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. 27, No. 9, 1988
Published online:
■ A Novel Coumaronochromone from the Stems of Euchresta japonica and Its Antibacterial Activity
Mizuo Mizuno,* Koh-ichi Tamura, Toshiyuki Tanaka, and Munekazu Iinuma
*Department of Pharmacognosy, Gifu College of Pharmacy, 6-1 Mitahora-higashi 5-chome, Gifu 502-8585, Japan
Abstract
The structure of a novel highly substituted coumaronochromone, designated as euchretin A, from the stems of Euchresta japonica was established by spectral evidences. Its antibacterial activity is also described.
Published online:
■ New Bisindole Alkaloids from Petchia Ceylanica
Atta-ur-Rahman,* Azra Pervin, Anjun Muzaffar, Kuruneruge Tuley Dayanada de Silva,* and Wellage Susil Jayalath Silva
*H. E. J. Postgraduate Institute of Chemistry, University of Karachi, Karachi-75270, Pakistan
Abstract
Two new bisindole alkaloids, ceylanine (1) and ceylanicine (2) have been isolated from Petchia cevlanica and their structures have been established on the basis of spectroscopic techniques.
Published online:
■ A Unique Formation of an Isoxazoline-N-oxide from Nitrodibromoacetonitrile and Tetramethylethylene
Joseph H. Boyer* and Thanikavelu Manimaran
*Department of Chemistry, University of New Orleans, New Orleans, LA 70148, U.S.A.
Abstract
Tetramethylethylene and nitrodibromoacetonitrile in dichloromethane at 25°C gave 3-cyano-4,4,5,5-tetramethyl-2-isoxazolin-2-oxide (45%) and 2,3-dibromo-2,3-dimethyl butane (42%).
Published online:
■ Rection of Isocynanic Acid and Isocynates with Diketene. Preparation of 2H-1,3-Oxazines, 4-Pyrones, and 2-Pyridones
Shoichiro Ozaki,* Toshio Nagase, and Takazo Kato
*Faculty of Engineering, Ehime University, 3 Bunkyo-cho, Matsuyama, 790-8577 Ehime, Japan
Abstract
Reaction of diketene with isocyanic acid gave the expected product, 2,4-dioxo-6-methyl-3,4-dihydro-2H-1,3-oxazine (2), but with aryl isocyanates gave 3-aryl-2,4-dioxa-6-methyl-3,4-dihydro-2H-l,3-oxazines (3), 3-(arylcarbamoyl)-2,6-dimethyl-4-pyrones (4), and 3-acetyl-1-aryl-4-hydroxy- 6-methyl-2-pyridones (5) depending on the reaction conditions.
Published online:
■ Sulphonation of β-Carbolines in Concentrated Sulphuric Acid Solutions
María A. Muñoz, Manuel Balón,* Carmen Carmona, José Hidalgo, and Manuel Lopez Poveda
*Departmento de Química Física, c/Prof. García González s/n, Facultad de Farmacia, Universidad de Sevilla, 41012 Sevilla, Spain
Abstract
Solutions of harmane and N,N’-dimethylharmane in concentrated sulphuric acid (16-18M) conducted to the corresponding C-6 sulphonated derivatives.
Published online:
■ Synthesis of Pyrrole, Pyrrolidone, Pyrrolo[3,4-c]pyrazole, Pyrrolo[3,2-b]pyridine and Pyrrolo[3,2-b]pyrrole Derivatives
Afaf A. A. Elbannany and Laila I. Ibrahim
*Department of Chemistry, Faculty of Science, Helwan University, Ain-Helwan, Cairo, Egypt
Abstract
A facile and one step route for the synthesis of substituted pyrroie derivatives 5a-g from reaction of ethyl arylidenecyanoacetate (1) with glycine (2) was reported. Also the pyrrolidone derivative ,12 was formed upon reaction of benzylidenemalononitrile (7) with 2 The synthesized 5 has been used as a precursor in the syntheses of pyrrolo[3,4-c]pyrazole 13, pyrrolo[3,2-b]pyridine 15 or its tautomer 16 and pyrrolo[3,2-b]pyrrole derivatives 18.
