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. 23, No. 6, 1985
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■ Amidoalkylation of Aromatic Compounds with Methylglyoxal-bismethylcarbamate. A New Synthesis of 1-Amino-1-phenyl-2-propanone Derivatives and Substituted Benzofurans
Dov Ben-Ishai* and Daniella Denenmark
*Department of Chemistry, Israel Institute of Technology, Haifa 32000, Israel
Abstract
The synthesis of 1-methoxycarbonylamino-1-aryl-2-propanones 4 and 3-methoxy carbonylamino-3-methylbenzofurans 7 by the direct amidoalkylation of aromatic compounds with methylglyoxal-bismethylcarbamate (3) is described. The amidopropanones (4) were further converted to the corresponding amidopropanols (5) and 2-oxazolidinones (6).
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■ Two New Morphinane Alkaloids from Beilschmiedia oreophila Schlechter (Lauraceae)
François Tillequin, Michel Koch,* Jacques Pusset, and Gérard Chauvière
*U.A. au C.N.R.S.n°484, Faculté des Sciences Pharmaceutiques et Biologiques, Université René Descartes, 4, Avenue de l‘Observatoire, F-75006 Paris, France
Abstract
Two new morphinane alkaloids, oreobeiline (1) and 6-epioreobeiline (2) have been isolated from the stem bark and wood of Beilschmiedia oreophila Schlechter. Their structures have been elucidated by spectroscopic studies and chcmical correlations.
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■ N,N’-Dialkyl-pyrazinium and Quinoxalinium Salts. N-Heterocycloc Redox Systems with the Radical Cation Intermediate as Most Persistent Oxidation State
Wolfgang Kaim*
*Institut für Anorganische, Niederurseler Hang, D-6000 Frankfurt am Main 50, Germany
Abstract
Two-step redox systems with the cation radical intermediate as most persistent oxidation state were found in electrochemical and ESR studies of the title compounds. The potentials measured in H2O and DMF range from -0.7 V to +0.7 V vs. saturated calomel electrode.
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■ Conformational Studies of 1- and 3-Ethyl-1,2,3,4,6,7,12,12b-octahydroindolo[2,3-a]quinolizines
Mauri Lounasmaa,* Reija Jokela, and Tarja Tamminen
*Laboratory of Organic Chemistry, Helsinki University of Technology, P.O. Box 6100,FIN-02015 HUT, Espoo, Finland
Abstract
A mainly 13C NMR based conformational study of the 1- and 3-ethyl-1,2,3,4,6,7,12,12b-octahydroindolo[2,3-a]quinolizines 1-4 is presented.
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■ Intermolecular Photoaddition of N-Methylphthalomide to Indole Derivatives: Regio- and Stereoselective Formation of Oxeto[2,3-b]indoles
Haruko Takechi,* Minoru Machida, and Yuichi Kanaoka
*Faculty of Pharmaceutical Scicences, Higashinihonngakuen University, 1757 Kanazawa, Toubetu-cho, Ishikari-gun, Hokkaodo 061-0212, Japan
Abstract
N-Methylphthalimide in the presence of N-acylindole derivatives underwent a photochemical [2+2]cycloaddition to give more sterically hindered oxetanes in moderate yields. Some reactions of these imide-oxetanes are also described.
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■ A Total Synthesis of (±)-Lysergol, a 9-Ergolene Type of Ergot Alkaloi
Toshiko Kiguchi, Chiyomi Hashimoto, and Ichiya Ninomiya*
*Kobe Women’s College of Pharmacy, Motoyamakita, Higashinad, Kobe, Hyogo 658, Japan
Abstract
According to the synthetic route established on the despyrrole analog of the alkaloid, the first total synthesis of (±)-lysergol was completed.
