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. 4, 1987
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■ Cycloaddition Reaction of 1,2,4-Triazolium Phenacylides with Cinnamic Esters
Gheorghe Surpateanu, Alain Lablache-Combier, Pierre Grandclaudon, and Bernard Mouchel
*Laboratoire de Chimie Organique, Faculté de Technologie Chimiqui, Institut Polytechnique de Iasi, Splai Bahlui Stg .71, 6600 Iasi, Romania
Abstract
1,2,4-Triazolium phenacylides generated in situ from the corresponding 1,2,4- triazoliumsalts reacted with cinnamic esters to afford tetrahydropyrroiotriazoie derivatives. These [3+2] dipolar cycloaddition reactions occur stereo- and regiospecific, giving only derivatives of the type (4a-d). The stereo- and regiochemistry of these products was mainly elucidated by 1H-NMR, 13C-NMR and DEPT analysis.
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■ Nitrogen Bridgehead Compounds Part 59. Nucleophilic Substitution Reactions of 9-Bromo-6,7,8,9-tetrahydro-4H-pyrido[1,2-a]pyrimidin-4-ones
István Bitter, Gábor Tóth, István Hermecz, and Zoltán Mészáros
*Department of Organic Chemical Technology, Technical University of Budapest, H-1521 Budapest, Gellért tér 4, Hungary
Abstract
Halogen replacement of 9-bromo-6,7,8,9-tetrahydro-4H-pyrido [1,2-a] pyrimidin-4-ones with C-, N-, 0-, and S-nucleophiles can be readily accomplished.
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■ A New Route to 4-Oxygenated β-Carbolines: The Total Synthesis of Crenatine
Yasuoki Murakami, Yuusaku Yokoyama, Chiyoko Aoki, Chiemi Miyagi, Toshiko Watanabe, and Taichi Ohmoto
*School of Pharmaceutical Sciences, Toho University, 2-2-1, Miyama, Funabashi, Chiba 274-8510, Japan
Abstract
Crenatine, a new type of β-carboline alkaloid having an oxygen function at its C4-position, was synthesized using ethyl 1-benzylindole-2-carboxylate as a starting material via cyclization of C2-substituent to C3-position of indole nucleus and AlCl3-catalyzed debenzylation for N-protected indoles.
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■ Total Synthesis of 7-Hydroxy-"9-oxa"-anthracyclinone and Glycoside Derivatives
Hanh Dufat-Trinh Van, Elisabeth Srguin, 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
The racemic title aglycone was prepared in seven steps from quinizarin 5 and its resolution achieved after glycosidation with 3,4-di-O-acetyl-2-deoxy-L-fucose.
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■ A Novel Ring Formation of 1,2-Dihydroquinoxalines
Shizuaki Murata, Takashi Sugimoto, and Sadao Matsuura
*Graduate School of Environmental Studies, Nagoya University, Chikusa, Nagoya, Aichi 464-8601, Japan
Abstract
Reaction of O-phenylenediamine with 2,3-epoxyaldehydes gives 2-hydroxyalkyl-1,2-dihydroquinoxalines, while the reaction with 2,3-epoxyesters gives either dihydroquinoxaline derivative or the uncyclized hydroxyamino ester.
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■ Chemistry of Penicillin Diazoketones. Part II. from Beta-lactam to Beta-lactone
Hans Ludescher, Ching-Pong Mak, Gerhard Schulz, and Hans Fliri
*Sandoz Forschungsinstitut, 1235 Wien, Brunnerstraße 59, Austria
Abstract
Carbenes formed by transition metal catalyzed decomposition of penicillin-derived diazoketones can undergo different reaction pathways, depending on the presence or absence of the gem-dimethyl group. In the presence of the gem-dimethyl group products are formed via a sulfur ylide intermediate. Bis-nor derivatives undergo Wolff-rearrangement into ketenes which react further to give isopenams. If an hydroxyethyl substituent is present at C-6 of the starting material the original β-lactam is converted into a β-lactone.
