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. 12, 1987
Published online:
■ Synthesis of Optically Active Hetero Alkylaryl Alcohols by Baker‘s Yeast
Mitsuhiro Takeshita, Katsuya Terada, Nami Akutsu, Sachiko Yoshida, and Takumi Sato
*Tohoku Pharmaceutical University, 4-4-1 Komatsushima, Aoba-ku, Sendai 981-8558, Japan
Abstract
Synthesis of optically active hetero alkylaryl alcohols have been examined using baker’s yeast
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■ Corialstonine, a Novel Quinoline Alkaloid from Alstonia coriacea
Abdallah Cherif, Georges Massiot, and Louisette Le Men-Olivier
*Laboratorie de Pharmacognosie, Facluté de Pharmacie, U.A. n°492 au C.N.R.S., 51, rue Cognacq-Jay, F-51096 Reims Cedex, France
Abstract
Corialstonine is a novel quinoline alkaloid isolated from Atstonia coriacea. Its structure illustrates a possible new transformation of indales into quinolines.
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■ Synthesis of 5,6,9,10,11,11a-Hexahydro-8H-naphtho[2,1-a]quinolizine
María Fernández Fernández and Mónica M. Söllhuber
*Departamento de Química Orgánica y Farmacéutica, Facultad de Farmacia, Universidad Complutense de Madrid, Ciudad Universitaria, 28040 Madrid, Spain
Abstract
Naphtho[2,1-a]quinolizidine was synthesized by the reaction of 1,2- dihydrobenz[f]isoquinoline with methyl vinyl ketone. The heterolytic fragmentation of l0-p-tosyl-5,6,9,10,11,11a-hexahydro-8H-naphtho[2,1-a]quinolizine(11) is described.
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■ A New Access to 2-Benzoylquinoline and 1-Benzoylisoquonoline Using a Novel Mode of Base-induces Decomposition of N-Alkoxypyridinium Salts
Henri Sliwa and Lassina Outtara
*Laboratoire de Chimie Organique et Environnement, Université des Sciences et Technologies de Lille, Bat. C4 -2eme Etage, 59655 Villeneuve d‘ Ascq Cedex, France
Abstract
A novel mode of fragmentation alkoxylogous of Katritzky’s mode A of decomposition of N-alkoxypyridinium salts can become exclusive in the quinoline and isoquinoline series, providing a new access to benzoyl derivatives of these hrterocycles.
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■ Reversible Formation of a Pseudobase from 1-Methylpyridinium-3-carb(ox)aldehyde
James F. Rusling and Petr Zuman
*Department of Chemistry, University of Connecticut, Storrs, CT 06269-3060, U.S.A.
Abstract
The geminal diol anion of 1-methylpyridinium-3-carb(ox)aldehyde hydrate in aqueous alkaline solutions forms an unstable pseudobase by nucleophilic attack of hydroxide ion at the pyridinium ring. This reaction with pKa - 14.4 is unique among 1-methylpyridiniumcarboxaldehydes for the 3-isomer.
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■ New Route to Phthalideisoquinoline Alkaloids: Synthesis of (±)-Cordrastine I and II
Kazuhiko Orito, Hiroshi Suginome, S. Osmund De Silva, 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
Acid-catalyzed isomerization of the keto-lactone (3) provided the immonium salt (6), sodium borohydride reduction of which gave (±)-cordrastine I (7) and II (8) after acid treatment.
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■ Intramolecular Cyclizations of Hantzsch 1,4-Dihydropyridines: Synthesis of Di- and Tetrahydroindeno[2,1-c]pyridines
Steven D. Young, Stella W. King, and David C. Remy
*Department of Medicinal Chemistry, Merck Sharp and Dohme Research Laboratories, West Point, PA 19486, U.S.A.
Abstract
Hantzsch 4-phenyl-1,4-dihydropyridines bearing electrophilic ortho substituents react with trimethylsilyl cyanide/zinc iodide or base resulting in an intramolecular cyclization reaction to give di-and tetrahydroindeno[2,1-c]pyridines in good yield.
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■ Syntheses of 1,4-Oxazepines, 1,4-Diazepines, and Their 5-Oxo Derivatives from 2-Pyridones
Jyoji Kurita, Takeharu Yoneda, Naoki Kakusawa, and Takashi Tsuchiya
*School of Pharmacy, Hokuriku University, 3-Ho, Kanagawa machi, Kanazawa 920-1181, Japan
Abstract
Thermolysis of the 3-aza-7-oxa- (11) and 3,7-diaza-4-oxotricyclo[4.1.0.02,5]heptanes (12), prepared from 2-pyridones via four steps, resulted in valence isomerization with ring opening to give the novel 1,4-oxazepin-5-ones (14) and 1,4-diazepin-5-ones N (15), respectively, which were treated with triethyloxonium tetrafluoroborate to afford the fully unsaturated 1,4-oxazepines (16) and 1,4-diazepines (17), respectively.
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■ Electrophilic ipso-Substitution of 5-Bromouridines with Diaryl Disulfides. Novel Synthesis of 5-Arylthiouridines
Kosaku Hirota, Tetsuo Tomishi, and Yoshifumi Maki
*Labolatory of Medicinal Chemistry, Gifu Pharmaceutical University, 6-1 Mitahora-higashi 5-chome, Gifu 502-8585, Japan
Abstract
Reaction of 5-bromo-2’,3’-O-isopropylideneuridine (1) with diaryl disulfides in the presence of base induced an electrophilic ispo-substitution to give 5-arylthiouridine derivatives (2).
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■ A New Route to Quassin Basic Skeleton via Allenecarboxylate Intramolecular Cycloaddition
Mitsutaka Yoshida 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
The new route to quassin basic skeleton, tetracyclic lactones has been realized via the intramolecular Diels-Alder reaction of allene-1,3-dicarboxylates.
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■ Reduction of 3,4-Disubstituted 1,6-Propano-1H,6H-3a-thia(SIV)-1,3,4,6-tetraazapentalene-2,5(3H,4H)-dithione with Sodium Borohydride
Noboru Matsumura, Masaaki Tomura, Osamu Mori, Masataka Ukawa, and Shigeo Yoneda
*Department of Applied Chemistry, College of Engineering, University of Osaka Prefecture, Sakai, Osaka 593-8531, Japan
Abstract
Reduction of tetraazapentalene derivatives with sodium borohydride (NaBH4) afforded the ring-opening compound, 1,3-bis(substituted thiocarbamoyl)perhydropyrimidine, in goad yields by the reduction-elimination of the C=SIV moiety.
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■ Synthesis of 1-(2-Pyridyl)indoles by the Photoreaction of 2-Fluoropyridine with Indoles
Koh-ichi Seki, Kazue Ohkura, Masanao Terashima, and Yuichi Kanaoka
*Faculty of Pharmaceutical Scicences, Higashinihonngakuen University, 1757 Kanazawa, Toubetu-cho, Ishikari-gun, Hokkaodo 061-0212, Japan
Abstract
Photoreaction of 2-fluoropyridine with indoles gave 1-(2-pyridyl)indoles regioselectively. The yields of the coupling products improved significantly by using the indole anion derivatives instead of the indoles.
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■ Synthesis and Properties of Norcaradiene-Cycloheptatriene System Fused with Isoxazole Ring
Nobuhiro Kanomata, Makoto Nitta, Kensuke Takahashi, Yutaka Takakura, and Katsuhiro Saito
*Department of Chemistry, School of Science and Engineering, Waseda University, 3-4-1 Okubo, Shinjuku-ku, Tokyo 169-8555, Japan
Abstract
Novel norcaradiene-cycloheptatriene systems fused with arylisoxazoles were synthesized and their temperature dependent 1H nmr spectra were studied. while the fusion of isoxazole ring much shifted the norcaradiene-cycloheptatriene equilibrium to the side of norcaradiene form, the rapid isomerizations of the norcaradienes with their enantiomers were observed and their δG‡c values were obtained.
