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. 27, No. 6, 1988
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■ Nitriles in Organic Synthesis. Synthesis of New Functionally Substituted Pyrazines and Pyrroles
Mona H. Mohamed, Nadia S. Ibrahim,* Mona M. Hussien, and Mohamed H. Elnagdi
*Department of Chemistry, Faculty of Science, University of Cairo, Giza, Egypt
Abstract
Whereas the reaction of 1a,b with 2a-c afforded pyrazines, compound 1c reacted with 2a-c to yield diaminopyrroles. Compound 1c reacted with 2a to yield triazacenaphthene derivative.
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■ Secondary Metabolites from the Roots of Ligusticum porteri (Umbelliferae). X-Ray Structure of Z-6.6’,7.3a’-Diligustilide
Guillermo Delgado,* Rosa G. Reza-Garduño, Rubén A. Toscano, Robert Bye, and Edelmira Linares
*Facultad de Química, Universidad Nacional Autónama de México, Circuito Exterior, Ciudad Universitaria, Coyoacán 04510, Mexico
Abstract
Z-Ligustilide (1), riligustilide (2), Z-6.6’,7.3a’-diligustilide (7), isovanillin and 4-hydroxy-3-methoxycinnamic acid, were isolated from the roots of Liqusticum porteri C. & R. (family Umbelliferae; common name: chuchupate), which are used in traditional medicine. The chemical characterization of 3,8-dihydro derivative of 7 (9),allowed the structural reassignment of a constituent previously isolated from L. wallichii.
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■ Synthesis of Anomalously Coupled Nucleosides by Addition of Purines to Unsaturated Sugar Aldehydes
Zbigniew Kaluza, Marek Chmielewski, and Erik B. Pedersen*
*Department of Chemistry, Odense University, Campusvej 55 DK-5230 Odense M., Denmark
Abstract
α,β-Unsaturated sugar aldehydes were reacted in a Michael type of reaction with purines in the presence of an organic base to give isonucleosides.
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■ Novel Mechanistic Aspects of the 4-Acyl-β-lactam Formation from 1,2-Iminoketones
Benito Alcaide, Gema Dominguez, Joaquin Plumet,* and Miguel A. Sierra
*Departamento de Química Orgánica, Facultad de Química, Universidad Complutense de Madridas, Ciudad Universitaria, E-28040 Madrid, Spain
Abstract
On the basis of chemical and stereochemical evidence the course of the formation of 4-acyl-β-lactams from 1,2-iminoketones by reaction with the acyl chloride/Et3N system or with the preformed ketene is discussed.
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■ Alkaloid Synthesis Using Furopyridone as Synthon —Synthesis of Key Intermediates for the Syntheses of (±)-Quinine, (±)-Ajmalicine, and (±)-7-Demethyltecomanine—
Takeaki Naito, Okiko Miyata, and Ichiya Ninomiya*
*Kobe Women’s College of Pharmacy, Motoyamakita, Higashinad, Kobe, Hyogo 658, Japan
Abstract
Furopyridones (4a, b, and c) have been proved as the potential synthons for alkaloid synthesis from their facile conversion to the key intermediates (9e), (10e), and (13) for the synthesis of quinine, ajmalicine, and 7-demethyltecomanine.
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■ A New Synthesis of 2-Amino-γ-lactones Involving Photochemical Addition Reaction of Alcohols to Enamide
Takeaki Naito and Ichiya Ninomiya*
*Kobe Women’s College of Pharmacy, Motoyamakita, Higashinad, Kobe, Hyogo 658, Japan
Abstract
Photochemical addition reaction of alcohols to the enamide (2) prepared from pyruvic acid ester has provided a new synthetic method of the 2-amino-γ-lactones (6a-d).
