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. 23, No. 4, 1985
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■ Convenient Phase Transfer N-Arylation of 1,3-Dihydro-1,5-benzodiazepin-2-ones
El Mokhtar Essassi,* Moussa Salem, Rachid Zniber, Philippe Viallefont, and Roger Gallo
*Laboratoire de Chimie des Plantes et de Sythese Organique et Bioorganique, Faculté des Sciences, Universite Mohammed V, P.B. 1014 Rabat-RP, Morocco
Abstract
The application of phase transfer catalysis to the N-arylation of heterocyclic molecules is described ; N-arylbenzadiazepines are prepared according to this method. The phase transfer technique is compared to conventional procedures. The dynamic stereochemistry of the ring is evidenced by the change in 1Hnmr spectra line.
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■ The Structure of Polyschistine A, B and C: Three New Diterpenoid Alkaloids from Aconitum polyschistum Hand-Mazz
Hongcheng Wang, Aina Lao, Yasuo Fujimoto,* and Takashi Tastuno
*The Institute of Physical and Chemical Research, Wako-shi, Saitama 351-0198, Japan
Abstract
Tree new diterpnoid alkaloids named polyschistine A, B and C were isolated from the roots of Aconitum polyschistum Hand-Mazz collected Sichuan province in China. The structures of polyschistine A, B and C were determined on the basis of their 1H- and 13C-NMR spectra.
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■ Penicillin Sulfoxide Termolysis in Trimethyl Orthoacetate
Ronald G. Micetich, Rajeshwar Singh, and Robert B. Morin*
*Faculty of Pharmacy , University of Alberta, Edmonton, Alberta T6G, 2N8, Canada
Abstract
The themolysis of trichloroethyl 6-phenoxyacetamidopenicillanate sulfoxide in trimethyl orthoacetate gave four -lactam cleaved products.
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■ Azabiocyclo[3.2.0]heptane-3,4-dione (10): A Thermal Azonia 1,3-Shift of 2-Azabicyclo[3.2.0]hept-2-enes to 2-Azanorborn-2-enes
Takehiro Sano,* Kazuhiko Tanaka, Yoshie Horiguchi, and Yoshisuke Tsuda
*Showa Pharmaceutical University, 3-3165, Higashi-tamagawagakuen, Machida, Tokyo 194-8543, Japan
Abstract
Thermolysis of 2-azabicyclo[3.2.0]hept-2-enes caused azonia 1,3-shift in non-stereospecific manner to give 2-azanorborn-2-enes. This rearrangement reaction was greatly affected by the stereochemistry of the substituent at the migrating center.
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■ Structures of Kuwanols A and B, Two Novel Stilbene Derivatives from the Cultivated Mulberry Tree (Morus bombycis Koidz.)
Yoshio Hano, Masato Itoh, and Taro Nomura*
*Faculty of Pharmaceutical Sciences, Toho University, 2-2-1, Miyama, Funabashi, Chiba 274-8510, Japan
Abstract
From an acetone extract of the reddish violet powder obtained from the surface of the root bark of cultivated mulberry tree (Ohshimaso, a variety of Morus bombycis Koidz.), two novel stilbene derivatives were isolated and named kuwanols A and B, whose structures were shown to be 1 and 2, respectively, on the basis of spectral evidence. These compounds are regarded biogenetically as variations of a Diels-Alder type adduct of a chalcone derivative and a dehydroprenylstilbene derivative.
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■ Synthesis of 3-Aryl-3,4-dihydroisocarbostyrils by Condensation of Lithiated N,N-Diethyl-O-toluamides with Benzaldimines
Robin D. Clark*
*Institute of Organic Chemistry, Syntex Research, Palo Alto, California 94304, U.S.A.
Abstract
The cyclocondensation of lithiated N,N-diethyl-o-toluamide (1) with benzaldimines (2) at -70°C gave directly 2-alkyl-3-aryl-3,4-dihydroisocarbostyrils (3) in 37-50% yield.
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■ Synthesis of the Sedum Alkaloid Sedinine
Masashi Ogawa and Mitsutaka Natsume*
*Research Foundation Itsuu Laboratory, 2-28-10 Tamagawa, Setagaya-ku, Tokyo 158, Japan
Abstract
The Sedum alkaloid sedinine (1) was synthesized in the racemic form from 1-methoxycarbanyl-2-(1-propynyl)-1,2-dihydropyridine (4) by way of tetrahydropyridine derivatives (5, 10a, 20, and 24b).
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■ The Total Synthesis of (—)-Dihydrocorynantheol
Toshio Suzuki,* Etsuko Sato, Katsuo Unno, and Tetsuji Kametani
*Department of Pharmaceutical Sciences, Akita University Hospital, Hondo, Akita 010, Japan
Abstract
The total synthesis of (-)-dihydrocorynantheol (4) has been achieved using a potentially useful chiral synthon, thioketal carboxylic acid (2).
