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. 22, No. 5, 1984
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■ Stereochemical Aspects of 1,3-Dipolar Cycloaddition of Benz[de]isoquinolinium-1-ide and Naphtho[1,8-cd]thiopyran
Masazumi Ikeda,* Yasumitsu Tamura, Masafumi Yamagishi, Yoshinobu Goto, Tokihiro Niiya, and Kunihiro Sumoto
*Kyoto Pharmaceutical University, Misasagi-Shichonocho, Yamashina, Kyoto 607-8414, Japan
Abstract
In contrast to naphtho[l,8-cd]thiopyran which undergoes 1,3-dipolar cycloaddition with maleimides to give exclusively or predominantly exo-adducts, 2-methylbenz[de]isoquinolinium-1-ide has been shown to react with maleimides to give exclusively endo-adducts. These results are rationalized in terms of frontier orbital theory.
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■ Synthesis of 2-(4,5-Dihydrofuryl)- and 2-(Tetrahydrofuryl)dimethylhydrosilanes. Rearrangement of 2-(Tetrahydrofuryl)dimethylhydrosilane with Ring Expansion
Edmunds Lukevics,* Vladimir Gevorgyan, Yuri Goldberg, Juris Popelis, Maris Gavars, Alexaneder Gaukhman, and Mariya Shimanska
*Institute of Organic Synthesis, Academy of Science of the Latvian SSR, 21 Aizkraukels, Riga-6, Latvia, Latvia
Abstract
2-(4,5-Dihydrofuryl)- and 2-(tetrahydrofuryl)dimethylhydrosilanes (I and II) have been synthesized. The latter rearranges easily and quantitatively to 1-oxa-2-sila-2,2-dimethylcyclohexane in the presence of palladium catalyst. The possibility of hydrosilylation of alkenes and alkynes by I and II has been demonstrated.
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■ Cocsuline-N-2-Oxide, a New Alkaloid from Cocculus hirsutus DC
Abdel O. El-Shabrawy, Paul L. Schiff, Jr., David J. Slatkin,* B. Das Gupta, Anil B. Ray, and Vyas J. Tripathi
*Department of Pharmacognosy, School of Pharmacy, University of Pittsburgh, Pittsburgh, PA 15261, U.S.A.
Abstract
Chromatography of an ethanol extract of Cocculus hirsutus DC. (Menispermaceae) over silicic acid afforded a new bisbenzylisoquinoline alkaloid, cocsuline-N-oxide (1). The alkaloid was characterized by a consideration of its physicochemical data and conversion to cocsuline (2).
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■ Structures of Cudraflavanone A and Euchrestaflavabobe C
Tomoko Fujimoto and Taro Nomura*
*Faculty of Pharmaceutical Sciences, Toho University, 2-2-1, Miyama, Funabashi, Chiba 274-8510, Japan
Abstract
From the benzene extract of the root bark of Cudrania tricuspidata (Carr. ) Bur. (Japanese name “Hariguwa”, Moraceae), an isoprene substituted flavanone derivative, named cudraflavanone A, was isolated, for which structure (I) was determined on the basis of the spectral and chemical evidences. From this result, the structure of euchrestaflavanone C which had been isolated from Euchresta japonica Hook. f. ex Regel, was reversed from the structure (I) to (II).
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■ A Novel Synthesis of Some Annelated Pyrimidines: Reaction of 6-Hydroxylamino-1,3-dimethylpyrimidine-2,4-dione with Imines and α-Chloroimines
Dipak Prajapati, Sivaprasad Attaluri, Jagir S. Sandhu,* and Jogendra Nath Baruah
*Division of Drug and Pharmaceutical Chemistry, Regional Research Laboratory, Jorhat 785 006, Assam, India
Abstract
Reaction of imines and α-chloroimines with 6-hydroxylamino-l,3-dimethylpyrimidine-2,4-dione gives isoxazolo[3,4-d] and pyrazolo[3 ,4-d]pyrimidines respectively in good yields.
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■ Structure of Mulberrofuran J, a 2-Arylbensofuran Derivative from the Cultivated Mulberry Tree (Morus lhou (ser.) Koidz.)
