HETEROCYCLES
An International Journal for Reviews and Communications in Heterocyclic ChemistryWeb Edition ISSN: 1881-0942
Published online by The Japan Institute of Heterocyclic Chemistry
Special Issue
Tetsuji Kametani's Special Issues, Vol. 15, No. 2, 1981
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■ Synthesis of 2-Aminothiazolyl Analogs of Ergothioneine
Katsuhiro Konno,* Haruhisa Shirahama, and Takeshi Matsumoto
*Faculty of Science, Hokkaido University, Kita 10 Nishi 8, Kita-ku, Sapporo, Hokkaido 060-0810, Japan
Abstract
Two new thiazolyl betaines 1 and 2, isomers of ergothioneine, have been synthesized as model compounds of a novel betaine isolated from a toxic mushroom.
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■ Aminolysis of 3-Acylthiazolidine-2-thione:A Synthesis of Macrolactam Containing Aromatic Ring(s)
Yoshimitsu Nagao, Tadayo Miyasaka, Kaoru Seno, and Eiichi Fujita*
*Institute for Chemical Research, Kyoto University, Uji, Kyoto 611-0011, Japan
Abstract
An efficient method for synthesis of macrolactams 9~12 containing aromatic ring(s) is described. It is based upon aminolysis of thiazolidine-2-thione derivatives 4a-d with diamines, 5 and 7, spermine 6, and spermidine 8.
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■ An NMR Investigation of the Geometrical Isomerism in the Anions of Aromatic Amino Compounds
Nico I. Kos, Koos Breuker, Henk C. van der Plas,* and Beb van Veldhuizen
*Laboratory of Organic Chemistry, Agricultural University, De Dreijen 5, 6703 BC Wageningen, The Netherlands
Abstract
The nmr spectra of the anions of 2-, 6- and 8-aminopurines, 2- and 4-aminopyrimidines, 3- and 4-aminopyridazines, aminopyrazine, 2-aminopyridine, aniline and its p-methyl derivative in liquid ammonia containing potassium amide at low temperature show the presence of two geometrical isomers, due to restricted rotation of the deprotonated amino group. The occurrence of coalescence has been observed with aminopyrazine and p-methylaniline.
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■ A Novel Purine to 1-Deazapurine Transformation Reaction:Synthesis of 1-Deazaadenosine Derivatives
Hideo Inoue, Sachiyo Takada, Sumiyo Tanigawa, and Tohru Ueda*
*Faculty of Pharmaceutical Sciences, Hokkaido University, Kita 12 Nishi 6, Kita-ku, Sapporo, Hokkaido 060-0812, Japan
Abstract
Sulfur-methylation of 1-methyl-6-thioinosine followed by treatment with diethyl sodiomalonate gave 1-methyl-6-bis(ethoxycarbonyl)methylene-1,6-dihydro-9-β-D-ribofuranosylpurine (5). Compound 5 underwent the Dimroth type rearrangement in methanolic potassium hydroxide to afford a 1-deazapurine derivative (7), which, on heating in aqueous alkali furnished 7-methylamino-3-β-D-ribofuranosyl-3H-imidazo[4,5-b]pyridin-5(4H)-one (8).
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■ Synthesis of a [3,4-f]-Linked Pyrazoloquinazolinone
Frieder W. Lichtenthaler* and Eckehard Cuny
*Institut für Organische Chemie, Technische Hochschule Darmstadt, Petersenstrasse, 22 D-6100 Darmstadt, Germany
Abstract
A convenient synthesis is described for pyrazolo[3.4-f]quinazolin-9-one (4), an internally expanded benzolog of the biologically relevant pyrazolo[4,3-d]pyrimidines (2).
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■ Synthesis and Cycloaddition Reactions of 1,3-Diphenyl-2,8-dihydrobenzo[e,h]-8-thiaazulen-2-one(Thiaazulenocyclone) with Acetylenes, Olefins and Benzyne
Mikio Hori,* Tadashi Kataoka, Hiroshi Shimizu, and Mitsuhito Okitsu
*Gifu Pharmaceutical University, 6-1 Mitahora-higashi 5-chome, Gifu 502-8585, Japan
Abstract
Thiaazulenocyclone was synthesized and its reactions with dienophiles were investigated. Reactions with N-phenylmaleimide, acenaphthylene or norbornene formed the Diels-Alder adducts, but cycloadditions with other dienophiles yielded the decarbonylated products derived from [4+2] adducts.
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■ The Absolute Configuration of (—)-Crebanine
Kalaya Pharadai,* Bamrung Tantisewie, Somsak Ruchirawat, S. Fazal Hussain, and Maurice Shamma
*Department of Pharmacognosy, Chulalonghorn University, Bangkok 5, Thailand
Abstract
The aporphine (-)-crebanine, found in Stephania spp. (Menispermaceae), possesses the D(R) absolute configuration.
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■ Intermediates in the Reactions of Oxazoles with Singlet Oxygen
Harry H. Wasserman,* James E. Pickett, and Frederick S. Vinnick
*Department of Chemistry, Yale University, P.O. Box 6666, New Haven, Connecticut 06511, U.S.A.
Abstract
An intermediate peroxidic product in the photooxidation of an oxazole has been trapped by intramolecular nucleophilic attack of a carboxylate residue. Evidence is presented to support the view of the oxygenation as an initial 4+2 concerted addition of singlet oxygen yielding an endoperoxide.
