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. 19, No. 11, 1982
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■ Synthesis of Cyclodextrin Appended Porphyrin and Its Guest-Induced Super Slow Multiconformational Changes
Nagao Kobayashi, Uichi Akiba, Kastuko Takatori, Akihiko Ueno, and Tetsuo Osa
*Department of Chemistry, Graduate School of Science, Tohoku University, Aramaki, Aoba-ku, sendai 980-8578, Japan
Abstract
Porphyrin and cyclodextrin were flexibly linked through one covalent bond and some of its properties in solution, especially, guest-induced, super slow diverse CD changes in aqueous solution are reported.
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■ Hindered Rotation in 2-Arylindolines. Isolation of Diastereomeric Atropisomers
Takeo Kitamura, Toshitaka Koga, Kazunobu Harano, and Tanezo Taguchi
*Daiichi College of Pharmaceutical Sciences, 22-1 Tamagawa-cho, Minami-ku, Fukuoka 815-0037
Abstract
The condensation reaction of 1-(p-chlorobenzoyl)-2-hydroxy-3,3-dimethylindoline with β-naphthol gave a pair of diastereomeric atropisomers due to restricted rotation about an sp3-sp2 carbon bond.
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■ Chemistry of Azidoquinones. Synthesis and Thermolysis of the Azido-o-quinone, 3-Azido-4-(4-methylcyclohexa-3,6-dione-1,4-dienyl)-1,2-naphthoquinone
Steward P. Lee and Harold W. Moore
*Department of Chemistrym University of California, One Shields Avenue, Davis, CA 95616-5295, U.S.A.
Abstract
The synthesis and thermal decomposition of 3-azido-4-(4-methylcyclohexa-3,6-dione-1,4-dienyl)1,2-naphthoquinone (7) is reported. This is the first example of the thermal chemistry of an azido-o-quinone and is shown to undergo facile ring closure to the carbazolebisquinone 9. Analogous ring closures were observed for the hydroquinone derivatives of 7, i.e., 10a and 10b.
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■ Diels-Alder Cycloaddition of 1,3-Disubstituted Butadienes to Isoquinolinopyrrolinediones: Solvent and Temperature Effect on cis-end to cis-exo Isomerization of the Adduct
Yoshisuke Tsuda, Takeshi Ohshima, Takehiro Sano, and Jun Toda
*School of Pharmacy, Hokuriku University, 3-Ho, Kanagawa machi, Kanazawa 920-1181, Japan
Abstract
Diels-Alder cycloaddition of 1,3-disubstituted butadienes to isoquinolinopyrrolinediones gives two cycloadducts, the previously reported cis-endo (regarding the dioxopyrroline ring) adduct and the new cis-exo adduct, with a variable ratio largely depending on the solvent and temperature of the reaction. Determination of their stereochemistries and isomerization experiments proved that the former adduct is a kinetic and the latter adduct is a thermodynamic product. Acceleration of dissociation and recombination of the former to the latter adduct in polar solvents (such as CHCl3) was also suggested.
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■ Structures of Forsythoside C and D, Antibacterial Principles of Forsythia suspensa Fruits
Katsuya Endo and Hiroshi Hikino
*Pharmaceutical Institute, Tohoku University, Aobayama, Sendai 980-8578, Japan
Abstract
New glycosides, forsythoside C and forsythoside D, which exhibit antibacterial activity, have been isolated from Forsythia suspensa fruits. Degradative and spectroscopic studies have established their structures as represented by formulas I and II, respectively.
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■ The Synthesis of 7,8-Dimethoxy-1-(3,4-dimethoxybenzyl)-2,3-dihydro-1H-3-benzazepine and Related Compounds
Roger F. Newton, Malcorm Sainsbury, and Paul L. R. Stanley
*Glaxo Group Research Limited, Ware, Hertfordshire SG12 0DJ, U.K.
Abstract
The title compound has been synthesised by the acid catalysed cyclisation of 2,3-bis-(3,4-dimethoxyphenyl)propylaminoacetaldehyde diethylacetal. The preparation of 7,8-dimethoxy-1-(3,4-dimethoxybenzylidene-4,5-dihydro-1H-3-benzazepine and its hydrogenation products is also described.
