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. 43, No. 9, 1996
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■ Recognition of Flavin Mononucleotide (FMN) by a Melamine Derivative Having a Guanidinium Ion via a Multisite Binding
Takeshi Kajiki, Norio Tamura, Tatsuya Nabeshima, and Yumihiko Yano*
*Department of Chemistry, Faculty of Engineering, Gunma University, 1-5-1 Tenjin-cho, Kiryu 376-8515, Japan
Abstract
A melamine derivative bearing a guanidinium ion was found to act as a flavin mononucleotide (FMN) receptor via complementaly hydrogen bonding. The receptor extracts FMN in H2O into CHCl3 and acts as as effective carrier for the transport of FMN through a liquid membrane of CHCl3.
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■ Molecular Structure Determination and Studies on Chemical and Electrochemical Redox Reactions of a Cyclic Triselenide Compound, 4,7-Dimethoxybenzotriselenole
Satoshi Ogawa, Tadahito Ohmiya, Takamasa Kikuchi, Yasushi Kawai, Shigeya Niizuma, and Ryu Sato*
*Department of Applied Chemistry and Molecular Science, Faculty of Engineering, Iwate University, 4-3-5 Ueda, Morioka, Iwate 020-8551, Japan
Abstract
Crystalline triselenide compounds, 4,7-dimethoxybenzotriselenole, was prepared and characterized by single-crystal X-ray analysis; in the unit cell the two molecules stack each other with distorted triselenide rings sticking out from the benzene column. Interconversion accompanying one-electron transfer steps between the triselenole and the corresponding triselenolium radical cation salt has been constructed by chemical and electrochemical trreatments.
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■ Synthesis of New Tetracyclic Oxazolocarbazoles as Functionalized Precursors to Antioxidative Agents, Antiostatins and Carbazoquinocins
Tominari Choshi, Hiroyuki Fujimoto, Eiichi Sugino, and Satoshi Hibino*
*Faculty of Pharmacy and Pharmaceutical Sciences, Fukuyama University, Fukuyama, Hiroshima 729-02, Japan
Abstract
New tetracyclic oxazolo[4,5-c]arbazole and oxazolo[4,5-c]carbazole ring systems as functionalized precursors to antioxidative antiosratins (A1-4 and B2-5) and carbazoquinocins (A-F) were synthesized.
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■ Preparations of 1-Hydroxyindole Derivatives and Their Potent Inhibitory Activities on Platelet Aggregation
Masanori Somei,* Koji Yamada, Masakazu Hasegawa, Mutsuko Tabata, Yoshiyuki Nagahama, Harunobu Morikawa, and Fumio Yamada
*Faculty of Pharmaceutical Scicences, Kanazawa University, 13-1 Takara-machi, Kanazawa 920-0934, Japan
Abstract
1-Hydroxymelatonin, 5-bromo- and 5,7-dibromo-1-hydroxytryptamine derivatives, 1,4-dihydroxy-5-nitroindole, 1-hydroxy-3-methylsulfinylmethylindole, and 5-acetyl-1,3,4,5-tetrahydro-1-hydroxypyrrolo[4,3,2-de]quinoline were synthesized for the first time. 1-Hydroxyindoles reveraled potent inhibitory activities on platelet aggregation.
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■ A Facile Synthesis of Nine- and Ten-membered Cyclic Ethers Utilizing Intramolecular endo-Mode Cyclization of the Cojugated Allenyl Ketones
Woo Song Lee, Norio Nakazawa, Motoo Shiro, and Yoshimitsu Nagao*
*Faculty of Pharmaceutical Sciences, University of Tokushima, Sho-machi, Tokushima 770-8505, Japan
Abstract
Intramolecular endo-mode cyclization reactions of the conjugated allenyl ketones (3) and (4) were carried out in the presence of BF3·OEt2, B(CF3SO3)3, and CF3SO3H in CH2Cl2 to give the corresponding nine- and ten-membered cyclic ethers (5-7) as crytalline compounds in satisfactory yields. The structure of 6 was confirmed by its X-ray crystallographic analysus.
