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. 12, 1983
Published online:
■ Synthesis of Cyclic Ether
Ajoy K. Banerjee, Héctor E. Hurtado, and Manuel S. Laya
*Centro de Química, Instituto Venezolano de Investigaciones Científicas, I.V.I.C., Apartado 21827, Caracas 1020-A, Venezuela
Abstract
A stereospecific synthesis of the 6β,20-epoxy-12-hydroxyabieta-8,11,13-triene (14) is described.
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■ Structure of Matopensine, a Novel Dimeric Indole Alkaloid from Strychnos Species
Georges Massiot, Bernard Massoussa, Philippe Thepenier, Marie-José Jaquier, Louisette le Men-Olivier, and Clément Delaude
*Facluté de Pharmacie, UPRES-A/CNRS 6013, Insitut des Biomoleculés, 51, rue Cognacq-Jay, F-51096 Reims Cedex, France
Abstract
A novel symmetrical bisindole alkaloid,matopensine, has been isolated from Strychnos matopensis and from Strychnos kasengaensis. Its structure has been elucidated by spectroscopic means including 401MHz 1H NMR; matopensine is 16S,16’S-dihydro-17R,17’R -oxybisnordihydrotoxiferine.
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■ Synthesis of a Difuryl Analog of the Oxophlorins
Timothy D. Lash and Yanet G. Motta
*Faculty of Chemistry, Northern State College, Aberdeen, South Dakota 57401, U.S.A.
Abstract
Condensation of 2,2’-bis(5-formylfuryl)methanone with a 2,2’-dipyrrylmethane-5,5’-dicarboxylic acid in trifluoroacetic acid afforded a macrocycle (6) analogous to the oxophlorin (oxyporphyrin) system. IR and UV spectra indicate that this compound exists as the keto tautomer (6) rather than the fully conjugated enol form (7a). (6) did not react with acetic anhydride-pyridine and the enol acetate (7b) could not be isolated, although the diperchlorate salt was formed under acidic conditions.
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■ The Synthesis of Furo[2,3-c]pyridazine, a Novel Heterocyclic System
Ales Krbavcic, Lidija Povse, and Branko Stanovnik
*Department of Chemistry, E. Kardelj University, Murnikova 6, 61000 Ljubljana, Slovenia
Abstract
A facile one-step synthesis of furo/2,3-c/pyridazines 10-14, derivatives of a novel heterocyclic system, from easily accessible pyridazines 2-6 is described.
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■ Amino-group Exchange and Ring-cleavage Reactions in Fused 1,2,6-Thiadiazine Dioxide Derivatives
Piedad Fernández-Resa, Pilar Goya, Rosa Nieves, Carmen Ochoa, and Manfred Stud
*Instituto de Química Orgánica General, C. S. I. C., Calle Juan de Cierva, 3, 28006 Madrid, Spain
Abstract
Reactions of 7-amino-4H-furazano[3,4-c][1,2,6]thiadiazine 5,5-dioxide (1) and its 4-methyl derivative (2) with nucleophilic agents under different conditions, are described. Besides the products resulting from the displacement of the 7-amino group, those produced by cleavage of the thiadiazine ring have also been obtained.
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■ Studies on the Synthesis of Carbapenem Antibiotics. Stereoselective Synthesis of a Potential Intermediate for 6-Amidocarbapenem Antibiotics
Tetsuji Kametani, Atsushi Nakayama, Akira Itoh, and Toshio Honda
*Institute of Medicinal Chemistry, Hoshi University, 2-4-41 Ebara, Shinagawa-ku, Tokyo 142-8501, Japan
Abstract
Stereoselective carbon-introducing reaction at the C4 position of an azetidinone has been achieved by the application of an intramolecular carbene reaction as a key step.
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■ Synthesis of Novel Potent Non-narcotic Less Side-effect Analgesics: 2’-Acylthio- and 2’-Alkylthio-6,7-benzomorphans
Mikio Hori, Masatoshi Ban, Eiji Imai, Noriyuki Iwata, Yutaka Baba, Hajime Fujimura, Masakatsu Nozaki, and Masayuki Niwa
*Department of Pharmacognosy, Gifu College of Pharmacy, 6-1 Mitahora-higashi 5-chome, Gifu 502-8585, Japan
Abstract
2’-Acylthio- and 2’-alkylthio-6,7-benzomorphans were synthesized from 2’-hydroxy-6,7-benzomorphans in 4 steps. Newman-Kwart rearrangement of 2’-N,N-dimethylthiocarbamoyloxy derivatives proceeded in almost quantitative yields to give rearranged 2’-N,N-dimethylcarbamoylthio derivatives. Reductive cleavage and successive acylation afforded title compounds. These novel sulfur-containing benzomorphans showed strong analgesic activities with less side effects.
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■ New Thiocarbonyl Ylides from Thiobenzophenone
Rolf Huisgen and Li Xingya
*Institut für Organische Chemie, Universität München, Karlstrasse 23, D-80333 München, Germany
Abstract
Thiobenzophenone is converted to 1,3,4-thiadiazolines by reaction with diazoethane, phenyldiazomethane or diphenyldiazomethane at -78 °C. Extrusion of nitrogen from the thiadiazolines furnishes thiocarbonyl ylides which, in turn, undergo electrocyclic ring closure to form thiiranes. Thiobenzophenone S-ethylide and S-benzylide can be intercepted by suitable dipolarophiles to provide 5-membered 1,3-cycloadducts.
