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. 26, No. 10, 1987
Published online:
■ Phaeanthine-2’a-N-oxide and Pycmanilline, New Bisbenzylisoquinoline Alkaloids from Pycnarrhena manillensis
Jacinto C. Regalado, Jr., Cong-yuan Gao, Emil Fu, Fu-tyan Lin, Mei-chao Lin, Lan K. Wong, and Paul L. Schiff, Jr.
*Department of Pharmacognosy, School of Pharmacy, University of Pittsburgh, Pittsburgh, PA 15261, U.S.A.
Abstract
Chromatography of an ethanolic extract of pycrarrhena manillensis over silica gel afforded phaeanthine-2’α-N-axide (1) and pycmanilline (2) which were characterized as new bisbenzylisoquinoline alkaloids by a consideration of physicochemical data and the utilization of simple chemical reactions. Phaeathine-2’α-N-axide (1) was reduced to phaeanthine (3) while pycmanilline (2), a secobisbenzyliso-quinoline alkaloid, was prepared via oxidation of phaeanthine (3).
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■ Asymmetric Synthesis via Heterocyclic Intermediates. Asymmetric Synthesis of (-)-(1S,2R)-Allocoronamic Acid
José L. Marco
*Instituto de Química Orgánica General, C. S. I. C., Calle Juan de Cierva, 3, 28006 Madrid, Spain
Abstract
The first total asynmetric synthesis of (-)-(1S, 2R)-allocoronamic acid is described.
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■ Pyridine N-Oxides as Catalysts for Thione-thiol Rearrangement
Kazunobu Harano, Ikuo Shinohara, Motoji Murase, and Takuzo Hisano
*Faculty of Pharmaceutical Sciences, Kumamoto University, 5-1 Oe-hon-machi, Kumamoto 862-0973, Japan
Abstract
Pyridine N-oxides are efficient catalysts for rearrangement of 0,S-dialkyl dithiocarbonates to S,S-dialkyi dithiocarbonates. A Solid-Phase copolymer of 4-vinylpyridine N-oxide (P4VPNO) is also a useful catalyst. being nonvolatile and easily handled. The rearrangement products are served as useful precursors of thiols.
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■ First Synthesis of 1-Trichloromethyl-6,7-dihydroxytetrahydroisoquinoline — An Imaginable Chloral-derived Mammalian Alkaloid
Gerhard Bringmann, Annette Hille, and Marianne Zsiska
*Organisch-Chemisches Institut, Universität Münster, Orleansring 23, D-4400 Münster, Germany
Abstract
1-Trichloromethyl-6,7-dihydroxy-1,2,3,4-tetrahydroisoquinoline (3c), a potential condensation product from dopamine (1) and chloral (2c), could be prepared for the first time, by a stepwise Bischler-Napieralski pathway, and, more directly, under special Pictet-Spengler conditions, The results indicate that 3c is not a probable alkaloid in man.
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■ Approach to Natural Occurring α-Methylene Bis-γ-butyrolactones from (R)-1,2,-(O)-Isopropylideneglyceraldehyde as a Chiral Template
Toshio Suzuki, Shinko Kamada, Etsuko Sato, Yasuyuki Matsuda, Katsuo Unno, and Tetsuiji Kametani
*Department of Pharmaceutical Sciences, Akita University Hospital, Hondo, Akita 010, Japan
Abstract
Both 4-substituted tetrahydrofurano-γ-butyrolactones (12) and (16) which could be key intermedates leading to natural occurring α-methylene bis-γ-butyrolactones were synthesized by regio and stereoselective haloetherification of (8) and (9), followed by a reductive coupling reaction for the preparation of (12), whereas a stereoselective hydrogenation of the enol ether (15) derived from the bromide (14) for the preparation of (16), respectively.
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■ Preparation of an α,β-Type of Ter- and Septithiophenes
Juzo Nakayama, Shigeru Murabayashi, and Masamatsu Hoshino
*Department of Chemistry, Faculty of Science, Saitama University, Saitama, Saitama 338-8570, Japan
Abstract
An α,β-type of thiophene oligomers, 2,3’:4’,2”-terthiophene and 2,3’:4’,2”:5”,3’’’:4’’’,2””:5””,3””’:4””’,2”””-septithiophene, were synthesized through intramolecular reductive coupling reaction of diketo sulfides with a low-valent titanium reagent.
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■ Synthesis of 1,2-Aziridino-2,3-dihydro-1H-pyrrolo[1,2-a]indole Derivatives Similar to the Activated Forms of Mitomycin
Shin-ichi Nakatsuka, Osamu Asano, and Toshio Goto
*Faculty of Agriculture, Gifu University, 1-1 Yanagito, Gifu, Gifu 501-1193, Japan
Abstract
Titled compounds, 8 and 12, were efficiently synthesized from 2,3-dihydro-1H-pyrrolo[1,2-a]indole derivatives by closure of the aziridine ring.
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■ Facile Deoxygenation of Sulfoxides by Using Metal/Chiloromethylsilanes
Kazuo Nagasawa, Akemi Yoneta, Toshiyuki Umezawa, and Keiichi Ito
*Hokkaido College of Pharmacy, 7-1 Katsuraoka-cho, Otaru 047-02, Japan
Abstract
Deoxygenation of a various kind of sulfoxides including optically active one by Zinc/Dichlorodimethylsilane proceeds under very mild conditions to furnish the corresponding sulfides in high yields.
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■ A Novel Synthetic Method of Lactams from1,3-Dioxin-4-ones via Intramorecular Ketene Trapping
Masayuki Sato, Hiromichi Ogasawara, Kazuhisa Takayama, and Chikara Kaneko
*Pharmaceutical Institute, Tohoku University, Aobayama, Sendai 980-8578, Japan
Abstract
A novel route to four- and five-membered lactams from 1,3-dioxin-4-ones having an α-aminoalkyl side-chain at 5-or 6-position through cycloreversion to acylketenes followed by intramolecular ketene trapping by the amino function is described.
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■ Nitrogen Bridgehead Compounds. Part 67. Preparation of Novel Policyclic Quaternary Salts
István Bitter, Béle Pete, Béle Ágai, László Töke, Gábor Tóth, István Hermecz, Kálmán Simon, Zoltán Mészáros, and László Párkányi
*Department of Organic Chemical Technology, Technical University of Budapest, H-1521 Budapest, Gellért tér 4, Hungary
Abstract
The first representatives of new polycyclic ring systems - thiazolo- end oxazolo-[2,3-b] triazaphenalenes, benzoxazolo-and benzothiazolo-[2,3-b] triazaphenalenes and isoquinolo-[1,2-b]triazazaphenalenes - are prepared by the cycloaddition of pyrido[1,2-a]pyrimidine derivatives with cyclic azomethines.
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■ Studies on Aconitum Species V. Constituents of Aconitum yesoense var. macroyesoense (Nakai) Tamura
Hideo Bando, Koji Wada, Takashi Amiya, Kimiko Kobayashi, Yasuo Fujimoto, and Toshio Sakurai
*Hokkaido College of Pharmacy, 7-1 Katsuraoka-cho, Otaru 047-02, Japan
Abstract
Five new C20-diterpenoid alkaloids, 12-acetyldehydro-Iucidusculine, 12-acetyllucidusculine. 15-benzoylpseudokobusine,15-veratroylpseudokobusine, and yesoxine and 14 known alkaloids were isolated from A. yesoense var. macroyesoense (Nakai) Tamura. Structures of those compounds were determined on the basis of their spectral and chemical data. Structure of an unusual epoxide, yesoxine, was determined by X-ray analysis and was a first example having an epoxy group at C(16 and 17).
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■ Thienospirans V: Thienospirans via Directed Lithiations
Fritz Sauter, Peter Stanetty, Hannes Fröhlich, and Wolfgang Ramer
*IInstitute of Organic Chemistry, Vienna University of Technology, Getreidemarkt 9, A-1060 Vienna, Austria
Abstract
Using halogen-metal exchange and orthodirected metalation methodologies spiro[thieno[b]-furans] 2 and 3 were synthesized starting from 3-bromothiophene, in one case proceeding via cyclization of the 2,3-difunctionalized thiophenes 6 and in the other case proceeding via cyclization of the isomeric compounds 8.
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■ Thienospirans VI: Spiro-substituted Thieno[3,2-c]furans by Regioselective Lithiations
Fritz Sauter, Peter Stanetty, and Hannes Fröhlich
*IInstitute of Organic Chemistry, Vienna University of Technology, Getreidemarkt 9, A-1060 Vienna, Austria
Abstract
The title substances 3 were obtained by cyclization of 3,4-disubstituted thiophenes 5 and 6, prepared in one-pot reactions starting from 3,4-dibromothiophene by means of two consecutive lithiations and additions of carbonyl compounds. By a combination of variation of the solvent and of the lithiating agent in the second metalation step and by influence of the substituent introduced in the first step it became possible to obtain good yields of either 3,4-disubstituted thiophenes ( 5 and 6) by metal-halogen exchange , 2,3-disubstituted 4-bromothiophenes (7) by directed lithiation, or 2,4-disubstituted 3-bromothiophenes (9) by a -I-effect controlled ortho-metalation.
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■ Synthesis and Structural Confirmation of 5,6-Cyclopenteno-5-deazapterin
Edward C. Taylor and John C. Warner
*Department of Chemistry, Princeton University , Princeton, New Jersey 08544, U.S.A.
Abstract
Condensation of 2,4-diamino-6(1H)-pyrimidinone with 1-formyl-1-cyclopentene in 60% acetic acid gives 5,6-cyclopenteno-5-deazapterin (2). The 2-pivaloyl derivative of 2 was then synthesized in an unequivocal manner by Diels-Alder cycloaddition of 2-pivaloylamino-7-methylthio-6-azapterin (3) with 1-(N-morpho1ino)cyclopentene to give 5,6-cyclopenteno-2-pivaloylamino-7-methylthio-5-deazapterin (4), followed by Raney nickel desulfurization.
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■ Flash Vacuum Pyrolysis of Pyridazine N-Oxides
Akio Ohsawa, Takashi Itoh, and Hiroshi Igeta
*School of Pharmaceutical Sciences, Showa University, 1-5-8 Hatanodai, Shinagawa-ku, Tokyo 142-8555, Japan
Abstract
Flash vacuum pyrolysis of 6-unsubstituted pyridazine 1-oxides afforded nitriles and pyrroles. 6-Phenylpyridazine 1-oxides gave 2-phenyloxazole together with nitriles and pyrroles. 6-Methylpyridazine 1-oxide and 3,6-dimethylpyridazine 1-oxide afforded naphthalene and benzene, respectively, together with other products. The formation mechanism of these products was speculated.
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■ Photoreaction of Phthalimides Possessing an ortho-Methylphenyl Group in Their N-Side Chain. Synthesis of Tetracyclic Nitrogen Heterocycles
Minoru Machida, Mayumi Nakamura, Kazuaki Oda, Haruko Takechi, Kosei Ohno, Hideo Nakai, Yasuhiko Sato, and Yuichi Kanaoka
*Faculty of Pharmaceutical Sciences, Health Sciences University of Hokkaido, Ishikari-Tobetsu, Hokkaido 061-0293, Japan
Abstract
Upon irradiation phthalimides (5 and 8) possessing an 9-methylphenyl group in their N-side chain gave mainly the tetracycilc ring systems (9 and 10). it was shown that the photocyclization occurs at ε- or ζ-position across the carbons of the benzene ring (B ring).
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■ Catalytic Hydrogenation of 2,5-Dialkylpyrazines and 3,6-Dialkyl-2-hydroxypyrazines
Akihiro Ohta, Yukari Okuwaki, Tsuyoshi Komaru, Mieko Hisatome, Yasushi Yoshida, Jun Aizawa, Yumi Nakano, Hiroko Shibata, Takuya Miyazaki, and Tokuhiro Watanabe
*Tokyo University of Pharmacy and Life Science, 1432-1 Horinouchi, Hachioji, Tokyo 192-0392, Japan
Abstract
Hydrogenation of several 2,5-dialkylpyrazines and 3.6-dialkyl-2-hydroxypyrazines was achieved in the presence of platinum oxide. In the former cases, the corresponding trans piperazines were mainly obtained. In the latter cases, the products were further treated with lithium aluminum hydride to give mainly the cis isomers.
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■ An Efficient Synthesis of 14-Halogenomethyl-substituted C-Normorphinans
Martin Kratzel and Wilhelm Fleischhacker
*Institute of Pharmaceutical Chemistry, University of Vienna, Währinger Strasse 10, A-1090 Vienna, Austria
Abstract
Nucleophilic ring-opening reaction of 7,14-cyclo-dihydrocodeinone 1 resulted in a watersoluble quaternary ammonium salt 3. However, similar reaction of 1 under acetalization conditions led to the ring cleavaged 14-halogenomethylacetals 4, 7 and 8 (a-c) in high yields. When the acetals were hydrolyzed, the formation of cyclic ammDnium compounds (3) was unavoidable.
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■ Palladium-catalyzed Cross-coupling of Phenylboronic Acid with Heterocyclic Aromatic Halides
Johannes Stavenuiter, Martin Hamzink, Rob van der Hulst, Gijsbert Zomer, Gerard Westra, and Erik Kriek
*National Institute of Public Health and Environmental Hygiene, P.O.Box 1, 3720 BA Bilthoven, The Netherlands
Abstract
The coupling reaction of bromo- and - iodopyridines 1 with phenylboronic acid (2a) by Pd(Ph3 P)4 provides a convenient route to phenylpyridines, even when electrondonating or - withdrawing substituents are present. The method is also successful for the preparation of other phenylated N-containing heterocycles 5 as phenylquinolines and -pyrimidines.
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■ A Novel Synthesis of Benzofuran and Related Compounds. IV. The Vilsmeier Reaction of 3,5-Dimethoxyphenylthiomethyl Compounds
Takashi Hirota, Yosuke Tashima, Kenji Sasaki, Tetsuo Namba, and Shohei Hayakawa
*Faculty of Pharmaceutical Sciences, Okayama University, 1-1-1 Tsushima-naka, Okayama 700-8530, Japan
Abstract
A novel synthesie of 2-substituted 4,6-dimethoxybenzothiophenes by the Vilsmeier reaction of 3,5-dimethoxyphenylthiomethyl derivatives is described.
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■ Synthesis of Vicinally Substituted Nitropyridine Derivatives and Their N-Oxides
Ryszard Gawinecki and Danuta Rasala
*Institute of Chemistry, Pedagogical University, 25-020 Kielce, Poland
Abstract
The synthetic methods leading to 4- and 2-substituted 3-nitropyridines and 3-substituted 4- end 2 nitropyridines are reviewed in this paper. Their preparative convenience is discueeed.
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■ The Chemistry of Antiaromatic Azacycl[3.3.3]azines
Yoshiro Matsuda and Hiromi Gotou
*Faculty of Environmental Studies, Nagasaki University, 1-14, Bunkyo-machi, Nagasaki 852-8521, Japan
Abstract
The syntheses and reactions of antiaromatic azacycl[3.3.3]azines are reviewed.