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■ Total Synthesis of (-)-Antirhine
Toshio Suzuki,* Etsuko Sato, Katsuo Unno, and Tetsuji Kametani
*Department of Pharmaceutical Sciences, Akita University Hospital, Hondo, Akita 010, Japan
Abstract
Total synthesis of (-)-antirhine (6) has been achieved from a potentially useful chiral synthon, (3S)-[3-hydroxy-(E)-prop-1-enyl]cyclopentanone (1), via β,γ-unsaturated aldehyde (5), which was obtained by mild hydrolysis of α-cyano-N,N-dimethylaminocyclopentanone (7).
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■ Chemo-, Regio- and Stereoselectivity and Mechanism of the Heterocyclization Reaction of Dialkyl (5-Methyl-1,3,4-hexatrien-3-yl)phosphonates with Methylselenenyl Chloride
Tchonka N. Tancheva, Christo M. Angelov,* and Diana M. Mondeshka
*Department of Chemistry, Higher Pedagogical Institute, 9700 Shoumen, Bulgaria
Abstract
The reaction path of dialkyl(5-methyl-1,3,4-hexatrien-3-yl)-phosphonates with methylselenenyl chloride was investigated in details. The spectral and chromatographic studies indicate that alongside the main reaction products - 2,5-dihydro-1,2-oxaphospholes, three different selenophenephosphonates and 1,3-alkadienylphosphonate are obtained too, i.e. the interaction of 1a-c with methylselenenyl chloride is regioselective but not chemo- and stereoselective reaction.
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■ 13C Dynamic NMR Studies on Restricted Rotation about C-N Bond in Carbamates of the 9-Azabicyclo[3.3.1]nonane System
Osamu Muraoka, Toshie Minematsu, Junko Tsuruzawa, and Takefumi Momose*
*Faculty of Pharmaceutical Sciences, Kinki University, 3-4-1, Kowakae, Higashi-Osaka 577-8502, Japan
Abstract
13C NMR spectra of carbamates of the 9-azabicyclo-[3.3.1]nonane and 8-azabicyclo[3.2.1]octane systems have been measured at various temperatures, and their free energies of activation (δG‡c) were estimated at the coalescence temperature (Tc) to be 60.6-69.7 ± 0.8 kJ/mol (14.5-16.6 ± 0.2 kcal/mol).
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■ Thallium(III) Nitrate Mediated Systhesis of Erythrinin-A, Dihydropyrano- and Pyranoisoflavones
Raghava Venkataramanna Suresh, Chandrashekarapuram Subramanyam Rukmani Iyer, and Parameswaran Ramasubramonia Iyer*
*Department of Chemistry, Indian Institute of Technology, Powai, Bombay 400 076, India
Abstract
Oxidative rearrangement of dihydropyranochalcones using thallium(III) nitrate-trimethylorthoformate (TTN-TMOF) reagent followed by acid catalysed cyclization yields the corresponding dihydropyranoisoflavones in good yields. Dehydrogenation of these isoflavones gave pyranoisoflavones. Demethylation of isoflavone (7) followed by dehydrogenation gave erythrinin-A (16).
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■ Effect of Metal Ions in Organic Synthesis. XXIX. Synthesis of New 1-Arylsulfonylamino-3-carboxtptrroles byCopper(II) Acetate-catalyzed Reaction of Arylsulfonylazoalkenes with β-Ketoesters
Orazio Attanasi,* Francesca Romana Perrulli, and Franco Serra-Zanetti
*Istituto di Chimica Organica , Facolta di Scienze, Università di Urbino, Piazza della Repubblica 13, I-61029 Urbino, Italy
Abstract
The synthesis of a number of new 1-arylsulfonylamino-3-carboxypyrroles by reaction of some arylsulfonylazoalkenes with certain β-ketoesters under copper(II) acetate monohydrate catalysis is reported.
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■ The Synthesis of Novel 1-Substituted 4H-[1,2,4]Triazolo[3,4-c][1,4]benzoxazin and Benzthiasin-4-ones
John H. Musser,* Vasil St. Georgiev, Robert Mack, Bernard Loev, Richard E. Brown, and Fu-chih Huang
*Research and Development Division, Revlon Health Care Group, Tuckahoe, New York 10707, U.S.A.
Abstract
The synthesis of novel 1-substituted 4H-[1,2,4]triazolo[3,4-c][1,4]benzoxazin and benzthiazin-4-ones is described. A minor modification in the synthetic sequence resulted in an entirely different heterocyclic system, i.e. a 2-(2-oxo-3H-1,3,4-oxadiazol-5-yl)benzoxazole.
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■ Convenient Synthesis of Esters of 2-Pyrrolecarboxylic Acid and of Pyridinecarboxylic Acids by Solid-liquid Phase Transfer Catalysis without Added Solvent
Jean Barry,* Georges Bram, and Alain Petit
*Laboratoire des Réactions Sélectives sur Supports, UA CNRS 478 Bât. 410, Université Paris-Sud, Orsay 91405, Orsay Cedex, France
Abstract
By reaction of aromatic K-carboxylates having nucleophilic N-atom in solid-liquid phasetransfer catalysis (PTC) conditions without added solvent (catalyst : tetraalkylammonium halide) with alkylating reagents, the corresponding esters are prepared. By a judicious choice of experimental conditions, the amounts of N-alkylated products can be lowered. From 2-pyrrolecarboxylic acid, the three isomers of pyridinecarboxylic acid and o-aminobenzoic acid, corresponding esters of ethyl, benzyl, n-octyl and n-cetyl, generally are obtained with good yields.
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■ The Chemistry of Drugs. VI. Thermal Decomposition of Qinghaosu
Xuan-De Luo,* Herman J. C. Yeh, Arnold Brossi, Judith L. Flippen-Anderson, and Richard Gilardi
*Laboratory of Chemistry, National Institute of Arthritis, Diabetes, and Digestive and Kidney Diseases, National Instituteof Health, Bethesda, Maryland 20205, U.S.A.
Abstract
Hearing qinghaosu in refluxing xylene for 22 h afforded decomposition products 2 and 4 in 15% yield each. Structures of 2 and 4 were assigned based on their 1H-NMR and 13C-NMR data and the former confirmed by a single crystal X-ray analysis. Structure 4, supported by spectral data and a successful O-acetylation of the OH group remains tentative. Structures 2 and 4 contain a newly formed tetrahydrofuran ring, originating by breakage of the original peroxide group.
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■ Synthesis of 8,9-Dihydro-3-methyl-6H-[1,4]thiazino[4,3-c][1,3]thiazine-1,4(3H,9aH)-dione, a Novel Heterocyclic Ring System
John H. Musser,* Kevin Bailey, and John T. Suh
*Research and Development Division, Revlon Health Care Group, Tuckahoe, New York 10707, U.S.A.
Abstract
The synthesis of the novel 8,9-dihydro-3-methyl-6H-[1,4]thiazino[4,3-c]thiazine-1,4(3H,9aH)-dione is described.
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■ Stereochemistry of 11,12-Dihydrodibenz[b,f]azocin-6(5H)-ones
Alba Chimirri,* Silvana Grasso, Giovanni Romeo, Maria Zappalà, and Giovanna Fenech
*Dipartimento Farmaco-Chimico, Università di Messina, Viale Annunziata, 98168 Messina, Italy
Abstract
The preferred conformation in solution of 11,12-dihydrodibenz[b,f]azocin-6(5H)-ones has been assigned by means of LIS assisted 1H nmr spectroscopy. The 1H nmr temperature-dependent behaviour of the 8-membered ring has been investigated; the activation parameters have been determined and the influence of N-5 substitution on the ring mobility is discussed.
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■ An Elegant Synthesis of 6H-Benzofuro-[3,2-c][1]benzopyran-6-ones
Rishi Pal Singh* and Daljeet Singh
*Department of Chemistry, University of Delhi, Delhi-110 007, India
Abstract
Etherification of 4-hydroxy-2H-1-benzopyran-2-ones with 2-bromocyclohexan-1-one and cyclisation with PPA followed by dehydrogenation with DDQ affords 6H-benzofuro[3,2-c][1]benzopyran-6-ones in overall good yield.
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■ Novel Fused Triheterocyclic Systems. Synthesis of 6H-Pyrido[2,3-c]-pyrrolo[1,2-e]-1,2,5-triazepines
Jean-Charles Lancelot, Daniel Ladurée, Hussein El Kashef, and Max Robba*
*Laboratoire de Chimie Thérapeutique, U. F. R. des Sciences Pharmaceutiques, Université de Caen, 1, rue Vaubénard, 14032 Caen Cedex, France
Abstract
The synthesis of 6H-pyrido[2,3-c]pyrrolo[1,2-e]-1,2,5-triazepines has been described.
