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. 20, No. 10, 1983
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■ Nitrogen Bridgehead Compounds Part 23. Ring Transformation of the 2,3a,6a-Triazaphenalenium Chlorides
István Bitter, Béla Pete, István Hermecz, Kálmán Simon, Gábor Tóth, Gábor Náray-Szabó, and Zoltán Mészáros
*Department of Organic Chemical Technology, Technical University of Budapest, H-1521 Budapest, Gellért tér 4, Hungary
Abstract
The 2,3a,6a-triazaphenalenium salts (1,2) undergo degenerated ring transformation in basic media resulting in stable mesomeric betaines (4,5).
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■ (—)-Dehydronorchelindonine and (—)-Isodidehydrochelidonine, Two Probable Biogenetic Precursors in the Benzophenanthridine Series of Isoquinoline Alakaloids
Luis Castedo, Domingo Domínguez, Alberto Puga, José M. Saá, and Rafael Suau
*Facultad de Química y Sección de Alcaloides, Deparamento de Química Orgánica, C. S. I. C., Santiago de Compostela, Spain
Abstract
The preparation of the title compounds 2 and 5 is described. Their probable biogenetic role is suggested on the basis of chemical evidence obtained by oxidation studies with a one electron oxidant.
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■ A Facile Rearrangement of Pyridinecarbohydroxamic Acids in Formamide
Zygmunt Eckstein, Ewa Lipczynska-Kochany, and Jerzy Krzeminski
*Institute of Organic Chemistry, Biochemistry and Biotechnology, Wroclaw University of Technology, Wyb. Wyspianskigo 27, 50-375 Wroclaw, Poland
Abstract
Five pyridinecarbohydroxamic acids were converted smoothly to the corresponding aminopyridines by means of the “amide modification” of the Lossen rearrangement.
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■ Double Sulfer Transfer and 1,2,3-Trithiolane Formation in the Photolysis of a Mesoionic 5-Acetyl-4-thiazolone
Tuvia Sheradsky and David Zbaida
*Department of Organic Chemistry, The Hebrew University of Jerusalem, Jerusalem 91904, Israel
Abstract
The photolysis of anhydro-5-acetyl-2,3-diphenylthiazolium hydroxide (1a) in alcohols yielded alkyl 2-acetyl-3-anilinocinnamates (3) and 1-acetyl-5,6-diphenyl-6-aza-2,3,4-trithiabicyclo[3.2.0]heptan-7-one (4), in a ratio of 2.6:1. A mechanism which involves two consecutive transfers of sulfur atoms between radical intermediates is suggested.
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■ Stereoselective [3+2] Cycloaddition Reaction of Pyridinium and Thiazolium Methylides to Electron-deficient Olefinic Dipolarophiles
Otohiko Tsuge, Shuji Kanemasa, and Shigeori Takenaka
*Graduate School of Engineering Sciences, Kyushu University, 6-1, Kasuga-koen, Kasuga 816-8580, Japan
Abstract
The cycloaddition reaction of pyridinium and thiazolium methylides to electron-deficient olefinic dipolarophiles has been found to take place through an endo approach of the anti-ylides to the dipolarophiles affording the stereoselective [3 + 2] cycloadducts in quantitative yields.
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■ Synthesis of 4H-Pyrazolo[1,5-a][1,3]diazepine
Takushi Kurihara, Eiji Kawasaki, and Keiko Nasu
*Faculty of Pharmaceutical Science, Osaka University of Pharmaceutical Sciences, 4-20-1 Nasahara, Takatsuki, Osaka 569-1094, Japan
Abstract
6-Acetyl-8-ethoxycarbonyl-4H-pyrazolo[1,5-a][1,3]diazepine-3-carbonitrile (5) was synthesized by treatment of 2 with silicic acid.
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■ Tautomeric Behaviors of 3-(1,3,4-Oxadiazol-2-yl)methylene-2-oxo-1,2,3,4-tetrahydroquinoxalines
Yoshihisa Kurasawa and Atsushi Takada
*School of Pharmaceutical Sciences, Kitasato University, Shirokane, Minato-ku, Tokyo 108-8641, Japan
Abstract
3-(1,3,4-Oxadiazol-2-yl)methylene-2-oxo-1,2,3,4-tetrahydroquinoxalines (2a,b) were found to exhibit the two tautomers in dimethylsulfoxide and three tautomers in trifluoroacetic acid, and their tautomeric species were assumed based on the NMR and UV spectral data.