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■ Formation of Novel Heterocycles, [1]Benzothiopyrano[3,4-b]pyrrole Derivatives by Unusual Cyclixation Reaction of 1-Benzothiopyran-1-oxide Derivatives
Mikio Hori,* Tadashi Kataoka, Hiroshi Shimizu, Eiji Imai, Noriyuki Iwata, Norihiko Kawamura, and Masayasu Kurono
*Department of Pharmacognosy, Gifu College of Pharmacy, 6-1 Mitahora-higashi 5-chome, Gifu 502-8585, Japan
Abstract
Treatment of 1-benzothiopyran-1-oxide derivatives (12a,b) with sulfuryl chloride and then with sodium hydride afforded a novel type of derivatives of [1]benzothiopyrano[3,4-b]pyrrole.
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■ A Short Synthesis of Rutecarpine and/or Vasicolinone from 2-Chloro-3-(indol-3-yl)ethylquinazolin-4(3H)-one: Evidence for the Participation of the Spiro Intermediate
Chikara Kaneko,* Takuo Chiba, Kouichi Kasai, and Chiemi Miwa
*Pharmaceutical Institute, Tohoku University, Aobayama, Sendai 980-8578, Japan
Abstract
A new route to rutecarpine and/or vasicolinone from 2-chloro-4-quinazolone through an acid catalyzed cyclization of 2-chloro-3-indolylethylquinazolin-4-one has been developed and the mechanism of the cyclization reaction clarified.
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■ Dihydroxygirinimbine, a New Carbazole Alkaloid from Murraya euchrestifolia
Hiroshi Furukawa,* Tian-Shung Wu, and Chang-Sheng Kuoh
*Faculty of Pharmacy, Meijo University, 150 Yagotoyama, Tenpaku, Nagoya 468-8503, Japan
Abstract
Dihydroxygirinimbine (1) was the first isolated from the root bark of Murraya euchrestifolia Hayata, and the structure was established by spectroscopic analysis and the transformation of girinimbine (3).
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■ 1,3-Dipolar Cycloaddition Reaction of Chromones and Coumarin with Pyridinium Ylides
Ichiro Yokoe,* Shunsuke Matsumoto, Yoshiaki Shirataki, and Manki Komatsu
*Faculty of Pharmaceutical Sciences, Josai University, 1-1 Keyakidai, Sakado, Saitama 350-0295, Japan
Abstract
1,3-Dipolar cycloaddition reaction of N-iminopyridinium ylide (2) with chromones (1) gave pyrazolo[1,5-a]pyridines (3) in moderate yields. Similarly coumarin (4) reacted with 2 to give 6H-[1]-benzopyrano [4’,3’:3,4]pyrazoro[1,5-a]pyridin-6-one (5) . Furthermore chromone (1) was cyclized with pyridinium phenacylide (6) to afford 1-(2’-hydroxybenzoyl)-3-benzoylindolizine (7)
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■ Boron Trifluoride Etherate-catalysed Rearrangement of 2,4,6,7-Tetraphenyl-1,3-oxazepine to Give Novel Pyridone Ring System
Tomoshige Kobayashi and Makoto Nitta*
*Department of Chemistry, School of Science and Engineering, Waseda University, 3-4-1 Okubo, Shinjuku-ku, Tokyo 169-8555, Japan
Abstract
The boron trifluoride etherate causes an efficient rearrangement of 2,4,6,7-tetraphenyl-1,3-oxazepine to lead to 2,2,4,6-tetraphenyl-3-pyridone and 3,3,4,6-tetraphenyl-2-pyridone. The BF3-coordinated pyridine-2,3-oxide is proposed as a reasonable intermediate.
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■ The Trapping of Sulfenic Acids from Penicillin Sulfoxides. Aryl Mercaptans
Ronald G. Micetich,* Samarendra N. Maiti, Motoaki Tanaka, Tomio Yamazaki, and Kazuo Ogawa
*Faculty of Pharmacy and Pharmaceutical Sciences, University of Alberta, Edmonton, Alberta, T6G 2G2, Canada
Abstract
Aryl mercaptans, unlike heterocyclic mercaptans, reacted exceptionally slowly with penicillin sulfoxides. These reactions are affected by the substituent at the C-6 position of the penam, and by the nature of the ester group at the C-3 position. The unsym-azetidinone disulfides obtained from these reactions, unlike those from heterocyclic mercaptans, did not react with halogenating agents such as cupric chloride.