Toshio Fukai, Yoshio Hano, Kazuhiro Hirakura, Taro Nomura,* Jun Uzawa, and Kazutaka Fukushima
*Faculty of Pharmaceutical Sciences, Toho University, 2-2-1, Miyama, Funabashi, Chiba 274-8510, Japan
Abstract
A 2-arylbenzofuran derivative, named mulberrofuran J, was isolated from ethyl acetate extracts of the root bark of cultivated mulberry tree (Morus Lhou(ser.) Koidz.), and its structure was determined to be 1 on the basis of the spectral evidence. Mulberrofuran J is a 3”-stereoisomer on the cyclohexene ring of mulberrofuran C (2) obtained from the root bark of cultivated mulberry tree (Morus alba L. and M. bombysis Koidz .) .
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■ Imidazo[2,1-b]benzothiazole. Nucleophilic Substitution Reaction on Sulfur by n-Butyl Lithium
Toshiyasu Mase and Kiyoshi Murase*
*Central Research Laboraories, Yamanouchi Pharmaceutical Co., Ltd., 1-1-8, Azusawa, Itabashi-ku, Toyko 174-0051, Japan
Abstract
The nucleophilic substitution reaction on sulfur of 2-(p-methoxyphenyl)-7-methylimidazo[2,1-b]benzothiazole by n-butyl lithium affords the C-S bond cleaved compound in excellent yield.
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■ Oxidation of Dithiols by 10-Thiaisoallxazine
Magoichi Sako, Yutaka Kojima, Kosaku Hirota, and Yoshifumi Maki*
*Gifu Pharmaceutical University, 6-1 Mitahora-higashi 5-chome, Gifu 502-8585, Japan
Abstract
Reactions of 3-methyl-10-thiaisoalloxazine (2) with dihydrolipoamide and 1,4-butanedithiol (4b) gave almost exclusively redox products, whereas reactions of 2 with 1,3-propanedithiol (4c) and 1,2-ethanedithiol (4d) resulted in the concurrent occurrence of 4a,10a-cyclic addition and the redox reactions.
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■ Preparation and Reducing Propertty of 5,6-Dianilinopyrimidinediones
Magoichi Sako, Yutaka Kojima, Kosaku Hirota, and Yoshifumi Maki*
*Gifu Pharmaceutical University, 6-1 Mitahora-higashi 5-chome, Gifu 502-8585, Japan
Abstract
5,6-Dianilinopyrimidinediones (3), prepared with ease by the reaction of 6-anilino-5-bromopyrimidinediones (1) with p-toluidine, are fairly stable to autoxidation but possess the capacity reducing a disulfide bond under mild conditions.
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■ Ring Transformation of Seven-membered Heterosyslic Sulfoxides, 2,2-Disubstituted 1,4- and 1,5-Benzothiazepine Sulfoxides
Hiroshi Shimizu, Norihiko Ueda, Tadashi Kataoka, and Mikio Hori*
*Gifu Pharmaceutical University, 6-1 Mitahora-higashi 5-chome, Gifu 502-8585, Japan
Abstract
Thermal ring transformations of 2-methyl-2-phenyl-1,4- and 1,5-benzothiazepine 1-oxides in the presence of catalytic amount of p-toluenesulfonic acid are described. trans-Sulfoxides (having methyl group cis to the sulfoxide oxygen) underwent ring expansion to afford benzothiazocine derivatives, whereas cis isomers interestingly afforded ring contraction products, indicating that the ring transformations proceeded stereospecifically.
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■ Two Hexahydroproaporphine Alkaloids, Lauformine and N-Methyllauformine from Phoebe formosana
Sheng-Teh Lu* and Ian-Lih Tsai
*School of Pharmacy, Kaohsiung Medical College, 100 Shih Chuen 1st Rd., Kaohsiung 80708, Taiwan, R.O.C.
Abstract
Lauformine and N-methyllauformine isolated from the barks of Phoebe formosana Hay. (Lauraceae), were assigned structures (4) and (5), respectively.
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■ Total Synthesis of Ergot Alkaloids, (±)-Elymoclavine and (±)-Isolysergol
Ichiya Ninomiya,* Chiyomi Hashimoto, and Toshiko Kiguchi
*Kobe Women’s College of Pharmacy, Motoyamakita, Higashinad, Kobe, Hyogo 658, Japan
Abstract
Two of the hitherto untouched ergot alkaloids, (±)-elymoclavine and (±)-isolysergol, were synthesized according to the synthetic route involving enamide photocyclization.
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■ Structure and Synthesis of Medicanine, a New Amino Acid from Medicago sativa
Shinji Fushiya, Tokuhiro Tanura, Takashi Tashiro, and Shigeo Nozoe*
*Faculty of Pharmaceutical Sciences, Tohoku University, Aramaki, Aoba-ku, sendai 980-8578, Japan
Abstract
A new amino acid derivative was isolated from seedlings of Medicago sativa. The structure of this compound, medicanine has been determined as (S)-N-(3-hydroxypropyl)azetidine-2-carboxylic acid (1) on the basis of nmr analysis and chemical synthesis.
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■ A Formal Synthesis of (±)-Deserpidine
Okiko Miyata, Yumiko Hirata, Takeaki Naito, and Ichiya Ninomiya*
*Kobe Women’s College of Pharmacy, Motoyamakita, Higashinad, Kobe, Hyogo 658, Japan
Abstract
A formal total synthesis of (±)-deserpidine (11) was completed by preparing the known key intermediate (10) from harmalane (1) via the route involving reductive photocyclization of the enamide (2) and functionalization of the basic skeleton (6b) of the alkaloid.
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■ Synthesis of 5,1-Benzothiazocines and Their Homologues
Susumu Sato, Kuniyuki Tomita,* Hiroshi Fujita, and Yasunobu Sato
*Sankyo Research Laboratories, Sankyo Co., Ltd., 1-2-58 Hiromachi, Shinagawa-ku, Tokyo 140-8710, Japan
Abstract
A facile one pot synthesis of 5,1-benzothiazocines and their homologues from acyclic aniline derivatives has been achieved by the effective synthetic control via aza-sulfonium intermediates.
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■ S-N Polyhetero-Claisen Rearrangements Promoted by Carboxyl Group
Tadashi Sasaki* and Ikuo Shimizu
*Faculty of Engineering, Nagoya Institute of Technology, Gokiso-cho, Showa-ku, Nagoya 466-8555, Japan
Abstract
S-N Polyhetero-Claisen rearrangements promoted by carboxyl group were studied. 2-Carboxyallyl groups in triazines (3a and b) migrated to nitrogen at 4-position of those rings and gave 4-(2-carboxyallyl)triazines ( 7a and b) by refluxing in ethanol. 2-(2-Carboxyallylthio)benzimidazole (10) and -thiazoline (12) were also converted to N-(2-carboxyallyl)heterocycles in the same fashion, respectively.
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■ Benzyne-induced Fragmentation Reactions of 1,3-Dithiolanes
Juzo Nakayama,* Hiroshi Ozasa, and Masamatsu Hoshino
*Department of Chemistry, Faculty of Science, Saitama University, Saitama, Saitama 338-8570, Japan
Abstract
2-Monosubstituted 1,3-dithiolanes, on reaction with benzyne, undergo two types of fragmentation, one of which gives phenyl vinyl sulfide and thioaldehydes (corresponding aldehydes as the final products) and the other gives phenyl dithiocarboxylates and ethylene. Meanwhile, 2,2-disubstituted 1,3-dithiolanes undergo the sole fragmentation yielding phenyl vinyl sulfide and thioketones.
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■ A Facile Intramolecular Cyclization of 4-Diazomethylcoumarins. A Convenient Route to Benzopyrano[3,4-c]pyrazol-4(3H)-ones
Keiichi Ito* and Junko Maruyama
*Hokkaido College of Pharmacy, 7-1 Katsuraoka-cho, Otaru 047-02, Japan
Abstract
The 7-substituted 4-diazamethylcoumarins 2 as the stable aryldiazomethanes were rapidly transformed into their cyclized isomers, benzopyrano[3,4-c]pyrazol-4(3H)-ones 3 in high yields in refluxing toluene.
