HETEROCYCLES
An International Journal for Reviews and Communications in Heterocyclic ChemistryWeb Edition ISSN: 1881-0942
Published online by The Japan Institute of Heterocyclic Chemistry
Regular Issue
Vol. 24, No. 3, 1986
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■ Efficient Synthesis of (±)-Emetine and (±)-Protoemetinol by the Stereoselective Intramolecular Michael Reaction
Yoshiro Hirai, Atsushi Hagiwara, and TakaoYamazaki*
*Faculty of Pharmaceutical Sciences, Toyama Medical and Pharmaceutical University, 2630 Sugitani, Toyama, Toyama 930-0194, Japan
Abstract
The intramolecular Michael Reaction of 8 and 12 gave stereoselectively 9 and 13, which were converted to the emetine precursor (11) and (±)-protoemetinol (2).
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■ Pyrrolothioenpyrimidines II. Synthesis of 4-Aminopyrrolo[1,2-a]thieno[3,2-e] (and [2,3-e])pyrimidines
Sylvain Rault, Yamien Effi, Jean-Charles Lancelot, and Max Robba*
*Laboratoire de Chimie Thérapeutique, U. F. R. des Sciences Pharmaceutiques, Université de Caen, 1, rue Vaubénard, 14032 Caen Cedex, France
Abstract
Cyclization of the appropriate cyanothienylpyrrolylcarboxylic acid azides in boiling ortho-dichlorobenzene conducted to the corresponding aminopyrrolothienopyrimidines.
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■ The Reactions of 1-Methylpyrrole and 1-Phenylpyrrole with 3,4,5,6-Tetrachloro-1,2-benzoquinone and 1,2-Naphthoquinone
Katsuhiro Saito* and Yoichi Horie
*Faculty of Engineering, Nagoya Institute of Technology, Gokiso-cho, Showa-ku, Nagoya 466-8555, Japan
Abstract
The reactions of pyrrole derivatives with 3,4,5,6-tetrachloro-1,2-benzoquinone and 1,2-naphthoquinone afforded the keto-enol-type and the hydroquinone-type substitution products, respectively, via the nucleophilic attack of the pyrrole derivatives on the o-quinone derivatives.
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■ Intramolecular Cyclisation Using Methyl(bismethylthio)sulphonium Salts. Part 4. Synthesis of Functionalized Indoles and Dihydroindoles
Giuseppe Capozzi,* Rosaria Ottana’, and Giovanni Romeo
*CNR, Centro di Studio Sulla Chimica e la Struttura dei Composti Eterociclici e lolo Applicazioni, c/o Dipartimento di Chimica Organica "Ugo Schiff", Università di Firenze, Via Gino Capponi 9, I-50121 Firenze, Italy
Abstract
The 3-methyl-2-methylthio-1-p-tolylsulphonylindole (7) and the 2-(methylthiomethyl)-1-p-tolylsulphonyldihydroindole (8) were synthesized in one pot reactions of methyl(bismethylthio)sulphonium hexachloroantimonate (1) with 2-(2-propenyl)-N-tosylaniline (5) and 2-allyl-N-tosylaniline (6) respectively.
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■ New Methods and Reagents in Organic Synthesis. 59. Lithium Trimethylsilydiazomethane: A New Synthon for the Preparation of 5-Substituted 1,2,3-Thiadiazoles
Toyohiko Aoyama,* Yuji Iwamoto, and Takayuki Shioiri
*Faculty of Pharmaceutical Sciences, Nagoya City University, Tanabe-dori, Mizuho-ku, Nagoya 467-8603, Japan
Abstract
Lithium trimethylsilyldiazomethane smoothly reacts with thionoesters, dithioesters, and carbon disulfide to give 5-substituted 1,2,3-thiadiazoles.
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■ Trifluoropyruvic Acid Hydrate in Heterocyclic Synthesis, Part II.: Synthesis of Trifluomethylated Benzoxazine, Benzothiazine, and Benzoxazole Derivatives
Mohamed El-said Mustafa, Akio Takaoka, and Nobuo Ishikawa*
*Department of Chemical Technology, Faculty of Engineering, Tokyo Institute of Technology, 2-12-1,Oh-Okayama, Meguro-ku, Tokyo 152-8552, Japan
Abstract
Synthesis of 2-hydroxy-2-trifluoromethyl-2H-1,4-benzoxazin-3(4H)-one derivatives, 3-trifluoromethyl-1,4-benzoxazin-2-one derivatives, 2,3-dihydro-2-trifluoromethylbenzoxazole derivatives and 2-hydroxy-2-trifluoromethyl-2H-1,4-benzothiazin-3(4H)-one, by the reaction of trifluoropyruvic acid hydrate with 4-substituted 2-aminophenols and 2-aminothiophenol, respectively, is reported. The effect of the substituent, in the aminophenol ring, on the ratio of the formed isomers of benzoxazine is also investigated.
