7-Azaindole derivatives

The Bischler-Napiralski reaction is used to synthesize 1-phenyl-3, 9-dimethyl-5, 6-dihydro-12-aza--carboline, and its 5-methyl and 5-ethyl derivatives, from 1-phenyl-4-methyl-3-aminoalkyl-T-azaindoles. 5, 6-Dihydro-12-aza--carbolines prepared by sodium borohydride reduction are converted into 1-phenyl-3, 9-dimethyl-3, 4, 5, 6-tetrahydro-12-aza--carboline and its 5-methyl and 5-ethyl derivatives. 1-Phenyl-9-methyl-12-azaharman is synthesized by palladium dehydrogenation of 1-phenyl-3, 9-dimethyl-5, 6-dihydro-12-aza--carboline.For Part XVII see [1].     

Reactions with β-cyanoethylhydrazine,III. A new approach for the synthesis of substituted 3,5-diaminopyrazole and 1,2,4-triazoles

The reactivity of -cyanoethylhydrazine toward enaminonitrile and aroyl isothiocyanates is reported. A variety of 3,5-diaminopyrazole and ³-1,2,4-triazolin-5-thione derivatives could be prepared.

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Reaktionen mit -Canyethylhydrazin, 3. Mitt.: Ein neuer Weg zur Synthese von substituierten 3,5-Diaminopyrazolen und 1,2,4-Triazolen

Zusammenfassung Es wird über die Reaktivität von -Cyanethylhydrazin gegenüber Enaminonitril und Aroylisothiocyanaten berichtet. Es konnte eine Reihe von 3,5-Diaminopyrazol-und ³-1,2,4-Triazolin-Derivaten hergestellt werden.

     

Cyclization of O-benzoyl-β-piperidinopropionamidoximes to form 5-phenyl-3-(β-piperidino)ethyl-1,2,4-oxadiazoles

The reactions of -piperidinopropionamidoxime with substituted benzoyl chlorides afforded O-benzoylation products, which underwent cyclization to form 5-phenyl-3-(-piperidino)ethyl-1,2,4-oxadiazoles upon heating in dimethylformamide in the presence of molecular sieves at 60 °C for 1—2.5 h. Heating of O-benzoyl--piperidinopropionamidoxime in dimethylformamide in the presence of K₂CO₃ at 85 °C for 4 h afforded a mixture of 5-phenyl-3-(-piperidino)ethyl-1,2,4-oxadiazole, benzoic acid, and N-(-piperidino)ethylurea.     

Reactions with heterocyclic amidines,VII: Synthesis of some new pyrazolo[1,5-c]-1,2,4-triazines,pyrazolo[1,5-a]-1,3,5-triazines and pyrazolo[1,5-a]pyrimidines

Diazotised 5-amino-3-methyl-4-phenyloyrazole (1) reacted with active methylene reagents and with -naphthol to yield the pyrazolo[1,5-c)-1,2,4-triazine derivatives2a-e and5. Compound1 reacted with benzoyl isothiocyanate and with phenyl isothiocyanate to yield the corresponding pyrazol-5-ylthiourea derivatives6a, b. 5a was converted into the thiourea derivative8 by the action of acids or alkalies. A synthesis of 2-methyl-3-phenyl-4,5,6,7-tetrahydropyrazolo[1,5-a]-pyrimidin-5-one from the reaction of -phenylacetoactonitrile (3-oxo-2-phenyl-butyric nitrile) and -cyanoethylhydrazine is reported.