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■ Utilization of Sulfoxides Containing Pyridine Nuclei as a New Type of Phase Transfer Catalysts: IV
Naomichi Furukawa, Satoshi Ogawa, Tsutomu Kawai, Keiko Kashimoto, Hisashi Fujihara, and Shigeru Oae
*Department of Chemistry, University of Tsukubaa, 1-1-1 Ten-nodai, Tsukuba-shi, Ibaraki, 305-8571, Japan
Abstract
Several sulfoxides containing pyridine nuclei were synthesized and their pKa values were determined. These sulfoxides were found to be good phase transfer catalysts which can promote alkylation reactions of phanylacetonitrile and benzyl methyl ketone with alkyl halides, and also can mediate the transport of alkali metal cations such as Li+, Na+, K+, through the liquid-liquid membrane system.
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■ Oxygen-bridged Thia[15]annulenes: Demonstration of a Strong Paramagnetic Ring Current in a 4nπ-Thia-annulene (n=4)
Haru Ogawa, Taiji Imoto, Izumi Miyamoto, Yoichi Taniguchi, Toshitaka Koga, and Yasuyoshi Nogami
*Faculty of Pharmaceutical Sciences, Kyushu University, 3-1-1 Maidashi, Higashi-ku, Fukuoka 812-8582, Japan
Abstract
The synthesis of 4,7:10,13-diepoxy-2-trans-8,14-di-cis-thia[15]annulene (9) and 4,7:10,13-diepoxy-2,8,14-tri-cis-thia[15]annulene (10) is described. The 1H-nmr spectrum of (9) revealed the existence of a paramagnetic ring current, showing that (9) has a planar and diminished bond alternate rigid frame, as expected for an anti-aromatic 16π system. Conversely, the 1H-nmr spectrum of (10) revealed that (10) is atropic and consequently non-planar.
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■ Δ2-Pyrroline-4,5-dione, and Ambident Dienophile in Diels-Alder Reaction
Yoshisuke Tsuda, Takeshi Ohshima, Takehiro Sano, and Jun Toda
*School of Pharmacy, Hokuriku University, 3-Ho, Kanagawa machi, Kanazawa 920-1181, Japan
Abstract
Thermal cycloaddition of activated 1,3-butadienes to benzazepinopyrrolinedione 4 took place to C=O instead of C=C in the enone system, yielding dihydropyrane derivatives. The change of reactivity compared to isoquinolinopyrrolinedione 1 was attributed to the steric hindrance on C=C of the enone due to non-planarity of the aromatic ring and the dioxopyrroline ring.
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■ Photocyclization of Succinimide Derivatives with Amido Group in Side Chains. Synthesis of Tricyclic Pyrrolo[1,2-a]pyrazine Ring Systems
Minoru Machida, Sumiko Oyadomari, Haruko Takechi, Kosei Ohno, and Yuichi Kanaoka
*Faculty of Pharmaceutical Scicences, Higashinihonngakuen University, 1757 Kanazawa, Toubetu-cho, Ishikari-gun, Hokkaodo 061-0212, Japan
Abstract
Succinimide derivatives (2) with amido group in their side chains were irradiated in acetonitrile to give bi- and tricyclic pyrrolo[1,2-a]pyrazines (3) .
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■ Ring-Transformation of 1,2,4-Oxadiazine Derivatives into 4-Hydroxypyrimidine Derivatives: Catalytic Hydrogenation of 3-Aryl-5-ethoxycarbonylmethelene-5,6-dihydro-4H-1,2,4-oxadiazine Derivatives
Katsumi Tabei, Estuko Kawashima, Toyozo Takada, and Tetsuzo Kato
*Tokyo University of Pharmacy and Life Science, 1432-1 Horinouchi, Hachioji, Tokyo 192-0392, Japan
Abstract
Catalytic hydrogenation of 3-aryl-5-ethoxycarbonylmethylene-5,6-dihydro-4H-1,2,4-oxadiazine derivatives (1) is described. The method leads to new synthesis of 2-aryl-4-hydroxypyrimidine derivatives (3) involving cyclization of ethyl 3-benzimidoylimino-4-hydroxybutanoate derivatives (2) by the elimination of ethanol. Nickel catalyzed hydrogenation of 1 gave ethyl 2-aryl-4-oxazolylacetate (4) as a by-product besides product 3.
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■ A Photochemical Conversion of a Spirobenzylisoquinoline into a Secoberbine
Belkis Gözler, Maurice Shamma, Zarouhi Mardirossian, and Violeta Chervenkova
*Department of Chemistry, The Pennsylvania State University, York Campus, P1031 Edgecomb Avenue, York, Pennsylvania 17403, U.S.A.
Abstract
Oxidative photolysis of the spirobenzylisoquinoline alkaloid (—)-fumaricine (1) provides the secoberbine (±)-2.
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■ Photolysis of Quinolyl and Isoquinolyl Azides in Alcohols Containing Sulfuric Acid
Hiroyuki Sawanishi, Toyoko Hirai, and Takashi Tsuchiya
*School of Pharmacy, Hokuriku University, 3-Ho, Kanagawa machi, Kanazawa 920-1181, Japan
Abstract
Photolysis of 3-azidoquinoline, 4-azidoisoquinoline, and 4-azidoquinoline N-oxide in alcohols containing sulfuric acid gave the corresponding α-alkoxy amino compounds (2,3,5,7) via nitrenium ion intermediates. In contrast, 3-azidoquinoline N-oxide, 5-azido- and 8-azidoquinoline, and 5-azidoisoquinoline, upon irradiation under similar conditions, gave the different type of α-alkoxy amino compounds such as 9 and 13 via azirine or azacycloheptatetraene intermediates.
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■ Stereoselective Total Synthesis of Necine Bases, (±)-Retronecine and (±)-Turneforcidine
Tatsushi Ohsawa, Masataka Ihara, Keiichiro Fukumoto, and Tetsuji Kametani
*Hoshi University, 2-4-41 Ebara, Shinagawa-ku, Tokyo 142-8501, Japan
Abstract
(±)-Retronecine (2) was synthesised by a coupling of a regioselective [3,3]sigmatropic rearrangement with a sulphenocycloamination as key steps and the first stereoselective total synthesis of (±)-turneforcidine (3) was also accomplished.
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■ An Unexpected Reaction of a 3-Amino-2H-azirine with 1,3-Benzoxazin-2,4-dione
B. Parthasarathi Chandrasekhar, Jost H. Bieri, Heinz Heimgartner, Gabriel Germain, and Jean-Paul Declercq
*Institute of Organic Chemistry, University of Zürich, Winterthurerstrasse 190, CH-8057 Zürich, Switzerland
Abstract
The reaction of 3-dimethylamino-2,2-dimethyl-2H-azirine (1) with 1,3-benzoxazin-2,4-dione (3) in refluxing 2-propanol led not to the formation of a medium sized heterocycle but to the formation of the imidazo[2,1-b]-1,3-benzoxazin-5-one 4 and the imidazolin-2-one 5 in 33% and 74% yield, respectively. The structure of 4 has been confirmed by X-ray crystallographic analysis while 5 has been identified by comparison with an independently synthesized material (cf. Scheme 2). In Scheme 3 a reaction mechanism for the formation of 4 and 5 is suggested.
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■ 3-Chloro-3-cyano-1-(2,4-dimethoxybenzyl)-4-phenylthioazetidin-2-one
Malcolm M. Campbell and David K. Donald
*Department of Chemistry, Heriot-Watt University, Riccarton, Currie, Edinburgh EH14 4AS, U.K.
Abstract
The Moore azetidin-2-one synthetic stratagem has been further developed to give the title compound, a potentially useful synthon in β-lactam chemistry.
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■ Synthesis of 9-Methoxy-1,6-diazaphenalene
Robert W. Weber and James M. Cook
*Department of Chemistry, University of Wisconsin-Milwaukee, Milwaukee, Wisconsin 53201, U.S.A.
Abstract
A new entry into the 1,6-diazaphenalene ring system via carbonylation of the anion derived from 4-methyl-5-amino-6-methoxyquinoline 6 is described. This method permits the preparation of 1,6-diazaphenalene derivatives not easily accessible through substitution reactions on the parent heterocycle.
