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. 23, No. 7, 1985
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■ Structure of Two Eudesmanolides, Moriforin A and B
Antonio González González,* Jaime Bermejo Barrera, Angel Yanes Hernández, Francisco Estévez Rosas, and Xorge A. Domínguez
*Instituto de QUímica Orgánica, Instituto de Productos Naturales Orgánicos, C. S. I. C./ Unversidad de La Laguna, La Laguna, Tenerife, Canary Islands, Spain
Abstract
Two new eudesmanolides, morifolin A and B, were isolated in addition to previously known compounds from Critonia morifolia (Compositae). The structures were established by spectroscopic methods.
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■ A Photochemical Route to Pyrrolo[1,4]benzodiazepine Antitumor Antibiotics
Paul H. Mazzocchi* and Ann DeCamp Schuda
*Department of Chemistry, University of Maryland, College Park, Marykland 20742, U.S.A.
Abstract
The parent pyrrolo[1,4]benzodiazepine ring system was synthesized. The key step was the photostimulated ring expansion reaction of N-pentenylphthalimide to give a pyrrolobenzazepinedione photoproduct. Conversion of the pyrrolobenzazepinedione ring system to the pyrrolo[1,4]benzodiazepine ring system was accomplished in several steps with the key step a Curtius rearrangement.
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■ Synthesis via Organoiron Complexes of 9-(4-Keto-1-methylcyclohex-2-enyl)-8-keto-des-AB-ergost-22,23-ene; a Useful Chiral Intermediate in Steroid Synthesis
Enrico Mincione,* Paolo Bovicelli, Silvio Cerrini, and Doriano Lamba
*Centro CNR per lo Studio della Chimica delle Sostanze Organiche Naturali, Dipartmento di Chimica, Università degli Studi di Roma "La Sapienza", Piazzale Aldo Moro 5, 00185 Roma, Italy
Abstract
The synthesis organoiron complexes of 9-(4-keto-1-methylcyclohex-2-enyl)-8-keto-des-AB-ergost-22,23-ene, a useful chiral intermediate in steroid synthesis, is described.
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■ Mesoionic Oxazolones in Heterocyclic Synthesis: A Facile Synthesis of Unconventional β-Lactams
Bir Sain and Jagir Singh Sandhu*
*Division of Drug and Pharmaceutical Chemistry, Regional Research Laboratory, Jorhat 785 006, Assam, India
Abstract
Reaction of 2,4-diphenyl-2-oxazolin-5-one 1 with imines 2 gave novel 3-amido-β-lactams 3 in good yields.
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■ Photocycloadditions of N-Methylmonothiophthalimide with Styrene Derivatives Accompanied by 1,2-Dithiane Formation
Minoru Machida,* Kazuaki Oda, Eiichi Yoshida, Shuji Wakao, Kosei Ohno, and Yuichi Kanaoka
*Faculty of Pharmaceutical Scicences, Higashinihonngakuen University, 1757 Kanazawa, Toubetu-cho, Ishikari-gun, Hokkaodo 061-0212, Japan
Abstract
Photolysis of N-methylmonothiophthalimide (1) with styrene analogs (2) gave thietane derivatives (3) accompanied by dithiane derivatives (4). The stereochemistry of thietanes was determined by spectroscopies.
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■ Synthesis of Pirido[2,1-c][1,4]benzothiazines by Reaction between 3-Alkoxycarbonylmethylene-4H-1,4-benzothiazines (β-Enamine Esters) and Dimethyl Acetylenedicarboxylate (DMAD)
Giuseppe Trapani,* Antonia Reho, Andrea Latrofa, Flaviano Morlacchi, and Gaetano Liso
*Dipartimento Farmaco-Chimico, Facolta di Farmacia, Università digli Studi di Bari, Via Orabona 4, I-70125 Bari, Italy
Abstract
By the title reaction pyrido[2,1-c][1,4]benzothiazines 3d,e and 4 together with dienamine esters 2d,e,f respectively are obtained. The latter compounds are Z,E Michael adducts of the enamine esters 1d-f to DMAD, and are cyclized in high yield to the former compounds by using p-toluenesulfonic acid as catalyst. Starting from benzothiazine 1f the phenothiazine 5 is also obtained.
