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. 57, No. 9, 2002
Published online:
■ Intermolecular Photoreaction of Arenecarbothioamide with 3-Methyl- and 2,4-Dimethylfurans: a Novel Formation of 2-Arylthiophene Derivatives through Photoinduced Reaction
Kazuaki Oda,* Hisao Tsujita, and Minoru Machida*
*Faculty of Pharmaceutical Sciences, Health Sciences University of Hokkaido, Ishikari-Tobetsu, Hokkaido 061-0293, Japan
Abstract
Photoreaction of arenecarbothioamides (1) with 3-methylfuran (2) in benzene-acetone mixed solvent gave 5-aryl-2,3-dihydrothiophene derivatives (3) accompanied by pyrrole compounds.
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■ Asymmetric Photocyclizations of Chiral Auxiliary-substituted N-Acyl-α-dehydroamino Acids into 1,2-Dihydrobenzoquinolinone Derivatives
Kei Maekawa,* Tetsutaro Igarashi, Kanji Kubo, and Tadamitsu Sakurai*
*Departmnet of Applied Chemistry, Faculty of Engineering
Kanagawa University, 3-27-1 Rokkakubashi, Kanagawa-ku, Yokohama 221-8686, Japan
Abstract
The irradiation of the title compounds [(Z)-1] with an (S)-alanine auxiliary in methanol containing a tertiary amine afforded a diastereomeric mixture of (S,S)- and (R,S)-1,2-dihydrobenzo[f]quinolinones, along with (E)-1, benzo[f]isoquinoline, and 1-azetine derivatives. It was found that electron transfer-initiated photocyclizations of (Z)-1 in polar solvents give (S,S)-1,2-dihydrobenzoquinolinones in diastereomeric excess whose value varies from 0 to 55% depending on the properties of the amine and solvent employed.
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■ A New General Route to Novel Azomethine Ylides for Cycloaddition Reactions
François-Xavier Lery, Nicole Kunesch, Pascal George, and Henri-Philippe Husson*
*Laboratoire de Pharmacognosie,UMR 8638 associee au CNRS, Faculté des Sciences Pharmaceutiques et Biologiques, Université René Descartes, 4, Avenue de l’Observatoire, 75270 Paris Cedex, France
Abstract
A general method providing access to stabilized azomethine ylides generated from substituted 1,3- and 3,1-aryloxazines was developed. A two-step sequence based on 1,3-dipolar cycloaddition reactions with N-arylmaleimides was elaborated to give a series of highly substituted pyrrolopyrrolidines in good yields.
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■ On Selective Functionalization of meso-Tetraphenylporphyrin Derivatives by Vicarious Nucleophilic Substitution of Hydrogen
Stanislaw Ostrowski,* Agnieszka Mikus, Young Key Shim, Jong-Cheol Lee, Eun-Young Seo, Kee-In Lee, and Marian Olejnik
*Institute of Chemistry, University of Podlasie, ul. 3-go Maja 54, 08-110 Siedlce, Poland
Abstract
The studies on selective derivatization of meso-tetraphenylpor-phyrin (TPP) using nitration and Vicarious Nucleophilic Substitution of Hydrogen (VNS) are reported. TPP, its metal complexes and N,N-dimethyl substituted derivatives do not enter the VNS reaction. On the other hand, meso-substituted TPP results in the mono-nitration of one phenyl ring and the intermediate obtained, after simple transformation to its metal complex, reacts with carbanions bearing leaving groups at the carbanionic center, according to VNS scheme. This gives new opportunities for the peripheral functionalization of porphyrins. In this work the copper and zinc complexes were investigated.
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■ Synthesis of Analogs of Wasabi Phytoalexin (Methyl 1-Methoxyindole-3-carboxylate)
Koji Yamada, Yukiko Kanbayashi, Saori Tomioka, and Masanori Somei*
*Faculty of Pharmaceutical Scicences, Kanazawa University, 13-1 Takara-machi, Kanazawa 920-0934, Japan
Abstract
Syntheses of wasabi phytoalexin analogs, such as 6-bromo-5-iodo, 2-bromo-5-iodo, 6-nitro, 5-chloroacetyl, and 6-chloroacetyl congeners, are reported. An interesting effect of the 1-methoxy group on the regioselectivity of electrophilic substitution reactions on indole nucleus is observed.
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■ Synthesis of 2- and 3-Benzoylindoles by Friedel-Crafts Reaction of Indole-2,3-dicarboxylic Anhydrides with Anisoles
Yasuyoshi Miki,* Yasuhiko Tsuzaki, Chika Kai, and Hiroko Hachiken
*Faculty of Pharmaceutical Sciences, Kinki University, 3-4-1, Kowakae, Higashi-Osaka 577-8502, Japan
Abstract
Reaction of 1-benzylindole-2,3-dicarboxylic anhydride with anisole in the presence of titanium(IV) chloride gave 2-(4-methoxybenzoyl)indole-3-carboxylic acid as the sole product. However, 1-benzenesulfonylindole-2,3-dicarboxylic anhydride with anisole afforded 3-(4-methoxybenzoyl)indole-2-carboxylic acid. These carboxylic acids could be converted to the corresponding benzoylindoles.
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■ Synthesis of 5H-Benzo[b]carbazole-6,11-diones from Benzoylindolecarboxylic Acids
Yasuyoshi Miki,* Yasuhiko Tsuzaki, and Hana Matsukida
*Faculty of Pharmaceutical Sciences, Kinki University, 3-4-1, Kowakae, Higashi-Osaka 577-8502, Japan
Abstract
Treatment of 1-benzyl-3-(4-methoxybenzoyl)indole-2-carboxylic acid with phosphorus pentachloride gave the corresponding acid chloride, which was treated with titanium(IV) chloride to afford 9-methoxy-5H-benzo[b]carbazole-6,11-dione. In a similar manner, 1-benzenesulfonyl-2-(4-methoxybenzoyl)indole-3-carboxylic acid provided 9-methoxy-5H-benzo[b]carbazole-6,11-dione. However, 1-benzyl-3-(4-methoxybenzyl)indole-2-carboxylic acid could be converted to 8-methoxy-5H-benzo[b]carbazole-6,11-dione.
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■ Amides from the Seeds of Piper nigrum Linn. and Their Insecticidal Activity
Bina S. Siddiqui,* Tahsin Gulzar, and Sabira Begum
*H. E. J. Research Institute of Chemistry, University of Karachi, Karachi-75270, Pakistan
Abstract
Two new amides pipertipine (1) and pipercitine (2) have been isolated from the dried seeds of Piper nigrum along with eight known constituents of β-sitosterol, (2E, 4E, 8Z)-N-isobutyleicosatrienamide, pellitorine, guineensine, piperine, piperettine, pipericine, and (3,4-methylenedioxyphenyl)cinnamaldehyde. The structures of 1 and 2 have been elucidated as 1-[8-(3′, 4′-methylenedioxyphenyl)-(7E)-octaenoyl]piperidine and 1-[(2E)-octadecenoyl]piperidine, through extensive spectral studies including 2D NMR. New compounds 1 and 2 and most of the known exhibited toxicity against fourth- instar larvae of Aedes aegypti.
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■ Syntheses of 3-Aminoquinoline-2,4(1H,3H)-diones
Stanislav Kafka, Antonín Klásek,* Jirí Polis, and Janez Kosmrlj
*Faculty of Technology, Tomas Bata University in Zlín, 762 72 Zlín, Czech Republic
Abstract
Reaction of 3-chloro- (2) and 3-bromoquinoline-2,4(1H,3H)-diones (3) with excess of primary alkyl- or arylamines in dimethylformamide provides the corresponding 3-alkyl- or 3-arylamino derivatives (4). Compounds (4) with the primary amino group at the 3 position were best prepared by reaction of 2 with in situ generated ammonia under anhydrous conditions. An alternative approach to the primary amines (4) via reduction of 3-azidoquinoline-2,4(1H,3H)-diones (5) was investigated. The reduction of 5 with zinc in acetic acid gave moderate to good yields of the desired products, while the reaction with triphenylphosphine afforded exclusively 4-hydroxyquinolin-2(1H)-one (1).
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■ Convenient Preparation of Tacrine Derivatives by the Reduction of 9-Aminoacridines with Nickel-aluminum Alloy
Kichinosuke Kamata,* Yoh-ichi Tominaga, Akiyoshi Tori-i, Thies Thiemann, Kazufumi Takahashi, and Shuntaro Mataka*
*Instituete of Advanced Material Study, Kyushu University, 6-1, Kasuga-koen, Kasuga 816-8580, Japan
Abstract
9-Amino-1,2,3,4-tetrahydro- and 9-amino-1,2,3,4,5,6,7,8-octahydro-acridine derivatives (2 and 3) were conveniently prepared in the reduction of the corresponding 2-substituted 9-aminoacridines (1a-f) with nickel-aluminum alloy under basic conditions. The reduction is dependent upon the nature of the substituent in the 2-position of the starting 9-aminoacridines.
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■ A Convenient Synthesis of Highly Conjugated 5-Nitroimidazoles
Kamel Benakli, Thierry Terme, José Maldonado, and Patrice Vanelle*
*Laboratoire de Chimie Organique, Faculté de Pharmacie, Université de la Méditerranée, 27, Boulevard Jean Moulin, 13385 Marseille Cedex 05, France
Abstract
A new series of highly conjugated 5-nitroimidazoles was prepared using electron transfer methodology in multi-steps synthesis from 2-chloromethyl-1-methyl-5-nitro-1H-imidazole.
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■ Unexpected Formation of Pyrrolo[2,1-b]thiazoles by Rearrangement of α-Hydroxydihydro-1,4-thiazines
Hoh-Gyu Hahn,* Kee Dal Nam, and Heduck Mah
*Organic Chemistry Laboratory, Korea Institute of Science and Technology, P.O. Box 131, Cheongryang, Seoul 136-791, Korea
Abstract
A new synthesis of pyrrolo[2,1-b]thiazoles (5) is described. Hydrolysis of acetoxy dihydro-1,4-thiazine (2) prepared by Pummerer reaction of dihydro-1,4-thiazine sulfoxide gave the intermediate α-hydroxy sulfide (4). Dehydration of 4 gave pyrrolo[2,1-b]thiazoles (5). The reaction mechanism for the formation of 5 including the intermediate thiol (6) is discussed.
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■ The Heterocyclic Natural Products of Gorgonian Corals of Genus Briareum Exclusive of Briarane-type Diterpenoids
Ping-Jyun Sung* and Ming-Chyuan Chen
*National Museum of Marine Biology and Aquarium, 2 Houwan Road, Checheng, Pingtung, Taiwan 944, Taiwan, R.O.C.
Abstract
An overview on the heterocyclic natural products of gorgonian octocorals of genus Briareum is presented. Based on previous studies, most of the heterocyclic natural products from Briareum are diterpenoid metabolites, including eunicellin, asbestinane, cembrane, and briarane-type derivatives. The structures, names, biological activities, and references of these natural products exclusive of briaranes are described in this review.
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■ 1,3-Dihydro-2,1-benzisothiazole 2,2-Dioxides (Benzosultams) in Organic Synthesis
Krzysztof Wojciechowski
*Institute of Organic Chemistry, Polish Academy of Sciences, ul. Kasprzaka 44/52, P.O.Box 58, PL-01-224 Warszawa 42, Poland
Abstract
Methods of synthesis of 1,3-dihydro-2,1-benzisothiazole 2,2-dioxides and their applications in the synthesis of heterocyclic compounds are reviewed.