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. 19, No. 2, 1982
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■ 1,2-Isopropylidene D-Glyceraldehyde as a Chiral Synthon for γ-Butyrolactone
Tetsuji Kametani, Toshio Suzuki, Masahiro Nishimura, Etsuko Sato, and Katsuo Unno
*Hoshi University, 2-4-41 Ebara, Shinagawa-ku, Tokyo 142-8501, Japan
Abstract
1,2-Isopropylidene D-glyceraldehyde (3) is shown to be a useful and inexpensive chiral starting material for a synthesis of γ-butyrolactones (8), (10) and (12) which are potential intermediates for secologanin and sesquiterpene lactones.
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■ The Reaction of Tertiary Amines with Dichlorocarbene
Luis Castedo, José L. Castro, and Ricard Riguera
*Departamento de Química Orgánica , Facultad de Farmacia, Universidad de Santiago de Compostela, E-15706, Santiago de Compostela, Spain
Abstract
Reaction of dichlorocarbene with phenethyl tertiary amines gives conjugated unsaturated compounds which are the result of a β-elimination. A similar reaction occurs with β-tertiary amino esters.
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■ Photochamical cis, trans-Isomerization in the 2,3-Diphenylpiperazine Series
L. Benadjila-Iguersira, J. Chastanet, and G. Roussi
*Institut de Chimie des Substances Naturelles, Centre National de la Recherche Scientifique, Avenue de la Terrasse, Bat. 27, 91198 Gif-sur-Yvette Cedex, France
Abstract
Irradiation of cis diphenyl substituted piperazines 2a, b (R = Me, H) in acetonitrile solution results in their conversion to trans compounds 1a, b (R = Me, H) while in the case of 2C (R = CH2ø) no isomerization is observed. On the other hand, none of the three trans-piperazines isomerizes under the same conditions. A general mechanism is proposed.
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■ The Isolation and Sturcture of Nahagenin
Atta-ur-Rahman, Akbar Ali Ansari, Steven A. Drexler, and John Clardy
*H. E. J. Postgraduate Institute of Chemistry, University of Karachi, Karachi-75270, Pakistan
Abstract
The isolation and structure of a new sapogenin, nahagenin (1), from the medicinal plant Fagonia indica Linn is presented.
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■ Correlation between 13C Chemical Shifts and Reactivity of Heteroaromatic Nitriles. A New Reactivity Index, γ, for the Condensation Reaction with Enolate Anion of Acetone
Yoshihiro Terui, Masumi Yamakawa, Tsunetoshi Honma, Yukio Tada, and Kazuo Tori
*Shionogi Research Laboratories, Shionogi & Co. Ltd., Fukushima-ku, Osaka 553-0002, Japan
Abstract
13C nmr studies of various heteroaromatic nitriles revealed an interesting correlation between a value composed of the chemical shifts, δCN and δC-CN’, and the reactivity of the nitriles in forming the corresponding enaminoketones through the reactions with enolate anion of acetone. Based on the correlation, a new reactivity index, γ , is proposed.
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■ On the Reaction of Indole with Sodium Borohydride in Formic Acid
Gordon W. Gribble and Stephen W. Wright
*Department of Chemistry, Dartmouth College, Hanover, New Hampshire 03775, U.S.A.
Abstract
The reaction of indole (1) with sodium borohydride in formic acid yields N-methylindoline (3) and a product derived from “indole dimer”, 3-(2-(2-N,N-dimethylaminophenyl)ethyl)-1-methylindoline (4), whose structure is proved by independent synthesis.
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■ The Facile Addition od Secondary Amines to Withaferin A. A Further Example of Alumina-Catalyzed Addition of Amines to α,β-Unsaturated Ketones
S. William Pelletier, Gulilat Gebeyehu, and Naresh V. Mody
*Department of Chemistry, Institute for Natural Products Research, The University of Georgia, Chemistry Building, Athens, Georgia 30602-2556, U.S.A.
