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. 29, No. 10, 1989
Published online:
■ Photochemical [2+2]- and [4+2]Cycloadditions of N-Methylphthalimide to Allytrimethylsilane
Yasuo Kubo,* Eiko Taniguchi, and Takeo Araki
*Department of Chemisttry, Faculaty of Science, Shimane University, 1060, Nishikawatsu-cho, Matsue 690-0823, Japan
Abstract
Irradiation of N-methylphthalimide (1) with allyltrimethylsilane (2) gave a [2+2]cycloadduct (9) possibly from the singlet excited state of 1 together with [4+2]-cycloadducts (3a,b) from the triplet excited state of 1. The adduct 9 was found to be extremely photoreactive.
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■ An Enantioconvergent Route to (-)-Anisomycin from Both (S)- and (R)-Enantiomers of Epichlorohydrin
Seiichi Takano,* Yoshiharu Iwabuchi, and Kunio Ogasawara
*Pharmaceutical Institute, Tohoku University, Aobayama, Sendai 980-8578, Japan
Abstract
An enantioconvergent route to (-)-anisomycin, an antibiotic isolated from Streptomyces species, has been established starting from both (R). and (S)-enantiomers of epichlorohydrin.
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■ A Total Synthesis of the Novel Cyclodepsipeptide (+)-Geodiamolide A
Yohiro Hirai, Katsuyuki Yokota, Hiroshi Sakai, Takao Yamazaki, and Takefumi Momose*
*Faculty of Pharmaceutical Sciences, Toyama Medical and Pharmaceutical University, 2630 Sugitani, Toyama, Toyama 930-0194, Japan
Abstract
A diastereo-controlled total synthesis of (+)-geodiamolide A (1) has been accomplished via a prior synthesis of the tetrapropionate derived fragment 11 and of the iodinated N-methyltyrosyltripeptide 17, the latter involving direct iodination of the tripeptide, and subsequent coupling of both fragments followed by the trichlorobenzoyl chloride-mediated macrolactonization.
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■ Intramolecular Diels-Alder Reaction of 3-(1H-Indol-3-yl)-2-propenoates: Synthesis of Fused Indole Compounds
Yasuo Shimoji,* Fujio Saito, Sadao Sato, Kuniyuki Tomita, and Yasuhiro Morisawa
*Sankyo Research Laboratories, Sankyo Co., Ltd., 1-2-58 Hiromachi, Shinagawa-ku, Tokyo 140-8710, Japan
Abstract
Intramolecular Diels-Alder reaction of 3-(1H-indol-3-yl)-2-propenoates having the olefinic substituents at the 1-position of the indole ring gave stereoselectively fused indole compounds.
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■ Heterosryl Stabilised Azinium Yields. 1,3,4-Thiadiazole as Stabilising Group
Rosa Carceller, Jose Luis Garcia-Navio, Maria Luisa Izquierdo, Julio Alvarez-Builla, Julia Sanz-Aparicio, and Feliciana Florencio
*Departamento de Química Orgánica, Universidad de Alcalá de Henares, 28871 Alcalá de Henares (Madrid), Spain
Abstract
Reaction of 1-[(1,3,5-thiadiazol-2-yl )]-methylpyridinium derivatives with diverse electrophilic produced disubstituted heteroarylmethylpyridinium ylides. Only with phenyl isothiocyanate 1,3-dipolar cycloaddition was observed.
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■ A New Unexpected Ring Closure from 3-Amino-1,5-diaryl-1H-1,2,4-triazoles
Éva K. Bozó,* Géza Szilágyi, József Langó, and István Pelczer
*Institute for Drug Research Ltd., H-1325 Budapest, POB 82, Hungary
Abstract
A new unexpected ring closure of 3-amino-1,5-diaryl-1H-1,2,4-triazoles with 2,2’-dithiobis(benzoyl chloride) to a polycondensed system is reported.
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■ Torvonin-B, a Spirostane Saponin from Solanum torvum
Pawan K. Agrawal,* Umar Mahmood, and Raghunath S. Thakur
*Central Institute of Medicinal and Aromatic Plants, Lucknow 226016, India
Abstract
A new steroidal saponin, ‘torvonin B’ (1) has been isolated from S. torvum leaves and its structure has been established as neosolaspigenin-3-O-β-D-fucopyranosyl-(1→2)-β-D-quinovopyranoside.
