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. 7, 1983
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■ The Quaterization of cis and trans 1-Hydroxyquinolizidine
Luis Castedo and Ricardo Riguera
*Facultad de Química y Sección de Alcaloides, Deparamento de Química Orgánica, C. S. I. C., Santiago de Compostela, Spain
Abstract
C-1-Hydroxyquinolizidine I gave with Mel a trans-fused quinolizidine methiodide II formerly believed to have a cis-fused structure. The t-1-hydroxyquinolizidine epimer III gave a mixture of two methiodides IV and V having trans and cis-fused quinolizidine structures respectively. Methiodide V exhibits temperature dependent nmr spectra (C-13 and 200 MHz 1H nmr) indicative of a conformational equilibrium.
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■ The Reactions of 4-Pyrimidinone Derivatives with Sodium Amide and with Hydrazine: Synthesis of Triazole
Yoshiro Hirai, Hiroyuki Egawa, Shoko Yamada, and Takao Yamazaki
*Faculty of Pharmaceutical Sciences, Toyama Medical and Pharmaceutical University, 2630 Sugitani, Toyama, Toyama 930-0194, Japan
Abstract
The 3,6-dialkyl-2-isopropyl-4-pyrimidinones (1)-(3) and 3,6-dimethyl-2-phenyl-4-pyrimidinone (6) were converted to the N-dealkylated 4-pyrimidinones (4), (5), and (7) by reaction with sodium amide in liq. ammonia. Also, these 4-pyrimidinones (1)-(3) and (6) were converted to the triazoles (10)-(12) by heating with hydrazine, respectively.
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■ Solvent Effect on the Bischler-Napieralski Reaction. Synthesis of 3-Aryl-3,4-dihydroisoquinolines
Esther Domínguez and Esther Lete
*Departmento de Química, Facultad de Ciencias, Universidad del País Vasco, Apartado 450, 01080 Vitoria-Gasteiza, Spain
Abstract
The classical Bischler-Napieralski cyclization of 1,2-diaryl-ethylamides always led to neutral compounds: the 3,4,3’,4’-tetramethoxystilbene (5) and/or the triaryl substituted tetralin (6). These characteristic by-products of the Bischler-Napieralski reaction arise as a consequence of competing equilibria involving nitrilium ions. The desired 3-aryl-3,4-dihydroisoquinolines were obtained in acceptable yields when the “appropiate” nitrile was used as solvent.
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■ Indolines through Intramolecular Imine Cyclizations
Jan Dijkink, Johannes N. Zonjee, Bart S. de Jong, and W. Nico Speckamp
*Laboratory of Organic Chemistry, Institute of Molecular Chemistry, University of Amsterdam, Nieuwe Achtergracht 129, 1018 WS Amsterdam, The Netherlands
Abstract
Indolines 3 are synthesized by intramolecular base-catalyzed cyclization of imines 2. Controlled basic hydrolysis of 3 affords indoline carboxylic acids 8 and 9. The compounds 3 are also useful for the synthesis of the mitomycin skeleton as exemplified by the preparation of 10.
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■ Thallium (III) Nitrate (TTN) Oxidation of 2,8-Dioxo-1,7-cycloerythrinans: A New Skeletal Rearrangement
Yoshisuke Tsuda and Akira Nakai
*Faculty of Pharmaceutical Scicences, Kanazawa University, 13-1 Takara-machi, Kanazawa 920-0934, Japan
Abstract
Oxidation of 2,8-dioxo-1,7-cycloerythrinans (1a, b) with excess TTN in MeOH gave rearrangement products (2a, b), whose structures were elucidated mainly on the basis of spectral evidence. The intermediate to 2 from the ketone (1) was found to be the dimethylketal.
