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. 14, No. 5, 1980
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■ A New Carbon-Carbon Bond Formation Reaction at the C-4 Position of a β-Lactam
Tetsuji Kametani,* Toshio Honda, Junko Sasaki, Hirofumi Terasawa, Yoshito Nakayama, and Keiichiro Fukumoto
*Pharmaceutical Institute, Tohoku University, Aobayama, Sendai 980-8578, Japan
Abstract
Reaction of 4-acetoxy-2-azetidinone (1) with various organolithiums gave the corresponding C-4 substituted compounds (2), (3), and (5). Treatment of 1 with bromoacetaldehyde diethyl acetal in the presence of magnesium afforded 4-ethoxy-2-azetidinone (6) as the only product.
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■ Mass Spectral Fragmentation of Some Indole Derivatives
Jean-Yves Laronze,* Jacqueline Laronze, Daniel Royer, Jean Lévy, and Jean Le Men
*Laboratoire d’Isolement, Transformation et Synthèse de Substances Naturelles, UFR de Pharmacie, associé au CNRS, Université de Champagne-Ardenne, 51 rue Cognacq-Jay-F 51096 Reims Cedex, France
Abstract
EI mass spectra of oxindoles C, iminoethers D, and dihydro β-carbolines E, arising from chloroindolenines B are analysed.
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■ The Synthesis of Rugosinone and Ledecorine
Natesan Murugesan and Maurice Shamma*
*Department of Chemistry, The Pennsylvania State University, York Campus, P1031 Edgecomb Avenue, York, Pennsylvania 17403, U.S.A.
Abstract
Hydrolysis with concomitant air oxidation of polyberbine (5), derived from berberine chloride (6), furnished dihydrorugosinone (7) which underwent further air oxidation in ethanolic sodium hydroxide to give rugosinone (2). m-Chloroperbenzoic acid oxidation of coptisine chloride (8) afforded enamide 9 whose successive reduction using lithium aluminum hydride in THF and sodium borohydride in methanol supplied a mixture of norledecorine (10) and ledecorine (3). N-Methylation of 10 with formaldehyde and sodium borohydride gave rise to ledecorine (3) in high yield. Polycarpine (1), rugosinone (2), and ledecorine (3) probably arise in nature from protoberberines.
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■ A Synthesis of 3-(α,β-Epoxy)-2-azatidinones Derivatives
Shinzo Kano,* Tsutomu Ebata, Yoko Yuasa, and Shiroshi Shibuya
*School of Pharmacy, Tokyo University of Pharmacy and Life Science, 1432-1 Horinouchi, Hachioji, Tokyo 192-0392, Japan
Abstract
Condensation of 1-phenyl-2-azetidinone with α-methylthio ketones yielded the corresponding β-hydroxy sulfides, which were converted to 3-(α,β-epoxy)-1-phenyl-2-azetidinones through two steps involving desulfurization of the sulfonium iodides. In a similar fashion, condensation of 1-phenyl-2-azetidinone with ethyl α-methylthioacetates gave the corresponding sulfenyl ketones, which were also converted to the 3-(α,β-epoxy)-2-azetidinone derivatives. These 2-azetidinones were further lead to α-anilinomethyl-1,2-butenolides by treatment with methanesulfonic acid.
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■ Synthesis of 4,11-Dimethyl-2,3,4,5-tetrahydro-2,5-iminomethano-6H-benzo[a][1,4,6]thiadiazocine-3,12-decane and 7,9-Dimethyl-8,10-dioxo-2,5-dithia-7,9-diazabicyclo[4.2.2]decane
Taisei Ueda, Noriyuki Sawaki, Noriichi Oda, and Isoo Ito*
*Faculty of Pharmaceutical Sciences, Nagoya City University, Tanabe-dori, Mizuho-ku, Nagoya 467-8603, Japan
Abstract
Two novel heterocyclic ring systems involving the piprazine ring and the benzothiadiazocine or dithiadiazabicyclodecane skeleton were synthesized : The reaction of 3,6-dibromo-1,4-dimethyl-2,5-piperazinedione (I) with an equivalent mole of o-aminothiophenol in ethanol in the presence of sodim ethoxide or in pyridine gave 4,11-dimethyl-2,3,4,5-tetrahydro-2,5-iminomethano-6H-benzo[a][1,4,6]thiadiazocine-3,12-decane (IIA), while the reaction of I with two moles of o-aminothiophenol gave 3,6-bis(2-aminophenyl)-thio-1,4-dimethyl-2,5-piperazinedione (IIIa). The reaction of I with an equivalent mole of ethanedithiol in ethanol in the presence of sodium ethoxide gave 7,9-diazabicyclo[4.2.2]decane (IV), which was also synthesized from 3,6-dihydroxy-1,4-dimethyl-2,5-piperazinedione (V) and ethanedithiol in dioxane in the presence of zinc chloride.
