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. 6, No. 8, 1977
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■ The Synthesis of 2-Substituted 3-Ketotetrahydrothiophenes Using a Highly Active Dieckmann Catalyst. 11-Desoxy-9-thiaprostaglandin
Wihelmus J. Vloon, Eduard R. de Waard,* and Henderikus O. Huisman
*Laboratory of Organic Chemistry, University of Amsterdam, Nieuwe Achtergracht 129,1018 WS Amsterdam, The Netherlands
Abstract
A highly active form of sodium methoxide permits the Dieckmann cyclisation of diesters of general structure 1 at r.t., without concomitant β-elimination of the sulfide moiety. The conversion of 2- (6’-methoxycarbonylhexyl)-3-ketotetrahydrothiophene (4) to 11-desoxy-9-thiaprostaglandin (8) is described.
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■ A Facile Synthesis of Furotropone Derivatives by an Application of Claisen Rearrangement
Hitoshi Takeshita,* Kozo Tajiri, and Isao Kouno
*Instituete of Advanced Material Study, Kyushu University, 6-1, Kasuga-koen, Kasuga 816-8580, Japan
Abstract
The reaction of 1,4-dichloro-trans-2-butene with dipotassium salt of 5-hydroxytropolone in presence of 18-crown-6-ether afforded 5-(4-chloro-trans-2-butenyloxy)tropolone and 2,5-di(4-chloro-trans-2-butenyloxy)tropone which were transformed into furotropone derivatives by dehydrochlorination under the conditions of Claisen rearrangement.
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■ A Stereoelectronic Requirement for the Cyclization of cis- and trans-N-Acrylyloctahydro-7(1H)-quinolones to Decahydro-3H,10H-benzo[i,j]quinolizine-3,10-diones
Takefumi Momose,* Shuji Uchida, Takeshi Imanishi, San-Wong Kim, Nobuko Takahashi, and Sen-ichi Horii
*Faculty of Pharmaceutical Sciences, Osaka University, 1-6 Yamadaoka, Toyonaka, Osaka 560-0043, Japan
Abstract
Cyclization of N-acrylyl-cis- and -trans-octahydro-7(1H)-quinolones to decahydro-3H,10H-benzo[i,j]quinolizine-3,10-diones is described. Possible stereoelectronic control in the intramolecular Michael addition step of cyclization, or a requirement for the successful ring closure, was discussed on the basis of experiments using stereoisomers of the model compounds.
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■ Photolysis of Amino-substituted 1,4-Naphthoquinones. A Novel Synthesis of Heterocyclic Quinones
Mitsuo Akiba,* Yoshiyuki Kosugi, Masao Okuyama, and Toyozo Takada
*School of Pharmacy, Tokyo University of Pharmacy and Life Science, 1432-1 Horinouchi, Hachioji, Tokyo 192-0392, Japan
Abstract
Irradiation of the 2-amino-substituted 1,4-naphthoquinones (1c and 1d) having an active methylene group at the 3-position with high-pressure mercury lamp resulted in the formation of 11,11-bisethoxycarbonyl-1,2,5,10,11,11a-hexahydro-5,10-dioxo-3H-pyrrolo[1,2-a]benz[f]indole or 12,12-bisethoxycarbonyl-1,2,3,4,6,11,12,12a-octahydro-6,11-dioxopyrido[1,2-a]benz[f]indole (6) via the oxazoline (2).
The solvent effects were also examined.
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■ Synthesis of N-Substituted Isoquinolones. Model for the Biosynthesis of Isoquinolone Alkaloids
Somsak Ruchirawat,* Ukrit Borvornvinyanant, Kesra Hantawong, and Yodhathai Thebtaranonth
*Department of Chemistry, Faculty of Science, Mahidol University, Rama 6 Road, Bangkok 10400, Thailand
Abstract
Reactions of enamine intermediate (II) derived from 1-benzylisoquinoline derivative (I) with cuprous chloride/oxygen or singlet oxygen gave isoquinolone derivative (III). The implication of the reaction of enamine intermediate with singlet oxygen to the biosynthesis of isoquinolone alkaloid is discussed.