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■ The Synthesis and Several Reactions of 2-Methylazuleno[2,1-d]thiazole
Kameji Yamane, Kunihide Fujimori, Shuji Ichikawa, Shiro Miyoshi, and Kenichi Hashizume
*Department of Chemistry, Faculty of Science, Shinshu University, Asahi, Matsumoto 390-8621, Japan
Abstract
2-Methylazuleno[2,1-d]thiazole was synthesized from 2-amino, 2-formylamino, and 2-acetylamino derivatives of ethyl azulene-1-carboxylate in four steps. The 9-dimethylaminomethyl, 9-piperidinomethyl, and 9-morpholinomethyl derivatives were prepared by Mannich reaction of 2-methylazuleno[2,1-d]thiazole. The Vilsmeyer-Haack reaction of 2-methylazuleno[2,1-d]thiazole gave the 9-formyl derivative, and dehydration of its oxime afforded the 9-cyano derivative.
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■ Structure of Murrayaquinone-B, a Novel Carbazole Alkaloid from Murraya euchrestifolia Hayata
Tian-Shung Wu, Tomoko Ohta, Hiroshi Furukawa, and Chang-Sheng Kuoh
*Faculty of Pharmacy, Meijo University, 150 Yagotoyama, Tenpaku, Nagoya 468-8503, Japan
Abstract
The structure of murrayaquinone-B, a novel carbazole alkaloid isolated from the root bark of Murraya euchrestifolia Hayata was established as formula 1.
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■ 3-Hydroxypyrazolo[1,2-b]1,2,3-triazinium-1-olates: Novel Mesoionic 10π-Systems
Willy Friedrichsen, Andreas Böttcher, and Tony Debaerdemaeker
*Institut für Organische Chemie, Universität Kiel, Olshausenstrasse. 40, D-24098 Kiel, Germany
Abstract
The syntheses and reactions of 3-hydroxypyrazolo[1,2-b] 1,2,3-triazinium-1-olates (7a,b) are reported. The structure of 7a has been confirmed by X-ray crystallography.
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■ Photochemical Reactions of 4-Methoxy-1-thiocoumarin and Synthesis of 1,2-Dihydrocyclobuta[c][1]benzothiopyran-3(3H)-ones
Chikara Kaneko, Toshihiko Naito, and Tetsuo Ohashi
*Faculty of Pharmaceutical Scicences, Kanazawa University, 13-1 Takara-machi, Kanazawa 920-0934, Japan
Abstract
4-Methoxy-1-thiocoumarin reacts photochemically with mono-substituted olefins to give the head-to-tail adducts: 1-substituted 8b-methoxy-1,2,2a,8b-tetrahydrocyclobuta[c] [1]benzothiopyran-3(3H)-ones, which eliminate methanol under appropriate conditions to give 1-substituted 1,2-dihydrocyclobuta[c][1]benzothiopyran-3(3H)-ones. Interesting photochemical ring-contraction reactions of 4-methoxy-1-thiocoumarin to benzo[b]thiophene derivatives are also reported.
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■ New Phthalazine- and Pyradazino[4,5-g]phthalazine Derivatives
Francesco De Sio, Stefano Chimichi, Rodolfo Nesi, and Lucia Cecchi
*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
Some new phthalazine- and pyridazino[4,5-g]phthalazine derivatives have been prepared through diethyl phthalazine-6,7-dicarboxylate (5), obtained by regioselective reduction of the tetraester (1) with sodium aluminium hydride at - 50 °C, and treatment of the intermediate diformyl derivative (2) with hydrazine. The tautomeric behaviour of both 1,4-dihydroxypyridazino[4,5-g]phthalazine (13) and the N-methyl derivative (14) were also investigated by comparison of their spectroscopic properties with those of the model compounds (15) and (16).
