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. 27, No. 10, 1988
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■ Synthetic Studies on Naulafine
David B. Repke,* Jahangir, Robin D. Clark, and Janis T. Nelson
*Institute of Organic Chemistry, Syntex Discovery Research, 3401 Hillview Avenue, Palo Alto, California 94304, U.S.A.
Abstract
The first synthesis of Naulafine, 7,12-dihydrocyclopent[de]indolo-[2’,3’:3,4]pyrido[1,2-b][2,7]- naphthyridin-4(6H)-one, is described.
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■ Design and Synthesis of Photoresponsive Crown Ethers via Olefin Metathesis
Kenji Hayakawa, Ryo Naito, and Ken Kanematsu*
*Institute of Synthetic Organic Chemistry, Faculty of Pharmaceutical Sciences, Kyushu University, 3-1-1 Maidashi, Higashi-ku, Fukuoka 812-8582, Japan
Abstract
Crowned cage compounds (5 and 9), prepared from crowned p-benzoquinone and cyclopentadienes by the sequence of the Diels-Alder reaction end photochemical [2+2] cycloaddition, constitute a new class of photoresponsive systems based on the reversible [2+2] cycloreversion/cycloaddition.
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■ Synthesis of 1,2,4-Triazolo Fused Heterocycles
Rajat B, Mitra,* Zainab Muljiani, and Sunita R. Deshpande
*National Chemical Laboratory, Poona-41108, India
Abstract
Synthesis of bicyclic and tetracyclic ring systems containing 1,2,4-triazole unit has been achieved by alkylation of substituted 1,2,4-triazoles followed by base catalysed cyclocondensation.
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■ A Convenient Synthesis of Ethyl-β-dioxohydropyridinyl, Ethyl-β-dihydrodioxopyrido[3,2-c]pyridazinyl and Ethyl-β-oxopyranylacrylate Derivatives
Fathy M. Abdel Galil,* Obeys K. Hashim, and Sohair S. Saleh
*Department of Chemistry, Faculty of Science, University of Cairo, Giza, Egypt
Abstract
A variety of pyridine, pyrido[3,2-c]pyridazine and pyran derivatives was synthesized from the enamino-nitrile derivative diethyl 3-amino-2-cyano-2-pentenedioafe (1) as a starting material.
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■ Reaction of N-Methyl-γ, δ-, and ε-lactams with t-Butyl Perbenzoate
Christopher J. Easton,* Steven C. Peters, and Stephen G. Love
*Department of Organic Chemistry, University of Adelaide, G.P.O. Box 498, Adelaide, S.A. 5001, Australia
Abstract
N-Methyl-γ-, δ-, and ε-lactams reacted with t-butyl perbenzoate to give, in each case, products of oxidation at endocyclic and exocyclic carbon adjacent to amide nitrogen.
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■ On the Structure of Licoricidin
Toshio Fukai, Masafumi Toyono, and Taro Nomura*
*Faculty of Pharmaceutical Sciences, Toho University, Toho University
Abstract
A prenylated isoflavan isolated from Sipei licorice (Glycyrrhiza sp., Leguminosae, Seihoku Kanzo in Japanese) was proved to be identical with already known compound licoricidin (2). From the spectral data, the structure (2) of licoricidin should be revised to the structure (1).
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■ Absolute Configuration of Natural Diels-Alder Type Adducts from the Morus Root Bark
Yoshio Hano, Shinkichi Suzuki, Taro Nomura,* and Yoichi Iitaka
*Faculty of Pharmaceutical Sciences, Toho University, 2-2-1, Miyama, Funabashi, Chiba 274-8510, Japan
Abstract
Absolute configuration of optically active Diels-Alder type adducts from the Morus root bark, which are regarded as adducts of chalcones and dehydroprenylphenols, were determined on the basis of X-ray crystallographic analysis and the cd spectra. Absolute configuration of the chiral centers on the methylcyclohexene ring in the cis-trans adducts was established to be 3”S, 4”R, 5”S, while in the all-trans adducts to be 3”R, 4”R, 5”S.