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■ Triethylamine Solubilised Phosphorous Pentasulphide as Thiation Reagent: A Novel Route to Totally Thiated Heterocycles
Bhabagrahi Dash, E. Khalli Dora, and Chandra Sekhar Panda
*Department of Chemistry, Berhampur University, Berhampur-760 007, Orissa, India
Abstract
Triethylamine solubilised phosphorous pentasulphide (P4S10) has been evolved as the thiation agent in heterocycles such as substituted benzoxazin-4-ones, 2-pyrazolin-4-ones and pyrimidine-2,5-dione derivatives. The simple and convenient operation involving stirring (24 h) of the reaction mixture at room temperature results in the isolation of the desired products in quantitative yield.
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■ Synthesis of Some New 6-Substituted Carbapenem Derivatives
Kapa Prasad, Kurt Adlgasser, Rajiv Sharma, and Peter Stütz
*Sandoz Research Institute, A-1235 Vieena, Austria
Abstract
Carbapenem acetonyl esters 9-12 and sodium salts 13-15 were prepared utilizing 3-substituted 4-acetoxyazetidinones as starting materials.
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■ Marsupsin, a New Benzofuranone from Pterocarpus marsupium Roxb.
Rakesh Maurya, Anil B. Ray, Francis K. Duah, David J. Slatkin, and Paul L. Schiff, Jr.
*Department of Pharmacognosy, School of Pharmacy, University of Pittsburgh, Pittsburgh, PA 15261, U.S.A.
Abstract
Chromatography of an ethyl acetate extract of defatted Pterocarpus Marsupium Roxb. (Leguminosae) heartwood over silica gel afforded marsupsin (1) which was characterized as a new 2-hydroxy-2-benzyl-3(2H)-benzofuranone by a consideration of physicochemical data and conversion to triacetylmarsupsin (3) and trimethylmarsupsin (tetramethylmaesopsin) (2).
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■ Byproducts in the O-Phenyltetrazolylation of (±)-2,4-Dihydroxy-N-formylmorphinan-6-one. Alkylation at C-5
Fu-Lian Hsu, Kenner C. Rice, and Arnold Brossi
*Section of Medicinal Chemistry, Laboratory of Bioorganic Chrmistry, NIDDK, National Institute of Health, Bethesda, MD 20892, U.S.A.
Abstract
O-Alkylation of (±)-2,4-dihydroxy-N-formylmorphinan-6-one (4) with 5-chloro-1-phenyl-1H-tetrazole in DMF in the presence of potassium carbonate afforded substantial amounts of the C-5 alkylated ketones 6 and 7 in addition to the desired ketone 5. The structures of 5, 6 and 7 were supported by chemical correlation and on the basis of spectral data.
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■ Novel Applications of the Modified Polonovski Reaction — II. Regiocontrolled Iminium Ion Formation
Mauri Lounasmaa and Ari Koskinen
*Laboratory of Organic Chemistry, Helsinki University of Technology, P.O. Box 6100,FIN-02015 HUT, Espoo, Finland
Abstract
Suitably substituted α-piperidinoacetic esters can be transformed to either the corresponding endocyclic or exocyclic α-amino nitriles. The latter case is accompanied with decarboxylation.
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■ Ring Transformations of Oxazoles and Their Benzo Analogues. New Synthetic Route for 2H-Imidazo[2,1-b][1,3,4]thiadiazine and N-Heteroaryl-o-aminophenol
Tadashi Sasaki, Eikoh Ito, and Ikuo Shimizu
*Institute of Applied Organic Chemistry, Faculty of Engineering, Nagoya University, Chikusa, Nagoya, Aichi 464-8601, Japan
Abstract
Ring transformations of certain functionalized oxazoles and their benzo analogues were studied. The α-(oxazol-2-ylthio) ketones 3a, b, c, and e gave 2H-imidazo[2,1-b][1,3,4]thiadiazines (4a, b, c, and e) on treatment with hydrazine hydrate in acetic acid. Similar treatment of ketones 3d and f-h resulted in the formation of the complex mixtures. The α-(benzoxazol-2-ylthio) ketones 5a and b reacted with ammonium acetate in acetic acid to give 2-(2-hydroxyphenylamino)thiazoles 6a and b in quantitative yields. With hydrazine, 5a afforded thiazoline derivative 7 while 5b provided 1,3,4-thiadiazine derivative 8 under the similar conditions. Aminophenols 6a and b were further converted into 1,4-benzoxazines 10a and b by treating with chloroacetone followed by phosphorus pentoxide in benzene. Mechanisms for these transformations are proposed.