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■ Photo-arylation. II. Photo-reaction of Halopyridines with Benzene
Masanao Terashim,* Kohichi Seki, Chihiro Yoshida, and Yuichi Kanaoka
*Faculty of Pharmaceutical Scicences, Higashinihonngakuen University, 1757 Kanazawa, Toubetu-cho, Ishikari-gun, Hokkaodo 061-0212, Japan
Abstract
Photolysis of halopyridines in benzene afforded corresponding phenylpyridines. The reactivities of halopyridines in the reactions increased in the order of Cl
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■ The BF3-Catalysed Reaction between 2-Methylfuran and Some α,β-Unsaturated Carbonyl Compounds.
J. ApSimon,* V. Seenu Srinivasan, M. R. L’Abbé, and R.Seguin
*Department of Chemistry, Carlton University, 1125 Colonel By Drive, Ottawa
Ont. KaS 5B6, Canada
Abstract
The reaction of 2-methylfuran with some αβ unsaturated compounds in the presence of BF3-etherate is described as well as studies of the cleavage of the furan ring of the products. Only 1,4-addition to the conjugated carbonyl system is observed even in the case of hindered species.
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■ Reaction of Quinoline N-Oxides with Barbituric Acid in the Presence of Acetic Anhydride
Mohammed M. Yousif, 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 (1) with barbituric acid in Ac2O (1.2 eq)-DMF afford resioselectively 2-substituted quinolines (3) or quinolinium ylides (4), depending upon the nature of 1 and the reaction conditions. The reactions of quinoline and lepidine N-oxides (1a, 1b) at room temperature give the N-ylides (4a, 4b), and those at 90° yield 2-substituted qunolines (3a, 3b). The directive effect of the reaction temperature is the very reverse in reactions of 4-methoxy- and 4-chloro-quinoline N-oxides (1c, 1d); nevertheless, the reactions in Ac2O at 90° afford 3c and 3d. While 3-cyanoquinoline N-oxide (1g) gives only 2-substituted product (3g), 4-morpholino-, 3-bromo- and 3-acetamido-quinoline N-oxides (1e, 1f, 1h) afford N-ylides (4e, 4f, 4h) independently of the reaction conditions.
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■ Syntheses of 3-Nitro-2-pyridinesulfenates
Rei Matsueda* and Emil Thomas Kaiser
*Department of Chemistry, The University of Chicago, 5735 South Ellis Avenue, Chicago, Illinois 60637, U.S.A.
Abstract
In the presence of tertiary amine under anhydrous conditions 3-nitro-2-pyridinesulfenyl (Npys) chloride reacts smoothly with hydroxy compounds, including various alcohols and hydroxy acids, to give the corresponding sulfenates.
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■ The Acid-catalyzed Oxido-reduction of Spiroketals. Evidence for Seteroelectronic Control in Hydride Transfer to Cyclic Oxenium lons
Pierre Deslongchamps,* Daryl D. Rowan, and Normand Pothier
*Department of Chemistry, University of Sherbrooke, Sherbrooke, Quebec, J1K 2R1, Canada
Abstract
Tricyclic spirokeral 1 undergoes an acid-catalyzed oxidation-reduction reaction which yields equatorial bicyclic ether aldehyde 5 specifically. Similarly, spiroketals 2, 3, and 4 gave equatorial bicyclic ether ketone 12. These results are interpreted by invoking an internal hydride transfer from an alcohol function to a cyclic oxenium ion which takes place with stereoelectronic control.
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■ A Novel Rearrangement of a 6-Ethoxycarbonyl-2,7,8-trioxoerythrinan to an Isoquinolino-α-pyridone Derivative
Yoshisuke Tsuda,* Yuki Sakai, and Takehiro Sano
*School of Pharmacy, Hokuriku University, 3-Ho, Kanagawa machi, Kanazawa 920-1181, Japan
Abstract
Acid catalysed cyclization of the dioxopyrroline derivative 1b smoothly gave the 2-oxoerthrinan derivative 2b after deacetalization of the intermediate 5. Further acid treatment of 2b gave the pentacyclic compound 7 which could rearrange into an isoquinolino-α-pyridone derivative 13 on additional treatment with anhyd. H3PO4 or PPA. Each compound, 5, 2b, 7, or 13, was isolable in a satisfactory yield by controlling the reaction condition.
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■ N-Alkylation of Azetidin-2-ones with Phase Transfer Catalysis
Yoshiro Hirai, Isao Kamide, and Takao Yamazaki*
*Faculty of Pharmaceutical Sciences, Toyama Medical and Pharmaceutical University, 2630 Sugitani, Toyama, Toyama 930-0194, Japan
Abstract
Various N-alkyl azetidin-2-ones were prepared by using 18-crown-6 catalysis involving pulverized KOH, azetidin-2-one derivatives, and alkyl halides in benzene in good yield.
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■ Photochemical Transformation of Unsaturated Sultones into Furans
Hideji Itokawa,* Toshio Tazaki, and Susumu Mihashi
*Tokyo College of Pharmacy, 1432-1 Horinouchi, Hachioji, Tokyo 192-0392, Japan
Abstract
Photolysis of unsaturated sultones I and IV afforded 2,4-dimethylfuran (III) and menthofuran (V), respectively.
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■ Synthesis of Vinca Alkaloids and Related Compounds XIV. A New Route to Cyclopropanecarboxylic Acid Derivatives
Cyörgy Kalaus, János Galambos, Mária Kajtár-Peredy, Lajos Radics, Lajos Szabó, and Casaba Szántay*
*Institute of Organic Chemistry, Technical University, 1521 Budapest, Hungary
Abstract
The reaction of α-halogen acrylic esters and α-halogen acrylic nitriles with some enamines gave rise unexpectedly to cyclopropane derivatives.
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■ A New One-pot Synthesis of 1-Arylmethyl-1,2,3,4-tetrahydroisoquinoline Derivatives from Isoquinolinium Salts
Takeo Iwakuma,* