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. 45, No. 3, 1997
Published online:
■ Synthetic Study Directed toward Novel Multi-Linked Heterocycles1
Masanori Somei,* Yoshikazu Yamada, Keiichi Kitagawa, Katsuko Sugaya, Yayoi Tomita, Fumio Yamada, and Kyoko Nakagawa
*Faculty of Pharmaceutical Scicences, Kanazawa University, 13-1 Takara-machi, Kanazawa 920-0934, Japan
Abstract
2-Amino-4-(1-methylindol-3-yl)thiazole (11c) has a characteristic nucleophilic nature at the 5-position and add to the 4-position of acetylpyridinium acetate (13) producing 2-acetylamino-5-(1-acetyl-1,4-dihydropyridin-4-yl)-4-(1-methylindol-3-yl)thiazole (1c). Its structure was established by X-ray single crystallographic analysis. Applying the results, simple syntheses of the related tris- (1a-b and 2-8) and tetrakis-linked heterocycles (9) were achieved.
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■ Total Synthesis of Sinomendine and Its Analogs
De-Min Zhou, Bao-Zhen Yue, Ji-Qiao Cui, Meng-Shen Cai, and Li-He Zhang*
*School of Pharamceutical Sciences, Beijing Medical University, Beijing, 100083, China
Abstract
Sinomendine (1), a good receptor antagonist of angiotensin II and rare oxoaporphine alkaloid isolated from traditional Chinese drug Sinomenium acutum (Thunb.) Rehd. et Wils, was synthesized from a bromobenzylidenetetrahydroisoquinolineenamide precursor (6). Photocyclization of this enamide led to a protected aporphine (7), which could be converted into oxoaporphine (9) and (±)-sinomendine (1) by Fremy’s salt oxidation followed an available Grignard reaction.
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■ Phase Transfer Catalyzed C- vs O-Alkylation of 3-Methyl-1-phenyl-2-pyrazolin-5-one in the Absence or Presence of Carbon Disulphide
Mohamed Ali Hassan* and Dietrich Döpp
*Department of Chemistry, Faculty of Science, Ain Shams University, Abbassiya 11566, Cairo, Egypt
Abstract
3-Methyl-1-phenyl-2-pyrazolin-5-one (1) was treated with differenet bromoorganic compounds such as benzyl bromide, 1,3-dibromopropane, methyl bromoacetaldehyde diethylacetal as alkylating agents either in the absence or in the presence of carbon disulphide and under phase-transfer catalysis conditions aimed at studying the reactivity of the title compound with respect to C- vs O-alkylation.
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■ Novel Pentacyclic π-Conjugated Cations Containing Both Heteroaromatic Units and a Tropylium Ion 2. Synthesis of Cyclohepta[a]benzofuro[c]naphthalenylium and Cyclohepta[a]benzothieno[c]-naphthalenylium Ions
Kimiaki Yamamura,* Taihei Yamane, Hideki Takagi, and Hideyoshi Miyake
*Department of Chemistry, Faculty of Science, Kobe University, Nada-Ku, Kobe 6557-8501, Japan
Abstract
TTwo isomeric pairs of cyclohepta[a]benzofuro[c]naphthalenylium ions (5 and 7) and cyclohephta[a]benzothieno[c]naphthalenylium ions (10 and 11) have been synthesized by an intramolecular Friedel-Crafts type reaction of o-benzofurylcycloheptatrienylbenzenes (3 and 8) and o-benzothienylcycloheptatrienylbenzenes (14 and 15), respectively, in a one-pot reaction.
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■ Synthesis of Isovincadine and 16-Epiisovincadine, Analogs of Vincadine and 16-Epivincadine with a New Rearranged Skeleton, from a Vincadifformine Derivative
Guy Lewin* and Corinne Schaeffer
*Laboratoire de Pharmacognosie, Faculté de Pharmacie, 5, Rue, Av. J.B. Clément, 92296 Châtenay-Malabry Cedex, France
Abstract
Treatment of the rearranged indole alkaloid (3) under reductive conditions [a) hydrogenolysis; b) NaBH3CN in AcOH] provided 16-epiisovincadine (6) and isovincadine (7), two new rearranged analogs of the alkaloids 16-epivincadine (9) and vincadine (10).
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■ 3-Amino-2(1H)-quinolones by Cyclizaion of N-Acylated Anthranilic Acid Derivatives
Matthias Rehwald,* Karl Gewald, Hans-Joachim Lankau, and Klaus Unverferth
*Department of Organic Chemistry, Technical University of Dresden, Mommsenstraße 13, D-01062 Dresden, Germany
Abstract
Reaction of secondary amines with the N-(iodoacetyl)anthranilic acid derivatives, 2-(iodoacetylamino)acetophenone and 2-(iodoacetylamino)benzophenone yields 3-amino-2(1H)-quinolones in two steps. Analogously heterocondensed 5-amino-6(7H)-pyrazolo[5,4-b]pyridones were prepared. Hydroxyquinolines were subjected to Cl/OH exchange to give chloroquinolines, which are convenient for consecutive reactions.
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■ New Syntheses of 2,4-Diaminothiophenes-Use of (1,3-Oxathiol-2-ylidene)-malononitrile
Matthias Rehwald,* Karl Gewald, and Gesine Böttcher
*Department of Organic Chemistry, Technical University of Dresden, Mommsenstraße 13, D-01062 Dresden, Germany
Abstract
Preparation of 2,4-diaminothiophenes using (1,3-oxathiol-2-ylidene)malononitrile as intermediate was achieved.
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■ Synthesis of 4-[(8-Amino-6-benzyl-10(9H)-oxo-4,5-dihydro-(6H)-isoxazolo[4,3-d]pyrimido[4,5-b]azepin-3-yl]benzoyl-L-glutamic Acid. A Novel Pyrimidoazepine-based Folic Acid Derivative
Michael L. Miller and Partha S. Ray*
*Department of Chemistry, The University of Memphis, Memphis, Tennessee 38152, U.S.A.
Abstract
Synthesis of the titled compound (13) is described using an intramolecular 1,3-dipolar cycloaddition reaction as the key step.
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■ The Conversion of Thioketones to 1,2,4,5-Tetrathianes and Its Mechanism
Rolf Huisgen* and Jochen Rapp
*Institut für Organische Chemie, Universität München, Karlstrasse 23, D-80333 München, Germany
Abstract
TThiobenzophenone and adamantanethione react with sulfur (1:1) under catalysis by sodium thiophenoxide in acetone at rt furnishing 1,2,4,5-tetrathianes (9 and 43) in high yields. An attack of the oligothiolate (R-Sx-) on the C-atom of C=S is proposed as initiating step. Thione S-sulfides (R2C=S+—S-, thiosulfines) cannot be intermediates, since they combine fast with thiones affording 1,2,4-trithiolanes with more sulfur pentathiepane-bis(spiroadamantane) (44) which interconverts with the tetrathiane, but not with the 1,2,4-trithiolane, in an equilibrium catalyzed by R-Sx-. According to 13C NMR evidence, the tetrathiane-bis(spiroadamantane) occurs in a twist conformation which inverts with δG= 16.0 kcal mol-1.
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■ Synthesis of 7-Amino-4,5,6,7-tetrahydrothieno[3,4-c]pyrid-4-ones
Lan Pham Khanh, Patrick Dallemagne, Abdellah Alsaïdi, and Sylvain Rault*
*Centre d'Etudes et de Recherch sur le Medicament de Normandie, Laboratoire de Pharmaceutiques, 1, rue Vaubenard, 14032 Caen Cedex, France
Abstract
Synthesis of 7-amino-4,5,6,7-tetrahydrothieno[3,4-c]pyrid-4-ones is achieved involving 6-amino-5,6-dihydro-4H-cyclopenta[c]thiophen-4-ones in Beckmann and Schmidt rearrangements.
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■ Synthesis of New Arylethanolamine and Aryloxypropanolamine Derivatives Including 1,4-Benzodioxine Moiety
Sophie Boyé, Gérald Guillaumet, and Marie-Claude Viaud*
*Institute de Chimie Organique et Analytique, associe au CNRS, Université d'Orléans, B.P. 6759, Rue de Chartres, 45067 Orleans Cedex 2, France
Abstract
The synthesis of new arylethanolamines and aryloxypropanolamines variously substituted on the nitrogen atom are described. Access to these compounds, which are potential β3-adrenergic ligands, involves, as key step, a reductive amination reaction between 2-amino alcohols and 1,4-benzodioxine aldehyde derivatives.