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■ Plumerinine — A Novel Lupin Alkaloid from Plumeria rubra
Syed Najam-ul-Hussain Kazmi, Zaheer Ahmed, Waseem Ahmed, and Abdul Malik*
*International Centre for Chemical Sciences, H. E. J. Research Institute of Chemistry, University of Karachi, Karachi-75270, Pakistan
Abstract
Plumerinine, a novel lupin alkaloid has been isolated from the stem of Plumeria rubra and assigned structure 1 on the basis of spectral studies. This constitutes the first example of the occurrence of bicyclic lupin alkaloids in subfamily Plumerioideae of the Apocyanaceae.
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■ Synthesis of New s-Triazolo[4,3-b]pyridazines
Adbel Moneim El Massry and Adel Amer
*Department of Chemistry, Faculty of Science, Alexandria University, P.O. Box 426, Ibrahimia, Alexandria 21321, Egypt
Abstract
The 2,3-dihydropyridazin-3-ones 9 were synthesized via functionalized pyruvic acids 7 with hydrazine hydrate. Transformation of 9 to s-triazolo[4,3-b]pyridazines 10a-c and 11a-c has been achieved through the 3-chloropyridazines 4 by treatment with semicarbazide aqd phenylacetylhydrazine, respectively.
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■ Synthesis and Biological Evalution of Methylated Derivatives of the Cooked Food Mutagen Metabolite 2-Amino-3,6-dihydro-3-methyl-7H-imidazo[4,5-f]quinolin-7-one (7-OH-IQ)
Mohammad Bashir, David G. I. Kingston,* Roger L. Van Tassell, and Tracy D. Wilkins
*Department of Chemisry, Virginia Polytecnic Institute and State University, Blacksburg, Virginia 24061-0212, U.S.A.
Abstract
The major anaerobic metabolite of the potent cooked food mutacarcinogen IQ is the oxidised product 7-OH-IQ,which is itself a powerful direct-acting mutagen. The O-methyl and N-methyl derivatives of 7-OH-IQ have been prepared to determine whether the tautomeric form of 7-OH-IQ plays any role in its bioactivity. Both N-methyl 7-OH-IQ and O-methyl 7-OH-IQ show comparable mutagenicity when tested directly against the T98 strain of S. typhimurium, indicating that the quinolone structure does not play a major role in the mutagenicity of 7-OH-IQ. Neither 7-OH-IQ nor the methylated derivatives cleaved DNA in the presence of metal cations.
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■ Vaccaxanthone, a Novel Xanthone Acid from Saponaria vaccaria
Syed Najam-ul-Hussain Kazmi, Zaheer Ahmed, and Abdul Malik*
*International Centre for Chemical Sciences, H. E. J. Research Institute of Chemistry, University of Karachi, Karachi-75270, Pakistan
Abstract
Vaccaxanthone (1), a novel 7-carboxy-1,3,5,8-tetraoxygenated xanthone has been isolated from Saponaria vaccaria. Its structure has been established from spectroscopic data including uv, ir, high resolution-ms, 1H- and 13C-nmr as 1,8-dihydroxy-3,5-dimethoxyxanthone-7-carboxylic acid.
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■ New 4-Ring Fused Heterocyclic Systems Derived from Pyrimido[6,1-a]isoquinolin-4-ones. Potent c-AMP Phosphodiesterase Inhibitors
Graham A. Howarth*
*Central Research Laboratories, Ciba-Geigy PLC, Tenax Road, Trafford Park, Manchester M17 1WT, U.K.
Abstract
The pyrimido[6,1-a]isoquinolin-4-one ring system has been annelated to form new 4-ring fused heterocyclic systems of interest as c-AMP phosphodiesterase inhibitors. The new ring systems prepared represent derivatives of triazolo[4,5-d]pyrimido[6,1-a]isoquinolin-5-one, imidazo[4,5-d]pyrimido[6,1-a]isoquinolin-5-one and thiazolo-[5,4-d]pyrimido[6,1-a]isoquinolin-5-one.
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■ The Synthesis of 5-Alkylaminomethylthieno[2,3-b]pyrrole-5-sulfonamides
George D. Hartman* and Wasyl Halczenko
*Department of Medicinal Chemistry, Merck Sharp and Dohme Research Laboratories, West Point, PA 19486, U.S.A.
