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. 11, 1984
Published online:
■ The Structures of Bonvalotine, Bonvalol and Bonvalone, Three New C19-Diterpenoid Alkaloids
Qing Ping Jiang and Wei Liang Sung*
*Institute of Materia Medica, Chinese Academy of MedicalSceince, Nan-wei Road, Beijing 100050, China
Abstract
Chemical investigation of the roots of Delphinium bonvalotii Franch results in the isolation of bonvalotine (1), bonvalol (2) and bonvalone (3), three new lycoctonine-type alkaloids with unique C(5)-OH substitution.
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■ Synthesis of Spiroimides of Pharmacologic Interest
Michael R. Borenstein,* Magid A. Abou-Gharbia, and Peter H. Doukas
*Department of Medical Chemistry, School of Pharmacy, Temple University, 3307 North Broad Street, Philadelphia, Pennsylvania 19140, U.S.A.
Abstract
Spiroimides of fluorene, indane and cyclopentane have been prepared as potential anticonvulsant agents. Certain azaspirane derivatives of fluorene are also reported.
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■ The Novel Ring Opening of an Oxazolo[5,4-d]pyrimidine and Subsequent Rearrangement to Form an Imidazo[4,5-d]pyrimidine
Ji-Wang Chern, Dean S. Wise, and Leroy B. Townsend*
*Department of Medical Chemistry, College of Pharmacy, University of Michigan , 930 North University, Ann Arbor, MI 48109-1055, U.S.A.
Abstract
A novel rearrangement from methyl 6-amino-4-benzylaminooxazolo-[5,4-d]pyrimidine-2-carbmate to methyl 9-benzylguanine-8-carbamate (3) is described.
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■ Synthesis of E- and Z-1,6-Dioxaspiro[4.5]decanes
Chuzo Iwata,* Hiroshi Atarashi, Katsuya Nakamura, and Shuji Uchida
*Faculty of Pharmaceutical Sciences, Osaka University, 1-6 Yamadaoka, Toyonaka, Osaka 560-0043, Japan
Abstract
An efficient synthesis of E- and Z-1,6-dioxaspiro[4.5]decanes has been achieved via the intramolecular ketallization of 5 bearing a bulky substituent(SPh) at the position α to the carbonyl group.
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■ Synthesis and Crystal Structure of Decahydro-dispiro[oxirane-2,3’-(2’H)benzofuran-2’,2’’-[2H]pyran]
Chuzo Iwata,* Katsuya Nakamura, Hiroshi Atarashi, Shuji Uchida, and Masaru Kido
*Faculty of Pharmaceutical Sciences, Osaka University, 1-6 Yamadaoka, Toyonaka, Osaka 560-0043, Japan
Abstract
(2’S*,3’R*,3’aS*,7’aR*)-Decahydro-dispiro[oxirane-2,3’(2’H)benzofuran-2’,2”- [2H]pyran] (E-6) and its isomer E-6’ with epimeric stereochemistry of the epoxide ring were prepared stereoselectively and an X-ray analysis of E-6’ is reported.
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■ Alkaloids Isolated from the Leaves of Phelline Sp. Aff. P. lucida (Phellinaceae)
Nicole Langlois,* Judith Razafimbelo, Ratremaniaina Z. Andriamialisoa, Jacques Pusset, and Gérard Chauvière
*Institut des Chimie des Substances Naturelles, C.N.R.S., 1 avenue de la Terrasse, Bat. 27, 91198 Gif-sur-Yvette Cedex, France
Abstract
Holidine 6, a new example of homoazaerythrinan skeleton was isolated from the leaves of Phelline sp. aff. P. lucida along with several other homoerythrinan and homoerythroidine type alkaloids.