Abstract
The alumina-catalyzed addition of various secondary amines to withaferin A (1) is facile and efficient. The addition is illustrated by the preparation in excellent yield of 3-aziridinyl-2,3-dihydrowithaferin A (2), a compound with significant in vivo antitumor activity.
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■ The Synthesis of Acenaphtho[1,2-c][1,2,3]thiadiazole and Phenanthro[9,10-c][1,2,3]thiadiazole
Matthew I. Levinson and Michael P. Cava
*Department of Chemistry, University of Pennsylvania, 231 South 34th Street Philadelphia, PA 19104-6323, U.S.A.
Abstract
Acenaphtho[1,2-c][1,2,3]thiadiazole 3 and phenanthro[9,10-c][1,2,3]thiadiazole 4 have been synthesized by the direct reaction of Lawesson’s reagent 5 with the respective α-diazoketones 1 and 2.
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■ Photochemical Synthesis and Reactivity of Tetradehydroaprophines
Luis Castedo, Teresa Iglesias, Alberto Puga, José M. Saá, and R. Suau
*Departamento de Química Orgánica , Facultad de Farmacia, Universidad de Santiago de Compostela, E-15706, Santiago de Compostela, Spain
Abstract
An efficient method to prepare 4,5,6a,7-tetradehydroaporphines is described. It is based on the photoreduction of benzophenone by amines. Oxidation of 4,5,6a,7-tetradehydroaporphines under several conditions gave oxoaporphines.
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■ Synthesis of 1,2-Diphenylpyrrolo[1,2-a]quinazolines
Jiroh Horiuchi, Masatoshi Yamato, Nobuya Katagiri, and Tetsuzo Kato
*Pharmaceutical Institute, Pharmaceutical Institute, Aobayama, Sendai 980-8578, Japan
Abstract
Heating of 2-aminobenzamide (1) with benzoin (4) in the presence of anhydrous zinc chloride gave 2-(1-benzoylbenzylamino)benzamide (5a) which, on treatment with acetic anhydride, was transformed to 1,2-diphenyl-4,5-dihydropyrrolo-[1,2-a]quinazolin-5-one (6).
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■ Aucubin, a Source of Prostanoid Synthons — New Hemisynthetic Pathways
Arlette Tixidre, Yves Rolland, Janine Garnier, and Jacques Poisson
*Laboratoire de Chimie Therapeutique, Faculte de Pharmacie, Université Paris XI, 5, rue Jean-Baptiste Clément, 92290 Chatenay-Malabry Cedex, France
Abstract
New preparation from aucubin of synthons with a monoterpenic iridoid framework, bearing an available lactol group. These synthons are useful for access to analogs of prostaglandins.
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■ Taxilaminbe, a Pseudobenzylisoquinoline Alkaloid
Gábor Blaskó, Maurice Shamma, Akbar Ali Ansari, and Atta-ur-Rahman
*H. E. J. Postgraduate Institute of Chemistry, University of Karachi, Karachi-75270, Pakistan
Abstract
The phenolic pseudobenzylisoquinoline taxilamine (1) has been obtained from Berberis aristata DC (Berberidaceae). Pseudobenzylisoquinolines are fairly widespread in nature, being found among members of the Berberidaceae, Annonaceae, Ranunculaceae and Fumariaceae.
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■ Structure of Forsythoside B, an Antibacterial Principal of Forsythia koreana Stems
Katsuya Endo, Kazuhiro Takahashi, Toyoko Abe, and Hiroshi Hikino
*Pharmaceutical Institute, Tohoku University, Aobayama, Sendai 980-8578, Japan
Abstract
A new glycoside, forsythoside B, exhibiting antibacterial activity, has been isolated from Forsythia koreana stems. Chemical and spectroscopic studies have established the structure of forsythoside B as shown in formula I.