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■ Homolytical Alkylation of Heteroaromatic Bases by Cyclic Acetals
Semen Solomonovitch Zlotsky,* Vladimir Victorovitch Sorin, Yuri Borisovitch Seletchonok, and Dilus Lutfullitch Rakhmankulov
*Ufa Oil Institute, Kosmonavtov Str., 1, Ufa, 450062, Russia
Abstract
Homolytical reaction between protonated bases and 1,3-diheterocycloalkanes was described.
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■ Heterocyclic Systems. V. Synthesis of 1H,4H,6H-Pyrazolo[3,4-e]pyrrolo[2,1-c][1,4]oxazepine Derivatives
Silvio Massa, Giorgio Stefancich, Marino Artico,* Federico Corelli, and Giovannni Ortenzi
*Isitituto de Chimica farmaceutica e tossicologica, Facolta di Farmacia, Università a degli Studi di Roma "La Sapienza", Piazza Aldo Moro, 5 - 00185 Roma, Italy
Abstract
The synthesis of derivatives of a new tricyclic heteroaromatic ring, 1H,4H,6H-pyrazolo[3,4-e]pyrrolo[2,1-c][1,4]oxazepine, is described. Formylation of 4-ethoxycarbonyl-1-phenyl-5-(1-pyrryl)pyrazole, prepared from 5-amino-4-ethoxycarbonyl-1-phenylpyrazole by Clauson-Kaas method, afforded 4-ethoxycarbonyl-5-(2-formyl-1-pyrryl)-1-phenylpyrazole, which was then reduced to 4-hydroxymethyl-5-(2-hydroxymethyl-1-pyrryl)-1-phenylpyrazole. Treatment of the diol with phosphorus pentoxide led to 1-phenyl-1H,4H,6H-pyrazolo[3,4-e]pyrrolo[2,1-c][1,4]oxazepine. 4-Methyl and 4-phenyl derivatives of the latter compound were also prepared.
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■ TiCl4-Induced Functionalisation of Dibenzo[b,f][1,4]diazocine-6,11-(5H,12H)-diones
Bindumadhavan Venugopalan,* Sivasailam Suresh Iyer, and Noel John de Souza
*Department of Chemistry, Research Centre, Hoechst India Limited, Mulund, Bombay 400 080, India
Abstract
Dibenzo[b,f][1,4]diazocine-6,11-diones (1) were converted to the corresponding 6,11-disubstituted amino derivatives (3) when treated with secondary amines in the presence of titanium tetrachlorideanisole complex. Formation of the (benzimidazol-2-yl)benzamides (4) as the side products was observed in the case of substituted 1.
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■ The Behaviour of Vicinal Alkyl Aminothiophenecarboxylates in the Sandmeyer and Schiemann Reactions
Carlos Corral,* Ana Lasso, Jaime Lissaveyzky, Alberto Sánchz Alvarez-Insúa, and Ana M. Valdeolmillos
*Instituto de Química Médica, C. S. I. C., Calle Juan de Cierva, 3, 28006 Madrid, Spain
Abstract
The diazotization of vicinal alkyl aminothiophenecarboxylates has been studied. 3-Amino compounds gave clear diazonium salts which yielded the expected halo derivatives in the Sandmeyer and Schiemann conditions. However, 2-amino compounds yielded self-coupling products.