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■ Unusual Reactions of 8β-Cyano-6,7-diazacholesterol
Jacek W. Morzycki* and Rafal R. Sicinski
*Department of Chemistry, University of Warsaw, Pasteura St.1, 02-093 Warsaw, Poland
Abstract
The synthesis of 8β-cyano-6,7-diazacholesterol (6) and attempts to convert it into azine 1 are described. The unexpected products 7, 8 and 9 are formed during reactions involving hydrogen cyanide elimination from 6.
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■ Ring Transformations of Oxazoles. Novel Rearrangements of Ethyl 5-Ethoxy-β-oxo-2-phenyl-4-oxazolepropionate to 4-Benzoylaminopyrazoles and 5-Benzoylaminopyrimidines
Ignatius J. Turchi* and Thomas G. Cullen
*Agricultural Chemical Group, FMC Corporation, P.O. Box 8, Princeton, New Jersey 08543, U.S.A.
Abstract
Reaction of ethyl 5-ethoxy-β-oxo-2-phenyl-4-oxazolepropionate (1) with hydrazines or guanidines provides the 4-benzoylaminopyrazoles 3a and b or the 2-amino-5-benzoylaminopyrimidines 5a and b respectively.
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■ Synthesis and Properties of Pyrrolo[3,2,1-ij]- and Pyrazolo[4,3,2-ij]-quinolinones, Aza-analogues of Phenalenones
Yasuyoshi Miki,* Noriko Nishikubo, Yasuo Nomura, Hisashi Kinoshita, Shoji Takemura, and Masazumi Ikeda
*Faculty of Pharmaceutical Sciences, Kinki University, 3-4-1, Kowakae, Higashi-Osaka 577-8502, Japan
Abstract
Pyrrolo[3,2,1-ij]- and pyrazolo[4,3,2-ij]-quinolinones were synthesized by the intramolecular aldol condensation of 1,8-diacylindolizines and 3,4-diacylpyrazolo[1,5-a]pyridines, respectively. These compounds showed properties analogous to those of 1H-phenalen-1-ones.
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■ An Alternative Synthesis of Dialkylpyridylboranes
MInoru Ishikura, Tsutomu Mano, Izumi Oda, and Masanao Terashima*
*Faculty of Pharmaceutical Scicences, Higashinihonngakuen University, 1757 Kanazawa, Toubetu-cho, Ishikari-gun, Hokkaodo 061-0212, Japan
Abstract
The reaction of lithiopyridines and dialkylmethoxyboranes gave an alternative route to the preparation of dialkylpyridylboranes.
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■ A Novel Synthesis of 3- and 4-Alkenylpyridines
Minoru Ishikura, Machiko Kamada, Tsukasa Ohta, and Masanao Terashima*
*Faculty of Pharmaceutical Scicences, Higashinihonngakuen University, 1757 Kanazawa, Toubetu-cho, Ishikari-gun, Hokkaodo 061-0212, Japan
Abstract
A new approach for the simple preparation of 3- and 4-alkenylpyridines that relys upon the palladium catalyzed cross coupling reaction of diethylpyridylboranes with vinylic bromides is described.
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■ 1,3-Dipolar Cycloaddition of 2-Diazopropane to Azoloazines, Derivatives of 10π-Electron System. The Synthesis of Pyrazolo[4,3-d]azolopyridazines and Pyrazolo[3,4-d]azolopyridazines
Branko Stanovnik,* Borut Furlan, Alenka Sarka, Miha Tisler, and Marko Zilcar
*Department of Chemistry, E. Kardelj University, Murnikova 6, 61000 Ljubljana, Slovenia
Abstract
1,3-Dipolar cycloaddition of 2-diazopropane occurs across C7-C8 partially localized double bond of azolopyridazines 1, derivatives of 10π-electron systems, to produce derivatives of novel heterocyclic systems pyrazoloazolopyridazines 4 and 5.
