Condensation of 4-azafluorenone and 9-phenacylidene-4-azafluorene with acetophenone. Synthesis of 3′-oxo-spiro-[4-azafluorene-9,1′-indane]

Condensation of 4-azafluorenone and 9-phenacylidene-4-azafluorene with acetophenone leads to the formation of 9,9-diphenacyl-4-azafluorene and 9-(1,2-dibenzoylethylidene)-4-azafluorene. The structures of these products were confirmed based on their spectral and chemical data. The conversion of 9,9-diphenacyl-4-azafluorene to 3-oxo-spiro-[4-azafluorene-9,1-indane] represents a novel method for the preparation of this heterocycle.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 9, pp. 1239–1242, September, 1988.     

Reaction of 9-diazo-4-azafluorene with unsaturated compounds and cyclic ketones

Spiro[4-azafluorene-9,1 cyclopropanes] were obtained by the reaction of 9-diazo-4-azafluorene with various alkenes in the form of a mixture of geometrical isomers differentiated according to the position of the substituents in the cyclopropane ring and also also according to position relative to the pyridine ring. In the reaction of 9-diazo-4-azafluorene with cyclopentanone, di(4-azafluorene-9 nyl) oxide is formed, while from its reaction with cyclohexanone, 2-oxo-spiro[4-azafluorene-9,1-cycloheptane] is obtained.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 4, pp. 495–501, April, 1990.     

Reaction of 9-amino(phenylamino)methylene- and 9-α-aminobenzylidene-4-azafluorenes with some electrophilic reagents

It was shown that initial protonation of 9-aminomethylene-4-azafluorene takes place at the pyridine nitrogen atom. In nitrosation of this azafluorene, 4-azafluorenone oxime is formed, and in reaction with dichlorocarbene, 1-amino-2, 2'-dichlorospiro[4-azafluorene-9,3-cyclopropane] is formed. Acylation yields mono- or diacyl derivatives as a function of the acylating agent and reaction conditions.Russian University of National Friendship, Moscow 117923. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 4, pp. 527–533, April, 1995. March 14, 1995.     

Study of furan compounds

Research on synthesis of polycyclic spirans of the 1, 6-dioxaspiro-[4, 4]nonane group is continued. Electrolysis of methanol solutions of 2-furylcyclopentanol, 2-(5-methyl-furfuryl)cyclopentanol, and 2-furfuryl-1-indanol, gives, by intramolecular alkoxylation, spiro{perhydrocyclopenta[b]furan-2, 2-(5dihydrofuran)}, spiro{perhydrocyclopenta[b]furan-2, 2-(5-methoxy-5-methyl-2, 5-dihydrofuran)}, and spiro{2, 3, 3a, 8b-tetrahydro-4H-indeno[1, 2-b]furan-2, 2-(5-methoxy-2, 5-dihydrofuran)}, hitherto undescribed in the literature. Depending on the conditions, catalytic hydrogenation of these gives: spiro{perhydiocyclopenta[b]furan-2, 2-(5-methoxytetrahydrofuran)}, spiro{2, 3a, 8b-tetrahydro-4H-indeno[1, 2-b]furan-2, 2-(5-methoxytetrahydrofuran)}, spiro{perhydrocyclopenta[b]furan-2, 2-tetrahydrofuran}, and spiro{2, 3, 3a, 8b-tetrahydro-4H-indeno[1, 2-b]furan-2, 2-tetrahydrofuran}.For Part XXXI see [1].     

(9-(Pyridazinyl-4)-4-azafluorenes and spiro compounds with 4-azafluorene and indeno[1,2-c]pyridazine (4h-5,6-dihydro-1,2-diazepine) fragments

9-(3,6-Diphenylpyridazinyl-4)-4-azafluorene has been synthesized, and its conversions at the C⁹ position have been studied. From its C⁹-hydroxy derivative, 3-phenylspiro-[4-azafluorene-9,5-indeno[1,2-c]pyridazine] has been obtained. From 9-(1,2-dibenzoylethylidene-4-azafluorene, 3,7-diphenylspiro-[4H-5,6-dihydro-1,2-diazepine-5,9-4-azafluorene] has been synthesized.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 10, pp. 1357–1360, October, 1992.     

Cyanoethylation of 3-methyl-2-azafluorene

3-Methyl-9,9-di(-cyanoethyl)-2-azafluorene was obtained from 3-methyl-2-azafluorene via the Michael reaction and was converted to the dibasic acid and its diester. Dieckmann condensation of the latter and subsequent hydrolysis gave 3-methyl-4-oxospiro(2-azafluorene-9,1-cyclohexane).Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 12, pp. 1668–1670, December, 1972.     

Formation of a spiran structure in the condensation of 2-azafluorene with esters of α, ß-unsaturated acids

4-Hydroxy-3-methyl-2,6-diphenyl-3ethoxycarbonylspiro(2-azafluorene-9, 1-cyclohex-3-ene) was obtained by condensation of 3-methyl-2-azafluorene with ethyl cinnamate in the presence of potassium. The chemical mechanism of its formation and its three-dimensional structure are discussed.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 9, pp. 1231–1234, September, 1976.     

