The supramolecular structures and reactivities of some complexes of chiral crown ethers with borane ammonia

Whereas 1 1 crystalline complexes have been isolated between borane ammonia and methyl 4,6-O-benzylidene-2,3-dideoxy--d-galactopyranosido [2,3-b]-1,4,7,10,13,16-hexaoxacyclo-octadecane (1), methyl 4,6-O-benzylidene-2,3-dideoxy--d-mannopyranosido [2,3-b] (methyl 4,6-O-benzylidene-2,3-dideoxy--d-mannopyranosido [2,3-k]-1,4,7,10,13,16-hexaoxacyclo-octadecane (3), and (1R,2R,7R,24R)-3,5,8,11,14,17,20,23,26,28-decaoxatricyclo-[21.4.0.0^2,7]octacosane (4), the hosts, methyl, 4,6-O-benzylidene-2,3-dideoxy--d-mannopyranosido[2,3-b] 1,4,7,10,13,16-hexaoxacyclo-octadecane (2) and 1,4 1,4 3,6 3,6-tetra-anhydro-2,2 5,5-bis-O-oxydiethylenedi-d-mannitol (5) have yielded 2 1 (guest:host) crystalline complexes with borane ammonia as guest. X-ray analyses of the supramolecular structures of BH₃NH₃ ·1, (BH₃NH₃)₂ ·2, BH₃NH₃ ·3, BH₃NH₃ ·4, and (BH₃NH₃)₂ ·5 have been carried out and BH₃NH₃ ·1, BH₃NH₃ ·2, and (BH₃NH₃)₂ ·5 have been shown to reduce acetophenone with enantiomeric excesses of 5, 13, and 10% respectively. Supplementary Data relating to this article (atomic coordinates of the hydrogen atoms and thermal parameters) are deposited with the British Library as Supplementary Publication No. SUP 82017 (74 pages).Dedicated to Professor H. M. Powell.     

Synthesis and spatial structure of methyl substituted 2-phenylpiperidine-4-spiro-5′-imidazolidine-2′,4′-diones

Piperidine-4-spiro-5-irnidazolidine-2, 4-diones have been synthesized from the appropriate methyl substituted 2 phenyl-4-hydroxypiperidines and 4-cyano-4-aminopiperidines by the Bucherer—Bergs and Strecker methods. The stereocheinical composition and spatial structure of the compounds synthesized have been established from¹H and¹³C NMR data.Moscow State Academy of Fine Chemical Technology, Moscow 117571. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 6, pp. 798–801, June, 1994. Original article submitted May 11, 1994.     

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%.     

(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.     

Synthesis of heterocycles from 1,5-diketones. 3. Alicyclic 1,5-diketones in reaction with phenylhydrazine

8-R-7aH-5,6,7,8,9,10,11,12-Octahydroindolo[3.2.1-d,e]acridines, 1,2,3,4-tetra-hydrocarbazole, 9-R-sym-octahydroacridines, and 9-R,10-phenyl-sym-octahydroacridinium salts are formed by the action of phenyl-hydrazine on alkylidene-2,2-dicyclohexanone or the corresponding 8-R-tricyclo(7.3.1.0^2,7)tridecan-2-ol-13-ones in an acid medium. Postulations were made for the paths of formation of these compounds.2,2-Dimethyl-3-oxa-4a-(2,2-dimethyltetrahydropyran-4-on-5yl-methyl)-4aH-1, 2,3,4-tetrahydrocarbazole, 3,3,14,14-tetramethyl-2-oxa-5a,10b-(methanoxyisobutane)-1,2,3,4,5a,10b,11,11a-octahydroquinindoline, 2,2-dimethyl-3-oxa-1,2,3,4-tetrahydrocarbazole and 3,3,6,6-tetramethyl-2,7-dioxa-sym-octahydroacridine were obtained by the reaction of methylene-3,3-di(6,6-dimethyltetrahydropyran-4-one) with phenylhydrazine in acetic acid. The quinindoline structure was confirmed by the synthesis of this compound from 2,2-dimethyl-3-oxa-4a-(2,2-dimethyl-tetrahydropyran-4-on-5-ylmethyl)-4aH-1,2,3,4-tetrahydrocarbazole by the action of ammonia.For article 2, see [1].Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 1, pp. 46–52, January, 1986.     

Mixed ligand complexes involving aminoacid dithiocarbamates,substituted phosphines and nickel(II)

Mixed ligand complexes involving four aminoacid dithiocarbamates (RRdtc=glydtc^– (R=H; R=H), methdtc^– (R=H; R=C₃H₇S), sardtc^– (R=Me; R=H), trydtc^– (R=H; R=C₉H₈N), substituted phosphines [PPh₃, Ph₂PCH₂CH₂PPh₂(dppe)] and nickel(II) are reported. All are diamagnetic. Thermal analyses of the complexes are in keeping with the proposed formulae. Thermal decomposition of the dithiocarbamate moiety proceeds through the formation of Ni(SCN)₂. PPh₃ and dppe are lost in the initial decomposition stages.     

Unusual transformation of 3-carbomethoxy-Δ2-pyrazoline under the influence of lead tetraacetate

3-Carbomethoxy-1-(1-carbomethoxy-1-cyclopropyl)pyrazole and 3-carbomethoxy-1-(3-carbomethoxy-1-pyrazolyl)-²-pyrazoline were obtained by the action of lead tetraacetate on 3-carbomethoxy-²-pyrazoline.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 9, pp. 1239–1242, September, 1976.     

Reaction of organylthiochloroacetylenes with organylselenols

The reaction of organylthiochloroacetylenes RSCCCl with selenols in a DMSO solution containing KOH leads to organylthio(organylseleno)acetylenes RSCCSeR. When the reaction of organylthiochloroacetylenes with selenols was carried out in diethyl ether, the previously unknown 1-organylthio-2-organylseleno-2-chloroethenes RSCH=CClSeR were obtained in the form of Z- and E-isomers. The hydrochlorination of organylthio(organylseleno)acetylenes results in Z- and E-1-organylthio-2-organylseleno-1-chloroethenes RSCCl=CHSeR.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 8, pp. 1865–1871, August, 1990.     

Nitration,amination, and halogenation of Di-O-methylphloracetophenone

Chlorination of the title compound gave 5- and 3-chloro-2-hydroxy-4,6-dimethoxyacetophenone. The nitration of its acetate, followed successively by reduction, diazotization, and reaction with cuprous chloride, gave the 3-substituted series, 2-acetoxy-4,6-dimethoxy-3-nitroacetophenone, 3-amino-2-hydroxy-4,6-dimethoxyacetophenone, and 3-chloro-2-hydroxy-4,6-methoxyacetophenone, respectively. The orientation of substituents in the products was proved. The amino and chloro members of the isomeric 5-substituted series were availablevia 2-hydroxy-4,6-dimethoxy-5-phenylazoacetophenone, the product of the reaction of the title compound with benzenediazonium chloride.

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Nitrierung, Aminierung und Halogenierung von Di-O-methylphloracetophenon

Zusammenfassung Chlorierung der Titelverbindung gab 5- und 3-Chlor-2-hydroxy-4,6-dimethoxyacetophenon. Die Nitrierung des Acetats, gefolgt von Reduktion, Diazotierung und Reaktion mit CuCl ergab die 3-substituierte Reihe: 2-Acetoxy-4,6-dimethoxy-3-nitroacetophenon, 3-Amino-2-hydroxy-4,6-dimethoxyacetophenon und 3-Chlor-2-hydroxy-4,6-dimethoxyacetophenon. Die Orientierung der Substituenten wird diskutiert. Die Amino- und Chlorderivate der isomeren 5-substituierten Reihe sind über 2-Hydroxy-4,6-dimethoxy-5-phenylacetophenon zugängig, dem Produkt der Reaktion der Titelverbindung mit Phenyldiazoniumchlorid.

     

Silica-immobilized binuclear chromium-molybdenum complexes

ESR and UV spectra of a binuclear complex [n-(C₄H₉)₄N]₃ CrMoOCl₉ in solution and supported on SiO₂ have been studied. Upon fixing this complex followed by oxidation-reduction treatment, a highly disperse state is observed, as evidenced by the ESR spectra of the Cr³⁺ ions.

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[H–(C₄H₉)₄N]₃CrMoOCl₉ SiO₂. - , Cr³⁺.

     

Derivatives of 3-aminopiperidine-2, 6-dione

Several N-substituted 3-phthalimidopiperidine-2,6-diones and 3-(3phthalimido-2,5-dioxopyrrolid-1-yl)piperidine-2,6-dione have been synthesized.     

Determination of the conformation of macrocyclic 1,8,9,20-tetrahydro3,6,9-trimethyl-1,8-diphenyldibenzo[c,m]dipyrazolo[3,4-f:4′,3′-j][1,2,5,8,9,12]hexaazacyclotetradecene

The conformation of the macrocyclic skeleton of 1,8,9,20-tetrahydro-3,6,9-trimethyl-1,8-diphenyldibenzo[c,m]dipyrazolo[3,4-f:4,3-j][1,2,5,8,9,12]-hexaazacyclotetradecene was determined by means of the ¹³C NMR spectra with respect to the known conformations of the macrocyclic skeleton in isomeric Ni(II) complexes of 1,8,9,20-tetrahydro-3,6-dimethyl-1,8-diphenyldibenzo[c,m] dipyrazolo[3,4-f:4,3-j][1,2,5,8,9,12]hexaazacyclotetradecene.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 9, 1256–1260, September, 1988.     

Simulation of induced peaks in indirect detection of non-electrolytes in high-performance liquid chromatography

Summary Induced peaks observed in indirect detection of nonelectrolytes in high-performance liquid chromatography are simulated. The equation representing the signal intensity of the induced peaks is derived, and it is verified by the experimental results. The peak area is proportional to (K _b +1) k _a /| _a —k _b |, where k _a ad k _b are the capacity factors of the visualization agent and the analyte, respectively.     

