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. 45, No. 4, 1997
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■ Facile and General Syntheses of 1-Alkyltoxoflavin and 8-Alkylfervenulin Derivatives of Biological Significance by the Regiospecific Alkylation of Reumycin (1-Demethyltoxoflavin, 8-Demethylfervenulin) Derivatives
Tomohisa Nagamatsu* and Hirofumi Yamasaki
*Faculty of Pharmaceutical Science, Okayama University, 1-1-1 Tsushima-naka, Okayama 700-8530, Japan
Abstract
Regiospecific alkylation of reumycins (6) under alkaline conditions with a dialkyl sulfate or alkyl halide in dioxane and in DMF to provide 1-alkyltoxoflavins (5) of biological significance and 8-alkylfervenulins (7), respectively, is described.
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■ Syntheses and Structural Properties of Severely Distorted Porphyrins: N-Methyl Derivatives
Todd E. Clement, Liem T. Nguyen, Richard G. Khoury, Daniel J. Nurco, and Kevin M. Smith*
*Department of Chemistry, University of California, Davis, One Shields Avenue, Davis, CA 95616-5295, U.S.A.
Abstract
Syntheses and characterization of a series of N-methylated derivatives of sterically distorted porphyrins are reported; the work includes the first example of a tetra-N-methylated porphyrin obtained by methylation of an intact porphyrin.
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■ Chemistry of Denudatine V. Rearrangement Reactions of Denudatine
Feng-Peng Wang,* Jian-Zhong Wang, and Rong Zhang
*Department of Chemistry of Medicinal Natural Products, School of Pharmacy, west China University of Medical Sciences, Chengdu 610041, China
Abstract
Treatment of denudatine 1 with 10% HCl solution at 30-50 °C leads to rearrangement to two pairs of epimers (5A) and (5B), (8A) and (8B) as well as 7 and 15. The rearrangement mechanisms are discussed. Conversion of 7→5A/5B→15 under acid catalysis can be realized. While the conversion of 15 to 5A/5B, can be realized with NaOH-DMF at 120-126 °C. Structures for 5A/5B, 7, 8A/8B and 15 were established on the basis of chemical and spectral methods.
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■ Pyridazines, 81. A Novel 1,2-Diazine Containing Tricyclic System: Synthesis of Pyridazino[3,4-b][1,5]benzodiazepin-5-ones as Potential HIV-1 Reverse Transcriptase Inhibitors
Gottfried Heinisch, Barbara Matuszczak,* and Kurt Mereiter
*Institute of Pharmaceutical Chemistry, University of Innsbruck, Innrain 52a, A-6020 Innsbruck, Austria
Abstract
Ring closure reactions of 3-alkylamino-6-chloro-N-phenylpyridazine-4-carboxamides (7, 10, 13) bearing a halogen function in ortho position of the carbocyclic moiety were shown to provide convenient access to the pyridazino[3,4-b][1,5]benzodiazepin-5-one system.
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■ Synthesis of 3-(4-Methoxyphenyl)-5,7-dimethoxy-(1H)-qunolin-2- or 4-ones and Derivatives
Martine Croisy, Christiane Huel, and Emile Bisagni
*UMR 176 CNRS, Institut Curie, Section de Recherche, Bâtiments 110-112, Centre Universitaire, 91405 Orsay Cedex, France
Abstract
Condensation of ethyl 2-(4-methoxyphenyl)-3-hydroxyacrylate with 3,5-dimethoxyaniline afforded, depending on experimental conditions, either 3-(4-methoxyphenyl)-5,7-dimethoxy-(1H)-quinolin-2-one or 3-(4-methoxyphenyl)-5,7-dimethoxy-(1H)-quinolin-4-one. Whereas chlorination with phosphorous oxychloride led to the corresponding 2- and 4-chloroquinolines derivatives, 2-chloro-3-(4-methoxyphenyl)-5,7-dimethoxyquinoline was also obtained by using the Meth Cohn method’s.