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■ Total Syntheses of (±)-Agroclavine-I, (±)-6-Nor-chanoclavine-II, and (±)-Chanoclavine-II
Masanori Somei, Fumio Yamada, and Yoshihiko Makita
*Faculty of Pharmaceutical Sciences, Kanazawa University, 13-1 Takara-machi, Kanazawa 920-0934, Japan
Abstract
The first total syntheses of (±)-6-norchanoclavine-II and (±)-chanoclavine-II are achieved. Total synthesis of (±)-agroclavine-I is also reported.
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■ Nitriles in Heterocyclic Synthesis: Synthesis of Some New Pyridine, Pyridazine, and Pyrimidine Derivatives
Mona Hassan Mohamed, Nadia Sobhy Ibrahim, and Mohamed Hilmy Elnagdi
*Department of Chemistry, Faculty of Science, University of Cairo, Giza, Egypt
Abstract
Pyrimidine, pyridazine, pyridine and - pyrazolopyrimidine derivatives were synthesised from 3-amino-2-cyano-4-ethoxycarbonylcrotononitile (1) as a staning material.
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■ Nitriles in Heterocyclic Synthesis: Novel Synthesis of Benzo[c]coumarin and of Benzo[c]pyrano[3,2-c]quinoline Derivatives
Ebtisam Abdel Aziz Hafez, Mohamed Hilmy Elnagdi, Abdel Ghani Ali Elagamey, and Fathy Mohamed Abdel Aziz El-Taweel
*Department of Chemistry, Faculty of Science, University of Cairo, Giza, Egypt
Abstract
Novel syntheses of beneo[c]coumarins and benzo[c]pyrano[3,2-c]quinolines utilizing 3-cyano-4-methylcoumarin and pyrano[3,2-c]quinolin are reported.
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■ Preparation of 2,5-Diacylslelnophenes by Condensation of α,α‘-Diketo Selenides with Glyoxal
Juzo Nakayama, Masahiro Shibuya, and Masamatsu Hoshino
*Department of Chemistry, Faculty of Science, Saitama University, Saitama, Saitama 338-8570, Japan
Abstract
The reaction of selenium oxychloride with 2 equiv. of ketones affords α,α’-diketo selenide dichlorides (1) in excellent yields. Portionwise addition of 1 to a stirred two-phase mixture of an aqueous sodium dithionite solution and benzene gives α,α’- diketo selenides (2) in good yields. The base-catalyzed condensation of 2 with glyoxal provides 2,5-diacylselenophenes (3) in moderate yields.
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■ A Facile Synthesis of 4-Mercaptoindoles
Masakatsu Matsumoto and Nobuko Watanabe
*Sagami Central Research Center, 4-4-1 Nishi-Ohnuma, Sagamihara, Kanagawa 229-0012, Japan
Abstract
4-(Ethoxythiocarbonylthio)-1-(p-toluenesulfonyl)indole was synthesized and used as a stable equivalent of 4-mercaptoindoles.
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■ Isomerization of N-Acly-1,2,5,6-tetrahydropyridines to N-Acyl-enamines by Palladium on Carbon
Klaus Th. Wanner and Annerose Kärtner
*Institut für Pharmazie und Lebensmittelchemie, Universität München, Sophienstraße 10, D-80333 München, Germany
Abstract
Allylic amides 1 were rearranged to enamides 2 using palladium on carbon as catalyst.
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■ Asymmetric α-Amidoalkylation. Synthesis of α-Substituted Piperidines of High Enantiomeric Purity
Klaus Th. Wanner and Annerose Kärtner
*Institut für Pharmazie und Lebensmittelchemie, Universität München, Sophienstraße 10, D-80333 München, Germany
Abstract
A stereoselective α-amidoalkylation was performed employing the chiral and cyclic enamide 1. The resulting amides 6 were employed in the synthesis of the title products.