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■ 2-(Heteroaroma-substituted)methyl Penems. III. Nitrogen Derivatives
Marco Alpegiani, Angelo Bedeschi, Ettore Perrone, Franco Zarini, and Giovanni Franceschi*
*Infectiond Diseases Dept., Farmitalia Carlo Erba R. & D., Via dei Gracchi 35, 20146 Milano, Italy
Abstract
The synthesis of “2-CH2 X” penems wherein X is N-imidoyl, N-heterocyclyl, amino or quaternary ammonium is described. The observed in vitro antibacterial activity marginally correlates with the electronic activation Induced by the X group on the β-lactam ring.
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■ Synthesis of Salvilenone
Guo-Chi Zheng, Tsutomu Kojima, and Hiroshi Kakisawa*
*Department of Chemistry, University of Tsukuba, 1-1-1 Ten-nodai, Tsukuba-shi, Ibaraki, 305-8571, Japan
Abstract
Acid treatment of a tetrahydrophenalenone derivative (5), which have been derived from resorcinol dimethyl ether by 12 steps reactions, afforded salvilenone (1) and hydroxydiketone (2).
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■ Anionic Cycloaddition of Methyl 2,4-Dimethoxy-6-methyl-5-pyrimidinecarboxylate with Acetylenes and Olefins
Akimori Wada,* Hiromi Yamamoto, and Shoichi Kanatomo
*School of Pharmacy, Hokuriku University, 3-Ho, Kanagawa machi, Kanazawa 920-1181, Japan
Abstract
The lithium salt of methyl 2,4-dimethoxy-6-methyl-5-pyrimidinecarboxylate reacts with electron deficient acetylenes and olefins to afford quinazoline derivatives via anionic cycloaddition in considerable yields.
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■ Efficient Preparation of Penicillanate Ester: A Reductive Debromination of Bromopenicillanate Ester and Bromopenicillante-S,S-dioxide Easter with Tri-N-butylphosphine
Ji-Wang Chern,* Min Huang, Jung-Hsiung Tien, and Shou-Hsiung Pai
*Medical Laboratories and Institute of Pharmacy, National Defense Medical Center, P.O. Box 90048-512, Taipei, Taiwan, R.O.C.
Abstract
Benzyl bromopenicillanate (5) and benzyl bromopenicillanate-S,S-dioxide (6) were subject to a reductive debromination in an effect of tri-n-butylphosphine furnishing benzyl penicillanate (7) and benzyl penicillanate-S,S-dioxide (8) in 50% and 81% yield respectively.
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■ Palladiun(0)-catalyzed Condensation of Bromopyridines with α-Substitutesd Acetonitriles
Takao Sakamoto, Eisaku Katoh, Yoshinori Kondo, and Hiroshi Yamanaka*
*Pharmaceutical Institute, Tohoku University, Aobayama, Sendai 980-8578, Japan
Abstract
The condensation of bromopyridines with the sodium salts of phenylsulfonylacetonitrile and diethyl cyanomethylphosphonate in the presence of tetrakis(triphenylphosphine) palladium in 1,2-dimethoxyethane gave the corresponding α-substituted pyridineacetonitrile derivatives in good yields.
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■ Pictet-Spengler Reactions in Aprotic Media. Stereospecific Conbersion of Optically Active cis-1,3-Disubstituted 1,2,3,4-tetrahydro-β-carbolines into Their Corresponding trans-Diastereomers
Lin-Hua Zhang and James M Cook*
*Department of Chemistry, University of Wisconsin-Milwaukee, Milwaukee, Wisconsin 53201, U.S.A.
Abstract
The Pictet-Spengler reaction in refluxing benzene of D-(+)- Na,-methyl-Nb-benzyltryptophan methyl ester 1 and methyl 3-formyl-propionate 2, regioselectively, furnished the trans-1,3-disubstituted-1,2,3,4-tetrahydro-β-carboline 3 (72%) with no detectable racemization at position-3. The optically active cis-diastereomer 4 (28%), which accompanied 3, was converted (CH3OH, HCI, δ) into the trans isomer 3 via the ring-cleaved carbocation intermediate 7, followed by stereospecific intramolecular cyclization.
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■ The Formation of Substituted Indoles by Acid Catalyzed Rearrangements of 4-Isoxazolines
Angelo Liguori, Rosaria Ottana, Giovanni Romeo,* Giovanni Sindona, and Nicola Uccella
*Dipartimento Farmaco-Chimico, Università di Messina, Viale Annunziata, 98168 Messina, Italy
Abstract
Thermal rearrangements of 4-isoxazolines from C,N-diphenylnitrone and substituted alkynes have been directed towards the formation of substituted indoles. Detection and isolation of the intermediates of the process elucidate the reaction pathway. The appropriate choice of substituents and experimental conditions has allowed the control of the single steps involved in the total process.
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■ Reactions of Carbon Suboxide and 2,3-Bifunctional Pyrido Compounds
Leonardo Bonsignore,* Giuseppe Loy, and Daniela Secci
*Tossicologica e Applicata, Instituto di Chimica Farmaceutica, Università di Cagliari, Via Ospedale 72, I-09124 Cagliari, Italy
Abstract
The preparation of pyridodiazepines, pyridodioxepins and pyridoxazepines is described here. The structure of the products has been determined by elemental analysis and spectroscopic data.
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■ New Synthetic Esters of Delphisine and Neoline
Samir A. Ross and S. William Pelletier*
*Department of Chemistry, Institute for Natural Products Research, The University of Georgia, Chemistry Building, Athens, Georgia 30602-2556, U.S.A.
Abstract
Delphisine 1-benzoate (3), delphisine 1-(3,4,5-trimethoxybenzoate) (4), delphisine 1-(para-nitrobenzoate) (5), delphisine 1-(ortho-methoxybenzoate) (6), delphisine 1-(para-methoxybenzoate) (7), neoline 1,14-dibenzoate (10), neoline 1,14-dibenzoate-8-acetate (11), neoline 1-(3,4,5-trimethoxybenzoate) (12), neoline 1 ,14-di(ortho-methoxybenzoate) (13), neoline 1-(3,4,5-trimethoxybenzoate)-14-acetate (14), neoline 1-(para-methoxybenzoate) (15), neoline 1,14-di(para-methoxybenzoate) (16), neoline 1,14-di(3,4,5-trimethoxybenzoate) (17), neoline 1-(para-methoxybenzoate)-14-acetate (18) and neoline 1,14-di(para-nitrobenzoate) (19) are new synthetic esters gF delphisine and neoline. The physical and spectral data of these fifteen new compouds are given.
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■ 3,3’;2’,2’’;3’’.3’’’ - Tetrathiophene: Synthesis and Crystal Structure
Nimal Jayasuriya, Jacques Kagan,* De-Bin Huang, and Boon K. Teo*
*Department of Chemistry, University of Illinois at Chicago, 845 West Taylor St., Chicago, IL 60607-7061, U.S.A.
Abstract
The title structure was obtained from X-ray data on the product formed when the monolithio derivative of 3,3’-bithienyl was treated with CuCl2. The thiophene rings were not coplanar: the angle between adjacent rings was about 20° in the 3,3’-bithienyl moieties, and 110° in the 2,2’-bithienyl moiety. The product was best forme (in 84% yield) by coupling 2-bromo-3,3’-bithienyI with its Grignard derivative by the Kumada procedure.
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■ 2D 1H- 13C Heteronuclear NMR Study of 9-Methoxyellipticine and of the Related Indole and Carbazole Derivatives
Gérard Commenges and Renée C. Rao*
*Laboratoire de Pharmacologie et de Toxicologie Fondamentales, C.N.R.S., 205 Route de Narbonne, 31400 Toulouse Cedex, France
Abstract
Unambiguous assignment based on 2D 1H-1H homonuclear and 1H-13C heteronuclear correlations is given for the 13 C-NMR spectrum of 9-methoxyellipticine (3) in DMSO-d6, settling the discrepancy existing between the earlier data. The 13C-NMR spectra of 5-methoxyindole (1), and 1,4-dimethylcarbazole (2), which have been used as model compounds for the earlier 13C assignments of (3) have also been reinvestigated.