Published online:
■ Syntheses of (1’R)-1’-Methyl-cis-zeatin and Its 9-β-D-Ribofuranoside
Tozo Fujii,* Masashi Ohba, and Miwa Sakari
*Faculty of Pharmaceutical Scicences, Kanazawa University, 13-1 Takara-machi, Kanazawa 920-0934, Japan
Abstract
The cis isomers III b and IVb of the recently isolated cytokinins (1’R) -1’-methylzeatin (IIIa) and (1”R) -1”-methylzeatin 9-riboside (IVa) have been synthesized from D-alanlne (V) through the intermediates VI, VII, I , V , X, and XI.
Published online:
■ Structure of Isorugosin B, and the Orientation of Valoneoyl Group in the Related Monomeric, Dimeric and Trimeric Hydrolyzable Tannins
Tsutomu Hatano, Reiko Kira, Taeko Yasuhara, and Takuo Okuda*
*Faculty of Pharmaceutical Sciences, Okayama University, 1-1-1 Tsushima-naka, Okayama 700-8530, Japan
Abstract
A new hydrolyzable tannin, named isorugosin B (1), was isolated from Liquidambar formosana, and the structure in which the orientation of valoneoyl group at 0-4 ~ 0-6 of the glucose core is the reverse of that in rugosin B (2) and in rugosin A (3), was determined. The orientation of valoneoyl group in rugosin A (3) was established by the long range 1H-13C correlation nmr spectroscopy. The structures of rugasins D (6), E (7) and G (8), coriariins C (9), D (10), E (11) and F (12), cornusiin A (13), camptothins A (15) and B (16), were fully established on the basis of chemical correlations with 1 or 3.
Published online:
■ 1,3-Oxazolindid-5-ones, not 1,3-Diazetidinones, are Formed in the Reaction of Tryptophan with Alkyl Isocyanates in the Presence of Acetone
Alf Claesson*
*Research and Development Laboratories, Astra Alab, SE-151 85 Södertälja, Sweden
Abstract
A recent paper in This Journal by Braña et al. (Heterocycles 1987, 26, 95) reports isolation of 2-[(3-alkyl-4,4-dimethyl-2-oxo)-1,3-diazetidinyl]-3-(3-indolylpropionic acids from reactions of tryptophan with alkyl isocyanates in acetone. It appears most likely that these products are instead 1,3-oxazolidin-5-ones.
Published online:
■ Synthesis of a New Skeleton, 2,6-Epithio-3-benzazocine
Mikio Hori,* Tadashi Kataoka, Hiroshi Shimizu, Eiji Imai, Noriyuki Iwata, Norihiro Kawamura, and Masayasu Kurono
*Department of Pharmacognosy, Gifu College of Pharmacy, 6-1 Mitahora-higashi 5-chome, Gifu 502-8585, Japan
Abstract
Treatment of isothiochroman 2-oxide derivative (9) with acetic anhydride followed by heating in Dowtherm A (a mixture of biphenyl and diphenyl ether) afforded a novel 2,6-epithio-3-benzazocine derivative (2).
Published online:
■ Synthesis of Amphimedine, a New Fused Aromatic Alkaloid from a Pacific Sponge, Amphimedon sp.
Akinori Kubo* and Shinsuke Nakahara
*Meiji Pharmaceutical University, 2-522-1 Noshio, Kiyose, Tokyo 204-8588, Japan
Abstract
Synthesis of the cytotoxic fused pentacyclic aromatic alkaloid, amphimedine 1, is described.