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■ Synthesis of Guaipyridine, Epiguaipyridine, and Related Compounds
Junko Koyama, Teruyo Okatani, Kiyoshi Tagahara, Yukio Suzuta, and Hiroshi Irie
*Kobe Women’s College of Pharmacy, Motoyamakita, Higashinad, Kobe, Hyogo 658, Japan
Abstract
Synthesis of sesquiterpene alkaloids, guaipyridine, epiguaipyridine, and related compounds, was accomplished by application of a method for constructing cycloalkenopyridines by thermal rearrangement of oxime 0-allyl ethers .
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■ Synthesis of Pyrrolidine Derivatives by Improves Aminoselenation via Addition of Boron Trifluoride Complex of Dihomoallylcuprate to Aldimines Containing α-Hydrogen
Makoto Wada, Hideki Aiura, and Kin-ya Akiba
*Department of Chemistry, Faculty of Science, Hiroshima University, 1-3-1 Kagamiyama, Higashi-Hiroshima, Hiroshima 739-8526, Japan
Abstract
Boron trifluoride complex of magnesium dihomoallylcuprate, (CH2=CHCH2CH2)2CuMgBr.BF3, reacted wlth aldimines containing α-hydrogen to afford the corresponding addltion products in good yields. The addition products were converted to pyrrolidine derivatives by treatment with phenylselenenyl chloride in the presence of trifluoroacetic acid and silica gel.
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■ Epimedins A, B and C, Flavonoid Glycosides of Epimedium koreanum Herbs
Yoshiteru Oshima, Maki Okamoto, and Hiroshi Hikino
*Pharmaceutical Institute, Tohoku University, Aobayama, Sendai 980-8578, Japan
Abstract
Three new flavonoid glycosides, epimedins A, B and C, have been isolated from Epimedium koreanum herbs, the structures of which have been elucidated on the basis of chemical and spectroscopic data as shown in fomulas I, II and III, respectively
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■ Preparation of α-Quinque- and α-Septithiophenes and Their Positional Isomers
Juzo Nakayama, Yoichi Nakamura, Shigeru Murabayashi, and Masamatsu Hoshino
*Department of Chemistry, Faculty of Science, Saitama University, Saitama, Saitama 338-8570, Japan
Abstract
α-Quinque- and α-septithiophenes were synthesized in four steps starting from α-bi- and α-terthiophenes, respectively. One of positional isomers of each oligothiophene described above is also synthesized.
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■ Thalocsessine, a New C20-Diterpenoid Alkaloid from Thalictrum sessile Hayata
Yang-Chang Wu, Tian-Shung Wu, Masataka Niwa, Sheng-Teh Lu, and Yoshimasa Hirata
*Faculty of Pharmacy, Meijo University, 150 Yagoto, Tempaku-ku, Nagoya, Aichi 468-8503, Japan
Abstract
The structure of thalicsessine, a new C20-diterpenoid alkaloid isolated from Thalictrum sessile Hayata (Ranunculaceae), together with a known diterpenoid alkaloid spiradine A, was elucidated on the basis of spectral and chemical evidence. This is the first report on diterpenoid alkaloids obtained from the plant of the genus Thalictrum.
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■ Two Acyclic Analogues of 2-β-D-Ribofuranosylthiazole-4-carboxamide (Tiazofurin)
Lajos Kovács, Pál Herczegh, Gyula Batta, and István Farkas
*Department of Organic Chemistry, Lajos Kossuth University, P.O.Box 20, H-4010 Debrecen, Hungary
Abstract
Two different synthetic strategies have been elaborated for the synthesis of 2-[(2-hydroxyethoxy)methyl] thiazole-4-carboxamide (4) and 2-{[2-hydroxy-1-(hydroxymethyl) ethoxy]methyl}thiazole-4-carboxamide (5).
