Synthese von 1,1′-Biphenyl-3-carbonsäure-und 3,5-dicarbonsäurederivaten unter Verwendung von Ethoxymethylenmalononitril

Reaction of ethoxymethylenemalononitrile with ethyl 4-phenylacetoacetate leads to ethyl 1,1-biphenyl-6-amino-5-cyano-2-hydroxy-3-carboxylate (3). Acid or basic hydrolysis of the ester and cyano group of3 affords the new derivatives4,5 and6.7 a, b are obtained bySandmeyer-reaction of3. Basic hydrolysis of7 a gives the 3,5-dicarboxylic acid derivative8.

     

Zur Reaktion von Permethylcyclosilanen mit Halogenen

The series of ,-diiodopermethylpolysilanes, I(SiMe ₂) _n I, (n=4–6) andX(SiMe ₂)₄ X, (X=Cl, Br) has been prepared by the action of halogen on the corresponding cyclic compounds (SiMe ₂) _n . The mass spectra, NMR-, IR- andRaman-spectra of these compounds have been recorded.

Herrn Prof. Dr.Josef Schurz zum 60. Geburtstag gewidmet.     

2,2′-Diphenyl-Δ3,3′-bi-3H-indole-1,1′-dioxide: Competitive demethylation and redox reactions

Competitive demethylation and redox reactions induced by 2,2-diphenyl-^3,3-bi-3H-indole-1,1-dioxide,1 (dinitrone) on several nitrogen bearing compounds (pyridines, amides, indoles, hydrazones and amines) are reported.Es wird über kompetitive Demethylierungen und Redoxreaktionen an stickstoffhaltigen Verbindungen (Pyridine, Amide, Indole, Hydrazone und Amine) berichtet, die durch das Dinitron 2,2-Diphenyl-3,3-bi-3H-indol-1,1-dioxid induziert werden.

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2,2-Diphenyl-3,3t-bi-3H-indol-1,1t-dioxid: Kompetitive Demethylierung und Redoxreaktionen

     

Zur Reaktion von Chlorsilanen mit Dialkylphosphonaten

Summary The reaction of dichlorodiorganosilanes with dialkylphosphonates is described. Depending on the reaction conditions diorganosilyl-bis(O-alkylphosphonates)R ₂Si[OP(O)H(OR)]₂ and diorganosilylphoshonates [-R₂Si-OP(O)HO-], respectively, are formed.Using this type of reaction, O-alkoxysilyl O-alkylphosphonates can be obtained both by interaction of dialkylphosphonates with dichlorodialkoxysilanes or chlorodialkoxyalkylsilanes, respectively.

Herrn Professor Dr. E. Hengge anläßlich seines 60. Geburtstages gewidmet     

Room temperature phosphorescence optosensing for gadolinium

An optosensing method for gadolinium based on the room-temperature phosphorescence behavior in aqueous solution induced by the transient adsorption of the complex formed by 1,4-bis (1-phenyl-3-methyl-5-pyrazolone-4-)butanedione (1,4) with Gd (III) on the chelating resin Chelex 100 (packed in a flow cell) is proposed. The proposed optosensing is satisfactory for the determination of the gadolinium ion in the range 8 × 10^–7–5 × 10^–5 M with a correlation coefficient of 0.995. The relative standard deviation was 2.0% for determination of 5× 10^–6 M gadolinium ion (n = 10). The response mechanism of the optosensing and the interferences of other lanthanide ions were also investigated. The method has been used to determine gadolinium ion in synthetic sample.     

Synthesis of formyl derivatives of benzocrown ethers containing N,S, and O heteroatoms in the macrocycle

A method for the synthesis of 4-bromobenzodithia-15(18)-crown-5(6) and 4-bromobenzodiaza-15 (18)-crown-5(6) by condensation of 3,4-di(2-haloethoxy)bromobenzene with polyoxaalkanes containing terminal SH or NHMe groups was suggested. The method for the synthesis of formyl derivatives of benzocrowns containing N, S, and O heteroatoms in the macrocycle based on the metallation of appropriate bromo derivatives with BuⁿLi followed by treatment of the resulting organolithium intermediates with DMF was developed. Oximes and semicarbazones of benzaldehydes containing a crown ether fragment were obtained, and their transformation into the original aldehydes by treatment with KNO₂ in an acid medium was studied.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 1, pp. 121–128, January, 1995.This study was financially supported by the Russian Foundation for Basic Research (Grant No. 94-03-08-531) and the International Science Foundation (Grant M8Q000).     