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■ 4-Dimethylaminopyridine N-Oxide as an Excellent Catalyst for Thione to Theol Rearrangement of Xathates
Kazunobu Harano, Hideo Kiyonaga, Shin-ichiro Sugimoto, Toshikazu Matsuoka, and Takuzo Hisano*
*Faculty of Pharmaceutical Sciences, Kumamoto University, 5-1 Oe-hon-machi, Kumamoto 862-0973, Japan
Abstract
4-Dimethylaminopyridine N-oxide effectively catalyzes the, thione to thiol rearrangement of O,S-dialkyl dithiocarbonates (xanthates) to provide S,S-diaikyl dithiocarbonates.
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■ The Structure of Subulacine-N-oxide
Tammo Winkler* and Roland Heckendorn
*CIBA-GEIGY AG, CH-4002 Basel, Switzerland
Abstract
The nmr spectra reported for subulacine-N-oxide are shown to be those of 1β,2β-epoxy-1α-hydroxymethyl-8α-pyrrolizidine.
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■ Guanidolide A, a Novel Antibiotic Produced by Streptomyces hygroscopicus var. Crystallogenes, the Copiamycin Source
Toshio Fukai, Chika Takahashi, Taro Nomura,* Jun Uno, and Tadashi Arai
*Faculty of Pharmaceutical Sciences, Toho University, 2-2-1, Miyama, Funabashi, Chiba 274-8510, Japan
Abstract
A new antibiotic, guanidolide A (2) was isolated, as well as demalonylmethylcopiamycin (1), from the mycelial cake of Streptomyces hygroscopicus var. crystallogenes. The structure of the compound (2) was determined by spectroscopic evidence.
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■ Regioselectivity in the Vilsmeier-Haack Reaction of N-Benzyl-1,2,3,4-tetrahydrocarbazole
Yasuoki Murakami,* Yuusaku Yokoyama, Tomoko Miura, Sumiko Nozawa, Emiko Takeda, and Hideharu Suzuki
*School of Pharmaceutical Sciences, Toho University, 2-2-1, Miyama, Funabashi, Chiba 274-8510, Japan
Abstract
The Vilsmeier-Haack reaction of N-benzyl-1,2,3,4-tetrahydrocarbazole (1) with various N,N-disubstituted formamides (6) and phosphorous oxychloride took place not only on the alicyclic portion but also on the benzene moiety depending on the reactivity and bulkiness of the reagents. It was also shown that N-methylformanilide (6e) is the most reactive reagent among 6.
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■ Nitoroolefins. I. A New and Convenient Access to Indolizines and Pyrazolo[1,5-a]pyridines Using 1-Nitro-2-(phenylthio)ethylene
Yoshinori Tominaga,* Yuichi Ichihara, and Akira Hosomi*
*Center of Instrumental Analysis, Nagasaki University, 1-14, Bunkyo-machi, Nagasaki 852-8521, Japan
Abstract
1-Nitro-2-(phenylthio)ethylene (1) reacts with a variety of N-ylides and N-imines (pyridinium, isoquinolinium, quinolinium, phthalazinium N-ylides and N-imines) in the presence of triethylamine to give the corresponding fused pyrrole and pyrazole derivatives (indolizines, pyrrolo[2,1-a]isoquinoline, pyrrolo[2,1-a]phthalazine, pyrazolo[1,5-a]-pyridine, pyrazolo[5,1-a]quinoline, and pyrazolo[5,1-a]isoquinoline) along with the corresponding l-nitropyrrolopyridines and 1-nitropyrazolopyridines, respectively, in moderate yields.
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■ Synthesis of α,β-Unsaturate γ-Butyrolactams by Knoevenagel Condensation
Masazumi Ikeda,* Takamasa Uchino, Kazumi Matuyama, and Ayami Sato
*Kyoto Pharmaceutical University, Misasagi-Shichonocho, Yamashina, Kyoto 607-8414, Japan
Abstract
When 2-alkylaminocyclohex-2-enones 1a-d were allowed to react with ethyl chloroformylacetate in the presence of pyridine and 4-(dimethylamino) pyridine. the carbamoylacetates 2a-d and the 2H-indol-2-ones 3a-d were obtained. Upon treating with ammonium acetate, 2a-d were converted into 3a-d. Reaction of 1a and 1c with cyanoacetyl chloxide gave only the 1H-indol-2-ones 6a,c. This reaction was extended to ttle synthesis of the erythrinan skeleton.