Abstract
Novel 2-aminomethylthieno[2,3-b]pyrrole-5-sulfonamides have been prepared by direct chlorosulfonation/amidation of N-protected intermediates.
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■ A New Heterocyclic Rearrangement: Conversion of 1,2-Dihydropyrimidines into Pyrroles
Antonio de la Hoz, José Elguero, and Carmen Pardo*
*Departamento de Química Orgánica, Facultad de Química, Universidad Complutense de Madridas, Ciudad Universitaria, E-28040 Madrid, Spain
Abstract
2-[hydroxy(methoxycarbonyl)methyl]-2-(methoxycarbonyl)-1-phenyl-1,2-dihydropyridines react with acetic anhydride to give 2-methoxycarbonyl pyrroles. A reaction intermediate has been isolated and a mechanism is proposed for the reaction process.
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■ Heterocycles from Nitrile Oxides. Part V. 4-Amino-Δ2-1,2,4-oxadiazolines
Mustafa M. El-Abadelah,* Ahmad Q. Hussein, and Adel M. Awadallah
*Chemistry Department, Faculty of Science, University of Jordan, Amman 11942, Jordan
Abstract
Aryl nitrile oxides undergo 1,3-dipolar cycloaddition with alkanone hydrazones to give 4-amino-3-aryl-5,5-dialkyl-δ2-1,2,4-oxadiazolines. Lead tetraacetate oxidation of these 4-amino-δ2-1,2,4-oxadiazolines brings about smooth heteroring cracking into the corresponding nitrile, ketone, and nitrogen.
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■ On the Nitration of 5-Phenyl- and 3-Methyl-5-phenylisoxazoles
Stefano Chimichi* and Barbara Cosimelli
*Dipartimento di Chimica Organica "Ugo Schiff", Università di Firenze, Via Gino Capponi 9, I-50121 Firenze, Italy
Abstract
The nitration of the title compounds 1 and 2 with HNO3-H2SO4 was reexamined; 4-nitro-5-phenylisoxazole (3) and 3-methyl-4-nitro-5-phenylisoxazole (4) were obtained by treatment of 1 and 2 with HNO3 in acetic anhydride under miid conditions.
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■ Some Observations on the Reactivity of β-Aminoenones towards Phenacylamine Hydrochloride
Angel Alberola,* José M. Andrés, Alfonso González, Rafael Pedrosa, and Martina Vicente
*Deparamento de Química Orgánica, Facultad de Ciencias, Universidad de Valladolid, 47005 Valladolid, Spain
Abstract
β-Aminoenones react with phenacylamine hydrochloride to give mixture of 2- and 3-acylpyrroles. The reaction is a two steps process: formation of an isolable β-phenacylaminoenone intermediate, and cyclization of this to the final 2- and/or 3-acylpyrroles, depending on the substituents on the starting compounds.
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■ Regioselective Synthesis of 2- and 3-Acylpyrroles by Reaction of β-Aminoenones with α-Aminoketone Hydrochloride
Angel Alberola,* José M. Andrés, Alfonso González, Rafael Pedrosa, and Martina Vicente
*Deparamento de Química Orgánica, Facultad de Ciencias, Universidad de Valladolid, 47005 Valladolid, Spain
Abstract
A high regioselective synthesis, with good to excellent yields, of 2- and 3-acylpyrroles from β-aminoenones and α-aminoketones is described. The formation of 2-acylpyrroles or their 3-acylisomers depends on the pattern substitution on the reactants.
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■ Preparation of Cyclopropa[4,5]pyrido[2,3-d]- and Pyrrolo[2,3-d]pyrimidine Derivatioves Using Intramolecular Carbene Reactions
Michihiko Noguchi,* Naohiko Fujimoto, Masatsugu Nagashima, and Shoji Kajigaeshi
*Department of Applied Chemistry, Faculty of Engineering, Yamaguchi University, 2-16-1 Tokiwadai, Ube, Yamaguchi 755-8611, Japan
Abstract
Some cyclopropa[4,5]pyrido[2,3-d]pyrimidine and pyrralo[2,3-d]pyrimidine derivatives were obtained from the intramolecular carbene reactions of the pyrimidine system.
