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. 5, 1985
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■ Crassifolazonine, a New Type of Dibenz[d,f]azonine Alkaloid
José Manuel Boente, Domingo Domínguez, and Luis Castedo*
*Facultad de Química y Sección de Alcaloides, Deparamento de Química Orgánica, C. S. I. C., Santiago de Compostela, Spain
Abstract
The isolation of crassifolazonine, a dibenzazonine with a new type of tetrasubstitution pattern at 2,3,12,13 positions is described. This is the first example of a dibenzazonine possibly derived from a diphenolic benzylisoquinoline by an ortho-para coupling.
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■ Acid-catalyzed Cyclization of 2-Hydroxy-3-pyrrolone Derivatives. 2-Methoxy-3(2H)-furanones as Precursors of Polycyclic Nitrogen Heterocycles
Jeremiah P. Freeman* and Mary Kay Fettes-Fields
*Department of Chemistry, University of Oregon, Eugene, OR 97403, U.S.A.
Abstract
Condensation of 2-methoxy-3(2H)-furanones with β-substituted ethylamines followed by treatment with various acid catalysts gives rise to polycyclic nitrogen heterocycles by way of two intramolecular cyclizations. The pathway depends upon the nature of the β-substituent. β-Aryl substituents underwent alkylation through the 2-position of the hetero ring while β-amino- and β-thio groups cyclized to the 5-position.
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■ LiAlH4 Reduction — A Facile Route to 2,5-Dihydropyrimidines
Alexander L. Weis* and Rosita Vishkautsan
*Department of Organic Chemistry, Weizmann Institute of Science, Rehovot 76100, Israel
Abstract
2,5-Dihydropyrimidines stabilized by electron-donating groups at position 4 and 6 were prepared quantitatively by LiAlH4 reduction of the corresponding pyrimidines.
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■ Facile Retro Dieckmann Reaction of 3-Oxo-carbapenam Esters
Johannes G. de Vries,* Gerhard Hauser, and Gerfard Sigmund
*Sandoz Forschungsinstitut, 1235 Wien, Brunnerstraße 59, Austria
Abstract
Bicyclic ketones 1b and 1c reacted with nucleophiles to give azetidinones 4. Azetidinone 4a was deprotected to give 5, which was antibacterially inactive.
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■ Regioselective Synthesis of Substituted Phthalides via Intramolecular "Diene-regenerative" Diels-Alder Reaction of 2-Pyrones
Michihiko Noguchi,* Shinji Kakimoto, Hisao Kawakami, and Shoji Kajigaeshi
*Department of Applied Chemistry, Faculty of Engineering, Yamaguchi University, 2-16-1 Tokiwadai, Ube, Yamaguchi 755-8611, Japan
Abstract
Some 2-pyrone-6-carboxylates bearing appropriate dienophiles in ester moieties underwent “diene-regenerative” Diels-Alder reaction to afford the dihydrophthalides, which were aromatized to phthalide derivatives in the presence of palladium-charcoal. In these reactions the substituents at 4 or 7-position of phthalides arose from those on the dienophile moieties in the starting 2-pyrones.
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■ (—)-9-Demethyltubulosine, an Alkaloid from Alangium vitiense (A. Gray) Baillon (Alangiaceae)
Christiane Kan-Fan, Raimundo Freire, Henri-Philippe Husson,* Tozo Fujii, and Masashi Ohba
*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 structure of (-)-9-demethyltubulosine, isolated from the trunk bark of Alangium vitiense (Alangiaceae), was determined from an analysis of its MS, 1H and 13C nmr data and by a direct comparison with the synthetic racemic alkaloid.
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■ Nitrogen Bridgehead Compounds. Part 54. New Route for the Preparation of 2,3a,6a-Triazaphenalene Skeleton
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
A new approach for the synthesis of 2,3a,6a-triazaphenalene skeleton has been developed by the reaction of 9 with aldehydes.
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■ Consturuction of Indolizidine and Quinolizidine Ring Systems by an Intramolecular 1-Aza-1,3-diene Diels-Alder Reaction. Synthesis of (±)-Epilupinine
Masataka Ihara, Tomoko Kirihara, Keiichiro Fukumoto,* and Tetsuji Kametani
*Pharmaceutical Institute, Tohoku University, Aobayama, Sendai 980-8578, Japan
Abstract
Indolizidines and quinolizidines were synthesized through an intramolecular 1-aza-1,3-diene Diels-Alder reaction; the method provides an efficient route to (±)-epilupinine (16).
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■ Synthetic Study for 1-Methoxyindoles and 1-Methoxy-2-oxindoles
Masanori Somei,* Haruhuko Sato, Naoko Komura, and Chikara Kaneko
*Faculty of Pharmaceutical Sciences, Kanazawa University, 13-1 Takara-machi, Kanazawa 920-0934, Japan
Abstract
The first syntheses of 1-methoxypimprinine, 9-methoxy-β-carboline derivatives, and 3,3-disubstituted 1-methoxy-2-oxindoles are reported. A practical short step synthetic method for 1-methoxyindole-3-acetonitrile is also reported.
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■ A New Synthetic Method for Proline Derivatives via the Azomethine Ylide Intermediate Generated from Methyl N-(Trimethylsilylmethyl)iminoacetate
Nobuyuki Imai, Yoshiyasu Terao, and Kazuo Achiwa*
*Schol of Pharmaceutical Sciences, Schol of Pharmaceutical Sciences, 52-1 Yada, Shizuoka 422-8526, Japan
Abstract
Proline derivatives were found to be synthesized by the 1,3-dipolar cycloaddition of the azomethine ylide, produced from methyl N-(trimethylsilylmethyl)iminoacetate and benzyl bromide or a catalytic amount of trifluoroacetic acid, to conjugated olefins.
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■ Total Synthesis of (±)-α-Cyclopiazonic Acid
Hideaki Muratake and Mitsutaka Natsume*
*Research Foundation Itsuu Laboratory, 2-28-10 Tamagawa, Setagaya-ku, Tokyo 158, Japan
Abstract
(±)-α-Cyclopiazonic acid (2) was synthesized from 1-methoxycarbonyl-4-(3-oxo-1-butyl)indol (1) by way of 17, 18, and 19, using a reaction of MeLi with a pyrroline derivative 33 in the presence of BF3·Et2O.
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■ 1,4-Benzodithiin 1,1,4,4-Tetraoxide as Dienophile
Juzo Nakayama,* Yoichi Nakamura, and Masamatsu Hoshino
*Department of Chemistry, Faculty of Science, Saitama University, Saitama, Saitama 338-8570, Japan
Abstract
1,4-Benzadithiin 1,1,4,4-tetraoxide undergoes the Diels-Alder reaction with a series of dienes under mild conditions to provide the corresponding adducts in excellent yields. The adduct with anthracene is desulfonated to afford dibenzobarrelene, thus showing that the title compound functions as an acetylene equivalent.
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■ 1,3-Dipolar Cycloadditions of Nitrile Imines with Aldazines
Dipak Prajapati, Jagir Singh Sandhu,* Tetsuji Kametani, Hiromasa Nagase, Ken-ichi Kawai, and Toshio Honda
*Division of Drug and Pharmaceutical Chemistry, Regional Research Laboratory, Jorhat 785 006, Assam, India
Abstract
C-Acetyl and C-ethoxycarbonyl nitrile imines reacted with various aldazines and yielded 1,3-dipolar cycloadducts (3) in good yields. Their structures were fully established with the help of spectral analyses and finally structure (3a) was confirmed by X-ray crystallography.
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■ Efficient Synthesis of 1,1‘-Methylenebis-1H-pyrrole Derivatives
Carlos Gonzalez R. and Robert Greenhouse*
*División de Investigación, Syntex S.A. de C.V., Apartado Postal 272 (CIVAC), Jiutepec, Morelos, México, cp 62500, Mexico
Abstract
The title compounds may be prepared efficiently by the reaction of methylene chloride with the pyrrolyl anion generated under phase-transfer conditions. The spectral characteristics of these relatively unknown compounds are discussed.
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■ Natsucitrine-I, -II: New Acridone Alkaloids from Citrus natsudaidai Hayata
Motoharu Ju-ichi,* Mami Inoue, Yukari Fujitani, and Hiroshi Furukawa
*Faculty of Pharmaceutical Science, Mukogawa-Women’s University, 11-68 Koushien Kyuban-Cho, Nishinomiya, Hyogo 663-8179, Japan
Abstract
Two new acridone alkaloids, natsucitrine-I (1a) and natsucitrine-II (1b) were isolated from the root bark of Citrus natsudaidai and their structures were elucidated on the basis of the spectral and chemical studies.
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■ New Synthesis of Pyrido[2,3-d]pyrimidines. I. Reaction of 6-Alkoxy-5-cyano-3,4-dihydro-2-pyridones with Guanidine and Cyanamide
Pedro Victory,* Rosa Nomen, Octavio Colomina, Miquel Garriga, and Ana Crespo
*Departmento de Química Orgánica, Instituto Químico de Sarriá, Universitat de Barcelona, 08028 Barcelona, Spain
Abstract
The first step of a new synthesis of pyrido[2,3-d]pyrimidines, the substitution of the enolic alkoxyl group of 6-alkoxy-5-cyano-3,4-dihydro-2-pyridones (2) by guanidine and cyanamide is described. By this procedure a series of 2,4-diamino-5,6-dihydropyrido[2,3-d]pyrimidin-7(8H)-ones (6) and 6-cyanamino-5-cyano-3,4-dihydro-2-pyridones (3) have been synthesized. Products 3 have been isolated in this work for the first time, and tautomeric equilibrium with the cyanimino form has been detected in every case.