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■ Methylene-indolines, Indoleines and Indoleniniums XVII. Rearrangement of De-ethyltabersonine in Acetic Acid
Ren Wen, Jean-Yves Laronze, and Jean Lévy*
*Laboratoire de Transformation et Syntheses deSubstances Naturelles, Faculté de Pharmacie, Université de Reims-Champagne-Ardenne, 51, rue Cognacq-Jay, F-51096 Reims Cedex, France
Abstract
De-ethyltabersonine 1 rearranged in boiling acetic acid to de-ethylcoronaridine 9 with a low yield.
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■ Synthesis of 2,3,9,10-Tetraoxygenated Protoberberine Alkaloid, Tetrahydropalmatine
Tetsuji Kametani,* Hirotaka Yukawa, Yukio Suzuki, Ryoji Yamaguchi, and Toshio Honda
*Hoshi University, 2-4-41 Ebara, Shinagawa-ku, Tokyo 142-8501, Japan
Abstract
Tetrahydropalmatine (15) was synthesized from the 3,4-dihydroisoquinoline derivative (13) by thermal electrocyclic reaction and subsequent reduction. An intermolecular Diels-Alder type reaction of the benzocyclobutene (6) with the 3,4-dihydroisoquinoline afforded the 13-cyanoprotoberberine (9) regioselectively.
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■ Electron Impact Mass Spectrometry of Some New Sulphur-containing Macrocycles
Gianni Podda,* Antonio Maccioni, Luciana Corda, Sergio Daolio, Pietro Traldi, and Enrico Vecchi
*Istituto di Chimica Farmaceutica, Tossicologica ed Applicate, University of Cagliari, Via Ospedale 72, 09100 Cagliari, Italy
Abstract
The electron impact mass spectrometrlc behaviour of five macrocyclic dithio-diesters is described and discussed in detail wlth the aid of exact mass measurements, linked scans and collisionally activated decomposition experiments. The analogies and differences in relation to the corresponding catecholic tetraesters are emphasized.
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■ Photolysis of Bromothiazoles in Hydrogen-donating Solvents. A Theoreticals Study and Physical Properties of Bromothiazoles
Cyril Párkányi,* Gaston Verrin, Rose-Marie Zamkostian, and Jacques Metzger
*Department of Chemistry, The University of Texas at El Paso, El Paso, Texaz 79968-0513, U.S.A.
Abstract
UV irradiation of bromothiazoles in various organic solvents (methanol, ether, cyclohexane) produces thiazole and the isomeric isothiazole as the main reaction products. The reactivity of monobromothiazoles in this reaction decreases in the order: 2-bromothiazole > 5-bromothiazole >> 4-bromothiazole. The PPP (LCI-SCF-MO) calculations of bromothiazoles were used to interpret and discuss their various properties. The uv, NMR, and mass spectra of bromothiazoles were measured.
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■ The Regiosilective Nucleophilic Addition of Organolithiums to 3-(4,4-Dimethyloxazolin-2-yl)pyridine. Synthesis of 1,2-, 1,4- and/or 1,6-Dihydropyridines
Sushil K. Dubey, Edward E. Knaus,* and Choo-Seng Giam
*Faculty of Pharmacy , University of Alberta, Edmonton, Alberta T6G, 2N8, Canada
Abstract
The nucleophilic addition of organolithium reagents to 3-(4,4-dimethyloxazolin-2-yl)pyridine afforded stabilized N-unsubstituted 1,2-, 1,4- and/or 1,6-dihydropyridines. Solvent, temperature and nature of the organolithium reagent influence the regioselectivity of the reaction.
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■ Reaction of Diketone with 3-Amino-5,6-disubstituted-1,2,4-triazine Derivatives
Mohsen Daneshtalab* and Mohammad Hassan Hooshdar Tehrani
*Department of Chemistry, College of Pharmacy, Tehran University, Tehran 14, Iran
Abstract
Reaction of diketene with 3-amino-5,6-dimethyl-1,2,4-triazine ( Ia ) in acetic acid or benzene medium afforded 3-acetonyl-2,3,6-trimethyl-3H-pyrimido[1,2-b]-1,2,4-triazin-8(5H)-one ( II ) . On the other hand, reaction of diketene with 3-amino-5,6-diphenyl-1,2,4-triazine ( Ib) gave rise to 3-acetoacetylamino- 5,6-diphenyl-l,2,4-triazine ( V ) and 3-(3-acetyl-4-hydroxy-6-methylpyridin-2- one-1-yl) -5,6-diphenyl-1,2 ,4-triazine ( VI ) , respectively. The reaction mechanism is discussed.
