Synthesis and protonation of 2,3′-biquinolyl dianions

It has been shown that the reaction of 2, 3-biquinolyls with an excess of lithium in tetrahydrofuran leads to the formation of dianions, treatment of which with water or D₂O gives 1, 4-dihydro-2, 3-biquinolyls or their 4-D derivatives in good yield. Oxidation of the latter leads to 4-D-2,3-biquinolyl. The reduction of 2, 3-biquinolyl has been studied.Stavropol State University, Stavropol 355009. Rostov State University, Rostov-on-Don 344090. Russian University of Chemical Technology, Moscow 125190. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 10, pp. 1391–1394, October, 1996. Original article submitted September 10, 1996.     

Characterization of perovskite-type oxide catalysts RECoO3 by TPR

Reducibility of a series of RECoO₃ (RE=La, Pr, Nd, Sm, Eu, Gd, Tb, Dy) perovskite-type oxides were measured by temperature programmed reduction (TPR) technique. Catalytic activity for CO oxidation of them were investigated. The relation among T_max in TPR, catalytic activity and surface oxygen binding energy is discussed.

---

RECoO₃ (RE=La, Pr, Nd, Sm, Eu, Gd, Tb, Dy) . CO. T_max , .

---

---

Project Supported by the Science Fund of the Chinese Academy of Sciences     

Flavonoids ofHaplophyllum perforatum. New glycosides of limocitrin

Two new glycosides of limocitrin have been isolated from the epigeal part ofHaplophyllum perforatum (M. B.) Kar. et Kir. On the basis of chemical transformations and spectral characteristics the structures of the substances isolated have been established as 7-(6-acetyl--D-glucopyranosyloxy)-3,4,5-trihydroxy-3,8-dimethoxyflavone and 7-[0--L-rhamnopyranosyl-(1 2)--D-glucopyranosyloxy]-3,4,5-trihydroxy-3,8-dimethoxyflavone.Institute of the Chemistry of Plant Substances, Academy of Sciences of the Uzbek SSR, Tashkent. Translated from Khimiya Prirodnykh Soedinenii, No. 2, pp. 192–196, March–April, 1985.     

Hysteresis of thermogravimetric curves of nickel catalysts for methane conversion in CH4+CO2 mixture

Characteristic peculiarities of the supercarbonization peak, i. e. the effect of carbon accumulation on the catalyst surface and its subsequent removal under heating in the CH₄+CO₂ mixture have been studied. Hysteresis of thermogravimetric curves in the heating/cooling cycle has been established.

---

— . -.

     

Über Dihydro-bzw. Tetrahydrospiro([1]benzopyran-2,4′(1′H)-pyrimidin)-2′(3′H)-one

On reaction of dihydro-4,4,6-trimethyl-2(1H)-pyrimidinone1 with o-hydroxybenzaldehydes, dihydro- and tetrahydrospiro([1]-benzopyran-2,4(1H)-pyrimidin)-2(3H)-ones resp.5, 6, 7 are formed.     

New chiral acyclic analogs of 2′-deoxynucleosides

Convenient methods for the synthesis of chiral 2,3-seco-2-deoxynucleosides were developed. An isopropylidene protective group was used to block the 3,5-hydroxy groups in 2,3-seco-uridine. Conversion of the hydroxymethyl group to a methyl group was accomplished by chlorination with a mixture of CCl₄ and Ph₃P with subsequent reduction with n-Bu₃SnH. 2,3-seco-2-Deoxyuridine was obtained after deacetonation. The (S) enantiomer was similarly synthesized starting from 1-(-D-arabinofuranosyl)uracil. 3-O-tert-Butyldimethylsilyl-5-O-(p-monomethoxytrityl)-2,3-seco-2-deoxyuridine, which has optically active centers at C₍₁₎ and C₍₄₎, was also synthesized.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 6, pp. 822–826, June, 1988.The authors thank Professor M. Ya. Karpeiskii for his constant interest in this research.     

Darstellung von 2′,3′-Dideoxy-2′-hydroxymethyl-nucleosiden

Zusammenfassung Die Synthese von geschützten 2,3-Dideoxy-2-hydroxymethyl-nucleosiden wird beschrieben. Die durch ein Mehrstufenverfahren aus Isopropylidenglycerol erhaltenen Nucleoside können als Bausteine zur Darstellung von Oligonucleotiden verwendet werden, deren 2- und 5-Positionen über eine Etherbrücke verbunden sind.

---

Synthesis of 2,3-dideoxy-2-hydroxymethyl nucleosides

Summary The synthesis of protected 2,3-dideoxy-2-hydroxymethyl nucleosides is presented. The nucleosides, obtained in a multi-step procedure starting from isopropylideneglycerol, may be used as building blocks for the synthesis of 2,5-ether linked oligonucleotides.

     

Etude de la séparation du thorium d'avec les terres cériques

Résumé Nous avons étudié les complexes que forment les acides éthylèneglycolbis-(-aminoéthyléther)] Sr,N-tétracétique et ,-diaminodiéthylétherN,N-tétracétique, soit avec le thorium, soit avec les terres cériques et, à la suite de cette étude, nous avons pu établir une méthode d'analyse et une séparation du thorium d'avec les terres cériques qui nous a donné satisfaction.

---

Summary A study has been conducted of the complexes formed by the ethyleneglycol-bis (-amino-ethylether)-N,N-tetraacetic acid and,-diaminodiethylether-N,N-tetraacetic acid with either thorium or the ceric earths. As a result of this investigation, it was possible to set up a method of analysis and a separation of thorium from the cerium earths. These procedures have proved satisfactory.

---

Zusammenfassung Die von Äthylenglykol-bis-(-aminoäthyläther)-N,N-tetraessigsäure bzw.von ,-Diaminodiäthyläther-N,N-tetraessigsäure mit Thorium bzw. mit den Cer-Erden gebildeten Komplexe wurden untersucht. Auf Grund der Ergebnisse konnte ein Analysenverfahren und eine Trennungsmethode für Thorium und Cer-Erden entwickelt werden.

---

---

Une communication de ce travail a été faite à Graz, lors de la commémoration du centenaire de la naissance deF. Emich.     

Cyclophosphate

Zusammenfassung Der second messenger Adenosin-3,5-monophosphat (A-3,5-MP) wird in den Organismen durch Phosphodiesterase abgebaut. Mit Hilfe einer Reihe verschiedener Cyclophosphate wurde die Abhängigkeit der Phosphodiesterase-Aktivität von der Struktur des Substrates untersucht. Das Enzym aus Herz spaltet Purinribosid-Cyclophosphate schneller als Pyrimidinribosid-Cyclophosphate. 6-Substitution am Purinring vermindert die Spaltgeschwindigkeit, dieser Effekt ist bei Substitution an der 8-Stelle noch stärker. Tritt ein Substituent an die 2O-Stellung, wird die Spaltrate in geringerem Maße wie bei 6-Substitution vermindert. Untersuchungen mit dem Enzym aus Fettgewebe brachten ähnliche Ergebnisse.

---

CyclophosphatesIII. Splitting of various cyclophosphates by phosphodiesterase from heart and adipose tissue

In organisms, the second messenger adenosine-3,5-monophosphate (A-3,5-MP) is degraded by phosphodiesterase. Employing a series of different cyclophosphates, the structural requirements for phosphodiesterase activity are investigated. With the heart enzyme, purine riboside cyclophosphates are split faster than pyrimidine riboside cyclophosphates. 6-substitution of the purine moiety lessens the splitting rate. This effect is still more pronounced when substitution takes place in the 8-position. Substitution in the 2O-position has also a diminishing effect on the splitting rate, which is less than the effect achieved by 6-substitution. Studies with the enzyme from adipose tissue gave similar results.

---

---

II. Mitteilung: Michal, G., du Plooy, M., Woschée, M., Nelböck, M., Weimann, G.: diese Z. 252, 183 (1970).

---

Wir danken Frau Grudrun Kreutzer, Frl. Gisela Jurz und Herrn Rolf Kieffer für die geschickte und sorgfältige Ausführung der Untersuchungen, sowie Herrn Haid und Herrn Mühlegger für synthetische Arbeiten.     

Transformed steroids. 160. Reaction of 20,20-dimethoxy-16α,17α-epoxypregn-5-ene-3β, 21-diol-20-one with pyridine thiocyanate and carbethoxyhydrazine

Conclusion The reaction of 20,20-dimethoxy-16,17-epoxypregn-5-ene-3,21-diol-20-one with pyridine thiocyanate in the presence of carbethoxyhydrazine proceeds by two competing paths: cisopening of the oxide ring by a -SCN ion at the C¹⁷ atom, and substitution of one of the methoxyl groups by -NCS ion. As a result 2,20-dicarbethoxyhydrazones of pregn-5-ene-3,21-diol-20-one-[17,16-d]-1,3-oxathiolan-2-one and 20-methoxy-16,17-epoxypregn-5-ene-3-ol-[20,21-d]-1,3-oxazolidine-2-thione are formed.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 4, pp. 911–914, April, 1987.     

