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. 26, No. 9, 1987
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■ Synthesis of Pyrrole, Pyrrolo[3,4-b]pyridine and Pyrrplo[3,2-b]pyridine Derivatives
Afaf A. A. Elbannany and Laila I. Ibrahim
*Department of Chemistry, Faculty of Science, Helwan University, Ain-Helwan, Cairo, Egypt
Abstract
The reaction of ethyl benzylidenecyanoacetate (1) with hippuric acid (2) in acetic anhydride leads to pyrrole derivative 5 together with the acetyl derivative 6. Treatment of 5 with ethyl acetoacetate, acetylacetone and malononitrile give the pyrrolo[3,4-b]pyridines 7, 10 and 11 respectively. Coupling of 5 and 7 with benzenediazonium chloride yield the phenylazo derivatives 8 and 9 respectively. On the other hand, ethyl cyanoacetate reacts with 5 to give the pyrrolo[3,2-b]pyridine derivative 13.
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■ Flash Vaccum Pyrolysis of α-Toluenesulfonyl Azide
Rudolph A. Abramovitch, Raymond R. Harder, and William D. Holcomb
*Department of Chemistry, Clemson University, Clemson, SC 29631, U.S.A.
Abstract
The flash vacuum pyrolysis of α-toluenesulfonyl azide (1) gave bibenzyl (2) , 2-(β-phenethyl)pyridine (3), and 2,1-benzisothiazole 2,2-dioxide (4); an authentic sample of the latter was prepared from 2-bromo-α-toluenesulfonamide and potassium amide in liquid ammonia. FVP of benzeneaulfonyl azide using benzene as carrier gas gave some diphenylamine, but not in the absence of benzene.
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■ Macrocentrine: An Unusual Diterpenoid Alkaloid
Michael H. Benn, Francis Okanga, John F. Richardson, and Raphael M. Munavu
*Department of Chemistry, The University of Alberta, Calgary, Alberta, T2N, 1N4, Canada
Abstract
Macrocentrine, a new diterpenoid alkaloid from Delphinium macrocentrum Oliv., has been shown to possess an unusual dictyzine-like structure.
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■ Imidoylation Reaction: (±)-Lupinine Synthesis
Mansour Haddad, Jean-Pierre Célérier, and Gérard Lhommet
*associé au CNRS, 4 Place Jussieu, Laboratoire de Chimie des Hétérocycles, Université P. et M. Curie, case courrier 43, 4 Place Jussieu, F-75252 Paris Cedex 05, France
Abstract
A short and simple synthesis of (±)-lupinine is described. The key intermediate in this sequence is an exocyclic vinylogous urethane, prepared by an imidoylation reaction which lnvolves an intramolecular cyclization.
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■ Cycloheptatriene Furanones and Bicyclo[5.3.0]decatrienone; Unusual Cycloaddition with 4-Phenyl-1,2,4-triazoline-3,5-dione (PTAD)
Antonio Saba and Ottorino De Lucchi
*Department of Chemistry, University of Sassari, Via Vienna 2, I-07100 Sassari, Italy
Abstract
Cycloheptatriene furanones (1), (2), (3) and bicyclo[5.3.0]decatrienone (4) react with PTAD to afford the formal (4+2) or (6+2)-tropilidene cycloadducts in contrast with other substituted cycloheptatrienes which give only norcaradiene type adducts.
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■ General Synthesis of 2-Hydroxy, 3-Hydroxy-, and 4-Hydroxyalkyldimethylsulfonium Salts from Cyclic Ethers
Kentaro Okuma, Shi-ichi Nakamura, and Hiroshi Ohta
*Department of Chemistry, Faculty of Sciences, Fukuoka University, 8-19-1 Nanakuma, Jonan-ku, Fukuoka 814-0180, Japan
Abstract
Epoxides, oxetane, and tetrahydrofuran were successfully transformed to 2-hydroxy-, 3-hydroxy-, and 4-hydroxyalkyldimethylsulfonium triflates by the reaction with dimethyl sulfide in the presence of trifluoromethanesulfonic acid. Several reactions of these salts are described.
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■ High-pressure Diels-Alder Reactions of 2-Methylthio- and 2-Acetoxyfuran. An Efficient Entry to 4-hydroxycyclohexanones
Hiyoshizo Kotsuki, Yuichiro Mori, Tatsuya Ohtsuka, Hitoshi Nishizawa, Masamitsu Ochi, and Kiyoshi Matsuoka
*Department of Material Science, Faculty of Science, Kochi University, 2-5-1, Akebono-cho, Kochi 780-8520, Japan
Abstract
Diels-Alder reactions of 2-methylthio- and - 2-acetoxyfuran were performed at 15 kbar and room temperature. The adducts were proved to be a useful precursor of 4-hydroxycyelohexanones.