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■ Protosappanin B, a New Dibenzoxocin Derivative from Sappan lignum
Masahiro Nagai* and Seiji Nagumo
*Hoshi University, 2-4-41 Ebara, Shinagawa-ku, Tokyo 142-8501, Japan
Abstract
A new dibenzoxocin derivative, named protosappanin B, C16H16O6, white amorphous powder, [α]D15 -11.4° (MeOH) was isolated from the heart-wood of Caesalpinia sappan L. (Leguminosae). It yielded a trimethyl ether (2) on methylation with diazomethane, a tetraacetate (5) and a pentaacetate (6) on acetylation, and sappanin (4) on alkali fusion. Protosappanin B (1) was chemically correlated with trimethyl ether (3) of protosappanin A (7). On the basis of the chemical and spectroscopic evidence, the chemical structure of 1 was established as 3,7,10,11-tetrahydroxy-7,8-dihydro-7(6H)-dibenz[b,d]oxocinmethanol. The cd spectrum of 1 indicated that its biphenyl system preferentially takes S configuration, from which S configuration was tentatively assigned to C-7 of 1.
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■ Medelline, First Bisbenzylisoquinoline Alkaloid with a Methylenedioxy Bridge
Diego Cortes, Jairo Saez, Reynald Hocquemiller, André Cavé,* and Adrien Cavé
*Laboratoire de Chimie Therapeutique, Faculte de Pharmacie, Université Paris XI, 5, rue Jean-Baptiste Clément, 92290 Chatenay-Malabry Cedex, France
Abstract
High resolution MS and 1H-NMR studies indicate that medelline, a minor alkaloid isolated from the bark of Pseudoxandra aff. lucida, is the first known example of a bisbenzylisoquinoline alkaloid with a methylenedioxy bridge joining both halves of the molecule. Medelline is probably biosynthesized via intramolecular condensation of the accompanying major bisbenzylisoquinoline alkaloid, antioquine.
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■ Intramolecular Dipolar Cycloaddition Reactions of C-Aryl Oxaziridines
Albert Padwa* and Konrad F. Koehler
*Department of Chemistry, Emory University, 1521 Pierce Drive Atlanta, Georgia 30322, U.S.A.
Abstract
Thermolysis of several C-aryl oxaziridines containing Π-unsaturation in close proximity to the three-membered ring results in the formation of intramolecular dipolar cycloadducts derived from transient nitrone intermediates.
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■ Phosphono Nucleoside. 1. Synthesis of 2,3’-Anhydro-1’-deoxy-1’-phosphono-1-β-D-fructofuranosyl Uracil
Toshio Tatsuoka,* Kayoko Imao, and Kenji Suzuki
*Suntory Institute for Biochemical Research, Suntory Institute for Biochemical Research, 1-1-1, Wakayamadai, Shimamotocho, Mishimagun, Osaka 618-0024, Japan
Abstract
New phosphono nucleosides, phosphono methyl derivatives of anhydro nucleoside substituted at C-1’, were synthesized starting from 2,3’-anhydro-1-β-D-fructofuranosyl uracil.
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■ A Diadtereoselective Synthesis of threo 2-(α-Hydroxyalkyl)piperdines via Oxacarbamoylinium Ion-(Z)-vinylsilane Cyclization
Shinzo Kano,* Tsutomu Yokomatsu, Yoko Yuasa, and Shiroshi Shibuya
*School of Pharmacy, Tokyo University of Pharmacy and Life Science, 1432-1 Horinouchi, Hachioji, Tokyo 192-0392, Japan
Abstract
Reduction of 5-alkyl-N-(Z-4-silyl-3-butenyl)oxazolidine-2,4-diones (5a,b) with NaBH4, followed by cyclization with TiCl4 afforded the corresponding 1,8a-trans-1-alkyl-1,5,6,8a-tetrahydro-3H-oxazolo[3,4-a]pyridines (9a,b), respectively, with high diastereoselectivity. Catalytic hydrogenation of 9a, followed by alkaline hydrolysis gave threo 2-(α-hydroxyethyl)piperidine (12a). In a similar fashion, threo 2-(α-hydroxypropyl)piperidine (12b), (±)-β-conhydrine, was obtained from 9b.