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■ Studies in the Chemical Constituents of the Seeds of Pegnum harmala: Isolation and Structure Elucidation of Two β-Carboline Lactams - Harmalanine and Harmalacidine
Salimuzzaman Siddiqui,* Obaid Yusuf Khan, Shaheen Faizi, and Bina Shaheen Siddiqui
*H. E. J. Postgraduate Institute of Chemistry, University of Karachi, Karachi-75270, Pakistan
Abstract
Two β-carboline lactams harmalanine and harmalacidine have been isolated from the seeds of Peganum harmala and their structures were elucidated as I and II respectively through chemical and spectroscopic studies. In the case of I, which is the simplest tetracyclic β-carboline lactam from any source, detailed nmr (1H and 13C) investigations including noe difference, 2D nmr (cosy-45, noesy, J-resolved) double resonance experiments and 1H-13C-hetero-COSY measurements have been used.
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■ Oxazolones; Part III. Reaction of 5(4H)-Oxazolones with Hydrazonoyl Halides: A New Synthesis of 5-Pyrazolones
Francesca Clerici, Riccardo Destro, Emanuela Erba, Maria Luisa Gelmi,* and Donato Pocar
*Dipartimento di Chimica Fisica ed Elettrochimica, Università digli Studi di Milano, Via Golgi 19, I-20133 Milano, Italy
Abstract
Reaction of 2-(4-methoxyphenyl)-4-phenyl-5(4H)-oxazolone (1) with hydrazonoyl chlorides 2 under phase transfer conditions afforded 1,4-diaryl-4-(4-methoxybenzamido)-5(1H)-pyrazolone-3-carboxylic acid alkylesters 3 as the main products. Besides ethanedioic acid monoesters 2-aryl-2-(2,4-diaryl-oxazol-5-yl)hydrazides 4 and 4,4’-bis-(1,2,4-triaryl-5(1H)-imidazolones) 5 were obtained
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■ A Facile Preparation of D-Penicillamine. Reaction of Benzylpenilloic Acid and Arylamines
Toshihisa Ogawa,* Kazuyuki Tomisawa, and Kaoru Sota
*Research Center, Taisho Pharmaceutical Co., Ltd., 1-403 Yoshino-Cho, Saitama-city, Saitama 330-8530, Japan
Abstract
The preparation of D-penicillamine (3) was achieved by the reaction of benzylpenllloic acid (1) with arylamines (2, 7, 13, 15) through ring fission of thiazolidine. The structures of the by-products formed in these reactions were determined.
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■ 1,3-Dipolar Cycloaddition of Diazomethane to Differently Substituted 2-Methylpyridazin-3(2H)-ones
Francisco Fariña,* M. Victoria Martín, Magali Romañach, and Félix Sánchez
*Instituto de Química Orgánica General, C. S. I. C., Calle Juan de Cierva, 3, 28006 Madrid, Spain
Abstract
Cycloaddition of diaomethane to 4- or 5-substituted 2-methylpyridazin-3(2H)-ones 1,2 occurs in a practically regiospecific manner to give the expected adducts, which are not stable enough to be isolated and under the reaction conditions are transformed into N,N’-dimethylpyrazolopyridazinones and/or 2,4 (or 2,5)-dimethyipyridazin-3(2H)-ones, depending on the nature and position of the substituents. The regiochemistry of the cycloaddition and the reactivity of pyridazin-3 (2H)-ones 1,2 have been accounted for theoretically by the FMO approach.
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■ Diastereoselective Synthesis of Hexahydro-3H-oxazolo[3,4-a]pyridin-3-one Derivatives by Cyclization of α-Acylaminoradical-Olefin System
Shinzo Kano,* Yoko Yuasa, Kenji Asami, and Shiroshi Shibuya
*School of Pharmacy, Tokyo University of Pharmacy and Life Science, 1432-1 Horinouchi, Hachioji, Tokyo 192-0392, Japan
Abstract
The substituent effect in α-acylaminoradical-olefin cyclization was examined. Treatment of 4-phenylthiooxazolidin-2-ones (10a-f) with tri-n-buytltin hydride in the presence of AIBN yielded 6,7-cis-6,8a-trans-6-alkyl-7-arylhexahydrooxazolo[3,4-a]pyridin-3-ones (11a-f), respectively, with high diastereoselectivity.