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■ New Regio- and Stereocontrolles Reactions of 2-Vinylindoles with CC-Dienophiles: Diels-Alder Reactions, Ene Reactions and Michael Additions
Manfred Eitel and Ulf Pindur*
*Department of Chemistry and Pharmacy, Institute of Pharmacy, University of Mainz, Saarstrasse 21, D-55122 Mainz, Germany
Abstract
The reactions of selectively functionalized 2-vinylindoles with some acyclic and cyclic CC-dienophiles yield Diels-Alder adducts, Diels-Alder ene products, and Michael adducts, respectively, with very high regio- and/or stereoselectivities. This methodology provides a convenient access to functionalized indoles, carbazoles, and [c]pyrroloannellated carbazoles with substitution patterns that are not so easily accessible by other routes.
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■ A Simple Synthesis of 7-Substituted 1-Acethy-2,3-dihydroindoles
Masanori Somei,* Toshiya Kawasaki, and Toshiharu Ohta
*Faculty of Pharmaceutical Sciences, Kanazawa University, 13-1 Takara-machi, Kanazawa 920-0934, Japan
Abstract
7-Cyano-, 7-hydroxy-, 7-methoxycarbonyl-, 7-methyl-, 7-nitro-, and 7-phenyl-1-acetyl-2,3-dihydroindoles are prepared in two steps (or one pot) from 1-acetyl-2,3-dihydroindole.
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■ Synthesis of Norsecocularines
Emilia Tojo, 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 transformation of cularines into N-norsecocularine alkaloids using a Cope elimination to cleave the nitrogenated ring is reported.
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■ Synthesis of Some 6-Arylamino-3-amino-1,2,4,5-dithiadiazines
Anirudh P. Singh, Rajendra Singh, and Vinay Kumar Verma*
*Department of Applied Chemistry, Institute of Technology, Banaras Hindu University, Varanasi-221 005, India
Abstract
The synthesis of some new 6-arylamino-3-amino-1,2,4,5-dithiadiaztaes (IIIa-e) has been achieved by following a novel route.
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■ Biomimetic Transformation of Hodgkinsine, a Pyrrolidinoindoline Alkaloid
Francine Libot, Nicole Kunesch,* Jacques Poisson, Manfred Kaiser, and Helmut Duddeck
*Laboratorie de Chimie des Substances Thérapeutiques Naturelles, Centre d’Etudes Pharmaceutiques, 92296 Châtenay-Malabry Cedex, France
Abstract
The transformation of hcdgkinsine 1 under mild acidic conditions provides a new compound whose structure has been shown to possess calycanthine and pyrrolidinoindoline subunits. This compound could be identified with calycosidine 2 previously isolated from Calycodendron milnei. General implications of this reaction are discussed.
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■ New Alkaloids from Delphinium andersonii Gray
S. William Pelletier,* A. Mukendi Panu, Palaniaooan Kulanthaivel, and John P. Olsen
*Department of Chemistry, Institute for Natural Products Research, The University of Georgia, Chemistry Building, Athens, Georgia 30602-2556, U.S.A.
Abstract
Andersonine (1) and 14-deacetylnudicauline (2), two new C19-diterpenoid alkaloids, have been isolated from Delphinium andersonii Gray. Structures were deduced by spectroscopic methods. The structures of andersonine and 14-deacetylnudicauline were confirmed by correlation with nudicauline (5). Six known alkaloids were also isolated: delavaine (3), delectinine (8) lycoctonine (7), methyllycaconitine (6), nudicauline (5), and takaosamine (4).