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■ Reaction of 3,4-Dibenzoyl-1,2,5-thiadiazole with Ethylamine Derivatives. Formation of Shiff Bases and Their Base-catalyzed Ring Closure Reactions
Shuntaro Mataka, Kazufumi Takahashi, and Masashi Tashiro
*Research Institute of Industrial Science, Faculty of Engineering, Kyushu University, 6-1, Kasuga-koen, Kasuga 816-8580, Japan
Abstract
The reaction of 3,4-dibenzoyl-1,2,5-thiadiazole (1) with phenethylamine (2a) and β-aminopropionitrile (2b) gave the corresponding Schiff bases (4a and 4b), which, on treatment with DBU, cyclized into thiadiazolopyridines (5a and 5b). Compound 5a or 5b was directly obtained in the reaction of 1 and 2 in the presence of DBU. The reaction with α,β-diphenylethylamine (2c) gave the triphenylthiadiazolopyridine (5d) in poor yield. The Schiff base (4c) was obtained in the reaction with ethyl β-amino-β-phenylpropionate (2d) and treatment of 4c with a base afforded the pyrrolinyl-1,2,5-thiadiazole (7).
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■ Synthesis and Elaboration of 3-Substituted 4-Nitroisoxazloles
John F. W. Keana and Garrick M. Little
*Department of Chemistry, University of Oregon, Eugene, OR 97403, U.S.A.
Abstract
A regioselective Mukaiyama reaction involving nitroacetals 1 and 9, phenyl isocyanate and 1-morpholino-2-nitroethene 2 in benzene provided, respectively, the 4-nitroisoxazole acetals 3 and 10 in excellent yield. These acetals in turn served as convenient synthetic entries into the series of 3,4-difunctionalized isoxazoles of structures 4-8 and 11-13, respectively.
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■ Synthesis of 4-Substituted β-Carbolines
Günter Neef, Ulrich Eder, Andreas Huth, Dieter Rahtz, Ralph Schmischen, and Dieter Seidelmann
*Research Laboratories, Schering AG, Berlin / Bergkamen, D-1000 Berlin 65, Germany
Abstract
Various 4-substituted β-carbolines are synthesized and further modified by electrophilic substitution reactions. The regioselectivity of electrophilic attack is demonstrated for a number of different reactions and strategies are outlined to achieve substitution at positions unaccessible by electrophilic attack.
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■ On the Reactivity of Some N-Amino Heterocycles towards Diazomethane
Fabio Ponticelli and Piero Tedeschi
*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
The occurrence of hydrogen bonding between the nitrogen atom of the NH2 group and a neighbouring enolic proton in tautomerizable N-amino heterocycles allows diazomethane methylation on the NH2 moiety.
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■ Photochemical Reactions of Condensed Azoles with Dimethyl Acetylenedicarboxylate IV
Tsuneo Itoh, Katsuko Matsuzaki, Shohei Suzuki, Kazuyuki Kishida, Haruo Ogura, Norio Kawahara, and Takako Nakajima
*School of Pharmaceutical Sciences, Kitasato University, 5-9-1, Shirokane, Minato-ku, Tokyo 108-8641, Japan
Abstract
Adducts of azole derivatives and dimethyl acetylenedicarboxylate on irradiation are described.
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■ Saturated Heterocycles, 47. Synthesis of Some Tetrahydroisoquinoline Condensed 1,3-Heterocycles
Ferenc Fülöp, M. Sami El-Gharib, Attila Sohajda, Gábor Bernáth, Jenö Kóbor, and György Dombi
*Institute of Pharmaceutical Chemistry, University of Szeged, H-6720 Szeged, Eötvös u. 6, Hungary
Abstract
Calycotomine (2) and homocalycotomine (3) reacted with isothiocyanates to give the corresponding thiocarbamides (4, 5). The latter were treated with methyl iodide, and subsequent elimination of methyl mercaptan on treatment with alkali afforded 1,3-oxazolo[4,3-a]isoquinolines (6) and 1,3-oxazino[4,3-a]isoquinolines (7). 1,3-Thiazolo[4,3-a]isoquinolines (8) and 1,3-thiazino[4,3-a]isoquinolines (9) were prepared from 4 and 5 with hydrogen chloride. Compound 7a was also synthesized by the reaction of 3 with phenyl isocyanate, followed by the elimination of water; 9a was obtainable from 7a by treatment with P4S10. The structures of compounds 6-9 were confirmed by 1H NMR.