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■ Studies of as-Triazine Derivatives. X. Addition Reaction of Phenylmagnesium Bromide with 1,2,4-Triazines
Shoetsu Konno, Mataichi Sagi, Nobuko Yoshida, and Hiroshi Yamanaka
*Pharmaceutical Institute, Tohoku University, Aobayama, Sendai 980-8578, Japan
Abstract
The reaction of 1,2,4-triazine with phenylmagnesium bromide was investigated. Every position of 3, 5, and 6 in a 1,2,4-triazine ring is active in the addition reaction of Grignard reagents. Since 5-phenyl-1,2,4-triazine, 5,6-diphenyl-1,2,4-triazine, and 3,5,6-triaryl-1,2,4-triazine were obtained subsequently, it was comfirmed that the most active position was position 5 and the least active one was position 3.
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■ Definite Total Synthesis of Coumarinolignans, Daphneticin and Its Regioisomer
Hitoshi Tanaka, Masaya Ishijara, Kazuhiko Ichino, and Kazuo Ito
*Faculty of Pharmacy, Meijo University, 150 Yagotoyama, Tenpaku, Nagoya 468-8503, Japan
Abstract
The synthesis of 7-benzyloxy-8-hydroxycoumarin (5) and 8-benzyloxy-7-hydroxycoumarin (11) was described and further, by use of 5 as a starting material, daphneticin (1) was synthesized. On the other hand, its regioisomer (2) was also synthesized from (8), readily prepared via two steps from 5, according to the method described in the synthesis of daphneticin.
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■ A New Route for the Synthesis of 6-Substitutes Imidazo[4-5,c]-1,2,6-thiadiazine 2,2-Dioxides: Nmr Study and Crystal Structure of a Complex with Dimethylformamide
Angela Herrero, Carmen Ochoa, Juan Antonio Páez, Martín Martínez-Ripoll, Concepción Foces-Foces, and Félix Hernadez Cano
*Instituto de Química Médica, C. S. I. C., Calle Juan de Cierva, 3, 28006 Madrid, Spain
Abstract
The synthesis of.6-substituted imidazo[4,5-c]-1,2,6-thiadiazine 2,2-dioxides from 3,4,5-triamino-1,2,6-thiadiazine 1,1-dioxide and aldehydes is described. 1H- and 13C-nmr studies of the synthesized compounds have been carried out. The crystal structure of the complex formed by the 6-(p-methoxyphenyl) derivative and dimethylformamide has been studied. The imidazothiadiazine ring has an envelope conformation in a packing by hydrogen interactions.
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■ Directed Synthesis of 1-Substituted Phenoxazines
Alan R. Katritzky, Luis M. Vazquez de Miguel, and Gordon W. Rewcastle
*Center for Heterocyclic Compounds, Department of Chemistry, University of Florida, P. O. Box 117200, Gainesville, FL 32611-7200, U.S.A.
Abstract
Phenoxazine protected as its N-lithiocarbamate undergoes lithiation exclusively at the C-1 carbon atom. Reaction of the lithiated species with a variety of alectrophiles readily produces several new 1-substituted phenoxazines, as well as two known compounds in superior yield to those of existing methods.
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■ New Methods for the Synthesis of 2-Arylpyrroles
Chris G. Kruse, Jan P. Bouw, Roelof van Hes, Aalt van de Kuilen, and Jack A. J. den Hartog
*Department of Chemistry, Duphar Research Laboratories, PO Box 2, 1380 AA Weesp, The Netherlands
Abstract
Two short and efficient synthetic approaches for -mostly unknown-2-arylpyrroles are presented. The key intermediates 3 are conveniently obtained from cammercially available acetophenones 5 (method I) or benzoic acid derivatives 10, (method II).
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■ An Improved Synthesis of 1-Alkyl-4-imidazolin-2-ones
Ooi Wong, Noriko Tsuzuki, Mark Richardson, Howard Rytting, Ryoji Konishi, and Takeru Higuchi
*Department of Pharmaceutical Chemistry, University of Kansas, 4070 Malott Hall, Lawrence, Kansas 66045-2506, U.S.A.