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Reaktionen mit heterocyclischen Amidinen, VII: Synthese einiger neuer Pyrazolo[1,5-c]-1,2,4-triazine, Pyrazolo[1,5-a]-1,3,5-triazine und Pyrazolo[1,5-a]pyrimidine

Zusammenfassung Diazotiertes 5-Amino-3-methyl-4-phenylpyrazol (1) reagiert mit einer aktiven Methylenkomponente und -Naphthol zu den Pyrazolo[1,5-c]-1,2,4-triazin-Derivaten2a-e und5. 1 ergibt mit Benzoylisothiocyanat und Phenylisothiocyanat die entsprechenden Pyrazol-5-yl-thioharnstoffe6a, b. 5a wurde mittels Säure oder Base in das Thioharnstoffderivat8 umgewandelt. Es wird über eine Synthese von 2-Methyl-3-phenyl-4,5,6,7-tetrahydropyrazolo[1,5-a]-pyrimidin-5-on aus -Phenylacetoacetonitril (3-Oxo-2-phenyl-butyronitril) und -Cyanoethylhydrazin berichtet.

     

A new method for the synthesis of esters of β-thiophenecarboxylic acids

A method for the synthesis of esters of -thiophenecarboxylic acids and diethyl 3-methyl-2,4-thiophenedicarboxylate by the deamination of derivatives of 2-amino-3-ethoxycarbonylthiophene has been proposed. Ethyl tetrahydrothionaphthene-3-carboxylate has been converted by dehydrogenation on heating with sulfur into ethyl thionaphthene-3-carboxylic acid. The corresponding acids have been obtained by the hydrolysis of the esters. A number of dialkylaminoalkyl esters has been obtained from -thiophenecarboxylic acids and 3-methyl-2, 4-thiophenedicarboxylic acid via the acid chlorides.     

A study of the reaction of sulfur with organic compounds

The reaction of sulfur with isomeric exo-polychloro derivatives of iso- and n-propylbenzenes containing from 4 to 6 chlorine atoms in the side chain at 200°–300° C has been studied. The reaction of sulfur with , , , -tetrachloro- and , , , , -pentachlorocumenes leads to the formation of the previously unknown thianaphtheno-[2, 3-d]-1, 2-dithiole-3-thione (yield 48%) and thionaphtheno[2,3-d]-3-chloro-1, 2-dithiolium chloride (yield 65%), respectively. The sulfuration reaction of the isomeric exo-tetrachloro-and exo-pentachloro-n-propylbenzenes leads to the formation of 4-chloro-5-phenyl-1, 2-dithiole-3-thione (yield 5–35%). The exo-hexachloro derivatives of iso- and n-bromobenzenes, on being heated with sulfur, form only resinous sulfuration products.For part XVI, see [1].     

Condensation of 4-amino-3-hydrazino-1,2,4-triazoline-5-thione with α- and β-dicarbonyl compounds

sym-Triazolo[3,4-b][1,2,4,5]tetraazepines were obtained by condensation of 4-amino-3-hydrazino-1,2,4-triazoline-5-thione with -dicarbonyl compounds, and 1-[4-amino-1,2,4-triazol-3-yl]-3,5-dialkylpyrazoles were obtained by condensation of the same thione with -dicarbonyl compounds.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 4, pp. 555–559, April, 1978.     

Über Dihydro-6-methyl- bzw.-6-styryl-4-phenyl-2(1H)-pyrimidinone (-thione) sowie Hexahydro-5-benzoyl- bzw.-cinnamoyl-4,7-diphenyl-2(1H)-chinazolinone (-thione)

Zusammenfassung Dihydro-6-methyl-4-phenyl-2 (1H)-pyrimidinone (-thione) (1) reagieren als -Methylalkenylharnstoffe bzw.-thioharnstoffe mit Säuren zu Hexahydro-4,4-methylendi-2(1H)-pyrimidinonen (-thionen) (3), mit Phenolen zu Tetrahydro-6-hydroxyphenyl-2(1H)-pyrimidinonen (-thionen) (2), mit Benzaldehyd zu 6-Styrylverbindungen (1 d, e, g) und mit ,-ungesättigten Ketonen zu Tetrahydro-2(1H)-chinazolinonen (7). Aus 1,5-Diphenyl-1,4-pentadien-3-on und Harnstoffen, Thioharnstoffen bzw. Ammonrhodanid entstehen Diphenyl-1,3,7,9-tetraazaspiro-5,5-undecan-2,8-dione (9) bzw. Hexahydrotriphenyl-6-cinnamoyl-2(1H)-chinazolinthione (10). Hexahydro-6-benzoyl-bzw.-6-cinnamoyl-2(1H)-chinazolinone (-thione) (10) bilden sich allgemein bei Einwirkung von ,-ungesättigten Ketonen auf Dihydro-4-phenyl-6-styryl-2(1H)-pyrimidinone (-thione) (1 d, e, g).