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■ N-Nitroso and N-Nitro Derivatives of Diazacycloalkanes and Tetraazabicycloalkanes from α,α’-Diaminodicarboxylate Esters
Govindarajulu Kumar, Vayalakkavoor T. Ramakrishnan, and Joseph H. Boyer*
*Department of Chemistry, university of San Diego, San Diego, CA 92110, U.S.A.
Abstract
A synthesis of 6,8-dinitro-2,4,6,8-tetraaza[3.3.1]bicyclononan-3-one 5c from dimethyl α,α’-diaminoglutarate 7 was brought about in six steps. A similar conversion of dimethyl α,α’-diaminosuccinate 8 to a derivative of 2,4,6,8-tetraaza[3.3.0]bicyclooctane 6 was unsucessful.
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■ Synthesis of 5-(4-Pyrazolyl and 4-Isoxazolyl)-1,3-dihydro-2H-1,4-benzodiazepin-2-ones
Takushi Kurihara,* Jun Sasaki, Kazunori Santo, Yutaka Nakamura, Ryuji Yoneda, and Shinya Harusawa
*Faculty of Pharmaceutical Science, Osaka University of Pharmaceutical Sciences, 4-20-1 Nasahara, Takatsuki, Osaka 569-1094, Japan
Abstract
Reaction of 3-(4-pyrazolyl)anthranil (5) with phenylzinc chloride in the presence of nickel acetylacetonate gave 4-(2-anilinobenzoyl) pyrazole (6). 3-(4-Isoxazolyl)anthranil (11) gave a mixture of 4-(2-anilinobenzoyl)isoxazole (12) and 1-phenyl-4-quinolone (16). The compounds 6 and 12 were readily transformed to the azidoacetanilides (9 and 15), which were cyclized to 1,4-benzodiazepin-2-ones (10 and 19), respectively, via aza-wittig reaction at room temperature. Treatment of azido derivative (25) with triphenyl phosphine gave the phosphinimine (26), which was eventually cyclized to the 1,4-benzodiazepine (27) in refluxing toluene. In contrast, the phosphinimine (41) prepared from 4-(2-azidoacetamido-3-theonyl)isoxazole (40) failed to cyclize to the condensed thieno-1,4-diazepine (42).
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■ Solid State Photodimerization of (E)-1-(3-Medthyl-4-nitroisoxazol-5-yl)-2-(2-thienyl)ehtene
Antonella Baracchi, Stefano Chimichi, Francesco De Sio, Cecilia Polo, Piero Sarti-Fantoni,* and Tomas Torroba
*Departamento de Química Orgánica, Facultad de Ciencias, Universidad de Extremadura, Avenida de Elvas s/n, 06071-Badajoz, Spain
Abstract
Solid state irradiation of (E)-1-(3-methyl-4-nitroisoxazol-5-yl)-2-(2-thienyl)ethene (1) leads to (1α,2α,3β,4β)-1,3-bis(3-methyl-4-nitroisoxazol-5-yl)-2,4-bis(2-thienyl)cyclobutane (2) which is then oxidized to (1α,2α,3β,4β)-2,4-bis(2-thienyl)cyclobutane-1,3-dicarboxylic acid (3).
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■ Isolation of Azirino[1,2-a]indole Derivatives by the Thermolysis of 2-Alkenyl-3-azido-2-cyclohexen-1-ones
Michihiko Noguchi,* Kenjiro Onimura, and Shoji Kajigaeshi
*Department of Applied Chemistry, Faculty of Engineering, Yamaguchi University, 2-16-1 Tokiwadai, Ube, Yamaguchi 755-8611, Japan
Abstract
The thermal reaction of 2-alkenyl-3-azido-2-cyclohexen-1-ones 1 in toluene gave azirino[1,2-a]indole derivatives 3 as major products together with indoles 2.
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■ Two New Diels-Alder Type Adducts, Mulberrofuran T and Kuwanol E, from Callus Tissues of Morus alba L.
Yoshio Hano, Taro Nomura,* and Shinichi Ueda
*Faculty of Pharmaceutical Sciences, Toho University, 2-2-1, Miyama, Funabashi, Chiba 274-8510, Japan
Abstract
Two new Diels-Alder type adducts, mulberrofuran T and kuwanol E, were isolated from callus tissues of Morus alba L. On the basis of spectral evidence, the structures of mulberrofuran T and kuwanol E were shown to be 1 and 2, respectively.