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■ On the Synthetic Utility of Thermally Generated Imines: The Retro-Ene Imino Diels-Alder Reaction
Richard A. Earl and K. Peter C. Vollhardt
*Department of Chemistry, University of California, Berkeley, Berkeley, California 94720, U.S.A.
Abstract
The flash vacuum pyrolysis of several allyl and propargyl amines provides a preparatively useful synthesis of imines by retro-ene fragmentation. Their synthetic potential is indicated by intramolecular Diels-Alder trapping to give indolizidines in a novel ring-expansion sequence.
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■ Constituents of Citrus depressa (Rutaceae). Characterizations of Five New Acridone Alkaloids
Tian-Shung Wu, Hiroshi Furukawa, and Chang-Sheng Kuoh
*Faculty of Pharmacy, Meijo University, 150 Yagotoyama, Tenpaku, Nagoya 468-8503, Japan
Abstract
Five new acridone alkaloids, citracridone-I (1a), citracridone-II (1b), citpressine-I (2a), citpressine-II (2b), and prenylcitpressine (3) have been isolated from the root bark of Citrus depressa as well as a known acridone alkaloid 5.
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■ Stilbene Photocyclization. Synthesis of Cepharanone B
Luis Castedo, Enrique Guitián, José M. Saá, and Rafael Suau
*Departamento de Química Orgánica , Facultad de Farmacia, Universidad de Santiago de Compostela, E-15706, Santiago de Compostela, Spain
Abstract
The photocyclization of enamides of type 2 is investigated. Photochemical electrocyclization did not take place due to an ineffectiveness of overlapping of the hexatriene system. However, radical induced cyclization gave a satisfactory result.
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■ Thermal Ring-expansion of 6-Ethynyl-1,2,5,6-tetrahydropyridine N-Imides into Diazonine Derivatives
Haruki Sashida and Takashi Tsuchiya
*School of Pharmacy, Hokuriku Universitym 3-Ho, Kanagawa machi, Kanazawa 920-1181, Japan
Abstract
The thermolysis of the 6-ethynyl-1,2,5,6-tetrahydropyridine N-imides (5 and 6) resulted in the [2,3]-sigmatropic rearrangement with the ethynyl group to give the novel dihydrodiazonines (9) via the allene intermediates (8).
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■ Oxidation at Nitrogen in Benzo- Benzodi- and Benzotrifuroxans
Joseph H. Boyer and Chorngbao Huang
*Department of Chemistry, University of Illinois at Chicago, 845 West Taylor St., Chicago, IL 60607-7061, U.S.A.
Abstract
Hydrogen peroxide in sulfuric acid oxidized 5-nitrobenzofuroxan into 1,2,4-trinitrobenzene and completed the oxidation of a mixture from benzodifuroxan and hydrogen peroxide in polyphosphoric acid into 1,2,3,4-tetranitrobenzene. The incompletely oxidized mixture also contained 4,7-dinitrobenzofurazan, a terminal oxidation product. Benzotrifuroxan was unreactive toward peroxidation.
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■ Desulfurisation of Penicillin-derived Disulfides — Synthesis of Some 4-Aza-azetidinones
Kapa Prasad, Gerhard Schulz, Helmut Hamberger, and Peter Stütz
*Sandoz Forschungsinstitut, 1235 Wien, Brunnerstraße 59, Austria
Abstract
Disulfides (1), (2) and (3) on treatment with triphenylphosphine in refluxing benzene yielded 4-aza-azetidinones (7),(8) and (9) in addition to the expected sulfides (4), (5) and (6). The structures of these compounds were determined by 1H NMR and 13C NMR data. Analogous products were also isolated from the reaction of azetidinone (10) with 2-mercaptobenzothiazole.
