Furan derivatives—III : Synthesis and properties of β-ketosulphides and sulphur derivatives of chalcones of 5-nitrofuran series

A series of 2-(5-nitro-2-furyl)-2-oxoethylarylsulphides 3a–3h has been prepared by the reaction of 5-nitro-2-furylbromomethylketone 1 with 4-substituted thiophenols 2a–2h. The determined rates of carbanion formation (log k'), pK values as well as ¹H NMR data show that in these compounds transmission of polar effects by the substituents through the -S- group occurs. Compounds 3a–3h react with aromatic aldehydes affording sulphur chalcone derivativěs of the 5-nitrofuran series 4a–4h. ¹H NMR, IR and UV spectra of prepared compounds are discussed.     

Tautomerism of xanthine: The second-order MØller-Plesset study

Four 9H and four 7H tautomers of DNA base xanthine were studied by the ab initio LCAO-MO method at the MP2/6-311G^**//HF/6-31G^** and MP2/6-31G^**//HF/6-31G^** approximations. All calculated structures are minima at the HF/6-31G^** potential energy surface with the dioxo 7H tautomer (A1) being the global minimum. The second most stable tautomer, dioxo-9H (B1) is by 9 kcal/mol less stable. For the A1 B1 transition the calculated MP2 energy gap corresponds to the equilibrium constant of 2 × 10^–7. Therefore, only the major tautomeric form A1 is predicted to be detectable in the gas phase. The 7H and 9H groups of tautomers are discussed separately. Within both groups, the dioxo form (A1-7H, B1-9H) is the most stable one and is succeeded by the 2-dihydroxy (A2, B2) form. However, while the energy difference between A1 and A2 is 10 kcal/mol, the energy difference between B1 a B2 is only 2 kcal/mol. The effect of polar environment was estimated by the SCRF method, using a spherical cavity, at the HF/6-31G^** level. These calculations did not change the gas phase stability order of the tautomers. However, the energy difference between A1 and B1 decreased from 9 kcal/mol at the HF/6-31G^** level to 4 kcal/mol at the SCRF HF/6-31G^** level.     

Behavior of radiocesium in atmospheric arerosol and fallout in Prague

Radiocesium in ground layer atmospheric aerosol and fallout in Prague has been examined. After a decline in 1986–1988, controlled by a sum of two negative exponentials,¹³⁷Cs aerosol concentration reached a constant level based on an equilibrium between its deposition and resuspension. Deposition velocity was compared to that of⁷Be and²²⁶Ra. It confirmed the supposed source of¹³⁷Cs as resuspension from the ground. Resuspension factor of the order of magnitude of 10^–9 was determined, reminding similar values found earlier in Prague as well as those found in Munich. It also agrees well with the USAEC resuspension model. Solubility of¹³⁷Cs was measured in combined wet and dry fallout. The average undissolved fraction of¹³⁷Cs was found to be about 70% which can be explained by the conditions of the¹³⁷Cs aerosol formation in Chernobyl.     

Organophosphines in PtP2Si2 derivatives – structural aspects

Abstract

In this review, the structural data of monomeric platinum(II) complexes with inner coordination spheres of Pt(η²-P₂L)(SiL)₂, Pt(η²-P₂L)(η²-Si₂L) and Pt(η²-P,SiL)₂ are classified and analyzed. These complexes crystallize in three crystal systems: monoclinic (8 examples), triclinic (4 examples) and orthorhombic (4 examples). Distorted square-planar environments about the Pt(II) atoms are built up by combination of homobi-P,P with two monodentate Si donor ligands; homobi-PP with homo-Si,Si donor ligands, or heterobi-P,Si donor ligands. The chelating ligands create metallacycles with the following angles: 65.0° (SiOSi) < 83.1° (SiC₂Si) < 85.2° (PC₂P) < 88.8° (SiSi₂Si)). The mean Pt-P and Pt-Si bond distances in Pt(η²-P₂L)·(SiL)₂ complexes are 2.319 and 2.365?Å; in Pt(η²-P₂L)(η²-Si₂L) the values are 2.316 and 2.360?Å. The complex [Pt{η²-Me₂P(C₂B₁₀H₁₀)SiMe₂}₂] exists in two isomeric forms, a monoclinic cis- and a triclinic trans-isomer. The structural data are compared and discussed with the complexes of inner coordination spheres: Pt(η²-P₂L)(XL)₂ (X?=?O, N, CN, BL, Cl, SL, SeL, Br, or I) and Pt(η²-P₂L)(η²-X₂L) (X?=?OL, NL, SL or SeL).     

