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. 36, No. 4, 1993
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■ Preparation of Novel Cyclophosphamides Derivatives of Sugars
Mitsuji Yamashita,* Chihiro Takahashi, and Kuniaki Seo
*Department of Applied Chemistry, Faculty of Engineering, Shizuoka University, 3-5-1 Johoku, Hamamatsu 432-8561, Shizuoka, Japan
Abstract
Novel cyclophosphamide derivatives bearing a sugar structure were prepared by the treatment of the amino sugars from D-glucose and D-xylose with bis-(2-chloroethyl)aminophosphoric dichloride as well as with phosphoryl chloride and nucleophiles.
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■ Revised Assignment of Olefinic Proton Signals in the 1H-Nmr Spectra of Dienoid-Type Erythrinan Alkaloids
Yoshisuke Tsuda,* Shinzo Hosoi, Takehiro Sano,* Hideki Suzuki, and Jun Toda
*Faculty of Pharmaceutical Scicences, Kanazawa University, 13-1 Takara-machi, Kanazawa 920-0934, Japan
Abstract
Previous assignment of the olefinic proton signals (H-1 and H-2) in the 1H-nmr spectra of dienoid-type erythrinan alkaloids was interchanged on the basis of the synthesis of the stereoisomers, nOe experiments, and theoretical calculations.
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■ First Asymmetric Diels-Alder Reactions in the Vinylhetarene Series: Cycloadditions with Vinylindoles to Enantiomerically Pure Carbazole Derivatives
Ulf Pindur,* Gundula Lutz, Werner Massa, and Ludger Schröder
*Institut für Pharmaize, Fachbereich Chemie und Pharmazie, Universität Maintz, Saarstrasse 21, D-6500 Maintz, Germany
Abstract
The first asymmetric Diels-Alder reactions of some 3- and 2-vinylindoles with (N-propenoyl)bornane-10,2-sultam are described. The experimental results are indicative of high to sufficient π-facial diastereoselectivity.
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■ Nucleoside Synthesis from Furanoid Glycals
Hiroshi Kawakami,* Takashi Ebata, Koshi Koseki, Koji Okano, Katsuya Matsumoto, and Hajime Matsushita
*Life Science Research Laboratory, Japan Tobacco Inc., 6-2, Umegaoka, Midori-ku, Yokohama, Kanagawa 227-8512, Japan
Abstract
Reaction of furanoid glycals with PhSCl afforded 1-chlorosugars, which were used for condensation reaction with silylated uracil in the presence of SnCl4. These two reactions proceeded in a highly stereoselective manner.
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■ Garcinol, a Novel Arylbenzofuran Derivative from Garcinia kola
Masatake Niwa,* Kenji Terashima, and Muhd Aqil
*Faculty of Pharmacy, Meijo University, 150 Yagotoyama, Tenpaku, Nagoya 468-8503, Japan
Abstract
A novel arylbenzofuran named garcinol was isolated from Garcinia kola Heckel (Guttiferae) collected in Nigeria and the structure was elucidated by spectroscopic methods.
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■ Two Novel Acridone-Coumarin Dimers, Neoacrimarines-A and -B, from Citrus Plants
Yuko Takemura, Satomi Maki, Motoharu Ju-ichi,* Mitsuo Omura, Chihiro Ito, and Hiroshi Furukawa
*Faculty of Pharmaceutical Science, Mukogawa-Women’s University, 11-68 Koushien Kyuban-Cho, Nishinomiya, Hyogo 663-8179, Japan
Abstract
Two novel acridone-coumarin dimers, named neoacrimarines-A (1) and -B (2), were isolated from the roots of Citrus plants and their structures were elucidated by spectroscopic method.
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■ 5-Amino Derivatives of 2’,3’-Dedeoxynucleosides for Evaluation of Anti-HIV Activity
Ahmed E.-S. Abdel-Megied, Henrik Pedersen, Erik B. Pedersen,* and Claus Nielsen
*Department of Chemistry, Odense University, Campusvej 55 DK-5230 Odense M., Denmark
Abstract
Reaction of protected 2,3-dideoxy-D-ribose (2) with silylatd 5-amino derivatives of uracil using trimethylsilyl trifluoromethanesulfonate as catalyst afforded the 2’,3’-dideoxynucleosides (3a-d) which were deprotected with methanolic ammonia and separated by chromatography to give α-anomers (4a-d) and β-anomers (5a-d). Compounds (3a-c) were converted to 4-(1,2,4-triazol-1-yl) derivatives (6a-c). Ammonia in dioxane converted the 4-(1,2,4-triazole-1-yl)pyrimidin-2(1H)-one moiety into cytosin-1-yl. In case of 6b, 4-methoxypyrimidin-2-one 2,3-dideoxyriboside was accomplised via transformation of the 4-triazolyl moiety with methanol on silica. Mathanolic ammonia was used for deprotection of the sugar moiety to afford 7-10.
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■ 3H-Azirino[1,2-d][1,4]benzodiazepin-4(5H)-ones: Synthesis and Stereochemistry
Alba Chimirri,* Silvana Grasso, Anna-Maria Monforte, Giovanni Romeo, and Maria Zappala
*Dipartimento Farmaco-Chimico, Università di Messina, Viale Annunziata, 98168 Messina, Italy
Abstract
The synthesis of 5-alkyl-1,9b-dihydro-3H-azirino[1,2-d][1,4]benzodiazepin-4(5H)-ones by cycloaddition of dichlorocarbene to N1-alkyl-1,4-benzodiazepine derivatives, is described. The lack of reactivity in analogous N1-H derivatives is explained on the basis of electronic factors.
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■ Organomercury Chemistry of Iridoid Glucosides — Part 3
Andrea D’Annibale,* Carlo Iavarone,* and Corrado Trogolo*
*Centro CNR per lo Studio della Chimica delle Sostanze Organiche Naturali, Dipartmento di Chimica, Università degli Studi di Roma "La Sapienza", Piazzale Aldo Moro 5, 00185 Roma, Italy
Abstract
The hydroxymercuration (OM) reaction of nonconjugated diene system of aucubin (1) with at least 2 equivalents of Hg(II) salts involved not only the enol ether Δ3 double bond, but also the less reactive Δ7 cyclopentene double bond; the unique intermediate was observed to be the organobismercurial derivative (10). Surprisingly, the reductive demercuration (DM) of 10 with NaBH4 gave a mixture of three products isoeucommiol (3), 6-hydroxy-8,9-dihydroxymethyl-2-oxabicyclo[3.2.1]oct-3-ene (5), and 7,8-dihydro-8-α-hydroxyisoeucommiol (6). The way these different compounds may be formed from common intermediate (10) is discussed. The aptitude to reversion showed by the OM reaction of the cyclopentene double bond of 1 was confirmed by the analogous tendency observed in the OM/DM of 3; this latter reaction afforded a good yield of the reaction product 6-hydroxy-8,9-dihydroxymethyl-2-oxabicyclo[3.2.1]octane (12) only when the DM of organomercurial intermediate (13) was carried out in basic conditions. Lastly, when the DM of monomercurial intermediate (2) was performed with Zn/CH3COOH, this led to the conservation of the hidden 1,5-dialdehydic system of 1 and the formation of aucubigenin (16), i.e. to the achievement of a nonenzymatic hydrolysis of 1.
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■ Alkaloidal Constituents of the Bark of Holarrhena antidysenterica
Sabira Begum, Shahid Bader Usmani, Bina Shaheen Siddiqui,* and Salimuzzaman Siddiqui
*H. E. J. Postgraduate Institute of Chemistry, University of Karachi, Karachi-75270, Pakistan
Abstract
Three steroidal alkaloids (1-3) of conanine series have been isolated from the bark of H. antidysenterica. 1 and 2 are new natural products while 3 has been reported earlier from this source.
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■ Structures of Insect Antifeeding Limonoids, Trichilins F and G, from Trichilia roka
Munehiro Nakatani* and Koji Nakanishi
*Department of Chemistry, Faculty of Science, Kagoshima University, 1-21-35 Korimoto, Kagoshima 890-0065, Japan
Abstract
Two new limonoids, trichilins F and G, have been isolated from the root bark of Trichilia roka and identified as antifeedant against some pest insects. Their structures were determined from spectral data and chemical means, in which the treatment of trichilin A with zinc borohydride induced an acyl migration to yield trichilin F.
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■ A Convenient Synthesis of 5-Substituted Tetrahydro-1,4,3-oxathiazine 4,4-Dioxides
Evelyne Grunder-Klotz,* Paul Humbert, and Jean-Daniel Ehrhardt
*Laboratoire de Pharmacologie Cardiovasculaire et Rénale, URA 589 CNRS, Université Louis Pasteur, 11 rue Humann, F-67000 Strasbourg, France
Abstract
An advantageous one pot procedure for the synthesis of tetrahydro-1,4,3-oxathiazine 4,4-dioxides by dialkylation of readily available α,N-alkyl- or arylsulfonamide dianions with gaseous formaldehyde is reported. Stability and some reactions of these heterocycles are also described.
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■ Photochemical Fries Rearrangement of N-Phenyl-2-pyrrolidone
Shunsaku Ohta,* Atsunori Sano, Masayuki Yamashita, and Masao Okamoto
*Kyoto Pharmaceutical University, Misasagi, Yamashina-ku, Kyoto 607-8412, Japan
Abstract
Photochemical Fries rearrangement of 1-phenyl-2-pyrrolidone (1) proceeded smoothly in methanol especially in the presence of piperylene. Continuous photo-irradiation of 1 successfully was carried out to raise the yield by utilizing a reaction mixturecirculation system consisting of a spiral quartz cell, a pump, a uv light source and a column packed with appropriate absorbents for the Fries rearranged product (3) and pigments.
