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. 10, 1985
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■ Ketone-generationg Reaction of 3-Methyl-2-(1’-hydroxydialkylmethyl)benzothiazolium Iodide under Basic Conditions
Hidenori Chikashita,* Masayuki Ishihara, and Kazuyoshi Itoh
*Department of Applied Chemistry, Faculty of Engineering, Kansai University, Suita, Osaka 564-8680, Japan
Abstract
Quaternized benzothiazol-2-yl moiety was found to be a good leaving group in the ketone-generating reaction of 3-methyl-2-(1’-hydroxydialkylmethyl)benzothiazolium iodides. The benzothiazolium salts easily obtained from ketones via methylation of 2-(1’-hydroxydialkylmethyl)benzothiazoles with methyl iodide, produced the corresponding ketones in excellent yields by the treatment with a variety of bases. Aldehydes and carboxylic esters were convertible to ketones by using the present methodology.
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■ Two New C20-Diterpenoid Alkaloids from Aconitum yesoense var. macroyesoense (Nakai) Tamura, Structures of Dehydrolucidusculine and N-Deethyldehydrolucidusculine
Koji Wada, Hideo Bando, and Takashi Amiya*
*Hokkaido College of Pharmacy, 7-1 Katsuraoka-cho, Otaru 047-02, Japan
Abstract
Two new C20-diterpenoid alkaloids, dehydrolucidusculine and N-deethyldehydrolucidusculine, and four known alkaloids, kobusine, pseudokobusine, delcosine, and 14-acetyldelcosine, were isolated from roots of Aconitum yesoense var. macroyesoense (Nakai) Tamura. The structures of dehydrolucidusculine and N-deethyldehydrolucidusculine were determined on the basis of their spectral data and the derivation from lucidusculine to dehydrolucidusculine.
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■ An Efficient Synthesis of Isoxazoles and Isoxazolines
Patrizia Caldirola, Marco De Amichi, Carlo De Micheli,* and Paolo Pevarello
*Instituto di Chimica Farmaceutica e Tossicologica, Università digli Studi di Milano, Viale Abruzzi, 42a, 20131 Milano,Italy
Abstract
Isoxazoles and isoxazolines can be efficiently prepared by refluxing a toluene solution of hydroximic acid chloride and dipolarophile.
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■ Two New Diterpenoid Alkaloids from Delphinium vestitum Wall
Haridutt K. Desai, Balawant S. Joshi, and S. William Pelletier*
*Department of Chemistry, Institute for Natural Products Research, The University of Georgia, Chemistry Building, Athens, Georgia 30602-2556, U.S.A.
Abstract
The isolation and structure determination of two C19-diterpenoid alkaloids, delvestine (1) and delvestidine (7) from Delphinium vestitum Wall. are described. The structures were based on spectroscopic data and correlation with compounds of known structures.
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■ Water-induced Azomethiene Ylide Generation from N-(Silylmethyl)thioimidates, Synthetic Equivalents of Nonstabilized Nitrile Ylides
Otohiko Tsuge,* Shuji Kanemasa, Toshiaki Yamada, and Koyo Matsuda
*Research Institute of Industrial Science, Faculty of Engineering, Kyushu University, 6-1, Kasuga-koen, Kasuga 816-8580, Japan
Abstract
N-(Silylmethyl)thioimidates undergo a water-induced desilylation generating azomethine ylide 1,3-dipoles which cycloadd to a variety of electron-deficient olefins providing 1- or 2-pyrrolines after the elimination of thiol, indicating that the thioimidates are synthetic equivalents of nonstabilized nitrile ylides.
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■ 2-Cyano-Δ3-piperideines XIV: The Involvement of Signal Election Transfer Processes in the Oxidation and Subsequent of the Ambident Anion of 2-Cyano-3-ethyl-1-methyl-Δ3-piperideine
David S. Grierson, Miguel Urrea, and Henri-Philippe Husson*
*Institut des Chimie des Substances Naturelles, C.N.R.S., 1 avenue de la Terrasse, Bat. 27, 91198 Gif-sur-Yvette Cedex, France
Abstract
The reaction of the ambident anion (2) derived from 2-cyano-3-ethyl-1-methyl-Δ3-piperideine (1) with trace quantities of O2 leads to the formation of compounds (3) to (7), and in particular the interesting dimer (5). The formation of these products is interpretted in terms of single electron transfer processes.