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Heterocycles, XXVII: Dihydro-6-methyl-(or-6-styryl-)-4-phenyl-2(1H)-pyrimidinones (-thiones); Hexahydro-5-benzoyl-(or-cinnamoyl-)-4,7-diphenyl-2(1H)-quinazolinones (-thiones)

Dihydro-6-methyl-4-phenyl-2(1H)-pyrimidinones (-thiones) (1) react as -methylalkenylureas (-thioureas) with acids to hexahydro-4.4-methylenedi-2(1H)-pyrimidinones (-thiones) (3), with phenols to tetrahydro-6-hydroxyphenyl-2(1H)-pyrimidinones (-thiones) (2), with benzaldehyde to 6-styryl compounds (1 d, e, g) and with ,-unsaturated ketones to tetrahydro-2(1H)-quinazolinones (7).On reacting 1.5-diphenyl-1.4-pentadien-3-one with ureas, thioureas or ammonium thiocyanate, the products formed are diphenyl-1.3.7.9-tetraazaspiro-5.5-undecane-2.8-diones (9) and hexahydrotriphenyl-6-cinnamoyl-2(1H)-quinazolinethiones (10), resp. Hexahydro-6-benzoyl- (or-6-cinnamoyl-)-2(1H)-quinazolinones (-thiones) (10) are formed generally by the action of ,-unsaturated ketones on dihydro-4-phenyl-6-styryl-2(1H)-pyrimidinones (-thiones) (1 d, e, g).

     

7-Azaindole derivatives

A study is made of new synthetic routes, based on accessible 3-formyl-7-azaindoles, to 3-substituted 7-azaindole. 2-Phenyl-4-(1-phenyl-4-methyl-7-azaindolyl-3-rnethylene)-1, 3-oxazol-5-one is synthesized, and it is converted to 1-phenyl-4-methyl-7-azatryptophane, 1-phenyl-4-methyl-7-azaindolyl-3-acetic acid,1-phenyl-3-(,-dihydroxypropyl)-4-methyl-7-azaindole, and 1-phenyl-4-methyl-7-azaindolyl-3-pyrotartaric acid.For Part XVIII see [1].     

Structure of the products of oxidation of vindoline by the Sarett reagent

The oxidation of vindoline with the Sarett reagent has given five lactams the structures of which have been established on the basis of the results of instrumental methods of analysis (the x-ray structural method, and the PMR, mass, and IR spectroscopy). Two of the vindoline derivatives — 4-acetoxy-7,8-dihydroxy-16-methoxy-3-methoxycarbonyl-3,6-epoxy-7,8,9,19-tetradehydrovincaminoreine 7,9-betaine and 4-acetoxy-16-methoxy-3-methoxycarbonyl-1-methyl-7,8-dioxo-3,6-epoxyaspidospermidine — have been obtained for the first time and are new compounds.All-Union Scientific-Research Institute of Medicinal Plants, Moscow. Translated from Khimiya Prirodnykh Soedinenii, No. 4, pp. 551–556, July–August, 1988.     

Synthesis of 2-phenyl-3-(2-furyl) — and 2-phenyl-3-[β-(2-furyl)vinyl]-1,2-dihydro-naphtho[1,2-d]-1,2,4-triazines

The corresponding 2-phenyl-3-(2-furyl)- and 2-phenyl-3-[-(2-furyl)vinyl]-1,2-dihydronaphtho-[1,2-d]-1,2,4-triazines were obtained by heating Schiff bases [prepared by reaction of 1-(phenyl-azo)-2-aminonaphthalene with furfural, -(2-furyl)acrolein, and their 5-bromo and 5-nitro derivatives] in glacial acetic acid.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 2, pp. 158–160, February, 1973.     