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■ A Study of the Michael Reaction of 2’-Hydroxychalcones and a Facile Formation of 4H-Pyran Derivatives
Amolak Chand Jain, Prabhat Arya, and Anita Sharma
*Department of Chemistry, University of Delhi, Delhi-110 007, India
Abstract
2’-Pydroxychalcones (8a) and (8b) when subjected to the Michael reaction with acetyl acetone in the presence of ethanolic piperidine gave the 4H-pyran derivatives (9a) and (9b) besides the cyclohexenone derivatives (10a & 11a) and (10b & 11b) respectively. However, 8c yielded under the same conditions only the 4H-pyran derivative (9c) together with some 5,7-dimethoxyflavanone (12c). Thus 4H-pyrans have, for the first time, been characterised during Michael condensation of chalcones having no electron withdrawing group in the α-position. Ethyl acetoacetate gives only cyclohexenone derivatives.
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■ Chemistry of Acronycine V. Unexpected Reactivity of Dihydronoracronycine
Shinji Funayama and Geoffrey A. Cordell
*Program for Collaborative Research in the Pharmaceutical Sciences, College of Pharmacy, University of Illinois at Chicago, 833 South Wood St., Chicago, IL 60612-7231, U.S.A.
Abstract
Dihydronoracronycine (6) undergoes a condensation-disproportionation reaction in methanolic hydrochloric acid with the dimers of noracronycine 2 and 4 which leads to their corresponding dihydro derivatives 8 and 9, and to the trimers 5 and 7, respectively.
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■ A Novel Heterocyclic Rearrangement: Conversion of Benzoyl Pyrazolines into Phenylpyridazinones
Ch. Bheemasankara Rao, P. V. Narasimha Raju, Robert Flammang, André Maquestiau, and José Elguero
*Instituto de Química Médica, C. S. I. C., Calle Juan de Cierva, 3, 28006 Madrid, Spain
Abstract
Diarylpyridazinones could be obtained, in a two-step procedure, from chalcones and diazomethane. The second step involves the rearrangement of a benzoylpyrazoline and proceeds with low yields. The structures have been established by mass and ion-kinetic energy spectrometry.
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■ A Novel Synthesis of Some 2,3-Dihydro-1,4-thiazine Derivatives
Yvonne Gelas-Mialhe, Evelyne Touraud, and Roger Vessière
*Laboratoire de Chomie Organique 2, Ecole Nationale Supérieure de Chimie de Clermont-Ferrand, Université de Clermont II, B. P. 45, 63170 Aubière, France
Abstract
The KSCN catalysed isomerization of N-vinylaziridines 1 and 2 afforded 2,3-dihydro-1,4-thiazine derivatives.
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■ A New Compound from an Old Reaction: The Condensation of ω-Cyanoacetophenone with Benzaldehyde
José L. Soto, Carmen Aparicio, Carlos Seoane, and José A. Valdés
*Departamento de Química Orgánica I., Facultad de Química., Universidad Complutense de Madrid, Ciudad Universitaria, E-28040 Madrid, Spain
Abstract
The reaction of ω-cyanoacetophenone with benzaldehyde affords a 4H-pyran together with the normal condensation product.
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■ One-pot Synthesis of 1,2,3,6,7,11b-Hexahydro-4H-benzo[a]quinolizin-4-ones: Key Synthons for Benzo[a]quinolizines
Anup Bhattacharjya, Pranab K. Bhattacharya, and Satyesh Chandra Pakrashi
*Indian Institute of Chemical Biology, Calcutta-700 032, India
Abstract
Michael adduct of 3,4-dihydro-1-methylisoquinolines (1) and methyl acrylate on NaBH4 reduction led to the title compounds (3)
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■ Reactivity of Arylcinnamates in Polyphosphoric Acid (PPA): Cyclisation and Rearrangement Reactions
Jean-François E. Dupin and Jacques Chenault
*Laboratoire d’etude des Composéa Phénoliques, U.E.R. de Sciences Fondamentales et Appliqués, Université d’Orléans, BP 6759, Rue de Chartres, 45067 Orleans Cedex 2, France
Abstract
In polyphosphoric acid (PPA), various phenyl-substituted cinnamates react to give 4-phenyl-3,4-dihydrocoumarins, flavanones or 3-phenylindanone owing to the nature of the substituents on the phenyl moiety.
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■ Syntheses with Nitriles LXX: Condensation Products of Dimeric Malononitrile Derivatives with 2,4-Diketones and Their Application for the Synthesis of Substituted 1,6-Naphtyridines
Gerald Koitz, Burkhard Thierrichter, and Hans Junek
*Institüt für Organische Chemie, Abteilung für Angewandte Organische, Karl-Franzens-Universität, A-8010 Granz, Germany
Abstract
Reaction of 2-amino-1,1,3-tricyanopropene 1a and methyl 3-amino-2,4-dicyanocrotonate 1b with 2,4-diketones 2a-c leads to the substituted 1,2-dihydropyridines 3a-d in good yields. The cyclisation of the resulting 1,3-dicarbonitrile system 3a in basic od acidic medium is explored. Structure proof of the resulting isomeric substituted 1,6-naphtyridines 4,5a,b is provided by spectroscopical means.
