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. 38, No. 2, 1994
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■ Ring Closure Reactions of Adducts of Methacryloyl Isocyanate to Arylhydrazines and Their Related Componds
Otohiko Tsuge,* Taizo Hatta, and Ryuzo Mizuguchi
*Graduate Course of Applied Chemistry, Faculty of Engineering, Kumamoto Institute of Technology, 4-22-1, Ikeda, Kumamoto 860, Japan
Abstract
Methacryloyl isocyanate (MAI) reacted with arylhydrazines (1) to give semicarbazides (2) in good yields. Treatment of 2 with aqueous potassium hydroxide gave the corresponding 1-aryl-3-hydroxy-1,2,4-triazoles (3), whereas thermal ring closure of 2 afforded isomeric 2,3-dihydro-2-aryl-1,2,4-triazole-3(1H)-ones (4). MAI reacted with benzamidine to give directly 1,3,5-triazine-2(1H)-one (10) by the loss of water. On the other hand, the reaction of MAI with 1,3-diphenylguanidine afforded the 1:1 adduct (11), which on thermal decomposition gave the perhydropyrimidin-6(1H)-one (12) and perhydro-1,3,5-triazine-2,6-dione (13). The pathways for the formation of 4, 12 and 13 are also described.
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■ Total Synthesis of Islandic Acid I Methyl Ester, Rosellisin and Rosellisin Aldehyde
Takeshi Shimizu,* Sayoko Hiranuma, Tsumoru Watanabe, and Masayuki Kirihara
*The Institute of Physical and Chemical Research, Wako-shi, Saitama 351-0198, Japan
Abstract
Total synthesis of islandic acid I methyl ester (2), rosellisin (3) and rosellisin aldehyde (4) has been accomplised starting from 4-hydroxy-5-hydroxymethyl-6-methyl-2H-pyran-2-one (9a) via formylation of 9a with dichloromethyl methyl ether and titanium tetrachloride as a key step.
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■ Novel Synthesis of Substituted Pyrimidines: A Ring Transformation of 3-Methyl-5-nitropyrimidin-4(3H)-one
Nagatoshi Nishiwaki, Tomoko Matsunaga, Yasuo Tohda, and Masahiro Ariga*
*Department of Chemistry, Osaka Kyoiku University, 4-698-1 Asahigaoka, Kashiwara, Osaka 582-8582, Japan
Abstract
A novel ring transformation of 3-methyl-5-nitropyrimidin-4(3H)-one with ketones in the presence of ammonia was found to be an elegant method for synthesizing 5,6-disubstituted pyrimidines. Tetrahydroquinazoline was readily obtained in good yields when cyclohexanone was employed as a substrate. The present reaction was applicable to cyclopentanone, acetophenone and p-nitroacetophenone to give the corresponding pyrimidine derivatives.
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■ Synthesis of the N(1)- and N(3)-Oxides of 7-Benzyladenine
Kazuo Ogawa, Tohru Saito, Taisuke Itaya, and Tozo Fujii*
*Faculty of Pharmaceutical Scicences, Kanazawa University, 13-1 Takara-machi, Kanazawa 920-0934, Japan
Abstract
Oxidation of 7-benzyladenine (9) with m-chloroperoxybenzoic acid in MeOH has been found to yield 7-benzyladenine 1-oxide (11) as the main product. Alternatively, the same N-oxide (11) has been synthesized in 81% yield from 1-benzyl-4-(ethoxymethyleneamino)imidazole-5-carbonitrile (12) and hydroxylamine. Treatment of 1-benzyl-4-(hydroxyamino)imidazole-5-carbonitrile (17), prepared in 63% yield from the corresponding 4-nitro derivative (13) by catalytic reduction (Pt/H2), with formamidine acetate in boiling EtOH gave 7-beznyladenine 3-oxide (16) in 83% yield.
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■ A Reaction of N-Fluoropyridinium Cation with Diazocarbonyl Compounds
Alexander S. Kiselyov and Lucjan Strekowski*
*Department of Chemistry, Georgia State University, University Plaza, Atlanta, GA 30303, U.S.A.
Abstract
1-Fluoro-1-(2-pyridyl)propan-2-one (4) and ethyl fluoro(2-pyridyl)acetate (5) are produced in the reaction of N-fluoropyridinium tetrafluoroborate with diazoacetone or ethyl diazoacetate, respectively.
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■ Dehydro-4-methoxycyclobrassinin, a Sulfur-containing Phytoalexin Isolated from Turnip Brassica campestris L. ssp. rapa
Kenji Monde, Kimio Tamura, Mitsuo Takasugi,* Kensuke Kobayashi, and Masanori Somei*
*Division of Material Science, Graduate School of Environmental Earth Science, Hokkaido University, Sapporo 060-0810, Japan
Abstract
Isolation, structure elucidation, and synthesis of dehydro-4-methoxycyclobrassinin (1), a turnip phytoalexin possessing a novel heterocyclic system, are described.
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■ A Short and Practical Synthesis of (+)-Pseudoconhydrine and (+)-N-Methylpseudoconhydrine via Osmium Catalyzed Asymmetric Dihydroxylation
Hiroki Takahata,* Kumiko Inose, and Takefumi Momose*
*Faculty of Pharmaceutical Sciences, Toyama Medical and Pharmaceutical University, 2630 Sugitani, Toyama, Toyama 930-0194, Japan
Abstract
A short and practical synthesis of (+)-pseudoconhydrine (1) and (+)-N-methylpseudoconhydrine (2) has been achieved by starting with asymmetric dihydroxylation of the α-amino acid-derived N-alkenylurethane (3).
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■ Nucleophilic Substitution Reactions on Indole Nucleus: Syntheses of 2-Substituted Indole-3-carboxaldehydes
Fumio Yamada, Daisuke Shinmyo, and Masanori Somei*
*Faculty of Pharmaceutical Sciences,. Kanazawa University, 13-1 Takara-machi, Kanazawa 920-0934, Japan
Abstract
1-Methoxyindole-3-carboxaldehyde is found to be a versatile substrate for the nucleophilic substitution reaction, culminating in the formation of 2-substituted indole-3-carboxaldehydes.
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■ Versatile Synthesis of an Intermediate for the 1β-Methylcarbapenem Synthesis
Koichi Hirai,* Yuji Iwano, Isamu Mikoshiba, Hiroo Koyama, and Takahide Nishi
*New Lead Research Laboratories, Sankyo Co., Ltd., 1-2-58 Hiromachi, Shinagawa-ku, Tokyo 140-8710, Japan
Abstract
A 1β-methylcarboxylate (1) which is a requisite intermediate for the synthesis of the 1β-methylcarbapenem was obtained in an efficient manner by the coupling reaction of a Z(O)-pyridylthiosilyl enol ether and a 4-acetoxyazetidinone derivative in the presence of ZnCl2 in CH2Cl2. The reactive silyl enol ether was prepared by the reverse addition method in high yield.
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■ Reactivity of the Pyridylthiosilyl Enol Ether — Route to β-Lactone and β-Lactam —
Koichi Hirai,* Hiroshi Homma, and Isamu Mikoshiba
*New Lead Research Laboratories, Sankyo Co., Ltd., 1-2-58 Hiromachi, Shinagawa-ku, Tokyo 140-8710, Japan
Abstract
A simple and facile method for β-lactone and β-lactam syntheses based on a Lewis acid promoted pyridylthiosilyl enol ether (1) addition to an aldehyde or Schiff base is described.
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■ Reaction of 1-Ethoxalylmethylpyrido[2,3-b]pyrazinium Bromide with Ammonium Acetate: Synthesis of Imidazo[1’,2’:1,2]pyrido[5,6-b]pyrazines
Yves Blache,* Alain Gueiffier, Olivier Chavignon, Ahmed Elhakmaoui, Henry Viols, Jean Claude Teulade, Jean Claude Milhavet, Gerard Dauphin, and Jean Pierre Chapat
*Laboratoire de Chimie Organique Pharmaceutique, URA-CNRS, Faculté de Pharamcie, Université Montpellier I, 15, Avenue Charles Flahault, 34060 Montpellier, France
Abstract
The synthesis of somes imidazo[1’,2’:1,2]pyrido[5,6-b]pyrazines by treatment of quaternary salts of pyrido[2,3-b]pyrazines with ammonium acetate in acetic acid media is described.
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■ Synthesis of [1,2,3]Triazolo[1,5-a][4,1]benzoxazepines via Intramolecular Azide Cycloaddition
Luisa Garanti,* Giorgio Molteni, and Gaetano Zecchi
*Dipartimento di Chimica Organica e Industriale, Centro C.N.R., Università degli Studi di Milano, via Golgi 19, I-20133 Milano, Italy
Abstract
Starting from isatoic anhydride and propargyl alcohols, we developed a synthetic approach to the title compounds, where the key step is an intramolecular cycloaddition of the azido group onto the acetylenic bond.
