Action of alkali metals in liquid ammonia on substituted thiophenes

The simultaneous action of lithium and alcohol on-alkyl- or-(-carboxyalkyl)thiophenes in liquid ammonia results in the elimination of sulfur and the formation of ketones, and, respectively, the corresponding ketoalkanoic acids in yields of 40–75%. Unsubstituted thiophene gives only an insignificant amount of a carbonyl compound.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 12, pp. 1633–1636, December, 1971.     

Action of alkali metals in liquid ammonia on substituted thiophenes

The action of lithium and alcohols in liquid ammonia on α-substituted thiophenes with subsequent hydrolysis of the products leads to conversion of the thiophene fragment of the molecule to a butyryl group. A number of amino ketones of the aliphatic series were obtained from α-(ω-dialkylaminoalkyl)thiophenes.     

Action of alkali metals in liquid ammonia on substituted thiophenes

,-Unsaturated thioethers of the aliphatic series were obtained by reduction of -alkyl- and -diethylaminoalkylthiophenes with lithium and alcohol in liquid ammonia and subsequent alkylation of the reduction product with alkyl halides.See [1] for communication IV.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 3, pp. 337–340, March, 1977.     

6-氯-1-茚酮的合成

以对氯氯苄和丙二酸二乙酯为原料,经缩合、碱性水解、脱羧、酰氯化、Friedel-Crafts酰基化等反应得到6-氯-1-茚酮,总收率62%,纯度99%.其结构经核磁共振谱(1H NMR)、质谱(MS)和元素分析确认.     

Action of alkali metals in liquid ammonia on substituted thiophenes VI. Preparation of derivatives of vinyl thioethers

Conclusions Reduction in liquid ammonia of -substituted derivatives of thiophene, followed by alkylation of the reduction product with organic halides or epoxy compounds, gave unsaturated thioethers, containing various functional groups in the molecule, in high yields.For communication V, see [1].Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 8, pp. 1877–1881, August, 1978.     

Pulse radiolysis of solutions of alkali metals in liquid amines

Pulse radiolysis of solutions of alkali metals in methylamine and ethylamine shows the formation of three distinct species; the solvated electron e^?_s, the alkali metal anion M^? and a species considered to be a metal—electron pair with stoichiometry M. Hitherto no kinetic or conclusive optical evidence has been obtained for the species M in amine solutions. The three species coexist in equilibrium according to the equation c^?_s + M⁺ ? M + e^? ? M^? with the corresponding rate constants markedly dependent on the solvent and nature of the alkali metal.     

Relaxation time scales in collective dynamics of liquid alkali metals

In this paper the investigation of the dynamical processes of liquid alkali metals is executed by analyzing the time scales of relaxation processes in liquids. The obtained theoretical dynamic structure factor S(k,omega) for the case of liquid lithium is found to be in excellent agreement with the recently received inelastic x-ray scattering data. The comparison and interrelation with other theories are given here. Finally, an important part of this paper is the confirmation of the scale uniformity of the dynamic processes in liquid alkali metals predicted by some previous molecular dynamic simulation studies.     

Reactions of non-activated aryl halides with nucleophilic agents induced by alkali amides in liquid ammonia

It has been shown that the reactions of nucleophiles with non-activated aryl halides, discovered by Bergstrom to be induced by alkali amides in liquid ammonia, proceed by way of a benzyne-type intermediate. The ease with which a given nucleophile can compete with amide ion does not appear to be a simple function of either its basic strength or nucleophilic character as measured in other reactions. Thus, the anions of a number of weak acids line up qualitatively in competitive power as follows: fluorenyl anion anilide> thiophenolate triphenylmethide> acetophenone enolate anion phenylacetylide> phenolate> pyrrolate> alkoxides, iodide or cynaide. The results indicate benzyne to be a highly unstable entity.     

Reduction of 4-hydroxy-3, 5-dialkylbenzaldehydes with complex hydrides of alkali metals

Conclusions A study was made of the reduction of seven 4-hydroxy-3,5-dialkylbenzaldehydes with aluminum lithium hydride and sodium borohydride.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 6, pp. 1311–1313, June, 1971.     