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■ Structure of Sanggenon O, a Natural Diels-Alder Type Adduct from Chinese Crude Drug "Sang-Bai-Pi" (Morus Root Bark)
Yoshio Hano 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 Chinese crude drug “Sang-Hai-Pi” (Japanese name “Sohakuhi”), the root bark of Morus sp. (Moraceae), a new flavanone derivative was isolated and named sanggenon O, whose structure was shown to be 1 on the basis of spectral and chemical evidence. Sanggenon O (1) is a structural isomer of sanggenon C (2), and was derived from 2 by treatment of an alkaline solution. The compound (1) is regarded biogenetically as a Diels-Alder type adduct of a chalcone derivative and a dehydroprenylflavanone derivative.
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■ Pagicerine — A New Indole Alkaloid from Pagiantha derifera (Pancher et Sébert) Markgraf (Apocynaceae)
Matyse Bert, Geneviève Baudouin, François Tillequin, and Michel Koch*
*U.A. au C.N.R.S.n°484, Faculté des Sciences Pharmaceutiques et Biologiques, Université René Descartes, 4, Avenue de l‘Observatoire, F-75006 Paris, France
Abstract
A new 2-acylindole alkaloid, pagicerine (1) has been isolated from the stem bark of Pagiantha cerifera (Pancher et Sébert) Markgraf. Its structure has been elucidated on the basis of spectroscopic analyses. It is the first indole alkaloid to present an additional tetrahydro-1,3-oxazine ring.
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■ 3-Methylbenzothiazolines as a New Protected Form for the Carbonyl Function
Hidenori Chikashita,* Nishiki Ishimoto, Shunichiro Komazawa, and Kazuyoshi Itoh
*Department of Applied Chemistry, Faculty of Engineering, Kansai University, Suita, Osaka 564-8680, Japan
Abstract
Protection of carbonyl groups with N-methyl-o-aminothiophenol in ethanol under neutral conditions gave the corresponding benzothiazoline derivatives which were stable against basic, acidic and other reaction conditions. Removal of the protecting group was also performed under neutral conditions by using AgNO3 or HgCI2 in aqueous acetonitrile to regenerate the parent carbonyl compounds.
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■ Diterpenoid Alkaloids from Delphinium Nudicaule Torr. and Gray
Palaniappan Kulanthaivel and Michael Benn*
*Department of Chemistry, The University of Alberta, Calgary, Alberta, T2N, 1N4, Canada
Abstract
Eight known and three apparently hitherto undescribed diterpenoid alkaloids were isolated from D. nudicaule: hetisine, 2-dehydrohetisine, 6-deoxydelcorine, dictyocarpine, dihydrogadesine, methyllycaconitine, lycoctonine, and takaosamine; and nudicaulamine, nudicauline, and nudicaulidine, the structures of which were deduced.
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■ Synthesis of the β-D-Deoxyribofuranoside of 6-Amino-1H-pyrazolo[3,4-d]pyrimidin-4(5H)-one — A New Isoster of 2’-Deoxyguanosine
Frank Seela* and Herbert Steker
*Laboratorium für Bioorganische Chemie, Fachbreich Chemie, Universität Paderborn, D-4790, Paderborn, Germany
Abstract
6-Amino-1-(2-deaxy-β-O-erythro-pentofuranosyl)-1H-pyrazolo[3,4-d]pyrimidin-4(5H)-one (8) has been synthesized via regio- and diastereo-selective phase-transfer glycosylation of 6-amino-4-methoxy-1H-pyrazolo[3,4-d]pyrimidine (4) with 2-deoxy-3,5-di-O-(p-toluoyl)-α-D-erythro-pentofuranosyl chloride (5). Compound 4 was obtained from 2-amino-4,6-dichloro-5-pyrimidinecarboxaldehyde (2a). Hydrolysis experiments under acidic conditions showed that the N-glycosylic bond of 8 is more labile than that of 2‘-deaxyguanosine.
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■ A New Synthesis of (±)-Celacinnine by Means of Non-spermoidine-based Methodology
Toshio Moriwake,* Seiki Saito, Hideaki Tamai, Seiichi Fujita, and Masami Inaba
*Faculty of Engineering, Okayama University, 3-1-1 Tsushima-naka, Okayama 700-8530, Japan
Abstract
(±)-Celacinnine was synthesized relying on the novel methodology which features nucleophilic ring opening of 2-substituted 5,6-dihydro-4H-1,3-oxazine as a carboxamide synthon and requires neither spermidine nor amino acid condensation process for the lactam framework.
