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. 34, No. 12, 1992
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■ Reactions of 5-Cyano-1,4-diphenylpyridazino[4,5-a]indolizines with Dimethyl Acetylenedicarboxylate: Regioselective Formation of 1:2 Michael Type Adducts
Kiyoshi Matsumoto,* Yukio Ikemi, Mitsuo Toda, Takane Uchida, and Akikazu Kakehi
*Graduate School of Human and Environmental Studies, Kyoto University, Kyoto 606-01, Japan
Abstract
Reactions of 5-cyano-1,4-diphenylpyridazino[4,5-a]indolizines with dimethyl acetylenedicarboxylate afforded regioselectively the 1:2 adducts in a Michael fashion rather than in a 1,3-dipolar manner. The structure was established by an X-ray crystallography.
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■ Electrophilic Reaction of Quinoline 1-Oxide through Base-induced Deprotonation
Yoshinobu Tagawa, Kazuya Hama, Yoshinobu Goto,* and Masatomo Hamana
*Faculty of Pharmaceutical Sciences, Fukuoka University, Nanakuma, Jonan-ku, Fukuoka, 814-01, Japan
Abstract
Lithiation of quinoline 1-oxide-BF3 complex (3) with LTMP and TMEDA in ether at -78 °C followed by treatement with benzaldehyde or cyclohexanone affords the corresponding 2-substituted derivatives (4, 5 or 6), while the reaction of quinoline 1-oxide (1) itself under the same conditions results in the formation of 2,2’-biquinoline 1-oxide (2).
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■ Branched Chain Carbohydrate Lactones from a Tandem SmI2 Deoxygenation-Carbonyl Addition Reaction
Eric J. Enholm* and Shujun Jiang
*Department of Chemistry, University of Florida, Gainesville, Florida 32611, U.S.A.
Abstract
Treatment of a carbohydrate lactone with a ketone in the presence of SmI2-HMPA produces a deoxygenation/carbonyl addition reaction to afford new C2-branched chain carbohydrates.
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■ Trimethylsilyl Triflate-promoted [2+3] Dipolar Cycloaddition of Nitrones with Allyltrimethylsilane
Dilip D. Dhavale and Claudio Trombini*
*Dipartimento di Chimica "G. Ciamician", Università di Bologna, Via Selmi 2, I-40126 Bologna, Italy
Abstract
3-Alkyl-5-trimethylsilylmethylisoxazolidines are accessible in good yields and at temperatures ≤ 20 °C, by the trimethylsilyl triflate-promoted reaction of allyltrimethylsilane with aliphatic nitrones.
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■ A Lewis Acid Mediated Intramolecular [2+2] Cycloaddition of 3-(9-Methylundeca-7,9-dienyl)-9-methylene-2,8-dioxabicyclo[4.3.0]nonane-5,7-dione
Kei Takeda,* Akihiko Shimotani, and Eiichi Yoshii*, and Kentaro Yamaguchi
*Faculty of Pharmaceutical Sciences, Toyama Medical and Pharmaceutical University, Sugitani 2630, Toyama 930-01, Japan
Abstract
Treatment of 3-(9-methylundeca-7,9-dienyl)-9-methylene-2,8-dioxabicyclo[4.3.0]nonane-5,7-dione (3) with SnCl4 in CH2Cl2 at -80 °C produced intramolecular [2+2] cycloadducts (6a-d) rather than intramolecular Diels-Alder adducts.
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■ A New Synthesis of 4,5,6,7-Tetrahydrothieno[3,2-c]pyridine
Aleksander Warm*
*LONZA AG, Research & Development, CH-3930 Visp, Switzerland
Abstract
The title compound was prepared via a sequence containing as the key step a thiophene ring formation from a 1,4-dicarbonyl intermediate.
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■ A Simple Four Step Synthesis and Optical Resolution of 4-Nitro-1,3,4,5-tetrahydrobenz[cd]indole, and the Syntheses of 1-Hydroxy Derivatives of 4-Nitro- and 4-Amino-1,3,4,5-tetrahydrobenz[cd]indoles
Kyoko Nakagawa, Naokatsu Aoki, Harunobu Mukaiyama, and Masanori Somei*
*Faculty of Pharmaceutical Sciences, Kanazawa University, 13-1 Takara-machi, Kanazawa 920, Japan
Abstract
4-Nitro-1,3,4,5-tetrahydrobenz[cd]indole was synthesized from indole-3-carboxaldehyde in four steps with an overall yield of 30%. Optical resolution of its enantiomers by chiral column chromatography was successful. Syntheses of 1-hydroxy derivatives of 4-nitro- and 4-amino-1,3,4,5-tetrahydrobenz[cd]indoles are also reported.
