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. 29, No. 7, 1989
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■ 2-Amino-3-cyano-4,5-dimethylfuran as Precursors to Butenolides and Arylacetic Acids
Hooshang Kooshakabadi, Walter F. Schmidt, Stephen J. Cutler, Fiesal M. El-Kabbani, and C. DeWitt Blanton, Jr.*
*Department of Medical Chemistry and Pharmacognosy, College of Pharmacy, The University of Georgia, Athens, Georgia 30602, U.S.A.
Abstract
A facile synthesis of butenolides and arylacetic acids via a Michael reaction of the title compound at C(5) is reported.
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■ A Convenient, One-pot Azulene Synthesis from Cyclohepta[b]furan-2-ones and Vinyl Ether and Its Analogues (I). Vinyl Ethyl Ether, Vinyl Acetates, Dihydrofurans, and Dihydropyrans as Reagent
Tetsuo Nozoe,* Paw-Wang Yang, Chi-Phi Wu, Tin-Shan Huang, Te-Hsiang Lee, Harue Okai, Hidetsugu Wakabayashi,* and Sumio Ishikawa
*Department of Chemistry, Faculty of Science, Josai University, 1-1 Keyakidai, Sakado, Saitama 350-0295, Japan
Abstract
Variously functionalized azulene derivatives (more than 40) were synthesized in one-pot and in good yields by the reaction of cyclohepta [b] furan-2-one derivatives with vinyl ethyl ether, vinyl acetate, isopropenyl acetate, dihydropyrans, and dihydrofurans on heating at 160-190 °C in aprotic solvent. Structures of formal cycloadducts in two cases were determined, and a possible pathway of the reaction is discussed.
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■ Synthesis of Novel Chiral2,3-Dihydro-1,3,4-thiadiazoles with Extremely High Optical Rotations: X-Ray Crystal Structure of (2R)-D-Mandelyl-5-methylthio-2-phenyl-2,3-dihydro-1,3,4-thiadiazole
Kouhei Toyooka,* Yoshiyuki Takeuchi, Zenei Taira, and Seiji Kuboto
*Faculty of Pharmaceutical Sciences, University of Tokushima, Sho-machi, Tokushima 770-8505, Japan
Abstract
The reaction of 4-bromobenzaldehyde methylthio (thiocarbonyl)-hydrazone with chiral 5-phenyl-1,3-dioxolane-2,4-dione in the presence of trifluoroacetic acid gave chiral 2-(4-bromophenyl)-3-mandelyl-2,3-dihydro-1,3,4-thiadiazoles with extremely high optical rotations; the absolute configuration of the 2,3-dihydro-1,3,4-thiadiazole (2) was established by single crystal X-ray analysis.
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■ Preparation of β-Lactams from β-Amino Acids with Di-2-pyridyl Sulfite
Sunggak Kim,* Kyu Yang Yi, and Ja-Young Namkung
*Department of Chemistry, Korea Advanced Institute of Science and Technology, 373-1, Kusung-Dong, Yusung-Gu, Taejon, 305-701, Korea
Abstract
β-Lactams are conveniently prepared in high yields by the reaction of β-amino acids with di-2-pyridyl sulfite in acetonitrile under very mild conditions.
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■ The First Synthesis of 4,5-Di-t-buthylpyridazine
Juzo Nakayama* and Atsushi Hirashima
*Department of Chemistry, Faculty of Science, Saitama University, Saitama, Saitama 338-8570, Japan
Abstract
3,4-Di-t-butylthiophene 1,1-dioxide (1) reacts with 2 equiv. of 4-phenyl-1,2,4-triazoline-3,5-dione in refluxing toluene to give the bis-adduct 4 in 87% yield. KOH-Induced methanolysis of 4, followed by spontaneous air-oxidation and nitrogen extrusion of the resulting hydrazo compound 5, affords 4,5-di-t-butylpyridazine (7) directly in one-pot in 80% yield.