Reactions of quaternized imidazo-quinazoline and-pyridopyrimidine with active methylene compounds

Summary Syntheses of 1-methylimidazo[1,2-c]quinazolinium iodide (3) and 1-methylimidazo[2,1-f]pyrido[3,2-d]pyrimidinium iodide (4) are described. These tricyclic compounds react with nucleophiles derived from active methylene compounds to give the corresponding open-chain enamines.

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Reaktionen von quaternisierten Imidazo-Chinazolinen und -Pyridopyrimidinen mit Verbindungen mit reaktiven Methylengruppen

Zusammenfassung Synthesen von 1-Methylimidazo[1,2-c]chinazoliniumjodid (3) und 1-Methylimidazo[2,1-f]pyrido[3,2-d]pyrimidiniumjodid (4) werden beschrieben. Diese tricyclischen Verbindungen reagieren mit einigen Carbanionen aus Verbindungen mit reaktiven Methylengruppen, wobei die offenkettigen Enamine entstehen.

     

P, p, T Surfaces of real gases and the Riemann-Hugoniot catastrophe

Analysing experimentally determined P, ?, T data of N₂, ethylene, propene, CO₂ and Xe by a new mathematical technique, we present evidence that their isothermal pressure-density dependence exhibits behaviour characteristic of a Riemann-Hugoniot catastrophe, in analogy to a van der Waals gas for above and sub critical isotherms.     

Stability constants of D(−)-ribose complexes with calcium in diluted aqueous and methanolic solutions

The study of D(?)-ribose complexing with calcium in aqueous solutions less than 1.64 × 10^?1M by potentiometric measurements with a calcium selective electrode afforded the value of K₁ = 1.70 liters × mole^?1 (SD = 1.05 × 10^?3). Numerical analysis indicated that complex species with 1:1 and 1:2 calcium to D(-)-ribose ratios are present simultaneously: k₁ = 1.13 liters × mole^?1 and K₂ = 8.47 liters × mole^?1 (SD = 0.95 × 10^?3).In methanolic medium 1.24 × 10^?2M with regard to calcium chloride both stoichiometric proportions were evidenced. A large error accompanying the stability constant K₁ = 28 kg × mole^?1 (RSD = 82%) renders unreasonable the K₂ value obtained from the product K₁ × K₂ = 96.5 kg² × mole^?2.The results are discussed with respect to the data published for more concentrated (1.27 M) aqueous solutions obtained on the basis of ₁H-NMR spectroscopic investigations.     

Results of three years of monitoring239,240Pu and238Pu concentrations in airborne effluents from the V-1 nuclear power plant with VVER 440 reactors in Jaslovské Bohunice in Czechoslovakia

The concentration of^239,240Pu and²³⁸Pu in airborne effluents in the years 1985–1987 from two reactors VVER 440/total power of 880 MW/ of a nuclear power plant V-1 in Jaslovské Bohunice in Czechoslovakia, was determined. The concentration of^239,240Pu in effluents ranged from 1.0 to 30.8 Bq.m^–3 and of²³⁸Pu from 1.6 to 41.1 Bq.m^–3. The activity ratio²³⁸Pu/^239,240Pu in airborne effluents kept within the range of 1.0–2.4. Total annual discharged activities of^239,240Pu in 1985, 1986 and 1987 were 28.5, 12.7 and 12.2 kBq, respectively. Total annual discharged activities of²³⁸Pu in 1986 and 1987 were 16.6 and 15.1 kBq, respectively.     

Determination of137Cs and134Cs in air samples collected near Belgrade /Yugoslavia/ following the Chernobyl accident

This paper presents the results of measurements of¹³⁷Cs and¹³⁴Cs content in air sampled during May 1986. Maximum concentrations:¹³⁷Cs 2.94±0.01 Bq m^–3 and¹³⁴Cs 1.38±0.01 Bq m^–3 were registered on May 3. Several other long lived radionuclides having -energies in the region 33 keV to 1365 keV were registered in the same samples two years later. The results of measurements of the total -activity in air for the same period are also presented.