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■ Novel Fused-ring 1,4-Benzodiazepines: Synthesis of [1,4]Oxathiano[5,6-b][1,4]benzodiazepin-2-ones
Alba Chimirri, Silvana Grasso, Giovanni Romeo,* and Maria Zappalà
*Dipartimento Farmaco-Chimico, Università di Messina, Viale Annunziata, 98168 Messina, Italy
Abstract
The synthesis of the novel [1,4]oxathiano [5,6-b][1,4] benzodiazepin-2-ones was performed by condensation-cyclization reaction between 7-chloro-1,3-dihydro-3-hydroxy-5-phenyl-2H-1,4-benzodiazepin-2-one and mercaptocarboxylic acids. The structures of obtained compounds were assigned by means of spectroscopic measurements.
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■ New Coumarins from Citrus funadoko
Motoharu Ju-ichi,* Mami Inoue, and Mika Ikegaki
*Faculty of Pharmaceutical Science, Mukogawa-Women‘s University, 11-68 Koushien Kyuban-Cho, Nishinomiya, Hyogo 663-8179, Japan
Abstract
From the roots of Citrus funadoko (Rutaceae), five new coumarins named funadonin (1), (Z)-suberenol (2), (Z)-methylsuberenol (3), (E)-methylsuberenol (4) and 6-hydroxymethylherniarin (5) were isolated and structures were elucidated on the basis of spectroscopic data.
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■ Preparation of Potassium 9-Alkyl-9-bortabicyclo[3.3.1]nonanes and Their Stereoselectivity in the Reduction of Cyclic Ketones
Jin Soon Cha,* Mal Sook Yoon, Kwang Woo Lee, and Jae Cheol Lee
*Department of Chemistry, Yeungnam University, Kyongsan 712-749, Korea
Abstract
Potassium 9-alkyl-9-boratabicyclo[3.3.1]nonanes (K 9-R-9-BBNHs) possessing a wide range of steric requirements were prepared from the reaction of the corresponding 9-alkyl-9-borabicyclo[3.3.1]nonanes (9-R-9-BBNs) and excess potassium hydride, and the stereoselectivities of these reagents in the reduction of representative cyclic ketones were examined. All reagents showed high stereoselectivities, with the stereoselectivities generally increasing with increasing steric requirements of the alkyl substituent. Especially, the tert-butyl derivative, K 9-TB-BBNH, achieved the most favorable stereoselectivity, comparable to that by lithium trisiamylborohydride at 0°C.
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■ The 1,3-Dipolar Cycloaddition as an Approach to Novel Tricyclic O,N- and S,N-Heterocycles
Herbert Bartsch* and Thomas Erker
*Institute of Pharmaceutical Chemistry, University of Vienna, Währinger Strasse 10, A-1090 Vienna, Austria
Abstract
A synthetic pathway to previously unknown trieyclic [1,5]benzothiazepines, [1,5]benzoxazepines, and [1,2,4]oxadiazolo[5,4-c][1,4]benzothiazine via 1,3-dipolar cycloaddition is described.
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■ Recent Advances in the Synthesis of Pyrrolizidines
Masazumi Ikeda,* Tatsunori Sato, and Hiroyuki Ishibashi
*Kyoto Pharmaceutical University, Misasagi-Shichonocho, Yamashina, Kyoto 607-8414, Japan
Abstract
This review briefly summarizes some recent advances in the synthesis of pyrrolizidines.
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■ Chemiastry of Benzo[b]thiophene-2,3-dione
Milinda Rajopadhye and Frank D. Popp*
*Department of Chemistry, University of Wisconsin-Milwaukee, Milwaukee, Wisconsin 53201, U.S.A.
Abstract
The synthesis and reactions of benzo[b]thiophene-2,3-diones are presented in this review. References to miscellaneous studies on the title compound are also included.