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■ Synthesis of Benzannelated 1-Azacycl[3.2.2]azine: 1-Azabenzo[h]cycl[3.2.2]azine
Yoshinori Tominaga,* Yoshihide Shiroshita, Masanori Kawabe, Hiromi Goto, Yukio Oniyama, and Yoshiro Matsuda
*Faculty of Pharmaceutical Sciences, Nagasaki University, 1-14, Bunkyo-machi, Nagasaki 852-8521, Japan
Abstract
1-Azabenzo[h]cycl[3.2.2]azine (3) was synthesized by the reaction sequence starting from 2-[1-ethoxycarbonyl-2,2-bis-(methylthio)vinyl]isoquinolinium iodide (4), involving the cycloaddition of 2-methylthioimidazo[2,1-a]isoquinoline (8) with dimethyl acetylenedicarboxylate as the key step. It was found that 3 and its 2-methylthio derivative (14) are typical aromatic compounds.
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■ Polyene Cyclization Teminated by Thiol
Akira Saito,* Hajime Matsushita, and Hajime Kaneko
*Central Reseasrch Institute, Japan Tobacco Inc., 6-2, Umegaoka, Midori-ku, Yokohama, Kanagawa 227-8512, Japan
Abstract
Acid-catalyzed cyclization of geranyl and neryl derivatives was effectively terminated by thiol, and afforded trans- and cis-fused alkyl substituted thiahydrindanes stereoselectively.
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■ Chemistry of Coumarins — Synthesis of Some 3,4-Substituted Coumarins Using the HSAB Principle
Ibro Tabakovic,* Katmerka Tabakovic, Radoslav Grujic, Nenad Trinajstic, and Zlatko Meic
*Faculty of Technology, The Gjuro Pucar Stari University, 78000 banja Luka, Bosnia and Herzegovina, Serbia and Montenegro
Abstract
Novel heterocyclic systems (2, 3, and 4) have been obtained by reactions of the corresponding bidentate nucleophiles, e.g. 2-mercaptoaniline, 3-mercapto-1,2,4-triazole and 2-mercaptobenzimidazole respectively, with 4-chloro-3-nitrocoumarin (1).
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■ Xanthones from Hypericum sampsonii
Ming-Tyan Chen and Chiu-Ming Chen*
*Department of Chemistry, National Tsing Hua University, Hsinchu, Taiwan 30013, Taiwan, R.O.C.
Abstract
Hypericum sampsonii Hance contains mangiferin, isomangiferin, 2-hydroxy-3,4-dimethoxyxanthone, toxyloxanthone B, and a new compound, hyperxanthone, which was identified as 5,9-dihydroxy-3,3-dimethylpyrano[3,2-a]xanthen-12(3H)-one on the basis of spectroscopic evidences. Characteristic fragment ions in the mass spectrum of pyranoxanthone are discussed.
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■ Nitrogen Bridgehead Compounds. Part 56. Reaction of 2,6a-Diaza-3a-azoniaphenalene Quaternary Salts with N-Nucleophiles and Carbaninos
István Bitter,* Béla Pete, Gábor Tóth, István Hermecz, and Zoltán Mészáros
*Department of Organic Chemical Technology, Technical University of Budapest, H-1521 Budapest, Gellért tér 4, Hungary
Abstract
2,6a-Diaza-3a-azoniaphenalene chlorides (1) smoothly condense with strong N-nucleophiles and carbanions generated from malonic ester derivatives affording tri- and tetracycles by ring transformation.
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■ A Base-catalysed Reaction of Arylidenemaiononitrile with 2,1-Benzisoxazoles
Dilip Konwar, Romesh Chandra Boruah, and Jagir Singh Sandhu*
*Division of Drug and Pharmaceutical Chemistry, Regional Research Laboratory, Jorhat 785 006, Assam, India
Abstract
Quinoline-N-oxide derivatives were prepared in good yields by a triethylamine-catalysed reaction of arylidenemalononitrile with 2,1-benzisoxazoles.
