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. 16, No. 5, 1981
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■ Synthesis of S-Triazolo[4,3-a]pyridinium Salts by Anodic Oxodation of Hydrazones in the Presence of Pyridine
Ibro Tabakovic* and Senka Crljenak
*Faculty of Technology, The Gjuro Pucar Stari University, 78000 banja Luka, Bosnia and Herzegovina, Yugoslavia
Abstract
The anodic oxidation of some aldehyde hydrazones in the presence of pyridine was investigated. From the reaction mixture derivatives of s-triazolo[4,3-a]pyridinium salts were isolated in 45-80% yield and identified. The mechanism of these transformations is outlined and discussed.
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■ The Mass Spectra of Furan Chalcone Analogues
Francesco P. Ballistreri, Giuseppe Musumarra, and Salvatore Occhipinti*
*Istituto di Chimica Farmaceutica e Tosshicologica, Università di Catania, Viale A. Doria 6, I-95125 Catania, Italy
Abstract
The electron impact mass spectra of 14 furan chalcone analogues (5-X-C4H2O-CH=CH-CO-C6H4-pY ; X = H, Me; Y = OMe, Me, H, F, CI, CN, NO2) are reported and the fragmentation pattern is discussed and compared to those of chalcones and their thiophene analogues.
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■ Kinetin Type Activity of Some s-Tiazole Systems
D. S. Deshpande,* A. P. Kulkarni, S. T. Jannawar, and D. V. Dev
*Chemistry Department, Science College, Nanded, India
Abstract
Expansion growth of cotyledon in light and dark in presence of some s-triazolo systems with condensed thiazole moiety exhibits some kinetin response. Presence of compensatory groups -CH3 and -NO2 helped in cotyledor expansion. Otherwise electron donating group at 3 - position is having inhibitory effect. Sulfhydryl group in triazole moiety showed photo sensitive effect. Dissociation of mercapto compound into the thianion might induce cotyledonary expansion in cucurbita.
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■ Oxygen Heterocycles by Sulphur Ylide Annulation: Reaction of O-Hydroxybenzalketones with Dimethyloxosulphonium Methylide
Pierfrancesco Bravo* and Calimero Ticozzi
*Dipartmento di Chimica del Polotecnico, Centro Studio Sostanze Organiche Naturali, C.N.R., Piazza Leonardo da Vinci 32, 20133 Milano, Italy
Abstract
Beside the expected cyclopropanes IV and 2,3-dihydrobenzofurans V, 2-(o-hydroxyphenyl)-2,3-dihydro-6H-pyrans X and 3-substituted-2,3-dihydrobenzofurans XII arise by transfer of methylenes, through the quinone methide intermediates IX, from dimethyloxosulphonium methylide on o-hydroxybenzalketones I.
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■ Reactions of Pyridylnitrilimines with Dimethyl Acetylene Dicarboxylate
Shigeru Tanaka and Atsusuke Terada*
*Central Research Laboratories, Sankyo Co.,Ltd., 1-2-58 Hiromachi, Shinagawa-ku, Tokyo 140 Japan
Abstract
Reaction of 2-(1-bromo-1-phenylhydrazono)methylpyridines (2) with dimethyl acetylene dicarboxylate in the presence of triethylamine gave rise to dimethyl 1-phenyl-3-(2-pyridyl)-4,5-dicarboxylates (3) and dimethyl 1-phenylazoindolizine-2,3-dicarboxylates (4). The former is the usual 1,3-dipolar cycloaddition product of a nitrilimine, while the latter is an unusual cycloaddition product.
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■ Reactions of New Cyclic Sulfer Ylides, 8-Thiaazulenes with Electrophiles
Mikio Hori,* Tadashi Kataoka, Hiroshi Shimizu, and Mitsuhito Okitsu
*Department of Pharmacognosy, Gifu College of Pharmacy, 6-1 Mitahora-higashi 5-chome, Gifu 502-8585, Japan
Abstract
The reactions of 8-alkyl-1,3-diphenyldibenzo[e,h]-8-thiaazulenes with acetylenic electrophiles yielded the considerably stable ylides. The ylides newly formed were not rearranged on refluxing in THF for 1 hr, but caused the intramolecular 1,4-rearrangement at 170 - 200°C. The reaction of 8-methyl-1,3-diphenyldibenzo[e,h]-8-thiaazuene with diphenylcyclopropenethione formed a thiete derivative.