N—H bond dissociation energies in <Emphasis Type="Italic">N,N</Emphasis>′-diphenyl-1,4-phenylenediamine and its aminyl radical

The N—H bond dissociation energy (D _NH) in the 4-anilinodiphenylaminyl radical formed from N,N-diphenyl-1,4-phenylenediamine was experimentally determined and calculated by the quantum-chemical method. The experimental D _NH value was found from the enthalpy of the reaction of N,N-diphenyl-1,4-benzoquinonediimine with 4-hydroxydiphenylamine taking into account the bond dissociation energies in 4-hydroxydiphenylamine and its aminyl and phenoxyl radicals, which were determined by the intersecting parabolas method from the kinetic data. The quantum-chemical calculations of D _NH used several semiempirical methods by the MOPAC program and the ab initio and DFT methods by the GAUSSIAN 94/98 program. The D _NH values, which were closest to the experimental values, were obtained by the B3LYP/6-31+G* method. The results of quantum-chemical calculations of the N—H and O—H bond dissociation energies in 4-hydroxydiphenylamine and its radicals are presented.Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 8, pp. 1549–1554, August, 2004.     

Direct spectrometric determination of proteins in body fluids using a near-infrared cyanine dye

A new near-infrared (NIR) dye, 1,1-disulfobutyl-3,3,3,3-tetramethylindotricarbocyanine (DTCY) has been developed for the quantitation of proteins in solution. The method is based on the binding of DTCY to proteins under acidic conditions. The binding of DTCY to proteins causes a new band at 814 nm. The maximum binding number of bovine serum albumin (BSA) with DTCY was measured as 100. The linear range is 0.3–40 g mL^–1 for BSA and human serum albumin (HSA), respectively. Except for Fe²⁺, Cu²⁺, and cetyltrimethylammonium bromide, all of the examined coexisting substances show no interference in the assay. The method has been applied to the quantitation of proteins in serum and urine with recoveries between 96 and 105%.     

N,N-dialkoxy-N′-alkylureas

The chlorination of N-alkoxy-N-alkylureas (1) by the action oft-BuOCl proceeds regiospecifically to give stable N-chloro-N-alkoxy-N-alkylureas (2). The alcoholysis of2 leads to N,N-dialkoxy-N-alkylureas (3). The alkaline hydrolysis of3 is a new, convenient method for the preparation of dialkoxyamines.N. N. Semenov Institute of Chemical Physics, Russian Academy of Sciences, 117913 Moscow. Translated from Izvestiya Akademii Nauk, Seriya Khimicheskaya, No. 10, pp. 2441–2443, October, 1992.     

Zur Chemie des „Dinaphthyldichinhydron”

Dinaphthyldiquinhydrone (4) first obtained byStenhouse andGroves ² reacts as well as 4,4-bi-(1,2-naphthoquinone)¹ with aniline and substituted anilines to give anilinoquinones2 a-h. However, yields of2 are considerable higher if4 is used. The IR-Spectrum of4 is very similar to that of 2,11-dihydroxy-3,10-perylenquinone, therefore we suggest for4 a the structure of a 3,3-dihydroxy-4,4-dioxo-1,1, 4,4-tetrahydro-1,1-binaphthylidene, at least in the solid state.

Herrn Prof. Dr.G. Zigeuner in traditionsverbundener Freundschaft zum 60. Geburtstag gewidmet.     

Aromatische Spirane. 15. Mitt. Darstellung von 2,2′-Spirobi-(s-hydrindacen)-1,1′-dion und von 4,4′-disubstituierten 2,2′-Spirobi-(s-hydrindacenen)

The title compound6 a was prepared by cyclisation of the diacid4 b. The diester4 a of4 b was synthesized by alkylation of2 with3 and following Retro-Claisen-reaction. After catalytic reduction of6 a to8 a two identical substituents were introduced byFriedel-Crafts-reaction (28). By transformation of the acetylgroups several other derivates (29–36) could be obtained. The unsymmetrical compounds (e.g.21) were prepared from20, whose precurser was the spiroketon10 a.

     

Optisch aktive,aromatische Spirane, 9. Mitt.: Überprüfung eines Näherungsansatzes für Chiralitätsfunktionen bei 5,5′,6′-trisubstituierten 2,2′-Spirobiindanen

In order to test the semiempirical value of chirality functions in their mathematically most simple form 23 new optically active 5,5-disubstituted 2,2-spirobiindanes1 of known chirality and enantiomeric purity were prepared. Thus a set of about hundred compounds is now available with altogether sixteen types of ligands (i.e. substituents including hydrogen); the experimental molar rotation of fifteen compounds is used to determine the value of a ligandspecific parameter occuring in the used chirality polynomial. According to theory this polynomial is an approximation for the total rotation of derivatives with ligands of three different types and it approximates an experimentally separable part of the rotation as far as compounds with four different ligands are concerned.The additional chirality component, occurring exclusively in the case of derivatives with four different types of ligands turns out to be relatively small but not vanishing. Accordingly, the molar rotation predicted by our method is very good for disubstituted spirobiindanes of type1 and rather good for others with three different types of ligands but is distinctly worse for those with four different ligands. The numerical trend, however, is clearly represented even in cases where our calculation in principle refers to a part of the phenomenon only and the predicted absolute configuration is in call cases in agreement with the experiment.An adequate criterion to judge the quality of our approximation is introduced.