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■ Alkylation of 1-(3,4-Dimethoxybenzyl)-6,7-dimethoxyisoquinoline (Papaverine)
André Buzas,* Jean-Yves Merour, and Gilbert Lavielle
*Instiut de Chimie Organique et Analytique, U. F. R. de Sciences, Université d‘Orléans, BP 6759, Rue de Chartres, 45067 Orleans Cedex 2, France
Abstract
Alkylation of papaverine carbanion with various alkyl halides is described. Intramolecular ring formation is observed with 1-iodo-3-chloropropane as electrophile. 1-[1-(3,4-Dimethoxyphenyl-3-oxopropyl]-6,7-dimethoxyisoquinoline is studied.
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■ An Oxidative 1,3-Dithiolane → Dihydro-1,4-dithiin Rearrangement
Luis Angel Maldonado* and Norberto Manjarrez
*Div. Estudios de Posgrado, Facultad de Química, Universidad Nacinal Autónoma, Circuito Exterior, Ciudad Universitaria, Coyoacán 04510, Mexico
Abstract
In hot DMSO, compound 1 is converted into 2 in excellent yield. This conversion involves a 1,3-dithiolane → dihydro-1,4-dithiin rearrangement to 3, followed by oxidation of the allylic CH2. Appropriate experiments established the mechanism of this rearrangement-oxidation sequence.
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■ N-Dideuterobutyryldeacetylcolchicine: Probes to Study Colchicine Binding Sites on Tubulin Protein
Maria A. Iorio, Antonio Doldo, Arnold Brossi,* and Colin F. Chignell
*Section of Medical Chemistry, Section of Medical Chemistry, National Institute of Health, Bethesda, MD 20982, U.S.A.
Abstract
N-Acryloyl- and N-crotonyldeacetylcolchicine prepared from deacetylcolchiceine by conventional methods showed good binding to tubulin protein in vitro. N-Dideuterobutyryldeacetylcolchicine, prepared from deacetylcolchicine with dideuterobutyryl chloride behaved similarly, suggesting that tritiated analogs of N-propionyl- and N-butyryldeacetylcolchicine should be useful probes to study the colchicine binding site on tubulin protein.
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■ Dihydrochalocones as Synthons for 2-Amino- and 2-Mercapto-4-aryl-5-arylmethylthiazoles
Vinod Kumar Ahluwalia,* Krishan Kumar Arora, and Gurvinder Kaur
*Department of Chemistry, University of Delhi, Delhi-110 007, India
Abstract
2-Amino- and 2-mercapto-4-aryl-5-arylmethylthiazoles have been synthesised by the respective condensation of thiourea and ammonium dithiocarbamate with α-bromo-α,β-dihydrochalcones which in turn are obtained by the bromination of the corresponding dihydrochalcones.
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■ The Synthesis of Racemic Azacarbapenams
Théophile Tschamber, Jean-Michel Henlin, David Pipe, and Jacques Streith*
*Ecole Nationale Supérieure de Chimie de Mulhouse, Université de Haute Alsace, 3, Rue Alfred Werner 68093 Mulhouse Cedez, France
Abstract
Ozonation of the tricyclic compounds 2, followed by photolysis of the secondary ozonides 6, led to a mixture of the rather unstable 2-azacarbapenems 7 and 8. Hydrogenation of 7 led to the expected 2-azacarbapenam derivatives 9.
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■ The Sintheses of Novel-2-(2-Quinoxalinyl)pyridazin-3(2H)-ones
Kenji Makino* and Gozyo Sakata
*Central Recearch Insttitute, Nissan Chemical Ind., Ltd., 722-1 Tsuboicho, Funabashi, Chiba 274-8507, Japan
Abstract
The first syntheses of 4-chloro-2-(2-quinoxalinyl)pyridazin-3(2H)-one derivatives are reported. They could be synthesized from 2-hydrazinoquinoxaline derivatives as starting materials.
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■ Synthesis of 6-Aryl-1,3-dimethyl-1H-1,2,4-triazolo[4,3-b][1,2,4]triazoles
Pedro Molina,* Mateo Alajarín, and María-Jesús Pérez de Vega
*Departmento de Química Orgánica, Facultad de Ciencias, Universidad de Murcia, 30071 Murcia, Spain
Abstract
The synthesis of various 1H-1,2,4-triazolo[4,3-b][1,2,4]triazoles has been achieved by reaction of 4-amino-1,3-dimethyl-5-thioxo-4,5-dihydro-1,2,4-triazole with aromatic nitriles in the presence of potassium t-butoxide.
