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. 22, No. 10, 1984
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■ Rhazicine — A New Alkaloid from Leaves of Rhazya stricta
Atta-ur-Rahman* and Sajida Khanum
*H. E. J. Postgraduate Institute of Chemistry, University of Karachi, Karachi-75270, Pakistan
Abstract
A new alkaloid, “rhazicine” has been isolated from the leaves of Rhazya stricta to which structure (3) has been assigned.
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■ Synthesis of 3-Benzenesulfonyl-isoxazolines and Isoxazolidines
Claudio Bellandi, Marco De Amici, Carlo De Micheli,* and Remo Gandolfi
*Instituto di Chimica Farmaceutica e Tossicologica, Università digli Studi di Milano, Viale Abruzzi, 42a, 20131 Milano, Italy
Abstract
Isoxazoline derivatives 5-8 were obtained in moderate yields upon refluxing a chloroform solution of electron-rich or moderate electron-poor dipolarophiles and nitronic ester 3. Electron-poor dipolarophiles react with 3 yielding N-methoxyisoxazolidines 9-11.
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■ Binding Forces and Catalysis: Rate Enhancements through Chelation at a Remote Site
Julius Rebek, Jr.* and Timothy Costello
*Department of Chemistry, University of Pittsburgh, Parkman Avenue & University Drive, Pittsburgh, PA 15260 ,U.S.A.
Abstract
The rate of an elimination reaction is increased by more than three decades through distortions induced by binding at a remote site.
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■ A Simple Synthesis of Showdomycin
Nobuya Katagiri,* Toru Haneda, and Naoko Takahashi
*Pharmaceutical Institute, Tohoku University, Aramaki, Aoba-ku, Sendai 980-8578, Japan
Abstract
Showdomycin has been synthesized from the methyl β-D-ribofuranosylacetate 4a which can be readily prepared by Wittig reaction of the protected D-ribose 2 with the chlorophosphorane 3a.
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■ Cycloaddition Reactions of Xanthinium N(7)-Ylides with Trans Olefinic Dipolarophiles
Mikio Hori,* Tadashi Kataoka, Hiroshi Shimizu, Eiji Imai, Yukiharu Matsumoto, Masanori Kawachi, Kazuyoshi Kuratani, Haruo Ogura, and Hiroaki Takayanagi
*Department of Pharmacognosy, Gifu College of Pharmacy, 6-1 Mitahora-higashi 5-chome, Gifu 502-8585, Japan
Abstract
The xanthinium N(7)-ylides reacted with olefinic dipolarophiles to give tetrahydropyrrolo[1,2-f]xanthine derivatives. Reaction with dimethyl fumarate gave the mixture of endo and exo adducts. The stereochemistry of these products was elucidated by 1H-NMR and X-ray analysis. Reaction with other trans olefins afforded solely endo-syn type addition products in excellent yields.
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■ (—)-Viteralone from Vitex rotundifolia L.
Haruhiko Tada* and Fumio Yasuda
*Shionogi Research Laboratories, Shionogi & Co. Ltd., Fukushima-ku, Osaka 553-0002, Japan
Abstract
A benzofuran derivative (-)-viteralone (1) was isolated from Vitex rotundifolia L. in a phytochemical survey of Japanese medicinal plants. The structure of 1 was mainly elucidated by spectroscopy and confirmed by x-ray analysis.
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■ Contraction of the Tropolonic Ring of Colchicine by Hydrogen Peroxide Oxidation
Maria A. Iorio*
*Laboratorio di Chimica del Farmaco, Istituto Superiore di Sanita, Viale Regina Elena, 299, 00161 Roma, Italy
Abstract
By hydrogen peroxide oxidation of colchicine the tropolonic ring underwent contraction to a benzene ring. Two compounds were obtained and identified (EIMS, 1H NMR) as N-acetylcolchinol methyl ether and 10-carbomethoxy-N-acetylcolchinol. Antimitotic activity is also reported.
