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. 3, 1977
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■ Synthesis of New Fundamental Heterocycles VI. Synthesis of 1-Azaxanthene
Henri Sliwa* and Dominique Blondeau
*Laboratoire de Chimie Organique et Environnement, Université des Sciences et Technologies de Lille, Bat. C4 -2eme Etage 59655 Villeneuve d‘ Ascq Cedex, France
Abstract
Condensation of the Mannich base of 3-pyridinol with 1-ethoxycyclohexene yielded 5,6,7,8,8a,10a-hexahydro-10a-ethoxy-1-azaxanthene (5) which was converted to 5,6,7,8-tetrahydro-1-azaxanthene (3). In contrast, the condensation product resulting from cyclohexanae could not be dehydrated to (3). The tetrahydro derivative (3) was aromatized to the novel and fundamental heterocycle, 1-azaxanthene (2).
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■ A Novel and Simple Synthesis of 1,3-Benzoxazin-4-one Derivatives
Tetsuji Kametani,* Terumi Higa, Chu Van Loc, Masataka Ihara, and Keiichiro Fukumoto
*Pharmaceutical Institute, Tohoku University, Aobayama, Sendai 980-8578, Japan
Abstract
Treatment of salicyl chloride (6) with 3,4-dihydro-β-carboline (7) gave indolo[21,31:3,4]pyrido[2,l-b][1,3]benzoxazin-4-one (9), which was also obtained by a reaction of with N-formyltryptamine (8). The same reaction of 6 with 3,4-dihydro-6,7-dimethoxy-1-methylisoquinoline (11) and isoquinoline (13) afforded the corresponding pyridobenzoxazinones (12) and (14), respectively.
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■ Synthesis of Oudenone and Its Related Compounds
Teruaki Tsujikawa,* Tasushi Nakagawa, Kazuo Tsukamura, and Katsutada Masuda
*Central Research Division, Takeda Chemical Industries, Ltd., 17-85 Jusohonmachi 2-chome, Yodogawa-ku, Osaka 532-8686, Japan
Abstract
Oudenone, a tyrosine hydroxylase inhibitor, was obtained by heating 1,3-cyclopentanedione with 2,2-diethoxy-5-propyltetrahydrofuran. A similar one-step synthesis afforded several related analogues.
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■ A New Flavone Glycoside from Sideritis romana L.
Pietro Venturella,* Aurora Bellino, and Anna Papucci
*Instituto de Chimica Organica , Facolta de Scienze, Università digli Studi di Palermo, 20 via Archirafi 90123 Palermo, Italy
Abstract
From the aerial part of Sideritis romana (Labiatae) a new flavone trioside was isolated and elucidated as chrysoeriol-7-β-glucosyl-β-1 → 2-glucosyl-β-1 → 2-glucose (I).
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■ New Syntheses of Fervenulin 4-Oxides
Keitaro Senga,* Misuzu Ichiba, and Sadao Nishigaki
*Pharmaceutical Institute, School of Medicine, Keio University, Shinanomachi 35, Shinjuku, Tokyo 160-0016, Japan
Abstract
Treatment of 1,3-dimethyl-6-hydrazino-5-nitrosouracil (I) with dimethylformamide-dimethyl sulfate, formic acid, or triethyl orthoformate afforded fervenulin 4-oxide (IIa), respectively. 3-Substituted fervenulin 4-oxides (IIb-c) were also prepared by the reaction of (I) with respective ortho esters.
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■ Synthesis of β-Apoplicatitoxin Trimethyl Ether
Takefumi Momose,* Takeshi Nakamura, and Ken-ichi Kanai
*Faculty of Pharmaceutical Sciences, Osaka University, 1-6 Yamadaoka, Toyonaka, Osaka 560-0043, Japan
Abstract
Irradiation of 3-(3,4,5-trimethoxyphenyl)methylene-4-(3,4-dimethoxyphenyl)methylenedihydro-2(3H)-furanone (VIII) afforded β-apoplicatitoxin trimethyl ether (V) and the isomer (IX). The isomer ratio (V/IX) was found solvent-dependent.
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■ New Six-membered Aromatic Betaines from 8-Acylaminoquinolines
Yasumitsu Tamura,* Yasuyoshi Miki, Hironori Hayashi, Yoshio Sumida, and Masazumi Ikeda
*Faculty of Pharmaceutical Sciences, Osaka University, 1-6 Yamadaoka, Toyonaka, Osaka 560-0043, Japan
Abstract
Some spectral and chemical properties of new six-membered aromatic betaines (3a and 3b) which are synthesized from the corresponding 8-acylaminoquinolines via N-amination followed by cyclization with alkaline treatment, are described.