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■ Δ2-Oxazolinium and Thiazolinium Cations as One Carbon Unit Transfer Agents
Harjit Singh* and Rakesh Sarin
*Department of Chemistry, Guru Nanak Dev University, Amritsar -143 005, Punjab, India
Abstract
N-Methyl-Δ2-oxazolinium and thiazolinium cations transfer their C2 units to binucleophiles in refluxing DMF or CH3CN and provide the corresponding heterocycles.
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■ Preparation of Fluoroheterocycles I. Synthesis and Reactivity of 2-Fluoropyrazine 1-Oxide
Misa V. Jovanovic*
*Department of Chemistry, Southern Methodist University, P.O. Box 750314, Dallas, TX 75275-0314, U.S.A.
Abstract
The title compound was prepared by three different methods: Balz-Schiemann reaction, halogen exchange, and by direct N-oxidation of 2-fluoropyrazine. The resulting 2-fluoro- pyrazine 1-oxide was reacted with a variety of nucleophiles to yield the corresponding 2-substituted pyrazine 1-oxides.
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■ Diazonium Coupling Reaction of Some Diazine N-Oxides
Misa V. Jovanovic*
*Department of Chemistry, Southern Methodist University, P.O. Box 750314, Dallas, TX 75275-0314, U.S.A.
Abstract
Attempted deoxygenation of 2-aminopyrazine 1-oxide with HF under the diazotization conditions yielded a coupling reaction product, 2,2’-bispyrazyltriazine 1,1’-dioxide. Similarly, diazotization of 2-aminopyrimidine 1-oxide in the presence of hydrofluoric acid gave a nucleophilic hydroxylative-deoxygenation product, 5-hydroxy-2-pyrimidinediozotic acid.
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■ 1-Acyloxypyridinium Ion: The Reactive Intermediate in a Modified Reissert-Henze Reaction
Wlmer K. Fife* and Brett D. Boyer
*Department of Chemistry, Indiana-Purdue University, PO Box 647, Indianapolis, IN 46223, U.S.A.
Abstract
Cyanation of 3-X-1-dimethylaminocarbonyloxypyridinium ions with trimethylsilane-carbonitrile or cyanide ion gives 3-methyl-2-pyridinecarbonitrile (~90%) contaminated with 5-methyl-2-pyridinecarbonitrile (~10%) when X = -CH3, and approximately equal amounts of the 3- and 5-X derivatives when X = -COOCH3. These product mixtures are identical to those obtained with the corresponding pyridine 1-oxides and dimethylcarbamoyl chloride in a modified Reissert-Henze reaction.
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■ Photolysis of 2-Aryloxy- or 2-Arylthio-1,3-benzodioxan-4-ones
M. Rosa Díaz-Mondéjar and Miguel A. Miranda*
*Departamento de Química Orgánica, Universidad de Valencia, Calle Dr. Moliner, 50, E-46100 Burjassot (Valencia), Spain
Abstract
Photolysis of 1,3-benrodioxan-4-ones 3b and 4a gives mainly products derived from photorearrangement, photoreduction and/or photosolvolysis. These results closely parallel those obtained by irradiation of the isomeric open-chain compounds 1b and 2a. A mechanism involving the intermediacy of radical pairs A and B, generated by successive homolysis of the aryloxy- or arylthio-carbon and carbonyl-oxygen bonds, is proposed.
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■ Novel Rearangement of N’-Alkyl-N-alkyl-N-[2-(4-pyridinyl)-4-pyrimidinyl]ureas with Sodium Hydride
Baldev Singh* and George Y. Lesher
*Sterling Winthrop Pharmaceuticals Research Division, Rensselaer, New York, 12144, U.S.A.
Abstract
Treatment of N’-alkyl-N-alkyl-N-[ 2-(4-pyridinyl)4-pyrimidinyl]ureas with sodium hydride in dimethylformamide gave mixtures of two N-alkyl-2-(4-pyridinyl)-4-pyrimidinamines.