Synthesis of hydrothioxanthenes. VII

On reaction with Grignard compounds, sym-octahydrothioxanthylium and 9-methyl-symoctahydrothioxanthylium perchlorates form 9-mono- and 9, 9-disubstituted sym-octahydrothioxanthenes. The reactions of the new sym-octahydrothioxanthene with perchloric acid and ferric chloride has been studied. The elimination of the benzyl group of 9-benzyl-sym-octahydrothioxanthene on salt formation has been observed.For part VI, see [1].     

Heterogyclization of triketones of the 2-(3-oxopropyl)-cyclohexane-1,3-dione series

Triketones of the 2-(3-oxopropyl) cyclohexane-1,3-dione series have been shown for the first time to react with boron trifluoride etherate to give the novel 5-oxo-5,6,7,8-tetrahydrochromylium fluoroborates, which in turn react with ammonia to give 5-oxo-5,6,7,8-tetrahydroquinolines. These were also obtained directly from ammonium acetate and 2-(3-oxopropyl)cyclohexane-1,3-diones.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 7, pp. 915–918, July, 1985.     

Condensation of aldehydes and ketones

The alkaline condensation of β-aceto-and β-propionaphthalenes with furfural has given, respectively, 2-(α-furfuryl)-1, 3-di(β-naphthoyl)-propane and 3-(α-furyl)-2,4-di(β-naphthoyl)pentane; both δ-diketones have also been obtained by the Michael condensation. Under more severe conditions, two molecules of furfural condense with three molecules of β-acetonaphthalene to form 2, 4-di(α-furyl)-1, 3, 5-tri(β-naphthoyl)pentane. Under similar conditions, benzaldehyde exhibits only a feeble capacity for triketone condensation with β-acetonaphthalene. The condensation of β-propionaphthalene with furfural has given the new compound furylidenepropionaphthalene. It has been shown that both under the conditions of the improved Chichibabin pyridine synthesis and under the conditions of the Leuckhardt reaction, 3-(α-furyl)-1, 3-di(β-naphthoyl)propane gives 4-(α-furyl)-2, 6-di(β-naphthyl)pyridine.     

Semiempirical and nonempirical quantum-chemical methods applied to the structure of P-substitute phosphaalkenes

Quantum-chemical studies have been performed on the structures of the phosphaalkenes RP = CH₂, in which the substituent R may have various electronic parameters; the nonempirical MO LCAO SCF method has been used with the OST-3G, OST-3G, 4-31G, 4-31G, 4-31G, and 4-31G(d) bases, as well as in the semiempirical MINDO approximation. The calculations with the 4-31G and 4-31G(d) bases give satsifactory values for the geometrical parameters and energies of the boundary MO. OST-3G is unsuitable for describing the energies of the MO, but MINDO can be used. The HOMO are of type, below which lie n-type MO. The gap between them for any R other than an alkyl group is increased by comparison with HP + CH₂. The P=C bond is appreciably polarized by R, particularly if it is capable of conjugation; the length varies little in this series because the resonance and polarization effects balance. The relative reactivities of the P-substituted phosphaalkenes in 1,2-addition reactions are discussed.Translated from Teoreticheskaya i Éksperimental'naya Khimiya Khimiya, Vol. 26, No. 5, pp. 547–555, September–October 1990.     

Saturated nitrogen-containing heterocycles. 13. Perhydroacridines. Synthesis and stereochemistry

The configurations of the perhydroacridines formed in the catalytic hydroamination of threo-methylenedicyclohexanone and the product of its cyclization — 2-hydroxy-2,3-tetramethylenebicyclo[3.3.1]nonan-9-one — were established by means of the ¹³C NMR spectra and alternative synthesis. It is shown that isomers with cis-anti-cis and cis-syn-cis configurations are formed as a result of the reactions. The results of x-ray diffraction analysis are presented for cis-syn-cis-N-(2-hydroxyethy1)perhydroacridine.See [1] for Communication 12.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 12, pp. 1645–1650, December, 1987.     

PBW-bases of coideal subalgebras and a freeness theorem

Let be a character Hopf algebra. Every right coideal subalgebra U that contains the coradical has a PBW-basis which can be extended up to a PBW-basis of If additionally U is a bosonization of an invariant with respect to the left adjoint action subalgebra, then is a free left (and right) U-module with a free PBW-basis over U. These results remain valid if is a braided Hopf algebra generated by a categorically ordered subset of primitive elements. If the ground field is algebraically closed, the results are still true provided that is a pointed Hopf algebra with commutative coradical and is generated over the coradical by a direct sum of finite-dimensional Yetter-Drinfeld submodules of skew primitive elements.

     

Radiation-induced modification of reflection spectra beyond the ion path region in polyimide films

Modification of the surface layers of polyimide films under γ-radiation and implantation with 30–100 keV Ni, Mn, Ag, Co, Fe and B ions in the dose range of 10¹⁵–1.5 × 10¹⁷ cm^–2 are investigated by reflection spectra measurements. Ion implantation is shown to lead to the modification of reflection from the rear (unimplanted) polymer side. Depending on the kind of ion and implantation mode a strong increase in the integrated reflection coefficient in the polymer opacity range is observed, as well as growth of the reflection intensity of optical bands λ₁ = 254 and λ₂ = 311 nm and their shifts to the short-wavelength region. The change in the reflection coefficient far beyond the implanted region is caused by the radiation-induced transformation of the polymer supermolecular structure near the surface and the relaxation of mechanical stress formed during film production.     

Preparation and Properties of a Representative of a New Series of Chalcogen-containing 1,5-Diketones, Di(1-oxo-1,2,3,4-tetrahydro-2-naphthyl) Sulfide

Di(1-oxo-1,2,3,4-tetrahydro-2-naphthyl) sulfide has been obtained and its behavior towards hydrogen sulfide in situ, ammonium acetate, hydrazine hydrate, and hydrogen peroxide has been studied. The structure of the compounds synthesized was established by IR and by ¹H and ¹³C NMR spectroscopy and by chromato-mass spectrometry.     

Detoxication of Aqueous Cyanide Solutions with Oxygen in the Presence of S(IV) and Cu(II) Compounds

Oxidation of cyanide anions with atmospheric oxygen in aqueous solutions in the presence of Na₂SO₃ and NaHSO₃ mixture and CuSO₄ as a catalyst was studied. The reaction mechanism was proposed.     

COMPREHENSIVE STRUCTURAL DIAGNOSTICS OF Ni–Ce1–xZrxO2 CATALYSTS PREPARED BY THE PECHINI METHOD

Journal of Structural Chemistry - Nickel-containing catalysts Ni/Ce1–xZrxO2 exhibit good activity in the methanation of carbon oxides. The studies devoted to the synthesis and testing of...