Published online:
■ Asymmetric Induction by Chiral Heterocyclic Compounds: Reaction of Chiral N-Methyl-4-phenyl-1,3-oxazolidines with Organometallic Reagents
Hiroshi Takahashi,* Hiroyuki Niwa, and Kimio Higashiyama
*Faculty of Pharmaceutical Sciences, Hoshi University, 2-4-41 Ebara, Shinagawa-ku, Tokyo 142-8501, Japan
Abstract
The reaction of (2S,4R)-2-alkyl-N-methyl-4-phenyl-1,3-oxazolidines (1a-c) with Grignard reagent gave (1R,1’R)-form compounds (2a-c) as the major product. On the contrary, the reaction of 1a-c with organotitanium reagent gave (1S,1’R)-form compounds (3a-c) as the major product. This stereoselectivity is a remarkable characteristic of the reaction of 1,3-oxazolidines with organometallic reagents.
Published online:
■ Reinvestigation of the Diels-Alder Reaction of (E)-(R)-4,5-Di-O-isopropylidepent-2-enoates and Cyclopentadiene
Seiichi Takano,* Takumichi Sugihara, Kiyohiro Samizu, and Kunio Ogasawara
*Pharmaceutical Institute, Tohoku University, Aobayama, Sendai 980-8578, Japan
Abstract
Diels-Alder reaction between (E)-(R)-4,5-di-O-isopropylidenepent-2-enoates and cyclopentadiene under both uncatalyzed and catalyzed conditions has been reinvestigated. Contrary to the preceding reports, no high diastereofacial selection has been observed under both conditions.
Published online:
■ Kinetic Resolution of 2-Furylcarbinols Using the Sharpless Oxidation and Its Application to the Synthesis of (5R,6S)-6-Acetoxy-5-hexadecanolide
Tetsuji Kametani,* Masayoshi Tsubuki, Yoko Tatsuzaki, and Toshio Honda
*Hoshi University, 2-4-41 Ebara, Shinagawa-ku, Tokyo 142-8501, Japan
Abstract
Kinetic resolution of 2-furylcarbinols employing 10 mol % of Ti(0iPr)4 in the presence of molecular sieves 3A under the Sharpless oxidation condition generally affords corresponding optically actlve 2-furylcarbinols in a range of 80-98% ee. Application of the optically active 1f to the synthesis of (5R,6S)-6-acetoxy-5-hexadecanolide (8), the major component of the oviposition attractant pheromone of the mosquito Culex pipens fatigans, has also been achieved.
Published online:
■ Synthesis and Structural Characterization of Octaethyl-17-thiochlorin and Octaethyl-7,17-dithioisobacteriochlorin
Ramesh D. Arasasingham, Alan L. Balch*, and Marilyn M. Olmstead
*Department of Chemistry, University of California, One Shields Avenue, Davis, CA 95616-5295, U.S.A.
Abstract
Conversion of the octaethyl-17-oxochlorin and octaethyl-7,17-dioxoisobacteriochlorin into their thio and dithio analogs using Lawesson’s reagent is reported. Spectroscopic data, along with X-ray crystallographic data for the dithio compound and its dioxo precursor, are reported.
Published online:
■ Facile Synthesis of Pyrazole[3,4-b]-pyridines
Abdulla Babaqi, Ali El-Shekeil,* Mohammed Hassan, and Sayed Shiba
*Chemistry Department, Faculty of Science, Sana‘s University, Sana‘s, Yemen
Abstract
The base-catalyzed Michael addition of cyclohexanone, 1,3-diphenyl-2-pyrazolin-5-one, ethyl acetoacetate, and diethyl malonate on 1-aryl-3-(5-chloro-1,3-diphenyl-1H-4-pyrazolyl)-prop-2-en-1-ones (2) in the presence of ammonium acetate at 130°C gave the corresponding pyrazolo [3,4-b] pyridine derivatives (3-6). Structures were confirmed by microanalysis, ir, 1H-nmr, and 13C-nmr.
