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. 2, 1992
Published online:
■ Chemistry of Indoles Carrying Basic Functions. Part II. Synthesis of 4-Substituted Cyclohept[c.d]indoles. A New Entry into the Ring System
István Moldval, Csaba Szántay Jr., and Csaba Szántay*
*Central Research Institute for Chemistry, Hungarian Academy of Sciences, H-1025 Budapest, P.O.Box 17, Hungary
Abstract
Cyclohept[c,d]indoles (7a), (7b), (12) were synthesized starting from 4-iodoindole-3-carboxaldehydes (3a) and (3b).
Published online:
■ Synthesis of 6-Alkylamino-3-pyridazinecarboxylic Acid Derivatives from Methyl 6-Chloro-3-pyridazinecarboxylate
Shoetsu Konno, Mataichi Sagi, Futoshi Siga, and Hiroshi Yamanaka*
*Pharmaceutical Institute, Tohoku University, Aobayama, Sendai 980, Japan
Abstract
The synthesis of methyl 6-alkylamino-3-pyridazinecarboxylates (4a-c) was accomplished by the following reaction sequence. On treatment of methyl 6-chloro-3-pyridazinecarboxylate (1) with methanolic ammonia, 6-chloro-3-pyridazinecarboxamide (5) was precipitated almost quantitatively, which reacted with primary alkylamines to give the corresponding 6-alkylamino-3-pyridazinecarboxamide (6a-c). These products were smoothly converted into the methyl esters (4a-c) by treatment with methanol in the presence of boron trifluoride etherate. The reaction of 1 with butylamine in THF gave a complicated mixture in which N-butyl-6-chloro-3-pyridazinecarboxamide (2), N-butyl-6-butylamino-3-pyridazinecalboxamide (3), 4b, and 1 were involved.
Published online:
■ 7-Deazaguanosine: Phosphoramidite and Phosphonate Building Blocks for Solid-Phase Oligoribonucleotide Synthesis
Frank Seela* and Karin Mersmann
*Laboratorium für Organische and Bioorganische Chemie, Fachbereich Biologie/Chemie, Universität Osnabrück, Barbarastr. 7, D-4500 Osnabrück, Germany
Abstract
The synthesis of oligoribonucleotide building blocks (phosphonates and phosphoramidites) of 7-deazaguanosine (2-amino-7-(β-D-ribofuranosyl)-7H-pyrrolo[2,3-d]pyrimidin-4(3H)-one, 1) is described. Silylation of the 2'-hydroxy group of 7-deaza-N2-isobutyryl-5'-O-(4-monomethoxytrityl)guanosine (5) was studied with regard to the 2'-selectivity. Best results were obtained with triisopropylsilyl chloride/AgNO3. The 2'-O-protected intermediates (6a and 6b) were converted into the phosphonates (3a, b) or methylphosphoramidites (4a, b), which were successfully used for solid-phase oligoribonucleotide synthesis of (c7G-C)3 (9).
Published online:
■ A Facile Synthesis of Fluorine-containing Bicyclic Oxadiazines
Yasuhiro Kamitori, Masaru Hojo,* Ryoichi Masuda, Toru Numai, Katsumasa Yamamoto, and Isao Nakamura
*Department of Industrial Chemistry, Faculty of Engineering, Kobe University, Kobe 657, Japan
Abstract
By treatment with trifluoroacetic acid fluorine-containing bicyclic oxadiazines (3) could be synthesized in satisfactory yields from hydrazones (1) which were prepared from aldehyde methylhydrazones bearing N-allylic group and trifluoroacetic anhydride.
Published online:
■ Preparation of (6R)- and (6S)-(1R,4R)-6-Methyl-2-(p-toluenesulfonyl)-5-phenylmethyl-2,5-diazabicyclo[2.2.1]heptanes, Intermediates in a Synthesis of New Quinolones
Philippe Remuzon,* Daniel Bouzard, Christian Dussy, Jean-Pierre Jacquet, and Massoud Massoudi
*Bristol-Myers Squibb Pharmaceutical Research Institute, BP 62, Lognes, 77422 Marne-la-Vallée Cedex 2, France
Abstract
An efficient chiral synthesis of both diastereoisomers (2a) and (2b) was performed using trans-4-hydroxy-L-proline as starting material. These bridged piperazines were used in the preparation of quinolones.
Published online:
■ 5,12-Di(1-alkyl)thioquinanthrenediinium Bis-salts and 1-Alkyl-3-alkylthio-1,4-dihydro-4-thiooxoquinolines
Andrzej Maslankiewicz* and Andrzej Zieba
*Department of Organic Chemistry, Silesian School of Medicine, ul. Jagiellonska Str. 4, 41-200 Sosnowiec, Poland
Abstract
The preparation of 5,12-di(1-alkyl)thioquinanthrenediinium bis-salts and their transformation into 1-alkyl-3-alkylthio-1,4-dihydro-4-thiooxoquinolines are described.
Published online:
■ Elecrophilic Substitution of Indoles: Part XI. Lewis Acid Induced Reaction of Skatole with Bezil
Asima Chatterjee,* Ratna Chakrabarti, Biswanath Das, Sanchayita Kanrar, Julie Banerji, Herbert Budzikiewicz, Alain Neuman, and Thierry Prangé
*Department of Pure Chemistry, University College of Science, 92 Acharya Prafulla Chandra Road, Calcutta-700009, India
Abstract
The electrophilic substitution of 3-methylindole with benzil in the presence of BF3·Et2O resulted in a novel heterocyclic system incorporating a stable boron difluoride chelate. The structure was established from spectral analysis (1H-, 13C-, 11B-, 19F-nmr) and X-ray crystallographic analysis.
Published online:
■ Synthesis of 2',3'-Dideoxy-D-erythro-hex-2'-enopyranosyl Nucleosides from 5-Aminouracils and 3,4,6-Tri-O-acetyl-D-glucal
Henrik Pedersen, Erik B. Pedersen,* and Carsten M. Nielsen
*Department of Chemistry, Odense University, DK-5230 Odense M, Denmark
Abstract
Condensation of silylated N,N-disubstituted aminouracils (4) and 3,4,6-tri-O-acetyl-D-glucal (3) in the presence of TMS triflate as catalyst gave anomeric mixtures of 2',3'-dideoxy-D-erythro-hex-2'-enopyranosylnucleosides (5) and (6). The pure β- and α-anomers were separated by chromatography and deprotected with a saturated solution of ammonia in methanol to give 1-(2',3'-dideoxy-β-D-erythro-hex-2-enopyranosyl)-5-aminouracils (7) and their corresponding α-anomers (8), respectively. The anomeric configurations of these nucleosides were assigned by nmr analysis of the dihydro derivatives 9 and 10 obtained by hydrogeneration of 7a and 8a, respectively. No significant activity against HIV-1 was found.
Published online:
■ Synthesis and Fluorescent Properties of New Heterobifunctional Fluorescent Probes
Thierry Besson, Benoit Joseph, Pascale Moreau, Marie-Claude Viaud, Gérard Coudert, and Gérald Guillaumet*
*Laboratoire de Chimie Bioorganique et Analytique, URA-CNRS n° 499, Université d'Orléans, BP 6759, 45067 Orléans Cedex 2, France
Abstract
Heterobifunctional fluorescent molecules possessing the same fluorescent properties as their monofunctional parent compounds are investigated. Two different functions of these probes do not alter their lasing properties and allow many potential applications in cellular biochemistry. This paper investigates two families of compounds derived from carbazole and coumarin. The synthesis and spectral properties of these probes are described.
Published online:
■ Study of the Asymmetric Induction of the 1,3-Dipolar Cycloaddition of Chiral Azomethine Ylides with Unactivated Double Bonds
Guillermo Negron, Georges Roussi,* and Jidong Zhang
*Institut de Chimie des Substances Naturelles, C.N.R.S., 91198 Gif-sur-Yvette Cedex, France
Abstract
The asymmetric induction of the 1,3-dipolar cycloaddition reaction between nonstabilized azomethine ylides generated by deprotonation of the corresponding tertiary amine N-oxides (1a-f) with a base and various unactivated olefins (2a-c) or dienes (2d-e) has been studied. The results show that an important induction can be reached with valinol derived N-oxide (1f). The elimination of the chiral substituent in 3-phenyl-N-(1-hydroxymethyl-propyl)pyrrolidine (8b) allowed to determine the absolute configuration of the major enantiomer (12b) in accordance with the proposed transition state.
Published online:
■ The [2-(Trimethylsilyl)ethoxy]methyl Function as a Suitable N-1 Protecting Group in Lithiation Reactions with Pyrazoles and 1,2,4-Triazoles
Natalie Fugina, Wolfgang Holzer,* and Michael Wasicky
*Institute of Pharmaceutical Chemistry, University of Vienna, Währinger Strasse 10, A-1090 Vienna, Austria
Abstract
Metallation of 1-[2-(trimethylsilyl)ethoxy]methyl-1H-pyrazole or 1-[2-(trimethylsilyl)ethoxy]methyl-1H-1,2,4-triazole, respectively, with one equivalent of n-BuLi followed by reaction with appropriate electrophiles leads to 5-substituted 1-[2-(trimethylsilyl)ethoxy]methyl-1H-pyrazoles and 5-substituted 1-[2-(trimethylsilyl)ethoxy]methyl-1H-1,2,4-triazoles. Deprotection can be achieved either by heating with aqueous ethanolic HCl or by treatment with anhydrous tetrabutylammonium fluoride.
Published online:
■ Oxazolones. Part VI. Reaction of 5(4H)-Oxazolones with Nitrile Imines: Synthesis of 1H-1,2,4-Triazoles through [3+2] Cycloaddition
Maria Luisa Gelmi,* Donato Pocar, and Raul Riva
*Istituto di Chimica Organica, Facoltà di Farmacia, Università di Milano, Via Venezian 21, 20133 Milano, Italy
Abstract
5(4H)-Oxazolones (1) react as dipolarophiles in [3+2] cycloaddition with nitrile imines generated from tetrazoles (2) in refluxing anisole affording two 1H-1,2,4-triazole derivatives (3) and diarylethylenes (4).