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■ Synthesis of N6-(2-Oxopyrrolidin-5-yl)adenosine Derivatives
Yoshiyuki Kosugi,* Tatsuo Nagasaka, Fumiko Hamaguchi, and Sadao Ohki
*School of Pharmacy, Tokyo University of Pharmacy and Life Science, 1432-1 Horinouchi, Hachioji, Tokyo 192-0392, Japan
Abstract
A convenient method for introducing a pyrrolidinyl moiety into adenosine N6-position by utilizing the acyliminium activity of ω-alkoxylactams is described. Condensation of 5-alkoxy-2-pyrrolidinones (3a-f) and adenosine triacetate followed by deacetylation gave N6-(2-oxopyrrolidin-5-yl)adenosines (6a-f) in good yields.
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■ Sequential Intramolecular Diels-Alder Reaction and Intermolecular 1,3-Dipolar Cycloaddition Reaction: One-pot [6.6.5]Annelation Reaction Leading to the Formation of Polyazasteroid Type Skeletons
Otohiko Tsuge,* Kazunori Ueno, and Shuji Kanemasa
*Research Institute of Industrial Science, Faculty of Engineering, Kyushu University, 6-1, Kasuga-koen, Kasuga 816-8580, Japan
Abstract
The reaction of methyl o-(2-furylmethyloxy)- and o-[N-ethyl-N-2-(furylmethyl)amino]cinnamate with phenyl azide provided the one-pot [6.6.5]annelation reaction leading to the formation of polyaza-steroid type skeletons through an intramolecular Diels-Alder reaction, followed by an intermolecular 1,3-dipolar cycloaddition reaction.
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■ Preparation of O-Protected (2S,3S)-1,2-Epoxy-3-butanols. Enantioselective Syntheses of (—)-Rhodinose and (+)-Epimuscarine Iodide
Susumi Hatakeyama, Kuniya Sakurai, and Seiichi Takano*
*Pharmaceutical Institute, Tohoku University, Aobayama, Sendai 980-8578, Japan
Abstract
Reductive cleavage of (S,S)-1,2-3,4-diepoxybutane with lithium triethylborohydride, followed by protection gave O-protected (2S,3S)-1,2-epoxy-3-butanols, which were employed in chiral syntheses of (-)-rhodinose and (+)-epimuscarine iodide.
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■ Preparation of Naturally Occurring α-Terthiophenes (2,2’:5’,2’’-Terthiophenes)
Juzo Nakayama,* Yoichi Nakamura, Takayuki Tajiri, and Masamatsu Hoshino
*Department of Chemistry, Faculty of Science, Saitama University, Saitama, Saitama 338-8570, Japan
Abstract
A series of naturally occurring α-terthiophenes (2,2’:5’,2”-terthiophenes) were prepared using readily accessible bis[2-oxo-2-(2-thienyl)ethyl] sulfide as the starting material.
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■ An Enantioselective Synthesis of (—)-6-Aza-6-carbethoxy-2-oxabicyclo[3.3.0]octan-3-one from S-(—)-Malic Acid
Kozo Shishido, Yuko Sukegawa, Keiichiro Fukumoto,* and Tetsuji Kametani
*Pharmaceutical Institute, Tohoku University, Aobayama, Sendai 980-8578, Japan
Abstract
An enantioselective synthesis of the title compound, a precursor for the Geissman lactone, from S-(-)-malic acid is described. The synthesis features the diastereoselective intramolecular Michael reaction of the carbamate (3).
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■ Synthesis and Crystal Structure of Dimethyl N,N’-Diethoxycarbonyl-3,4,7,8-tetrahydro-4,7-phenanthroline-3,8-diphosphonate
Isao Takeuchi, Yasuhiro Shibata, Yoshiki Hamada,* and Masaru Kido
*Faculty of Pharmacy, Meijo University, 150 Yagotoyama, Tenpaku, Nagoya 468-8503, Japan
Abstract
Reaction was performed of 4,7-phenanthroline with trimethyl phosphite and ethyl chlorocarbonate in the presence of sodium iodide in acetonitrile as a solvent, to yield dimethyl N,N’-diethoxycarbonyl-3,4,7,8-tetrahydro-4,7-phenanthroline-3,8-diphosphonate (3) and 3,10-diphosphonate (4). 3,8-Diphosphonate (3) was processed in the column chromatogram and was separated into isomers 3a and 3b whose structures were determined by X-ray analysis.