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■ The Enantioselective Synthesis of (+)-Retronecine, (—)-Platynecine, and (+)-Croalbinecine and Its C-1 Epimer
Heinrich Rüeger and Michael Benn
*Department of Chemistry, The University of Alberta, Calgary, Alberta, T2N, 1N4, Canada
Abstract
The Geissman-Waiss lactone, (+)-6-aza-2-oxabicyclo[3,3,0]octan-2-one, obtained from (2S,4R)-4-hydroxyproline was used as a synthon for the preparation of (+)-retronecine. (-)-platynecine, and (+)-croalbinecine (helifolinecine) and its C-1 epimer.
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■ Synthesis of Pyrazolo[4,3-d]oxazoles from 1-(2,4-Dinitrophenyl)-3-methyl-5-pyrazolon-4-oxime
Mohamed Salah Kamel Youssef
*Chemistry Department, Faculty of Science, Assiut University,Assiut 71516, Egypt
Abstract
1-(2,4-Dinitrophenyl)-3-methyl-5-pyrazolon-4-oxime (I) reacts with benzylamine to give 1-(2,4-dinitrophenyl)-3-methyl-5-phenyl-1H-pyrazolo[4,3-d]oxazole (II). Its structure has been established by another route involving reaction of I with benzyl cyanide in the presence of sodium ethoxide. 1-(2,4-Dinitrophenyl)-3-methyl-1H-pyrazolo[4,3-d]oxazole (III) has been prepared by the interaction of I with methyl iodide in the presence of K2CO3. Its structure has been elucidated by an unambiguous synthesis involving reaction of diazomethane with I.
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■ The Synthesis of 2,2’:5’,3”-Terthiophene
Jacques Kagan, Sudershan K. Arora, Indra Prakash, and Ayse Üstünol
*Department of Chemistry, University of Illinois at Chicago, 845 West Taylor St., Chicago, IL 60607-7061, U.S.A.
Abstract
2,2’:5,3”-Terthiophene has been synthesized by two different routes. One utilized the Cadiot-Chodkiewicz coupling of 2-(bromoethynyl)thiophene with 3-ethynylthiophene, followed by sodium sulfide treatment of the resulting 1-(2-thienyl)-4-(3’-thienyl)-1,3-butadiyne. The other featured a Grignard reaction starting from 5-iodo-2,2’-bithiophene and 3-oxotetrahydrothiophene, followed by thermal aromatization with sulfur. The new terthiophene was an efficient singlet oxygen sensitizer.
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■ The Diterpenoid Alkaloids of Delphinium tatsienense Franch
S. William Pelletier, Jan A. Glinski, B. S. Joshi, and Szu-ying Chen
*Department of Chemistry, Institute for Natural Products Research, The University of Georgia, Chemistry Building, Athens, Georgia 30602-2556, U.S.A.
Abstract
From the roots of Delphinium tatsienense Franch (Ranunculaceae) two new and six known alkaloids have been isolated. The isolation and structure determination of deacetylambiguine (2) and a novel C19-diterpenoid alkaloid designated as tatsiensine (1) are described. The structure of tatsiensine was established on the basis of spectroscopic data and correlation with delpheline (12). Deacetylambiguine (2) has been isolated for the first time from a natural source. The known alkaloids that were isolated are the C19-diterpenoid alkaloids, browniine (3), delcosine (4), lycoctonine (8), and the C20-alkaloids ajaconine (6), hetisine (7) and hetisinone (5).
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■ Lewis Acid Induced Electrophilic Substitution of Indoles: Part 6
Julie Banerji, Reba Mustafi, and James N. Shoolery
*Chemistry Department, University College of Science, 92 Acharya Prafulla Chandra Road, Calcutta-700009, India
Abstract
The eleotrophilic substitution of 3-methylindole with mesityl oxide and acetone in the presence of BF3·Et2O has been discussed.
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■ An Alternative Chiral Route to Sulcatol
Seiichi Takano, Michiyasu Hirama, and Kunio Ogasawara
*Pharmaceutical Institute, Tohoku University, Aobayama, Sendai 980-8578, Japan
Abstract
A key intermediate [(R)-(5)] for the enantioselective synthesis of both enantiomers of sulcatol (1), the aggregation pheromone of Gnathotrichus sulcatus, has been prepared from (S)-benzyl 2,3-epoxypropyl ether (8).
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■ Mesoionic Six-membered Heterocycles, XVII. Cycloaddition of Benzyne to Mesoionic Pyrimidines
Thomas Kappe and Dietmar Pocivalnik
*Abteilung fur Angewandte, Organische Chimie, Institut fur Organische Chimie, Karl-Franzens Universitat, Heinrichstr. 28, A-8010 Graz, Austria
Abstract
Benzyne (1) reacts with mesoionic pyrimidines (2a-e) yielding below 40 °C the primary cycloadducts 3a-e. At higher temperatures the isoquinolin-3-ones 4a-e are formed under the loss of phenyl isocyanate. Further addition of 1 to 4e yields the adduct 5, which is converted at 200 °C into the anthracene derivative 6.
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■ Synthesis of Nitroethylindoles from Nitrovinylindoles by Alkoxyborohydride Reduction
Lawrence I. Kruse and Eileen L. Hilbert
*Chemical Reserch and Development, Smith Kline and French Laboratories, Philadelphia, PA 19101, U.S.A.
Abstract
The reduction of substituted nitrovinylindoles to the corresponding nitroethylindoles proceeds in excellent yield, with the suppression of dimeric Michael byproducts, when an alkoxyborohydride is the reducing agent. A study of the reaction demonstrates the equivalence of preformed sodium trimethoxyborohydride and alkoxyborohydride generated in situ from excess sodium borohydride and methanol.
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■ The Present Use and the Possibilities of Phase Transfer Catalysis in Drug Synthesis
Pierre Cocagne, José Elguero, and Roger Gallo
*Facluté des Sciences et Techniques de Saint Jérôme, Université d’Aix-Marseille III, Avenue Escardille Normandie Niemen (Case 552), 13397 Marseille Cedex 13, France
Abstract
After a short introduction, the actual possibilities and the prospective use of phase transfer catalysis in drug preparation are reviewed (198 ref.)
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■ Stereoselective Synthesis of the Geometric and Optical Isomers of Unsaturated 3-Mono- and 3,6-Disubstituted 2,5-Piperazinediones
Chung-gi Shin
*Departmnet of Applied Chemistry, Faculty of Engineering, Kanagawa University, 3-27-1 Rokkakubashi, Kanagawa-ku, Yokohama 221-8686, Japan
Abstract
Four kinds of naturally occurring 3,6-dibenzylidene (1)-, 3-(p)-anisilidene-6-benzylidene (2), -3-isobutylidene-6-benzylidene (3; antibiotic albonoursin)-, and 3-benzyl-6-benzylidene-2,5-piperazinediones (4), isolated from Streptomyces and Actinomyces strains, and their possible geometric and optical isomers were stereoselectively synthesized. Based on the spectral data and the independent preparation, the configuration and conformation of the natural products 1, 2, and 3 could be clearly determined to be (3Z, 6Z)-isomers and 4 to be (3R, 6Z)-isomer. Particularly, from the NMR and CD spectral data, the useful criterion for the configurational determination of the geometry of exocyclic C=C bond was obtained and the conformation of the half boat structure of 2,5-piperazinediones was unambiguously confirmed. Moreover, the methylation of 1, 2, and 3 was achieved to give mainly three kinds of derivatives, 1-, 4-mono-, and 1,4-dimethylated 1, 2, and 3 respectively.
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■ Synthesis and Preparative Applications of Monosaccharide Thiocyanates
Zbigniew J. Witcazk
*Department of Organic Chemistry, Medical Academy, ul. Grodzka 9, 50-137 Wroclaw, Poland
Abstract
This review describes the synthetic methods which have been developed for the preparation of monosaccharide thiocyanates as well as their transformation to derivatives such as deoxysugars thiosugars.