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■ Phosphorus Pentoxide in Organic Synthesis - Part 23. Synthesis of 1,2,3,4-tetrahydro-9-acridinamines
Peter Finlander, Hans Peter Fischer, and Erik Bjerregaard Pedersen*
*Department of Chemistry, Odense University, Campusvej 55 DK-5230 Odense M., Denmark
Abstract
1,2,3,4-Tetrahydro-9(10H)-acridinone 2 was synthesized from methyl anthranilate and cyclohexanone using a mixture of P2O5 and N,N-dimethylcyclohexylamine as a condensing reagent. 1,2,3,4-Tetrahydro-9-acridinamines 3 were prepared, either directly from 2, using the new phosphoric amide reagents, or via the corresponding 9-chloro derivative 7 by reaction with amines.
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■ Oxodation Studies of Beta-lactam Antibiotics. The 6(7)-Iminoethers of Penicillins and Cephalosporins
Ronald G. Micetich* and Rajeshwar Singh
*Faculty of Pharmacy and Pharmaceutical Sciences, University of Alberta, Edmonton, Alberta, T6G 2G2, Canada
Abstract
The oxidation of the 6-iminoethers of penicillins using m-CPBA gave the 1β-sulfoxide of the respective 6-iminoerher; whereas with H2O2-CH3CO2H, the 6-iminoetherpenicillins and 7-iminoethercephalosparins gave the respective 1β-sulfoxides of the 6(7)-amido compounds
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■ Synthesis of the Alkaloids and Laurifonine Using a Chloroformate-madiated Ring Expansion
John B. Bremner* and Charles Dragar
*Department of Chemistry, University of Tasmania, GPO Box 252C Hobart, Tasmania, 7001, Australia
Abstract
A convenient synthesis of the reduced dibenz[d,f]azonine ring system is described affording laurifonine in 29% overall yield from homoveratrylamine. The alkaloid laurifine is also accessible in 15% overall yield (as the oxalate salt) by the same route, which employs a methyl chloroformate-induced ring expansion of an erythrinan-3-one derivative.
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■ Termolysis of 4-Azidopyrimidines and 4-Azidoquinazolines
Lorenzo Giammanco* and Francesco Paolo Invidiata
*Instituto di Chimica Farmaceutica e Tossicologica, Università digli Studi di Palermo, Via Archirafi 32, 90123 Palermo, Italy
Abstract
A facile thermolysis of 4-azidopyrimidines and 4-azidoquinazolines leading, by ring contraction, in excellent yields to 1-cyanoimidazoles and benzimidazoles is reported.
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■ New Difunctionalaized 4-Nitroisoxazoles from α-Nitroacetophenone Oxime
Rodolfo Nesi,* Stefano Chimichi, Piero Sarti-Fantoni, Annalisa Buzzi, and Donatella Giomi
*CNR, Centro di Studio Sulla Chimica e la Struttura dei Composti Eterociclici e lolo Applicazioni, c/o Dipartimento di Chimica Organica "Ugo Schiff", Università di Firenze, Via Gino Capponi 9, I-50121 Firenze, Italy
Abstract
The title compound (1) reacted smoothly with the acyl chlorides (2a-d) to give the derivatives (3a-d) which were converted in high yields into the nitroisoxazoles (4a-d), respectively, through a base-induced cyclization.
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■ Thienopyrrolizidines II. Synthesis of 4-Imino (and 4-amino)-4H-thieno[2,3-b]pyrrolizines
Catherine Laporte-Wojcik, Anne-Marie Godard, Sylvain Rault, and Max Robba*
*Laboratoire de Chimie Thérapeutique, U. F. R. des Sciences Pharmaceutiques, Université de Caen, 1, rue Vaubénard, 14032 Caen Cedex, France
Abstract
Vilsmeier’s thienopyrroliziniminium salts were treated with primary amines to give N-substitued thienopyrrolizinimines. Reduction of these imines gave the corresponding amino derivatives.
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■ A Novel Synthesis of 1,6-Dihydro-2-methyl-6-oxo[3,4’-bipyridine]-5-carbonitrile (Milrinone)
Baldev Singh*
*Sterling Research Group, Rensselaer, New York 12144, U.S.A.