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■ A New Synthetic Approach to Fused 1,4-Dihydropyridazines
Tetsuo Yamasaki, Mitsuo Oda, Yoshinari Okamoto, Tadashi Okawara, and Mitsuru Furukawa*
*Faculty of Pharmaceutical Sciences, Kumamoto University, 5-1 Oe-hon-machi, Kumamoto 862-0973, Japan
Abstract
Cyclization of the halohydrazones (3) prepared by the reaction of 5-hydrazinopyridazinones (1) with ethyl bromopyruvate (2a) and phenyl bromide (2b) in EtOH produced pyrrolo[2,3-d]pyridazinones (4). On the other hand, heating of ethyl bromopyruvate pyridazinylhydrazone (3a) in dioxane afforded 1,4-dihydropyridazino[4,5-c]pyridazine (5a) in low yield. Compounds (5) were also obtained in good yields by heating the dihalohydrazones (7), which were synthesized from 4-chloro-5-hydrazinopyridazinones (6) and 2a,b in the presence of An(Cu). Heating of furylhydrazone (9) under similar consitions to those of the cyclization of 7 provides 3,6-provided 3,6-dihydrofuro[3,4-c]pyridazine (10).
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■ Synthesis and 13C-Nmr Studies of Quinoxaline Spirans and Carboxyureides
Petrus J. Zeegers* and Malcolm J. Thompson
*Department of Chemistry, The Flinders University of South Australia, PO Box 2100 Adelaide SA 5001, Australia
Abstract
New quinoxaline spirans were synthesized by the condensation reaction between alloxan and a series of 2-amino-N,N-dimethylanilines derived from substituted nitrophenols. The spiro compounds were then subjected to treatment with hydrogen peroxide in acidic media. This procedure leads to the formation of coloured compounds which were previously proposed to be parabanic acid imines. This study shows the compounds to be quinoxaline carboxyureides.
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■ Synthesis of an Antibacterial and Antifungal Cinnoline Derivative by Rearrangement of a β-Carboline Derivative
Shazia Anjum, Tahira Sarfraz, Yusuf Ahmed, and Atta-ur-Rahman*
*H. E. J. Postgraduate Institute of Chemistry, University of Karachi, Karachi-75270, Pakistan
Abstract
A heterocyclic system (6) containing a β-carboline moiety is descibed. o-Nitrophenylpyruvic acid and tryptamine hydrochloride were condensed to give 1-(2’-nitrobenzyl)-1,2,3,4-tetrahydro-β-carboline (3). 3, on dehydrogenation, gave 1-(2’-nitrobenzyl)-β-carboline(4) which was treated with methanolic KOH to furnish 1-(3’-2’-1’-benzisoxazole)-β-carboline (5) ehich on thermolysis or photolysis afforded the indolocinnoline derivative (6).
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■ Convenient Access to 3,4,5-Trisubstituted Pyridines
Angela De Munno,* Vincenzo Bertini, Nevio Picci, Francesca Iemma, and Marco Pocci
*Dipartimento di Chimica e Chimica Industriale, Universita di Pisa, Via Risorgnimento 35, I-56126 Pisa, Italy
Abstract
The reaction of 3,5-dochloro-4-pyridinecarbonitrile towards nucleophilic substitution of chlorine atoms and nucleophilic addition to the cyano group has been studied in presence of different nucleophiles and solvents in order to evidence the best conditions for the synthesis of 3,4,5-trifunctionalized pyridines. Besides the products of substitution of only one chlorine atom, 3,5-bis(ethylthio)-4-pyridinecarbonitrile and 3,5-bis(tert-butylthio)-4-pyridinecarbonitrile have been prepared in high yields and the reduction of their cyano to amino group has been studied in order to obtain model molecules and new selective inhibitors of extramitochondrial amine oxidase enzymes.
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■ Conformational and Configurational Analysis of 2-Substituted 7-Oxabicyclo[2.2.1]heptadienic α-Tetralones
Olivier Duval,* Michael A. Lynch, Pascal Richomme, and Louis M. Gomès
*UFR de Médecine et Pharmacie, SONAS, Université d'Angers, 16 Bd. Daviers, 49100 Angers, France
Abstract
The diastereoisomeric pairs of 1-(2-tetralonyl)-2,3-dicarbomethoxy-7-oxabicyclo[2.2.1]hepta-2,5-dienes were purified and separated using tlc procedures and their 1H and 13C spectra were recorded nd assigned. The respective conformations and configrations of the enantiomeric pairs were determined using a combination of selective homonuclear decoupling techniques, NOE difference spectroscopy and 2D heteronuclear correlation sequences (HECTORR and COLOC).