Corresponding states theory and thermodynamic properties of liquid alkali metals

According to phenomenological scaling and the law of corresponding states, reduced coordinates F ^*-T ^*, where F* represents the reduced thermodynamic properties (enthalpy of vaporization, speed of sound, surface tension, saturated liquid density) and T ^* is the reduced temperature, are introduced for the prediction of the thermodynamic properties of alkali metals. Values of the thermodynamic properties from the melting point up to boiling point are correlated. It has been shown that the correlation between reduced thermodynamic properties, as well as with the reduced temperature, can be expressed as a unique straight-line plot with a linear correlation coefficient of 0.9998. The proposed correlation has a simple form for easy calculation, requires only the melting and boiling point parameters, which are usually easy to acquire, and can predict the thermodynamic properties from the melting temperature up to the boiling temperature accurately.     

Reduction of several thiolene 1,1-dioxides by lithium in liquid ammonia

Conclusions The isoprene and piperylene thiolene dioxide derivatives undergo regioselective oxidative ring cleavage at the C⁵-S bond upon reduction using lithium in liquid ammonia.The authors thank K. M. Gitis for assistance in carrying out the gas chromatographic analysis.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 12, pp. 2799–2800, December, 1984.     

Reduction of pyracylene by alkali metals: Mechanism and formation of aggregates

Five reaction stages have been identified in the reduction of pyracylene to its dianion. The same stages were also observed in the photochemical oxidation starting with the dianion. The formation of dimers of anions and of mixed valence aggregates is discussed.     

Action of alkali metals in liquid ammonia on substituted thiophenes. Communication 10. Opening of the thiophene ring in thiophene-3-carboxylic acids

Conclusions A regio- and stereoselective method of synthesis of -alkylthio--Z-alkenoic or -oxoalkanoic acids has been developed by reductive opening of the thiophene-3-carboxylic acids using Na and alcohol in liquid ammonia.For Communication 9 see [1].Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 11, pp. 2530–2532, November, 1985.     

Inclusion extraction of alkali metals by emulsion liquid membranes bearing nano-baskets

Nano-assisted inclusion separation of alkali metals from basic solutions was reported by inclusion-facilitated emulsion liquid membrane process. The novelty and significance of this study is application of nano-baskets of calixarene in the selective and efficient separation of alkali metals, as both carrier and surfactant. For this aim, four derivatives of p-tert-calix[4]arene bearing different sulfonamide moieties were synthesized and their inclusion-extraction parameters were optimized. Maximum extraction was achieved using calixarene scaffold 03 (3.45 × 10^?2 M) as carrier/demulsifier, commercial kerosene as diluent in membrane, sulphonic acid (0.2 M) and ammonium carbonate (0.4 M) as the strip and the feed phases, the phase and the treat ratios of 0.8 and 0.3, mixing speed (300 rpm), and initial solute concentration (100 mg/L). The selectivity of membrane over more than ten interfering cations was examined and the results reveled that under the optimized operating conditions, the extraction percent of alkali metals was 98–99 %.     

Tungsten oxide bronzes with alkali metals

Single-phase samples of tungsten bronzes M _x WO₃ (M = K⁺, Rb⁺, Cs⁺) are prepared by solid-state synthesis. The reversibility of the M_0.33WO₃/M⁺-solid electrolyte interface is studied subject to the alkali metal nature and humidity over a wide temperature interval. The exchange current density at 24°C and 58%-relative humidity is 3.6 × 10^?4 A/cm² for the Rb_0.33WO₃/Rb⁺-solid electrolyte interface; 2.2 × 10^?4 A/cm² for the Cs_0.33WO₃/Cs⁺-solid electrolyte interface; and 1.3 × 10^?4 A/cm² for the K_0.33WO₃/K⁺-solid electrolyte interface. A correlation between the reversibility of the bronze|solid electrolyte interface, which is characterized by the exchange current density, and the rate of potential equilibration in sensor systems, where the bronze is a reference electrode, is revealed. Ionic component of the conductivity of the synthesized tungsten oxide bronzes is measured at a background of the predominant electronic conductivity. The ionic conductivity is three orders of magnitude lower than the electronic conductivity; it decreases in the series Rb_0.33WO₃ > Cs_0.33WO₃ > K_0.33WO₃, amounting to 2.3 × 10^?2, 2.1 × 10^?3, and 2 × 10^?4 S cm^?1, respectively. The working capacity of the M_0.3WO₃ bronzes as reference electrodes in sensor systems for carbon dioxide detection is evaluated. The plots of the cell potential vs. the CO₂ concentration in the electrochemical cells are linear, their slopes (59 ± 1 mV/decade) are characteristic for one-electron process. The fastest response to changes in the CO₂ concentration was obtained with the sensor system that used Rb_0.33WO₃ as reference electrode.