Abstract
Milrinone (3) was prepared either by reacting ethoxymethylenemalononitrile with 1-(4-pyridinyl)-2-propanone or malononitrile with 4-ethoxy-3-(4-pyridinyl)-3-buten-2-one.
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■ Synthesis of Phenolic Metanolites of an Antifugal Imidazole Derivatives (Cloconazole Hydrochloride)
Kimio Takahashi, Sumio Shimizu, and Masaru Ogata*
*Shionogi Research Laboratories, Shionogi & Co. Ltd., Fukushima-ku, Osaka 553-0002, Japan
Abstract
Syntheses of phenolic metabolites of antifungal vinylimidazole derivative 6·HCl (Cloconazole hydrochloride) are described. Phenolic compound 8 was prepared from 2 using selective mono THP protection, followed by imidazolation and deprotection. 10 was synthesized from 12 and spontaneously decomposed to 4 and 19 in acidic methanol. Synthesis of 11 started from 20 via nucleophilic aromatic substitution to introduce an oxygen function at the m-position of the chlorine substituent.
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■ Organogermanium Compounds. New Simplified Synthesis of Germatranes Substituted with Novel Functional Groups
Norihiro Kakimoto,* Katsuyuki Sato, Toyozo Takada, and Mitsuo Akiba
*Asai Germanium Research Institute, 1-6-4, Izumihon-cho, Komae-shi Tokyo 201, Japan
Abstract
New general methods for the synthesis of 5-substituted germatranes (4) have been directly developed using the corresponding germyl adducts (2) obtained by germylation of α,β-unsaturated compounds (1) with trichlorogermane.
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■ Synthesis of (5-Styryl-2-thienyl)-phenylacrylic Acids
Grace Karminski-Zamola* and Miro Bajic
*Organic Chemistry Department, Faculty of Technology, University of Zagreb, Marulicev trg 20, 41000 Zagreb, Croatia
Abstract
We describe the synthesis of E-3-(5-styryl-2-thienyl)-2-phenylacrylic acid 7, E-3-(5-styryl-2-thienyl)-2-(4-methoxyphenyl)acrylic acid 8, E-3-[5-(4-methoxyphenylethenyl)-2-thienyl]-2-phenylacrylic acid 9 and E-3-[5-(4-methoxyphenylethenyl)-2-thienyl]-2-(4-methoxyphenyl)acrylic acid 10 by Oglialoro condesation.
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■ A 400 MHz 1H NMR Study of Twelve Ajmaline-type Alkaloids
Mauri Lounasmaa* and Reija Jokela
*Laboratory of Organic Chemistry, Helsinki University of Technology, P.O. Box 6100,FIN-02015 HUT, Espoo, Finland
Abstract
The chemical shifts and most of the main coupling constants of twelve ajmaline alkaloids 1 - 12 determined in a 400MHz 1H NMR study.
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■ Mono- and Di-substituted 3-Aza-α-tropolones
Yoshie Horiguchi, Takehiro Sano,* and Yoshisuke Tsuda
*Showa Pharmaceutical University, 3-3165, Higashi-tamagawagakuen, Machida, Tokyo 194-8543, Japan
Abstract
New mono- and di-substituted 3-aza-α-tropolones 6 were synthesized by deethoxycarbonylation and subsequent DDQ oxidation of dihydroazatropolones 4. In methanol, 6 undergoes a skeletal rearrangement to give methyl pyridine-2-carboxylates 7, suggesting that the reaction is characteristic of the azatropolone nucleus.
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■ The Chemistry of N-Substituted Pyridinium Salts
Wanda Sliwa,* Grazyna Matusiak, and Anna Postawka
*Institute of Chemistry, Pedagogical University, 25-020 Kielce, Poland
Abstract
Syntheses, physicochemical and biological properties of N-substituted pyridinium salts, as well as their applications are described.