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. 1, 1984
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■ Synthesis of Heterocyclic Compounds XXXVI. Preparation of Alkyl Substituted Pyrancarbonitriles
José L. Soto,* Carlos Seoane, Nazario Martín, and Margarita Quinteiro
*Departamento de Química Orgánica, Facultad de Química, Universidad Complutense de Madridas, Ciudad Universitaria, E-28040 Madrid, Spain
Abstract
The cyclizatian of the ketonitriles obtained from the reaction of suitably substituted propenones with propanedinitrile leads to alkyl substituted 4H-pyrans. Some of the starting propenones had to be prepared by base promoted opening of an isoxaxole ring in the presence of an aldehyde. An exception to the general synthesis is also reported.
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■ The Intramolecular Opening of the Oxirane Ring in Butyl 4,5-Epoxy-2-hydroxyhexanoate. A New Simple Synthesis of Racemic Allomuscarine
Marek Chmielewski* and Piotr Guzik
*Institute of Organic Chemistry, Polish Academy of Sciences, ul. Kasprzaka 44/52, P.O.Box 58, PL-01-224 Warszawa 42, Poland
Abstract
The new simple synthesis of racemic allomuscarine via the intramolecular opening of the trans substituted epoxide ring in butyl 4, 5-epoxy-2-hydroxyhexanoate is described.
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■ Amyris of Jamaica. 2,5-Diaryloxazoles and a Chromane from Amyris plumieri D.C (Rutaceae)
Saleela Philip,* Basil A. Burke, and Helen Jacobs
*Department of Chemistry, Mona Campus, University of the West Indies, Mona, Kingston 7, Jamaica
Abstract
The isolation and identification of three new heterocyclic compaunds (two oxazoles and a chromene) from Amyris Plumieri is presented.
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■ Reactions of 10-Thiaisoalloxazine with Primary and Secondary Alcohols
Yoshifumi Maki,* Miyuki Tanabe, Yutaka Kajima, Magoichi Sako, and Kosaku Hirota
*Gifu Pharmaceutical University, 6-1 Mitahora-higashi 5-chome, Gifu 502-8585, Japan
Abstract
Reaction of 10-thiaisoalloxazine 1 with lower primary alcohols glves 4a,10a-diadducts 4 or 4a,10a-cyclic adducts 5 across the conjugated diimine moiety, whereas 1 oxidizes secondary alcohols in the neutral medium under irradiation with daylight to afford the corresponding carbonyl compounds.
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■ Structures of Gadenine and Pentagyline, Two New Diterpenoid Alkaloids
Antonio G. González,* Gabriel de la Fuente, and Rafael Díaz Acosta
*Instituto de Productos Naturales y Agrobiologia de Canrias, C. S. I. C./ Unversidad de La Laguna, P.O. Box 195, 38206- La Laguna, Tenerife, Spain
Abstract
The structures of pentagyline and gadenine, two new diterpenoid alkaloids isolated from Delphinium pentagynum, were determined with the aid of 1H and 13C-NMR spectroscopy. A biogenetic scheme is proposed by which karakoline could afford the C-19 diterpenoid alkaloids found in this plant.
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■ The Chemistry of an Isolable Azomethine Ylide
Rolf Huisgen* and Karl Niklas
*Institut für Organische Chemie, Universität München, Karlstrasse 23, D-80333 München, Germany
Abstract
The 4-isoxazoline 3 undergoes ring contraction to the acylaziridine 5 which is converted to the azomethine ylide 4. The small influence of solvent polarity on the rate constant of the conversion 3 → 4 suggests a mechanism via a trimethylene type species for the rate-determining step. Whereas 4 is the first azomethine ylide which can be isolated without being stabilized by aromatic resonance, the ylides 20 - 22 dimerize to piperazine derivatives. 1,3-Dipolar cycloadditions of the azomethine ylides 4 and 20 - 22 are described.
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■ Rearrangement of 1,4,2-Benzodithiazines to 2-Imino-1,3-benzodithioles. Its Unprecedented Characteristic Features (An Extreme Case of Solvent Effect)
Juzo Nakayama,* Atsuhiro Sakai, Shoichi Tokita, and Masamatsu Hoshino
*Department of Chemistry, Faculty of Science, Saitama University, Saitama, Saitama 338-8570, Japan
Abstract
3-Unsubstituted 1,4,2-benzodithiarines undergo a new thermal rearrangement to give 2-imino-1,3-benzodithioles. The most characteristic feature of this rearrangement is that it occurs smoothly only when benzodithiazines were heated without solvent, but it does not take place in non-polar solvents. A plausible mechanism of this rearrangement is proposed on the basis of available experimental data.
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■ Biotransformation of the 13-Hydroxytetrahydroprotoberberine N-Methyl Salts by Callus Cultures of Corydalis Species
Kinuko Iwasa,* Akiko Tomii, and Narao Takao
*Kobe Pharmaceutical University, Motoyamakita, Higashinada, Kobe 658-8558, Japan
Abstract
Each N-methyl salt of trans- and cis-13-hydroxytetrahydroprotoberberines, ophiocarpine and epiophiocarpine, was biotransformed via corresponding protopine-type alkaloid into a benzindanoazepine.
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■ The Effect of Triethylborane in the Reduction of Epoxides with Lithium Borohydride
Nung Min Yoon,* In Hwan Oh, Kyung Ill Choi, and Hoon Ju Lee
*Department of Chemistry, Sogang University, Mapoku, Seoul 121-742, Korea
Abstract
The presence of triethylborane dramatically accelerated the reduction of epoxides with lithium borohydride. Thus the all three epoxides tested, namely, 1,2-butylene oxide, cyclohexene oxide and styrene oxide were reduced rapidly in 1 h at room temperature in the presence of 25 mole % of triethylborane whereas more than 24 h was required for these reductions with lithium borohydride itself.
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■ A Total Synthesis of (±)-Lysergene abd (±)-Agroclavine
Toshiko Kiguchi, Chiyomi Hashimoto, and Ichiya Ninomiya*
*Kobe Women’s College of Pharmacy, Motoyamakita, Higashinad, Kobe, Hyogo 658, Japan
Abstract
A preliminary study on the exploitation of a general synthetic route to the ergoline group of alkaloids on the despyrrole analogs was successfully extended to the first total synthesis of racemic lysergene and agroclavine via the route involving reductive photocyclization of the furylenamide (10) followed by ring opening of the resulting dihydrofuran ring (11).
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■ A Novel Erythrinan and Homoerythrinan Synthesis by Tetra-n-butylammonium Fluoride Induced Oxy-vinyl 1,3-Shift. Synthesis of a 6-Methoxycarbonyl-2,8-dioxo-1,7-cyclo-B-homoerythrinan, a Potential Intermediate to Schelnammera Alkaloids
Takehiro Sano,* Jun Toda, Yoshisuke Tsuda, and Takeshi Ohshima
*Showa Pharmaceutical University, 3-3165, Higashi-tamagawagakuen, Machida, Tokyo 194-8543, Japan
Abstract
Photocycloaddition of trimethylsilyloxybutadiknes to an isoquinolinopyrrolinedione followed by treatment of the [2+2]adduct with TBAF furnished erythrinan derivatives in high yields as a result of 1,3-shift. By this method, a practical synthetic route to B-homoerythrinan derivatives is now opened and a 6-methoxycarbonyl-2,8-dioxo-l,7-cyclo-B-homoerythrinan 20, a potential intermediate to Schelhammera alkaloids, was synthesized in an acceptable yield.
