Synthesis and properties of photochromic bisindolinospiropyrans

Bisspiropyrans were obtained by reaction of diquaternary salts — 1,1-polymethylenebis-(2,3,3-trimethylindoleninium) halides — or the corresponding methylene bases with 5-nitro-salicylaldehyde in the presence of piperidine. Bisspiropyrans of another type were obtained by reaction of 1-propyl-2,3,3-trimethylindoleninium iodide with 5,5-methylenedisalicylaldehyde and 5,5-methylenedi(3-nitrosalicylaldehyde). The photochemical and spectral properties of the bisspiropyrans were compared with those of the corresponding monospiropyrans.Communication VII from the series Photochromism of Organic Substances. See [1] for communication VI.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 12, pp. 1631–1638, December, 1973.     

Condensed thiolane 1,1-dioxide systems. 3. Two modes of cyclization of N-substituted trans-3-chloro-4-thioureidothiolane 1,1-dioxides

Reaction of trans-3-chloro-A-aminothiolane 1,1-dioxide hydrochloride with aryl isothiocyanates gives, according to the base involved, cis-perhydrothieno[3,4-d]imidazole-2-thione 5,5-dioxides or the hitherto undescribed cis-2-aryliminoperhydrothieno 3,4-d] thiazole 5,5-dioxides.For Part 2, see [1].Deceased.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 10, pp. 1420–1423, October, 1988.     

Polynuclear π-allyl complexes of palladium (II)

Conclusions Polynuclear -allyl complexes of palladium (II) containing 5,5-methylenebis(salicylate) or polydentate Schiff bases as ligands were synthesized.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 8, pp. 1855–1856, August, 1972.     

Reaction of Zinc and Sodium Enolates of 3-Alkyl-6-aryl-5,5-dimethyl-2,3,5,6-tetrahydropyrane-2,4-diones with Acyl Chlorides or Benzyl Bromides

Zinc enolates of 3-alkyl-6-aryl-5,5-dimethyl-2,3,5,6-tetrahydropyrane-2,4-diones react with acyl chlorides to form O-acylation products, 4-acyloxy-3-alkyl-6-aryl-5,5-dimethyl-5,6-dihydropyrane-2-ones. Sodium enolates of these pyranediones react in DMSO with substituted benzyl bromides to give mainly C-alkylation products, 3-alkyl-6-aryl-3-(4-R-benzyl)-5,5-dimethyl-2,3,5,6-tetrahydropyrane-2,4-diones, as single geometric isomers. In some cases, O-alkylation products, 4-alkoxy-3-alkyl-6-aryl-5,5-dimethyl-5,6-dihydropyrane-2-ones, are formed as by-products (10-15%).     

Tetrazoles. 10. Acid-base properties of 5,5′-ditetrazolyls

The constants of detachment (pK_a 1.41 and 4.25) and addition (pK_BH –5.47 and –10.91) of protons for 5,5-ditetrazolyl and of protonation of 1,1-diphenyl-5,5-ditetrazolyl (pK_BH+ –7.47) in aqueous solutions were determined by spectrophotometric and potentiometric methods. By comparison of the acid-base properties of the two compounds it was established that the latter exists in the trans form.See [1] for Communication 9.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 11, pp. 1563–1566, November, 1981.     

Mechanism of the electrochemical reduction of 2-halo-5-nitrothiophenes in dimethylformamide

The reduction of 2-bromo-5-nitrothiophene and 2-iodo-5-nitrothiophene in dimethylformamide (DMF) was studied by means of classical and commutated polarography, EPR spectroscopy, a rotating platinum disk electrode with a ring, and preparative electrolysis. It was established that, depending on the nature of the halogen, their anion radicals may undergo further reduction to 2-nitrothiophene anion radicals or decomposition with splitting out of a halide anion and conversion to nitrothienyl radicals, which were identified on the ring electrode. The latter are capable of undergoing dimerization to 2,2-dinitro-5,5-dithienyl. The spectra of the anion radicals of 2-nitrothiophene and 2,2-dinitro-5,5-dithienyl were recorded by means of EPR. A mechanism for the reduction of halonitrothiophenes is proposed.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 2, pp. 195–198, February, 1981.     

Über die Struktur der künstlichen Harze

p-Nitrophenol reagiert mit Hexamethylentetramin zum 2,2-Dihydroxy-5,5-dinitro-dibenzylamin und nicht, wieJ. C. Duff undE. J. Bills annehmen, zum 2,2-Dihydroxy-5,5-dinitro-dibenzyl-N-hydroxymethyl-amin.     

Mass spectrometric study of mixed fluorinated rare earth element β-diketonates with triphenylphosphine oxide

A series of new adducts of fluorinated REE -diketonates with triphenylphosphine oxide was synthesized. The paths of their fragmentation under electron impact were investigated. It was shown that in contrast to the complex with 1,1,1,2,2,3,3-heptafluoro-7,7-dimethyloctane-4,6-dione, the complexes of europium with 1-trifluoromethoxy-1,1-difluoro-5,5-dimethylhexane-2,4-dione and 1, 1,1-trifluoro-5,5-dimethylhexane-2,4-dione form dimeric associates in the gaseous phase. The reasons for this difference in the behavior of the complexes and the possible structure of one of the dimers are discussed.Translated from Teoreticheskaya i Eksperimental'naya Khimiya, Vol. 26, No. 2, March–April, 1990.     

Oxidation of the methyl ester of O-amino-p-tert-butylphenol by lead dioxide

Conclusions As a result of the oxidation of the methyl ester of O-amino-p-tert-butyl-phenol with lead dioxide, two products were isolated and characterized -2,2-dimethoxy-5,5-di-tert-butylazobenzene and 2,6-di-tertbutylphenazine.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 10, pp. 1851–1854, October, 1966.     

Chirale Erkennung bei Trisdiimin -Metallkomplexen: 1. Strukturen von Tris-(3,3′-bi-1,2,4-triazin)eisen(II)-Komplexen

Summary By cyclo-condensation of -diketones with oxamiddihydrazone 3,3-bi-triazines with different substituents in 5,5-, 6,6-position and their corresponding iron(II)-trischelates were synthesized. The structures of the complexes tris-(3,3-bi-1,2,4-triazine, 5,5,6,6-tetramethyl)iron(II) ditetrachloroferrate(III) and tris-(3,3-bi-1,2,4-triazine, 5,5,6,6-tetraphenyl)iron(II) ditetrachloroferrate(III) could be solved by means of single crystal X-ray-analysis. Both complexes crystallize from racemic solutions in an enantiomorphic space group (P2₁3 and P2₁2₁2₁ respectively) with one molecule in the asymmetric unit, i.e. the rare phenomenon of spontaneous resolution by crystallization is observed. Hence, homochiral intermolecular interactions are strongly preferred over heterochiral ones.

     

Bisindoles. 10. Synthesis of 1,2-(5,5′-diindolyl)ethane

A 2,2-diethoxycarbonyl derivative of a new bisindole system, viz., 1,2-(5,5-diindolyl)ethane, was obtained by cyclization of ethyl pyruvate sym-4,4-diphenyleneethanedihydrazone. 5-(-Phenylethyl)-2-ethoxycarbonylindole was also isolated in very low yield from the reaction products. Saponification of the 2,2-diethoxycarbonyl derivative gave the corresponding dicarboxylic acid, the thermal decarboxylation of which leads to the formation of 1,2-(5,5-diindolyl) ethane. The syn,syn and anti,anti forms of ethyl pyruvate sym-4,4-diphenyleneethane-dihydrazone were also obtained and characterized.See [1, 2] for Communications 8 and 9.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 3, pp. 348–351, March, 1982.     

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).     

Bisindoles. 28. Synthesis of 7,7′-dimethyl-5,5′-bis-1H-indole

Cyclization of the 3,3-dimethyl-4,4-diphenylendihydrazone of ethyl pyruvate in polyphosphoric ester gave 7,7-dimethyl-2,2-dicarbethoxy-5,5-bis-1H-indole which was hydrolyzed and decarboxylated to give 7,7-dimethyl-5,5-bis-1H-indole.For Communication 27 see [1].Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 3, pp. 343–345, March, 1990.     

Ultrasonic assistance syntheses of new nano-sized lead(II) coordination polymers: motifs for PbO preparation

Nanoparticles of two new coordination polymers, [Pb(5,5′-dm-2,2′-bpy)Cl₂] _n (1) and [Pb(5,5′-dm-2,2′-bpy)Br₂] _n (2), {5,5′-dm-2,2′-bpy = 5,5′-dimethyl-2,2′-bipyridine}, have been synthesized by ultrasonic assistance at different concentrations and characterized by scanning electron microscopy, X-ray powder diffraction, IR spectroscopy and elemental analyses. Metal oxide nanoparticles were prepared from thermal decomposition of compounds 1 and 2 at 600 °C under air atmosphere. Scanning electron microscopy images of the residue which are obtained from calcination of compounds 1, 2 show the formation of lead(II) oxide nanoparticles with an average diameter of about 80 and 90 nm for compounds 1 and 2, respectively.     

Some Specific Features of Acid Nitration of 2-Substituted 4,6-Dihydroxypyrimidines. Nucleophilic Cleavage of the Nitration Products

The nitration of 2-substituted 4,6-dihydroxypyrimidines in concentrated sulfuric acid yields the corresponding 5,5-dinitro derivatives. When the substituent in position 2 is an alkyl group, the nitration occurs both at position 5 and at the -carbon atom of the side chain. Hydrolysis of 2-substituted 4,6-dihydroxy-5,5-dinitropyrimidines leads to formation of 1,1-diamino-2-R-2-nitroethylene derivatives. 1,1-Diamino-2,2-dinitro-ethylene was obtained by nitration of 4,6-dihydroxy-2-methylpyrimidine and subsequent hydrolysis of 4,6-dihydroxy-5,5-dinitro-2-(dinitromethylene)-2,5-dihydropyrimidine.     

Investigation of dipiperidyls

The oxidation of o-phenanthroline with potassium permanganate gives 2,2-dipyridyl-5,5-dicarboxylic acid (I). The corresponding esters of I were obtained by esterification with methanol, ethanol, propyl alcohol, isopropyl alcohol, butyl alcohol, and benzyl alcohol.See [10] for communication XI.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 12, pp. 1644–1646, December, 1972.     

Preparation of the simplest Δ1-pyrazolines by isomerization of Δ2-pyrazolines

²-Pyrazolines that do not have substituants in the 1- and 3-positions are not capable of isomerization to 3-substituted pyrazolines and can be converted to ¹-pyrazolines by slow distillation in the presence of bases. This method, which is completely analogous to the synthesis of azo compounds from alkylhydrazones, gives good results when applied to 4-alkyl- and 5,5-dialkyl-²-pyrazolines and makes it possible to obtain the corresponding ¹-pyrazolines in yields of 40–70%. 4-Ethyl-, 5-methyl-5-ethyl-, and 5,5-diethyl-¹-pyrazolines are described for the first time.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 7, pp. 956–957, July, 1971.     

Oxidation of 2,6-disubstituted phenols as a route to 3,5,3′,5′-tetrasubstituted diphenoquinones and 4,4′-dihydroxydiphenyls

Conclusions Oxidation of 2,6-disubstituted phenols by atmospheric oxygen in the presence of a cuprammonium complex gave 3,3,5,5-tetraalkyldiphenoquinones which were converted to the corresponding 4,4-dihydroxydiphenyls.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 8, pp. 1808–1810, August, 1987.     

Design of postmetallocene Schiff base-like catalytic systems for polymerization of olefins: XII. Synthesis of tetradentate bis-salicylaldehyde imine ligands

Reactions of salicylaldehyde, 3-tert-butylsalicylaldehyde, and 3,5-di-tert-butylsalicylaldehyde with 1,4-diaminobutane, 1,6-diaminohexane, 4,4′-diaminodiphenylmethane, 4,4′-diamino-3,3′,5,5′-tetramethyldiphenylmethane, 4,4′-diamino-5,5′-dicyclopentyl-3,3′-dimethyldiphenylmethane, 4,4′-diamino-5,5′-dicyclohexyl-3,3′-dimethyldiphenylmethane, bis(4-aminophenyl) sulfone, o,o′- and p,p′-diaminodiphenyl ethers, 1,4-bis(4-aminophenoxy)benzene, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, and 4,4″-diamino-p-terphenyl gave a series of the corresponding Schiff bases which can be used as tetradentate ligands for the synthesis of titanium and zirconium complexes.     

Spektrophotometrische und fluorometrische Bestimmung von Myricetin (3,3′,4′,5,5′,7-Hexahydroxy-Flavon)

Zusammenfassung Myricetin (3,3,4,5,5,7-Hexahydroxyflavon) wird aus Pflanzenextrakten chromatographisch abgetrennt, mit Methanol eluiert. Das gelbgrüne Fluoreszenzlicht seines Aluminiumchelats wird in Gegenwart von Essigsäure und Ammoniumacetat gemessen. 10^–4% Myricetin lassen sich mit einem relativen Fehler von ±4% bestimmen.

---

Spectrophotometric and fluorometric determination of myricetin (3,3,4,5,5,7 -hexahydroxyflavone)

Summary Myricetin (3,3,4,5,5,7-hexahydroxyflavone) is separated chromatographically from plant extracts and eluted with methanol. The yellow-green fluorescent light of its aluminium chelate is measured in the presence of acetic acid and ammonium acetate. 10^–4% Myricetin can be determined with a relative error of ±4%.