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■ Dipolar Cycloaddition Reaction of C-Acetylnitrile Imine with Aldonitrones
Dipak Prajapati and Jagir Singh Sandhu*
*Division of Drug and Pharmaceutical Chemistry, Regional Research Laboratory, Jorhat 785 006, Assam, India
Abstract
1,2,4-Δ2-Triazolines have been obtained in good yields by reacting aldonitrones and C-acetylnitrile imine.
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■ New Flavonoids from Bonannia graeca (L.) Halacsy
Maurizio Bruno,* Giuseppe Savona, Liliana Lamartina, and Francesca Lentini
*Dipartimento di Chimica Organica, Università digli Studi di Palermo, Via Archirafi 20 90123 Palermo, Italy
Abstract
A new C-geranylated flavanone, bonannione A, and two new C-geranylated dihydroflavonols, bonanniol A and B, were isolated from Bonannia Graeca (umbelliferae). The structures were deduced from spectral data and chemical evidence.
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■ Reaction of Azomethine N-Oxides. Part 4. A New Mode of Reaction of Azomethine N-Oxides with Dibenzoylacetylene
Ahmed Moukhtar Nour El-Din,* Aboul-Fetouh El-Said Mourad, and Ramadan Mekamer
*Chemistry Department, Faculty of Science, El-Minia University, El-Minia 61519, Egypt
Abstract
A new mode of 1,3-dipolar cycloaddition reaction with dibenzoylacetylene as dipolarophile was observed. The addition of this dipolarophile to different substituted open chain N-arylnitrones afforded 3-anilino-1,4-diphenylbutane-1,2,4-trione. Its formation by 1,3-dipolar cycloaddition reaction followed by interamolecular rearrangement and ylide decomposition is discussed. On the other hand, the conformationally rigid cyclic nitrones form either 4-oxazoline or enamine compounds.
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■ Reactions with Maleimides: Synthesis of Several New Fused Pyrazolidines, Δ2-Pyrazoline and Pyrazole Derivatives
Sami S. Ghabrial,* Hussein H. Moharram, and Suzan I. Aziz
*National Organization for Drug Control and Research, P.O. Box 29, Cairo, Egypt
Abstract
Several new pyrrolidinopyrazolidinedione, pyrrolidino-Δ2-pyrazolinedione and pyrrolopyrazoledione derivatives were synthesised via the reaction of different arylhydrazones with N-arylmaleimides. The structures of the synthesized heterocyclic derivatives were established on the basis of elemental analyses and spectroscopic data studies.
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■ Nitrogen Bridgehead Compounds. Part 53. New Synthesis of 2,3a,6a-Triazaphenalene-3-thiones
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
Starting from α-chloroenamine 1 and iminochloride 13 a new approach of the neutral 2,3a,6a-triazaphenalene ring has been described.
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■ Potential Anticancer Agents: Pharmacologically Active Benzo[b]thiophene Derivatives
Sayeed Saraf,* Mustafa Edun, and Muhammad Akram Khan
*Department of Chemistry, Faculty of Science, University of Kuwait, Safat 13060, P.O. Box 5969, Kuwait
Abstract
The synthesis of potential antitumor compounds namely, 5-bis[2-(chloroethyl)amino-(3-benzo(b)thienyl)]-α-aminopropionic acid and 5-bis[2-(chloroethyl)amino-benzo(b)thiophene)]-3-propionic acid, using the key intermediate 5-nitro-3-methylbenzo(b)thiophene, is described.
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■ Stereospecific Synthesis of Thiazolidine-2-thiones
Ernesto Brunet, M. Carmen Carreño, and José Luis Garcia Ruano*
*Departamento de Química Orgánica, Facultad de Ciencias, Universidad Autónoma de Madrid, Cantoblanco, 28049-Madrid, Spain
Abstract
The synthesis of thiazolidine-2-thiones from vic-iodoalkanecarbamates, stereospecifically obtained from cis and trans-butene, is reported. Reaction of the iodo-derivatives with potassium ethylxanthate and sodium hydroxide, allowed the stereospecific formation of thiazolidine-2-thiones. The stereochemistry of the latter reaction could be controlled by the experimental conditions. 4-Phenylthiazolidine-1-thione was obtained from the vic-iodoalkanecarbamate generated from styrene. A separable mixture of thiazolidin-2-ones (major camponent) and thiazolidine-2-thiones was obtained by reduction with NaBH4 from the substitution product of vic-iodoalkanecarbamates with potasium ethylxanthate.