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■ 2-Azabicyclo[3.2.0]heptane-3,4-dione (8): A Novel Acid Catalyzed Skeletal Rearrangement of 7-Oxy-7-vinyl Derivatives to 2-Azatricyclo[4.3.0.04,9]nonane-3,7-diones
Takehiro Sano,* Jun Toda, and Yoshisuke Tsuda
*Showa Pharmaceutical University, 3-3165, Higashi-tamagawagakuen, Machida, Tokyo 194-8543, Japan
Abstract
Treatment of 7-trimethylsilylaxy-7-vinyl-2-azabicyclo[3.2.0]heptane-3,4-diones with various acids yielded novel caged compounds, 2-azabicyclo[4.3.0.04,9]nonane-3,7-diones, whose formation is explained in terms of intramolecular Prins type cyclization with concomitant 1,2-shift.
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■ Oxidative Transformation of Tryptophan to 5-Hydroxy-N’-formylkynurenine
Masako Nakagawa,* Yukio Yokoyama, Shiro Kato, and Tohru Hino
*Faculty of Pharmaceutical Sciences, Chiba University, 1-33 Yayoi-cho, Inage-ku, Chiba 263-8522, Japan
Abstract
Dye-sensitized photooxygenation of L-tryptophan in an alkaline phosphate buffer followed by NaBH4 reduction afforded 3a,5-dihydroxypyrroloindoIe 5 which readily underwent air oxidation to give 5-hydroxy-N’-formylkynurenine 6a.
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■ Six-membered Mesoionic Heterocycles, VII. Synthesis and Structure of 1,2,4,6-Thiatriazinium-5-olate-1,1-dioxides
Willy Friedrichsen,* Gisela Möckel, and Tony Debaerdemaeker
*Institut für Organische Chemie, Universität Kiel, Olshausenstrasse. 40, D-24098 Kiel, Germany
Abstract
The synthesis of 1, 2,4,6-thiatriazinium-5-olate-1,1-dioxides (3a-f) is described. The geometry of 3e has been determined by X-ray crystallography.
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■ Internal Photodimerization of Some Pyrimidine-6-azapyrimidine Dinucleotide Analogues
Krzysztof Golankiewicz,* Jadwiga Jankowska, and Henryk Koroniak
*Department of Chemistry, Adam Mickiewicz University, ul. Grunwaldzka 6, 60-780 Poznán, Poland
Abstract
The UV irradiation of dinucleotide analogues in which 6-azauracil moiety was connected with trimethylene chain to uracil and thymine led to internal photodimers containing azacyclobutane ring. The geometry of these photodimers has been discussed on the basis of NMR data.
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■ Synthesis of Potential Interferon Inducers and DNA Intercalators. Part I. Derivatives of 1,8-Diazafluorene — The Novel Analogues of Tilorone
Zdzialaw Szulc, Jacek Mlochowski,* Magdalena Fikus, and Anna D. Inglot
*Institute of Organic and Physical Chemistry, Technical University of Wroclow, 50-370 Wroclaw, Poland
Abstract
The novel isosteric aza-analogues of tilorone and its congeners, bearing 1,8-diazafluorene nucleus, have been prepared and their biological and biochemical properties are presented.
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■ The Synthesis and Some Reactions of Chloropyrimidines
Darek T. Hurst*
*School of Analytical and Biological Chemistry, Kingston Polytechnic, Kingston-on-Thames, KT1 2EE, U.K.
Abstract
Several chloro-hydroxy- and amino- chloropyrimidines have been prepared. The chloro groups have been replaced by hydrogen, mercapto, or hydroxyarmino substituents to give useful synthetic intermediates.
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■ Gomaline — A New Indolenine Alkaloid from Catharanthus roseus
Atta-ur-Rahman,* Irshad Ali, and M. Bashir
*H. E. J. Postgraduate Institute of Chemistry, University of Karachi, Karachi-75270, Pakistan
Abstract
A new indolenine alkaloid, gomaline, has been isolated from the leaves of Catharanthus roseus to which structure (1) has been assigned.
