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. 8, 1984
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■ Synthesis and Structure of a 1,2,5,7-Benzothiatriazonine
Marlise Schläpfer-Dähler, Roland Prewo, Jost H. Bieri, and Heinz Heimgartner*
*Organische-chemisches Institut, Universitat Zürich, Winterthurerstrasse 190, CH-8057 Zürich, Switerland
Abstract
3-Dimethylamino-2,2-dimethyl-2H-azirine (1) and 4-phenyl-3,4-dihydro-2H-1,2,4-benzothiadiazin-3-on-1,1-dioxide (6) react already below room temperature to give a nine-membered heterocyclic product, namely 3-dimethylamino-4,4-dimethyl-7-phenyl-4,5,6,7-tetrahydro-l,2,5,7-benzothiatriazonin-6-on-1,1-dioxide (7, Scheme 2) in a quantitative yield. The structure of this new heterocycle has been confirmed by X-ray crystallographic analysis (Fig. 1 and 2). In Scheme 2 a reaction mechanism for the formation of 7 is discussed, the zwitterion b being the key intermediate.
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■ Antimicrobial Agents from Higher Plants. Erycristagallin, a New Pterocarpene from the Roots of the Bolivian Coral Tree, Erythrina crista-galli
Lester A. Mitscher,* Jeffrey A. Ward, Steven Drake, and Gollapudi S. Rao
*Department of Medicinal Chemistry, University of Kansas, 4070 Malott Hall, Lawrence, Kansas 66045-2506, U.S.A.
Abstract
Bioassay directed fractionation of extracts of the roots of Erythrina cristagalli produced the new pterocarpene, erycristagallin (1) as the main antimicrobial constituent. Structural assignment is based upon degradation and spectroscopic studies.
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■ Nitriles in Heterocyclic Synthesis: A New Approach for the Synthesis of Thiazinones
Nadia S. Ibrahim,* Nosrat M. Abed, and Zaghloul E. Kandeel
*Department of Chemistry, Faculty of Science, University of Cairo, Giza, Egypt
Abstract
Synthesis of thiazines via the reaction of thiosalicylic acid with malononitrile, ethyl cyanoacetate and other polyfunctional nitriles is reported.
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■ On Cardioactive Steroids XIV. The Preparation of (21R)-21Methyldigitoxin
Thomas Y. R. Tsai and Karel Wiesner*
*Natural Products Research Center, Department of Chemistry, University of New Brunswick, Bag Service #45222, Fredericton, New Brunswick, E3b 5A3, Canada
Abstract
A high yield direct conversion of digitoxin into (21R)-21methyldigitoxin is described.
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■ β-Aminosyryl Derivatives via Folate Models. Approach to Yohimbane Skeleton
Axel R. Stoit and Upendra K. Pandit*
*Organic Chemistry Department, University of Amsterdam, Nieuwe Achtergracht 129, 1018 WS Amsterdam, The Netherlands
Abstract
2-Methoxycarbonyl-(α-methoxycarbonyl-β-trytaminyl)styrene, prepared by transfer of CH3OOC-2-C6H4CH(COOCH3)CH via a methylenetetrahydrofolate model, to tryptamine, yields the pentacyclic system of yohimbane in two steps.
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■ Synthesis of 3-Ethylpyrazolo[3,4-e][1,3]oxazin-5,7-dione, a Derivative of a New Heterocyclic Ring System
Vladimir G. Beylin and Leroy B. Townsend*
*Department of Chemisry, University of Michigan , 930 North University, Ann Arbor, MI 48109-1055, U.S.A.
Abstract
The Synthesis of 3-ethylpyrazolo[3,4-e][1,3]oxanin-5,7-dione, a derivative of a new ring system, by annulation of 3(5)-ethyl-4-hydroxy-5(3)-carboxamidopyrazole with ethyl chloroformate or N,N’-carbonyldiimidazole is described.
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■ Facile Synthesis of Thiazolo[4,5-b]- and Thieno[3,2-b]pyridine Derivatives by a Novel Pyridine Cyclization Reaction via Enamine Intermediates
Isao Hayakawa* and Yoshiaki Tanaka
*Exploratory Research Laboratories I, Daiichi Pharmaceutical Co., Ltd., 16-13, Kitakasai 1-chome, Edsogawa-ku, Tokyo 134, Japan
Abstract
Thiazolo[4,5-b]- and thieno[3,2-b]pyridine-6-carboxylic acid derivatives were synthesized by formation of the thiazole or the thiophene ring bearing o-amino-β-ketoester moiety, followed by a novel pyridine cyclization reaction with DMF-dimethylacetal .
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■ Antitumor Diterpenoids from Rabdosia Trichocarpa: Trichorabdal E, F, and H and G Acetate
Manabu Node, Midori Sai, Eiichi Fujita, and Kaoru Fuji*
*Institute for Chemical Research, Kyoto University, Uji, Kyoto 611-0011, Japan
Abstract
The structure determination and conformation of antitumor diterpenoids, trichorabdal E, F, and H, are described.
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■ Photochemistry of N-Aroylanthranilic Adids
Takeaki Naito and Ichiya Ninomiya*
*Kobe Women’s College of Pharmacy, Motoyamakita, Higashinad, Kobe, Hyogo 658, Japan
Abstract
Irradiation of the N-aroylanthranilic acids (1b), (7), (11), and (15) in the presence of either sodium borohydride or potassium hydroxide afforded a mixture of the dihydrophenanthridones (3a and b) , (6), (8), (12), (14), and (16), the phenanthridones (2), (9), and (13), and the biphenyls (4), (10), and (17).
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■ Reaction of N-p-Toluenesulfonyldiphenylcyclopropenimine with Pyridinium N-Imines
Albert Kascheres,* J. Augusto R. Rodrigues, and Ronaldo Pilli
*Instituto de Química, Universidade Estadual de Campinas (UNICAMP), Caixa Postal 6154, CEP 13083-970, Campinas, Sao Paulo, Brazil
Abstract
Pyridinium N-imines (1) react with N-p-toluenesulfonyldiphenylcyclopropenimine (2) to afford pyridopyridazinimines (3).
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■ Synthesis of Potassium 3S-Phenylacetamido-1-(1-carboxy-methyltetrazol-5-yl)-azetidin-2-one and Potassium 3S-Phenylacetamido-1-(2-carboxymethyl-tetrazol-5-yl)-azetidin-2-one
Alex Andrus,* Beverly Partridge, James V. Heck, Burton G. Christensen, and James P. Springer
*Merck Sharp and Dohme Research Laboratories, Rahway, NJ 07065, U.S.A.
Abstract
The synthesis and some biological properties of the title compounds, beta-lactam antibiotics, are described.
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■ On the Stereochemistry of Carbonyl Substitutents at the 8-Position in the Lysergic Acid Derivatives and Their Despyrrole Analogs
Toshiko Kiguchi, Chiyomi Hashimoto, Takeaki Naito, and Ichiya Ninomiya*
*Kobe Women’s College of Pharmacy, Motoyamakita, Higashinad, Kobe, Hyogo 658, Japan
Abstract
The isomerization of the carbonyl substituents at the 8-position in some despyrrololysergic acid derivatives was discovered and stereochemical studies on the configuration of the 8-substituents and on the conformation of ring D in the lysergic acid derivatives and their despyrrole analogs were also carried out.
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■ New Short Step Synthesis of 3-Hydroxyethy-4-cyanoazetidin-2-one Derivative: A Potential Precursor of the Penems and the Carbapenems
Masao Shiozaki,* Hiroshi Maruyama, and Noboru Ishida
*Chemical Research Laboratories and Analytical & Metabolic Research Laboratories, Sankyo Co., Ltd., 1-2-58 Hiromachi, Shinagawa-ku, Tokyo 140-8710, Japan
Abstract
3-Hydroxyethyl-4-cyanoazetidin-2-one derivative was synthesized from (2R,3R)-2,3-epoxybutyric acid in two steps.