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■ Reactions of Acyl-aminoquinone Tosylhydrazones. Synthesis of Pyrrolo[1,2-a]indoloquinone via Banzoxazoline by Thermolysis and Photolysis
Mitsuo Akiba, Yoshiyuki Kosugi,* and Toyozo Takada
*School of Pharmacy, Tokyo University of Pharmacy and Life Science, 1432-1 Horinouchi, Hachioji, Tokyo 192-0392, Japan
Abstract
The photolysis and thermolysis of the acetylpyrrolidinoquinone tosylhydrazone (1) afforded the benzoxazoline (5) in a good yield, which then turned into 2,3-dihydro-6,9-dimethyl-5,8-dioxo-1H-pyrrolo[l,2-a]indole (8) having the mother skeleton of mitomycins.
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■ Heteroyohimbines and Their Corresponding Oxindoles, III. A Chemical Correlation through seco-Oxindoles
François Sigaut-Titeux, Louisette Le Men-Olivier, Jean Lévy, and Jean Le Men*
*Laboratoire de Transformation et Syntheses deSubstances Naturelles, Faculté de Pharmacie, Université de Reims-Champagne-Ardenne, 51, rue Cognacq-Jay, F-51096 Reims Cedex, France
Abstract
Seco-oxindoles were obtained both from oxindoles and 7-chloro indolenines through reduction with a 1 : 1 of formic acid and formamide.
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■ Synthesis of 1,2,3,4-Tetrahydro-β-carbolines
Joseph Sandrin, Dave Soerens, Patti Mokry, and James M. Cook*
*Department of Chemistry, University of Wisconsin-Milwaukee, Milwaukee, Wisconsin 53201, U.S.A.
Abstract
The Pictet-Spengler condensation of acid labile aldehydes with Nb-benzyl tryptophan methyl ester and Nb-benzyl tryptamine has been carried out with carbonyl compounds such as glyoxal diethylacetal and ethyl-3-formylpropionate under non-protic conditions. The condensation in aprotic media does not occur with the free base, tryptamine, but works quite well for Nb-benzyl tryptamine. A study of the influence of various Nb-alkyl groups on the ease of cyclization has been explored. This has resulted in synthesis of β-carbolines, such as 1-salicyl-3-methoxycarbonyl-1,2,3,4-tetrahydro-β-carboline (5b), which were previously very difficult to prepare.
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■ New Route to the Synthesis of cis-Jasmone from the Ketene Derivatives
Seiichi Takano,* Tsutomu Sugahara, Masamichi Ishiguro, and Kunio Ogasawara
*Pharmaceutical Institute, Tohoku University, Aobayama, Sendai 980-8578, Japan
Abstract
3-Undecyne-7,10-dione (12) and 2-methyl-5-(3-hexynyl)furan (24), which are key intermediates for the synthesis of cis-jasmone (16), have been synthesized from ketene dimer (6) or the ketene dichlorides, (21) and (22), respectively.
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■ Synthesis of Vinca Alkaloids and Related Compounds. VI. Synthesis of Eburanamonine and Isoburnamonine
Lajos Novák, János Rohály, Csaba Szántay,* and László Czibula
*Institute for Organic Chemistry, Technical University Budapest, H-1521 Budapest, P.O. Box 91Gellért tér 4, Hungary
Abstract
Eburnamonine and isoeburnamonine are synthesized in five steps starting from 3,4-dihydro-β-carboline.
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■ Studies in the (+)-Morphinan Series I. An Alternative Conversion of (+)-Dihydrocodeinone into (+)-Codeine
Ikuo Iijima, Kenner C. Rice,* and J. V. Silverton
*Metabolism, Laboratory of Chemistry, National Institute of Arthritis, Bethesda, Maryland 20014, U.S.A.
Abstract
A novel four-step transformation of (+)-dihydrocodeinone (1) to unnatural (+)-codeine (5) via N-carbethoxy-7-phenylselenonordihydrocodeinone (3) (40% overall yield) is described. The structure and absolute configuration of 3 were confirmed by single crystal X-ray analysis.
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■ Efficient Synthesis of Tryptamine
Seiichi Takano,* Takashi Nishimura, and Kunio Ogasawara
*Pharmaceutical Institute, Tohoku University, Aobayama, Sendai 980-8578, Japan
Abstract
Efficient synthesis of tryptamine by the decarboxylation of tryptophan is described.
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■ The Thieno[3,4-c]-1,2,5-oxadiazole System, a Nonclassical 10π-Electron Heterocycle
Otohiko Tsuge,* Toshiaki Takata, and Michihiko Noguchi
*Research Institute of Industrial Science, Faculty of Engineering, Kyushu University, 6-1, Kasuga-koen, Kasuga 816-8580, Japan
Abstract
Diphenylthieno[3,4-c]-1,2,5-oxadiazole, a new nonclassical 10Π-electron heterocycle, was prepared by two routes starting from dibenzoylfurazane. Cycloadditions of maleimides, dimethyl fumarate and maleate occurred across the thiocarbonyl ylide dipole, giving the corresponding adducts.
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■ A Sinthesis of Flavins by Nitrosative Cyclization of 6-(N-Alkylaminilino)uracils with N-Nitrosodimethylamine-Phosphorus Oxychloride Mixture
Fumio Yoneda,* Kazuo Shinozuka, Yoshiharu Sakuma, and Keitaro Senga
*Faculty of Pharmaceutical Sciences, Kumamoto University, 5-1 Oe-hon-machi, Kumamoto 862-0973, Japan
Abstract
Treatment of 6-(N-alkylanilino)uracils with a mixture of N-nitrosodimethylamine (NDA) and phosphorus oxychloride gave directly the corresponding isoalloxazines (flavins).
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■ A Novel, Mild Preparation of thew 2H-1-Benzopyran-2-one (Coumarin) Ring System
Seppo I. Pennanen*
*Laboratory of Organic Chemistry, Helsinki University of Technology, P.O. Box 6100,FIN-02015 HUT, Espoo, Finland
Abstract
A facile synthesis of coumarins from o-hydroxycarbonyl compounds and 1-diethylaminopropyne is described. The reaction takes place under very mild conditions, giving coumarins in 38-47% yield. The unwanted sideproducts, the (E)-isomers, produced more coumarins after treatment the reaction mixture with acid, thus bringing the overall yields to 68-84%.
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■ Thermolysis of N-Substituted Benzazocine Hydrochlorides
Tetsuji Kametani,* Kazuo Kigasawa, Mineharu Hiiragi, Takehiko Iwata, and Kazumi Ohkubo
*Pharmaceutical Institute, Tohoku University, Aobayama, Sendai 980-8578, Japan
Abstract
Heating 1,2,3,4,5,6-hexahydro-8-hydroxy-6,11-dimethyl-3-(3-methyl-2-butenyl)-2,6-methano-3-benzazocine (1) hydrochloride (pentazocine hydrochloride) in silicon oil or diphenyl ether gave the secondary amine (3) which was formed by an elimination of 3-methyl-2-butenyl group on nitrogen in a moderate yield. The same secondary amine (3) was also obtained from several N-substituted benzazocine derivatives (4, 5 and 6).
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■ The Chemistry of the Banzo[a]quinolizine Ring System
Frank D. Popp* and Raymond F. Watts
*Department of Chemistry, University of Missouri-Kansas City, Kansas City, Missouri 64110, U.S.A.
Abstract
The synthesis and reactions of the benzo(a)quinolizine ring system have been reviewed. This ring system appears in s number of natural products and compounds of medicinal interest.
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■ Pyrroloquinolines I. 1H-Pyrrolo[2,3-b]quinolines
Misbahul Ain Khan* and João Ferreira da Rocha
*Seção de Quimica, Instituto Militar de Engenharia, Urca, 20.000 Rio de Janeiro, RJ, Brazil
Abstract
This article surveys the chemistry of 1H-pyrralo[2,3-b]quinoline including various synthetic routes employed for the preparation of its derivatves, their spectra and some of their properties.