8. Mitt.:H. Neudeck undK. Schlögl, Mh. Chem.110, 541 (1979).     

Synthesis of a C60 complex withN,N,N′,N′-tetramethyl-p-phenylenediamine and its crystal structure

The complex of fullerene C₆₀ withN,N,N,N-tetramethyl-p-phenylenediamine (TMPD) was synthesized and studied by X-ray analysis.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 5, pp. 1285–1287, May, 1996. 1996     

Polyimides from complexes of benzophenonetetracarboxylic acid diesters with diamines. 5. Mechanism of thermal cyclization of H-complexes

The results of a study, by thermal mass spectrometric analysis and NMR spectroscopy, of the polycondensation of H-complexes are presented from which it is possible to propose a mechanism for the reaction. It is shown that conversion of the H-complexes into polyimides takes place through the formation of intermediate zwitterions with an amino acid bond after initial separation of methanol, following which elimination of water commences in one stage to form an imide ring. The role of theortho position of the functional groups in the acid ester during the formation of the hydrogen bond is discussed.Institute of Macromolecular Compounds, Russian Academy of Sciences, 199004 St. Petersburg. Translated fromIzvestiya Akademii Nauk, Seriya Khimicheskaya, No. 11, pp. 2517–2524, November, 1992.     

Molecular and crystal structure of 4,5,4′,5′-tetrahydro-2,2′-(1,4-phenylene)bisoxazoline

4,5,4,5-Tetrahydro-2,2-(1,4-phenylene)bisoxazoline, which is one of the most promising stabilizers-consolidators of heterochain polymers, was studied by X-ray structural analysis.Deceased.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 10, pp. 2506–2507, October, 1996.     

Aromatische Spirane, 17. Mitt.: Darstellung von anellierten und substituierten 2,2′-Spirobiindan-1-onen und 4,5′-disubstituierten 2,2′-Spirobiindanen

Summary The spiroketones9, 16, and28 were prepared by cyclisation of the carboxylic acids7c, 13b, and25c and their acid chlorides, resp. (7d, 13c, and25d) with polyphosphoric acid (PPA) or SnCl₄. The precursors of the latter compounds were synthesized by alkylation of the appropriate -ketoester1 or2 with the benzylchlorides3 or4 with NaH inDMF. Subsequent hydrogenation with Pd/C led to the desired alkylated indane-esters. The chiral compounds11, 17, and31 were obtained by Friedel-Crafts acetylation. The chiral disubstituted 2,2-Spirobiindanes22 and36 were prepared from the ketones20 and32/33 by catalytic reduction followed by Friedel-Crafts acetylation.

     

Formation of asymmetric N-hydroxyaryl-N′-aryl(hetaryl)diazenes in the reaction of N-aryl(hetaryl)-N′-phosphoryldiazene-N-oxides with bases

Aromatic and heterocyclic N-phenoxyphosphoryldiazene N-oxides react with bases to give asymmetric N-hydroxyaryl-N-aryl- and N-hydroxyaryl-N-hetaryldiazenes.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 3, pp. 609–610, March, 1993.     

Natural product chemistry. Part 121. Synthesis of dicoumarinyl ethers with the structures proposed for fatagarine and oreojasmine

Synthesis of the 7,8-dicoumarinyl ethers: 7-methoxy-7,8-oxydicoumarin and 6,7-dimethoxy-7,8-oxydicoumarin, established that the structures of fatagarine and oreojasmine for which these two structures have been proposed, have to be revised. Synthesis of 7-methoxy-5,7-oxydicoumarin and 8-methoxy-7,7-oxydicoumarin exclude the possibility of these dicoumarinyl ether structures for fatagarine.

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Naturstoffchemie. 121. Mitt.: Synthese von Dicumarinylethern mit den für das Fatagarin und das Oreojasmin vorgeschlagenen Strukturen

Zusammenfassung Durch die Synthese der 7,8-Dicumarinylether: 7-Methoxy-7,8-oxydicumarin und 6,7-Dimethoxy-7,8-oxydicumarin, ließ sich nachweisen, daß die für das Fatagarin und Oreojasmin vorgeschlagenen Strukturen revidiert werden müssen. Die Darstellung des 8-Methoxy-7,7-oxydicoumarin und 7-Methoxy-5,7-oxydicumarin schließen die Möglichkeit dieser Strukturen für das Fatagarin aus.