Synthesis of pyrrolidines,pyrrolines, and pyrroles

As compounds of potential physiological activity, new sulfamide derivatives, Schiffs bases derived from N-arylpyrrolines, are obtained by reacting sulfanilamide, 2-(p-aminobenzenesulfamide) thiazole, 2-(p-aminobenzenesulfamido)-pyrimidine, and 1-phenyl-3-ethyl-4-methyl-5-(p-aminobenzenesulfamido) pyrazole with -(2-chloroethyl)--chlorocrotonaldehyde.For Part XIV see [1].     

Polyhydroxysteroids from the Far-Eastern starfishCtenodiscus crispatus

Four new polyhydroxysteroids, 5-cholesta-3,5,6,15,16,25,26-heptaol, 24-ethyl-5-cholesta-3,5,6,15,28,29-heptaol-29-sulfate, (22E)-24-methyl-5-cholest-22-ene-3,5,6,15,25,26-hexaol-26-sulfate, 24-propyl-5-cholesta-3,5,6,8,15,28,29-heptaol, and the known 5-cholesta-3,5,6,15,16,26-hexaol, have been isolated from the starfishCtenodiscus crispatus.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 10, pp. 1821–1825, October, 1994.     

Steroid compounds from the starfish Lysastrosoma anthosticta collected in the Sea of Japan

Six polyhydroxylated steroids and their derivatives were isolated from the starfish Lysastrosoma anthosticta collected in the Posyet Bay, Sea of Japan. These include a new glycoside of the steroid polyol, lysastroside A (1), which was identified as (25S)-26-O--d-xylopyranosyl-5-cholestane-3,6,8,15,16,26-hexaol, and the previously known pycnopodioside C monoglycoside (2), marthasterone sulfate (3), (25S)-5-cholestane-3,6,8,15,16,26-hexaol (4), (25S)-5-cholestane-3,6,7,8,15,16,26-heptaol (5), and (25S)-5-cholestane-3,6,7,8,15,16,26-heptaol (6). The compounds were tested for the haemolytic activity and the action on the embryogenesis of the sea urchin Strongylocentrotus intermedius.     

Oligomeric proanthocyanidin glycosides ofRhodiola pamiroalaica. II

In a continuation of investigations of proanthocyanidins of the roots ofRhodiola pamiroalaica, we have isolated proanthocyanidins RP-3 and RP-4. Their compositions, structures, and relative configurations have been investigated: RP-3 is 7-O-(6-O-galloyl--D-Glcp)-3-O-galloyl-(-)-epigallocatechin-(4-8)-[(-)-epicatechin-(4-8)-(3-O-galloyl-(-)-epigallocatechin)]₂-(4-8)-[5-O-(-D-GlcpO--D-Glcp)-(+)-catechin], and RP-4 is 7-O-(6-O-galloyl--D-Glcp-3-O-galloyl-(-)-epigallocatechin-(4-8)-[3-O-galloyl-(-)-galloyl-5-(-D-GlcpO--D-Glcp)-(-)-epigallocatechinTranslated from Khimiya Prirodnykh Soedinenii, No. 1, pp. 42–49, January–February, 1999.     

Stereoselective Hydrogenation of Thymol over Rh/alumina in the Presence of β:-cyclodextrin and its Derivatives

Stereoselective hydrogenation of thymol over Rh/alumina in the presence of various equivalents of -cyclodextrin (-CD) and itsderivatives in the solid state was studied. Hydrogenation of thymol in the absence of -CD gave 76.8% epimeric alcohols with a menthol/neomenthol (M/N) ratio of 5.6 and an alcohol/ketone ratio of 4.5, whereas the presence of 0.1 equivalent (to thymol) of -CD gave rise to 94.6% of epimeric alcohols with a M/N ratio of 6.3 and an alcohol/ketone ratio of 45.4. The effect of -cyclodextrin and its derivatives on the modification of the yield and the proportion of epimeric alcohols formed were found to be the salient features of this investigation. Inclusion complexation of thymol by -CD studied by UV-Visible spectroscopyindicated a 2:1 stoichiometry ofthymol: -CD complex with a binding constant value of 480 ±40 M^-2.     

Radiation-induced reactions of cholesterol in an aqueous medium

⁶⁰Co -ray radiolysis of cholesterol /3-hydroxy-5-cholestene/ /I/ in the two-phase system /water-ethyl acetate/ and in the presence of air has been studied using TLC and GC methods. The following products were observed in the irradiated mixture: 3, 7-dihydroxy-5-cholestene /II/, G O. 36, 3-hydroxy-7-keto-5-cholestene /III/, G 1.48, 3-hydroxy-7-keto-5-cholestane /IV/, G 0.22, 3,5,6-trihydroxy-5-cholestane /V/, G 0.83, 5,6-epoxy-3-hydroxy-5-cholestane /VIa/, G 0.26, 5,6-epoxy-3-hydroxy-5-cholestane /VIb/, G 0.24, and 2, 3-dihydroxy-5-cholestene /VII/, G 0.22. The dose dependence of the formation of these products shows that the cholesterol derivatives substituted in the position 7 /II–IV/ are formed from a common precursor — the radical Ia. On the other hand, the products of the 5–C=C double bond reactions /V and VI/ are formed independently. Also the product VII is formed independently. A reaction scheme that is in agreement with these results is proposed.     

Glycosylation of triterpene alcohols of the lupane series

The glycosylation of lupeol, allobetulin, 3-28-dihydroxy-18-lupene, 3-28-dihydroxy-18, 19-epoxylupane and of betulin monoacetates in acetonitrile with mercury cyanide has been studied. The 3- and 28-mono- and the 3,28-di-O--D-glucopyranosides of 3-28-dihydroxy-18-lupene and of 3-28-dihydroxy-18, 19-epoxylupane have been synthesized for the first time. Preparative methods for the synthesis of glucosides of lupeol, of allobetulin, and of betulin 3- and 28-monoacetates are proposed.Pacific Ocean Institute of Bioorganic Chemistry, Far Eastern Branch, USSR Academy of Sciences, Vladivostok. Translated from Khimiya Prirodnykh Soedinenii, No. 2, pp. 212–217, March–April, 1988.     

Inclusion Complexes of Cyclodextrins with Tetrakis(4-carboxyphenyl)porphyrin and Tetrakis(4-sulfonatophenyl)porphyrin in Aqueous Solutions

In neutral and alkaline solutions, tetrakis(4-carboxyphenyl)porphyrin (TCPP) and tetrakis(4-sulfonatophenyl)porphyrin (TSPP) form 1:1 and 2:1 host–guest inclusion complexes with -cyclodextrin (-CD), -cyclodextrin (-CD), and 6-deoxy-6-diethylamino--CD (DEA--CD), except for DEA--CD in alkaline solution. On the other hand, TCPP and TSPP form only 1:1 inclusion complexes with 6-deoxy-6-dihexylamino--CD (DHA--CD). The limited solubilities of DEA--CD in alkaline solution and DHA--CD are likely responsible for no observation of the 2:1 inclusion complex containing DEA--CD in alkaline solution and that containing DHA--CD. The equilibrium constants (Ks) of TCPP and TSPP for the formation of the inclusion complexes have been estimated from the absorption and/or fluorescence intensity changes in neutral and alkaline solutions. The K₂ values, which are the equilibrium constants for the formation of the 2:1 host–guest inclusion complex from the 1:1 inclusion complex, are about one tenth the corresponding K₁ values, except for the -CD–TSPP system in alkaline solution. In neutral solution, where DEA--CD and DHA--CD are in protonated forms, the electrostatic force operates between DEA--CD (DHA--CD) and TCPP (TSPP), leading to the greater K values than those in alkaline solution, where DEA--CD and DHA--CD exist as neutral species.