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■ A Novel Ring Transformation of Benzofuroxanes to 1-Hydroxy-2-arylbenzimidazole-3-N-oxide with Nitrones
Harsha Narayan Borah, Romesh Chandra Boruah, and Jagir Singh Sandhu*
*Division of Drug and Pharmaceutical Chemistry, Regional Research Laboratory, Jorhat 785 006, Assam, India
Abstract
Benzofuroxanes (1) react with nitrones (2) to give 1-hydroxy-2-aryl-benzimidazole-3-N-oxide (3) in good yields.
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■ A Chiral Route to Pyrrolizidine Alkaloids via Intramolecular Michael Reaction
Kozo Shishido, Yuko Sukegawa, Keiichiro Fukumoto,* and Tetsuji Kametani
*Pharmaceutical Institute, Tohoku University, Aobayama, Sendai 980-8578, Japan
Abstract
Wittig-Horner reaction of 10 gave the pyrrole (11) as a diastereomeric mixture via the intramolecular Michael reaction, one of the diastereomers could be converted to the Geissman lactone (4), a synthon for some pyrrolizidine alkaloids.
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■ Reaction of N-Alkylheteroaromatic Cation with Phosphite
Isao Takeuchi, Yasuhiro Shinata, and Yoshiki Hamada*
*Faculty of Pharmacy, Meijo University, 150 Yagotoyama, Tenpaku, Nagoya 468-8503, Japan
Abstract
Treatment of N-methylquinolinium iodide (1) with trimethyl phosphite afforded dimethyl N-methyl-1,4-dihydroquinoline-4-phosphonate (3), whereas when 1 was treated with dimethyl sodiophosphonate, dimethyl N-methyl-1,2-dihydroquinoline-2-phosphonate (2) was obtained. The 2-phosphonate (2) underwent thermal rearrangement to the more stable 4-phosphonate (3). Similar results were obtained with some analogous heteroaromatics.
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■ Preparation of Pyrimidines and Pyridines from Alkyl Ketones and Nitriles in Presence of Phosphoryl Chloride
Wojciech Zielinski*
*Instiute of Organic Chemistry and Technology, Silesian University of Technology, ul. Krzywoustego 4, 44-101 Gliwice, Poland
Abstract
The reaction of alkyl ketones with nitriles in the presence of POCl3 has been examined. It has been found that N-vinylimidoyl dichlorophosphates initially formed react further with excess nitriles or ketones to afford pyrimidine or pyridine derivatives, respectively.
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■ The Sequential Lithiation of 1-Phenyl-1,2,4-triazoles
Ronald G. Micetich,* Paul Spevak, Tse W. Hall, and Baljit K. Bains
*Faculty of Pharmacy , University of Alberta, Edmonton, Alberta T6G, 2N8, Canada
Abstract
1-Phenyl-1,2,4-triazole is lithiated exclusively at the C-5 position. 5-Methyl-1-phenyl-1,2,4-triazole produces the 5-lithiomethyl derivative; while the 5-ethyl, 5-methoxymethyl, and 5-acetic acid derivatives af 1-phenyl-1,2,4-triazole undergo exclusive lithiation of the C-5-methylene group. 5-Thiomethyl-1-phenyl-1,2,4-triazole is lithiated on the C-5 thiomethyl group.