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■ A Novel Access to 3-Benzazepines and to 3-Benzoxepines via SRN1 Reactions
René Beugelmans and Helène Ginsburg*
*Institut des Chimie des Substances Naturelles, C.N.R.S., 1 avenue de la Terrasse, Bat. 27, 91198 Gif-sur-Yvette Cedex, France
Abstract
A common intermediate formed by an SRN1 reaction between halohomoveratic acid and various ketone enolates leads to either benzazepines (5a,b,c) or to benzoxepines (8a,b,c) in yields ranging from 50 to 70%.
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■ Isolation of 2,18-Dithia[3.1.3.1]metacyclophane and 2,3,19,20-Tetrathia[4.1.4.1]metacyclophane from Coupling Reactions Directed toward the Synthesis of Strained Thiacyclophanes
Yee-Hing Lai* and Teong-Beng Soo
*Department of Pharmacy, National University of Singapore, Lower Kent Ridge Road, 119260, Singapore
Abstract
Intramolecular coupling reactions of bis(3-bromomethylphenyl)methane or bis(3-mercaptomethylphenyl)methane failed to yield the strained thia[3.1]- and dithia[4.1]metacyclophanes respectively. Two previously unknown medium-sized cyclophanes, namely a dithia[3.1.3.1]metacyclophane and a tetrathia[4.1.4.1]metacyclophane, have been isolated and characterized. Variable temperature NMR studies have revealed that both these metacyclophanes have a very high degree of conformational mobility.
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■ On the Crystal Structure of the Diels-Alder Adduct of the Hydrogenated Lactams Obtained by Reductive Photocyclization of N-Cyclohex-1-enylbenzamide
Takeaki Naito, Ichiya Ninomiya,* Mitsunobu Doi, and Masatoshi Inoue
*Kobe Women’s College of Pharmacy, Motoyamakita, Higashinad, Kobe, Hyogo 658, Japan
Abstract
The stereostructure of the Diels-Alder adduct (5) of the hydrogenated lactam (3) with maleic anhydride was unequivocally established by X-ray analysis, thus confirmed the stereochemical course of reductive photocyclization of the enamide (1).
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■ Antiinflammatory 2,3-Dihydro-1H-pyrrolizins. II: Addition of 6,7-Diphenyl-2,3-dihydro-1H-pyrrolizine to Domethyl Acetylenedicarboxylate and Diethyl Azosicarboxylate
Gerd Dannhardt* and Ludwig Steindl
*Naturwissenschaftliche Fakultät IV, Universität Regensburg, Universitätsstraße 31, D-93040 Regensburg , Germany
Abstract
The addition of the litle compound to the acetylene and the azo derivative,resp., leads to C5 functionalized dihydropyrrolizines. Competitive 1 : 1 and 1 : 2 adduct formation is observed using the diethyl azodicarboxylate. A significant antiinflammatory activity is shown for the 5-hydrazopyrrolizine derivative (1 : 1-adduct) .
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■ Reactivity of Conjugated Enaminothioamides toward Activated Acetylenic Compounds
Serge Coen, Bernard Ragonnet, Catherine Vieillescazes, and Jean-Pierre Roggero*
*Faculté des Sciences, Laboratorie de Chimie Organique, 33, rue Louis Pasteur, 84000 Avignon, France
Abstract
Conjugated enaminothioamides react in high-yield with acetylenedicarboxylic acid or its ester derivatives to give 2-enaminathiazolin-4-ones. A similar reaction is observed with propiolic acid and derivatives, giving 2-enamino-1,3-thiazin-4-ones. A substituted thiazoline is quantitatively obtained from propargyl bromide.
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■ Proton Magnetic Resonance Spectra of Benzo(b)thiophene Derivatives
Sayeed Saraf,* Saleh Al-Mousawi, and Muhammad Akram Khan
*Department of Chemistry, Faculty of Science, University of Kuwait, Safat 13060, P.O. Box 5969, Kuwait
Abstract
Proton magnetic resonance spectra of substituted benza(b)thiophenes is reviewed.
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■ Syntheses of Ellipticine and Related Pyridocarbazole Alkaloids — A Review
Gordon W. Gribble and Mark G. Saulnier
*Department of Chemistry, Dartmouth College, Hanover, New Hampshire 03775, U.S.A.
Abstract
Synthetic approaches to the anticancer alkaloid ellipticine and related pyridocarbazoles covering the period 1977 through November 1984 are reviewed.