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■ Synthesis of 3-Hydroxyethyl-4-oxoazetidin-2-ylphosphonate Derivatives: Potential Precursors to Carbapenem and α-Aminophosphonic Acid Derivatives
Masao Shiozaki* and Hidekazu Masuko
*Chemical Research Laboratories and Analytical & Metabolic Research Laboratories, Sankyo Co., Ltd., 1-2-58 Hiromachi, Shinagawa-ku, Tokyo 140-8710, Japan
Abstract
Optically active 3-hydroxyethyl-4-oxoazetidin-2-ylphosphonate derivatives were synthesized.
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■ Structural Elucidation of the Pyrolysis Products of 1,4-Benzoxazine Derivatives
Norio Kawahara,* Takako Nakajima, Tsuneo Itoh, Hiroaki Takayanagi, and Haruo Ogura
*Hokkaido College of Pharmacy, 7-1 Katsuraoka-cho, Otaru 047-02, Japan
Abstract
The thermal reaction of trimethyl 2,3-dihydro-6-chloro-2-oxo-4H-1,4-benzoxazine-Δ3,γ-aconitate afforded novel cyclization products. These compounds were characterized by spectral data and X-ray crystallographic analysis.
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■ Pseudoesters and Derivatives. XXII. Synthesis of 5-Hydroxy-3-pyrrolin-2-ones and 5-Hydroxypyrrolidin-2-ones by Ammonolysis of 5-Methoxyfuran-2(5H)-ones and Derivatives
Francisco Fariña,* M. Victoria Martín, M. Carmen Paredes, M. Carmen Ortega, and Amelia Tito
*Instituto de Química Orgánica General, C. S. I. C., Calle Juan de Cierva, 3, 28006 Madrid, Spain
Abstract
The ammonolysis of 4-substituted 5-methoxyfuran-2(5H)-ones 4a-e under mild conditions affords the respective 5-hydroxy-3-pyrrolin -2-ones 5a-e. However, 4-dialkylamino derivatives 4f,g do not react with ammonia under the same conditions. Similar ammonolysis of furanone derivatives 7a,b,10 and 13 yields the pyrrolidinones 8a,b and hexahydroisoindolones 11, and 14, respectively. The corresponding methoxylactams 6a-e, 9a-b and 12 are readily obtained by refluxing the hydroxylactams 5a-e, 8a,b and 11, respectively with acid-catalyzed methanol.
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■ 1,2,3,4-Tetrahydro-1,2-diazepine Derivatives from Isoxazolo[3,4-d]pyridazin-7(6H)-ones
Vittorio Dal Piaz,* Giovanna Ciciani, Annarella Costanzo, Gabriella Auzzi, and Stefano Chimichi
*Dipartimento di Scienze Farmaceutiche, Università di Firenze, Via Gino Capponi 9, I-50121 Firenze, Italy
Abstract
Treatment of isoxazolo[3,4-d]pyridazin-7(6H)-ones (2a-f) with alkali give rise to the new 6-cyano-2,3-disubstituted 1,2,3,4-tetrahydro-5H-1,2-diazepin-5-one derivatives (5a-f) through Michael type addition.
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■ An Improved Synthesis of 2-Methyl-4-(2’-carboxyethyl)pyrrole. Potential Inhibitors of Porphobilinogen Deaminase
Samuel H. Wilen,* DeKang Shen, Joseph M. Licata, Enoch Baldwin, and Charlotte S. Russell
*Department of Chemistry, The City College of the City University of New York, Convent Avenue @ 138th Street, New York, NY 10031, U.S.A.