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■ Synthesis of Some Isomeric 4H,10H[1]benzoxepino[4,3-d]isoxazol-4-ones and 4H,10H[1]benzoxepino[3,4-c]isoxazol-4-ones and Benzothiepino Analogs
Christian Deshayes, Michel Chabannet, Boubker Najib, and Suzanne Gelin*
*Département de Biochimie, Laboratoire de Chimie Organique, Institut National des Sciences Appliquées, 20 Avenue Albert Einstein 69621 Villeurbanne Cedex, France
Abstract
The regiospecific formation of 5- or 3-(phenoxymethyl) or 5- or 3-(phenylthiomethyl)isoxazole-4-carboxylic acids is described. These isoxazoles are utilized as the starting material for the synthesis of isomeric 4H,10H[1]benzoxepino[4,3-d] or [3,4-c]isoxazol-4-one derivatives and benzothiepino analogs.
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■ "One-step" Synthesis of an Indeno-indolizine Nucleus
Angelo Carotti,* Giovanni Casini, Enrico Gavuzzo, and Fernando Mazza
*Dipartimento Farmaco-Chimico, Università di Bari, Via Amendola 173, 70126 Bari, Italy
Abstract
The reaction of 2-hydroxy-2-phenacyl-1,3-indanedione with tosyl chloride in pyridine directly afforded in high yield the 11-benzoyl-10H-indeno[2,1-b]indolizine-10-one the structure of which has been determined by single crystal X-ray diffraction. A possible pathway of this unexpected novel annulation reaction is discussed.
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■ Synthesis of N(2)-Hydroxy-1,2,3,4-tetrahydro-β-carbolines
So-Yeop Han, M. V. Lakshmikantham, and Michael P. Cava*
*Department of Chemistry, University of Pennsylvania, 231 South 34th Street Philadelphia, PA 19104-6323, U.S.A.
Abstract
N-Hydroxytryptamine condensed readily with a series of aldehydes in the presence of a catalytic amount of acetic acid to give the corresponding nitrones (4a-f), which in turn were cyclized by hydrochloric acid to the stable N(2)-hydroxytetrahydro-β-carbolines (5a-f). β-Carbolines of this type have not previously been synthesized, and are of interest because of their structural relationship to several potent antiviral marine alkaloids (eudistomins C, E, K and L).
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■ Novel Ring Contraction of 4,6-Dihydro-3,7-diphenyl-5-(p-tosyl)-1,2,5-triazepine via a Chlorination
Kichinosuke Kamata and Otohiko Tsuge*
*Department of Applied Chemistry, Sojo University, 4-22-1, Ikeda, Kumamoto-shi, 860-0082, Japan
Abstract
In the chlorination 4,6-dihydro-3,7-diphenyl-5-(p-tosyl)-1,2,5-triazepine undergoes a novel ring contraction in methanol to afford pyrrolidines and morpholines which are arisen from the extrusion of nitrogen, in contrast to the formation of the 4-(p-tosylamino)pyridazine and/or 4,6-dichlorodihydrotriazepine in an aprotic solvent.
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■ The Syntheses of 4-Aminonicotine and 4-Aminocotinine
Makoto Shibagaki,* Hajime Matsushita, and Hajime Kaneko
*Life Science Research Laboratory, Japan Tobacco Inc., 6-2, Umegaoka, Midori-ku, Yokohama, Kanagawa 227-8512, Japan
Abstract
4-Aminonicotine and 4-aminocotinine were synthesized via 4-nitrocotinine-N-oxide, which obtained by the nitration of cotinine-N-oxide.
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■ Regioselective Synthesis of N-1 and N-2 Substituted Pyrimidinones Employing a Novel 1,3-Oxazine Preparation
Harvey I. Skulnick and Wendell Wierenga*
*CNS Research, The Upjohn Company, Kalamazoo, MI 49001, U.S.A.
Abstract
Reaction of ethyl benzoylacetate with methylthiopseudourea resulted in expulsion of methylmercaptan to afford 2-amino-6-phenyl-4H-1,3-oxarin-4-one in good yield. This novel oxazine synthesis was exploited to secure N-1 and N-2 substituted pyrimidinones regiospecifically.