Published online:
■ Synthesis of Substituted Pyridines Using α,β-Unsaturated Nitriles and Active Cyano Compounds
Luis Fuentes,* Juan José Vaquero, Maria Isabel Ardid, Antonio Lerente, and José Luis Soto*
*Departamento de Química Orgánica, Universidad de Alcalá de Henares, 28871 Alcalá de Henares (Madrid), Spain
Abstract
Several unknown 2-amino-substituted 3,4-dihydropyridines and pyridines are prepared by the reaction of α, β-unsaturated nitriles with active cyano compounds in the presence of a nucleophile reagent.
Published online:
■ Biginelli Type Reaction with Tetroses Derivatives
M. Valpuesta Fernández,* F. J. López Herrera, and T. Lupión Cobos
*Departamento de Quimica Organica, Facultad de Ciencias, Universidad de Málaga, Campus de Teations, E-29071 Malaga, Spain
Abstract
The reaction of 2,4-0-ethylidene-D-erythrose and -threose with methyl acetoaoetate and urea, or thiourea, under the conditions of the Biginelli type reaction, gives as principal reaction products C-polyhydroxyalkylpyrimidines derivetives.
Published online:
■ Synthesis of New 8-Phenyl[1,2]dithiolo[1,5-b]naphtho[2,1-d][1,2]dithiole-10-SIV, 2,5-Diphenyl-3,4-dihydro-1,6,6a-trithia(6a-SIV)cyclopenta[cd]pentalene and 2,6-Diphenyl-4,5-dihydro-3H-[1,2]dithiolo[4,5,1-hi][1,2]benzodithiole-8-SIV Derivatives
Anotonino Arcoleo,* Giovanni Abbate, Mario Gottuso, Giacomo Fontana, and Gaetano Giammona
*Facolta‘ di Scienze, Dipartimento di Scienze Botaniche - Sezione Fitochimica, Università digli Studi di Palermo, Via Archirafi 20 90123 Palermo, Italy
Abstract
In order to investigate the anti-oxidant properties on lubricant oils, 5,6-dihydro-8-phenyl[1,2]dithiolo[1,5-b]naphtho[2,1-b][1,2]dithiole-10-SIV and a number of phenyl substituted derivatives have been synthesized by cyclization with P2S5 of the corresponding 1,3,5-triketones in toluene. Moreover, some 2,5-diphenyl-3,4-dihydro-1,6,6a-trithia(6a-SIV)cyclopenta[cd]pentalene and 2,6-diphenyl-4,5-dihydro-3H-[1,2]dithiolo[4,5,1-hi][1,2]benzodithiole-8-SIV derivatives have been synthesized by cyclization with P2S5 of the corresponding 2,5-dibenzoylcyclopentanone and 2,6-dibenzoylcyclohexanone derivatives in toluene.
Published online:
■ Thermal and Photochemical Oxetane Formation with α-Ketoesters
Jochen Mattay* and Karl Buchkremer
*Institut für Organische Chemie, Rheinisch-Westfälische, Technische Hochsch, Professor-Pirlet-Straße 1, D-52074 Aachen, Germany
Abstract
The thermal and photochemical [2+2]-cycloadditions of ethyl pyruvate, diethyl mesoxalate and biacetyl with 1,1-diethoxyethene, 2,2-diisopropyl-1,3-dioxole and 1,1-dimethoxy-2-methylpropene have been studied. 1,1-Diethouyethene forms oxetanes at room temperature with all carbonyl compounds as well as 1,1-dimethoxy-2-methylpropene and diethyl mesoxalate whereas the other electron-rich olefins generally react only in presence of Lewis-acids as catalysts.These observations indicate the energetic preference of the [1DS+1AS] geometry of the transition state according to Houk’s MO-treatment rather than the [2DS+1AS] geometry for symmetrical olefins. In general the photoreaction is complementary to the therrnal oxetane formation in both the reactivity and the regioselectivity. Only the electron poorest acceptor diethyl mesoxalate did not show any photochemical addition onto these olefins.
Published online:
■ Studies on the Constituents of Aconitum Species. VII. On the Components of Aconitum Japonicum Thunb
Hideo Bando, Koji Wada, Takashi Amiya,* Yasuo Fujimoto, and Kimiko Kobayashi
*Hokkaido College of Pharmacy, 7-1 Katsuraoka-cho, Otaru 047-02, Japan
Abstract
Two new diterpenoid alkaloids, subcumine (1) and subcusine (2), were isolated from the roots of Aconitum japonicum Thunb. The structures of these alkaloids were determined on the basis of spectral data, chemical evidence, and X-ray analysis. We also have isolated two known alkaloids, ezochasmaconitine (3) and anisoezochasmaconitine (4).
Published online:
■ 2,3,6-Triazaphenothiazine
John Barltrop and Terence C. Owen*
*Department of Chemistry, University of South Florida, Tampa, Florida 33620, U.S.A.
Abstract
2,3,6-Triazaphenothiazine has been definitively synthesized and characterrized. A previously reported synthesis appears to be wrong.
Published online:
■ An Efficient Synthesis of 5-Aryl(or Alkyl)amino-4-ethoxycarbonyl-2-methylthio-1,3-thiazoles from Dimethyl N-(Ethoxycarbonylmethyl)iminodithiocarbonate and Isothiocyanates
Carlos Alvarez-Ibarra,* Matilde Gil, Paloma Ortiz, and Maria L. Quiroga
*Departamento de Química Orgánica, Facultad de Química, Universidad Complutense de Madridas, Ciudad Universitaria, E-28040 Madrid, Spain
Abstract
An efficient synthesis of perfunctlonalyzed 1,3-thiazoles 2a-2b with good Yields has been carried out by a cyclocondensation reaction between the α-metallated dimethyl N-(ethoxycarbonylmethyl)iminodithiocarbonate and aryl or alkylisothiocyanates.
Published online:
■ New Synthetic Route to Butanolide Lignans by a Ruthenium Complex Catalyzed Hydrogenation of the Corresponding Stobbe‘s Fulgenic Acids
Massimo Bambagiotti-Alberti,* Silvia A. Coran, Franco F. Vinvieri, Nadia Mulinacci, and Giuseppe M. L. Pieraccini
*Dipartimento di Scienze Farmaceutiche, Università di Firenze, Via Gino Capponi 9, I-50121 Firenze, Italy
Abstract
A new two-step total synthesis of butanolide lignans (or dibenzylbutyrolactone lignans) is described, which affords the title compounds in good yield and with a very short work-up time. It involves a ,ruthenium carbonyl hydride complex-catalyzed hydrogenation of the corresponding dibenzylidene succinic acids (fulgenic acids). Since the catalytic hydrogenation (second step) is a total yielding Process, the overall yield determining step is the preparation of the fulgenic acid intermediates by the Stobbe condensation (first step), which has consequently been revised to Improve many details. This simple process moreover allows hexadeuterated butanolide lignans to be readily obtained for isotopic dilution mass spectral measurements. The syntheses of a selection of lignans, namely enterolactone, matairesinol, hinoknin, dimethylmatairesinol and cordigerine, are described to illustrate the whole procedure.
Published online:
■ New Acridone Alkaloid and Coumarin from Citrus Plants
Motoharu Ju-ichi,* Hiromi Kaga, Miki Muraguichi, Mami Inoue, Ichiro Kajiura, Mitsuo Omura, and Hiroshi Furukawa
*Faculty of Pharmaceutical Science, Mukogawa-Women‘s University, 11-68 Koushien Kyuban-Cho, Nishinomiya, Hyogo 663-8179, Japan
Abstract
A new acridone alkaloid citramine (1) and a new coumarin osthenon (2) were isolated from the root of the hybrid seedlings of Ogonkan x Hyuganatsu and their structures were elucidated on the basis of spectroscopic data.