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■ N-Substituted 5,5-Dimethyl-2,5-dihydro-4H-isoindol-4-ones: Synthesis and NMR-Investigation
Helmut Spreitzer*, Wolfgang Holzer, Gunther Fülep and Christiane Puschmann
*Institute of Pharmaceutical Chemistry, University of Vienna, Althanstrasse14, A-1090 Vienna, Austria
Abstract
The synthesis of novel N-substituted 5,5-dimethyl-2,5-dihydro-4H-isoindol-4-ones by reaction of 5,5-dimethyl-2,5-dihydro-4H-isoindol-4-ones (1) with appropriate electrophiles (methyl iodide, 3,3-dimethylallyl bromide, 2-N,N-dimethylethyl chloride, ethyl 3-bromopropionate, benzoyl chloride, N,N-dimethylchloroformate, phenyl chloroformate) is described. Moreover,detailed nmr spectroscopic studies (1H, 13C) with the title compounds are presented.
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■ A Mild Preparation of 2,6-Piperidinediones
Jiarong Zhu, Pham Huy Choung, Pascale Lemoine, Alain Tomas, and Hervé Galons
*Laboratoire de Chimie Therapeutique, Faculte de Pharmacie, 4 avenue de l'Observatoire75270 Paris Cedex 06, France
Abstract
Substituted glutaric acids reacted with alkyloxyamines in the presence of N-ethyl-N-dimethylaminopropylcarbodiimide hydrochloride to form 1-alkyloxy-2,6-piperidinediones. The protecting group on the nitrogen was easily removed in high yield. This process is exemplified by the preparation of aminoglutethimide.
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■ Efficient Synthesis of 2-Iodo and 2-Dicyanomethyl Derivatives of Thiophene, Selenophene, Tellurophene, and Thieno[3,2-b]thiophene
Kazuko Takahashi* and Shinji Tarutani
*Department of Chemistry, Graduate School of Science, Tohoku University, Sendai 980-8578, Japan
Abstract
An effective synthesis of 2-iodothiophene, 2-iodotellurophene, and 2-iodothieno[3,2-b]thiophene and a Pd-catalysed carbon-carbon coupling reaction of these iodo derivatives as well as 2-iodoselemophene with malononitrile affording novel thienyl-, tellurienyl-, thieno[3,2-b]thienyl- and selenienylmalononitrile are described. These heteroarylmalononitriles are important synthons for the preparation of 2-dicyanomethylene-2,5-dihydroheterophene chromophores.
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■ Substituent Effect of the Fluorine Atom on Electrophilic Deuteration of Benzo[h]quinoline
Wei Wu, Ken-ichi Saeki,* and Yutaka Kawazoe
*Faculty of Pharmaceutical Sciences, Nagoya City University, Tanabe-dori, Mizuho-ku, Nagoya 467-8603, Japan
Abstract
Substituent effect of the fluorine atom on electrophillic substitution using the deuterium cation was examines by treating monofluorinated derivatives of benzo[h]quinoline with 96% D2SO4 at 80°C. The effect of the fluorine atom could not simply be explained by potent electron-withdrawing I-effect and electron-donating R-effect. The observed reaction rates were not simply correlated either with the stability of the σ-complexes estimated by a semiempirical molecular orbital MOPAC PM3 method. A fair correlation was found but not sufficiently for quantitative prediction of the rate.
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■ Syntheses of Imidazo[1,2-c]pyrimidines and 1,3,5-Triazepines from 2-Azabuta-1,3-dienes and 1,2-Diamines
Antonio Lorente* and Marta Casillas
*Department of Organic Chemistry, University of Alcalá, 28871 Alcalá de Henares (Madrid), Spain
Abstract
Syntheses of imidazo[1,2-c]pyrimidines and 1,3,5-triazepines from 2-azabuta-1,3-dienes and 1,2-diamines are reported.
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■ Hydrogen N-Excange Reaction of Methyl-substituted N-Amino- and N-Methylquinolinium Ions
Wei Wu, Ken-ichi Saeki,* Isamu Terashima, and Yutaka Kawazoe
*Faculty of Pharmaceutical Sciences, Nagoya City University, Tanabe-dori, Mizuho-ku, Nagoya 467-8603, Japan
Abstract
H-D Exchange rates of the hydrogens of methyl-substituted N-amino-quinolinium ions were comperad with those of the corresponding N-methylquinolinium derivatives. Intreatment carried out below 90°C in phosphate-buffered D2O solvents at pD’s ranging from 3.4 to 11.7, only the ring α-hydrogen and the α- and γ-methyl hydrogens underwent H-D exchange. The N-amino group facilitated exchanges of the ring α-hydrogen several tens of times more than did the N-methyl group, whereas the former facilitated the exchange of substituent methyl hydrogens only several times more than the latter. The pD-dependence of the exchange reactions are described.
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■ Formation of a Ten-membered Lactam by Chloroacetamide Photocyclization on the Indole 4-Position
M.-LLuïsa Bennasar, Ester Zulaica, Antonio Ramírez, and Joan Bosch*
*Laboratory of Organic Chemistry, Faculty of Pharmacy, University of Barcelona, Av. de Joan XXIII, s/n, 08028 Barcelona, Spain
Abstract
Photocyclization of tricyclic chloroacetamide (3) occurs on the indole 4-position to give the ten-membered lactam (4), whose structure was confirmed by conversion to the tetracyclic amine (6). Some conformational aspects of lactam (4) and thiolactam (5), namely the observation of conformers by nmr as a consequence of a restricted inversion of the ten-membered ring, are discussed.
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■ Synthesis of New Pyridazino Anellated Heterocycles via Inverse-Electron-Demand Diels-Alder Reactions on Cyclic Ketene-S,N-acetals
Susanne Pippich and Herbert Bartsch*
*Institute of Pharmaceutical Chemistry, University of Vienna, Althanstrasse14, A-1090 Vienna, Austria
Abstract
Bicyclic ketene-S,N-acetals were synthesized and their reactivity as electron-rich dienophiles was investigated employing electron-deficient azadienes. A series of new condensed pyridazines was obtained.
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■ Claisen Orthoester Rearrangement in the Direct Preparation of Deplancheine Derivatives Possessing a Malonyl Group at C-15
Mauri Lounasmaa* and Pirjo Hanhinen
*Laboratory for Organic and Bioorganic Chemistry, Technical University of Helsinki, P.O. Box 6100, FIN-02150 HUT Espoo, Finland
Abstract
The Claisen orthoester rearrangement utilizing allylic alcohols (1) and (2), and triethyl ortho-2-ethoxycarbonylacetate (= ethyl triethyl orthomalonate) (4) leads directly to deplancheine derivatives (12-14) possessing a malonyl group at C-15. Compounds (12-14) represent the prototype of highly desired intermesiates for the preparation of Corynanthé alkaloids and similar compounds.
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■ Saturated Polyheteroperylenes from the Reaction of Glyoxal and Pyruvaldehyde with 3-(2-Hydroxyethyl)- and 3-(2-Aminoethyl)-1,3-propanediamines and Prediction of Their Stereochemistry
Tadashi Okawara,* Yoshinari Okamoto, Shuji Ehara, Tetsuo Yamasaki, and Mitsuru Furukawa
*Faculty of Pharmaceutical Sciences, Kumamoto University, 5-1 Oe-hon-machi, Kumamoto 862-0973, Japan
Abstract
Reaction of 3-(2-hydroxyethyl)- and 3-(2-aminoethyl)-1,3-propanediamines with glyoxal gave dioxatetraaza- and hexaazaperhydroperylenes. Each of the possible stereoisomers for the products was presicted 1H- and 13C-nmr spectra and heats of formation from a molecular orbital methos (AM1).
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■ Two New Dimeric Xanthones in Mesua ferrea
Munekazu Iinuma,* Hideki Tosa, Yoshiyuki Tanaka, and Soedarsono Riswan
*Departmeny of Pharmacognosy, Gifu Pharmaceutical University, 6-1 Mitahora-higashi 5-chome, Gifu 502-8585, Japan
Abstract
The new dimeric xanthones linked through a C5 unit, mesuferrols A and B, were isolated from the bark of Mesua ferres (Guttiferae), in addition to two known xanthones (1,7-dihydroxy- and 5-hydroxy-1-methoxyxanthone) and a flavonoid ((-)-epicatechin). The structures of these compounds were estsblished by the aids of spectroscopic analysis including 2D nmr technique.
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■ Cycloaddition Reactions of Pyridinium Ylides and Oxidopyridiniums
Wanda Sliwa
*Institute of Chemistry and Environment Protection, Pedagogical University, Al. Armii Krajowej 13/15, 42-201 Czestochowa, Poland
Abstract
Inter- and intramolecular cycloaddition reactions of pyridinium ylides and o oxidopyridinums are presented, along with such reactions of related azaaromatics.