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■ Direct Synthetic Approach to N-Substituted 1-Amino-2,3-dihydro-1H-imidazole-2-thiones
Joachim G. Schantl* and Irene M. Lagoja
*Institut für Organische Chemie, Universität Innsbruck, Innrain 52, A-6020 Innsbruck, Austria
Abstract
In a efficient one-pot procedure, the title compounds (8) were obtained by the reaction of α-halo ketones (1) with potassium thiocyanate and monosubstituted hydrazines (3). The reaction is considered to proceed via the formation of azo-alkenes (5) and thiocyanic acid. These intermediates, in turn, undergo a [3+2] cycloaddition reaction; the resultant azomethine imine cycloadducts (6) are transformed into the final products (8). The structure of compounds (8) has been confirmed by utilization of various NMR techniques.
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■ Total Synthesis of Polyhydroxylated Piperidine and Pyrrolidine : Expect as Glucosidase Inhibitor
Sang Gyeong Lee,* Yong-Jin Yoon, Sung Chul Shin, Bu Yong Lee, Su-Dong Cho, Sung Kyu Kim, and Ji-Hyun Lee
*Department of Chemistry, Research Institute of Natural Science, Gyeongsang National University, Chinju, 660-701, Korea
Abstract
A new method for preparation of optically active (-)-deoxymannojirimycin (3) and 2R,5S-dihydroxymethyl-3R,4R-dihydroxypyrrolidine (13) based on regioselective epoxide ring opening of 2-tert-butoxycarbonylamino-2-deoxy-3,4-O-isopropylidene-5,6-epoxy-D-glucitol (12) by intramolecular nucleophilic amination has been described.
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■ One-Pot Synthesis of 1,10-Dihydro-2H-imidazo[3,4-a]quinazolin-1-ones from 3-Acyl-1,2-dihydrocinnoline-1,2-dicarboximides
Kazuyoshi Seguchi* and Satoko Tanaka
*Faculty of Human Environmental Sciences, Mukogawa-Women's University, 11-68 Koushien Kyuban-Cho, Nishinomiya, Hyogo 663-8179, Japan
Abstract
3-Substituted 1,10-dihydro-2H-imidazo[3,4-a]quinazolin-1-ones were prepared from 3-acyl-1,2-dihydrocinnoline-1,2-dicarboximides and piperidine in DMSO in moderate yields via Michael additions, skeletal rearrangements, and subsequent decarboxylation.
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■ Remarkable Fast N-Alkylation of Azaheterocycles under Microwave Irradiation in Dry Media
Dariusz Bogdal,* Jan Pielichowski, and Krzysztof Jaskot
*Institute of Organic Chemistry, Politechnika Krakowska, ul. Warszawska 24, 31-155 Krakowska, Poland
Abstract
Under microwave irradiation a number of azaheterocycles (i.e., pyrrole, imidazole, pyrazole, indole, and carbazole) react remarkably fast with alkyl halides to give exclusively N-alkyl derivatives.
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■ Synthesis of 1-[ω-[(Arylamino)carbonyl]-alkyl]-4-(benzocycloalkyl)piperazines
Youssef El-Ahmad, Philippe Maillet, Elisabeth Laurent, Akram Talab, Gilles Tran, and Roland Ollivier*
*Centre de Recherche, Coorpération Pharmaceutique Française, 13, rue Benjamin Franklin, 77000 La Rochette, France
Abstract
A series of 1-[ω-[(arylamino)carbonyl]alkyl]-4-(benzocycloalkyl)piperazines (1a-v) was prepared either by reacting the precursor 4-[ω-[(arylamino)carbonyl]alkyl]piperazine (2a-j) with 1-chlorobenzocycloalkanes (3a-c) (Procedure A) or by reacting the N-aryl-ω-chloroalkanamides (5a-j) with the 4-(benzocycloalkyl)piperazines (10a-c) (Procedure B). The best yields were obtained using procedure A.
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■ Reactivity of 1,3-Di-tert-butylaziri-dinones with Phenyl Substituents. A New Fragmentation of α-Lactams
Masako Shimazu, Yasuyuki Endo,* and Koichi Shudo
*Faculty of Pharmaceutical Sciences, University of Tokyo, Hongo, Bunkyo-ku, Tokyo 113, Japan
Abstract
Several isolable aziridinones with bulky substituents were prepared and their reactions with nucleophiles, i.e., methanol, sodium methoxide and benzylamine, were investigated. A novel fragmentation of aziridinones having a phenyl group on the C3 moiety was found.