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■ N,N’-Linked Biozoles. Part 5. Synthesis of Pyrazolyl Dimers by the Reaction of 3-Methoxycarbonyl-2-pyrazoline with Lead Tetraacetate
Javier de Mendoza,* M. Rosario González-Muñiz, M. Rosario Martín, and José Elguero
*Departamento de Química Orgánica, Facultad de Ciencias, Universidad Autónoma de Madrid, Cantoblanco, 28049-Madrid, Spain
Abstract
Contrary to a previous report by Akhrem et al. (Tetrahedron Lett. 1973, 2655), the reaction of 3-methoxycarbonyl-2-pyrazoline with lead tetraacetate affords not only 3-methoxycarbonyl-1-(3-methoxycarbonyl-2-pyrazolin-1-yl)pyrazole (8) and 3-methoxycarbonyl-1-(1-methoxycarbonyl-1-cyclopropyl)pyrazole (9), but a complex mixture of pyrazoles and pyrazolines depending on the reaction conditions (LTA/pyrazoline ratio and temperature). The structures of all compounds have been established, and a new mechanism is proposed for the reaction. The oxidation of 8 with N-bromosuccinimide gave the symmetrical 3,3’-dimethoxycarbonyl-1,1’-bipyrazole (17).
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■ N,N’-Kinked Biazoles. Part 6. On the Structure of Compounds Derived from the Oxidation of 7-Methyl-4,5,6,7-tetrahysroindazole
Javier de Mendoza,* Pilar Prados, and José Elguero
*Departamento de Química Orgánica, Facultad de Ciencias, Universidad Autónoma de Madrid, Cantoblanco, 28049-Madrid, Spain
Abstract
The structure of 7,7’-dimethyl-2,2’-bi-4,5,6,7-tetrahydroindazole, the main product from the bromine oxidation of the silver salt of 7-methyl-4,5,6,7-tetrahydroindazole, is corrected in favor of a C,N’-linked cyclic trimer (mixture of diastereoisomers). Although a C,N’-linked dimer was also isolated, N,N’-linked dimers were not found.
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■ Polycondensed Nitrogen Heterocycles. Part 18. Influence of pH in the Intramolecular Coupling Reaction of Diazotized 2-(2-Aminophenyl)-pyrroles
Girolamo Cirrincione, Gaetano Dattolo, Anna Maria Almerico,* and Enrico Aiello
*Instituto di Chimica Farmaceutica e Tossicologica, Università digli Studi di Palermo, Via Archirafi 32, 90123 Palermo, Italy
Abstract
1H-pyrrolocinnolines (3) or pyrrolobenzotriazines (4) are obtained for amines (1) depending on the pH of the medium. The reaction course was explained on the basis of the position of the equilibrium 2⇔2’ affected by the substituents.
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■ New Pyrazolo[3,4-b]pyridine and Pyrazolo[3,4-d]pyrimidine Derivatives from 4-Acetyl-5-amino-1,3-diphenylpyrazole
Vittorio Dal Piaz,* Giovanna Ciciani, and Stefano Chimichi
*Dipartimento di Scienze Farmaceutiche, Università di Firenze, Via Gino Capponi 9, I-50121 Firenze, Italy
Abstract
4-Acetyl-5-amino-1,3-diphenylpyrazole (1) undergoes cyclization with compounds of the type R-CH2X ( X=COCH3 and/or COPh, R=H and CH3CO; X=R=CN) and with formamide to give new pyrazolo[3,4-b]pyridine and pyrazolo[3,4-d]pyrimidine derivatives, respectively.
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■ A Convenient Synthesis of 2-Aryl- and 2-Arylamino-4-aryl-5-cyanothiazoles
Antonino Corsaro* and Giovanni Puglisi
*Dipartimento di Scienze Chimiche, Università di Catania, Viale A. Doria 8, I-95125 Catania, Italy
Abstract
The reactions of a series of para-substituted 3-amino-3-aryl-propenenitriles 1a-f with N-phenyl- (2a) and N-methyl-S-chloroisothiocarbamoyl chloride (2b), followed by triethylamine treatment, provide 2-phenyl- and 2-methyl-4-aryl-5-cyanothiazoles 3a-i. N-Monosubstituted enaminonitriles 1g,h react with 2a affording 3-substituted 2-phenylimino-δ4-thiazolines 6a,b, but in very poor yields. A mechanism which accounts for the formation of thiazole and thiazoline structures is presented.