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■ The N,N’-Diacyl-4,5-dihydroimidazolium Ion as an Electrophile
Jan Bergman, Harris Goonewardena, and Birger Sjöberg
*Department of Organic Chemistry, Royal Institute of Technology, SE-100 44 Stockholm, Sweden
Abstract
2-Methyl-4,5-dihydroimidazole/acetic anhydride reacts smoothly with indole at room temperature giving N,N’-diacetyl-2-methyl-2-(3-indolyl)-imidazolidine. This adduct can be hydrolysed to 3-acetylindole. Other aromatics, like 1,3-dimethoxybenzene, undergo similar reactions.
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■ Synthesis and Alkaline Hydrolysis of 1,1-Bis(N-acetylindol-3-yl)alkenes
Jan Bergman and Birger Sjöberg
*Department of Organic Chemistry, Royal Institute of Technology, SE-100 44 Stockholm, Sweden
Abstract
1,1-Bis(N-acetylindol-3-yl)alkenes are prepared by the reaction between indole and 2-alkyl-4,5-dihydrooxazoles/acetic anhydride in refluxing acetic anhydride. Alkaline hydrolysis of the products in ethanol/water resulted in a cleavage giving indole and a 3-acylindole. Only the 2-unsubstituted 1,1-bis(N-acetylindol-3-yl)alkene yielded the parent alkene.
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■ Synthesis of Heterocyclic Compounds. XXII. Preparation of 6-Aryl-2-thioxopyrimidines
José L. García Navío, Antonio Lorente, and José L. Soto
*Departamento de Química Orgánica, Universidad de Alcalá de Henares, 28871 Alcalá de Henares (Madrid), Spain
Abstract
The reactions of different ethyl benzylidenecyanoacetates (I) and benzylidenemalononitriles (V) with thiourea in an alcohol-alkoxide medium, provide a new and simple method for the synthesis of 6-aryl-5-cyano-4-oxo-2-thioxohexahydropyrimidines (III) and 4-amino-6-aryl-5-cyano-2-thioxotetrahydropyrimidines (VI), respectively. Similarly, the reaction of ethyl benzylidenemalonate leads to 5-ethoxycarbonyl-4-oxo-6-phenyl-2-thioxohexahydropyrimidine (XI).
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■ Conversion of Berberine into Benzindanoazepines via 8,14-Cycloberbines
Miyoji Hanaoka, Mitsuru Inoue, Kazuyoshi Nagami, Yasuji Shimada, and Shingo Yasuda
*Faculty of Pharmaceutical Scicences, Kanazawa University, 13-1 Takara-machi, Kanazawa 920-0934, Japan
Abstract
Acidic treatment of the 8,14-cycloberbine (2) effected regioselective C14-N bond cleavage to give the trans- and cis-benzindanoazepine (8a and 8b) as the kinetically and thermodynamically controlled product, respectively. Dehydration of their N-methyl derivatives (11a and 11b) afforded the unsaturated benzindanoazepine (13). Similarly the 11,12-oxygenated cycloberbine (19) was converted to the benzindanoazepines (20a, 20b, 21b, and 22). All these benzindanoazepines have been shown to be the key intermediates for the rhoeadine skeleton.
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■ A Study of the Effect of Nitro Group in the Synthesis of Pyrazoles and Thiadiazolines from Hydrazidoyl Halides
Hamdi Mohmoud Hassaneen, Abdou Osman Abdelhamid, Ahmad Sami Shawali, and Richard Pagni
*Department of Chemistry, Faculty of Science, University of Cairo, Giza, Egypt
Abstract
The reaction of C-acetyl-N-(2-nitrophenyl)hydrazidoyl chloride 5 with sodium ethoxide and ethyl cyanoacetate yields only one isolable product identified as ethyl 1-(2-nitropheny1)-3-acetyl-5-aminopyrazole-4-carboxylate 6, in contrast to the C-phenyl-N-(2-nitrophenyl)hydrazidoyl bromide analog 1. The nitrilimine derived from 5 adds to the C=C double bond of the enol tautomers of acetylacetone and dibenzoylmethane and gives the corresponding pyrazole derivatives 7 and 8, which upon hydrazinolysis yield 11 and 12, respectively. These results indicate that the ortho nitro group in 5 seems to have no influence on the course of the reactions of 5 with dipolarophilic reagents. Nucleophilic substitution of the halogen atom in 5 by thiocyanate anion and morpholine seems to proceed in a normal way as other hydrazidoyl halides to give the corresponding thiadiazoline and amidrazone derivatives 13 and 19 respectively.
