Preparation and evaluation of nickelmesogen for micropacked gas chromatography

The preparation and mesomorphic properties of a substituted bis(dithiolene)nickel complex derived from 4, 4'-dimethoxybenzil are reported. The phase transition temperatures were based on data obtained by polarized light microscopy and differential scanning calorimetry. The mesogenic phase existed over the temperature range from 77 to 175 degrees C. A novel micropacked column (1.5 or 3 m x 1 mm i.d.) prepared from the slurry of bis[1,2-bis(4-n-undecyloxyphenyl)ethane-1,2-dithiolene] nickel(II) (5%, w/w), coated on Chromosorb W was applied for the separation of dialkyl sulfides. The non-linearity (discontinuity) of Van't Hoff plots suggests that the liquid crystal property existed even in the coated phase. Factors affecting the retention and the sample selectivity on the prepared column were examined by using a flame photometric detector (FPD). The separation might be based on the mechanism of ligand exchange, shape selectivity and polarity interaction besides the vapor pressure. LOD for the determination of dialkyl sulfides was below 1 ng for most of the analytes.     

A new method for the synthesis of functionalized maleimides

An effective route to novel maleimides is described, which involves the reaction of an enamine derived from the addition of a secondary amine to a dialkyl acetylenedicarboxylate with an arylsulfonyl isocyanate. These maleimides in solution indicate dynamic NMR because of restricted rotation around the carbon-nitrogen bond, resulting from conjugation of the side-chain nitrogen with the adjacent α,β-unsaturated ester group.     

Addition reactions of 2-polyfluoroalkyl substituted 1,3-thiazolin-4-one derivatives

2-Polyfluoroalkyl-5-methoxycarbonylmethylene-thiazolin-4-ones react as dienophiles on the exo-cyclic ylidene bond to give spiro-derivatives and as 1,3-dienes with olefins to give dihydropyranothiazole derivatives. The endo-cyclic CN bond in these compounds do not enter into the cycloaddition reactions.     

One-pot three-component reaction of isocyanides, dialkyl acetylenedicarboxylates and phthalhydrazide: synthesis of highly functionalized 1H-pyrazolo[1,2-b]phthalazine-5,10-diones

Protonation of the highly reactive 1:1 intermediate produced in the reaction between alkyl isocyanides and electron-deficient acetylenic esters with phthalhydrazide, leads to a vinylisonitrilium cation, which undergoes an addition reaction with the conjugate base of the phthalhydrazide to produce dialkyl 3-(alkylamino)-5,10-dioxo-5,10-dihydro-1H-pyrazolo[1,2-b]phthalazine-1,2-dicarboxylates in fairly good yields at room temperature.     

5-Diazo-6,6-dimethyl-4-oxo-4,5,6,7-tetrahydroindazoles in [3+2] cycloaddition reactions

The [3+2] cycloaddition reactions of a series of 1,3-substituted 5-diazo-6,6-dimethyl-4-oxo-4,5,6,7-tetrahydroindazoles with maleic anhydride and dimethyl acetylenedicarboxylate gave 1′,3′-substituted 3-spiro[4,6-dioxo-4,6,3a,6a-tetrahydro-3H-furo[3,4-c]pyrazole]-5′-[6′,6′-dimethyl-4′-oxo-4′,5′,6′,7′-tetrahydroindazoles] and 1′,3′-substituted 3-spiro[4,5-di(methoxycarbonyl)-3H-pyrazole]-5′-[6′,6′-dimethyl-4′-oxo-4′,5′,6′,7′-tetrahydroindazoles] respectively. When heated the former eliminate nitrogen and are transformed into 1′,3′-substituted 6-spiro[2,4-dioxo-3-oxabicyclo[3.1.0]hexane]-5′-[6′,6′-dimethyl-4′-oxo-4′,5′,6′,7′-tetrahydroindazoles]. __________ Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 12, pp. 1784–1791, December, 2007.     

Thermal characteristics of solid-solid phase transitions in long-chain dialkyl ammonium salts

A series of symmetrical dialkyl ammonium salts, DC_nX, has been prepared and characterized with respect to temperature and enthalpy of solid-solid phase transitions, temperature of melting, thermal stability as well as the reversibility of the phase transitions. The number of carbon atoms, C_n, was varied between 8 and 18 and as anions X halides, nitrate, chlorate, perchlorate and hydrogen sulphate had been chosen. In dependence on chain length and anion type transition temperatures from 20 to 100 °C were observed. Mass specific solid-solid transition enthalpies reach values of 185 J g⁻¹, which makes this class of substances attractive for heat storage applications. The influence of anion type on the transition enthalpies is explained in terms of packing requirements, hydrogen bond network formation and contributions from hindered anion rotation.     

Synthesis of 4‐Arylthio‐3‐hydroxyphthalate by the Diels–Alder Reactionof 4‐Arylthio‐3‐hydroxy‐2‐pyrone

Treatment of 4‐arylthio‐3‐hydroxy‐2‐pyrones with acetylenedicarboxylates gave 4‐arylthio‐3‐hydroxyphthalates by the base‐catalyzed Diels–Alder reaction via a decarboxylation in good yields.     

A Facile One-Pot Synthesis of Highly-Functionalized Stable Heterocyclic Phosphorus Ylides in Aqueous Media

Phthalimide or succinimide undergo a reaction with dialkyl acetylenedicarboxylates and triphenylphosphine to produce highly-functionalized stable heterocyclic phosphorus ylides in good yields in water-tetrahydrofuran (6:1). This methodology is of interest because of the use of water as solvent, thus minimizing the cost, operational hazards, and environmental pollution.     

Facile,one-pot synthesis of new phenanthridine derivatives through 1,4-dipolar cycloaddition of phenantridine,activated acetylenes,and aromatic aldehydes

A facile, one-pot synthesis of new phenanthridine derivatives by a three-component reaction between phenantridine, dialkyl acetylenedicarboxylates（DAADs）, and aromatic aldehydes is described. The reaction is characterized by mild conditions, high selectivity, and tolerance to various functional groups.     

Efficient synthesis of multiply substituted furans using BF@Propyl/dopamine/Pd as a green catalyst

One of the commonly used methods to synthesize furans is the three-component reaction among aromatic aldehyde, arylamine, and acetylenedicarboxylate. The main advantages of this work are easy reaction work-up, short reaction time, high yield and easy recyclability, reusability of the catalyst. And also basalt fiber applications are surely innovative in many industrial and economic fields, because of its good mechanical, chemical and thermal performances.