Published online:
■ Syntheses of (±)-Z-Geissoschizol, (±)-3-epi-Z-Geissoschizol, (±)-Corynantheidol, (±)-Dihydrocorynantheol, (±)-3-epi-Dihydrocorynantheol and the Corresponding Corynan-17-oic Acid Methyl Esters
Mauri Lounasmaa,* Reija Jokela, Birgit Tirkkonen, Jari Miettinen, and Minna Halonen
*Laboratory for Organic and Bioorganic Chemistry, Technical University of Helsinki, SF-02150 Espoo, Finland
Abstract
The utility of the Claisen rearrangement using carefully separated, diastereoisomerric allylic alcohols (1a) and (1b) in the preparation of (±)-Z-geissoschizol (4a), (±)-3-epi-Z-geissoschizol (4b), (±)-corynantheidol (7a), (±)-dihydrocorynantheol (8a), (±)-3-epi-dihydrocorynantheol (8b) and the corresponding corynan-17-oic acid methyl esters (3a, 3b, 5a, 6a, and 6b) is shown. Special attention is paid to the stereochemical outcome of catalytic (PtO2) hydrogenation of the C(20) Z-ethylidene side chain.
Published online:
■ Synthesis and Attempted [4+2] Cycloaddition Reaction of 2,4,6-Tris(phenylseleno and aryltelluro)-1,3,5-triazines with Diethyl Acetylenedicarboxylate
Hiroyuki Tani,* Tokuo Inamasu, and Hitomi Suzuki*
*Advanced Instrumentation Center for Chemical Analysis, Ehime University, Bunkyo-cho 2-5, Matsuyama 790, Japan
Abstract
2,4,6-Tris(phenylseleno and aryltelluro)-1,3,5-triazines were synthesized by the reaction of 2,4,6-trichloro-1,3,5-triazine with corresponding arylchalcogenide anions. These 2,4,6-tris(arylchalcogeno)-1,3,5-triazines failed to undergo the Diels-Alder reaction with diethyl acetylenedicarboxylate.
Published online:
■ Use of Chiral Amidals in the Synthesis of 6-Methylperihydropyrimidin-4-ones, Protected Form of β-Amino Acids
Rosa Amoroso, Giuliana Cardillo,* and Claudia Tomasini
*Dipartimento di Chimica "G. Giamician", Università di Bologna, Centro per lo Studio della Fisica delle Macromolecole, via Selmi 2, 40126 Bologna, Italy
Abstract
The synthesis of 6-methylperihydropyrimidin-4-ones (7a and 7b) is described by mercury cyclization of the β,γ-unsaturated amidal (3). After reduction of the intermediate organomercury compound (6) and separation of the diastereomeric mixture, the perihydropyrimidin-4-ones (7a and 7b) have been obtained. Their structure has been fully characterized by means of 1H nmr spectroscopy and, after acid hydrolysis, the 3-aminobutyric acids (8a and 8b) have been obtained.
Published online:
■ Amidoalkylation of Pyrazine-2,3-dicarbonitrile by the Radical Generated from N-Alkanoylanilinoalkanoic Acid
Masaru Tada,* Reiko Furuse, and Hiroko Kashima
*Department of Chemistry, School of Science and Engineering, Waseda University, 3-4-1 Okubo, Shinjuku-ku, Tokyo 169, Japan
Abstract
N-Alkanoylanilinoacetic acid and 2-N-alkanoylanilinopropionic acid gave N-alkanoylanilinomethyl radical and 1-N-alkanoylanilinoethyl radical respectively by the peroxodisulfate oxidation catalized by silver ion. The former radical reacts with pyrazine-2,3-dicarbonitrile to give both monosubstitution product (6) and disubstitution product (7), whereas the latter radical gives only monosubstitution product due to the steric hindrance for the second radical substitution.
Published online:
■ Synthesis of (2S,4S)-2-Hydroxy-4-hydroxymethyl-4-butanolide, a Hunger Substance
Katsuya Matsumoto,* Takashi Ebata,* Koshi Koseki, Hiroshi Kawakami, Koji Okano, and Hajime Matsushita
*Life Science Research Laboratory, Japan Tobacco Inc., 6-2 Umegaoka, Midori-ku, Yokohama, Kanagawa 227, Japan
Abstract
(2S,4S)-2-Hydroxy-4-hydroxymethyl-4-butanolide (1a), which is a hunger substance, was synthesized stereoselectively starting from D-γ-ribono-1,4-lactone (2).
Published online:
■ Four-membered Heterocycles Containing One Phosphorus and One Other Heteroatom
Kamyar Afarinkia
*Department of Chemistry, The Johns Hopkins University, Baltimore, Maryland 21218, U.S.A.
Abstract
Syntheses and properties of oxaphosphetanes, thiaphosphetanes, azaphosphetidines and diphosphetanes are reviewed.