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■ A New Synthesis of 3H-Cycl[3.2.2]azino[1,2-e]cycl[3.3.2]azin-3-one Derivative
Yoshiro Matsuda,* Hiromi Gotou, Makoto Yamashita, Kimitoshi Takahashi, Shizuki Ide, Kazuki Furuno, Katsura Torisu, Takahiro Itou, and Chieko Motokawa
*School of Pharmaceutical Sciences, Nagasaki University, 1-14 Bunkyo-machi, Nagasaki 852, Japan
Abstract
Treatment of indolizinoquinolizinium salt (6) with dimethyl acetylenedicarboxylate in the presence of K2CO3 in refluxing nitrobenzene gave a nitrogen-bridged annulenoannulenone, 3H-cycl[3.2.2]azino[1,2-e]cycl[3.3.2]azinone derivative (7).
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■ Chiral, Potentially Irreversible Ligands for the Sigma Receptor Based on the Structure of 3-(3-Hydroxyphenyl)-N-propylpiperidine (3-PPP)
Neile A. Grayson, Wayne D. Bowen, and Kenner C. Rice*
*Laboratory of Medicinal Chemistry, Bldg 8, Rm B1-22, NIDDK, National Institutes of Health, Bethesda, MD 20892, U.S.A.
Abstract
(+)-3-PPP is an optically active, highly potent and selective ligand for sigma receptors. The resolved enantiomeric pairs of potential irreversible sigma ligands (5a,b) and (9a,b) were designed and synthesized based on the structure of 3-PPP. An improved method of resolution was developed for the common intermediate (2a,b).
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■ Expected and Unexpected Reactions of N,N-Diphenylhydrazones with Chlorocarbonylsulfenyl Chloride
Chang He Xi and Gert Kollenz*
*Institute of Organic Chemistry, Isotope Department, University of Graz, Heinrichstrasse 28, A-8010 Graz, Austria
Abstract
The N,N-diphenylhydrazones (1) and chlorocarbonylsulfenyl chloride cyclize to give the thiazolones (2), with the benzoyl derivative (1i) the 1,3-oxathiolone (3) is obtained. At low temperatures the hydrazines (1f,g,i), are selectively oxidized affording α-oxohydrazones (4). From all thiazolones (2a,d) only can be rearranged into the indole derivatives (6) via a Fischer-indolizatioin process.
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■ Synthesis and Biological Activity of Novel N-1-Aryl-6-fluoro-5-methyl 1,8-Naphthyridine-3-carboxylic Acids
Jean-Pierre Jacquet,* Daniel Bouzard, Pierre Di Cesare, Nicolas Dolnic, Massoud Massoudi, and Philippe Remuzon
*Bristol-Myers Squibb Pharmaceutical Research Institute, B.P. 62, 77422 Marne-La-Vallée Cedex 2, France
Abstract
A series of 5-methyl-4-oxo-1,8-naphthyridine-3-carboxylic acids was prepared in which the N-1 position was substituted by various aryl groups. Seven compounds showd excellent in vitro antibacterial activity against Gram-positive and Gram-negative strains.
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■ Photochemical Behaviour of 1,2,5-Oxadiazoles — Irradiation of Some 3-Acylamino-1,2,5-oxadiazoles in the Presence of Nucleophiles
Silvestre Buscemi, Vincenzo Frenna, Tullio Caronna, and Nicolo Vivona*
*Dipartimento di Chimica Organica, Università di Palermo, Via Archirafi 20, 90123 Palermo, Italy
Abstract
The photochemical behaviour of some 3-acylamino-1,2,5-oxadiazoles (furazans) has been investigated. On irradiation at 254 nm in the presence of nucleophiles (ammonia, primary or secondary amines), the photoreaction produced 3-substituted 1,2,4-oxadiazoles in which the substituent at C(3) arises from the used reagent. Some mechanistic considerations are reported.
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■ Stereoselective Total Synthesis of (±)-Peperomin C
Raymundo Cruz-Almanza* and Fernando Padilla Higareda
*Instituto de Química, Universidad Nacional Autónoma de México, Circuito Exterior Ciudad Universitaria, Coyoacán, 04510, México, D.F., México
Abstract
A simple and efficient stereoselective total synthesis of (±)-peperomin C(1) was performed employing the 1,4-addition reaction of the organolithium salt (10) to the 3-methyl-2(5H)-furanone (7) catalized by cuprous iodide as the key steps. On the other hand, α-methyl-β-(diphenylmethyl)-γ-butyrolactone (4), an analogous of peperomin C, was also synthetized by the 1,4-addition reaction of the organocuprate (6) on the same 3-methyl-2(5H)furanone (7).