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■ Cyclization Reaction of 1-Methylene-2-nicotinoyl-1,2,3,4-tetrahydroisoquinolines and a Total Synthesis of Alamarine
Takeaki Naito, Okiko Miyata, Ichiya Ninomiya,* and Satyesh C. Pakrashi
*Kobe Women’s College of Pharmacy, Motoyamakita, Higashinad, kobe, Hyogo658, Japan
Abstract
Under photochemical, thermal and acylating conditions, cyclization of 1-methylene-2-nicotinoyltetrahydroisoquinolines was investigated and as a result the alkaloid alamarine was synthesized via the route involving enamide cyclization under both thermal and photochemical conditions.
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■ Synthesis of 1-Acyl-1,2-dihydro-1-benzazocine Derivatives
Norio Kawahara,* Takako Nakajima, Tsuneo Itoh, and Haruo Ogura
*Hokkaido College of Pharmacy, 7-1 Katsuraoka-cho, Otaru 047-02, Japan
Abstract
Substituted 1,2,3,4-tetrahydroquinolin-3-one (7) was synthesized from nitrobenzene derivatives (1) in several steps. The compound (7a) was converted the pyrrolidine enamine, and then treated with dimethyl acetylenedicarboxylate (DMAD) to give a ring expanded heterocyclic product ; dimethyl 1-acetyl-1,2-dihydro-3-hydroxy-8-methoxy-9-methyl-1-benzazocine-4,5-dicarboxylate (13a).
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■ Synthesis of 3-Substituted 5-Oxo-5H-[1]benzopyrano[2,3-b]pyridine Derivatives
Toshihiro Ishiguro,* Kiyoshi Ukawa, Hirosada Sugihara, and Akira Nohara
*Central Research Division, Takeda Chemical Industries, Ltd., 17-85 Jusohonmachi 2-chome, Yodogawa-ku, Osaka 532-8686, Japan
Abstract
3-Cyano-, 3-alkoxycarbonyl-, and 3-formyl-5-oxo-5H-[1]benzopyrano[2,3-b]pyridine derivatives were prepared by reactions of 2-amino-4-oxo-4H-1-benzopyran-3-carboxaldehydes 1 with acetylene derivatives (methods A-C) or with reactive methylene compounds (methods D-E) and also by catalytic hydrogenation of 2-chloro-5-oxo-5H-[1]benzopyrano[2,3-b]pyridine-3-carbonitriles 12 (method F).
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■ Bromination of α-Ergocryptine and Other Ergot Alkaloids with 3-Bromo-6-chloro-2-methylimidazo[1,2-b]pyrimidazine-Bromine Complex as a New Brominating Agent
Branko Stanovnik,* Miha Tisler, Milan Jurgec, and Rudolf Rucman
*Department of Chemistry , E. Kardelj University, Murnikova 6, 61000 Ljubljana, Yugoslavia
Abstract
A new and improved bromination of α-ergocryptine and some other ergot alkaloids of the type 1, 2, and 3 using 3-bromo-6-chloro-2-methylimidazo[1,2-b]pyridazine-bromine complex (5) as a new brominating agent, to give purified 2-bromo derivatives in yields up to 81%, is described.
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■ Delcaroline, a Novel Alkaloid from Delphinium carolinianum Walt.
S. William Pelletier,* Naresh V. Mody, and Ranjit C. Desai
*Department of Chemistry, Institute for Natural Products Research, The University of Georgia, Chemistry Building, Athens, Georgia 30602-2556, U.S.A.
Abstract
The structure of delcaroline (1), a novel C19-diterpenoid alkaloid isolated from Delphinium carolinianum Walt., has been determined with the aid of proton and carbon-13 NMR spectroscopy. Delcaroline is the first C19-diterpenoid alkaloid bearing a C(10) hydroxyl group in which the C(4) methyl and C(7)-C(8) methylenedioxy groups are absent.
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■ Transformation of 5-(2-Nitrophenyl)-2-furylcarbamate into 4-Hydroxy-2-quinolinecarboxamide 1-Oxide
Kenichi Yakushijin, Rika Suzuki, Tomoko Tohshima, and Hiroshi Furukawa*
*Faculty of Pharmacy, Meijo University, 150 Yagotoyama, Tenpaku, Nagoya 468-8503, Japan
Abstract
5-(2-Nitrophenyl)-2-furylcarbamates 1a-d are spontaneously cyclized to 4-hydroxy-2-quinolinecarboxamide 1-oxides 2a-d in benzene at room temperature by intramolecular reaction. This reaction provides a new synthetic route to kynurenic acid derivatives.
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■ A New Route to 8-Substituted Pyrrolizidines
Seiji Miyano,* Osamu Yamashita, Shinichiro Fujii, Takao Somehara, Kunihiro Sumoto, Fumio Satoh, and Toru Masuda
*Faculty of Pharmaceutical Sciences, Fukuoka University, 8-19-1 Nanakuma, Jonan-ku, Fukuoka 814-0180, Japan
Abstract
A new route to 8-substituted pyrrolizidines starting with Δ4(8)-dehydropyrrolizidinium perchlorate is described.
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■ Structure of Mulberrofuran C, a Natural Hypotensive Diels-Alder Adduct from Root Barks of the Cultivated Mulberry Tree (Morus bombycis Koidzumi)
Taro Nomura,* Toshio Fukai, Junko Matsumoto, Kazutaka Fukushima, and Yasunori Momose
*School of Pharmaceutical Sciences, Toho University, 2-2-1, Miyama, Funabashi, Chiba 274-8510, Japan
Abstract
A new 2-arylbenzofuran derivative with a fused dihydrochalcone partial moiety was isolated from root barks of the cultivated mulberry tree (Morus bombycis Koidzumi) and named mulberrofuran C. The structure was shown to be I on the basis of spectral data. Mulberrofuran C (I) is regarded biogenetically as a Diels-Alder adduct of a chalcone derivative and dehydromoracin C (II) or its equivalent. Intravenous injection of I (1 mg/Kg) produced a significant hypotension in rabbit.
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■ An Asymmetric Synthesis for the Synthetic β-Lactam Intermediate of Thienamycin via Isoxazoline Derivative
Tetsuji Kametani,* Takayasu Nagahara, and Masataka Ihara
*Pharmaceutical Institute, Tohoku University, Aobayama, Sendai 980-8578, Japan
Abstract
An asymmetric synthesis for the synthetic intermediate to thienamycin was examined via an isoxazoline derivative prepared by 1,3-dipolar cycloaddition between the nitrile oxide and menthyl crotonate. 3(R)-[1’(S)-Hydroxyethyl]-4(S)-(2’,2’-dimethoxyethyl)-2-azetidinone (6B) and its derivative (9B) showed a positive Cotton effect at 214 ~ 213 nm in the cd spectra, respectively.
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■ Selective Preparation. 32. Phosphoric Acid Catalyzed Cyclization and De-tert-butylation of 2,2’-Diamino-4,4’-di-tert-butylbiphenyl Affording Carbazole
Masashi Tashiro,* Yasuhisa Fukuda, and Takehiko Yamato
*Research Institute of Industrial Science, Faculty of Engineering, Kyushu University, 6-1, Kasuga-koen, Kasuga 816-8580, Japan
Abstract
Heating of 2,2’-diamino-4,4’-di-tert-butyldiphenyl (5) in 85% H3PO4 afforded carbazole (2). However, use of diethylene glycol as a solvent did not give 2 but 2,7-di-tert-butylcarbazole (7) was formed in 64% yield.
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■ E. I. Induced Fragmentation of Some Aliphatic Bi- and Tricycloimides
Roberto D’Alessio, Dario Ghiringhelli, and Pietro Traldi*
*Dipartmento di Chimica del Polotecnico, Centro Studio Sostanze Organiche Naturali, C.N.R., Piazza Leonardo da Vinci 32, 20133 Milano, Italy
Abstract
The mass spectrometric behaviour of two 3-azabicyclo[3.3.0]-1-octene-2,4-diones, 3-aza-6,8-dicarboxybicyclo[3.3.0]octane-2,4-dione, three endo-bicyclo[2.2.1]heptane-2,3-dicarboximides, endo-bicyclo[2.2.1]heptane-2,3-dicarboximide and spiro[bicyclo[2.2.1]hept-2,3-ene-2,3’-pirrolidin-2’,5’-dione] is discussed in detail with the aid of exact mass measurements and E, B linked scans for metastable data collection. No general pattern was possible to propose, being the E. I. induced fragmentations strongly affected by structural differences and substituent effects.
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■ The Cycloaddition Reaction of 4,6-Diphenylthieno[3,4-c][1,2,5]oxadiazole with Norbornene
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
4,6-Diphenylthieno[3,4-c][1,2,5]oxadiazole containing tetra-valent sulfur reacted with norbornene to give four stereoisomeric 1:2 adducts, isoxazolinyltetrahydrothiophene derivatives. The reaction proceeds via initial formation of both the endo-exo and exo-exo cycloadducts across the thiocarbonyl ylide dipole. Subsequent ring cleavage of the oxadiazole ring of initial strained cycloadducts generates the nitrile oxide intermediates capable of undergoing cycloaddition to norbornene to afford the 1:2 adducts.
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■ Synthesis of (±)-1,2-Diacetoxyaporphine via an O-Quinol Acetate
Osamu Hoshino, Minoru Ohtani, and Bunsuke Umezawa*
*Faculty of Pharmaceutical Sciences, Science University of Tokyo, 2641 Yamazaki, Noda, Chiba 278-8510, Japan
Abstract
Treatment with conc. H2SO4-Ac2O of a solution of o-quinol acetates (1) - in CH3CN gave (±)-1,2-diacetoxyaporphines (2) in good yields.
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■ Synthesis of 1-Aryl-3-pyrrolin-2-one Derivatives
Katsumi Tabei,* Hideharu Ito, and Toyozo Takada
*Tokyo University of Pharmacy and Life Science, 1432-1 Horinouchi, Hachioji, Tokyo 192-0392, Japan
Abstract
1-Aryl-3-pyrrolin-2-one derivatives (6a-e) were obtained from the corresponding γ-bromoacetoacetanilide derivatives (1a-e) in the overall yields of 31 - 48% through the reduction of the β-carbonyl group, acetylation of the hydroxyl group, and subsequent cyclization and elimination to the 3-pyrrolin-2-one structure.
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■ An Alternative Route to (±)-Emetine and (±)-Dihydrocorynantheine
Seiichi Takano,* Masayuki Sato, and Kunio Ogasawara
*Pharmaceutical Institute, Tohoku University, Aobayama, Sendai 980-8578, Japan
Abstract
An alternative synthesis of (±)-emetine (11) and (±)-dihydrocorynantheine (13) has been developed in formal sense starting from methyl 3-formylhexanoate (3).
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■ The Chemistry of the Benzo[a]- and Benzo[c]quinolizinium Ions
Sayeed-Ud-Din Saraf*
*Department of Chemistry, Faculty of Science, University of Kuwait, Safat 13060, P.O. Box 5969, Kuwait
Abstract
This paper reviews the various synthetical methods for the preparation of the two angular benzologs of quinolizinium ions. The best method involves the irradiation of styrylpyridinium salts and stilbazoles for the preparation of benzo(a)- and benzo(c)quinolizinium salts respectively. Some of the alkaloids containing benzoquinolizine system are also reviewed. Various reactions of the two benzologs are also discussed.