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■ Molecular Structure and Stability of Isoxazolium Enolates
Gury Zvilichovsky and Mordechai David
*Department of Medicinal Chemistry, The Hebrew University, P.O. Box 12065, Jerusalem 91120, Israel
Abstract
Single crystal X-ray diffraction analysis, spontaneous formation and solvolytic stability of the dipolar Schiff base isoxazolium enolate, derived from aldehydes and ketones were studied. The cross conjugated betaine (V) derived from 2,4-dimethoxybenzaldehyde by condensation with 4-phenyl disic acid (II), showed coplanarity and cis configuration. The X-ray results revealed exceptionally long bonds between the two units, that of the anion and that of the cation. Results obtained by omega beta calculations were in line with the experimental observations. Cyclopentanone was the only ketone that gave a stable dipolar condensation product. Derivatives of aromatic aldehydes are generally more stable probably for the reason the coplanarity of the cationic part of the molecule is more feasible. There is evidence for attractive C-H..0 interactions which might contribute to stability in aldehyde derivatives (IIIa). Ketisates (IIlb), which were synthesized by an alternative route were found to hydrolyze spontaneously when dissolved in moist solvents. Analogous betaines that have N1-substituted pyrazole instead of isoxazole were also studied, leading to a scheme for facile decomposition of oximes and hydrazones.
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■ Interaction of Thietes with Electron-deficient Molecules
Sharon Marinuzzi-Brosemer, Bhalchandra H. Patwardhan, Kenneth A. Greenberg, and Donald C. Dittmer
*Department of Chemistry, Syracuse University, Syracuse, New York 13244-1200, U.S.A.
Abstract
Thietes (thiacyclobutenes) give substituted 1,4-benzodioxanes when treated with the o-quinones, o-chloranil and o-bromanil, but dehydrogenation occurs vith the p-quinane, 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (DDQ), as indicated by the formation of the hydroquinone in good yield. Colored solutions are formed when thietes are mixed with the electron acceptors DDQ, tetracyanoethylene (TCNE) and tetracyanoquinodimethane (TCNQ). The stoichiometry of the charge transfer complexes appears to be 1:1 (donor:acceptor) according to Job plots. Formation constants do not vary greatly from complex to complex. Blue-black solids have been obtained from thietes and TCNQ. The material obtained from 2H-thiete is electrically conducting - a semiconductor - but that from 3-phenyl-2H-thiete is an insulator. Several of the isolated charge-transfer complexes give satisfactory elemental analyses for 1:1 complexes and most of them give broad electron spin resonance spectra.
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■ Proton-ionizable Macrocycles Containing 1,2,4-Triazole and 4-Amino-1,2,4-triazole Subunits
José M. Alonso, M. Rosario Martín, Javier de Mendoza, Tomás Torres, and José Elguero
*Departamento de Química Orgánica, Facultad de Ciencias, Universidad Autónoma de Madrid, Cantoblanco, 28049-Madrid, Spain
Abstract
Macrocycles 2a and 2b, containing a proton-ionizable 1,2,4-triazole subcyclic unit, havebeen obtained from the appropriate 3,5-disubstituted N-amino-1,2,4-triazoles and tetraethyleneglycol derivatives. The N-amino function was used as a protective group in the macrocyclization step. The method allowed the preparation of the chiral macrocycle 2b in three steps, from S-lactic acid, in high optical purity and an overall yield of 16%. Triazolyl lone pairs of the macrocycles 2a and 2b, and of their N-aminated precursors 1a and 1b, participate in the complexation of Eu(fod)3 and Pr(fod)3, as well as the crown ether moieties, but not N-amino groups which, when present, were found to be inside the cavity. Ion transport rates towards alkali-metal ions through a bulky chloroform phase were low and showed little selectivity.