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■ A Novel Synthesis and Transformations of 1H-Pyrazino[2,3-e]-1,3,4-thiadiazine Derivatives
Bozidar Koren, Branko Stanovnik,* and Miha Tisler
*Department of Chemistry, E. Kardelj University, Murnikova 6, 61000 Ljubljana, Slovenia
Abstract
1,4-Disubstituted thiosemicarbazides 2, 4, and 9 cyclize thermally into 1H-pyrazino[2,3-e]-1,3,4-thiadiazine derivatives 3, 5, 6 and 8. These can be converted under mild reaction conditions into derivatives of the same bicyclic system 10, 17, and 21. However, under acidic or alkaline conditions a cleavage of the C3-S bond of the 1,3,4-thiadiazine ring is taking place to give either the 1,4-disubstituted semicarbazide 12, or rearranged products, derivatives of s-triazolo[4,3-b]pyrazine, 7, 11, 13, 14, 15, 16, 18, 22, 23 and 24.
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■ N-Substituted 2-Aminocyanocyclopentenes Reactivity with Dimethylacetylenedicarboxylate
Catharine Viellescazes, Serge Coen, Bernard Ragonnet, and Jean-Pierre Roggero*
*Faculté des Sciences, Laboratorie de Chimie Organique, 33, rue Louis Pasteur, 84000 Avignon, France
Abstract
2-Aminocyanocyclopentene and its N-phenylamino and N-methyl-N-phenyl-2-aminocyanocyclopentene derivatives react in good yields with dimethyl acetylenedicarboxylate, leading to cycloheptadiene derivatives through ring expansions and/or condensed ring heterocycles via cycloaddition mechanisms.
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■ Synthesis of 3-Acetyl-1,4,6,7,12,12b-hexahydroindolo[2,3-a]quinolizine
Sukhendu B. Mandal and Satyesh C. Pakrashi*
*Indian Institute of Chemical Biology, Calcutta-700 032, India
Abstract
A facile synthesis of the title compound (5), a key synthon for ajmalicine and related indole alkaloids, is described.
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■ Preparation of 7-Methoxy-3,4-dihydro-β-carboline
Annie Pouilhès and Yves Langlois*
*Institut des Chimie des Substances Naturelles, C.N.R.S., 1 avenue de la Terrasse, Bat. 27, 91198 Gif-sur-Yvette Cedex, France
Abstract
7-Methoxy-3,4-dihydro-β-carboline (4a), starting material in total synthesis of several indole alkaloids, has been prepared in a three-steps sequence from 3-methoxyaniline.
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■ Lacotonic Amines from Garnieria spathulaeforia
Mauri Lounasmaa,* Arto Tolvanen, Lassi Hiltunen, Jacques Pusset, and Gérard Chauvière
*Laboratory of Organic Chemistry, Helsinki University of Technology, P.O. Box 6100,FIN-02015 HUT, Espoo, Finland
Abstract
An investigation of Garnieria spathulaefolia led to the isolation and characterization of two nitrogen-containing α-methylene-γ-butyrolatone derivatives.
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■ The Sequential Lithiation of 1-Phenylpyrazoles
Ronald G. Micetich, Verne Baker,* Paul Spevak, Tse W. Hall, and Baljit K. Bains
*Faculty of Pharmacy , University of Alberta, Edmonton, Alberta T6G, 2N8, Canada
Abstract
1-Phenylpyrazole is lithiated exclusively at the C-5 position. Suitable 5-substituted 1-phenylpyrazoles undergo lithiation at the ortho position of the phenyl ring. 5-Thiomethyl-1-(o-tolyl)pyrazole is laterally lithiated at the ortho methyl group. In the case of 5-methoxymethyl-1-phenylpyrazole, lithiation occurs at both the C-5 methylene group and the ortho position of the phenyl ring with n-butyllithium, but essentially exclusive lithiation occurs at the C-5 methylene group with LDA.
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■ Nigellimine N-Oxide — A New Isoquinoline Alkaloid from the Seeds of Nigella sativa
Atta-ur-Rahman,* Sohail Malik, Sultan Ahmad, Iqbal Chaudhary, and Habib-ur-Rehman
*H. E. J. Postgraduate Institute of Chemistry, University of Karachi, Karachi-75270, Pakistan
Abstract
A new minor isoquinoline alkaloid, nigellimine N-oxide, has been isolated from the seeds of Nigella sativa and its structure has been determined on the basis of spectral studies.
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■ Indoles with C-3 as Spiro Atom
Krishna C. Joshi,* Renuka Jain, and Pooran Chand
*Department of Chemistry, University of Rajasthan, Jaipur 302 004, India
Abstract
This review article covers the synthesis, reactions and uses of spiro indoles with C-3 as spiro atom.
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■ 3,5-Diaryl-1,2,4-dithiazolium Salts as Synthons for Open-chained and Heterocyclic Compounds
Jürgen Liebscher* and Horst Hartmann
*Sektion Chemie, Humboldt-Universität Berlin, Hessische Strasse 1-2, D-10115 Berlin, Germany
Abstract
The preparation and application of 3,5-diaryl-1,2,4-dithiazolium salts in the synthesis of various open-chained and heterocyclic compounds is summarized.