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■ Simple Preparations of C-4-tert-Butylated NADH/NAD+ Analogs
Agnès Anne*
*Laboratorie d’Electrochimie Moléculaire, Université de Paris 7, URA 438, 2, Place Jussieu, 75251, Paris Cedex 05, France
Abstract
The addition of tert-butyl Grignard reagent to the 1-benzyl-3-carbamoylpyridinium salt (1) gives a mixture of the C-4-(2), C-6-(3), and C-2-tert -butylated dihydronicotinamides (4) in which the desired 1,4-isomer predominates. Stable cristalline 1-benzyl-4-tert-butyl-1,4-dihydronicotinamide (2) can be easily isolated. Oxidation of the product with the 1-benzyl-3-cyanoquinolinium ion (6) was found to be strongly solvent-dependent. In acetonitrile, exclusive hydride transfer gives the corresponding C-4-tert-butylated pyridinium ion (5). In methanol, an interesting tert-butyl transfer from 1,4-dihydronicotinamide (2) to quinolinium (6) occurs competitively, and predominates in the presence of a catalytic amount of formic acid; the resulting C-4-tert-butylated 1,4-dihydroquinoline derivative (8) can be readily isolated.
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■ Formations of 1,1’-Biazaazulanones through [8+2]-Type Cycloaddition Reactions of Tropone Azine with Heterocumulenes
Kazuaki Ito, Katsuhiro Saito,* and Kensuke Takahashi
*Department of Applied Chemistry, Nagoya Institute of Technology, Gokiso-cho, Showa-ku, Nagoya 466, Japan
Abstract
Reaction of N-aryl-2,4,6-cycloheptatrien-1-imine with hydrazine afforded tropone azine, which reacted with chloroketenes to give 1,1’-biazaazulanones via [8+2]-type cycloadducts followed by elimination of hydrochloride. The similar reaction using phenyl isocyanate afforded a [8+2]-type 1:2 cycloadduct, while the reaction with phenyl isothiocyanate yielded only a 1:1 cycloadduct. 15N and 13C nmr spectra on C=N bond of tropne azine showed a minor contribution of a dipolar structure compared with the case of N-aryl-2,4,6-cycloheptatrien-1-imines.
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■ Regioselective Bromination of Methoxy Derivatives of Ethyl Indole-2-carboxylate [Synthetic Studies of Indoles and Related Compounds. XXX]
Masanobu Tani, Hiroyo Ikegami, Mayumi Tashiro, Tetsuji Hiura, Hiroko Tsukioka, Chiaki Kaneko, Toshiko Notoya, Mikiko Shimizu, Masahiko Uchida, Yoshiyuki Aida, Yuusaku Yokoyama, and Yasuoki Murakami*
*School of Pharmaceutical Sciences, Toho University, 2-2-1, Miyama, Funabashi, Chiba 274, Japan
Abstract
Bromination of ethyl methoxyindole-2-carboxylates (1) with bromine in acetic acid proceeded on the benzene moiety of 1, whereas the reaction of 1 with pyridinium bromide perbromide in pyridine or N-bromosuccinimide in dimethylformamide gave ethyl 3-bromo-methoxyindole-2-carboxylate (2).
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■ New Acrimarines from Citrus Plants
Yuko Takemura, Mami Inoue, Hisayo Kawaguchi, Motoharu Ju-ichi,* Chihiro Ito, Hiroshi Furukawa, and Mitsuo Omura
*Faculty of Pharmaceutical Sciences, Mukogawa Women’s University, Nishinomiya, Hyogo 663, Japan
Abstract
Five new acrimarines (acridone-coumarin dimers) were isolated from some Citrus plants (Rutaceae) and their structures were elucidated by spectroscopic method.
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■ A Convenient and New One-Step Synthesis of 1H-Imidazole-2-carboxamides
Baldev Singh*
*Department of Medicinal Chemistry, Sterling Winthrop Pharmaceuticals Research Division, Rensselaer, NY 12144, U.S.A.
Abstract
1,2-Diketone monophenylhydrazones (2) reacted with aminomalonamide in 1-methyl-2-pyrrolidinone to provide 1H-imidazole-2-carboxamides (4). The condensation of 1-(4-pyridinyl)-2-propanone with phenyldiazonium chloride gave 1-phenylhydrazono-1-(4-pyridinyl)-2-propanone (2a). 4-Methyl-5-(4-pyridinyl)-1H-imidazole-2-carboxamide (4a) was converted to the corresponding nitrile (5a) by the action of phosphorous oxychloride.
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■ Condensed Heteroaromatic Ring Systems. XXII. Simple and General Synthesis of 1H-Pyrrolopyridines
Takao Sakamoto, Chisato Satoh, Yoshinori Kondo, and Hiroshi Yamanaka*
*Pharmaceutical Institute, Tohoku University, Aobayama, Sendai 980, Japan
Abstract
Four kinds of 1H-pyrrolopyridines having no substituent were simply and easily synthesized by the palladium-catalyzed reaction of easily available nitropyridine derivatives with (Z)-1-ethoxy-2-tributylstannylethene as a key reaction.
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■ Synthesis of Pyridoacridines
Mercedes Alvarez and John A. Joule*
*Chemistry Department, University of Manchester, Manchester M13 9PL, U.K.
Abstract
The synthesis of pyridoacridines is reviewed.