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■ Electrophilic Cyanations. I. Synthesis of Thiocyanatoheteroarenes and Tosylheteroarenes from Mercaptoheteroarenes Using p-Toluenesulfonyl Cyanide
Akira Miyashita,* Izuru Nagasaki, Akiko Kawano, Yumiko Suzuki, Ken-ichi Iwamoto, and Takeo Higashino
*Schol of Pharmaceutical Sciences, University of Shizuoka, 52-1 Yada, Shizuoka 422-8526, Japan
Abstract
Mercaptoheteroarenes (1) underwent electrophilic cyanation with p-toluenesulfonyl cyanide (TsCN) in THF in the presence of NaH to give the corresponding thiocyanatoheteroarenes (2) in moderate to good yields. In DMF, tosylheteroarenes (4) were formed by substitution with p-toluenesulfinate ion through thiocyanatoheteroarenes (2).
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■ Novel Entry into Benzo[c]phenanthridine Systems through a Tandem Alkene Acylation-Cyclodehydration
Raul SanMartín, Eduardo Martínez de Marigorta, Isabel Moreno, and Esther Domínguez*
*Kimika Organikoa Saila, Zientzi Fakultatea, Euskal Herriko Unibertsitatea, Vasco, P.O. Box 644, 48080-Bilbao, Basque Country, Spain
Abstract
12-alkylbenzo[c]phenanthridines have been obtained by an overall high yielding synthetic methodology. Key steps involve Peterson methylenation and an efficient one-pot alkene acylation-cyclization. Smooth oxidation to the benzo[c]phenanthridinone system is also reported.
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■ Arylation of 1,3-Dimethyllumazines by Arenediazonium Salts
Takashi Sugimoto* and Wolfgang Pfleiderer
*Department of Natural Science Informatics, School of Informatics and Sciences, Nagoya University, Chikusa, Nagoya, Aichi 464-8601, Japan
Abstract
Reaction of 7-methoxy-1,3-dimethyllumazine with benzenediazonium chloride in an alkaline aqueous solution afforded 6-phenyl- and 6-biphenyl-7-methoxy-1,3-dimethyllumazines. Treatment of 7-dimethylamino-1,3-dimethylluamzine with benzenediazonium chloride similarly gave the 6-phenyl and 6-biphenyl derivatives of the substrate together with 7-methylamino-6-phenyl-1,3-dimethyllumazine. Analogous reactions of 7-substituted 1,3-dimethyllumazines with several arenediazonium chlorides are described.
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■ New Ring Transformation Reaction of Imidazothiazole with Acetylenic Acid Esters
Dong Chan Kim, Dong Jin Kim, Kye Jung Shin, Sang Woo Park*, and Kyung Ho Yoo*
*Biochemicals Research Center, Division of Applied Science, Korea Institute of Science and Technology, P.O. Box 131, Cheongryang, Seoul 130-650, Korea
Abstract
3-Phenyl-5,6-dihydroimidazo[2,1-b]thiazole (1) as a nucleophile reacted with acetylenic acid esters such as ethyl propiolate and dimethyl acetylenedicarboxylate to give the new ring transformation compounds (2-oxo-imidazoline-1-yl)acrylic acid ethyl esters (6a-b) and [2-oxo-imidazoline-1-yl]but-2-enedioic acid diethyl esters (7a-b), respectively. Similarly, treatment of reactive imidazo[2,1-b]thiazolium betaines (3a-b) with acetylenic acid derivatives led to the corresponding ring transformation compounds. This reaction proceeded by the participation of water, and the resulting compounds were obtained in a mixture of cis and trans isomers.