Synthetic studies in the field of chlorobium chlorophyll

By the condensation of -halogenomethyl derivatives of pyrroles with -unsubstituted pyrroles the synthesis of the following unsymmetrical dipyrrolylmethanes has been effected: 5-benzyloxycarbonyl-5-ethoxycarbonyl-3, 3-di(-methoxycarbonylethyl)-4,4-dimethyl-2,2-dipyrrolylmethane (IIIa), 5-benzyloxycarbonyl-5-ethoxycarbonyl-3-(-methoxycarbonylethyl)-4, 4-diniethyl-3-n-propyl-2,2-dipyrrolylmethane(IIIb), 3-acetyl-5-benzyloxycarbonyl-4-ethyl-5-methoxycarbonyl-3, 4-dimethyl-2,2-dipyrrolylmethane (IIIc), and 3-bromo-5-benzyloxycarbonyl-4-ethyl-5-methoxycarbonyl-3, 4-dimethyl-2,2-dipyrrolylmethane (IIId). Hydrogenation of the unsymmetrical dipyrrolylmethanes IIIa, b, c, and d has given the corresponding monocarboxylic acids IVa, b, c, and d. The formylation of the dipyrrolylmethanemonocarboxylic acid IVa has given 5-ethoxycarbonyl-5-formyl-3,3-di(-methoxycarbonylethyl)-4, 4-dimethyl-2,2-dipyrrolylmethane (V).For communication II, see [1].Deceased.Translated from Khimiya Geterotsiklicheskikh Soedinenii, Vol. 6, No. 8, pp. 1045–1047, August, 1970.     

Synthesis and Use of Some p-Substituted 6-O-Phenyl Ethers of Glucose as Water Soluble ‘Molecular Tweezers’

Refluxing 4,4-isopropylidenediphenol (1) and 5,6-anhydro-1,2-O-isopropylidene--d-glucofuranose (2) with potassium carbonate in dry acetonitrile afforded molecular tweezers (3) and (4) which, on deprotection with aqueous acetic acid, yielded water soluble tweezers (5) and (6). These water soluble tweezers were explored for the solubilization of neutral arenes, viz. naphthalene, biphenyl, durene, fluorene, anthracene and phenanthrene in aqueous medium. These solid liquid extraction studies revealed that 6,6-O-(4,4-isopropylidenediphenyl)bis[-d-glucopyranose] (5) causes an approximate 17-fold increase in the solubility of naphthalene in aqueous medium.     

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.     

Kinetics of the selective hydrogenation of phenol to cyclohexanone over a Pd-alumina catalyst

The most suitable kinetic equation for the selective hydrogenation of phenol to cyclohexanone on a 0.96wt.% Pd-9.63wt.%CaO-alumina (Harshaw AL-3965) catalyst is determined among a series of models based on Langmuir-Hinshelwood-Hougen-Watson theory.

---

0,96 . %Pd-9,63 .%CaO/Al₂O₃ (Harshaw AL-3965). , ---.

---

     

Pyrimidines. 70. Relative reactivities of the chlorine atoms of 2,2′,4-trichloro-4′,5-dipyrimidinyl in its reaction with piperidine

2,2,4-Trichloro-6-phenyl-4,5-dipyrimidinyl, for which nucleophilic substitution with piperdine under various conditions was studied, was obtained from 2,2,4-trioxo-6-phenyl-1, 1,2,2,3,4-hexahydro-4,5-dipyrimidinyl. It is shown that there is an appreciable difference in the rates of substitution of the first, second, and third chlorine atoms, and this made it possible to obtain reaction products that contain one, two, and three piperidino groups. The chlorine atom in the 4 position is replaced initially, after which the chlorine atom in the 2 position undergoes substitution. The structures of the compounds were proved by chemical transformations and analysis of the PMR spectra.See [1] for communication 69.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 6, pp. 821–826, June, 1979.     

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.

---

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.

     

1,4-bis(4′-hydroxy-1′,2′,5′-trimethyl-4-piperidyl)-1,3-butadiyne and its derivatives

1.4-Bis(4-hydroxy-1,2,5-trimethyl-4-piperidyl)-1.3-butadiyne has been synthesized from the individual isomers of 4-ethynyl-1,2,5-trimethyl-4-piperidol. Hydrogenation, bromination, and cleavage have given, respectively, 1,4-bis(4-hydroxy-1,2,5-trimethyl-4-piperidyl)butane, 1,4-bis(4-nydroxy-1,2,5-trimethyl-4-piperidyl)-1,2,3,4-tetrabromo-1, 3-butadiene, and 4-(1,3-butadiynyl)-1,2,5-trimethyl-4-piperidol.     

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.     

Pyrimidines

It is shown that the reaction of benzalbisurea with 3-amino-5-hydroxy-1-R-pyrazoles gives 1-R-dipyrazolo[3,4-b:4,3-e]pyridine (R=CH₃) or a spiro(pyrazole-4,5-pyrimidine) derivative (R=C₆H₅). Similar reactions of benzalbisurea with 3-hydroxy-5-amino-1-methylpyrazole give 2-methyldipyrazole[3,4-b:4,3-e]pyridine or substituted tetrahydropyrazolo[3,4-d] pyrimidine. Only the corresponding dipyrazolo[3,4-b:4,3-e]pyridines are formed in the reaction of 1-methylhydroxyaminopyrazoles with methylenebisurea.See [1] for communication XXXIX.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 6, pp. 823–827, June, 1974.