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■ Meso-ionic Oxazolones in Heterocyclic Synthesis: Reaction of 4-Methyl-2-phenyl-Δ2-oxazolin-5-one with Aldazines
Dilip Konwar, Dipak Prajapati, Jagir Singh Sandhu,* Tetsuji Kametani, and Toshio Honda
*Division of Drug and Pharmaceutical Chemistry, Regional Research Laboratory, Jorhat 785 006, Assam, India
Abstract
Reaction of 4-methyl-2-phenyl-Δ2-oxazolin-5-one (2) with various aldazines (1) yielded pyridazinones (3) in good yields. Their structures were fully supported by spectral data.
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■ Synthesis and Reactions of C(3)-Azido Cephem
Douglas O. Spry* and Anita R. Bhala
*Lilly Reserach Laboratories, Lilly Corporate Center, Eli Lilly & Company, Indianapolis, IN 46285-4813, U.S.A.
Abstract
The C(3)-azido cephem 2 reacts with Grignards to give triazines and with a variety of electron rich dipolarophiles to give C(3)-substituted amidines, imidates, iminolactones and aziridines.
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■ Synthesis of Debromo-8,8a-dihydroflustramine C. A Model Experiment Related to the Total Synthesis of Amauromine
Shigehiro Takase,* Itsuo Uchida, Hirokazu Tanaka, and Hatsuo Aoki
*Fujisawa Pharmaceutical Co. Ltd., 2-1-6 Kashima, Yodogawa-ku, Osaka 532, Japan
Abstract
A derivative (1) from marine alkaloid, flustramine C, was synthesized utilizing thio-Claisen rearrangement at the key step. The method of the synthesis would be applied to synthesis of alkaloids possessing the reversed prenyl group at 3a position of hexahydropyrrolo[2,3-b]indole skeleton such as amauromine.
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■ Synthesis and Biological Evaluation of Oxygenated Ftorafur (FT-207) Derivatives
Gerrit-Jan Koomen, John B. M. van Rhijn, Richard Carels, and Upendra K. Pandit*
*Organic Chemistry Department, University of Amsterdam, Nieuwe Achtergracht 129, 1018 WS Amsterdam, The Netherlands
Abstract
The synthesis and the chemical and biological of 5’-hydroxy, 5’-oxo and 3’-hydroxy-5’-oxoftorafur are reported.
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■ New Di-isoprenylated Indole Derivatives from Hexalobus crispiflorus
Hans Achenbach,* Christian Renner, and Ivan Addae-Mensah
*Institute of Pharmacy, Department of Pharmaceutical Chemistry, University of Erlangen, D-8520 Erlangen, Germany
Abstract
From the stem bark of H. crispiflorus twelve new isoprenylated indoles were isolated and their structures determined; some of these compounds exhibit antifungal activity.
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■ A Single Step Biomimetic Systhesis of Bicyclic Oxazolo, Imidazolo and Thiazolopyrimidines
Harjit Singh* and Subodh Kumar
*Department of Chemistry, Guru Nanak Dev University, Amritsar -143 005, Punjab, India
Abstract
4-Isothiocyanatobutan-2-one with ethanolamine, ethylene diamine and 2-mercaptoethylamine give title systems through intramolcular nucleophilic addition on enamine double bond of pyrimidine derivative first formed.
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■ Novel Ring-contraction of 5-Anilidene-6-(N-methylanilino)pyrimidine-2,4(3H,5H)-dione
Magoichi Sako, Yutaka Kojima, Kosaku Hirota, and Yoshifumi Maki*
*Gifu Pharmaceutical University, 6-1 Mitahora-higashi 5-chome, Gifu 502-8585, Japan
Abstract
Treatment of 5-anilidene-6-(N-methylanilino)pyrimidine-2,4(3H,5H)-dione (1) with primary alcohcls without any catalyst causes smooth ring-contraction leading to 4-alkoxycarbonyl-4-anilino-5-(N-methylanilino)imidazol-2(3H,4H)-ones (2) in high yields.
