual compounds were isolated and purified by liquid chromatography and characterized by NMR spectroscopy ((11)B, (1)H and (13)C) combined with two-dimensional [(11)B-(11)B]-COSY and (1)H-{(11)B(selective)}NMR techniques.     

Half-pseudoferrocene cations from nucleophilic addition of o-carboranyl anions to the [(η6-mesitylene)2Fe](2+) dication

Reactions between the mesitylene (mes) dication [(η(6)-mes)(2)Fe](2+) (1a) [(PF(6)(-))(2) salt] and lithium o-carboranes Li[1-R-1,2-C(2)B(10)H(11)] (2) (R = H, 2a; Me, 2b; Ph, 2c) at low temperature (-60 °C, 1 h, followed by stirring for 2 h at r.t.) in THF resulted in a clean addition of the corresponding carborane anions to one of the unsubstituted arene sites in 1a, forming a series of orange monocations of general structure [(η(5)-mes-exo-6-{2-R-1,2-C(2)B(10)H(11)})Fe(η(6)-mes)](+) (3) (R = H, 3a; Me, 3b; Ph, 3c) which were isolated as PF(6)(-) salts (3PF(6)) in yields ranging 50-75%. Individual complexes were obtained on purification by LC or preparative TLC on a silica gel substrate, using MeCN-CH(2)Cl(2) mixtures as the mobile phase. Interestingly, the room-temperature reaction between 2a (threefold excess) and 1a(PF(6))(2) with a reverse order of addition of the reaction components yielded an orange salt [(η(5)-mes-exo-6-{1,2-C(2)B(10)H(11)})Fe(η(6)-mes)](+)[closo-nido-H(11)B(10)C(2)-C(2)B(10)H(12)](-) (3acCA) (cCA = conjucto-carborane anion = [closo-nido-H(11)B(10)C(2)-C(2)B(10)H(12)](-)) as a sole product in 71% yield. The formation of this conjucto anion can be taken as a strong support for the participation of a radical-chain mechanism in the ostensible nucleophilic addition which we suppose to be initiated by the formation of the [(mes)(2)Fe(+)]˙ radical cation. The structures of both 3PF(6) and 3acCA have been established by X-ray diffraction and the constitution of all compounds isolated is in agreement with elemental analyses, multinuclear NMR data, and MS spectra.     

O− centre formation in YAG crystals doped with rare earth ions

Colour changes of YAG crystals doped with rare earth ions and annealed in hydrogen, oxygen, vacuum or argon are described. The influence of UV irradiation is also given. Some crystals were further doped with Ca, Sr, Ba, or Cr, respectively. Yellow or brown colouring of the crystals is attributed to the O⁻ centre formation which causes an increase of the absorption peak at 395–410 nm. Most intensive colouring showed the crystals containing a combination of Yb or Eu with Nd or Cr after oxygen annealing followed by UV irradiation.