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■ Synthesis of an Amaryllidaceae Alkaloid, (±)-Hippeastrine
Jun‘ichi Katakawa, Haruo Meguri, and Hiroshi Irie*
*Faculty of Pharmaceutical Sciences, Nagasaki University, 1-14, Bunkyo-machi, Nagasaki 852-8521, Japan
Abstract
Total synthesis of one of Amaryllidaceae alkaloids, hippeastrine, was accomplished starting from methyl 2c-(N-methoxycarbonylamino)-3t-(3,4-methylenedioxyphenyl)cyclohex-4-enyl-r-acetate in stereoselective manner.
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■ Simple Syntheses of Pyrrolo- and Furopyrimidine Derivatives
Norio Kawahara,* Takako Nakajima, Tsuneo Itoh, and Haruo Ogura
*Hokkaido College of Pharmacy, 7-1 Katsuraoka-cho, Otaru 047-02, Japan
Abstract
Simple and efficient syntheses of furo[2,3-d]pyrimidine-2,4-diones, 7-deazacaffeines and dihydrofuropyrimidine-2,4-diones from 5- or 6-substituted pyrimidines by acid catalyzed cyclization reactions are described.
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■ Two New Sesquiterpene-ester Alkaloids from Maytenus myrsinoides Reiss. (Celastraceae)
Geneviève Baudouin, François Tillequin, Michel Koch,* Marie-Elise Tran Huu Dau, Jean Guilhem, and Henri Jacquemin
*E.R.A. au C.N.R.S. N°950, Faculté des Sciences Pharmaceutiques et Biologiques, Département de Pharmacognosie, Université René Descartes, 4, Avenue de l’Observatoire, F-75006 Paris, France
Abstract
Two new alkaloids belonging to the dihydroagarofuran series, maymyrsine (1) and acetylmaymyrsine (2) have been isolated from the fruits of Maytenus myrsinoides Reiss. Their structures have been elucidated by M.S., 1H NMR and X-ray diffraction analysis.
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■ Synthetic Studies on Optically Active β-Lactams. Asymmetric Synthesis of β-Lactams by the Cyclocondensation Utilizing Chiral Heterocyclic Compounds Derived from L-(+)-Tartaric Acid and (S)-Glutamic Acid
Nobuo Ikota* and Akira Hanaki
*9-1, Anagawa-4-Chome, Inage-ku, Chiba 263-0024, Japan
Abstract
Asymmetric cyclocondensation of the chiral heterocyclic compounds (2,4) with imines (5) gave either cis- or trans-β-lactams with high diastereomeric purity up to 96%, and the optically pure phenylalanine derivative (9) was obtained from the β-lactams produced.
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■ The Stereochemistry at C-13 for the Proaporphine-benzylisoquinoline Alkaloids
Inge Weiss,* Alan J. Freyer, Maurice Shamma, and Alejandro Urzúa
*Department of Chemistry, The Pennsylvania State University, York Campus, P1031 Edgecomb Avenue, York, Pennsylvania 17403, U.S.A.
Abstract
Berberis actinacantha Mert. ex Schult. (Berberidaceae) has yielded the new proaporphine-benzylisoquinolines (+)-epiberbivaldine (13) and (+)-rupancamine (15). The first of these dimers belongs to the epi stereochemical series, while the second incorporates the normal stereochemistry at C-13.
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■ Novel Synthesis of Pyrazolo[1,5-a]pyridine Derivatives via Pyrido[1,2-d]-1,3,4-thiadiazine Intermediates
Akikazu Kakehi,* Suketaka Ito, Masayoshi Ito, and Toshiaki Yotsuya
*Department of Chemistry and Material Engineering, Faculty of Engineering, Shinshu University, 4-17-1 Wakasato, Nagano 380-8553, Japan
Abstract
Alkaline treatment of 1-[(ethoxycarbonylmethylthio)methyleneamino]- and 1-[(phenacylthio)methyleneamino]pyridinium bromides afforded 3-ethoxycarbonyl- and 3-aroylthiopyrazolo[1,5-a]pyridine derivatives, respectively, in good yields. The intermediacy of pyrido[1,2-d]-1,3,4-thiadiazine derivatives was confirmed by the nmr follows of these reactions.
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■ Studies on as-Triazine Derivatives. IV. Synthesis of Unsymmetrical 5,6-Disubstituted 1,2,4-Triazines
Shoetsu Konno, Mataichi Sagi, Mitsuko Agata, Yuichi Aizawa, and Hiroshi Yamanaka*
*Pharmaceutical Institute, Tohoku University, Aobayama, Sendai 980-8578, Japan
Abstract
The reaction of 5-chloro-6-methyl-3-phenyl-1,2,4-triazine (4a) with ethylidenetriphenylphosphorane followed by the hydrolysis of the resulting as-triazinylphosphorane afforded 5-ethyl-6-methyl-3-phenyl-1,2,4-triazine (6a) in 88 % yield. The condensation of 5-chloro-6-ethyl-3-phenyl-1,2,4-triazine (4b) with dimethyloxosulfonium methylide and subsequent desulfurization of the resulting triazinylmethylide gave 6-ethyl-5-methyl-3-phenyl-1,2,4-triazine (6g) in 32 % overall yield. Using these triazines (6a,6g) as standard specimens, the ratio of isomers (6a,6g) formed from the condensation of 2,3-pentanedione with benzamidrazone, was determined to be 3:1.
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■ Studies on as-Triazine Derivatives. V. Synthesis and Hydration of Alkynyl-1,2,4-triazines
Shoetsu Konno, Satoshi Fujimura, and Hiroshi Yamanaka*
*Pharmaceutical Institute, Tohoku University, Aobayama, Sendai 980-8578, Japan
Abstract
Palladium catalyzed cross-coupling reaction of 3- and 5-iodo-as-triazines with monosubstituted acetylenes gave the corresponding alkynyl-as-triazines in good yields. The hydration of 3- and 5-trimethylsilylethynyl-as-triazines thus obtained in the presence of mercuric sulfate afforded 3- and 5-acetyl-as-triazines, whereas the reaction of the other alkynyl-as-triazines with piperidine followed by the hydrolysis of the resulting enamines gave the acylmethyl-as-triazines, as expected.
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■ Benzo-derivatives of Mutagenic-carcinogenic 2-Aminodipyrido[1,2-a:3’,2‘-d]imidazole
Ching-Shing Lee, Yuichi Hashimoto, Koichi Shudo,* and Minako Nagao
*Faculty of Pharmaceutical Sciences, University of Tokyo, Hongo, Bunkyo-ku, Tokyo 113, Japan
Abstract
Benzo-derivatives of mutagenic-carcinogenic 2-aminodipyrido[1,2-a:3‘,2‘-d]imidazole (Glu-P-2) were synthesized in short steps. The interaction of the compounds with DNA and their mutagenicity were investigated.
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■ DDQ Oxidation of Some Erythrinan Enones and Dienones: Syntheses of (±)-Erytharbine and (±)-Crystamidine
Yoshisuke Tsuda,* Shinzo Hosoi, Fumiyuki Kiuchi, Takehiro Sano, Jun Toda, and Ryuzo Yamamoto
*Faculty of Pharmaceutical Scicences, Kanazawa University, 13-1 Takara-machi, Kanazawa 920-0934, Japan
Abstract
DDQ oxidation of 3,8-dioxoerythrinan-1(6)-ene 1 in dioxane gave the ring C/D oxidized product, the dienone 2, while that of 3,8-dioxoerythrinan-1-ene 4 gave the ring B dehydrogenated product 5. The either product was convertible to the same trienone 3 on further oxidation in different solvents. The trienone 3a and 3b were transformed by a conventional procedure to the highly dehydrogenated oxo-erythrinan alkaloids, erytharbine 8a and crystamidine 8b, respectively.
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■ Novel Synthesis of 2-Thiocytosine Derivatives via Pyrimidine-to-pyrimidine Ring Transformation
Kosaku Hirota,* Yukio Kitada, Hironao Sajiki, and Yoshifumi Maki
*Labolatory of Medicinal Chemistry, Gifu Pharmaceutical University, 6-1 Mitahora-higashi 5-chome, Gifu 502-8585, Japan
Abstract
The reaction of 1,3-disubstituted 5-cyanouracils (1) with thioureas (2) and sodium hydroxide causes novel pyrimidine-to-pyrimidine ring transformation to give 2-thiocytosines (3) and 6-amino-5-formyluracils (4), respectively.
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■ A Total Synthesis of (±)-Corydaine from Coptisine
Miyoji Hanaoka,* Atsuyuki Ashimori, and Shingo Yasuda
*Faculty of Pharmaceutical Scicences, Kanazawa University, 13-1 Takara-machi, Kanazawa 920-0934, Japan
Abstract
Regioselective protection of C8-hydroxy of the spiro-diol (6b) derived from coptisine (1b), followed by oxidation of C13-hydroxy afforded the keto-oxazolidine (8b) which was treated with sodium cyanoborohydride to provide (±)-corydaine (5b) in an excellent yield.
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■ Ring Transformation of 5H-1,2-Diazepinones into Pyrazoles
Giovanna Ciciani, Vittorio Dal Piaz,* and Stefano Chimichi
*Dipartimento di Scienze Farmaceutiche, Università di Firenze, Via Gino Capponi 9, I-50121 Firenze, Italy
Abstract
6-Cyano-2,3-disubstituted 1,2,3,4-tetrahydro-5H-1,2-diazepin-5-ones (1a-f) underwent ring transformation in acidic media to give in good yields 4-cyano-5-[2-(substituted ethenyl)]-3-phenylpyrazoles (2a-f) which can be easily oxidized to pyrazoles containing o-functional groups.
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■ Polycondensed Nitrogen Heterocycles. Part 15. Reactivity of 3-Diazopyrroles. 3. 1H-Pyrrolo[3,2-c]cinnoline and Pyrrolo[3,4-c]pyridazine
Gaetano Dattolo,* Girolamo Cirrincione, Anna Maria Almerico, Giuseppe Presti, and Enrico Aiello
*Instituto di Chimica Farmaceutica e Tossicologica, Università digli Studi di Palermo, Via Archirafi 32, 90123 Palermo, Italy
Abstract
3-Diazopyrroles of type 5 were prepared and refluxed in acetic acid. In the case of 5a, an intramolecular coupling reaction between the diazonium group and the methoxyphenyl substituent in the 2-position leads to the 1H-pyrrolo[3,2-c]cinnoline derivative 6, whilst in the case of 5b an intramolecular coupling with the acetyl group in the 4-position affords the pyrrolo[1,4-c]pyridazine derivative 7.
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■ Synthesis with Hydroxylactamines III. A Facile Entry to the 1-Oxo-β-carboline Skeleton. Synthesis of Strychnocarpine
Claus Herdeis* and Anna Dimmerling
*Institut für Pharmazie und Lebensmittelchemie, Universität München, Sophienstraße 10, D-80333 München, Germany
Abstract
Strychnocarpine 1c is synthesized via hydrogenation of 1-methyl-3-hydroxypyridone(2) with Ru/C. Fischer indole cyclization of phenylhydrazone 11 yields 1c.
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■ Nitrogen Bridgehead Compounds Part 47. Synthesis and Some Reactions of 4H,10H-Pyrimido[1,2-a]azepin-4-ones
István Hermecz,* József Kökösi, Zoltán Mészáros, György Szász, Gábor Tóth, and Attila Almásy
*CHINOIN Pharmaceutical and Chemical Works Ltd., P. O. Box 110, H-1325 Budapest, Hungary
Abstract
4-Oxo-4H,10H-pyrimido[1,2-a]azepine-3-carboxylate (3) was prepared from 2-amino-3H-azepine (4) and diethyl ethoxymethylenemalonate (5). The compound (3) was transformed into the isomeric 4H,6H-pyrimido[1,2-a]azepine-3-carboxylate (8) by proton migration, in a symmetry-allowed [1,5]-sigmatropic shift. The isomers (3) and (8) were characterized by their UV, IR, 1H NMR and 13C NMR spectra. From the ester (3) the 3-carboxylic acid (9), the amide (10) and the hydrazide (11) were prepared.
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■ New Heterocyclic Ring System. XIV. 7,11-Dithiaoxasteroids Analogues
Violetta Cecchetti, Arnaldo Fravolini,* Renata Fringuelli, and Fausto Schiaffella
*Istituto di Chimica Organica, Facoltà di Farmacia, Università degli Studi di Perugia, Via del Liceo 1, 06123 Perugia, Italy
Abstract
By reaction of 1,2-benzooxathiin-4(3H)-one 2,2-dioxide (II) with mercaptopropionic acid the new tricycle 4-oxo-3,4-dihydro-2H-thiopyrano[3,2-c][1,2]benzooxathiin 5,5-dioxide (IV) together with tetracycle V and pentacycle VII were obtained. The key ketone IV was then converted to β-diketone IX, enamino ketone XVI and α-bromoketone XX intermediates to give with nucleophilic reagents 7,11-dithiaoxasteroids analogues.
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■ A Piscicidal Chromanol and a Chromenol from the Brown Alga Dictyopteris undulata
Muanza-Nkongolo Dave, Takenori Kusumi, Midori Ishitsuka, Takashi Iwashita, and Hiroshi Kakisawa*
*Department of Chemistry, University of Tsukuba, 1-1-1 Ten-nodai, Tsukuba-shi, Ibaraki, 305-8571, Japan
Abstract
From the brown alga, Dictyopteris undulata, several piscicidal compounds including a new chromenol (1), chromazonarol (7), and isochromazonarol (8) were isolated, and their structures and stereochemical features were elucidated on the basis of spectroscopic analyses.
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■ Chemical and Photochemical Behaviours of 5-Benzoylamido-4-diazo-1-methyl-3-phenylpyrazole
Francesco De Sio,* Lucia Cecchi, and Fabrizio Melani
*CNR, Centro di Studio Sulla Chimica e la Struttura dei Composti Eterociclici e lolo Applicazioni, c/o Dipartimento di Chimica Organica "Ugo Schiff", Università di Firenze, Via Gino Capponi 9, I-50121 Firenze, Italy
Abstract
Diazo compound (1) photochemically reacts to give rise mainly to compound (2). Alkaline hydrolysis of (1) yields compound (5).
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■ A Facile Synthesis of 4-Oxo-4,5,6,7-tetrahydroindoles
Masakatsu Matsumoto* and Nobuko Watanabe
*Sagami Central Research Center, 4-4-1 Nishi-Ohnuma, Sagamihara, Kanagawa 229-0012, Japan
Abstract
Condensation of 1,3-cyclohexanedione with chloroacetaldehyde followed by dehydration gave 4-oxo-4,5,6,7-tetrahydrobenzofuran in a good yield. The tetrahydrobenzofuran was quantitatively converted into 4-oxo-4,5,6,7-tetrahydroindoles.
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■ Introduction of the Methyl Group into the Pyrazine Ring
Akihiro Ohta,* Akira Inoue, and Tokuhiro Watanabe
*Tokyo University of Pharmacy and Life Science, 1432-1 Horinouchi, Hachioji, Tokyo 192-0392, Japan
Abstract
By the coupling reaction of mono- and dichloropyrazines with trimethylaluminum in the presence of a palladium catalyst, the corresponding mono- and dimethylpyrazines were prepared in excellent yields.
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■ Base Catalysed Reaction of Arylidinemalononitriles with Benzofuroxanes
Harsha Narayan Borah, Romesh Chandra Boruah, and Jagir Singh Sandhu*
*Division of Drug and Pharmaceutical Chemistry, Regional Research Laboratory, Jorhat 785 006, Assam, India
Abstract
Arylidinemalononitriles (2) react with benzofuroxanes (1) to afford quinoxaline N,N’-dioxides (3) in good yields.
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■ A Stereoselective Synthesis of 5-Aryl- and 6-Aryloxazolo[4,3-a]isoqionolines
Shinzo Kano,* Yoko Yuasa, and Shiroshi Shibuya
*School of Pharmacy, Tokyo University of Pharmacy and Life Science, 1432-1 Horinouchi, Hachioji, Tokyo 192-0392, Japan
Abstract
Reduction of N-(α,β-diaryl)ethyl and N-(β,β-diaryl)ethyl ethoxycarbonylmethyl carbamates, obtained from the corresponding 2,3-diaryl- and 3,3-diarylpropionic acids, with diisobutylaluminum hydride, followed by cyclization with formic acid at room temperature gave the corresponding 5-aryl- and 6-aryloxazolo[4,3-a]isoquinolines, respectively, with high stereoselectivity.