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■ Total Synthesis of (±)-Eburnaminol and (±)-Larutensine
Mauri Lounasmaa* and Esko Karvinen
*Laboratory for Organic and Bioorganic Chemistry, Technical University of Helsinki, P.O. Box 6100, FIN-02150 HUT Espoo 15, Finland
Abstract
Short syntheses are described for the (±)-forms of the recently isolated eburnane type alkaloids (-)-eburnaminol [(-)-1] and (+)-larutensine [(+)-2], and for the not yet naturally found 18-hydroxyeburnamonine (3) and 16-epieburnaminol (4).
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■ Chemical Modification of Erythromycins. X. Removal of Benzyloxycarbonyl and 2-Chlorobenzyl Groups of Erythromycin Derivatives by Use of Catalytic Transfer Hydrogenation
Yoshiaki Watanabe,* Masato Kashimura, Toshifumi Asaka, Takashi Adachi, and Shigeo Morimoto
*Research Center, Taisho Pharmaceutical Co., Ltd., 1-403 Yoshino-Cho, Ohmiya, Saitama 330-8530, Japan
Abstract
The benzyloxycarbonyl and the 2-chlorobenzyl groups of ethythromycin derivatives were easily removed by catalytic transfer hydrogenation (CTH). Their deprotection reaction was dependent on both the hydrogen donor and the solvent for use. Application of CTH to removal of the protective groups is discussed.
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■ A Simple Synthesis of 2-Methoxypyridine-3-carbonitriles
Pedro Victory,* José I. Borrell, and Anton Vidal-Ferran
*Departament de Química Orgànica, CETS Institut Químic de Sarrià, Universitat Ramon Llull, Via Augusta 390, E-08017 Barcelona, Spain
Abstract
The condensation of propanedinitrile with several enals or enones in a methanol-sodium methoixde system provides a one-step route to 2-methoxypyridine-3-carbonitriles. Together with these compounds substituted 2-aminobenzene-1,3-dicarbonitriles, were obtained as by-products.
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■ Synthesis of 2-Cyanamino-4,6-diphenylpyridine-3-carbonitrile
Pedro Victory,* José I. Borell, Joan Cirujeda, and Anton Vidal-Ferran
*Departament de Química Orgànica, CETS Institut Químic de Sarrià, Universitat Ramon Llull, Via Augusta 390, E-08017 Barcelona, Spain
Abstract
The nucleophilic displacement of bromo, alkylthio and alkylsulphonyl groups from pyridine systems by cyanamide is studied in order to obtain a previously unreported 2-cyanaminopyridine-3-carbonitrile. A one-step synthesis of the same compound by cyclization in basic medium of the non-isolated Michael adduct of (E)-1,3-diphenylpropenone and propanedinitrile is also described.
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■ Kinetic and Theoretic Aspects of Regiochemistry in the Reaction of 4,5-Dihalo-3(2H)-pyridazinones with Benzylamines
Péter Mátyus* Klára Czakó, Ágnes Behr, Ildikó Varga, Benjamin Podányi, Malte von Arnim, and Péter Várkonyi
*Institute for Drug Research Ltd., 47-49 Berlini st.1 H-1045 Budapest, Hungary
Abstract
Regioselectivity of nucleophilic substitution reactions of 4,5-dihalo-3(2H)-pyridazinones (1a-d) with benzylamines was studied under different conditions. Second-order kinetics were obtained for reactions of 1a with benzylamine in ethanol-d6 and toluene-d8 as well. Experimental results obtained were interpreted on the bases of Klopman-Salem equation and analyses of the reaction paths.
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■ Ring-Opening of Isoxazolidine Nucleus by Trimethyl Posphate Treatment: Formation of Tertiary Allylic Alcohols via Intermediate 1,3-Oxazinium Salts
Ugo Chiacchio, Angelo Liguori, Giovanni Romeo,* Giovanni Sindona, and Nicola Uccella*
*Dipartimento Farmaco-Chimico, Università di Messina, Viale Annunziata, 98168 Messina, Italy
Abstract
5,5-Disubstituted Isoxazolidines undergo ring opening reaction, leading to tertiary allylic alcohols, by sequential treatment with trimethyl phosphate (TMP) and NaH. The reaction proceeds through sequence steps which involve an initial alkylation to isoxazolidinium intermediate, followed by ring expansion to tetrahydro-1,3-oxazine, further alkylation and a Hofmann-like elimination towards the final products promoted by NaH.
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■ Selective Acetylation of Berbin-8-one. Synthesis of 2-Methoxyberbine
Jean-Francois Stambach* and Louis Jung
*Laboratoire de Chimie Thérapeutique, U.F.R. des Sciences Pharmaceutiques, Université Louis Pasteur, 74, route du Rhin, BP 24, 67401 ILLKIRCH Cedex, France
Abstract
In the presence of excess aluminum chloride, berbin-8-one (1) could be selectively acetylated at the C-2 position to give 2-acetylberbin-8-one (2) in good yield. In fact this exclusive orientation was due to a complex between the amide carbonyl and the Lewis acid which deactivated the aromatic ring D for electrophilic substitution. Further chemical degradation of the acetyl group afforded the corresponding phenol derivative (3) which was converted to 2-methoxyberbin-8-one (4). Reduction of this latter gave finally 2-methoxyberbine (5). Spectral data comparison of compound (4) and 3-methoxyberbin-8-one permitted us to conclude unambiguously in favour of the C-2 orientation of the acetylation.
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■ The Structures of Spiramines E, F and G; The New Diterpene Alkaloids from Spiraea japonica var. Acuminata Franch
Xiao-Jiang Hao, Manabu Node,* Jun Zhou, Si-Ying Chen, Tooru Taga, Yoshihisa Miwa, and Kaoru Fuji
*Kyoto Pharmaceutical University, Misasagi, Yamashina-ku, Kyoto 607-8412, Japan
Abstract
Structures of spiramines E (1), F (2) and G (3) were elucidated by chemical and spectroscopic means.
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■ Synthesis of Pyrazole C-Glycosides by 1,3-Dipolar Cycloaddition of Nitrilimines Formed by Lead Tetraacetate Oxidation of p-Nitrophenylhydrazones of Aldehydo Sugars
Jean M. J. Tronchet,* Jeannine F. Tronchet, and Françoise Barbalat-Rey
*Institute of Pharmaceutical Chemistry, University of Geneva, 30, Quai e.-Ansermet, CH-1211 Geneva 4, Switzerland
Abstract
Aldehydo sugars p-nitrophenylhydrazones upon treatment with lead tetraacetate in the presence of an excess of methyl acrylate afforded, besides N’-acetylhydrazide derivatives, methyl 3-glycosyl-1-p-nitrophenylpyrazoline-5-carboxylates which were readily oxidized to the corresponding pyrazoles. The methyl pyrazole-5-carboxylates were converted to 5-carboxamides.
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■ A Facile and Convenient Synthesis of Fluorine-containing Naphth[1,2-d][1,3]oxazines by Novel Cyclization of N,N-Dialkyl-2,4-bis(trifluoroacetyl)-1-naphthylamines
Etsuji Okada, Ryoichi Masuda, Masaru Hojo,* and Takeshi Tomifuji
*Department of Industrial Chemistry, Faculty of Engineering, Kobe University, Rokkodai-cho, Nada-ku, Kobe 657-8501, Japan
Abstract
N,N-Dialkyl-2,4-bis(trifluoroacetyl)-1-naphthylamines (1a-j) underwent acid catalyzed cyclization by trifluoroacetic acid or silica gel to give naphth[1,2-d][1,3]oxazines (2a-j) in excellent yields. Naphthylamines (1b, d, e, h-j) were found to perform this type of cyclization easily in refluxing butyronitrile or acetonitrile even in the absence of acids. Remarkably high regioselectivities were exhibited in the cyclization of unsymmetrically N,N-dialkyl-substituted naphthylamines (1g-j) and the corresponding naphth[1,2-d][1,3]oxazines (2g-j) were obtained in high yields.
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■ A New Synthesis of Pyrazolo[3,4-d]thiazoles
Chiara B. Vicentini, Augusto C. Veronese, Mario Guarneri, Maurizio Manfrini, and Paolo Giori*
*Dipartimento di Scienze Farmaceutiche, Università di Ferrara,via Fossato di Mortara 17, I-44100, Ferrara, Italy
Abstract
An efficient synthesis of pyrazolo[3,4-d]thiazoles (6) was achieved by treatment of N-(4-amino-5-pyrazolyl)thiocarboxamides (4) with sodium nitrite in acidic medium followed by irradiation with uv light.
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■ Annelated 1,5-Benzodiazepines. Part II. Six Membered Rings
Alba Chimirri,* Rosaria Gitto, Silvana Grasso, Anna Maria Monforte, Giovanni Romeo, and Maria Zappalà
*Dipartimento Farmaco-Chimico, Università di Messina, Viale Annunziata, 98168 Messina, Italy
Abstract
This review describes the synthetic approaches to mono and diannelated 1,5-benzodiazepines with six-membered ring fused to different edges of the 1,5-benzodiazepine skeleton.