Electronic and Steric Structure of the Methanofullerene C61(CO2Me)[P(O)(OMe)2]. A Density Functional Study

The asymmetric addend in the methanofullerene C₆₁(CO₂Me)[P(O)(OMe)₂] polarizes and divides the fullerene shell into four nonequivalent fragments. According to DFT/PBE calculations, the most stable conformers of the methanofullerene C₆₁(CO₂Me)[P(O)(OMe)₂] involve Coulomb interactions of the phosphoryl oxygen with one of the fullerene carbon atoms, which produces polarization of the corresponding fragment and asymmetry in bond lengths and atomic charges in the fullerene shell. Alternation and attenuation of changes in bond lengths along the conjugation branches was revealed.     

Novel fluorene-containing fullerenes C<Subscript>60</Subscript>: synthesis and structures

Reactions of fullerene C₆₀ with fluorene-2-carbaldehyde or 2,7-diacetylfluorene in toluene gave novel spiromethanofullerenes containing a reactive free formyl group. A novel fluorene-containing fullerenopyrrolidine was obtained by the Prato reaction. The purity and compositions of the compounds obtained were confirmed by MALDI TOF mass spectrometry and HPLC. Their structures were confirmed by 2D homo-and heterocorrelation NMR techniques. Dedicated to Academician G. A. Abakumov on the occasion of his 70th birthday. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 9, pp. 1780–1785, September, 2007.     

Darzens reaction as a convenient method for the synthesis of α-chloroketones, α-chloroepoxides,and symmetrically substituted dioxines

Summary TheDarzens reaction of dichloroacetophenone (DCAP) with substituted benzaldehydes has been studied. The structure of the products was shown to depend on the phenyl group substituents. Reaction of benzaldehyde, 4-bromo-, and 2,4-dichlorobenzaldehydes results in 1-phenyl-3-aryl-3-chloropropane-1,2-diones (2a–c), reaction ofpara- ormeta-nitrobenzaldehydes yields 1-phenyl-2-chloro-3-aryl-2,3-epoxypropane-1-ones (3a, b). Upon the introduction of an alkoxy group into the phenyl ring of benzaldexyde and/or dichloroacetophenone, symmetrically substituted dioxines were obtained (6a–c). The structure of the reaction products has been established by single crystal X-ray investigations.

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Darzens-Reaktion als bequemes Verfahren zur Synthese von -Chloroketonen, -Chloroepoxiden und symmetrisch substituierten Dioxinen

Zusammenfassung DieDarzens-Reaction von Dichloracetophenon (DCAP) mit substituierten Benzaldehyden wurde untersucht. Die Struktur der Produkte ist von den Substituenten an der Phenylgruppe abhängig. Die Umsetzung mit Benzaldehyd, 4-Brom- und 2,4-Dichlorbenzaldehyd liefert 1-Phenyl-3-aryl-3-chloropropan-1,2-dione (2a–c), die Reaktion vonpara- odermeta-Nitrobenzaldehyd 1-Phenyl-2-chloro-3-aryl-2,3-epoxipropan-1-one (3a,b). Durch Einführung einer Alkoxygruppe in den Phenylring des Benzaldehyds und/oder des Dichloracetophenons erhält man symmetrisch substituierte Dioxine (6a–c). Die Struktur der Reaktionsprodukte wurde mittels Röntgenstrukturanalyse bestätigt.

     

Concentration Fluctuations in FexMn1 – xSi Chiral Ferromagnets in an External Magnetic Field

Physics of the Solid State - Magnetic h–T diagrams of FexMn1&nbsp;–&nbsp;xSi chiral helicoidal ferromagnets with the Dzyaloshinskii–Moriya interaction are studied within...     

Thiophene-2-aldehyde in the Darzens reaction

The reaction of the title compound with dichloroacetic acid esters in the presence of butyllithium gave esters of 3-thienyl-3-hydroxy-2,2-dichloropropionic acid.A. E. Arbuzov Institute of Organic and Physical Chemistry, Kazan' Scientific Center of the Russian Academy of Sciences, 420083 Kazan', Russia. Translated from Izvestiya Akademii Nauk, Seriya Khimicheskaya, No. 8, pp. 1870–1873, August, 1992.     

Reaction of 2,2-dichloroacetophenone and benzaldehydes under conditions of the darzens condensation

The reaction of 2,2-dichloroacetophenone with benzaldehydes was studied under Darzens condensation conditions. Benzaldehyde, p-bromobenzaldehyde, and o,p-dichlorobenzaldehyde condensed with 2,2-dichloroacetophenone to give 1-phenyl-3-aryl-3-chloro-1,2-propanediones. In the case of p-nitrobenzaldehyde, 1-phenyl-2-chloro-3-(p-nitrophenyl)-2,3-epoxy-1-propanone, which is the product of the first step of the Darzens condensation, was isolated.A. E. Arbuzov Institute of Organic and Physical Chemistry, Kazan Science Center, Russian Academy of Sciences, 420083 Kazan. Translated from Izvestiya Akademii Nauk, Seriya Khimicheskaya, No. 1, pp. 204–206, January, 1992.     

Reaction of methyl 3-phenyl-3-chloro-2-oxopropionate with 2-mercapto- and 2-hydroxy-ethanolamines: The products and some of their transformations

It was found that the nature of the SH and OH groups in 2-mercapto- and 2-hydroxyethanolamines plays a decisive role in the reactions between these compounds and methyl 3-phenyl-3-chloro-2-oxopropionate, the products comprising 1,4-thiazine and 1,4-oxazane derivatives, respectively. Some of the reactions of these products were investigated.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 2, pp. 250–252, February, 1993.     

Structure of surface films of malonate mono- and dinitroxyl methanofullerenes

An effect of aqueous subphases composition on the character of change of the bilayer structure of malonate mono- and dinitroxyl methanofullerenes surface films has been established. Their transformation to monolayers takes place in the presence of hydroxy-containing compounds (quercetin, dihydroquercetin, 4-methylphenol, ascorbic acid, as well as in a buffer mixture with pH 10). A loosening of mixed films on the basis of nitroxyl methanofullerenes in the presence of compounds affecting radical processes (2,4,6-tri(tert-butyl)phenol, 2-methyl-3-nitrosopropane, and TEMPO) has been demonstrated. The character of compression isotherms π = f(A ₀) (π is a surface pressure, A ₀ is an effective molecular area of methanofullerene) of the mixed films on water depends on the nature of component incorporated and the reaction time in solution: in all the cases, A ₀ increased almost 2-fold, to 1.05 nm² molecule⁻¹, whereas a compressibility parameter β decreased 2–3-fold, to (1–2)·10¹⁷ N m⁻³. Visualization of the thin film surfaces (atomic force spectroscopy) showed that a decrease of parameter β in the Langmuir layers corresponds to the particle aggregation and structurization of the films. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 9, pp. 1920–1931, September, 2008.     

Reaction of monoethyleneimides of acids of pentavalent phosphorus with thioacetic acid

Conclusions The reaction of monoethyleneimides of acids of pentavalent phosphorus with thioacetic acid has given the corresponding N-phosphorylated S-acetylmercaptoethylamines the structure of which has been confirmed by their IR spectra.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 8, pp. 1466–1467, August, 1966.