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■ Fluorescence Spectra and Cation-Pseudobase Equilibria of Some Benzophenanthridine Alkaloids
Daniela Walterová, Vladimír Preininger, Frantisek Grambal, Vilím Simánek, and Frantisek Santavy*
*Institute of Medical Chemistry, Palacky University, 3, Hnevotínská, 775 15 Olomouc, Czech Republic
Abstract
The fluorescence spectra of sanguinarine (1), chelerythrine (2), nitidine (3), and N-methylphenanthridinium iodide were studied in different solvents and in dependence upon pH. The equilibrium constants (pKR +) of pseudobase formation of the investigated compounds were measured.
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■ Facile Synthesis of 2-Azetidinones with an Olefinic Substituent at the C-4 Position
Masayuki Shibuya* and Seiju Kubota
*Faculty of Pharmaceutical Sciences, University of Tokushima, Sho-machi 1, Tokushima 770-8505, Japan
Abstract
A novel, facile synthesis of 2-azetidinones having an olefinic side chain at the C-4 position is described. Isoxazolones (7) derived from β-keto esters (6) were converted to β-amino esters (8) in excellent yield by reduction with sodium in isopropyl alcohol followed by esterification. Then reaction of the β-amino esters with o-tolylmagnesium bromide in dichloromethane gave the desired 2-azetidinones (2) ~ (5).
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■ Conversion of 3-(N,N-Dimethylaminocarbonyl)furo[2,3-b]quinoxaline to Novel Pyridazino[3,4-b]quinoxalines
Yoshihisa Kurasawa* and Atsushi Takada
*School of Pharmaceutical Sciences, Kitasato University, Shirokane, Minato-ku, Tokyo 108-8641, Japan
Abstract
3-(N,N-Dimethylaminocarbonyl)furo[2,3-b]quinoxaline was converted to 4-substituted 1,2-dihydropyridazino[3,4-b]quinoxalines via 3-(quinoxaline-2’-yl)-2H-pyrido[1,2-a]pyrimidine-2-ones.
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■ Stereoselective Synthesis of dl-Prosafrinine and dl-Pseudocarpamic Acid
Mitsutaka Natsume* and Masashi Ogawa
*Research Foundation Itsuu Laboratory, 2-28-10 Tamagawa, Setagaya-ku, Tokyo 158, Japan
Abstract
The SnCl2-effected carbon-carbon bond formation of endo-peroxides was applied to alkyl substituted 1,2-dihydropyridines 1a-h to produce 3a-h and 4a-h, whose stereochemistry was clarified. Starting from 3e and 4e, piperidine alkaloids, prosafrinine and pseudocarpamic acid were synthesized in racemic forms.
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■ Some Novel Reactions of 1,3-Dimethyluracils II. Studies on New Stable Pyrimidine Ring-Opened Compounds
Norio Kawahara,* Tsuneo Itoh, Haruo Ogura, and Kyoichi A. Watanabe
*Hokkaido College of Pharmacy, 7-1 Katsuraoka-cho, Otaru 047-02, Japan
Abstract
The reaction of various 1,3-dialkyl-6-(N-substituted)aminouracils (I) with dimethyl acetylenedicarboxylate (DMAD) in aprotic solvents gave new stable pyrimidine ring-opened compounds (II).
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■ Minor Alkaloids in Commercial Samples of Colchicine
Maria A. Iorio, Anna Mazzeo-Farina, Guido Cavina, Luigi Boniforti, and Arnold Brossi*
*Section of Medicinal Chemistry, Laboratory of Bioorganic Chrmistry, NIDDK, National Institute of Health, Bethesda, MD 20892, U.S.A.
Abstract
Commercial samples of colchicine contain a total of about 5% of minor alkaloids as revealed by HPLC. Three minor alkaloids were isolated by preparative ThLC and identified by Mass Spectrometry to be N-formyldeacetylcolchicine, C-17-hydroxycolchicine and C-5 (or -6)-hydroxycolchicine.
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■ A Formal Total Symthesis of the Alkaloid Yohimbine
Ichiya Ninomiya,* Yukiko Tada, Okiko Miyata, and Takeaki Naito
*Kobe Women’s College of Pharmacy, Motoyamakita, Higashinad, Kobe, Hyogo 658, Japan
Abstract
Photocyclization of the enamide (3a), which was readily prepared from harmalane and substituted benzoyl chloride, provided a simple preparation of the key intermediate (4a) for total synthesis of the alkaloid yohimbine.
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■ An Alternative Synthesis of Dipeptido-Aminobenzophenone and Novel Heterocyclic Formations of Ring-Opened 1,4-Benzodiazepine Derivatives
Kentaro Hirai,* Teruyuki Ishiba, Toshio Fujishita, and Hirohiko Sugimoto
*Shionogi Research Laboratories, Shionogi & Co. Ltd., Fukushima-ku, Osaka 553-0002, Japan
Abstract
An alternative synthesis of Gly-Gly-N-methylaminobenzophenone (1a) via iodoacetyl glycylaminobenzophenone (2) is described. Novel ring closures of 2 and cyano derivative 3 are also reported.