Synthesis of isomeric spiro[azafluoreneoxiranes] from 3-methyl-2-azafluorene and 4-azafluorene

Compounds that belong to the class of new spiran heterocyclic systems that contain azafluorene and oxirane fragments were obtained from the corresponding azafluorenes and benzaldehyde under interphase-catalysis conditions. The Z and E isomers of 3-methyl-3-phenylspiro(2-azafluorene-9,2-oxirane) and 3-phenylspiro(4-azafluorene-9,2-oxirane) were isolated, and their configurations were established by NMR spectroscopy.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 10, pp. 1393–1395, October, 1982.     

Reaction of dibepin with amino acids on chromatographic paper

A method was developed for the development of amino acids and some of their derivatives on Chromatographic paper by means of dibepin-8-[2,3(CO),6,5(CO)-dibenzoylene-4-pyridyl]-l-naphthoyl chloride. The sensitivity was 2 g in the case of glycine ethyl ester hydrochloride.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 3, pp. 357–358, March, 1972.     

Spiro compounds with fragments of 4-azafluorene-[indeno)2,3-e)-1,2-dihydropyridine] and pyrazoline

9-Phenacylidene-4-azaf luorene and 9-bromo-9-(-bromophenacyl)-4-azafluorene have been used in the synthesis of spiro compounds with fragments of substituted pyrazolines. 1-Methyl-2-oxo-5 phenacylidene-indeno[2, 3-e]-1,2-dihydropyridine and hydrazine gave 1-methyl-2-oxo-3 phenylspiro[indeno(2, 3-e)-1,2-dihydropyridine-5,5-pyrazoline-2].     

Synthesis of 2,3-dimethyl-6,7-benzo-5,9-(1′,2′-indano)-2-azabicyclo[3.3.1]non-6-ene

A structural analog of morphinan- 2,3-dimethyl-6,7-benzo-5,9-(1,2-indano)-2-azabicyclo-[3.3.1]non-6-ene -was synthesized from 3-methyl-2-azafluorene.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 12, pp. 1671–1672, December, 1972.     

Spiro[4-azafluorenepyrazolenines] and their thermal rearrangement to pyrazoloazaphenanthrenes

Reaction of 9-diazo-4-azafluorene with phenylacetylene gives spiro[4-azafluorene-9,3-pyrazolenines], isomeric according to the position of the substituent in the pyrazolenine ring. Their thermal rearrangement to pyrazolo-4-azaphenanthrenes that are isomeric according to ring linkage and position of the substituent in the pyrazole ring has been studied.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 11, pp. 1522–1525. November, 1988.     

Podand-porphyrins with peripheral chelates

Alkylation of 5-(3-nitro-4-hydroxyphenyl)-10,15,20-triphenylporphyrin with chloropyridines[2,6-dichloromethyl-and 2-chloromethyl-6-(2-nitrophenoxymethylpyridine)] as well as condensation by a mixed-aldehyde method starting with formylpyridines [2-(2-nitro-4-formylphenoxymethyl)-6-(2-nitrophenoxy-methyl-) or 2,6-di(2-nitro-4-formylphenoxymethyl)pyridine], benzaldehyde, and pyrrole are used to synthesize previously unknown podand-porphyrins containing from one to four peripheral chelates.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 4, pp. 475–481, April, 1991.     

Synthesis of 2,3,7,8-tetramethyldibenzofuran

3,4,3,4-Tetramethyldiphenyl ether readily forms 2,2-dihalo derivatives on bromination and iodination. Heating 2,2-diiodo-4,5,4,5-tetramethyldiphenyl ether with copper powder or oxidation, of 2,2-dilithio-4,5,4,5-tetramethyldiphenyl ether gives 2,3,7,8-tetramethyldibenzofuran, the structure of which was proved by alternative synthesis from 2,2-dinitroand 2,2-diamino-4,5,4,5-tetramethyldiphenyls.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 12, pp. 1597–1599, December, 1972.     

Simple and effective method for the synthesis of 3′,5′-substituted 1-β-D-arabinofuranosyluracil

3,5-Substituted arabinofuranosyluracil is a starting compound in 2-modifications. A convenient and effective method is proposed for the synthesis of 1-(3,5-di-o-trityl--D-arabinofuranosyl)uracil by successive reactions of 2,2-cyclization of uridine, 3,5-tritylation of the 2,2-anhydrouridine, and hydrolytic cleavage of the 2,2-anhydro bond.Institute of Organic Synthesis, Riga LV-1006. Odense Universitet, Kemisk Institut, Odense, Denmark. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 7, pp. 975–977, July, 1996. Original article submitted April 25, 1996.     