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■ A Stereoselective Synthesis of Oxygenated Catharanthine Derivatives. Possible Precurors for Bisindole Alkaloids
Yasushi Honma and Yoshio Ban*
*Faculty of Pharmaceutical Sciences, Hokkaido University, Sapporo 060-0812, Japan
Abstract
In order to synthesize the bisindole alkaloids (Ia,b) of vinblastine type, catharanthine (IIa) was converted to the lactones (IIIa,b,c) and the epoxy derivatives (IVa,b), which would be available as the precursors for the synthesis of the above natural alkaloids.
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■ The Modified Polonovski Reaction of Catharanthine Lactone N-Oxide for Coupling with Vindoline
Yasushi Honma and Yoshio Ban*
*Faculty of Pharmaceutical Sciences, Hokkaido University, Sapporo 060-0812, Japan
Abstract
For synthesis of bisindole alkaloids of vinblastine type, catharanthine lactone N-oxide (2) was submitted to the modified Polonovski reaction for coupling with vindoline according to Potier’s method. The products were proved to be 5 as a main product, 6 and the other one of an uncertain structure as by-products.
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■ Studies on the Synthesis of Bisindole Alkaloids. VIII. The Coupling of Several 3α,4α-Substituted Catharanthine Derivatives with Vindoline
James P. Kutney,* Alummoottil V. Joshua, and Ping-huang Liao
*Department of Chemisry, University of British Columbia, Vancouver 8, V5T 1W5, Canada
Abstract
A detailed study involving the Polonovski-type coupling of vindoline with 4α-hydroxydihydrocatharanthinic acid lactone (1) and 3α,4α-epoxydihydrocatharanthine (9), two catharanthine derivatives prepared earlier in our laboratories, is described.
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■ The Cyclisation Reactions of γ-Amidoalcohols and Synthesis of 2-Benzazepin-3-one Derivatives by Acid Catalysed Rearrangement of 1,3-Oxazepin-4-one Derivatives
Tetsuji Kametani,* Kazuo Kigasawa, Mineharu Hiiragi, Nagatoshi Wagatsuma, Toshitaka Kohagizawa, and Toshihisa Nakamura
*Pharmaceutical Institute, Tohoku University, Aobayama, Sendai 980-8578, Japan
Abstract
The cyclisation reaction of the secondary amides (1), possessing a hydroxyl group at γ-position, with formalin and hydrochloric acid gave the 1,3-oxazepin-4-one derivatives (2). The acid catalysed rearrangement of the resulting products was carried out successfully to give the 2-benzazepin-3-one derivatives (15) and (16).
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■ Reaction of 1,3-Dithiole-2-thiones with Enamines. Formation of 1,3-Dithionin-2-thione, a Novel Heterocycle
Fumio Ishii, Renji Okazaki, and Naoki Inamoto*
*Department of Chemistry, Scool of Science, University of Tokyo, 7-3-1 Hongo, Bunkyo-ku, Tokyo 113-0033
Abstract
Reaction of 4-phenyl- (4a) and 4,5-diphenyl-1,3-dithiole-2-thione (4b) with 1-pyrrolidinocyclopentene gave 1,3-dithionin-2-thiones (5a,b), novel heterocycles, while reaction of 4a with 1-pyrrolidinocyclohexene afforded thiophene (7).
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■ A Simple Synthesis of 2,2’,5’,2”-Terthienyl
Takashi Asano,* Shota Ito, Norio Saito, and Kiyotaka Hatakeda
*Goverment Industrial Research Institute, Tohoku, Nigatake, Haranomachi, Sendai 983, Japan
Abstract
The synthesis of 2,2’,5’,2”-terthienyl (IV) is reported. A key intermediate in this synthesis was 1,4-di(2-thienyl)-1,4-butanedione (III), which was prepared from trimethylsilyl enol ether (II) of 2-acetylthiophene (I). Corresponding furyl derivatives were also synthesized by the similar procedure.
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■ Synthesis of Vinca Alkaloids and Related Componds. III. Stereoselective Synthesis of Isovincine
György Kalaus, Lajos Szabó, Judith Horváth, and Csaba Szántay*
*Central Research Institute for Chemistry, Hungarian Academy of Sciences, H-1025 Budapest, Pusztaszeri ut 59-67, P.O.Box 17, Hungary
Abstract
When enamine 2a was reacted with methyl α-acetoxyacrylate, and the adduot obtained was reduced, 8a was formed stereoselectively. Deacetylation of 8a and subsequent oxidation furnished isovincine (1c).