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■ Autoxidation of Lithio Derivative of 2-Isoxazolines
Sergio Auricchio* and Aldo Ricca
*Dipartimento di Chimica, Politecnico di Milano, Piazza Leonardo da Vinci 32, 20133 Milano, Italy
Abstract
4-Lithio-2-isoxazolines are oxidized to the 4-peroxides or 4-hydroxy derivatives by air or oxygen at -80 °C. The concentration of oxygen in the solution is a decisive parameter. When it is bubbled into the lithium salt solution, the 4-hydroperoxide derivatives are mainly formed. However if oxygen is slowly absorbed in the liquid phase, 4-hydroxy derivatives predominate. In the reaction, the hydroperoxide anions has been confirmed to be the precursors of the 4-hydroxy-2-isoxazolines.
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■ Studies on Friedel-crafts Acylation of N-Acetylhompveratrylamine and Preparation of 1-Substituted 3,4-Dihydro-6,7-dimethoxyisoquinolines
Kazuhiko Orito,* Tsutomu Matsuzaki, Hiroshi Suginome, and Russel Rodrigo
*Division of Molecular Chemistry, Graduate School of Engineering, Hokkaido University, Kita 13 Nishi 8, Kita-ku, Sapporo, Hokkaido 060-0828, Japan
Abstract
Friedel-Crafts acylation of N-acetylhomoveratrylamine in a molar ratio of 1:2:3 of 1, AlCl3 and the appropriate acid chloride using nitrobenzene as solvent gave the corresponding 2-acyl derivatives 2a-j in good yields. Subsequent treatment of 2 in boiling 1N-hydrochloric acid afforded a variety of 1-substituted 3,4-dihydro-6,7-dimethoxyisoquinolines 3a-j in almost quantitative yields. The dihydroisoquinolines-3h-j having carboxyalkyl groups at C1-position were further converted to the benzo[a]quinolizine analogues 6a-j.
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■ Conversion of 2,3-O-Cyclohexylidene-(D)-ribonolactone into 2,3-O-Cyclohexylidene-(L)-ribonolactone
Seiichi Takano,* Kohei Inomata, and Kunio Ogasawara
*Pharmaceutical Institute, Tohoku University, Aobayama, Sendai 980-8578, Japan
Abstract
A convenient method forthe chirality inversion of 2,3-O-cyclohexylidene-D-rlbonolactone to 2,3-O-cyclohexylidene-L-ribonolactone has been established.
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■ Photochemistry of the N-Acyllactam and Acyclic Thioimide Systems. Competition between Paterno-Büchi Type and Norrish Type 1 Reactions
Kazuaki Oda,* Minoru Machida, and Yuichi Kanaoka
*Faculty of Pharmaceutical Scicences, Higashinihonngakuen University, 1757 Kanazawa, Toubetu-cho, Ishikari-gun, Hokkaodo 061-0212, Japan
Abstract
Irradiation of semlcyclic- (4) and acyclic thioimides (9) gave thietanes (6, 7, and 10) and/or α-cleavaged products (8 and 11), formations of those were explained in terms of Paterno-BÜchi type and Norrish type I processes.
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■ Structure and Synthesis of Cucumopine, a New Crown Gall and Hairy-root Opine
Elisabeth Davioud, Jean-Charles Quirion, Max E. Tate, Jacques Tempé, 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 opine known as cucumopine 1 produced by crown gall tumours and hairyroot exhibited chemical and spectroscopic data corresponding to 4-(2-carboxyethy1)-4,5,6,7-tetrahydroimidazo[4,5-c]pyridine-4,6-dicarboxylic acid. The identification was verified by a biogenetic type synthesis from L-histidine and α-ketoglutaric acid.
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■ Reactivity of Isoselenazole Derivatives towards Electrophilic Reagents
Francesco Lucchesini, Nevio Picci, Marco Pocci, Angela De Munno,* and Vincenzo Bertini
*Dipartimento di Chimica e Chimica Industriale, Università di Pisa, Via Risorgnimento 35, I-56126 Pisa, Italy
Abstract
The behaviour of isoselenazoles towards electrophilic reagents including reversible protonation at the nitrogen atom, hydrogen-deuterium exchange, bromination and nitration is explored. Electrophilic substitutions take place only in the 4 position.