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■ Revised Structure of Sanggenon B
Yoshio Hano, Masato Itoh, Toshio Fukai, Taro Nomura,* and Shiro Urano
*Faculty of Pharmaceutical Sciences, Toho University, 2-2-1, Miyama, Funabashi, Chiba 274-8510, Japan
Abstract
The structure of sanggenon B which had been isolated from the extract of the Chinese crude drug “Sang-Bai-Pi”(Japanes name “Sohakuh”),the root bark of Morus sp. (Moraceae), was reversed from the structure (1’) to (1) on the basis of spectral data.
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■ The Katada Reaction: A Study of Experimental Conditions
Alexander McKillop* and Manjeet K. Bhagrath
*School of Chemical Sciences, University of East Anglia, Norwich, Northfolk NR4 7TJ, U.K.
Abstract
Experimental conditions for the Katada reaction have been studied usiang 2-picoline N-oxide as a model substrate. Using a mixture of acetyl chloride and acetic anhydride, the reaction takes place rapidly at room temperature to give an excellent yield of 2-acetoxymethylpyridine.
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■ Synthesis of Ethyl 7,10-Ehtano-4-amino-4-deoxypteroate
Edward C. Taylor,* Jerauld S. Skotnicki, and Donald J. Dumas
*Department of Chemistry, Princeton University , Princeton, New Jersey 08544, U.S.A.
Abstract
Ethyl 7,10-ethano-4-amino-4-deoxypteroace (4) was prepared in three steps from 1-(4-carbethoxyphenyl)-4-pyrrolidino-1,2,5,6- tetrahydropyridine (1).
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■ 13C NMR Spectra and Stereochemical Analysis of Piperidine Derived α-Aminonitriles
Reija Jokela, Tarja Tamminen, and Mauri Lounasmaa*
*Laboratory of Organic Chemistry, Helsinki University of Technology, P.O. Box 6100,FIN-02015 HUT, Espoo, Finland
Abstract
Carbon-13 NMR spectra of several α-aminonitriles are reported, along with their preparation via the mdified Polonovski reaction or the reductive cyanation of Fry. The subtituent effects for the cyano group in the different nitrogen heterocycles were determined and stereochemical conclusions are made.
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■ Electrophilic Addition of Schiff Bases to Allenic Esters
Latchezar S. Trifonov and Alexander S. Orahovats*
*Centre of Ohyrochemistry, Centre of Ohyrochemistry, Bulgarian Academy of Sciences, 1113 Sofia, Bulgaria
Abstract
The reaction between the Schiff base 1 and allenic esters 2a and 2b leads to the formation of the butenolide 3a and 1,2-oxaphosphole 3b instead of the Diels-Alder adducts 3a’ and 3b’ under catalysis with boron trifluoride.
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■ A Facile Synthesis of Novel Tricyclic Compounds, 2,3-Dihydro-1H-pyrido[3,2,1-i,j]quinoxalin-5-ones
Kenji Makino,* Gozyo Sakata, Katsushi Morimoto, and Yoshinori Ochiai
*Central Research Institute, Nissan Chemical Industries Ltd., 722-1 Tsuboicho, Funabashi, Chiba 274-8507, Japan
Abstract
Novel 2,3-dihydro-1H-pyrido[3,2,1-i,j]quinoxalin-5-one-7-oxide (1) was synthesized from 8-nitro-1,2,3,4-tetrahydroquinoline in one pot reaction. 1 could be converted into 2,3-dihydro-1H-pyrido[3,2,1-i,j]quinoxalin-5-one (3), 6-methyl-2,3-dihydro-1H-pyrido[3,2,1-i,j]quinoxalin-5-one (4), and 6-chlaro-2,3-dihydro-1H-pyrido[3,2,1-i,j]quinoxalin-5-one (5).
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■ Synthesis of the Ixoquinuclidine Ring System
Mauri Lounasmaa,* Tarja Tamminen, and Reija Jokela
*Laboratory of Organic Chemistry, Helsinki University of Technology, P.O. Box 6100,FIN-02015 HUT, Espoo, Finland
Abstract
The formation of the biochemically important isoquinuclidine ring system by intramolecular condensation of an appropriately substituted piperidine-5-carbaldehyde derivative 6 is described. The direct acylation of the intermediate α-aminonitrile 5a (prepared by the modified Polonovski reaction) to the piperidine-5-carbaldehyde derivative 6 could be achieved only in low yield. However, if the α-aminonitrile 5a was transformed, before the acylation, to the “dimer” 7 of tetrahydroanabasine type, the piperidine-5-carbaldehyde derivative 6 could be obtained in much higher total yield.
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■ Transformation of (Isochroman-1-yl)methylketones to Naphthalene Derivatives
Masatoshi Yamato,* Kuniko Hashigaki, Sabroh Yoshioka, and Yasuo Takeuchi
*Faculty of Pharmaceutical Sciences, Okayama University, 1-1-1 Tsushima-naka, Okayama 700-8530, Japan
Abstract
Treatment of (isochroman-1-yl)methylketones (2c-h) with potassium tert-butoxide gave different naphthalene derivatives (5-14) via novel ring transformation, depending on the presence or absence and the nature of the substituents adjacent to the carbonyl group in 2.
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■ Novel Applications of the Modified Polonovski Reaction - VIII. Synthetic Studies in the Pseudovincamine Series
Reija Jokela, Siv Schüller, and Mauri Lounasmaa*
*Laboratory of Organic Chemistry, Helsinki University of Technology, P.O. Box 6100,FIN-02015 HUT, Espoo, Finland
Abstract
1β-Ethyl-(2’-methoxycarbonyl)-3α-ethyloctahydro-1,2,3,4,6,7,12,12b-indolo[2,3-a]quinolizine 7, a potential intermediate in the pseudovincamine series, was synthesized via the modified Polonovski reaction. Conformational considerations are presented.
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■ Synthesis of 2-Acyl-1-methyl-1H-imidazoles and Reactivity of the Acyl Group
Shunsaku Ohta, Satoshi Hayakawa, Hiroki Moriwaki, Shin-ichi Tsuboi, and Masao Okamoto*
*Kyoto Pharmaceutical University, Misasagi, Yamashina, Kyoto 607-8414, Japan
Abstract
2-Alkanoyl- and 2-aroyl-1-methyl-1H-imidazoles (3) were prepared in good yields by treating 1-acylpyrrolidine (1) with 2-lithio-1-methyl-1H-imidazole (2) at -78°C. Although 2-benzoyl-1-methyl-1H-imidazole (3a) was stable under n-Pr-NH2/80°C/10h; 2% K2CO3/aq. CH3OH/80°C /10h; 20% H2SO4/80°C/10h; CF3COOH/r.t./17h, it was hydrolysed into benzoic acid and 1-methyl-1H-imidazole by heating in 1.3N-NaOH - aq. ethanol at 80°C for 30h. The acyl group of 3 was activated by conversion to the corresponding imidazolium salt (4), which could react with various nucleophiles.
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■ Kinetics and Mechanisms of Nucleophilic Displacements at sp3 Hybridized Carbon Atoms with Heterocyclic Leaving Groups
Alan R. Katritzky,* Kumars Sakizadeh, and Giuseppe Musumarra
*Center for Drug Discovery, College of Pharmacy, University of Florida, Gainesville, Florida 32611-7200, U.S.A.
Abstract
Following a description of experimental methods, kinetic results are summarized, dealing successively with 2nd order and 1st order rates. In each of these sections, studies of product formation are described, followed by the effects of leaving group (steric and electronic), alkyl group structure, solvent, nucleophile and temperature. Finally, overall conclusions are presented together with the outlook for further work.