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■ Oxonitine Revisited: Its Mechanism of Formation from Aconitine
Palaniappan Kulanthaivel 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
Oxidation of aconitine (2) to oxonitine (1) with KMnO4 proceeds by three mechanisms, involving the CH3 and CH2 carbons of the N-ethyl group and the carbon of the solvent as sources of the N-CHO group of oxonitine.
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■ A One-step Synthesis of Pyrimido[4,5-c]isoquinoline Ring System by Reaction of 6-(N-Methlfurfurymino)uracils with DMAD
Michihiko Noguchi, Seiji Nagata, and Shoji Kajigaeshi
*Department of Applied Chemistry, Faculty of Engineering, Yamaguchi University, 2-16-1 Tokiwadai, Ube, Yamaguchi 755-8611, Japan
Abstract
Several pyrimido[4,5-c]isoquinoline derivatives were obtained from the reaction of 6-(N-methylfurfurylamino)uracils 1 and DMAD in refluxing ethanol. The formation of the pyrimidoisoquinoline system was due to a sequence of the initial Diels-Alder reaction of the furan moiety of 1 and DMAD, and the successive intramolecular Michael addition.
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■ Competitive Electrocyclic Reaction of o-Quinodimethane: Sequential Electrocyclic-double[3,3]sigmatropic Reactions for the Construction of 4-Alkylideneisochroman-3-ones
Kozo Shishido, Hironori Komatsu, Keiichiro Fukumoto, and Tetsuji Kametani
*Pharmaceutical Institute, Tohoku University, Aobayama, Sendai 980-8578, Japan
Abstract
Thermolysis of allyl 1-alkenylbenzocyclobutenyl-1-carboxylate (5a-f) produced a mixture of 4,4-disubstituted isochroman-3-ones (6a-f), dihydronaphthalenes (8a-f), and 4-alkylideneisochroman-3-ones (7a-f) in good yield. The third product (7a-f) was generated via an unprecedented sequential electrocyclic-double[3,3]sigmatropic reactions of Z-o-quinodimethane.
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■ First Stable Selenabenzene Analogue, 2-Cyano-1-methyl-4-phenyl-1-selenanaphthalene: Synthesis and Reactions
Mikio Hori, Tadashi Kataoka, Hiroshi Shimizu, Kazuhiro Tsutsumi, and Shinya Imaoka
*Department of Pharmacognosy, Gifu College of Pharmacy, 6-1 Mitahora-higashi 5-chome, Gifu 502-8585, Japan
Abstract
2-Cyano-1-methyl-4-phenyl-1-selenanaphthalene (1) was synthesized as the first isolable selenabenzene. Its ylidic structure was characterized by the spectral and chemical evidence. The thermal reaction of the selenanaphthalene 1 afforded [1,2]- (5) and [1,4]-rearranged products (6) together with dimeric compounds 7. The photochemical reaction afforded the different [1,4]-rearranged product, ketenimine 9 and the photo-oxygenated product, 4-phenylcoumarin (10).
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■ Syntheses of (—)-1-epi-Swainsonine and (+)-1,8-Di-epi-swainsonine
Nobuo Ikota and Akira Hanaki
*National Institute of Radiological Sciences, 9-1, Anagawa-4-Chome, Inage-ku, Chiba 263-0024, Japan
Abstract
The syntheses of (-)-1-epi-swainsonine and (+)-1,8-di-epi-swainsonine have been achieved from (S)-glutamic acid.
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■ N-Halosuccinimide-sulfuric Acid: An Efficient Reagent for the Synthesis of Fused Benzothiazoles
Javier Garín, Carmen Guillén, Enrique Meléndez, Francisco L. Merchán, Jesús Orduna, and Tomás Tejero
*Department of Organic Chemistry, Instituto de Ciencias de Materiales de Aragón, University of Zaragoza, 50009-Zaragoza, Spain
Abstract
A new version of Hugershoff’s synthesis is reported. The cyclizing agent, N-halosuccinimide/sulfuric acid permits the preparation of complex fused benzothiazoles in very good yields.
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■ Synthesis of 5-Oxa-13-thiaprotoberberine Derivatives
János Szabó, Gábor Bernáth, and Pál Sohár
*Institute of Pharmaceutical Chemistry, University of Szeged, H-6720 Szeged, Eötvös u. 6, Hungary
Abstract
With phosgene or aliphatic aldehydes, 6,7-dimethoxy-2- (2-hydroxyphenyl)-3,4-dihydro-2H-1,3-benzothiazine afforded novel 10,11-dimethoxy-6H,8H,13aH[1,3]benzoxazino[4,3-b][1,3]benzothiazine derivatives, members of a new heterocyclic ring system.