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■ Synthesis of 2-Amino-3-ethoxybenzebethiol and Its Conversion into 4H-1,4-Benzothiazines
Radha Raman Gupta* and Rakesh Kumar
*Department of Chemistry, University of Rajasthan, Jaipur 302 004, India
Abstract
Synthesis of 2-amino-3-ethoxybenzenethiol and 5-ethoxy- 4H-1,4-benzothiazines is reported for the first time. Synthesis of 4H-1,4-benzothiazines involves the condensation and oxidative cyclisation of 2-amino-3-ethoxybenzenethiol with β-diketones in DMSO.
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■ Regioselective Cyanation of 3-Substituted Pyridine 1-Oxides
Wilmer K. Fife*
*Department of Chemistry, Indiana-Purdue University, PO Box 647, Indianapolis, IN 46223, U.S.A.
Abstract
Cyanstion of 3-X-pyridine 1-oxides with trimethylsilanecarbonitrile and dimethylcarbamoyl chloride occurs quantitatively to give 3-X-2-pyridinecarbonitriles ≥ 90% isolated yields when X = -CH3, -OCH3, -OH and -Cl, and approximately equal amounts of the 3- and 5- X derivatives when X = -CN and -COOCH3.
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■ The Photochemical Cyclization of 2-Alkylamino-3-aryl-2-cyclohexenones
Janine Cossy* and Jean-Pierre Pete
*Laboratoire de Photochimie, U.A. CNRS n°459, UFR Sciences, 51062 Reims, France
Abstract
The irradiation of 2-alkylamino-3-aryl-2-cyclohexenones gives access to polycyclic heterocycles.
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■ An Approach to the Mechanism of Photooxidation of Berberine under Basic Conditions
M. Leonor Contreras,* Sergio Rivas, and Roberto Rozas
*Department of Chemistry, Facluty of Science, University of Santiago of Chile, Casilla 56559, Santiago-2, Chile
Abstract
The unsensitized photooxidation of berberine (1) catalyzed by basic reagents such as -SC6H13, -N3, Et3N, -OCH3 or -OC2H5, in solution, is described. As a possible mechanism, the formation of an initial berberine-oxygen exciplex followed by a nucleophilic attack to intermediate (3) and rearrangement of this compound to dioxetane (4) is proposed taking in consideration the new isolated lactamic aldehyde structures (2a) and (2b) from the bulk of the reaction. The intervention of both singlet oxygen and the dihydroberberine (5) in these reactions is disregarded.
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■ New Isoquinoline Alkaloids from Corydalis claviculata
Hélène Guinaudeau* and Daovi P. Allais
*Faculté de Médecine et de Pharmacie, Universíte de Limoges, 87032 Limoges Cedex, France
Abstract
The alkaloids (+)-cressifoline (6), (+)-claviculine (9) and (+)-norcularidine (12) have been obtained from Corydalis claviculata. (+)-Crassifoline possesses the S configuration at C-1. The phenolic groups in (+)-claviculine are at C-7 and C-3’. (+)-Norcularidine is a new natural product.
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■ Reaction of N-(1-Oxido-4-pyridylmethyl)-3,5-dimethylbenzamide with Malononitrile in Acetic Anhydride
Miguel F. Braña,* José M. Castellano, and María J. R. Yunta
*Departamento de Química Orgánica I., Facultad de Química, Universidad Complutense de Madrid, Ciudad Universitaria, E-28040 Madrid, Spain
Abstract
Reaction of N-(1-oxido-4-pyridylmethyl)-3,5-dimethylbenzamide with malononitrile in acetic anhydride gives 5-cyano-2-(3,5-dimethylphenyl)-6-(4-pyridyl)-4-(3H)-pyrimidinone.
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■ Some New 2-Substituted 5-Trifluoromethylpyridines
Takahiro Haga,* Kan-ichi Fujikawa, Tohru Koyanagi, Toshio Nakajima, and Kouji Hayashi
*Central Resarch Laboratories, Ishihara Industrial Co. Ltd., Nishi-shibukawa2-3-1, Kusatsu, Shiga 525-0025, Japan
Abstract
The preparation of the derivatives of 2-amino-, hydrazino-, hydroxy-, and mercapto-5-trifluoromethylpyridines via 2-chloro precursors is described. Experimental and spectral data of the products together with those of the precursors are presented.
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■ A Neat Synthesis of Geibalansine, O-Acetylgeibalansine, Ribalinine and Platydesmine
Manian Ramesh, Ponnusamy Rajamanickam, and Periappa Shanmugam*
*Department of Chemistry, Bharathiar University, Coimbatore - 641 046, Tamil Nadu, India
Abstract
A convenient high yield methodology has been evolved for the synthesis of geibalansine, O-acetylgeibalansine, ribalinine and platydesmine starting from atanine.
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■ Some 3-Carboxamides of β-Carboline and Tetrahydro-β-carboline
Ronald T. Coutts,* Ronald G. Micetich, Glen B. Baker, Abraham Benderly, Tim Dewhurst, Tse Wei Hall, Anthony R. Locock, and Jerry Pyrozko
*Faculty of Pharmacy , University of Alberta, Canada
Abstract
A series of tetrahydro-β-carboline-3-carboxamides (L- and D-series) was made by the interaction of the respective amine with the appropriate methyl tetrahydro-β-carboline-3-carboxylate. The β-carboline-3-carboxamides were prepared by a similar route from methyl β-carboline-3-carboxylate or by aromatization of the respective tetrahydro-β-carboline-3-carboxamide. The diastereomers of N-sec-butyl tetrahydro-β-carboline-3-carboxamide (L- and D-series) were separated by chromatography.
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■ Synthesis of the New Tricyclic System. Thieno[3’,2’:3,4]pyrido[1,2-a]pyrazin-4-one
Daniel Fréhel* and Jean-Pierre Maffrand
*Linge Hémobiologie, Sanofi Recherche, 195 route d‘Espagne, 31036 Toulouse, France
Abstract
The new tricyclic system thieno[3’2’, : 3,4] pyrido(1,2-a)pyrazin-4-one, a thiophenic isostere of the heterocyclic system pyrazino(1,2-a)isoquinolin-4-one is synthesised by cyclisation in acidic medium from 4-acyl-6-hydroxy-1-[2-(2-thienyl)ethyl]piperazin-2-one. Those hydroxyimides result from selective reduction of corresponding piperazine-2,6-diones.
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■ Regioselective Addition of Grignard Reagents to the 1-Phenoxycarbonyl Salts of Alkyl Nicotinates
Daniel L. Comins,* Eric D. Stroud, and James J. Herrick
*Department of Chemistry abd Biochemistry, Utah State University, Logan, Utah 84332-0300, U.S.A.
Abstract
The addition of Grignard reagents to the 1-phenoxycarbonyl salts of alkyl nicotinates affords substituted 1,2- and 1,4-dihydropyridines. The crude dihydropyridines were aromatized with o-chloranil or sulfur to give 6- and 4-substituted alkyl nicotinates. The regioselectivity of this two-step process, 6- vs. 4- substitution, was examined and found to be dependent upon the structure of the Grignard reagent. When a catalytic amount of cuprous iodide is present during the Grignard reaction, nearly exclusive 1,4-addition results. The crude 1,4-dihydropyridines were aromatized with sulfur to provide 4-substituted methyl nicotinates in moderate yield and high isomeric purity.
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■ A New Synthetic Approach to Benzoquinolizidine Alkaloids Isolated from Alangium lamarkii
Tozo Fujii,* Masashi Ohba, and Shigeaki Akiyama
*Faculty of Pharmaceutical Scicences, Kanazawa University, 13-1 Takara-machi, Kanazawa 920-0934, Japan
Abstract
New general synthetic routes from 3-acetylpyridine (IV) to some ipecac and Alangium alkaloids possessing the 9,10-dimethoxy- and 8-hydroxy-9,10-dimethoxybenzo[a]quinolizidine skeletons have been established.