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■ Nitrogen Assisted Enol Ether Formation
Mauri Lounasmaa* and Arto Tolvanen
*Laboratory for Organic and Bioorganic Chemistry, Technical University of Helsinki, P.O. Box 6100, FIN-02150 HUT, Espoo 15, Finland
Abstract
A nitrogen assisted enol ether formation via cyclic acetal ring opening is described.
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■ A Facile Synthesis of Functionalized Novel Monocyclic trans-β-Lactams
Dilip Kumar Dutta, Romesh Chandra Boruah, and Jagir Singh Sandhu*
*Division of Natural Products Chemistry, Regional Reseach Labratory (CSIR), Jorhat-6, Assam, India
Abstract
Treatment of copper acetylide (1) with aroyl-N-aryl nitrone (2) afforded a novel class of 4-aroyl functionalized monocyclic trans-β-lactam (3). Oxidative N-dearylation of 3e with cerric ammonium nitrite (CAN) gave N-unsubstituted trans-β-lactam (4) in good yield.
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■ Radical Mechanism in the Photoreaction of Organic N-Oxides: Some Paradiazine N,N-Dioxides
Lin Shukun and Wang Hanqing*
*Lanzhou Institute of Chemical Physics, Chinese Academy of Sciences, China
Abstract
Based on the e.s.r. identified nitroxyl radicals 4,5, and 6 produced in organic solvent, a radical mechanism in the photoreaction of some paradiazine N,N-dioxides was suggested. The intermediate radicals 8 were produced , in the photoreduction process such as deoxygenation and hydrogen abstraction, from either triplet excited state or from diradicals 7.
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■ Reaction of 3a,4-Dihydrophthalides with Acetylenic Dienophiles
Michihiko Noguchi,* Shinji Kakimoto, and Shoji Kajigaeshi
*Department of Applied Chemistry, Faculty of Engineering, Yamaguchi University, 2-16-1 Tokiwadai, Ube, Yamaguchi 755-8611, Japan
Abstract
The tricyclo[2.2.2]octa-2,5-diene-4,7-carbolactones, the initially-formed Diels-Alder adducts from 3a,4-dihydrophthalides and acetylenic dienophiles, were so strained that they underwent the retro-Diels-Alder reaction to afford the benzene derivatives in good yields.
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■ Anodic Dimerization of 1,2,3,4-Tetrahydrocabazole and Some of Its Derivatives
James M. Bobbitt,* Paul M. Scola, Chidambar L. Kulkarni, Anthony J. DeNicola, Jr., and Thomas T. -t. Chou
*Department of Chemistry, University of Connecticut, Storrs, CT 06269-3060, U.S.A.
Abstract
The anodic oxidation of 1,2,3,4-tetrahydrocarbazole and two of its derivatives in aqueous acetonitrile at about +0.7 V (vs a standard calomel electrode and using a graphite felt anode) gave dimers having a linkage between carbon 4a of one unit and carbon 7 of the other. The oxidation of 5-methyl-5,6,7,8,9,10-hexahydrocyclohept[b]indole gave a corresponding dimer with a 5a-8’ linkage. This is a correction and an extension of our earlier work.
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■ Synthesis of 2-Mercapto- and 2-Methylthio- Dihydropyrimidine Derivatives by Biguinelli Type Reaction
M. Velpuesta Fernández,* F. J. Herrera, and T. Lupión Cobos
*Departamento de Quimica Organica, Facultad de Ciencias, Universidad de Málaga, Campus de Teations, E-29071 Malaga, Spain
Abstract
The preparation of 6-(2,2-dimethyl-1,3-dioxolan-4-yl)-4-methyl-5-methoxycarbonyl-2-thio-1,2,3,6-tetrahydropyrimidine (1) and 6-(2,2-dimethyl-1,3-dioxolan-4-yl)-4-methyl-2-methylthio-5-methoxycarbonyl-1,6-dihydropyrimidine (6) by Biguinelli type reaction is described. The products resulting from the acidic hydrolysis are studied.
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■ Dynamic 13C N.M.R. Studies of Electrochemically Formed 4a-N’ and 4a-4a’ Dehydrodimers of 1,2,3,4-Tetrahydrocarbazole
James M. Bobbitt,* Thomas T. -t. Chou, and Thomas K. Leipert
*Department of Chemistry, University of Connecticut, Storrs, CT 06269-3060, U.S.A.