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■ Cyclocondensation of β-Oxonitriles with Ketones or Aldehydes
Jean-François Stambach,* Louis Jung, and Raymond Hug
*Laboratoire de Chimie Thérapeutique, U.F.R. des Sciences Pharmaceutiques, Université Louis Pasteur, 74, route du Rhin, BP 24, 67401 ILLKIRCH Cedex, France
Abstract
β-Oxonitriles (1) are easily condensed with cyclic ketones (2a-e) in anhydrous strong acidic conditions to give 1-oxa-5-azaspiro[5.5]undec-2-en-4-ones (3a-e). In the same manner acyclic ketones (2f,g) or aldehydes (2h,i) afford 2,3-dihydro-4H-1,3-oxazin-4-ones (3f-i). The mechanism of this cyclocondensation is discusssed.
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■ Synthesis of 2,2-Dimethylbenzoxazepinones by the Beckmann Rearrangement of 2,2-Dimethyl-4-chromanone Oximes
Albert Lévai,* Gábor Tóth, Judit Halász, Tibor Timár, László Frank, and Sándor Hosztafi
*Department of Organic Chemistry, Lajos Kossuth University, P.O.Box 20, H-4010 Debrecen, Hungary
Abstract
2,3-Dihydro-2,2-dimethyl-1,4-benzoxazepin-5(4H)-ones and 2,3-dihydro-2,2,6-trimethyl-1,5-benzoxazepin-4(5H)-ones have been synthesized by the Beckmann rearrangement of 2,2-dimethyl-4-chromanone oximes.
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■ Synthesis, Stereochemistry and Synthetic Potential of 6-(Benzotriazol-1-yl)-6-(morpholin-4-yl)bicyclo[3.1.0]hexane
Alan R. Katritzky,* Barbara Galuszka, Stanislaw Rachwal, Balbino Mancheno, and Peter J. Steel
*Center for Heterocyclic Compounds, Department of Chemistry, University of Florida, P. O. Box 117200, Gainesville, FL 32611-7200, U.S.A.
Abstract
Reaction of 4-(cyclohexen-1-yl)morpholine with 1-chlorobenzotriazole in the presence of triethylamine gave 6-(benzotriazol-1-yl)-6-(morpholin-4-yl)bicyclo[3.1.0]hexane (1e)(70%) as confiremed by X-ray crystallography. Treatment of 1e with Grignard reagents substituted the benzotriazolyl moiety with a phenyl (7a, 91%) or a benzyl (7b, 98%) group.
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■ Isolation of a New Insect Antifeeding Azadirachtin Derivative from Okinawan Melia azedarach Linn.
Munehiro Nakatani,* Shoko Arikawa, Hiroaki Okamura, and Tetsuo Iwagawa
*Department of Chemistry , Faculty of Science, Kagoshima University, 1-21-35 Korimoto, Kagoshima 890-0065, Japan
Abstract
A new azadirachtin-type insect antifeedant, 1-cinnamoyl-3-acetyl-11-methoxymeliacarpinin, was isolated from the stem bark of Okinawan Melia azedarach Linn.
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■ New 5-Substituted Derivatives of Ethyl 2,3-Dihydro-3-oxoisothiazolo[5,4-b]pyridine-2-acetate
Victor Martinez-Merino,* Maria J. Gil, Alberto Gonzalez, Jose M. Zabalza, Javier Navarro, and Maria A. Mañu
*Departamento de Quimica, Universidad Publica de Navarra, 31006 Pamplona, Spain
Abstract
New series of ethyl 5-substituted 2,3-dihydro-3-oxoisothiazolo[5,4-b]pyridine-2-acetate was prepared either a) directly by reaction of 5-substituted 2-chlorothio-3-pyridinecarbonyl chlorides with ethyl glycinate or b) by oxidation of the correspondent 2-mercapto-3-pyridinecarboxamides. New 5-substituted 1,2-dihydro-2-thioxo-3-pyridinecarboxylic acids as starting materials are described.
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■ Benzotriazolylalkylation of Aromatic Compounds by 1-Benzenesulphonylbenzotriazole and Synthesis of Triarylmethanes
Alan R. Katritzky,* Vandana Gupta, Catherine Garot, Christian V. Stevens, and Mikhail F. Gordeev
*Center for Heterocyclic Compounds, Department of Chemistry, University of Florida, P. O. Box 117200, Gainesville, FL 32611-7200, U.S.A.
Abstract
Mesitylene, 2-methoxynaphthalene, 1,3,5-trimethoxybenzene, xylene and anisole were all benzotriazolylalkylated by treatment with 1-(benzenesulphonyl)benzotriazole and an aromatic aldehyde. Upon displacement of benzotriazole, the functionalized aromatic compounds were transformed into asymmetrically trisubstituted methanes and functionalized indoles.