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■ Studies on the Synthesis of Benzolactam Rings. II. Synthesis of 1,4-Dihydro-3(2H)-iaoquinolinone Derivatives
Yasuko Kamochi and Yasuo Watanabe
*Daiichi College of Pharmaceutical Sciences, 22-1 Tamagawa-cho, Minami-ku, Fukuoka 815-0037
Abstract
A new synthesis of 1,4-dihydro-3(2H)-isoquinolinones by the amidomethylation with arylacetamide or arylacetonitrile and paraformaldehyde in some acid-catalysts is described.
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■ Intermolecural Rhodium Carbenoid Insertions into the N-H Bond and β-Lactams. Synthesis of O-2-Isocephems
Micahel Hrytsak and Tony Durst
*Ottawa-Carleton Chemistry Institute, Department of Chemistry, University of Ottawa, Ottawa, Ontario, K1N 6N5, Canada
Abstract
A new, convergent synthesis of 0-2-isocephems is reported. Rhodium carbenoid insertion of α-diazo-β-ketoesters into the N-H bond of a preformed β-lactam, followed by cyclization of the resulting enol-alcohols by Mitsunobu reaction gives the title compounds.
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■ A Derivative of Azepine and Its Application as a Specific Optical Resolution Agent
Franco Fernández and Cristina Pérez
*Departamento de Química Orgánica , Facultad de Farmacia, Universidad de Santiago de Compostela, E-15706, Santiago de Compostela, Spain
Abstract
The synthesis o f (-)-(2S,trans)-perhydro-2-isopropyl-5-methylazepln-1-amine (I) and its use as a specific optical resolution agent of ketones is described. A method for the resolution of ketones and its application to three ketones is described. This method also involves the synthesis and separation of the pairs of hydrazones diastereomers followed by removal of hydrazines by hydrolysis to give the individual enantiomers of II, III and IV with high chiral purities.
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■ 3-Phenyl-5-carbomethoxymethylene-5H-isoxazolo[4,5-e][1,4]diazepine-6,8(4H,7H)-dione: A New Seven Membered Binuclear System
Rodolfo Nesi, Donatella Giomi, Laura Quartara, Sandro Papaleo, and Piero Tedeschi
*CNR, Centro di Studio Sulla Chimica e la Struttura dei Composti Eterociclici e lolo Applicazioni, c/o Dipartimento di Chimica Organica "Ugo Schiff", Università di Firenze, Via Gino Capponi 9, I-50121 Firenze, Italy
Abstract
The ring closure of the Michael-type adduct (5), easily available from the nitro ester (2) through the corresponding amino derivatives (3) and (4), afforded the previously unreported heterocyclic system (6) in good yields; some spectral features of the new products were emphasized.
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■ 1,3-Dipolar Cycloaddition of 2-Diazopropane to Coumarin. The Synthesis of Derivatives of [1]Benzopyrano[4,3-c]pyrazol-4(3H)-one and [1]Benzopyrano[3,4-c]pyrazol-4(1H)-one
Andreja Cercek, Branko Stanovnik, Anton Stimac, and Miha Tisler
*Department of Chemistry, E. Kardelj University, Murnikova 6, 61000 Ljubljana, Slovenia
Abstract
1,3-Dipolar cycloaddition of 2-diazopropane (2) to unsubstituted coumarin (1) is taking place nonregiospecifically to give a mixture of cycloadducts 3 and 5. These are thermally transformed into cyclopropane derivative 6 and 4-isopropyl derivative 7, respectively. In the presence of potassium hydroxide or 2 substituted pyrazoles 8, 9 and 10 are produced. The oxidation of 3 and 5 with bromine in acetic acid gives tricyclic systems 15 and 16.
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■ The Four 6-Halo-7-nitroquinoxalines
Raymonde Nasielski-Hinkens, Pierre Levêque, Daniel Castelet, and Jacques Nasielski
*Laboratoire de Chimie Organique CP 160, Université Libre de Bruxelles, Av. F.D. Roosevelt, 50, B-1050 Bruxelles, Belgium
Abstract
The study of relative nucleofugicities of nitro and halogen in quinoxalines required the synthesis of the four 6-halo-7-nitroquinoxalines 2a-d. The fluoro-, chloro- and bromo-derivatives were made from the commercially available or readily accessible 1,2-diamino-4-halobenzenes, using the nitration of the corresponding p-toluenesulfonamides. This scheme failed in the case of the iodo compound because of extensive nitrodeiodination. The synthesis of 6-iodo-7-nitroquinoxaline was finally achieved from m-fluoroiodobenzene by taking advantage of the high reactivity of fluorine, compared to iodine, in 2,4-dinitrohalobenzenes.