Abstract
Improved syntheses of 2-methyl-4-(2’-carboxyethyl)pyrrole (10) (49% overall yield) and of several O- and S-containing β-(5-ring heterocyclic)-substituted propionic acids are described. Some of these compounds have been found to be inhibitors of porphobilinogen deaminase.
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■ A Revised Structure for the Product of the Acid Catalyzed Rearrangement of N-(1-Phentlpropionyl)-N-phenylhydroxylamine
Giuseppe Capozzi, Alba Chimirri, Silvana Grasso, and Giovanni Romeo*
*Dipartimento Farmaco-Chimico, Università di Messina, Viale Annunziata, 98168 Messina, Italy
Abstract
The reaction of N-(1-phenylpropionyl)-N-phenylhydroxylamine 2 with trifluoromethanesulphonic acid at 80°C gives the 1-phenyl-1,2,3,4-tetrahydroquinolin-2-one 3. For this compound a 5,6,7,8-tetrahydro-dibenz[b,d]azocin-6-one 1 has bean previously reported. Spectroscopic evidences support the proposed structure.
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■ Photochemical Wolff Rearrangement of 5-Diazo-6-phenyluracil in Neutral Solutions. The Synthesis of Alkyl 5-Phenyl-2-oxo-4-imidazoline-4-carboxylic Acid Derivatives
Wilhelm Klötzer,* Gerhard Dörler, Branko Stanovnik, and Miha Tisler
*Department of Chemistry, E. Kardelj University, Murnikova 6, 61000 Ljubljana, Slovenia
Abstract
A photochemical Wolff rearrangement of 5-diazo-6-phenyluracil (6), the compound which does not form the corresponding hydrate or alcohol adducts, into alkyl 5-phenyl-2-oxo-4-imidazoline-4-carboxylic acid derivatives 8a-h in neutral solutions is described.
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■ Synthesis of 1,2,3,4,5,6-Hexahydro-2,6-methano-1-banzazocin-11-ones
Ahmed A. Hamam and John A. Joule*
*Department of Chemistry, University of Manchester, Oxford Road, Manchester, M13 9PL, U.K.
Abstract
4aH-4a-Methyl-2,3,4-9-tetrahydrocarbazoles can be converted into 1,2,3,4,5,6-hexahydro-2,6-methano-6-methyl-1-benzazocin-11-ones by successive reaction with bromine and aqueous ammonium carbonate.
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■ Formation and Reactions of Trichloro-γ-lactones
Seiichi Takano,* Shin’ichi Nishizawa, Masashi Akiyama, and Kunio Ogasawara
*Pharmaceutical Institute, Tohoku University, Aobayama, Sendai 980-8578, Japan
Abstract
The allyl trichloroacetates, (6) and (7), have been converted into the trichloro-γ-lactones, (8) and (9), by cuprous chloride. On dechlorination using tri-n-butyltin hydride, regioselective reaction has occurred initially at α position to convert the trichlorides, (8) and (9), into the dichlorides, (11) and (12), which in turn have been converted into the rnonochlorides, (13) and (14), depend on amount of the reducing agent. On dehydrochlorination, both the trichlorides, (8) and (9), have furnished the dihalobutenolides, (16) and (17), via 1,2-elimination with DBU, while the monohalides, (13) and (14), have yielded the cyclopropa[2,3]butyrolactones, (26) and (27), via 1,3-elimination with potassium tert-butoxide.
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■ A Synthesis of Carbamic Acid [Imidazo-heteroaromatic] Methyl Ester Derivatives Using Methoxycarbonyl Isothiacyanate
Siya Ram, 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
Methoxycarbonyl isothiocyanate (1), in the presence of N,N-dicyclohexylcarbodiimide, has been found to be a versatile reagent for the one-pot synthesis of a bicyclic imidazo-heteroaromatic system.
