Preparation of CF3-containing 1,3-di- and 1,1,3-trisubstituted allenes

Novel synthetic pathway to access trifluoromethylated allenes with 1,3-di- as well as 1,1,3-trisubstitution patterns was developed from a variety of 4,4,4-trifluorobut-2-yn-1-ols which were then transformed into the corresponding vinylic iodides in highly regio- and stereospecific manners, and zinc-mediated beta-elimination after trifluoroacetylation of the hydroxyl group eventually realized the formation of the target molecules in good to excellent overall yields in facile and short steps.     

Synthesis of Some New Derivatives of 1,3-Dichloro-1,1,3, 3-tetraphenyldisilazane

Recently, the silicon-nitrogen compounds have received more consideration for their attractive application prospects. Both low molecular weight silazane and polysilazane with high molecular weight are widely used in many aspects. For example, in the processing industry of silicone rubber, silizanes not only can be used as "structure-control additives"1, but also can be used to improve the rubber's heat-resistance and mechanical properties; silicon-nitride ceramics can be prepared by pyrolysis …     

Absorption and Luminescence Spectra of 1,1,3-Trimethyl-3-Phenylindan

Electronic absorption and luminescence spectra of cyclic dimer of -methylstyrene, 1,1,3-trimethyl-3-phenylindan, were described. The quantum yield and lifetime of fluorescence were determined.     

Stereochemistry and cycloaddition of 1,1,3-trioxy butadienes from β-keto esters

Spectroscopic analysis of the 1,1,3-trioxy dienes (1), (2) shows them to possess ($\text{Z}$)-stereochemistry, contrary to several literature assignments; characterisation of derived cycloadducts and crystallographic analysis of one of them (20) establishes $\text{endo}$ cycloaddition.     

Reactions of 2,2-disubstituted 1,1-dicyanoethenes with β-dimethylaminoacrolein aminal and 3-dimethylamino-1,1,3-trimethoxypropane

A reaction of 2,2-disubstituted 1,1-dicyanoethenes with β-dimethylaminoacrolein aminal and 3-dimethylamino-1,1,3-trimethoxypropane leads to substituted 6,6-dicyano-1-dimethyl-aminohexatrienes and an organic salt containing 1,1,9,9-tetracyano-2,8-diphenylnona-2,4,6,8-tetraenide as the anion and (dimethylaminopropenylidene)dimethylammonium as the cation, on the basis of which new cation-anionic polymethine dyes were obtained. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 8, pp. 1639–1643, August, 2008.     

1,1,3-Trisubstituted cyclobutanes containing thiazole and thiourea fragments

The synthesis of 1-aryl-3-(2-chloro-1-hydroxyethyl)-1-methylcyclobutanes, 1-aryl-3-(2-chloro-1-oxoethyl)-1-methylcyclobutanes, 2-amino-4-(3-aryl-3-methylcyclobutyl)thiazoles, and N-[4-(3-aryl-3-methylcyclobutyl)thiazole-2-yl]-N′-arylthioureas is reported. Published in Khimiya Geterotsiklicheskikh Soedinenii, No. 3, pp. 424–429, March, 2006.     

Bis(1,1,3-trihydroperfluoropropyl)isocyanato Phosphite and Tris(1,1,3-trihydroperfluoropropyl) Phosphite in Reactions with Carbonyl Compounds

Abstract

Nucleophilicity of (I) in reactions with such carbonyl compounds as chloral, benzyl, ester and nitrile of benzoylformic acid is found to be notably reduced by the electronoaccepting perfluoropropyl groups. Unlike of dialkyl isocyanatophosphites (I) afford the cycloaddition products with ≡P-N- fragment (II) which being unable for the imide-amide rearrangement undergo dimerization into crystalline cyclodiphosphazanes (III) with pentacovalent phosphorus atoms.     

An improved and facile synthesis of 2-amino-1,1,3-tricyanopropene

A simple method for the dimerization of malononitrile using alkali hydroxides in methanol or ethanol is described. Thereby 2-Amino-1,1,3-tricyanopropene, a keyintermediate for heterocyclic chemistry, is obtained in high yield.

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Eine verbesserte und bequeme Synthese von 2-Amino-1,1,3-tricyan-propen (Kurze Mitteilung)

Zusammenfassung Eine einfache Dimerisierung von Malononitril unter Verwendung von Alkalihydroxid in Methanol und Ethanol wird beschrieben. Dabei entsteht in guter Ausbeute 2-Amino-1,1,3-tricyan-propen, ein wichtiges Ausgangsprodukt zur Synthese von Heterocyclen.

     

Keto-Enol Tautomeric Equilibrium in 4-Oxo-1,1,3-Cyclohexanetricarboxylic Acid Trialkyl Esters and 4-Oxo-1, 1, 3-Cyclopentanetricarboxylic Acid Trialkyl Esters

4-Oxo-1,1,3-cyclohexanetricarboxylic acid trialkyl esters in deuterochloroform and dimethylsulfoxide-d⁶ (DMSO) exist exclusivly in the enol form. The keto form is the major component in the analogous compounds of five-membered ring. The 1, 3 interaction between carboalkoxy groups in the six-membered ring should be the reason why the carboalkoxy group at 3-position is in equatorial configuration and engages in the intramolecular hydrogen bond, so that the enol form is dominating.     

Synthesis and Crystal Structure of μ1,1,3 Formic Bridging 3D Microporous Ni(Ⅱ) Complex

A μ1,1,3 formic bridging Ni2 complex [Ni3(HCOO)6·H2O]]n 1 has been synthesi-zed under hydrothermal conditions. The single-crystal X-ray diffraction analysis shows that 1 exhibits a 3D open microporous tube formed by covalent and coordination bonds. Complex 1 crystallizes in the monoclinic system, space group P21/c with a = 11.1487(13), b = 9.7763(11), c =17.9685(17) A, β= 126.948(6)°, C6H6Ni3O13, Mr = 462.02, V = 1565.2(3) A3 Z = 4, Dc= 1.961 g/cm3, μ = 3.630 mm-1, F(000) = 917.7, Rint = 0.0234, the final R = 0.0234 and wR = 0.0734 for 3469 observed reflections (Ⅰ>2σ(Ⅰ)).     

Formation of 1,1,3-trimethyl-3-(4-methylphenyl)butyl hydroperoxide complex with tetrabutylammonium bromide

The interaction of 1,1,3-trimethyl-3-(4-methylphenyl)butyl peroxide with tetrabutylammonium bromide has been studied by means of ¹H NMR spectroscopy. The complex formation between the reacting species has been confirmed, its equilibrium constant being K = (3.01±0.09) L/mol at 294 K.