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■ Reactions of Ethyl (Z)-2-[2,2-Bis(ethoxycarbonyl)vinyl]amino-3-dimethylaminopropenoate with C-Nucleophiles. Synthesis of Substituted 3-Amino-2H-pyran-2-ones
Renata Toplak, Lovro Selic, Gorazd Sorsak, and Branko Stanovnik*
*Faculty of Chemistry and Chemical Technology, University of Ljubljana, Askerceva 5, P.O. Box 537, SLO-1000 Ljubljana, Slovenia
Abstract
The reactions of ethyl (Z)-2-[2,2-bis(ethoxycarbonyl)vinyl]amino-3-dimethylaminopropenoate (1) with C-nucleophiles, such as β-keto esters (2, 4, 6), cyclic 1,3-diketones (8a-e), aromatic hydroxy compounds (10, 12, 14, 16 and 18), and heterocyclic hydroxy compounds (20, 22, 24, 26 and 28) gave 2H-pyran-2-ones (3, 5, 7), tetrahydrobenzopyranones (9a-c), benzopyranone (11), naphthopyranones (13, 15, 17 and 19), pyranopyranone (21), pyranobenzopyranone (23), pyranopyridinone (25), pyranoquinolinone (27), and pyranopyridazinone (29) derivatives.
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■ Novel Preparation and Reaction of N-Benzenesulfonyl- and N-Methanesulfonyltroponimines. New Entry to 1-Azaazulene Derivatives
Tohru Takayasu, Hiroshi Katayama, and Makoto Nitta*
*Department of Chemistry, School of Science and Engineering, Waseda University, 3-4-1 Okubo, Shinjuku-ku, Tokyo 169-8555, Japan
Abstract
N-Benzenesulfonyl- and N-methanesulfonyltroponimines were prepared through the reaction of tropone oxime with benzenesulfinyl- and methanesulfinyl chloride. The troponimines reacted with enamines to give formal [8+2] cycloadducts, which subsequently underwent elimination-dehydrogenation sequences to give 1-azaazulene derivatives in modest yields.
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■ Synthesis of Cyclic Halooxatelluranes via Dehalogenation of α-Halo Carbonyl Compounds with Tellurides Containing Hydroxy Group on Side Chain
Jian Zhang, Shinichi Saito, Tamiko Takahashi, and Toru Koizumi*
*Faculty of Pharmaceutical Sciences, Toyama Medical and Pharmaceutical University, 2630 Sugitani, Toyama, Toyama 930-0194, Japan
Abstract
The synthesis of cyclic halooxatelluranes (3a, 4a-d, 5a) has been achieved via dehalogenation of α-halo carbonyl compounds (2A-F) with tellurides (1a-d) containing hydroxy group on the side chain. Halophilicity of the tellurides was compared with that of selenides and a plausible reaction mechanism is discussed.
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■ Regiospecific Hetero Diels-Alder Synthesis of Pyrido[2,3-b]- and Pyrido[3,2-b]carbazole-5,11-diones
Ambroise Poumaroux, Zouhair Bouaziz, Monique Domard, and Houda Fillion*
*Laboratoire de Chimie Organique, Université Claude Bernard, Lyon I, 8 avenue Rockefeller, 69373 Lyon Cedex 08, France
Abstract
Diels-Alder reactions of 2- or 3-bromocarbazolequinones (8) or (9) with azadienes (1) afford regiospecifically pyrido[2,3-b]- or pyrido[3,2-b]carbazole-5,11-diones (3) or (4). Structural assignment of the regioisomers is made by 1H-NMR NOE DIFF experiments. The orientation of the cycloadditions is under control of the bromine atom position on quinones (8) or (9). Calculations by the semiempirical method PM3 of the HOMO and LUMO orbital coefficients of azadienes (1) and quinones (2c), (8) and (9) indicate that the larger ones are situated at C-4 for azadienes (1) and C-3 for the dienophiles.