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■ New 1,10-Phenanthrolinethioles
Max Hunziker and Urs Hauser
*Department of Physics, Stanford University, Stanford, CA 94305, U.S.A.
Abstract
Reaction of KHS with 2-chloro- and 2,9-dichloro-1,10-phenanthroline in ethanol at elevated temperature and pressure afforded the corresponding phenanthrolinethiols which were characterized by spectroscopic and chemical methods. 2,2’-Thiobis(1,10-phenanthroline) and other heteroaryl sulfides derived from 1,10-phenanthroline-2-thiol were prepared by amide promoted nucleophilic substitution of aryl halide by thiolate anion.
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■ Oxidation of 2-Indolinones with Cobalt(II) Schiff’s Base Complexes
Akira Inada and Yutaka Morita
*Faculty of Pharmaceutical Sciences, Josai University, 1-1 Keyakidai, Sakado, Saitama 350-0295, Japan
Abstract
The oxidation of 2-indolinones (1) catalysed with cobalt(II) Schiff’s base complexes gave isatins (2), O-aminoketones (3). 3-hydroxy-2-indolinones (4), and dimers (5).
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■ A Formation of Pyrrolo[2,1-a]isoquinoline Derivatives by the Reaction of Isoquinoline N-Oxides with Ethyl Propiolate
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
Diethyl pyrrolo[2,1-a]isoquinoline-1,3-dicarboxylates were obtained by the reaction of the corresponding isoquinoline N-oxides with ethyl propiolate.
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■ Ring Expansion of 2-Ethynylthiacycloalkanes via Sulfonium Ylides by [2,3]-Sigmatropic Rearrangement
Haruki Sashida and Takashi Tsuchiya
*School of Pharmacy, Hokuriku University, 3-Ho, Kanagawa machi, Kanazawa 920-1181, Japan
Abstract
Treatment of the α-ethynyl cyclic sulfonium salts (8) with DBU gave the corresponding ring-expansion products (11), presumably via the allenic intermediates (10) derived from the initially formed S-ylides (9) by [2,3]-sigmatropic rearrangement.
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■ Base-catalyzed Racemization of Nicotine
Yasuko Tsujino, Saizo Shibata, Akio Katsuyama, Takuro Kisaki, and Hajime Kaneko
*Central Reseasrch Institute, Japan Tobacco Inc., 6-2, Umegaoka, Midori-ku, Yokohama, Kanagawa 227-8512, Japan
Abstract
Catalytic activities of various bases on the racemization of nicotine were investigated. S-(—)-Nicotine was completely racemized by refluxing with a catalytic amount of potassium-t-butoxide for a short time. Thus, a facile preparation method of racemic nicotine was provided.
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■ Synthesis and Reactivity of 2-Azabicyclo[2.2.1]heptanes, Heptenes and Heptadienes
Dominique Blondet and Christophe Morin
*Unité de Chimie Organique, Départment de Biochimie et de Génétique Moléculaire, ERA/CNRS927, Institut Pasteur, 28, rue du Docteur Roux, 75724 Paris, Cedex 15, France
Abstract
It is purpose of this review to cover all known methods of preparation of 2-azabicyclo[2.2.1]heptanes, heptenes, and heptadienes. The reactivity of these systems will then be discussed, stressing their synthetic potential as it has already been demonstrated for example in the field of nucleoside antibiotics.
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■ Syntheses and Reactions of Cyclobutane-fused Six-membered Heteroaromatics
Chikara Kaneko and Toshihiko Naito
*Pharmaceutical Institute, Tohoku University, Aobayama, Sendai 980-8578, Japan
Abstract
Syntheses of cyclobutane-fused heteroaromatics and their reactions via the corresponding heterocyclic diquinomethane intermediates are reviewed.