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■ A Simple Synthesis of (R)-Glycerol Acetonide from Ascorbic Acid
Seiichi Takano, Hirotoshi Numata, and Kunio Ogasawara
*Pharmaceutical Institute, Tohoku University, Aobayama, Sendai 980-8578, Japan
Abstract
A simple synthesis of (R)-glycerol acetonide (5) has been developed using (L)-ascorbic acid (1) as a chiral precursor.
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■ Facile Syntheses of (Z)- and (E)-2,5-Dimethyl-3-styrylpyrazines, Isolated from the Argentine Ants
Yasuo Akita and Akihiro Ohta
*Tokyo University of Pharmacy and Life Science, 1432-1 Horinouchi, Hachioji, Tokyo 192-0392, Japan
Abstract
Syntheses of (Z)- and (E)-2,5-dimethyl-3-styrylpyrazines, isolated from Iridomyrmex humilis, were performed by replacing the chlorine atom of 3-chloro-2,5-dimethylpyrazine with C-substituents, utilizing tetrakis(triphenylphosphine)palladium as catalyst.
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■ A Convenient Synthesis of Polyfused Heterocyclic Systems from Heterocyclic Amines and 2,3-Dichloronaphthquinone Using Phase Transfer Catalysis
Ahmad Kamal El-Shafei, Adel Sultan, and Gaston Vernin
*Fac. des Sciences et Techniques de St Jérome, Av. Escadrille Normandie-Niemen Case 552, 13397 Marseille Cedex 20, France
Abstract
Some new polyfused heterocyclic systems were obtained by reacting 2,3-dichloronaphthoquinone with some dianionic ambident heterocyclic compounds containing N-, S-, C- or O- poles under phase transfer catalysis conditions.
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■ New Synthetic Approach for Pyrazolo[3,4-b]pyrazines and Isoxazolo[4,5-b]pyrazines
Marjan Kocevar, Miha Tisler, and Branko Stanovnik
*Department of Chemistry, E. Kardelj University, Murnikova 6, 61000 Ljubljana, Slovenia
Abstract
A new synthetic approach has been developed for the synthesis of pyrazolo[3,4-b]pyrazines (7) and isoxazolo-[4,5-b]pyrazines (22) from the corresponding substituted pyrazines.
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■ The Direct Alkylation of Pyrrole with Allyl Bromide
Eleftherios P. Papadopoulos and Calvin A. Vanderwerf
*Department of Chemistry, University of New Orleans, New Orleans, LA 70148, U.S.A.
Abstract
In the presence of silver carbonate, potassium carbonate, or sodium bicarbonate, pyrrole reacts with allyl bromide to form 2-allylpyrrole together with smaller amounts of 3-allylpyrrole and di(poly)allylpyrroles.
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■ 13C-NMR Studies of Antitumoral Alkaloids. II. Cryptopleurine
Mónica Söllhuber, Gregorio González Trigo, José Elguero, and Alain Fruchier
*Instituto de Química Médica, C. S. I. C., Calle Juan de Cierva, 3, 28006 Madrid, Spain
Abstract
For sixteen compounds related to cryptopleurine the carbon-13 chemical shifts and some first-order coupling constants were measured. Excepting the case of very close signals (less than 0.3 ppm of separation) all the signals were assigned. For cis-stilbene and phenanthrene series some useful SCS for methoxy and carboxy groups were calculated.