Equilibria in complexes ofn-heterocyclic molecules,part XXVI. Reactions of hydroxide and water with the tris-(2,2′-bipyrazine)iron(II) and tris-[2,2′-bis-(5,6-dihydro-4-H-1,3-oxazine)]iron(II) ions

Summary The reactions of [Fe(bipyz)₃]²⁺ (bipyz = 2,2-bipyrazine) and [Fe(box)₃]²⁺ [box = 2,2-bis-(5,6-dihydro-4-H-1,3-oxazine] with H₂O and HO^– in aqueous solution have been followed. The [Fe(bipyz)₃]²⁺ ion is attacked at the ligand with both nucleophiles and the ligand is cleaved. A similar reaction between HO^– and [Fe(box)₃]²⁺ is observed. Detailed kinetics for all reactions are reported.phen 1,10-phenanthroline - bipy 2,2-bipyridyl - bipym 2,2-bipyrimidine Part XXV: R. D. Gillard, W. S. Walters and P. A. Williams,J. Chem. Soc. Dalton Trans., in press.     

BISPHENYLENECOSAN as highly selective Cs+ extraction agent

A new reagent for the highly selective extraction of cesium (e-1,7–2,2)4,8–8,4-(bis--o-phenylene)bisdicarbollidocobalt(1–)ate, [(C₂B₉H₉)₂(C₆H₄)₂Co]^–, abbreviated as BISPHECOSAN is described in this paper. The choice of organic solvent and solubilizer, dependence of distribution ratio of Cs⁺ on acidity and other parameters are studied. The extraction mechanism based on selective binding of Cs⁺ cation between two phenylene rings is presented and factors influencing the chemical stability of the reagent are determined.     

9-(2′,5′-Dimethyl-4′-pyridyl)fluorene in syntheses of fluorospirodihydrofuropyridine and pyridofluoranthene

1,2,5-Trimethyl-4-(9-fluorenylidene)piperidine, which is formed by condensation of fluorene with 1,2,5-trimethyl-4-piperidone, is converted catalytically to 9(2,5-dimethyl-4-pyridyl)fluorene, from which 2-methylpyrido[4,5-a]fluoranthene and its demethylated analog were obtained by catalytic dehydrocyclization. Oxidation of 9-(2,5-dimethy1-4-pyridyl)fluorene gave 9-(2,5-dimethyl-4-pyridyl)9-fluorenol and fluorene-9-spiro-4-(6-oxo-2-carboxypyrido[4,5-c]-4-6-dihydrofuran). 6-Methyl-2-phenyl-7-(9-fluorenyl)indolizine was synthesized by the Chichibabin method.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 8, pp. 1087–1090, August, 1978.     

Photochromic and electrochromic properties of 1′,3′,3′-trimethyl-6-piperidino- and -morpholinospiro[indoline-2′,3-3H-naphtho[2,1-b][1,4]-oxazines]

Electrochromic properties of 1,3,3-trimethyl-6-piperidino- and-morpholinospiro[indoline-2,3-3H-naphtho[2,1-b][1,4]-oxazines] resulting from their ionization and the formation of intermediate products were studied. The characteristic features of the photochromic behavior of these compounds are positive solvatochromism for absorption spectra of a colored form and an increase in the rate constant for thermobleaching with increasing solvent polarity.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 5, pp. 836–838, May, 1994.     

Studies in the area of 2,3′-biquinolyl. 1. Arylation and hetarylation of 2,3′-biquinolyl dianion

The 2,3-biquinolyl dianion, when reacting with aryl- and hetaryl halides, forms arylation products at the 4 position, and treatment of these products with alkyl halides or water yields 1-alkyl-4-aryl-1,4-dihydro-2,3-biquinolyls or 4-aryl-1,4-dihydro-2,3-biquinolyls, respectively. Oxidation of the latter yields 4-aryl-2,3-biquinolyls. The cation dependence of the arylation reaction is demonstrated.Stavropol' State University, Stavropol' 355009. Russian Chemical Engineering University, Moscow 125190. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 8, pp. 1094–1099, August, 1997.     

Die Dissoziationskonstanten von 2,3′-und 2,4′-Dihydroxydiphenylmethanderivaten

The pK-values of the first and second degree of dissociation of 2.3-dihydroxy-6-methyl-3.5-dinitro-diphenylmethane, 2.3-dihydroxy-6-methyl-5-nitro-diphenylmethane, 2.3-dihydroxy-5.6-dimethyl-3-nitro-diphenylmethane, 2.4-dihydroxy-3. 5-dimethyl-3.5-dinitro-diphenylmethane, 2.4-dihydroxy-3. 5-dimethyl-5-nitro-diphenylmethane and 2.4-dihydroxy-3.5.5-trimethyl-3-nitrodiphenylmethane were determined in aqueous solution at 25°C by the spectrophotometric method. The observed pK-values are compared with those of 2-methyl-4.6-dinitro-phenol, 2-methyl-4-nitrophenol, 2.4-dimethyl-6-nitrophenol, 3.4-dimethylphenol and 2.4.6-trimethylphenol which serve as model compounds for the single phenolic units.     

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].