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■ Synthesis of Heterocyclic Compounds XIX. Preparation of 4,6-Diaryl-3,5-dicyano-2-pyridones
C. Seoane, J. L. Soto,* and M. P. Zamorano
*Departamento de Química Orgánica, Facultad de Química, Universidad Complutense de Madridas, Ciudad Universitaria, E-28040 Madrid, Spain
Abstract
Reaction of cyanoacetamide with α-benzoylcinnamonitriles (I) leads to a new series of 4,6-diaryl-3,5-dicyano-2-pyridones (IV).
The initial Michael’s addition is followed by a cyclization to a 6-hydroxy-2-piperidone ring (II), whose acid dehydration gives rise to 3,4-dihydro-2-pyridones (III). The latter are easily aromatized to 4,6-diaryl-3,5-dicyano-2-pyridones (IV) by treatment with sodium nitrite in sulfuric acid.
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■ A Facile Synthesis of Desoxysesbanine. An Approach to the Sesbanine Skeleton
Martinus J. Wanner, Gerrit-Jan Koomen, and Upendra K. Pandit*
*Organic Chemistry Department, University of Amsterdam, Nieuwe Achtergracht 129, 1018 WS Amsterdam, The Netherlands
Abstract
Reaction of ethyl cyclopentanecarboxylate anion with N-benzylnicotinamide salt leads to the formation of the spiro-tricyclic skeleton of sesbanine.
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■ On the Reactivity of Thiophene as a Trap for Benzyne
Dario Del Mazza and Manfred G. Reinecke*
*Department of Chemistry, Texas Christian University, Fort Worth, Texas 76129, U.S.A.
Abstract
The thermal decomposition of diphenyliodonium-2-carboxylate in thiophene solution gives naphthalene as the major product thereby demonstrating the effectiveness of thiophene as a trap for benzyne in solution.
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■ New Condensed Triheterocyclic Systems; Pyrrolothienopyrazines
Sylvain Rault, Michel Cugnon de Sévricourt, and Max Robba*
*Laboratoire de Chimie Thérapeutique, U. F. R. des Sciences Pharmaceutiques, Université de Caen, 1, rue Vaubénard, 14032 Caen Cedex, France
Abstract
Cyclization of the azide derivatives of 2 (3)-(1-pyrrolyl)-3-(2)-thienylcarboxylic acids resulted in the formation of the 4,5-dihydropyrrolo[1,2-a]thieno[3,2-e]pyrazin-5-one and the 4,5-dihydropyrrolo[1,2-a]thieno[2,3-e]pyrazin-5-one.
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■ A Synthesis of Ethyl 2-(8-cis-7-Thia-9-azabicyclo[4.3.0]nonanyl)acetate
Paul D. Woodgate,* David Chambers, Peter S. Rutledge, and Richard C. Cambie
*Department of Chemistry, University of Auckland, Private Bag 92019, Auckland, New Zealand
Abstract
A diastereomeric mixture of ethyl 2-(8-cis-7-thia-9-azabicyclo[4.3.0]nonanyl)acetate (3), a useful model for cepham synthesis, is readily prepared from 2-methyl-2-thiazoline via the tautomeric mixture of ethyl 2-(2-cis-3a,4,5,6,7,7a,-hexahydrobenzothiazolyl)acetate (2) and 8-(ethoxycarbonylmethylene)-cis-7-thia-9-azabicyclo[4.3.0]nonane (6).
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■ A One Pot Reaction Involving Hydrolysis-Reduction of Biphthalylidene in an Alkaline Medium
Masashi Tashiro,* Tsuyoshi Sumida, and Gouki Fukata
*Research Institute of Industrial Science, Faculty of Engineering, Kyushu University, 6-1, Kasuga-koen, Kasuga 816-8580, Japan
Abstract
The hydrolysis of biphthalylidene (2) in a varying alkaline medium afforded selectively 2,2’-dicarboxybenzoin (3) or 5,5’-dihydro-5-oxo-diphthalylidene (4) in good yields depending upon the conditions used. In one pot reaction involving hydrolysis of 2 followed by reduction with Raney-alloys, 4b,10b-dihydrobenzopyrano[4,3-c]benzopyrano-6,12-dione (9) was almost selectively obtained in good yields. In the case of the combination of hydrolysis in 10% KOH aq and Al-Ni alloy reduction, 2,2’-dicarboxybibenzyl (8) yielded in 51% as a sole product.
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■ A Synthesis of γ-Butyrolactone and Related Compounds
Shinzo Kano,* Shiroshi Shibuya, and Tsutomu Ebata
*School of Pharmacy, Tokyo University of Pharmacy and Life Science, 1432-1 Horinouchi, Hachioji, Tokyo 192-0392, Japan
Abstract
Synthetic methods for γ-butyrolactone derivatives were reviewed. Contents were selected from the recent literatures.