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■ Synthesis of Quino[2,3-b][1,5]benzoxazepines: A Novel Tetracyclic Ring System
Giampiero Pagani Zeccini, Ines Torrini, and Mario Paglialunga Paradisi
*Dipartimento Farmacochimico, Tossicologico e Biologico, Università degli Studi di Palermo , Via Archirafi 32, 90123 Palermo, Italy
Abstract
The one-pot synthesis of quino[2,3-b-][1,5]benzoxazepines 3a-c from 2-chloroquinoline-3-carbaldehydes 1a-c and ortho aminophenol is described. Reduction of 3a-c with lithium aluminum hydride afforded 11,12-dihydroquino-[2,3-b][1,5]benzoxazepines 4a-c in high yields.
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■ Ethylation of Pyrazines Using Alkylmetals, Such as Triethylaluminum, Diethylzinc, and Triethylborane
Akihiro Ohta, Masakatsu Ohta, Yohsiaki Igarashi, Kaemi Saeki, Kayo Yuasa, and Tomoko Mori
*Tokyo University of Pharmacy and Life Science, 1432-1 Horinouchi, Hachioji, Tokyo 192-0392, Japan
Abstract
Triethylaluminum, diethylzinc and triethylborane were used for the ethylation of pyrazines. Among these reagents, triethylborane gave the best results.
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■ Rearrangement of a Substituted Epoxytetrahydropyran to the Corresponding Tetrahydrofurancarbaldehyde
Urs Séquin and Andreas Schneider
*Institut für Organische Chemie, Universitat Basel, St. Johanns-Ring 19, CH-4056 Basel, Switzerland
Abstract
The aluminum chloride catalyzed reaction of a substituted 3,4-epoxytetrahydropyran with N,N-dimethyl-trimethylsilylamine did not lead to the expected silylated β-aminoalcohol but rather to a tetrahydrofurancarbaldehyde.
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■ Chiral Synthesis of (R)-(+)-Citronellal via Stereoselective Protonation
Seiichi Takano, Hiroyuki Chiba, Junko Kudo, Michiyasu Takahashi, and Kunio Ogasawra
*Pharmaceutical Institute, Tohoku University, Aobayama, Sendai 980-8578, Japan
Abstract
Protonation of the enolates (8) and (12) generated from an epimeric mixture of the α,γ-disubstituted γ-lactone (7) is shown to yield the syn-α/γ-disubstituted γ-lactone (10) predominant over the anti-α/γ-disubstituted γ-lactone (11). When the silyl enol ether (12) generated in situ is protonated with trifluoroacetic acid, the best selectivity is obtained. The syn-epimer (10) thus obtained is converted into (R)-(+)-citronellal (17) in four steps of reactions.
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■ An Unexpected Reaction between 2,3-Dihydro-2,2,4-trimethyl-1H-1,5-benzodiazepine and Mercaptoacetic Acid
Alba Chimirri, Silvana Grasso, Rosaria Ottanà, Giovanni Romeo, Gionanni Valle, and Maria Zappalà
*Dipartimento Farmaco-Chimico, Università di Messina, Viale Annunziata, 98168 Messina, Italy
Abstract
The reaction of 2,3-dihydro-2,2,4-trimethyl-1H-1,5-benzodiazepine with mercaptoacetic acid gave two unexpected main derivatives 2,3-dihydro-4-(2,3,4,5-tetrehydro-2,2-dimethyl-4-oxo-3-thienyl)-2,2-dimethly-1H-1,5- benzodiazepine and 1,1-dimethyl-1H,3H-thiazolo[3,4-a]benzimidazole. The structures of obtained compounds have been assigned by means of spectroscopic measurements. A mechanism for their formation is also suggested.
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■ Benzodiazocines
Silvana Grasso, Maria Zappalà, and Alba Chimirri
*Dipartimento Farmaco-Chimico, Università di Messina, Viale Annunziata, 98168 Messina, Italy
Abstract
Synthesis and stereochemistry of benzodiazocines are reviewed.
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■ X-Ray Crystal Structures of C19-Diterpenoid Alkaloids
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 X-ray diffraction analysis of 30 C19-diterpenoid alkaloids is reviewed. During the course of structure determination, many naturally-occurring alkaloids have been correlated with alkaloids whose structures were established by X-ray crystal studies. The relative stereochemistry of these alkaloids at all the centres can be assumed to be correct. The absolute stereochemistry has been established for some of the alkaloids.