On the dynamic mechanical behavior of nylon 66

Summary The dynamic mechanical properties of nylon 66 films and fibers have been examined, as a function of annealing and drawing, with a Vibron viscoelastometer. It is found that the transition is little affected by annealing treatments, but increase in orientation causes the transition to move to a higher temperature. Experiments, with X-ray diffraction of samples at elevated temperatures, lead to the conclusion that the triclinic to hexagonal phase change does not contribute significantly to the transition. Samples cut parallel and perpendicular to the drawing direction of nylon 66 film, have been used to show that the curves of dynamic tensile modulus versus temperature, for the parallel and perpendicular directions, cross in the neighborhood of the transition. This observation is discussed in relation to the suggestion that the transition is the glass transition in nylon 66.

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Zusammenfassung Die dynamisch-mechanischen Eigenschaften von Filmen und Fasern aus Nylon 66 wurden als Funktion der Temperung und Verstreckung mit einem Virbon-Viskoelastometer untersucht. Die -Umwandlung wird wenig durch die Temperung beeinflußt, aber erhöhte Orientierung läßt siezu höheren Temperaturen verlagern. Messungen der Röntgenstreuung bei erhöhten Temperaturen führen zu dem Schluß, daß der Übergang triklin/hexagonal nicht wesentlich zu der -Umwandlung beiträgt. Proben aus verstrecktem Nylon-66-Film, parallel und senkrecht zur Streckrichtung geschnitten, zeigen, daß die Kurven des dynamischenE-Moduls gegen die Temperatur für beide Orientierungen sich in der Nachbarschaft der -Umwandlung überkreuzen. Diese Beobachtung wird hinsichtlich der Vermutung diskutiert, daß die -Umwandlung den Glasübergang in Nylon 66 darstellt.

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With 5 figures and 2 tables     

Synthesis of obtusinin and 7-(3′-hydroxymethylbut-2′-enyloxy)-6-methoxy-2H-1-benzopyran-2-one

Obtusinin (1) has been synthesised by the reaction of 6-methoxy-7-(3-methylbut-2-enyloxy)-2H-1-benzopyran-2-one (3) with OsO₄. Synthesis of 7-(3-hydroxymethylbut-2-enyloxy)-6-methoxy-2H-1-benzopyran-2-one (2) has been achieved by the regiospecific oxidation of3 with SeO₂ followed by reduction of the formed aldehyde with KBH₄.

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Synthese von Obtusinin und 7-(3-Hydroxymethylbut-2-enyloxy)-6-methoxy-2H-1-benzopyran-2-on

Zusammenfassung Obtusinin (1) wurde über 6-Methoxy-7-(3-methylbut-2-enyloxy)-2H-1-benzopyran-2-on (3) mit OsO₄ synthetisiert. Die Darstellung von 7-(3-Hydroxymethylbut-2-enyloxy)-6-methoxy-2H-1-benzopyran-2-on (2) wurde mittels regioselektiver Oxidation von3 mit SeO₂, gefolgt von Reduktion des gebildeten Aldehyds mit KBH₄, bewerkstelligt.

     

Diacetylenic Derivatives of Fe2(CO)6(μ-EE′): Spectroscopic Investigations of Fe2(CO)6{μ-EC(H) = C(C≡ CMe)E′} (E = E′, E ≠ E′; E, E′ = S, Se, Te)

The diacetylenic adducts, Fe₂(CO)₆{-EC(H) = C(C CMe)E} (E = E, E E; E, E = S, Se, Te) (1–8) have been obtained from the room temperature stirring of Fe₂(CO)₆(-EE) with HC CC CMe in methanol solvent containing sodium acetate. Compounds 1–8 have been characterized by IR and multinuclear NMR (¹H, ¹³C, ⁷⁷Se, and ^l25Te) spectroscopy. Trends in the chemical shifts of ⁷⁷Se and ¹²⁵Te NMR spectra of Fe₂(CO)₆{-EC(H) = C(C CMe)E} with a variation of EE are discussed.     

Spectrophotometric determination of vanadium with 4-(1′H-1′,2′,4′-Triazolyl-3′-azo)-2-methylresorcinol

Summary 4-(1H-1,2,4-Triazolyl-3-azo)-2-methylresorcinol reacts with vanadium(V) at pH 8.10 (Tris-HClO₄ buffer solution) to produce a pink-violet 11 complex ( _max=525 nm,=2.55×10⁴l·mol^–1· cm^–1) in a 50% (v/v) methanol-water medium, which allows the spectrophotometric determination of 0.1 to 1.51 ppm of vanadium. The method has been applied for the determination of the vanadium content in low alloy steels.

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Spectrophotometriscbe Bestimmung von Vanadin mit 4-(1H-1,2,4-triazo-lyl-3-azo)-2-methylresorcin

Zusammenfassung Vanadin bildet bei pH 8,10 (Tris-HClO₄-buffer) mit 4-(1H-1,2,4-tri-azolyl-3-azo)-2-methylresorcin ein rosenrot-violettes Chelat, dessen Absorptionsmaximum bei 525 nm in Gegenwart von 50% Methylalkohol gemessen wird. Dieser 11-Komplex entspricht bei einer Vanadin-Konzentration von 0,1–1,51g/ml dem Beerschen Gesetz; seine molare Absorptivität ist 2,55×10⁴l·mol^–1·cm^–1. Das Verfahren wurde zur Bestimmung des Vanadins in Stahl verwendet.