Synthesis of 1,2,4-substituted hexahydropyridazines and X-ray structural investigation of 4-hydroxyimino-2-methyl-1-phenethylhexahydropyridazine

A series of new 1,2,4-substituted hexahydropyridazines was prepared in order to evaluate qualitatively and quantitatively the role and influence of substituents on the biological activity of this system. An X-ray structural investigation of 4-hydroxyimino-2-methyl-1-phenethylhexahydropyridazine was performed. The compounds considered exhibit moderate local anesthetic, antihistaminic, and anticonvulsive activity.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 3, pp. 539–541, March, 1993.     

Zur Chemie der Pyrrolpigmente, 54. Mitt.: Phytochrommodellstudien: Ein 2,3-Dihydrobilatrien-abc-3-Cholesterylderivat

The diastereomeric 2,3-Dihydrobilatrienes-abc derivatives (4Z, 9Z, 15Z)-7 and (4Z, 9Z, 15E)-7 bearing a cholesterylacetate moiety in position 3 of the chromophore are prepared. The reaction sequence contains an isomerisation step providing quantitative enantioselective formation of the chiral center in position 3. Configurations and conformations of the diastereomers are elucidated using¹H- and¹³C-NMR spectra, NOE-difference spectra, 2D-NMR experiments (NOESY) and arguments from UV-VIS and CD data. It is concluded that the hydrophobic interactions between chromophore and cholesteryl-fragment yield a compact conformation where the two substructures are in close contact with each other. On the other hand these interactions seem to be too weak to induce significant changes in the chemistry, absorption spectra and conformational characterics of the bile pigment chromophore. Therefore hydrophobic interactions between chromophor and apolar amino acid residues of the protein in phytochrome should be of minor relevance for determining spectroscopic shifts.

     

An electronic structure investigation of the BNO-BON-NBO system

The potential energy hypersurface of the ground triplet states of the BNO-BON-NBO system has been investigated using traditional ab initio electronic structure theory. The molecules studied have the molecular formula BON and include three linear and three angular species, and two transition states for the isomerization of an angular N-B-O to an angular B-O-N and a linear B-NO, respectively. All stationary points on the BNO-BON-NBO isomerization potential energy surface have been characterized employing UMP2, UMP4, and Gaussian-2 (G2) theory with the 6-311G(d), 6-311G(2d), and TZ2P basis sets. The isomerization for an angular N-BO to the linear B-NO has a lower energy barrier than that of the former to an angular B-ON. Energetics are presented with G2 energies. Two sets of resonance structures for both bent B-NO (boron nitrosyl) and B-ON (boron isonitrosyl) were proposed and the bonding in the two species was analyzed. For the purpose of comparison, the density functional theory based hybrid methods B3LYP/6-311G(d) and B3LYP/TZ2P have also been applied to both geometry optimization and single-point calculations. It is found that the B3LYP prediction of the nature of the linear B-O is contradictory to that made by all MPn(n = 2 and 4) calculations. The cause for this contradiction is discussed.     

RESEARCH ON CATALYSTS OF ANTI-CARBON DEPOSITION FOR CH_4 REFORMING WITH CO_2

IntroductionMethaneandcarbondioxidearetWomaincompositionsforthegreenhouseeffectandtheworldglobewanningll].ItisbeneficialtoourlivingenviroIUnenttocontrolthereleaseofthesetwogases.Theconversionofmethanetothecommonfeedstocksynthesisgas(carbonmonoxideandhydro…     

Synthesis ofS-(+)-hydroprene

A novel path toS-(+)-hydroprene (1) starting from the technical gradeS-(+)-dihydromyrcene (2, e.e. 50%) is proposed. The latter was selectively transformed intoS-3,7-dimethyloctanal (5) in three steps including hydroalumination. The reactions of5 with allyl- or methallylmagnesium chloride followed, respectively, either by oxygenation in the presence of PdCl₂/CuCl or by ozonolysis, affordS,E-6,10-dimethyl-3-undecen-2-one (7) which was treated with ethoxyethynylmagnesium bromide to give the title juvenile hormone analogue in 23% overall yield.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No 1, pp. 110–112, January, 1993.     

A model for the etching of silicon in SF6/O2 plasmas

A model has been developed to describe the chemistry which occurs in SF₆/O₂ plasmas and the etching of silicon in these plasmas. Emphasis is placed nn the gas-phase free radical reactions, and the predictions n( the model are compared with experimental results. Forty-seven reactions are included, although a subset of 18 reactions describes the chemistry equally well. Agreement between the calculated and measured concentrations of stable products downstream of the plasma is better than a factor of 2. The need for additional kinetic data and fàr well-characterized diagnostic studies of SF₆/O₂ plasmas is discussed.     

Convenient and High-Yielding Preparations of Mono(5-carboxy-2-ethylpentyl) Phthalate and its Ring-Deuterated Isomer – The “Third” Major Metabolite of Bis(2-ethylhexyl) Phthalate

Summary. The synthesis of an oxidative major metabolite of bis(2-ethylhexyl) phthalate is described. The target molecule and its ring-deuterated isomer were obtained via acylation of the appropriate -hydroxy benzyl ester or the corresponding carboxylate with phthalic anhydride or phthalic anhydride-d₄. All transformation steps proceed with high yields.     

Stereochemistry of ketone olefination with methyl trimethylsilylacetate

High (Z)-stereoselectivity of olefination of methyl α-phenylthioalkyl and methyl α-phenylthioalkenyl ketones with methyl trimethylsilylacetate decreases in the case of ketones containing a higher alkyl-substituent in place of the methyl group. Dedicated to Corresponding Member of the Russian Academy of Sciences E. P. Serebryakov on the occasion of his 70th birthday. __________ Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 4, pp. 1020–1021, April, 2005.     

A comparison of ring-chain tautomerism in heterocycles derived from 2-aminobenzenesulfonamide and anthranilamide

A number of anthranilamide and 2-aminobenzenesulfonamide derivatives with aromatic aldehydes and 1,3-dicarbonyl compounds were synthesized. Substituted benzaldehyde derivatives of neither aminoamides showed tautomerism in solutions. Reaction products of 2-aminobenzenesulfonamide with p-substituted benzoylacetic aldehydes and p-substituted benzoylacetones undergo ring-chain tautomerism with a good linear correlation between the ring-chain equilibrium constants (log K, where K=[ring]/[chain]) and the Hammett-Brown σ⁺ parameters of the aromatic substituents. The equilibrium constant was measured for the reaction products of 2-aminobenzenesulfonamide with unsubstituted benzoylacetaldehyde at several temperatures which enabled the enthalpy and entropy of this reaction to be evaluated.     

[Hg3]4+ Cation in Inorganic Crystal Structures

The crystal-chemical structure of the minerals and inorganic compounds kuznetsovite [Hg₃](AsO₄)Cl and terlinguaite [Hg₃][HgO₂]Cl₂, as well as [Hg₃]₃(AsO₄)₄ and [Hg₃]₂[HgO₂](PO₂ and their analogs, is considered from the viewpoint of the packing of large supramolecular atomic groups. The cationic layer of polyhedra around the large [Hg₃]⁴⁺ cations, alternating with the anionic layer of [HgO₂]^2-, (AsO₄)^3-, (PO₄)^3-, Cl^-, plays the major role in structure formation. Segregation of mercury cations of different valences possibly reflects the solid-state transformations occurring in nature and accompanied by mercury liberation.