Published online:
■ Tautomerism in Pyrazino[2,3-c]-1,2,6-thiadiazine 2,2-Dioxides
Pilar Goya, Angela Herrero, Ma. Luisa Jimeno, Carmen Ochoa,* Juan Antonio Páez, Félix Hernández Cano, Concepción Foces-Foces, and Martín Martínez Ripoll
*Instituto de Química Médica, C. S. I. C., Calle Juan de Cierva, 3, 28006 Madrid, Spain
Abstract
Tautomerism of pyrazino [2,3-c]-1,2,6-thiadiazine 2,2-dioxides has been studied, in solution, by uv, 13C-, and natural abandance 15N-nmr spectroscopiea and in the solid state by X-ray crystallography. The 1-NH tatutomer is present in solid state and in the majority of solvents. Depending on the 6,7-substituent, the 8-NH tautomer is preferred in water solution. An improved synthesis of 6,7-diaryl substituted pyrazinothiadiazine derivatives is described.
Published online:
■ The Effects of Solvent and Temperature on the Orientation of Cycloaddition Reaction of 1,2,3-Triazine Enamines: Its Application to the Synthesis of Alkaloids, Onychine and 6-Methoxyonychine
Teruyo Okatani,* Junko Koyama, Yukio Suzuta, and Kiyoshi Tagahara
*Kobe Women’s College of Pharmacy, Motoyamakita, Higashinad, Kobe, Hyogo 658, Japan
Abstract
4-Methyl-1,2,3-triazine was treated with several enamines in chloroform to afford 2,5,6-trisubstituted pyridines. In each case, cycloaddition occurs N-3/C-6 of the 1,2,3-triazine nucleus. On the other hand, when high boiling solvent was employed, cycloaddition took place involving the N-3/C-6 cycloadduct and N-1/C-4 cycloadduct. As application of synthetic method, we accomplished the synthesis of alkaloids, onychine and 6-methoxyonychine.
Published online:
■ Synthesis of (±)-Roxburghilin and (±)-Epiroxburghilin
Tatsuo Nagasaka,* Hiroto Yamamoto, Akio Sugiyama, and Fumiko Hamaguchi
*School of Pharmacy, School of Pharmacy, 1432-1 Horinouchi, Hachioji, Tokyo 192-0392, Japan
Abstract
The synthesis of (±)-roxburghilin (15) and (±)-epiroxburghilin (16) in six steps from 2-pyrrolidinone is described.
Published online:
■ Synthesis of Condensed Heteroaromatic Compounds Using Palladium-Catalyzed Reaction
Takao Sakamoto, Yoshinori Kondo, and Hiroshi Yamanaka*
*Pharmaceutical Institute, Tohoku University, Aobayama, Sendai 980-8578, Japan
Abstract
The authors summarize the palladium-catalyzed synthesis of the key intermediates to condensed heteroaromatic rings such as indole, quinoline, isoquinoline, and their azaanalogs and also describe the palladium-catalyzed cyclization to condensed heteroaromatics.
Published online:
■ Synthesis of [2.2.3]Cyclazines, Aza[2.2.3]cyclazines and Their Related Compounds
Yoshinori Tominaga,* Yoshihide Shiroshita, and Akira Hosomi*
*Center of Instrumental Analysis, Nagasaki University, 1-14, Bunkyo-machi, Nagasaki 852-8521, Japan
Abstract
Recent developments in the synthesis of [2.2.3]-cyclazines, benzo[g][2.2.3]cyclazines, benzo[a][2.2.3]cyclazines, dibenzo[a,h][2.2.3]cyclazines, dibenzo[a,g][2.2.3]cyclazines, 1-aza[2.2.3]cyclazines, 5-aza[2.2.3]cyclazines, and 1-azabenzo[h][2.2.3]cyclazines by the [8 + 2] cycloaddition reaction of dimethyl acetylenedicarboxylate (DMAD) with the various type indolizines are summarized by major emphasis that is placed on the results obtained in our own laboratory. The synthesis of indolizines, imidazo[1,2-a]pyridine, and their related compounds which are key intermediates for the synthesis of cyclazines is also described.