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■ Synthesis of Thieno[3,4-c]pyridine and Thieno[3,4-c]azepine Derivatives by N-Acyliminiun Ion-induced Cyclization
Shinzo Kano, Yoko Yuasa, Tsutomu Yokomatsu, and Shoroshi Shibuya
*School of Pharmacy, Tokyo University of Pharmacy and Life Science, 1432-1 Horinouchi, Hachioji, Tokyo 192-0392, Japan
Abstract
Reduction of N-[2-(3-thienyl)]ethylthiazolidine-2,4-diones (3a and 3b) with diisobutylaluminum hydride followed by treatment of the reduction products with formic acid at 60 °C for 14 h yielded the corresponding thieno[3,4-c]pyridines (5a and 5b), respectively. In a similar way, thieno[3,4-c]pyridines (5c - 5e) and thieno[3,4-c]azepines (9a, 9b and 9d) were obtained from the corresponding N-substituted hydroxyoxazolidinone, hydroxyimidazolidinones and hydroxythiazolidinones.
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■ Synthesis of 6’-Methylated Reticulines and Tetrahydropapaverolines
Padam N. Sharma, Kenner C. Rice, and Arnold Brossi
*Section on Medical Chemistry, Bldg.4, Room 135, Metabolism and Digestive and Kideny Deseases, National Institute of Health, Bethesda, MD 20892, U.S.A.
Abstract
Racemic 6’-methylreticuline and the racemate and both enantiomers of 6’-methyl-N-norreticuline and 6’-methyltetrahydropapaveroline were synthesized from the appropriate isomers of coreximine diacetate (1). Reduction of crystalline chloromethylcarbamate 2 with LAH gave (±)-6’-methylreticuline (5) directly. Hydrogenation (±)-2 and the optical isomers followed by hydrazinolysis provided the corresponding. 6’-methyl-N-norreticulines (6, 6a, 6b) which were converted to the racemate and enantiomers of 6’-methyltetrahydropapaveroline (8, 8a, 8b) by O-demethylation with 48% hydrobromic acid.
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■ Synthesis of 6,7,2’,3’-Tetramethoxy-5,4’,6’-trihydroxyflavone
Munekazu Iinuma, Toshiyuki Tanaka, and Shin Matsuura
*Gifu Pharmaceutical University, 6-1 Mitahora-higashi 5-chome, Gifu 502-8585, Japan
Abstract
6,7,2’,3’-Tetramethoxy-5,4’,6’-trihydroxyflavone and its positional isomers were synthesized, and any of them were not identical with the flavone isolated from Notholaena aschenborniana.
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■ A Facile Synthesis of 1,3-Dialkyl-5-fluororacils by Means of Phase Transfer Catalysis
Tomonori Hoshiko, Yutaka Watanabe, and Shoichiro Ozaki
*Faculty of Engineering, Ehime University, 3 Bunkyo-cho, Matsuyama, 790-8577 Ehime, Japan
Abstract
The reaction of 5-fluorouracil with an alkyl halide in the presence of a phase transfer catalyst and potassium hydroxide gives 1,3-dialkyl-5-fluorouracil in good yield.
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■ The Coupling Reactions of 3-Acylindoles and Proof of Structure of the Palladium (II) Acetate Mediated Cyclisation Reaction Product of 3-Benzoyl-1-methylindole
Kevin Bill, Gerald G. Black, Christpher P. Falshaw, and Malcom Sainsbury
*School of Chemistry, University of Bath, Bath, Avon. BA2 7AY, U.K.
Abstract
The structure previously proposed for the oxidative cyclisation of 3-benzoyl-1-mthylindole in the presence of palladium(II)acetate has been confirmed. Attempts to form homologues of the product by similar reactions fail.
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■ Recent Developments in Chemistry of 3(5)-Aminopyrazoles
Mohamed H. Elnagdi, Fathy M. Abdel-Galil, Bahia Y. Riad, and Galal Eldin Hamza Elgemeie
*Department of Chemistry, Faculty of Science, University of Cairo, Giza, Egypt
Abstract
The methods of preparation, structure, chemical properties and synthetic potentiality of 3(5)-aminopyrazoles are reported.
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■ Elaboration of the Ethylidene Substituent in the Synthesis of Indole Alkaloids
Joan Bosch and Ma Lluïsa Bennasar
*Laboratory of Organic Chemistry, Faculty of Pharmacy, University of Barcelona, Av. de Joan XXIII, s/n, 08028 Barcelona, Spain
Abstract
Some indole alkaloids have a C-20 ethylidene substituent as a common structural feature. All methods for the elaboration of this exocyclic, E-configurated double bond developed in indole alkaloid synthesis are reviewed.