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.

     

Isoflavones of the roots of Lupinus luteus

Conclusions For the first time in the isoflavone series, a compound which has the structure of 5,7-dihydroxy-3,4-methylenedioxyisoflavone (3,4-methylenedioxyorobol) and two of its glucosides — 3,4-methylenedioxyorobol 7-O--D-glucoside and 3,4-methylenedioxyorobol 7-O--D-glucosylglucoside — and also a genistein C-monoglucoside, have been described. The isoflavones were isolated from the roots ofLupinus luteus L. by preparative chromatography on paper and on columns of polyamide. In addition, the previously known genistein, genistein 7-O--D-glucoside (genistin), and genistein 7-O--D-glucosylglucoside have been obtained.V. F. Kuprevich Institute of Experimental Botany, Academy of Sciences of the Belorussian SSR. Translated from Khimiya Prirodnykh Soedinenii, No. 2, pp. 162–166, March–April, 1974.     

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.     

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.     

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.

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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.

     

Kinetics of the catalytic transformation of isobutene into methacrylonitrile with NO on supported nickel oxide aerogel

Kinetic studies of the nitroxidation of isobutene by NO show that the reaction follows a redox mechanism in the temperature range of 300–400°C. This mechanism implies an interaction between dehydrogenated isobutene -allyl radical and atomic nitrogen due to the decomposition of NO by the reduced catalyst, which is then reoxidized.

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NO , 300–400°C. - , NO , .

     

Preparation of silver sulfate microcrystals suitable for profile angle measurement

Summary In this paper is described a method of preparing microcrystals of silver sulfate suitable for profile angle measurement. The value of the obtuse profile angle of rhombic Ag₂SO₄ crystals was determined as 121° 2±12.

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Zusammenfassung Die Herstellung von Silbersulfat-Mikrokristallen für die Profilwinkelmessung wurde beschrieben. Der stumpfe Winkel rhombischer Silbersulfatkristalle beträgt 121° 2±12.

     

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.     

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.     

Organoboron compounds. 374. Cyclic compounds of the chelate type from 2-pyridyl-and 2-pyrimidinylaminoboranes and dicyclohexylcarbodiimide

Conclusions New chelate compounds of boron, in which the chelating agents are, respectively, N.N-dicyclohexyl-N'-(2-pyridyl)guanidine and N,N-dicyclohexyl-N'-(2-pyrimidinyl)guanidine, have been synthesized by adding 2-pyridylaminodiorganylboranes and 2-pyrimidinylaminodiorganylboranes to dicyclohexylcarbodiimide.For the preceding report see [1].Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 3, pp. 659–663, March, 1980.     

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].     

The autocatalytic character of the reaction methanol to hydrocarbons over amorphous silica-alumina catalysts

Conversion of methanol to hydrocarbons was studied on an amorphous silica-alumina over the 330–420°C temperature range and contact times up to 8 h. The reaction was confirmed as autocatalytic from the results of varying both contact time and temperature.

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330–420°C 8 . , , , .

     

Molecular orbital studies on nucleoside antibiotics X. Conformation of nebularine and isoguanosine

Summary Conformational properties of two nucleoside analogs, namely nebularine and isoguanosine have been investigated by using PCILO (Perturbative Configuration Interaction using Localized Orbitals) method. Nebularine (9--ribofurnosyl purine) is a naturally occurring purine nucleoside which is structurally similar to adenosine and it inhibits the growth of tumor cells and influenza B virus. Isoguanosine is one of the two naturally occurring analogs of guanosine. Both C2-endo and C3-endo sugar puckerings have been considered for both the molecules with preselected values of torsion angles around C2–O2 and C5–O5 bonds. The results indicate that nebularine has conformational preferences very similar to those of its parent nucleoside, adenosine; whereas the conformational properties of isoguanosine are very different from those of guanosine as well as adenosine. The important implications of these results have been discussed in terms of the biological activity of these molecules.     

Umsetzungen des Diphenylphosphinsäureanilids

Zusammenfassung Diphenylphosphinsäureanilid-kalium wurde in Lösung von Dioxan erhalten und mit Alkylhalogeniden zu Diphenylphosphinsäure-alkylaniliden umgesetzt. Mit Methylenjodid entsteht N,N-Bis-[diphenylphosphinsäure]-N,N-diphenylmethylendiamid, während mit Äthylenbromid Acetylen und Diphenylphosphinsäureanilid erhalten wird. Mit Ph₂P(O)Cl bzw. PhP(O)Cl₂ erhält man N,N-Bis-[diphenylphosphinsäure]-N-phenyl-amid bzw. Phenylphosphonsäure-N,N-diphenyl-N,N-bis-[diphenylphosphinsäure]-diamid.     

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.     

Application of the Arbuzov reaction to establish the structure of D-mannitol tricyclic triethyl triphosphite

Conclusions The previously expressed theory that the tricyclic triethyl triphosphite of D-mannitol is 2-ethoxy-4, 5-bis-(2-ethoxy-1, 3, 2-dioxaphospholan-4-yl)-l,3,2-dioxa-4-phospholane was corroborated on the basis of the differential-thermal analysis and³¹P NMR data.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 6, pp. 1390–1395, June, 1972.     

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.     

New route for the synthesis of 2-thiouracil analogues of 3′-azido-2′,3′-dideoxy nucleosides

Summary Reaction of 3-azido-5-O-tert-butyldiphenylsilyl-2,3-dideoxy-D-erythro-pentofuranoside (5) with silylated 2-thiouracil and 5-alkoxy-2-thiouracils in the presence of trimethylsilyl trifluoromethanesulfonate afforded an anomeric mixture of the corresponding 3-azido-2,3-dideoxy-2-thiouridine derivatives with the -anomer as the main product. Deprotected nucleosides were obtained by treatment with tetrabutylammonium fluoride.

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Ein neuer Weg zur Synthese von 2-Thiouracil-Analogen von 3-Azido-2,3-dideoxy-Nucleosiden

Zusammenfassung Die Reaktion von 3-Azido-5-O-tert-butyldiphenylsilyl-2,3-dideoxy-D-erythro-pentofuranosid (5) mit silyliertem 2-Thiouracil und 5-Alkoxy-2-thiouracil in Gegenwart von Trimethylsilyltrifluormethansulfonat ergab eine anomere Mischung der entsprechenden 3-Azido-2,3-dideoxy-2-thiouridin-Derivate, wobei das -Anomer das Hauptprodukt darstellte. Die ungeschützten Nucleoside wurden mittels Behandlung mit Tetrabutylammoniumfluorid erhalten.

     

Haploside A — A new acylated flavonol glycoside fromHaplophyllum perforatum

The epigeal part ofHaplophyllum perforatum has yielded a new acylated flavonol glycoside, haploside A, for which the structure of 3,4,5,7,8-pentahydroxy-3-methoxyflavone 7-O-(6-O-acetyl--D-glucopyranoside) has been established. The aglycone of the glycoside isolated — 3,4,5,7,8-pentahydroxy-3-methoxyflavone — has also proved to be new and it has been called haplogenin. The structures of the compounds mentioned have been established on the basis of UV, IR, PMR, and mass spectra and the products of acetylation and of acid and alkaline hydrolysis.Institute of the Chemistry of Plant Substances, Academy of Sciences of the Uzbek SSR, Tashkent. Translated from Khimiya Prirodnykh Soedinenii, No. 3, pp. 330–334, May–June, 1980.