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■ Reaction of 6-Glycosylaminopyrimidin-4-ones with Diethyl Ethoxymethylenemalonate in Acidic Medium
José A. García, Adolfo Sánchez, and Manuel Nogueras
*Dept. Química Orgánica, Colegio Universitario de Jaén, Universidad de Granada, 23071 Jaén, Spain
Abstract
Starting from the already known 6-glycopyranosylaminopyrimidin-4-ones, some novel (E)-5-(2-carbethoxyvinyl) derivatives have been synthesized by the reaction with diethyl ethoxymethylenemalonate (EMME) in acetic acid.
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■ Pyrazoles 3. N-1 Protected 4-Substituted Pyrazoles — Synthesis and Nmr Investigation
Gottfried Heinisch and Wolfgang Holzer*
*Institute of Pharmaceutical Chemistry, University of Vienna, Währinger Strasse 10, A-1090 Vienna, Austria
Abstract
13C-Nmr Data (chemical shifts, substituent chemical shifts (SCS), coupling constants) are reported for 26 1,4-disubstituted pyrazoles, bearing a benzyl, benzoyl or (substituted) benzenesulfonyl protecting group at N-1. The pyrazole derivatives 8a-d were prepared from the corresponding NH-pyrazoles. In the synthesis of compounds 2-5 l-benzyl-4-pyrazolecarbaldehyde served as the starting material.
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■ Improved Preparation of Precocene II. Unexpected Results in the Reduction of Alkoxy Substituted Acetophenones and 4-Chromanones with Sodium Borohydride
Pilar Teixidor, Francisco Camps, and Angel Messeguer*
*Departmenr of Biological Chemistry, C.I.D. (CSIC), J. Giroba 18. 08034-Barcelona, Spain
Abstract
An improved preparation of natural pro-allatocidin precocene II (6) is reported. Starting from methoxyhydroquinone (1). Fries condensation with acid 2 led to the hydroxychromanone 2, which by further methylation, reduction and dehydration afforded chromene 6 in 77% overall yield. In addition, complementary studies related to the synthetic sequence have also been carried out, i.e., the influence of water contents on the initial Fries rearrangement and the scope of an anomalous reaction course in the reduction of aromatic ketones with NaBH4/MeOH in which, depending upon the activation of the carbonyl group, the formation of the methyl ether instead of that of the corresponding alcohol might be observed.
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■ Delstaphigine and 14-O-Benzoyldelphonine, New Alkaloids from Delphinium staphisagria Linne‘
S. William Pelletier,* Samir A. Ross, and Jpseph T. Etse
*Department of Chemistry, Institute for Natural Products Research, The University of Georgia, Chemistry Building, Athens, Georgia 30602-2556, U.S.A.
Abstract
Delstaphigine (1) and 14-O-benzoyldelphonine (2), two new C19-diterpenoid alkaloids, and chasmaconitine (4) have been isolated from the seeds of Delphinium staphisagria. The structures of these alkaloids were determined from spectral data and by correlation with alkaloids of established structures. Thus methylation of delstaphigine (1) afforded delphinine (3). 14-O-Benzoyldelphonine (2) was synthesized from both delphinine (3) and delphonine (5). Chasmaconitine (4) has not been previously isolated from a Delphinium species.
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■ Synthesis of 5-Alkylpyrrolizin-3-ones from the Lukes-Sorm Lactam by Grignard Reaction and Recyclization of Intermadiate 5-Bromoalkylpyrrolidin-2-ones
Kimio Takahashi and Arnold Brossi*
*Section of Medical Chemistry, Laboratory of Analytical Chemistry, NIDDK, National Institute of Health, Bethesda, MD 20982, U.S.A.
Abstract
Synthesis of 5-alkylpyrrolizidin-3-ones 2 and 8 from pyrrolizidin-3,5-dione 1 is described. Grignard reaction of 1 gave 5-(3’-oxobutyl)pyrroiidin-2-one 2. Reduction of 2 with sodium borohydride, followed by mesylation, bromination, and cyclization afforded a diastereomeric mixture 7a and 8a, which were separated by chromatography. The same procedure with 3, also obtained from 1 by a Grignard reaction, afforded 7b and 8b.