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. 4, No. 4, 1976
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■ Photochemical Reactions of 1,2,3,3a,4,5-Hexahydro-N-phenylacetylindol-6-ones
Hideo Iida,* Sakae Aoyagi, and Chihiro Kibayashi
*Tokyo University of Pharmacy and Life Science, 1432-1 Horinouchi, Hachioji, Tokyo 192-0392, Japan
Abstract
Upon irradiation, 1,2,3,3a,4,5-hexabydro-N-(2-iodo-4,5-dimethoxyphenylacetyl)indol-6-one (2) underwent photocyclization to the indolo[l,7-ab][3]benzazepine derivative (3) and deiodination followed by nonaromatic photo-Fries rearrangement to 1,2,3,3a,4,5-hexahydro-7-(3,4-dimethoxyphenylacetyl)indol-6-one (5), which, upon further irradiation, gave rise to the bibenzyl (11), aldehyde (12), and carboxylic acid (13). The production of these compounds (11 to 13) was accounted for by a mechanism involving an α-cleavage and subsequent ketene formation. The latter process was demonstrated by experiments using several nucleophiles as trapping agents.
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■ Cycloaddition Extrusion Reaction of 2- or 4-(Methylthio)thiocarbonylimino-1,2 or 1,4-Dihydropyridine Derivatives with Dimethyl Acetylenedicarboxylate
Kazumichi Mizuyama, Yoshinori Tominaga, Yoshiro Matsuda, and Goro Kobayashi*
*Faculty of Pharmaceutical Sciences, Nagasaki University, 1-14, Bunkyo-machi, Nagasaki 852-8521, Japan
Abstract
Reaction of (methylthio)thiocarbonylimino derivatives of pyridine (Ia-d, IV) with dimethyl acetylenedicarboxylate (DMAD) afforded 2 or 4-(1,2-dimethoxycarbonyl-2-thioxoethy1idene)-1,2 or 1,4-dihydropyridine derivatives (IIa-d, V), accompanied with extrusion of methyl thiocyanate1) from 1,4-cycloadduct, spiro-1,3-thiazine derivatives.
Further, reaction of IV with DMAD (2 mole) gave cyclobuteno[l,2-b]azocine derivative (VI). Reaction of (methylthio)thiocarbonylimino derivative of benzothiazole (VII) with DMAD afforded 4H-pyrrole-2-spiro-2-(2,3-dihydrobenzothiazole) (VIII), accompanied with desulfrization.
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■ The Reactions of Ethyl 2-Quinolyl- and 2-Pyridylcyanoacetate
Takao Yamazaki,* Katsuhide Matoba, and Suguki Imoto
*Faculty of Pharmaceutical Sciences, ToyamaUniversity, Gofuku 3190, Toyama 930-8555, Japan
Abstract
Ethyl 2-quinolylcyanoacetate (II) was refluxed in trifluoroacetic acid to give a chemically very stable substance. The potassium salt (IVa) of II reacted with methyl iodide to afford selectively the C-methylated product, which was treated with alkali in ethanol to give methyl 2-quinolyl ketone (VIIa) in good yield. On the other hand, ethyl 2-cyano-2-(2-pyridyl)-propionate (XII) gave only 2-(2-pyridyl)propionitrile (XIV).
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■ Synthesis of 9-Azaprostaglandin Analogs
Gerard P. Rozing, Theo J. H. Moinat, Henk de Koning,* and Henderikus O. Huisman
*Laboratory of Organic Chemistry, University of Amsterdam, Nieuwe Achtergracht 129,1018 WS Amsterdam, The Netherlands
Abstract
9,11-Dideoxy-9-aza-prostaglandin derivatives are synthesized in nine steps starting from diethyl 7-cyanoheptylidenemalonate.
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■ Structure Elucidation of Six New Non-phenolic Alkaloids Isolated from Corydalis ochotensis var. Raddeana
Tetsuji Kametani,* Makoto Takemura, Masataka Ihara, and Keiichiro Fukumoto
*Pharmaceutical Institute, Tohoku University, Aobayama, Sendai 980-8578, Japan
Abstract
Six new alkaloids, raddeanamine (1), raddeanine (2), raddeanidine (3), raddeanone (4), aobamine (5) and aobamidine (6), were isolated from the non-phenolic alkaloidal fraction of Corydalis ochotensis var. raddeana in addition to the known alkaloids, protopine, adlumidine (7) and ochotensimine (8).
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■ The Reaction of Indoles with Succinimido-sulfonium Salts. I. A Convenient Synthesis of Indole-3-thioethers
Kuniyuki Tomita,* Atsusuke Terada, and Ryuji Tachikawa
*Biomedicinal Chemistry Research Laboratories, Sankyo Co., Ltd., 1-2-58 Hiromachi, Shinagawa-ku, Tokyo 140-8710, Japan
Abstract
Reaction of indoles with succinimido-dialkyl- or alkylarylsulfonium chlorides, prepared from dialkyl or alkylaryl sulfides and N-chlorosuccinimide, afforded indole-3-dialkyl- or alkylarylsulfonium chlorides which gave 3-alkylthio- or arylthioindoles on pyrolysis.
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■ The Reaction of Indoles with Succinimido-sulfonium Salts. II. A New Syntehsis of 2-Alkyl and Allyl Indoles
Kuniyuki Tomita,* Atsusuke Terada, and Ryuji Tachikawa
*Biomedicinal Chemistry Research Laboratories, Sankyo Co., Ltd., 1-2-58 Hiromachi, Shinagawa-ku, Tokyo 140-8710, Japan
Abstract
Reaction of indole with succinimido-diallyl- or alkylallylsulfonium chlorides afforded 2-allyl-3-allylthio- or 2-allyl-3-alkylthioindoles which gave 2-alkyl- or 2-allylindoles by the reductive desulfurization with Raney Ni or Zn — acetic acid.
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■ Reactions of Phenyl-pyrylium Salts with Phenacylidenedimethylsulfurane
Yoshizo Suzuki,* Takashi Toda, and Toshio Mukai
*Department of Chemistry, Faculty of Science, Tohoku University, Aoba-ku, Ssendai 980-8578, Japan
Abstract
Reactions of 2,4,6-triphenyl- (1) and 2,6-diphenylpyryliun (6) salts with phenacylidenedimethylsulfurane (2) gave corresponding addition products (3 and 7) which possess ylid structures. Alkali treatment of 3 and 7 afforded 2,4,6-triphenylthioanisole (4) and 4-benzoylmethylene-2,6-diphenyl-4H-pyran (8), respectively.
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■ Syntheses of the Basic Structures of Corynoline and Related Alkaloids
Ichiya Ninomiya,* Okiko Yamamoto, and Takeaki Naito
*Kobe Women’s College of Pharmacy, Motoyamakita, Higashinad, Kobe, Hyogo 658, Japan
Abstract
Syntheses of the compounds (XII, VII, and XI) having the basic structures of corynoline (Ia) and related alkaloids (Ib and Ic) are described.
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■ A Novel Conversion of 7-Azapteridines to Purines
Fumio Yoneda* and Tomohisa Nagamatsu
*Faculty of Pharmaceutical Sciences, Kumamoto University, 5-1 Oe-hon-machi, Kumamoto 862-0973, Japan
Abstract
Treatment of 7-azalumazines such as toxoflavins and fervenulins with formamide led to the formation of the corresponding xanthine derivatives.
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■ Thalibrine and Northalibrine, New Bisbenzylisoquinoline Alkaloids from Thalictrum rochebrunianum
José M. Saá, Michael J. Mitchell, Michael P. Cava,* and Jack L. Beal
*Department of Chemistry, University of Pennsylvania, 231 South 34th Street Philadelphia, PA 19104-6323, U.S.A.
Abstract
Thalibrine and northalibrine, new alkaloids from Thalictrum rochebrunianum, have been assigned the mono-ether-bridged tail-to-tail bisbenzylisoqulnoline structures 1 and 2.
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■ Semisynthetic β-Lactam Antibiotics. I. α-Isocyanobenzyl-penicillins and Cephalosporins
Giorgio Pifferi,* Giuseppe LiBassi, and Giampietro Broccali
*Laboratories for Biomedical Research, ISF, Trezzano s/N, Milan, Italy
Abstract
The preparation of the new β-lactam antibiotics α-isocyanobenzyl-penicillins and cephalosporins from the corresponding amino derivatives and their microbiological properties are reported.
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■ Application of Benzofurazan Oxide to the Synthesis of Heteroaromatic N-Oxides
Makhluf J. Haddadin and Costas H. Issidorides
*Department of Chemistry, American University of Beirut, Beirut, Lebanon
Abstract
Benzofurazan oxide (BFO) reacts with enamines, enolate anions, phenolate anions, and related species to give a variety of heteroaromatic N-oxides, hitherto difficult to prepare.
PDF (639KB)Published online:
■ Furanosequiterpenoids
Hiroshi Hikino* and Chohachi Konno
*Pharmaceutical Institute, Tohoku University, Aobayama, Sendai 980-8578, Japan
Abstract
This article aims to review the occurrence, the structural variability, and the general chemistry of the known furanosesquiterpenoids and to cover developments in their synthesis as well as to discuss their biogenesis. A brief survey of the biological activities of some furanosesquiterpenoids is also made.