Abstract
Two 1-alkyl-4-imidazolin-2-ones were prepared by acid-catalysed cyclization of N-(2,2-dialkoxyethyl)-N-alkylureas, with improved yields of over 90%. The amount of HC1 used in the reaction and the proper isolation procedure are the important factors in obtaining the high yields.
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■ Nucleophilic Substitution Reactions on Sulfur by n-Butyllithium 2
Toshiyasu Mase and Kiyoshi Murase
*Central Research Laboraories, Yamanouchi Pharmaceutical Co., Ltd., 1-1-8, Azusawa, Itabashi-ku, Toyko 174-0051, Japan
Abstract
The reaction of some 2-phenylimidazo[2,1-b]benzothiazoles (1) with organometal reagents (n-BuLi, n-Bu2CuLi, i-Pr2NLi and EtMgBr) has been investigated. Two reagents (n-BuLi and n-Bu2CuLi) induced the nucleophilic substitution reaction on sulfur of 1 and to give the C-S bond cleaved compounds.
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■ Synthesis of 1,2,3,4,4a,5,9,10,16,16a-Decahydro-2-methyl[1]benzazepino [3,2,1-jk]Pyrido[3,4-b][1]benzazepine: A Conformationally Rigid Imipramine Analog
Philip G. Dunber and Arnold R. Martin
*Department of Pharmaceutical Sciences, College of Pharmacy, The University of Arizona, Tucson, AZ 85721, U.S.A.
Abstract
Ortho lithiations and acylations of 10,11-dihydro-5H-dibenz[b,f]azepine and N,N-diethylnicotinamide respectively led to the convenient synthesis of the key intermediate 4-[(10,11-dihydro-5H-dibenz[b,f]azepin-4-yl)hydroxymethyl]-N,N-diethylnicotinamide 2a, Catalytic reduction of 2, and subsequent cyclization of the resulting carboxylic acid 3, provided the pentacyclic lactam 4 required for further elaboration of the rigid imipramine analog. Difficulties in amide hydrolysis are discussed. Further reductions and N-methylation provided both cis and trans ring fusion isomers 8a and 8b identified by 1H and 13C nmr.
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■ Cycliaddition Reactions of 2,3-Diphenylquinoxaline-5,8-dione. Synthesis of Novel Pyrazolo[3,4-g]quinoxalinequinone, Isoxazolo[4,5-g]quinoxalinequinone and Pyrrolo[3,4-g]quinoxalinequinone
Bindumadhavan Venugopalan, Sivasilam Suresh Iyer, Pravin Jayant Karnik, and Noel John de Souza
*Department of Chemistry, Research Centre, Hoechst India Limited, Mulund, Bombay 400 080, India
Abstract
2,3-Disubstituted quinoxalinequinones were prepared. Synthesis of pyrazolo [3,4-g]quinoxalinequinones 4 and 5, isoxazolo [4,5-g]quinoxalinequinone 7 and pyrrolo [3,4-g]quinoxa1inequinone 10 using dipolar cycloaddition reactions of quinoxalinequinones 3 with respective dipoles are reported.
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■ Synthesis of Arglecin
Akihiro Ohta, Yutaka Aoyagi, Yohko Kurihara, Kayo Yuasa, Makoto Shomazaki, Teruo Kurihara, and Hiroshi Miyamae
*Tokyo University of Pharmacy and Life Science, 1432-1 Horinouchi, Hachioji, Tokyo 192-0392, Japan
Abstract
Arglecin (1) and its analogue, 6-(3-aminopropy1)-3-isobutyl-2(1H)-pyrazinone (2). were synthesized from DL-alanyl-leucyl anhydride in several steps.
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■ A Facile Preparation of 3-Substituted 2-Thioxo-tetrahydoquinazolin-4-ones by the Reaction of Anthranilamide with Isothiocynates
Chao-Han Chan, Fang-Jy Shish, Kang-Chien Liu, and Ji-Wang Chern
*Medical Laboratories and Institute of Pharmacy, National Defense Medical Center, P.O. Box 90048-512, Taipei, Taiwan, R.O.C.