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■ Structure and Synthesis of a Quercetin Glucoxyloside from Kalanchoe prolifera (Raym.-Hamet)
Bakonirina Razanamahefa, Costas Demetzos, Alexios-Léandros Skaltsounis, Marta Andriantisiferana, and François Tillequin*
*Laboratoire de Pharmacognosie,Université René Descartes, Unitè associèe au C.N.R.S. n˚ 1310, Facultè de Pharmacie, 4, Avenue de l‘Observatoire, 75270 Paris Cedex, France
Abstract
A quercetin glycoside has been isolated from Kalanchoe prolifera. Its structure has been establised as quercetin-3-O-β-D-glucopyranosyl-(1→2)-β-D-xylopyranoside on the basis of its synthesis starting either from 1,2-O-isopropylidene-α-D-xylofuranose or from 1,3,4-tri-O-acetyl-α-D-xylopyranose.
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■ Syntheses of 2,4-Diaminopyrimidines and 1-Aminoisoquinolines in the Reactions of Alkyl and Benzyl Ketones with Cyanamide and N,N-dimethylcyanamide
Wojciech Zielinski* and Monika Mazik
*Instiute of Organic Chemistry and Technology, Silesian University of Technology, ul. Krzywoustego 4, 44-101 Gliwice, Poland
Abstract
The reaction of alkyl and benzyl ketones with cyanamide and N,N-dimethylcyanamide in the presence of POCl3 was examined. At the first stage, chloroformamidine derivatives were formed. In the presence of TiCl4, they underwent further reactions to the derivatives of 1-aminoisoquinoline and 2,4-diaminopyrimidine. The effect of a constitution of substrates on adequate ratios of heterocyclic compounds is discussed.
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■ Sesquiterpene Pyridine Alkaloids from Maytenus ilicifolia
Osamu Shirota, Hiroshi Morita, Koichi Takeya, and Hideji Itokawa*
*Department of Phamacogncsy, Tokyo College of Pharmacy, 1432-1 Horinouchi, Hachioji, Tokyo 192-0392, Japan
Abstract
Three sesquiterpene pyridine alkaloids with a dihydroagarofuran core, cangorinines W-I (1), W-II (2), and E-I (3) were isolated from the root bark of Maytenus ilicifolia Mart. (Celastraceae). Their structures were elucidated by spectroscopic methods.
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■ Synthesis of 9-Methoxyellipticine N-Oxide and Its Transformation into 1-Functionalized Ellipticine Derivatives
Christian Rivalle* and Emile Bisagni
*URA 1387 CNRS, Section de Biologie Batiments 110-112, Institut Curie, 15 Rue Georges Clemenceau 91405 Orsay, France
Abstract
9-Methoxy-5,11-dimethyl-(and 5-methyl)-6H-pyrido[4,3-b]carbazole-1-carbonitriles (8) were synthesized through methoxyellipticine N-oxides (4) and subsequent deoxygenation-functionalization by diethyl cyanophosphonate. Hydration of these nitriles (8) into 1-carboxamidoellipticines (9) and cytotoxicities of these last compounds are also reported.
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■ Preparation of Some New Benzylidenemalononitriles by an SNAr Reaction: Application to Naphtho[1,2-b]pyran Synthesis
Jason Bloxham, Colin P. Dell,* and Colin W. Smith
*Lilly Research Centre, Eli Lilly and Company, Erl Wood Manor, Windlesham, Surrey GU20 6PH, U.K.
Abstract
The reaction of 4-fluoro-3-nitrobenzylidene malononitrile (3) with piperidine and 1-naphthol yields the addition-elimination product (9) rather than the expected naphtho[1,2-b]pyran (7). This reaction is extended to produce other 3,4-disubstituted benzylidenemalononitriles (10)-(13). These compounds are then reacted with 1-naphthol and 4-methylmorpholine producing the naphtho[1,2-b]pyrans (14)-(17).
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■ [Hydroxy(tosyloxy)iodo]benzene: A Useful Hypervalent Iodine Reagent for the Synthesis of Heterocyclic Compounds
Om Prakash,* Neena Saini, and Pawan K. Sharma
*Department of Chemistry, Kurukshetra University, Kurukshetra-132 119, India
Abstract
[Hydroxy(tosyloxy)iodo]benzene, a hypervalent iodine reagent finds extensive use in the synthesis of a wide variety of heterocycles. In this review an effort has been made to present the prolific development in recent years in this area.