Abstract
The electrochemical oxidation of 1,2,3,4-tetrahydrocarbazole in strong base (KOCH3 in CH3OH) at a potential of + 0.15 V (vs S.C.E.) on a graphite felt anode produced a series of dehydrodimers having interesting stereochemical and 13C dynamic N.M.R. properties. The 4a-N’ dimer was isolated as a pair of atropisomers due to restricted rotation around a nitrogen-sp3 carbon bond. Meso and dl forms of the 4a-4a’ dimer were also isolated. Low temperature 13C N.M.R. spectra of the 4a-4a’ dimers showed that they represent a unique case of stereochemistry when rotation is restricted. The case corresponds to a situation where the anti conformation around an acyclic sp3-sp3 carbon-carbon bond is forbidden, and only the two gauche forms are present.
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■ Titanium Trichloride Mediated Reduction of Nitrostyrenes
Akira Sera,* Shoji Fukumoto, Takako Yoneda, and Hiroaki Yamada
*Department of Chemistry, Faculty of Science, Kobe University, Nada-Ku, Kobe 6557-8501, Japan
Abstract
Reactions of substituted nitrostyrenes with aqueous titanium trichloride afforded pyrroles, carbonyl compounds, and oximes. In some instances, divinylamines were produced as well. The reaction mechanism is rationalized taking account of electron transfer to nitroethylenes from Ti(III), followed by protonation, dimerization, cyclization, and hydrolysis.
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■ Bhimberine — A New Indole Alkaloid from Rhazya stricta
Atta-ur-Rahman,* Habib-ur-Rehman, and Sohail Malik
*H. E. J. Postgraduate Institute of Chemistry, University of Karachi, Karachi-75270, Pakistan
Abstract
A new Corynanthe type indole alkaloid, bhimberine, has been isolated from Rhazya stricta. Its structure has been assigned as (1) on the basis of spectral studies. Its stereochemistry has been determined by a series of NOED measurements and 13C-NMR assignments made by DEPT pulse sequences.
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■ Heterocycles 2: Synthesis of 1-Hydroxycarbazoles and Mukonine Isomers
Desikachari Sowmithran* and Karnam Jayarampillai Rajendra Prasad
*Department of Chemistry, Indian Institute of Technology, Powai, Bombay 400 076, India
Abstract
Cyclohexan-1’,2’-dione-1’-diazabenzoic acids obtained from diazotised aminobenzoic acids and 2-hydroxymethylenecyclohexanone on cyclization afford 1-oxo-1,2,3,4-tetrahydrocarbazole derivatives. These on esterification followed by aromaisation and methylation gave the Mukonine isomers, 19, 20 and 22.
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■ Synthesis and Structural Study of New Derivatives of 6,8-Diaryl-3-thia-7-azabicyclo[3.3.1]nonane Systems
Emilio F. Llama* and Gregorio G. Trigo
*Departamento de Química Orgánica y Farmacéutica, Facultad de Farmacia, Universidad Complutense de Madrid, Ciudad Universitaria, 28040 Madrid, Spain
Abstract
The synthesis and structural analysis of new derivatives of the 6,8-diaryil-3-thia-7-azabicyclo[3.3.1]nonane systems were studied. The high reactivity and stereoselectivity presented by this type of system demonstrates the rigid special arrangement acquired by this type of molecule. Nucleophilic attack on the carbonyl group of 6,8-diaryl-3-thia-7-azabicyclo[3.3.1]nonan-9-one (Grignard and Reformatsky reactions) exclusively produce β-isomers, unlike the Bucherer-Bergs reaction which produced a mixture of isomeric hydantoins. The percentage of isomers and the configuration at C-9 was determined by 1H-NMR spectroscopy. An IR study of solid state association in this type of molecule is presented.
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■ Convenient Method for the Synthesis of Some New 2-(2-Carboxystyryl)-5-(2-methoxycarbonylstyryl)furans
Grace Karminski-Zamola,* Miro Bajic, Marina Tkalcic, and Lelja Fiser-Jakic
*Organic Chemistry Department, Faculty of Technology, University of Zagreb, Marulicev trg 20, 41000 Zagreb, Croatia
Abstract
It is described very convenient method for the synthesis of some 2-(2-carboxystyryl)-5-(2-methoxycarbonylstyryl)furans. The configuration on the both ethene chain is “E”.
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■ Synthesis of Homoadamantano[4,5-d]imidazoles via Photochemical Ring Transformations
Shoji Eguchi,* Koji Asai, and Tadashi Sasaki
*Faculty of Engineering, Nagoya University, Chikusa, Nagoya, Aichi 464-8601, Japan
Abstract
The irradiation of homoadamantano[4,5-b]-5’,6’-dihydropyrazines afforded homoadamantano[4,5-d]imidazoles via photochemical ring cleavage followed by cyclization and proton transfer.