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■ New Condensed Tri- and Tetracyclic Pyrazole Ring System
Jan Svetlík*
*Drug Research Institute, Palárikova 31, 811 04 Bratislava, Slovakia
Abstract
1 -Phenylpyrazolo[4,3-e]pyrrole[1,2]pyracolo[1,2-a]pyrazine and its 5-aza analogue were synthesized from ethyl 5-amino-1-phenylpyrazole-4-carboxylate. Additional azole ring amelations onthe pyrazine part of the first heterocycle afforded new tetracyclic systems with two common nitrogen atoms,
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■ A Novel Approach to Functionalization of Azines. Oxiranyl and Thiiranyl Derivatives of Pyridine, Quinoline and Isoquinoline
Krystian Kloc, Elzbieta Kubicz, and Jacek Mlochowski*
*Institute of Organic and Physical Chemistry, Technical University of Wroclow, 50-370 Wroclaw, Poland
Abstract
Convenient methods for synthesis of the oxiranyl and thiiranyl derivatives of pyridine, quinoline and isoquinoline have been elaborated. Oxiranes have been synthesized from corresponding aldehydes with dimethylsulfonium methylide in anhydrous medium. Exchange of the oxygen atom in the oxirane ring on sulfur with potassium thiocyanate gave thiiranylazines.
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■ Reactions with Nitriles: A Novel Synthesis of Furo[2,3-c]pyrazoles and Pyrano[2,3-c]pyrazoles
Suzan I. Aziz,* Sanaa O. Abd-Allah, and Nadia S. Ibrahim
*Department of Chemistry, Faculty of Science,University of Cairo, Giza, Egypt
Abstract
Several new furo[2,3-c]pyrazole and pyrano[2,3-c]pyrazole derivatives were synthesised via the reaction of the 4-bromo-2-pyrazolin-5-one derivative 1 with activated nitriles and their ylidene derivatives. The synthesised products were established based on elemental analyses, IR and 1H NMR spectral data.
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■ Reaction of Diphenylcyclopropenone with 2-Aminothiazoles and Related Compounds
Albert Kascheres,* Juan L. Reyes R., and Suzana M. Fonseca
*Instituto de Química, Universidade Estadual de Campinas (UNICAMP), Caixa Postal 6154, CEP 13083-970, Campinas, Sao Paulo, Brazil
Abstract
Diphenylcyclopropenone (1) reacts readily with 2-aminothiazole (7a) in THF to produce cis-5,6-dihydro-5,6-diphenyl-7H-thiazolo[3,2-a]pyrimidin-7-one (8a) in high yield. 2-Amino-5-ethyl-1,3,4-thiadiazole (7b) and 2-aminothiazoline (7c) react similarly, while 2-amino-4-methylthiazole (7d) affords both 8d and the cis-2,3-diphenylacrylamide 11. 2-Amino-4-ethyl-5-methylthiazole (7e) and 2-aminobenzothiazole (7f) give no 8, the products isolated being the corresponding cis-2,3-diphenylacrylamides 12 and 13. 2-Aminobenzimidazole (16a) yields 17a and 17b, while 2-amino-5-chloro-benzimidazole (16b) produces 18a, 18b, and 19.
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■ Chemistry of Nuphar Alkaloids. Part VIII. Hofman Degradation of Thiobinupharidine Dimethiodides
Jacek Cybulski, Krystyna Wojtasiewicz, and Jerzy T. Wrobel*
*Department of Chemistry, University of Warsaw, Pasteura St.1, 02-093 Warsaw, Poland
Abstract
The two-step Hofmann degradation of thiobinupharidine dimethiodides has been carried out. The structure and stereochemistry of the obtained products have been determined by means of spectroscopic analysis.