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■ Intramolecular Cycloadditions with Isobenzofuran -VIII. Synthesis of Precurosors via an Oppé Reaction
Knut Hildebrandt and Willy Friedrichsen*
*Institut für Organische Chemie, Universität Kiel, Olshausenstrasse. 40, D-24098 Kiel, Germany
Abstract
The diazoesters 3 and 9 were prepared via an Oppé reaction. Generation of isobenzofurans (e.g. 4) and subsequent intramolecular Diels-Alder reaction yields polycyclic systems (6, 10). Compound 10 can be transformed into an 11-oxasteroid 14.
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■ Enantioselective Synthesis of (+)-Acetylphomalactone from 2-Furylcarbinols
Tetsuji Kametani, Yoko Tatsuzaki, Masayoshi Tsubuki, and Toshio Honda*
*Faculty of Pharmaceutical Sciences, Hoshi University, 2-4-41 Ebara, Shinagawa-ku, Tokyo 142-8501, Japan
Abstract
A facile synthesis of (+)-acetylphomalactone (1) has been developed in seven steps employing the kinetic resolution of the racemic secondary furylcarbinol (2) as a key reaction.
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■ A New and Simple Synthesis of 1-Hydroxyindole Derivatives
Masanori Somei* and Toshiya Kawasaki
*Faculty of Pharmaceutical Sciences, Kanazawa University, 13-1 Takara-machi, Kanazawa 920-0934, Japan
Abstract
A new and straightforward simple synthesis method for 1-hydroxyindole derivatives is developed.
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■ Palladium Homogeneous and Supported Catalysis: Synthesis of Functional Acetylenics and Cyclisation to Heterocycles
Didier Villemin* and Delphine Goussu
*I.S.M.Ra, URA 480 C.N.R.S., Université d’Orléans, 5 avenue d’Edimbourg, F-14032 Caen Cedex, France
Abstract
Homogeneous and supported palladium catalysis is a good way to synthesize functional orthu-phenylacetylenes from acetylenes and orthohalogenated aromatics. Functional ortho-phenylacetylenes are cyclised into various benzoheterocyclic compounds.
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■ Cyclization of Allyl Silanes — A Novel Approach to 2-Azabicyclo[3.3.0]octanes
Jean-Claude Gramain and Ronald Remuson*
*Laboratoire de Chimie des Substances Naturelles, U.A. CNRS 485, Université Blaise Pascal (Clemont II), 63177 Aubière Cedex, France
Abstract
The methodology which consists in the electrophilic substitution of α-acyl and N-acyl iminium ions on allyl silanes has been used to accede to 2-azabicyclo[3.3.0] octane derivatives and realizes a formal total synthesis of azacarboprostacyclin analogs.
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■ Synthesis of 5β-Androsta-17β-(1’-oxocyclohex-2’-en-3’-yl)-3β,14β,diol-3-β-D-glucopyranoside, a Potent Cardiac Glucoside with High Safety Margin
Uttam K. Pati* and Karel Wiesner
*Natural Products Research Center, Department of Chemistry, University of New Brunswick, Bag Service #45222, Fredericton, New Brunswick, E3b 5A3, Canada
Abstract
Starting from testosterone 1, an efficient preparation of a cardioactive glucoside 13 with a modified 17β- functionality is described. The glucoside 13, in spite of no lactone group at the 17β- position, is found to be potent and showed a high margin of safety.
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■ Generation and Cyclization of Nitrilium Ions from Amides
Robert E. Gawley* and Sanjay R. Chemburkar
*Department of Chemistry, College of Arts of Sciences, University of Miami, 1301 Memorial Dr., Coral Gables, FL 33124-0431, U.S.A.
Abstract
Amides are shown to be eflcient precursors to nitrilium ions, which may cyclize onto styryl terminators to form pyrrolines. Comparison of several cyclization substrates defines the steric and stereoelectronic scope and liminations of the process. Appropriately functionalized pyrrolines may be reduced with chiral borohydrides and further elaborated to nonracemic pyrrolizidines and indolizidines.
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■ Two New Diterpenoid Alkaloids from Delphinium pacific giant and Revised 13C-Nmr Assignment of Delpheline
Hideo Bando, Koji Wada, Junko Tanaka, Sachie Kimura, Ekumi Hasegawa, and Takashi Amiya
*Hokkaido College of Pharmacy, 7-1 Katsuraoka-cho, Otaru 047-02, Japan
Abstract
Two new C19-diterpenoid alkaloids, paciline (1) and pacinine (2), and a known alkaloid, delpheline (1) were isolated from Delphinium pacific giant. Structures of those alkaloids were determined on the basis of their spectral data and chemical correlation with delpheline (3). Paciline (1) was afforded by methylation of delpheline (3) and pacinine (2) was afforded by oxidation of delpheline (3). 13C-Chemical shifts assigned to C-1, C-9, C-10, C-14, and C-16 of delpheline (3) were revised on the basis of 2D nmr measurement.
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■ Heterocyclic Photorearrangements - Photochemical Behavior od Some 3-Acetylamino-5-aryl-1,2,4-oxadiazoles. A Photoinduced iso-Heterocyclic Rearrangement
Silvestre Buscemi, Gabriella Macaluso, and Nicolò Vivona*
*Dipartimento Chimica Organica, Università digli Studi di Palermo, Viale delle Scienze, 90128 Palermo, Italy
Abstract
The photochemical behaviour of some 3-acetylamino-5-aryl-1,2,4-oxadiazoles in methanol at 254 nm has been investigated. A photoinduced rearrangement to the corresponding 2-acetylaminoquinazolin-4-one derivatives has been pointed out and explained as proceeding through a preliminary iso-heterocyclic photoinduced rearrangement to the corresponding 3-aroylamino-5-methyl-1,2,4-oxadiazoles,followed by a subsequent photoreaction of the latter. Some mechanistic considerations are reported.
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■ Pyridazines XLII. On the Synthesis of N-5-substitutes Pyridazino[4,5-b]quinolin-10(5H)-ones
Norbert Hainder, Gottfried Heinisch,* and Ivo Volf
*Institute of Pharmaceutical Chemistry, University of Vienna, Währinger Strasse 10, A-1090 Vienna, Austria
Abstract
Procedures for the preparation of diazaacridones 6 bearing branched or higher alkyl chains at N-5 were developed utilizing the pyridazinone 7 as a key compound. An unexpected side reaction observed in the course of the synthesis of 7 is described.
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■ Condensed Thienopyrimidines 5. Studies on the Thermal Cyclization of Various ortho-Formylthiophenecarbamates with Ethanolamine
Mitsuo Sugiyama, Toshiaki Sakamoto, and Hiroshi Fukumi*
*Medicinal Chemistry Research Laboratories, Sankyo Co., Ltd., 1-2-58 Hiromachi, Shinagawa-ku, Tokyo 140-8710, Japan
Abstract
Condensatlo of various ortho-formylthiophenecarbamates with ethanolamine afforded angular annelated tricyclic oxazolothienopyrimidine derivatives, 2,3,6,9b-tetrahydro-5H-oxazolo [3,2-c] thieno [2,3-e]-, and [3,2-e] pyrimidin-5-ones (2), which have new heterocyclic ring systems. The reaction mechanism on the formation of 2 is discussed.
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■ Nucleophilic Aromatic substitution in 4,5-Dicyanoimidazoles
Paul G. Apen and Paul G. Rasmussen*
*Department of Chemisry, University of Michigan , 930 North University, Ann Arbor, MI 48109-1055, U.S.A.
Abstract
Nucleophilic aromatic substitution reactions in 4,5-dicyanoimidazoles are described. For example, reaction of 1-methyl-2-bromo-4,5-dicyanoimidazole (5) with good nitrogen nucleophiles, such as n-butylamine, piperidine and imidazole, gave the highly functionalized 2-substituted 1-methyl-4,5-dicyanoimidazoles (6-10). Reaction of 5 with weaker nucleophiles, such as carbazole, did not occur.
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■ An Unusual Photochemical Reaction of Indene with Furan and Thiophene Derivatives
Maurizio D’Auria,* Antonella De Mico, and Franco D’Onofrio
*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
2-Indenylfuran and -thiophene derivatives are synthesized through a photochemical approach.
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■ The Formation of 1-Methyl-3-nicothinoylpyrrolidine from Nicotine-1’-oxide
Nancy J. Joyce and Edward Leete*
*Natural Products Labratory, Department of Chemistry, University of Minnesota, Misseapolis, Minnesota 55455, U.S.A.
Abstract
Several new compounds were obtained when nicotine-1’-oxide was treated with ferric nitrate in the presence of tartaric acid, the most unexpected being 1-methyl-3-nicotinoylpyrrolidine. A unified mechanism is proposed to explain the formation of this substance and other pyridine derivatives.
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■ On the Protonation Site of Rauwolfia Alkaloids in Highly Concentrated Sulphuric and Solutions
María A. Muñoz, Carmen Carmona, Jose Hidalgo, Manuel Balón, and Manuel López-Poveda
*Departamento de Química Física, Instituto de Ciencias de los Materiales, Universidad de Sevilla-C.S.I.C., 41012-Sevilla, Spain
Abstract
13C-Nmr spectroscopy has been used to investigate the protonation site of the Rauwolfia alkaloids yohimbine, reserpine and reserpiline in highly concentrated sulphuric acid solutions (~189M H2SO4). The chemical shifts which occur upon protonation reveal unambiguously that the alkaloids protonate on C-7, the β-position with respect to their indole ring, and suggest that the indoleninium cations of the methoxy-substituted alkaloids have principally an enamine structure.
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■ Reaction of o-Isocyanatobenzoyl Chloride with Cyanotrimethylsilane. Formation of 4-Oxo-4H-benzoxazine-2-carbonitrile and Its Ring Transformation to 3,4-Dihydro-1H-1,3,4-benzotriazepine-2,5-diones
Masahiko Takahashi* and Akira Hiratsuka
*Department of Materials Sciences, Faculty of Engineering, Ibaraki University, 4-12-1 Nakanarusawamachi, Hitachi, Ibaraki 316-8511, Japan
Abstract
Reaction of O-isocyanatobenzoyl chloride (1) with cyanotrimethylsilane gave 4-oxo-4H-3,1-benzoxazine-2-carbonitrile (2), which was transformed to 3,4-dialkyl-3,4-dihydro-1H-1,3,4-benzotriazepine-2,5-diones (9) on treatment with 1,2-dialkylhydrazines. Halogenation of 9 gave 7-halotriazepines 10.
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■ Syntheses and Chiroptical Properties of Some New N-(5-benzofurazanoyl)-L-α-amino Acids and Esters
Sadiq A. Saleh* and Mustafa M. El-Abadelah
*Chemistry Department, Yarmouk University, Irbid, Jordan
Abstract
A series of new N-(5-benzofurazanoyl)-L-α-amino acids (Ia) and esters (Ib) have been prepared. The cd spectra of the L-aliphatic and L-aromatic amino acid derivatives (Ia) display, in organic solvents, sign inversion for the measured Cotton effect (CE) bands. Comparable trend is also observed for the respective amino ester analogues (Ib). This chiroptical behaviaur might be attributed to differences in conformational equilibria of either series. 1H-Nmr and ms spectra of the title compounds are discussed.
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■ Four New Prenylated Flavonoids from Aerial Parts of Glycyrrhiza uralensis
Toshio Fukai, Qing-Hua Wang, and Taro Nomura*
*Faculty of Pharmaceutical Sciences, Toho University, 2-2-1, Miyama, Funabashi, Chiba 274-8510, Japan
Abstract
Three new prenylated isoflavones were isolated from the aerial parts of Glycyrrhiza uralensis Fisch. et DC. (Leguminosae) and the structures of the new compounds, gancaonins B, C, and D, were elucidated as 5,7,3’-trihydroxy-4’-methoxy-6-prenylisoflavone, (E)-5,7,4’-trihydroxy-8-(3-hydroxymethyl-2-butenyl)isoflavone, and (E)-5,7,3’-trihydroxy-4’-methoxy-8-(3-hydroxymethyl-2-butenyl)isoflavone, respectively. Gancaonin E, from the same material, was confirmed as 5,7,3’,4’-tetrahydroxy-8,5’-diprenylflavanone. Gancaonin A, 5,7-dihydroxy-4’-methoxy-6-prenylisoflavone, was isolated for the first time as a natural product. Four known phenolic compounds, scopoletin, formononetin, lupiwighteone, and sigmoidin B, were also isolated.
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■ Synthesis of 3,5,6-Trisubstitutued 1,2,4-Triazines from 3,6-Disubstituted 1,2,4,5-Tetrazines and N-(Trimethylsilyl)benzaldimines
Masahiko Takahashi,* Yoshihiro Hikita, and Makoto Fukui
*Department of Materials Sciences, Faculty of Engineering, Ibaraki University, 4-12-1 Nakanarusawamachi, Hitachi, Ibaraki 316-8511, Japan
Abstract
Reation of 3,6-disubstituted 1,2,4,5-tetrazines (1) with N-(trimethylsilyl)benzaldimine gave 3,5,6-trisubstituted 2,5-dihydro-1,2,4-triazines (2), which were oxidized with potassium permanganate to afford 3,5,6-trisubstituted 1,2,4-triazines (6).
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■ An Unusual Base-induces Debromination Reaction of 3,4-Dibromo-3-methoxycarbonylsulfolane
Ta-Shue Chou* and Lee-Jui Hwang
*Institutue of Chemistry, Academia Sinica, 128, Yan-Chiu-Yuan Road, Sec II, Nankang, Taipei,11529, Taiwan, R.O.C.
Abstract
Treatment of the title compoumd with several bases gives neither dehydrobromination nor substitution reaction. An unusual debromination reaction takes place to give 3-methoxycarbonyl-3-sulfolene.
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■ Enzymatic Cyclization of 2-(Carbamoyloxy)benzoates, 2-(Sulfamoyloxy)benzoates and 2-(Carbamoyloxy)benzophenones with Yeast and Lipase
Ahmed Kamal,* Maddamsetty V. Rao, Adari B. Rao, and Pralhad B. Sattur
*Division of Organic Chemistry, Regional Research Laboratory, Hyaderabad 500 007, India
Abstract
The cyclizatton of labile functionalized 2-(carbamoyloxy)-benzoates, 2-(sulfamoyloxy)benzoates and 2-(carbamoyloxy)benzophenones to 1,3-benzoxazine-2,4-diones, 4-oxo-3,4-dihydro-1,2,3-benzoxathiazine 2,2-dioxides and 4-phenyl-1,3-benzoxazin-2-ones with yeast as well as lipase is described. This approach establishes the application of enzymes for gram seale cyclization of such substrates under mild conditions. Further, it is revealed that baker’s yeast is most suitable for this process.
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■ Pyridazines 47. The Configuration of Novel Thiosemicarboazone Derivatives of Pyridazinecarbaldehydes and Alkyl Pyridazinyl Ketones
Johnny Easmon, Gottfried Heinisch,* and Wolfgang Holzer*
*Institute of Pharmaceutical Chemistry, University of Vienna, Währinger Strasse 10, A-1090 Vienna, Austria
Abstract
Structure and configuration of thiosemicarbazone derivatives 1-6, containing a 3-pyridazinyl (1,2,3), 4-pyridazinyl (4,5) or 2-pyridyl moiety (6) were determined by means of 1H and 13C nmr spectroscopy.
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■ Synthesis of Pyrimidine Derivatives and Their Related Compounds Using Ketene Dithioacetals
Yoshinori Tominaga,* Shinya Kohra, Harumasa Honkawa, and Akira Hosomi
*Faculty of Pharmaceutical Sciences, Nagasaki University, 1-14, Bunkyo-machi, Nagasaki 852-8521, Japan
Abstract
Ketene dithioacetals bearing electron-with-drawing groups are useful and versatile reagents for the synthesis of pyrimidine derivatives. This review article describes the synthetic usefulness and importance of ketene dithioacetals in the preparation of pyrimidines and fused pyrimidine derivatives.