Abstract
3-Substituted 2-thioxa-tetrahydroquinazolin-4-ones (4a-d) can be synthesized in a convenient procedure directly by a treatment of anthranilemide with isothiocyanates at room temperature. However, anthranilamide was reacted with 4-isothiocyanato-1-benzylpiperidme (2e) leading to the formation of 2-[3-(1-benzyl-4-piperidinyl)]thioureidobenzarnide (3e) which was subsequently cyclized to 4e under a basic condition.
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■ The [3+2] Cycloaddition Reaction of Nonstabilized Azomethine Ylide Generated from Trimetylmine N-Oxide to C=C, C=N, and C=S Bonds
René Beugelmans, Jacqueline Chastanet, and Georges Roussi
*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 reported cycloaddition reactions between nonstabilized azomethine ylide Y generated from trimethylamine N-oxide 1 and unactivated C≡C 2 - 4, C=N 5 and C=S 6, 7 bonds constitute an attractive entry respectively to pyrrolines and pyrroles 10 - 13, imidazalidine 14 and thiazolidines 15, 16.
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■ Stereochemistry of Diastereomeric 9,10-Dimethoxy-1,3,4,6,7,11b-hexahydrospiro[banzo[a]quinolizin-2,5‘-imidazolidine]-2‘,4‘-diones
J. Carlos Meréndez and Mónica M. Söllhuber
*Departamento de Química Orgánica y Farmacéutica, Facultad de Farmacia, Universidad Complutense de Madrid, Ciudad Universitaria, 28040 Madrid, Spain
Abstract
The structures of the two diastereomeric title compounds obtained by the Bucherer-Bergs and Read procedures are respectively assigned to α and β isomers on the basis of 1H -nmr, 13C-nmr and chemical reactivity data. Both compounds present a predominant trans conformation as shown by ir, 1H-nmr and 13C-nmr data.
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■ Polycyclic N-Hetero Compounds. XXX. Synthesis and Antidepressive Evaluation of 3-Substituted 3,4,5,6-Tetrahydrobenzo[h]quinazolin-4-ones
Takashi Hirota, Kenji Sasaki, Hiroshi Yamamoto, and Takashi Katsu
*Faculty of Pharmaceutical Sciences, Okayama University, 1-1-1 Tsushima-naka, Okayama 700-8530, Japan
Abstract
Syntheeis of 3-substituted 3,4,5,6-tetrehydrohenzo[h]-quinaeolin-4-ones is described. Antidepressive evaluation of these compounds was performed by antireserpine action and compounds IX and X exhibited the positive action.
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■ Photochemical Route to Cyclobut[b]isoxazolo[4,5-e]pyridine, a New Heterocyclic System
Giorgio Adembri, Donato Donati, Stefania Fusi, and Fabio Potticelli
*Istituto di Chimica Organica, Università di Siena, Pian dei Mantellini 44, 53100 Siena, Italy
Abstract
Photochemical adducts between 3-carbamoyl- or 3-ethoxycarbonyl- 1-benzyl-1,4-dihydropyridine and CH2=CH-CN were transformed to derivatives of title compound (6a,b and 7a,b) via regio- and stereospecific 1,3-dipolar addition of p-C1-benzonitriloxide. Isomers 8 and 9 with inverted configuration at carbon bearing CN group can be obtained in EtOH/EtO- solution.
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■ A Convenient Synthesis of 3-Aryl Coumarins
Yang Ming and David W. Boykin
*Department of Chemistry, Georgia State University, University Plaza, Atlanta, GA 30303, U.S.A.
Abstract
A new, convenient, one-step synthesis of 3-aryl coumarins from 2-fluorobenzaldehyde and aryl acetic acids is reported.
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■ A Convenient Route to 6-Aminocyclopenta[b]thiophene Derivatives
Patrick Dallemagne, Sylvain Rault, Marina Gordaliza, and Max Robba
*Departamento de Química Orgánica y Farmacéutica, Facultad de Farmacia, Universidad de Salamanca, Av. Campo Charro s.n. 37007-Salamanca, Spain
Abstract
The intramolecular cyclization of 3-amino-3-(2-thienyl) propionic acid to 6-amino-5,6-dihydrocyclooenta[b] thiophene was achieved by Friedel-Crafts reaction.