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■ Constituents of the Chinese Crude Drug "Sang-Bái-pí" (Morus Root Bark) V. Structures of Three New Flavanones, Sanggenons L, M, and N
Yoshio Hano, Masato Itoh, Nanae Koyama, and Taro Nomura*
*Faculty of Pharmaceutical Sciences, Toho University, 2-2-1, Miyama, Funabashi, Chiba 274-8510, Japan
Abstract
Three new isoprene substituted flavanones, named sanggenons L (1), M (2), and N (3) were isolated from the benzene extract of the Chinese crude drug “Sàng-BÁi-Pi” (Japanese name “Sohakuhi”), the root bark of Morus sp. (Moraceae). The structures 1, 2, and 3 were proposed for these compounds on the basis of the spectrometric and chemical evidence.
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■ Novel Amination of 6-Aryl-3(2H)-pyridazinones with Hydrazine
Baldev Singh*
*Sterling Winthrop Pharmaceuticals Research Division, Rensselaer, New York, 12144, U.S.A.
Abstract
Treatment of 6-aryl-3(2H)-pyridazinones with hydrazine hydrate gave 4-amino-6-aryl-3(2H)-pyridazinones
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■ Quinolizidines. IX. An Improved Procedure for the Synthesis of Indolo[2,3-a]quinolizidine from 3-(2-Piperidinoethyl)indole
Tozo Fujii,* Masashi Ohba, and Noriko Sasaki
*Faculty of Pharmaceutical Scicences, Kanazawa University, 13-1 Takara-machi, Kanazawa 920-0934, Japan
Abstract
The procedure and yield of the oxidative cyclization of 3-(2-piperidinoethyl)indole (V) to produce indolo[2,3-a]quinolizidine (X) have been improved by the use of 3 molar equivalents of Hg(OAc)2-edetate disodium in boiling aqueous EtOH for 3 h. Similar oxidation of the piperidinoethanol IIIb in boiling 1% aqueous AcOH failed to give the expected lactam alcohol XIIb, an alternative intermediate for the synthesis of X.
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■ Facile Formation of 2,2’-Diquinolylmethane N,N’-Dioxides and Mono-N-oxides And Related Reactions
Genji Iwasaki, Kazuko Wada, Seitaro Saeki, and Masatomo Hamana*
*Faculty of Pharmaceutical Sciences, Kyushu University, 3-1-1 Maidashi, Higashi-ku, Fukuoka 812-8582, Japan
Abstract
Reactions of quinoline N-oxides with derivatives of quinaldine or its N-oxide in the presence of t-BuOK in THF at low temperatures afford mono-N-oxides or N,N’-dioxides of 2,2’-diquinolylmethanes, respectively. Some related reactions are also described, which involve reactions of p-chloronitrobenzene giving 2-substituted 4-chloronitrobenzenes.
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■ Synthesis of (±)-3-Demethoxyerythratidinone, an Alkaloid of Erythrina lithosperma BLUME
Yoshisuke Tsuda,* Akira Nakai, Kazuo Ito, Fumio Suzuki, and Mitsumasa Haruna
*Faculty of Pharmaceutical Scicences, Kanazawa University, 13-1 Takara-machi, Kanazawa 920-0934, Japan
Abstract
3-Demethoxyerythratidinone, an alkaloid of Erythrina lithoaperma Blume was synthesized in a racemic form by five different routes.
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■ Utility of Hydrazines and Hydrazine Derivatives in Heterocyclic Synthesis
Ebtisam Abdel Aziz Hafez,* Nosrat Mustafa Abed, Mohamed Rifaat Hamza Elmoghayer, and Abdel Ghani Ali El-Agamey
*Department of Chemistry, Faculty of Science, University of Cairo, Giza, Egypt
Abstract
Recent utilities of hydrazine and hydrazine derivatives in the synthesis of hydrazines and hydrazine derivatives for synthesis of heterocycles are surveyed. Several novel approaches for the synthesis of azoles, azines and azoloazines are reported.