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■ Synthesis of (±)-Cathenamine and (±)-19-Epicathenamine, Isolated as Their C-21α-Cyano Derivatives
Mauri Lounasmaa,* Reija Jokela, Pirjo Hanhinen, and Ulla Anttila
*Laboratory for Organic and Bioorganic Chemistry, Technical University of Helsinki, P.O. Box 6100, FIN-02150 HUT Espoo, Finland
Abstract
A short synthetic route from the easily accessible O-Boc-Z-geissoschizine (2a) to (±)-cathenamine (3) and (±)-19-epicathenamine (4) is presented. Both compounds, which are important biogenetic intermediates in the formation of heteroyohimbine alkaloids, were isolated as their synthetic equivalents, (±)-21α-cyanotetrahydroalstonine (5) and (±)-21α-cyano-19-epiajmalicine (6), respectively.
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■ Heterocycles from 2-Aminopyridine and Derivatives of 3-Methylbenzofuran-2-carboxylic Acid
Yvette A. Jackson* and Mark F. Williams
*Department of Chemistry, Mona Campus, University of the West Indies, Mona, Kingston 7, Jamaica, West Indies
Abstract
3-Bromoethyl-2-carboethoxy-5,6-dimethoxybenzofuran (3b) reacted with 2-aminopyridine to give not only the expected 2-carboethoxy-5,6-dimethoxy-3-benzofuranmethyl-2’-aminopyridinium bromide (4b), but also N-(2-carboethoxy-5,6-dimethoxy-3-benzofuranmethyl)-N-2-pyridylamine (5). Synthesis of 3-methoxy-6,7,12-trihydro-6-oxo-[1]benzofurano[2,3-c]-1H-pyrido[1,2-a][1,3]diazepinium bromide (12) is also described.
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■ One Pot Synthesis of Selenides Containing Polyarylthioether Moiety
Song Seok Shin and Kyongtae Kim*
*Department of Chemistry, Seoul National University, San 56-1, Shillim-Dong, Kwanak-Gu, Seoul 151-742, Korea
Abstract
The reactions of 5-arylthianthreniumyl perchlorates with sodium hydrogen selenide in ethanol and lithium n-butylselenolate in tetrahydrofuran under nitrogen at reflux afforde bis[2-(2-arylthiophenylthio)phenyl] selenides and 2-arylthio-2’-(n-butylseeleno)diphenyl sulfides in 26 - 83% and 23 - 98% yields, respectively. A sulfurane mechanism is proposed.
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■ AICI3-DMF Reagent in the Friedel-Crafts Reaction. Application to the Synthesis of Symmetrical Benzophenones Derivatives
Huseyin Ucar,* Kim Van derpoorten, and Jacques H. Poupaert
*Unité de Chimie Pharmaceutique, Ecole de Pharmacie, Université Catholique de Louvain, Avenue E. Mounier 73, B-1200 Bruxelles, Belgium
Abstract
Synthesis of series of symmetrical benzophenone derivatives by C-alkylation reaction of 2(3H)-benzoxazolone and 2(3H)-benzothiazolone with carbon tetrachloride in presence of AlCl3-DMF reagent is reported.
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■ Reaction of Pyridine-N-oxide with a Strained Seven-membered Cycloalkyne. A Correction
Hans Jörg Lindner, Adolf Krebs,* Jan-Hinrich Förster, and Volker Sinnwell
*Institut für Organische Chemie, Universitat Hamburg, Martin-Luther-King-Platz 6, D-20416 Hamburg, Germany
Abstract
Pyridine-N-oxide adds at room temperature to 3,3,6,6-tetramethyl-1-thia-cycloheptyne to give the 3H-azepine (3). A mechanism of formation for 3 is discussed. On heating 3 rearranges to yield the 3-substituted pyridine (8).
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■ Fumaflorine, a New 1-Benzylisoquinoline Alkaloid from Fumaria densiflora
Eva Táborská, Hana Bochoráková, Jaromír Sousek, Petr Sedmera, Vladimír Havlícek, and Vilím Simánek*
*Institute of Medical Chemistry, Palacky University, 3, Hnevotínská, 775 15 Olomouc, Czech Republic
Abstract
Fumaflorine (1), a new 1-benzylisoquinoline alkaloid, was isolated from the aerial parts of Fumaria densifloira. Its structure was determined by spectroscopic methods.