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■ Synthesis of 5,7-Dihydroxy-8-cinnamoyl-4-phenyldihydrocoumarins
Munekazu Iinuma, Shin Matsuura, and Fujio Asai
*Gifu Pharmaceutical University, 6-1 Mitahora-higashi 5-chome, Gifu 502-8585, Japan
Abstract
5,7-Dihydroxy-8-cinnamoyl-4-phenyldihydrocoumarins isolated from Pityrogramma trifoliata were synthesized for their structures confirmation.
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■ Pachygonamine and N-Methylpachygonamine, New Bisbenzylisoquinoline Alkaloids from Pachygone ovata
M. Uvais S. Sultanbawa, Subramaniam Sotheeswaran, Sinnathamby Balasubramaniam, Moustafa Abd El-Kawi, David J. Slatkin, and Paul L. Schiff, Jr.
*Department of Pharmacognosy, School of Pharmacy, University of Pittsburgh, Pittsburgh, PA 15261, U.S.A.
Abstract
Chromatography of methanolic extract of Pachygone ovata over silica gel afforded pachygonamine (1) and N-methylpachygonamine (2) which were characterized as new dibenzo-p-dioxin biphenyl bisbenzylisoquinoline alkaloids by a consideration of physicochemical data and conversion to N-methyltiliamosine (7). In addition, tiliamosine (3) was isolated for the first time from nature as the free base instead of the previously isolated N-acetylamide (4).
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■ Remarkable Difference in the Cycloaddition Reactivity between 2-(1-Trimethylsilyloxyvinyl)furan and -thiophene
Tadashi Sasaki, Yukio Ishibashi, and Masatomi Ohno
*Institute of Applied Organic Chemistry, Faculty of Engineering, Nagoya University, Chikusa, Nagoya, Aichi 464-8601, Japan
Abstract
The title thiophene (4) showed better Diels-Alder reactivity than the corresponding furan (3) in the mode and relative rate of the reaction with a dienophile; this is the reverse of the well-known ‘endo-diene’ reactivity.
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■ The Synthesis od Alpha-thiophene Oligomers by Oxidative Coupling of 2-Lithiothiophenes
Jacques Kagan and Sudershan K. Arora
*Department of Chemistry, University of Illinois at Chicago, 845 West Taylor St., Chicago, IL 60607-7061, U.S.A.
Abstract
Alpha-thiophene oligomers containing an even number of thiophene rings can be obtained with very good yields by reacting a suitable thiophene precursor with 0.5 equivalent of lithium diisopropylamide in dry THF, followed by the oxidation of the α-lithio derivative with cupric chloride. The Scheme is illustrated with the synthesis of 2,2’-bithienyl, α-quaterthienyl, and α-sexithienyl in 83, 85, and 73% yields from thiophene, 2,2’-bithienyl, and α-terthienyl respectively.
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■ 2,5-Di(2’-thienyl)furan and an Improved Synthesis of Alpha-Terthienyl
Jacques Kagan and Sudershan K. Arora
*Department of Chemistry, University of Illinois at Chicago, 845 West Taylor St., Chicago, IL 60607-7061, U.S.A.
Abstract
The first synthesis of 2,5-di(2’-thienyl)furan was performed by oxidizing the lithium enolate of 2-acetylthiophene with cupric chloride, to 1,4-di(2’-thienyl)1,4-butanedione. This product was dehydrated with acetic anhydride in the presence of hydrogen chloride, to give the title compound in 74% overall yield. The same route provided a most convenient synthesis for alpha-terthienyl, which was obtained in 73% yield from 2-acetylthiophene.
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■ A Facile Synthesis of 4-Aryl-1,2,3,4-tetrahydroisoquinolines: A Total Synthesis of (±)-Cherylline
Hiroshi Hara, Ryuichi Shirai, Osamu Hoshino, and Bunsuke Umezawa
*Faculty of Pharmaceutical Sciences, Science University of Tokyo, 2641 Yamazaki, Noda, Chiba 278-8510, Japan
Abstract
Reaction of benzylamines (3a-d) and styrene oxide at 140 °C gave quantitatively β-hydroxyphenethylamine (2a-d), acid treatment of which afforded 4-aryl-1,2,3,4-tetrahydroisoquinolines (8a-d) in high yields. On the other hand, the styrene oxide (10 or 15) was treated with BF3-Et2O in MeOH yielding regioselectively a β-methoxyphenethyl alcohol (12 or 16), the mesylate of which reacted with the benzylamine (3e) in the presence of Hünig’s base to give the N-benzyl-β-methoxyphenethylamine (2f or 2g). Acid treatment of 2f or 2g afforded (±)-cherylline (1) or (±)-4’-O-methylcherylline (14) in 85 or 67% overall yield from O-benzylisovanillin.