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■ Chemistry of Penicillin Diazoketones. Part III. Transformation of Tricyclic Beta-lactams
Ching-Pong Mak, Gerhard Schulz, and Hans Fliri
*Sandoz Forschungsinstitut, 1235 Wien, Brunnerstraße 59, Austria
Abstract
The transformation of tricyclic beta-lactams 1a-c, which are obtained from the corresponding penicillin diazoketones, into carbapenams 7-11 are described. Whereas reduction of 1c with tetra-n-butylammonium borohydride gave cleanly the hydmxy-lactam 3c, the isomeric ketone 1b yielded 3c, together with two tricyclic lactones 5a/b Azido-lactones 5c/d were obtained similarly when we reacted 1b with aluminium chloride/sodium azide. The structural assignment of these novel compounds was based mainly on spectroscopic analysis and comparison with the corresponding tricyclic lactam 3c.
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■ Cyclization of C- and O-Acyl Derivatives of p-Toluamide O-Acetoacetyloxime
Etsuko Kawashima, Yuko Ando, Katsumi Tabei, and Hiroshi Miyamae
*Tokyo University of Pharmacy and Life Science, 1432-1 Horinouchi, Hachioji, Tokyo 192-0392, Japan
Abstract
Reaction of p-toluamide 0-acetoacetyloxime (1) with acyl chloride (2) in the presence of basic catalyst gave the corresponding 0- and C-acyl derivatives (3 and 4). Cyclization of 3 afforded 5-(2-acyloxypropeny1)-3-(p-toly1)-1,2,4-oxadiazole derivatives (6) and 5-acetonyl-3-(p-toly1)-1,2,4-oxadiazole (7). Cyclization of 4 gave 5-(1-acyl-2- oxopropy1)-1,2,4-oxadiazole derivatives (8), 4-[ 1-amino-1 - (p-tolyl)]methylene-3-methyl-2-isoxazolin-5-one (9) and 5-substituted 3-(p-to1yl)-1,2,4-oxadiazole derivatives (10).
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■ The Preparation of Pyrido[4,3,2-de]quinazoline and Pyrido[3,4,5-de]quinazoline
Paul D. Woodgate, John M. Herbert, and William A. Denny
*Department of Chemistry, University of Auckland, Private Bag 92019, Auckland, New Zealand
Abstract
The preparation of the novel ring systems, pyrido[4,3,2-de]quinazoline and pyrido[3,4,5-de]quinazoline, from quinoline and isoquinoline respectively, is described.
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■ Formation of peri-Fused Heterocycles by Intramolecular Displacement of Halide
John M. Herbert, Paul D. Woodgate, and William A. Denny
*Department of Chemistry, University of Auckland, Private Bag 92019, Auckland, New Zealand
Abstract
The preparation of phthaloperin-12-one and naphtho[l,8-de]-1,3-thiazine using copper-assisted displacement of aryl halogen is described.
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■ Behaviour of Some Perimidines towards Oxidants
John M. Herbert, Paul D. Woodgate, and William A. Denny
*Department of Chemistry, University of Auckland, Private Bag 92019, Auckland, New Zealand
Abstract
The oxidation of some perimidines with 3-chloroperbenzoic acid, trifluoroperacetic acid, and dipotassium nitrosodisulphonate is reported. Perimidine-2-thione is oxidised to perimidine-2-sulphonic acid, while other perimidines are oxidised to give 4-and 6-perimidinones.
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■ Chlorosulfonyl Isocyanate: A Novel Reagent for the Synthesis of Heterocycles
Ahmed Kamal and Pralhad B. Sattur
*Medical Chemistry & natural Products Division, Regional Research Laboratory, Hyaderabad 500 007, India
Abstract
Chlorosulfonyl isocyanate, a novel reagent employed towards the synthesis of heterocycles and related compounds, finds extensive use. An effort has been made in this review to catalogue and update its applications for the synthesis of nitrogen, oxygen and sulphur containing ring systems.
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■ Azlactones: Retrospect and Prospect
Arya K. Mukerjee
*Department of Chemistry, Faculty of Science, Banaras Hindu University, Varanasi - 221005, India
Abstract
Interest in the chemistry of azlactones continues unabated because of their usefulness as intermediates in the synthesis of diverse products. The present review attempts to present the prolific development of recent years in this area and gives a critical and unified account of azlactones under the following headings: