N. A. Kurchavov

Macrocyclic Complexes of Palladium(II) with Benzothiacrown Ethers: Synthesis, Characterization, and Structure of cis and trans Isomers

A series of palladium(II) complexes with nitro- and formylbenzothiacrown-ether derivatives was synthesized. The spatial structure of the complexes was studied by NMR, X-ray diffraction analysis, and quantum chemical calculations (density functional theory). The cavity size and the ligand denticity were found to be crucial factors determining the geometric configuration of the thiacrown-ether complexes. Palladium(II) complexes with benzodithia-12(18)-crown-4(6) ethers were demonstrated to have a cis-configured S(2)PdY(2) fragment (Y = Cl, OAc). In the case of Pd(II) and benzodithia-21-crown-7 ethers, only complexes with a trans configuration of the S(2)PdY(2) fragment form. In the case of Pd(II) and nitrobenzomonothia-15-crown-5 ether, only 2(ligand):1(Pd) complex with trans configuration of the core fragment forms.

A New Phosphoramidite Reagent for the Incorporation of Diazaphenoxazinone Nucleoside With Enhanced Base-Pairing Properties into Oligodeoxynucleotides

Abstract New phosphoramidite reagent 7 suitable for incorporation of dC analogue was synthesized. ODNs containing diazaphenoxaziione residues in defined positions were prepared. The stability of duplexes formed was increased up to 3-5°C per modified base. Preliminary results of molecular biological testing were reported. This work was partly supported by RFBR grant 96-04-49209, by grant HHMI#75195-544201, LLNL P99U, and grant DOE agreement No. B307902 mod. 04. The authors would like to thank Dr. Tatyana L. Azhikina for valuable help in DNA sequencing and Dr. Natalya P. Potapova for NMR spectra recording.

Synthesis, structure, and characterization of chromo(fluoro)ionophores with cation-triggered emission based on N-methylaza-crown-ether styryl dyes.

Novel 2-benzothiazole-, 4-pyridine-, and 2- and 4-quinoline-based styryl dyes containing an N-methylbenzoaza-15(18)-crown-5(6)-ether moiety were synthesized. A detailed electronic spectroscopy study revealed high performance of these compounds as optical molecular sensors for alkali and alkaline-earth metal cations. They were shown to considerably surpass analogous chromoionophores based on N-phenylaza-crown ethers regarding both the ionochromism and the cation-binding ability. In addition, they act as fluorescent sensors for the metal cations by demonstrating cation-triggered emission. Upon complexation with Ba(2+), the fluorescence enhancement factor reaches 61. The structural features of dyes and their metal complexes were studied by NMR spectroscopy and X-ray diffraction. The high degree of macrocycle preorganization was found to be one of the factors determining the high cation-binding ability of the sensor molecules based on N-methylbenzoaza-crown ethers.

Building up of Macroring in the New Synthesis of Azacrown Ethers. Structure and Complex Formation of Nitrobenzoazacrown Ethers

A cyclization of azapodand haloderivatives into nitrobenzoazacrown ethers under treatment with various bases and in their absence was investigated. The nitrobenzoazacrown ethers obtained and their complexes with metal cations were studied by X-ray diffraction method and by 1H NMR titration. In nitrobenzoaza-15-crown-5 a capability to complex Ca2+ cation was found that significantly exceeded similar ability of nitrobenzocrown ether with the same size of the macroring.

Host-guest complexes of nitro-substituted N-alkylbenzoaza-18-crowns-6

A number of N-alkyl(nitrobenzo)aza-18-crowns-6 in which the nitrogen atom in the macroring is conjugated with the benzene ring were synthesized, and their complexing power was compared with that of model nitro derivatives of benzo-18-crown-6 and N-phenylaza-18-crown-6 using 1H NMR spectroscopy and DFT/PBE quantum-chemical calculations. The stability constants of the complexes formed by crown ethers with NH4/+, EtNH3/+, Li+, Na+, and K+ in CD3CN were determined by 1H NMR titration. The complexing power of N-alkyl(nitrobenzo)aza-18-crowns-6 toward metal and ammonium cation was considerably higher than that of N-(4-nitrophenyl)aza-18-crown-6 and N-alkyl(nitrobenzo)aza-15-crown-5 and was comparable or higher than that of nitrobenzo-18-crown-6.

Synthesis, structure and complexation of biscrown-containing 1,4-distyrylbenzenes

An improved method for the synthesis of two symmetric biscrown-containing and one model tetramethoxy-substituted 1,4-distyrylbenzenes was suggested. The structures of compounds were established by 1H and 13C NMR spectroscopy and X-ray diffraction analysis. Spectrophotometric and fluorescent titration were used to determine spectral properties, stoichiometry, and stability of complexes of biscrown-containing 1,4-distyrylbenzenes with alkali and alkaline-earth metal cations. The stability of the complexes was found to depend on the metal cation size and charge, as well as on the size of the crown ether fragment. The electrochemical oxidation and reduction potentials of the biscrown-containing 1,4-distyrylbenzenes and the model compound in solution were determined and their basic differences from the corresponding characteristics of biscrown-containing stilbenes were identified.

Formation of 4-arylpyridines from pyridinium salts under the action of methylammonium sulfite

Reactions of pyridinium salts or nonquaternized pyridine with 4-methylpyridinium salts in the presence of methylammonium sulfite in aqueous methylamine afford 4-phenylpyridine in 29—57% yields. The probable mechanism of ring transformation in simplest pyridine derivatives under the action of nucleophiles is discussed.

Synthesis, structure, spectral properties, and electrochemistry of bis(crown ether) containing 1,3-distyrylbenzenes

The reaction of tetraethyl [1,3-phenylenedi(methylene)]bis(phosphonate) with formyl derivatives of benzocrown-ethers or formyl derivatives of o-dimethoxybenzene lead to high yield formation of the respectful bis(crown ether) containing 1,3-distyrylbenzenes or tetramethoxy-substituted 1,3-distyrenebenzenes. NMR spectra and quantum-chemical calculations showed the prevalence of unsymmetrical syn/anti,(syn,anti),syn/anti-conformations in 1,3-distyrylbenzenes. 1,3-Distyrylbenzenes absorb in shorter wavelength spectral region and have a weaker fluorescence than 1,4-distyrylbenzenes. The difficulty in the electrochemical reduction of 1,3-distyrylbenzenes comparing with 1,4-distyrylbenzenes is due to a less effective conjugation system in the metaderivatives.