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■ O-Methylcimiacerol, a New Triterpene from Cimicifuga acerina
Genjiro Kusano, Shigeo Nozoe, Zenei Taira, and Tsunematsu Takemoto
*Pharmaceutical Institute, Tohoku University, Aobayama, Sendai 980-8578, Japan
Abstract
The structure of O-methylcimiacerol, a new triterpene obtained from Cimicifuga acerina (Sieb. et Zucc.) C. Tanaka after hydrolysis of the glycosides, has been established by spectroscopic and X-ray crystallographic analysis.
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■ Structure of Mahuannin D, a Hypotensive Pronciple of Ephedra Roots
Yoshimasa Kasahara and Hiroshi Hikino
*Pharmaceutical Institute, Tohoku University, Aobayama, Sendai 980-8578, Japan
Abstract
From the crude drug “mao-kon”, the roots of Ephedra plants, a new flavano-flavanol, mahuannin D, exhibiting the hypotensive activity has been isolated. The stereostructure of mahuannin D has been determined as represented by formula I based on chemical and physical evidence.
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■ Synthetic Approach to the Antitumor Antibiotic Lavendamycin: a Synthesis of Demethallavendamycin Methyl Ester
Satoshi Hibino, Miko Okazaki, Kohichi Sato, Itsuko Morita, and Masataka Ichikawa
*Graduate School of Pharmacy and Pharmaceutical Sciences, Faculty of Pharmacy and Pharmaceutical Sciences, Fukuyama University, Fukuyama, Hiroshima 729-0292, Japan
Abstract
A synthetic approach to the lavendamycin has been achieved by a formation of β-carboline derivative and oxidation of bromophenol derivative to the quinolinequinone system using cerium ammonium nitrate.
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■ The Product from the Reaction of Diazomethane with 1,3-Oxaselenole Derived from Dimedone
Katsuhide Matoba and Takao Yamazaki
*Faculty of Pharmaceutical Sciences, Toyama Medical and Pharmaceutical University, 2630 Sugitani, Toyama, Toyama 930-0194, Japan
Abstract
The 1,3-oxaselenole derivative (VI) obtained from dimedone was treated with an excess of diazomethane to give 1,4,7-dioxaselenocine derivative (VII) in a quantitative yield. The deselenization of VII was carried out by the benzyne-hydrogenolysis method to give 3-methoxy-5,5-dimethyl-2-(5,5-dimethyl-3-oxo-1-cyclohexen-1-yl)oxy-2-cyclohexenone (VIII). Treatment of VII with aqueous alkali gave 5,5,5’,5’-tetramethyl-1,1’,3,3’-tetroxo-2,2’-cyclohexylmethane (IX), and it afforded 4,4-dibromo-3,3-dimethoxy-5,5-dimethylcyclohexanone (X) with bromine in MeOH. VII was reduced spdium borohydride to an allyl alcohol (XIa) which was converted to its acetate (XIb).
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■ Total Synthesis of (±)-Clavicipitic Acids I and II
Hideaki Muratake, Takumi Takahashi, and Mitsutaka Natsume
*Research Foundation Itsuu Laboratory, 2-28-10 Tamagawa, Setagaya-ku, Tokyo 158, Japan
Abstract
Ergot alkaloids, clavicipitic acids (3 and 4) were synthesized respectively in racemic forms from 4-(3-oxo-1-butenyl)-indole (5) by way of 6 and 7. Names of clavicipitic acids I and II were proposed for 3 and 4.
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■ A Synthesis of Mixed Tetrahydroisoqunoline Dimers via p-Quinol Acetate
Hiroshi Hara, Masatoshi Murakata, Osamu Hoshino, Bunsuke Umezawa, and Yoichi Iitaka
*Faculty of Pharmaceutical Sciences, Science University of Tokyo, 2641 Yamazaki, Noda, Chiba 278-8510, Japan
Abstract
Several mixed tetrahydroisoquinoline dimers (4, 6, 7, 10b, 11b, 12b, and 13b) were prepared by reaction of the p-quinol acetate (1a) and the corresponding phenolic tetrahydroisoquinolines. In the case of 5-hydroxytetrahydroisoquinoline (14), a different kind of dimer (16) was obtained together with 15. A radical mechanism was presented for these reactions.
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■ An Efficient Synthesis of (S)-(—)-Befunolol Hydrochloride Involving the Regioselective Condensation of (R)-Glycidol and 2-Acetyl-7-hydroxybenzofuran
Jun Nakano, Mitsuo Mimura, Mitsuo Hayashida, Kazuhiko Kimura, and Teruo Nakanishi
*Kaken Pharmaceutical Co., Ltd., Shinomiya, Minamikawara-cho, Yamashina-ku, Kyoto 607-8042, Japan
Abstract
(S)-(—)-Befunolol·HCl (S)-(—)-(1) was synthesized via (S)-(+)-2-acetyl-7-(2,3-epoxypropoxy)benzofuran (5) which was prepared by redox dehydrative condensation of 2-acetyl-7-hydroxybenzofuran (3) and (R)-glycidol (4).
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■ Synthesis of 5,7-Ethano-4,5,5a,6,7,11b-hexahydro-2,6,7-trimethyl-1H-benzo[g]homoquinolin-9-ol and 4,6-Ethano-3,4,4a,5,6,10b-hexahydro-2,5,6-trimethylbenzo[f]quinolin-8-ol
Mikio Hori, Tadashi Kataoka, Hiroshi Shimizu, Eiji Imai, Yoshinari Suzuki, and Norihiko Kawamura
*Department of Pharmacognosy, Gifu College of Pharmacy, 6-1 Mitahora-higashi 5-chome, Gifu 502-8585, Japan
Abstract
Novel 1,3-bridged 1,2,3,4,5,6-hexahydro-2,6-methano-3-benzazocine derivatives (3,9,13, and 16) were synthesized stereospecifically by acid-catalyzed cyclization in PPA starting from 6,11-dimethyl-8-methoxy-3,4,5,6-tetrahydro-2,6-methano-3-benzazocin-1(2H)-one.
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■ A Facile Synthesis of 4-Substituted 3-Formylindoles
Masanori Somei, Toshifumi Hasegawa, and Chikara Kaneko
*Faculty of Pharmaceutical Sciences, Kanazawa University, 13-1 Takara-machi, Kanazawa 920-0934, Japan
Abstract
A new synthetic method for 3-formylindoles having a carbon side chain at the 4-position was elaborated by means of thallation-palladation method.
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■ Valence Tautomerism of 3-Azidopyrazine-1-oxide
Misa V. Jovanovic
*Department of Chemistry, Southern Methodist University, P.O. Box 750314, Dallas, TX 75275-0314, U.S.A.
Abstract
The first azido-tetrazolo valence tautomerism of a π-deficient N-oxide, 3-azidopyrazine-1-oxide, is reported. It exists in its azido form in CDCI3 and in the tetrazolo form in the solid state or in DMSO-d6. Both valence tautomers are present in acetone-d6.
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■ Synthesis of Some 3-Arylimino-5-(N-4-methoxybenzylidenehydrazono)-1,2,4-dithiazolidines
Mohammad Ramzan Ali, Rajendra Singh, and Vinay Kumar Verma
*Department of Applied Chemistry, Institute of Technology, Banaras Hindu University, Varanasi-221 005, India
Abstract
A simple and convenient synthesis of some 3-arylimino-5-(N-4-methoxybenzylidenehydrazono)-1,2,4-dithiazolidines (IV a-e) has been achieved by oxidative debenzylation and cyclization of the corresponding 5-aryl-1-(4-methoxybenzylideneamino)-2-S-benzyliso-2,4-dithiobiurets (III a-e) which in turn were prepared by the condensation of certain potentially active S-benzyliso-4-methoxybenzylidenethiosemicarbazone (II) with appropriate aryl isothiocyanate. These dithiazolidines have been characterized by their synthesis through alternative routes (Scheme 1), elemental analyses and also by ir spectra.
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■ Oxidation of Coronaridine
Kamesh Rastogi, Randhir S. Kapil, and Satya P. Popli
*Central Drug Research Institute, Lucknow 226001, India
Abstract
A variety of oxidising reagents were used for the oxidation of coronaridine. In this study four new alkaloids 16-hydroxymethylene-3-oxoibogamine (7), 2,3,7-(2H,7H)-trioxo-2,7-(2H,7H)-secocoronaridine (10), bisindole alkaloids 5-(coronaridin-10-yl)-5-hydroxy-6-oxocoronaridine (11) and 5-(6-oxocoronaridin-10-yl)-6-oxocoronaridine (12) were obtained and their structures elucidated. Additionally alkaloids 5-hydroxy-6-oxocoronaridine (3), 5-oxocoronaridine (6) and 6-oxocoronaridine (13) are being reported for the first time semisynthetically.
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■ Diazotization of Some Aminodiazine N-Oxides
Misa V. Jovanovic
*Department of Chemistry, Southern Methodist University, P.O. Box 750314, Dallas, TX 75275-0314, U.S.A.
Abstract
Diazotization of a number of aminopyrazine and aminopyrimidine N-oxides affords intermediate diazonium compounds which can be converted to the corresponding bromo and chloro analogs in the presence of the appropriate halide ions. In some instances, electrophilic aromatic substitution takes place prior to the diazotization step. Nucleophilic halogenation accompanying deoxygenation occurs with 2-aminopyrimidine N-oxide in the same manner as described for some 3-amino-1,2,4-triazine 2-oxides.
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■ Synthesis and Structure of Some 1-(2-Thienylmethyl)-1H-imidazole Derivatives as Potential Antimicrobial Agents
Elena Belgodere, Ricardo Bossio, Stefano Chimichi, Stefano Marcaccini, and Roberto Pepino
*CNR, Centro di Studio Sulla Chimica e la Struttura dei Composti Eterociclici e lolo Applicazioni, c/o Dipartimento di Chimica Organica “Ugo Schiff”, Università di Firenze, Via Gino Capponi 9, I-50121 Firenze, Italy
Abstract
A series of 1-(2-thienylmethyl)-1H-imidazole derivatives were synthesized starting from 2-thienylmethylamine (I) and ethyl chloroacetate. The structure of all the new compounds were determined by uv, ir, and 1H-nmr spectroscopy. Preliminary tests of biological activity on these compounds showed that 1-(2-thienylmethyl-1H-imidazole-5-carbohydroxamic acid (XII) is fairly active against Escherichia Coli and Bacillus Subtilis.
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■ Palladium(O) and Phase Transfer Catalyzed Conversion of Azirines to Styrylindoles
Howard Alper and Chulangani P. Mahatantila
*Ottawa-Carleton Chemistry Institute, Department of Chemistry, University of Ottawa, Ottawa, Ontario, K1N 6N5, Canada
Abstract
2-Styrylindoles were obtained in modest yields by the exposure of azirines to carbon monoxide, a palladium(0) catalyst, sodium hydroxide, benzene as the organic phase, and benzyltriethylammonium chloride as the phase transfer agent. The reaction is sensitive to the atmosphere used.
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■ High Valent Chromium Heterocyclic Complexes-1 Naphthyridinium and Parazinium Chlorochromates
Harry B. Davis, Roger M. Sheets, Jeanne M. Brannfors, William W. Paudler, and Gary L. Gard
*Department of Chemistry, Portland State University, Portland, Oregon 97207, U.S.A.
Abstract
The new mild oxidizing agents, 1,8-naphthyridinium chlorochromate (NapCC) and pyrazinium chlorochromate (PzCC) have been prepared and characterized. A study of the oxidative behavior of NapCC and PzCC relative to pyridinium chlorochromate (PCC) with primary and secondary alcohols is reported.
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■ Synthesis of 2-Substituted 3,5-Dibromothiophenes through Base-catalyzed Halogen Dance Reaction of 2,5-Dibromothiophene
Shinzo Kano, Yoko Yuasa, Tsutomu Yokomatsu, and Shiroshi Shibuya
*School of Pharmacy, Tokyo University of Pharmacy and Life Science, 1432-1 Horinouchi, Hachioji, Tokyo 192-0392, Japan
Abstract
Treatment of 2,5-dibromothiophene with LDA in THF at -78 °C, followed by quenching with electrophiles afforded the corresponding 2-substituted 3,5-dibromothiophenes in good yield.