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■ Phospholipid-like Porphinato Iron and Zinc Complexes: Synthesis and Properties
Yoh-ichi Matsushita, Etsuo Hasegawa, Kiyoshi Eshima, and Eishun Tsuchida*
*School of Science and Engineering, Waseda University, 3-4-1 Okubo, Shinjuku-ku, Tokyo 169-8555, Japan
Abstract
A new amphiphilic porphyrin having one hydrophilic group, 5,10,15-tri(α, α, α-o-pivalamidophenyl)-20-mono{α-o-[12-(2’-trimethylammonioethoxy)phosphinatoxy-2,2-dimethyldodecanamido]phenyl}porphine, and its zinc and iron complexes were prepared. These were efficiently embedded in a micelle or a liposome because of their amphiphilicity.
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■ Activated Nitriles in Heterocyclic Synthesis: The Reaction of Cyanoacethydrazide with α-Substituted Cinnamonitrile Derivatives
Ezzat Mohamed Zayed,* Ebtisam Abdel Aziz Hafez, Said Ahmed Soliman Ghozlan, and Abdel Azim Hady Ibrahim
*Department of Chemistry, Faculty of Science, University of Cairo, Giza, Egypt
Abstract
The cinnamonitrile derivatives reacted with cyanoacethydrazide at room temperature to yield N-aminopyridones. The latter underwent a rearrangement reaction on refluxing in ethanolic triethylamine. The same rearrangement products could be directly obtained from the reaction of cinnamonitrile derivatives and cyanoacethydrazide in refluxing ethanol-triethylamine. The mechanism of the reactions involved is suggested.
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■ Detection of Metabolite of Qinghaosu in Nanomolar Quantities: DADF-Esters of Dihydroqinghaosu and Its Epoxy Analog. The Chemistry of Drugs. V
Xuan-de Luo, Herman J. C. Yeh, and Arnold Brossi*
*Laboratoryof Chemistry, Medical Chemistry Section, National Arthritis Institute, National Institute of Health ,Behesda, Maryland 20892, U.S.A.
Abstract
Esters of dihydroqinghaosu (2) and its 4,6-epoxy analog 4 were prepared with diacetyldihydrofluorescein (DADF). Both esters 3 and 5 can be separated by tlc and made visible on plates after exposure to ammonia and iodine vapors as deep red colored spots.
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■ Synthesis of 1,3-Dioxin-4-ones Unsubstituted at the 5- and 6-Positions and Their Photoaddition to Alkenes
Masayuki Sato, Hiromichi Ogasawara, Keiko Sekiguchi, and Chikara Kaneko*
*Pharmaceutical Institute, Tohoku University, Aobayama, Sendai 980-8578, Japan
Abstract
A general synthetic method of 5,6-unsubstituted 1,3-dioxin-4-ones and their photoadditlon to alkenes are described. The photoadducts thus obtained were found to give, merely by refluxing in water, alkanes having carboxaldehyde and acetic acid appendages at the vicinal position.
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■ Novel 1,2-Dihydroisoquinoline Synthesis via Intramolecular 1,3-Dipolar Alkylazide-olefin Cycloaddition
Jenn-Jong Young and Chin-Kang Sha*
*Department of Chemistry, National Chung Hsing University, China
Abstract
Treatment of ethyl o-bromomethylcinnamate (1) with sodium azide in dimethylforamide at room temperature afforded ethyl o-azidomethylcinnamate (2). Compound 2 underwent intramolecular 1,3-dipolar cycloaddition to give triazoline 3. Subsequent rearrangement of 3 gave ethyl isoindoline-1-diazoacetate (4) at room temperature. Reaction of 4 with rhodium acetate in benzene gave 3-ethoxycarbonyl-1,2-dihydroisoquinoline (6) (53% overall from 1).
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■ Direct α-Bromination of Morphinan-6-one Bases
Yoshiro K. Sawa, Masaaki Kobayashi, and Haruhiko Tada*
*Shionogi Research Laboratories, Shionogi & Co. Ltd., Fukushima-ku, Osaka 553-0002, Japan
Abstract
Bromination of morphinan-6-one base in the presence of HBr afforded α-bromoketone without aromatic substitution. This method may be applicable to other basic compounds, such as alkaloids, except for compounds having acid-sensitive functional groups.