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].     

Vanadyl ion complexes with nucleotides

Summary Complexes of adenosine-5-triphosphate, adenosine-5-monophosphate, guanosine-5-monophosphate, inosine-5-monophosphate, cytidine-5-monophosphate and uridine-5-monophosphate with vanadyl ion, have been studied in the solid state by i.r. spectroscopy and magnetochemically. All complexes have normal magnetic moments, very close to the spin-only values. From the i.r. spectra it is suggested that the vanadyl ion is interacting with adenosine-5-triphosphate, through the N-1 of the purine ring, with adenosine-5-monophosphate, guanosine-5-monophosphate, inosine-5-monophosphate, through the N-7 of the purine ring, with cytidine-5-monophosphate through the N-3 of the pyrimidine ring, and most probably through the phosphate group with uridine-5-monophosphate. The complexes of vanadyl ion with the nucleotides are probably polymeric.     

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.     

A new vicinal-dioxime and its mono and trinuclear complexes containing the monoazatetraoxa macrocyclic moiety

Mononuclear [Co(HL)2LCl)], [Co(LBF2)2LCl] or [Cu-(HL)2] H2L = {N,N-bis (4-N-phenylaza [15]crown-5)diaminoglyoxime} and a trinuclear, [Cu(L)2(CuL)2](NO3)2, complex of the ligand were synthesized and characterized. The mononuclear copper(II) species coordinates to two copper(II) ions through the deprotonated oximate oxygens to yield a trinuclear structure cis-bridged by the oximate groups, with 1,10-phenanthroline as an end-cap ligand. The terminal copper adopts an essentially planar configuration with the nitrogen atoms of H2L. The structure of the ligand and its complexes is proposed and formulated according to the elemental analyses, 1H- and 13C-n.m.r, i.r. and m.s. spectral data.     

Optisch aktive,aromatische Spirane, 11. Mitt.: Synthese optisch aktiver mono- bis heptasubstituierter 5-Methyl- und 5-Ethyl-2,2′-spirobiindane und analoger Naphthalinderivate bekannter Chiralität und enantiomerer Reinheit

Starting from optically active 5,5-dimethyl, diethyl, and 5-ethyl-5-methyl-2,2-spirobiindane as well as from 5-ethyl-spirobiindane-5-carboxylic ester of known enantiomeric purity and configuration 75 mono to polysubstituted 2,2-spirobiindanes have been prepared. Amongst these are several compounds with rings anellated in the 6,7 (and 6, 7) positions, especially a spirohydrocarbon4 x with orthogonal naphthalene units the circular dichroism of which is reported and discussed.Several mono and disubstituted 5-methyl and ethylindanes (1,2) have been prepared as models for synthetic transformations in the spirobiindane series.From the molar rotations of symmetrically diacylated 5,5-dimethyl and diethyl spirobiindanes (4a, 7b, 7c) empirical ligand parameters for acetyl and methoxycarbonyl were determined which gave much better results in the calculation of the rotations of appropriate spirobiindanes (with the shortened polynomal Ansatz) than the -values deduced previously from 5,5-disubstituted spirobiindanes. The significance of these results is briefly discussed.

10. Mitt.:Neudeck, H., Schlögl, K., Angew. Chem.92, 318 (1980), Intern. Ed. Engl.19, 308 (1980).     

Synthesis and structure of o-bis(2-fluoro-2,2-dinitroethyl)-nitromethyl ester of 2′-fluoro-2′, 2′-dinitroethyl-2″-fluoro-2″-nitroethylenecarboxime

Conclusions The product of conversion of O-bis(2-fluoro-2,2-dinitroethyl)nitromethylbis(2-fluoro-2,2-dinitroethyl)carboxime in methanol or ether is O-bis(2-fluoro-2,2-dinitroethyl)nitromethyl-2-fluoro-2,2-dinitroethyl-2'-fluoro-2-nitroethylenecarboxinie, the structure of which has been established by x-ray diffraction analysis.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 9, pp. 2019–2021, September, 1987.     

New terpenoid coumarins from Ferula tadshikorum

Summary Two new terpenoid coumarins — tadzhiferin (I) and tadzhikorin (II) — have been isolated from the fruit ofFerula tadshikorum M. Pimen.On the basis of physicochemical and spectral investigations, the structure of 7-(9-hydroxy-3,7,11-trimethyldodeca-2,6,10-trienyloxy)coumarin is proposed for (I) and that of 7-(4-acetoxy-9-hydroxy-3,7,11-trimethyldodeca-2,6,10-trienyloxy)coumarin for (II).All-Union Scientific-Research Institute of Medicinal Plants, Moscow. M. V. Lomonosov State University. Botanical Garden, Moscow. Translated from Khimiya Prirodnykh Soedinenii, No. 5, pp. 593–599, September–October, 1976.     

Synthesis of N-(indol-3-yl)-N′,N′-dialkylamidines by the vilsmeier reaction with 3-aminoindoles

3-Aminoindoles substituted at C-2 and C-5 of the indole ring are converted by the action of Vilsmeier complexes into N-(indol-3-yl)-N,N-dialkylamidines. When C-2 is unsubstituted, the formylation proceeds but not the acetylation of this position. N-(Indol-3-yl)-N,N-dimethylacetamidine reacts with the complex obtained from DMF and POCl₃ to give 2-dimethylamino-3-formyl--carboline. The optimal conditions were found for the conversion of amidines to amides.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 1, pp. 76–81, January, 1985.     

Synthesis of 9-diazo-4-azafluorenes

Stable diazo compounds of the azafluorene series, viz., 9-diazo-4-azafluorenone and 1,3-diphenyl-4-azafluorene, were obtained from 4-azafluorenone and 1,3-diphenyl-4-azafluorene tosylhydrazones. 1,2-Dicarbomethoxyspiro(4-azafluorene-9,3-cyclopropane) was obtained from 4-azafluorenone tosylhydrazone, and 4,5-dicarbomethoxyspiro(4-azafluorene-9,3-pyrazolenine) was obtained from 9-diazo-4-azafluorene. It is assumed that the product in the latter case is obtained as a result of reaction of a carbene, viz., 4-azafluorenylidene carbene, which is formed from 9-diazo-4-fluorene, with dimethyl acetylenedicarboxylate.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 7, pp. 951–953, July, 1979.     

Analysis of NMR spectra of magnetically inequivalent nuclei using perturbation theory

A method of analysis of NMR spectra based upon degenerate-state perturbation theory is developed. The technique can be applied to the analysis of NMR spectra of sets of nuclei which are magnetically inequivalent, i.e., sets of nuclei which have different couplings between chemically equivalent groups. The method is illustrated by analysis of the spectrum of 1-indanone, which is of the type AABB. Satisfactory results can be obtained by a second order analysis, even for quite strongly coupled spectra. Closed form expressions have been derived for the AABB spectrum which are correct to second order.

---

Zusammenfassung Für die Analyse von Kernresonanzspektren wird eine Methode angegeben, die auf der Störungsrechnung für entartete Systeme beruht und die auch im Fall mehrerer Kopplungs-konstanten zwischen zwei unter sich chemisch äquivalenten Gruppen von Protonen gilt. Als Beispiel dafür wird das Spektrum des 1-Indanons (Typ AABB) behandelt, wobei bereits die zweite Näherung befriedigende Ergebnisse liefert und in geschlossener Form angegeben wird.

---

Résumé Sur base de la théorie des perturbations des états dégénérés, nous avons développé une méthode pour analyser des spectres NMR. Cette méthode s'applique à des molécules, qui ont de couplages différents entre plusieurs groupes d'atomes équivalents. Le procédé est illustré par l'analyse du spectre de 1-indanone du type AABB. Le second ordre du calcul rend de résultats satifaisants, même au case de couplages assez forts. Des expressions closes, correctes jusqu'au second ordre, sont dérivées pour le spectre AABB.

     

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.

---

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.

---

---

With 5 figures and 2 tables     

Mass spectral and thermogravimetric studies of some iron(III) binuclear complexes with bridging thiuram disulfide ligands

Mass spectral and thermal studies by TG and DTG of some iron(III) binuclear complexes of the general type Fe₂(R₂dtc)₂(tds)X₂X/ have been carried out to determine their modes of decomposition. Fragmentation patterns are given and possible mechanisms are discussed.

---

Zusammenfassung Massenspektrometrische und thermische Untersuchungen (TG und DTG) einiger zweikerniger Eisen(III)-Komplexe des allgemeinen Typs (R₂dtc)₂(tds)X₂X₂ wurden ausgeführt, um deren Zersetzungsmechanismus zu ermitteln. Fragmentspektren werden angegeben und mögliche Mechanismen diskutiert.

---

- ( ) Fe₂(R₂dtc)₂(tds)X₂X₂ . .

     

Synthesis of novel heterocycles from thiazolecarbohydrazides

Cyclization of 2-methyl (or -phenyl)-5-phenylthiazole-4-carbohydrazides (1) and (2) under various conditions gives differing oxadiazoles: 2-(2-substituted-5-phenyl-4-thiazolyl)-1,3,4-oxadiazole-5-thiones (7) and (8), and 2-(2-substituted-5-phenyl-4-thiazolyl)-1,3,4-oxadiazoles (9) and (10). Cyclodehydration of thiazolecarbonyl-thiosemicarbazides (3)–(6) with NaOH givesthe 3-(2-substituted-5-phenyl-4-thiazolyl)-4-substituted-4H-5-mercapto-1,2,4-triazoles (11)–(14), while H ₃ PO ₄ gives the 2-(2-substituted-5-phenyl-4-thiazolyl)-5-phenylamino-1,3,4-thiadiazoles (15) and (16).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. 3, pp. 679–683, March, 1992.     

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.     

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.     

Antimicrobial activity studies of mononuclear and binuclear mixed-ligand copper(II) complexes derived from Schiff base ligands and 1,10-phenanthroline

Mixed-ligand complexes of copper(II) with 1,10-phenanthroline and various Schiff bases have been prepared and characterized by elemental analysis, electronic and i.r. spectra, magnetic moment and molar conductance data. The Schiff base behave as bidentate ligands, and the mixed-ligand copper(II) complexes of the ligands HL1, HL2 and HL4 are binuclear. The conductivity data for all the complexes are consistent with those expected for an electrolyte. Antimicrobial activities of some of the ligands and complexes have been tested against Bacillus megaterium and Candida tropicalis. 1H and 13C n.m.r. spectra have been recorded in order to solve the solution structure of the ligands. Thermal properties of all complexes have been studied by the d.t.a. and t.g.a. techniques.     

Synthesis of 2-O-ethyl analogues of 3′-azido- and 3′-fluoro-2′,3′-dideoxyuridines and evaluation of their biological activity against HIV

Summary 2-O-Ethyluracil and 2-O-ethylthymine were silylated with 1,1,1,3,3,3-hexamethyldisilazane and condensed in the presence ofTMS triflate with 2,3-dideoxy-3-fluoro-D-erythro-pentofuranoside, 3-azido-2,3-dideoxy-D-erythro-pentofuranoside, and 2,3-dideoxy-3-phthalimido--D-erythro-pentofuranose derivatives to give the corresponding 2-O-ethyl nucleosides. Deprotection with saturated methanolic ammonia afforded the 2,3-dideoxy-3-fluoro-2-O-ethyluridines, whereas 3-azido-2,3-dideoxy-3-O-ethyluridine was obtained by deprotection with tetrabutylammonium fluoride in tetrahydrofuran. 3-Amino-2,3-dideoxy-3-O-ethyluridine could be obtained only by treatment of the corresponding 3-azido nucleoside with triphenylphosphine in pyridine. 3-Deoxy-2-O-ethyl-3-fluorothymidine (6b) showed moderate activity against HIV-1.

---

Synthese von 2-O-Ethyl-Analogen von 3-Azido- und 3-Fluor-23-dideoxyuridinen und Bestimmung ihrer biologischen Aktivität gegenüber HIV

Zusammenfassung 2-O-Ethyluracil und 2-O-Ethylthymin wurden mit 1,1,1,3,3,3-Hexamethyldisilazan silyliert und in Gegenwart vonTMS-triflat mit 2,3-Dideoxy-3-fluoro-D-erythro-pentofuranosid, 3-Azido-2,3-dideoxy-D-erythro-pentofuranosid und 2,3-Dideoxy-3-phthalimido--D-erythro-pentofuranosederivaten zu den entsprechenden 2-O-Ethyl-Nucleosiden umgesetzt. Entfernung der Schutzgruppe mit gesättigter methanolischer Ammoniaklösung lieferte 2,3-Dideoxy-3-fluor-2-O-ethyluridin; 3-Azido-2,3-dideoxy-3-O-ethyl-uridin wurde durch Entschützung mit Tetrabutylammoniumfluorid in Tetrahydrofuran erhalten. 3-Amino-2,3-dideoxy-3-O-ethyl-uridin konnte nur durch Behandeln des entsprechenden 3-Azido-Nucleosids mit Triphenylphosphin in Pyridin hergestellt werden. 3-Deoxy-2-O-ethyl-3-fluor-thymidin (6b) zeigt geringe Aktivität gegenüber HIV-1.

     

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.     

1-Aryl-6-azauracile, 5. Mitt.: Die Synthese von 1-(β-Pyridyl)-6-azauracil-5-carbonsäure und einiger ihrer Derivate

Zusammenfassung Analog wie in vorherigen Mitteilungen^1–4 wurden -Pyridyl-hydrazono-cyanacetylcarbamidsäureäthylester (1), 1-(-Pyridyl)-5-cyan-6-azauracil (2), 1-(-Pyridyl)-6-azauracil-5-carbonsäure (3), deren Thioamid (4), und Amidoxim (5), welches in 1-(-Pyridyl)-5-[5-methyl-1,2,4-oxdiazolyl(3)]-6-azauracil (6) überge-führt wurde, hergestellt.

---

-Pyridylhydrazono-cyanacetylcarbamic acid ethyl ester (1), l-(-pyridyl)-5-cyano-6-azauracil (2), 1-(-pyridyl)-6-azauracil-5-carboxylic acid (3), its thioamide (4) and amidoxime (5) were prepared as described in preceding communications. (5) was converted into l-(-pyridyl)-5-[5-methyl-1,2,4-oxdiazolyl(3)]-6-azauracil (6).

     

Kinetics of the Dissociation of Transition Metal Complexes with α,α-Dipyrrolylmethene in Acetic Acid–Benzene as a Binary Proton-Donating Solvent

The kinetics of the dissociation of Co(II), Ni(II), and Zn(II) complexes with 4,4-dibutyl-3,3,5,5-tetramethyldipyrrol-2,2-ylmethene was studied in acetic acid–benzene as a binary proton-donating solvent. The metal nature was found to affect the kinetic parameters of the process. Assumptions were made about the limiting step of the process and the effectiveness of d metal ions in the template synthesis of porphyrins from dipyrrolylmethenes.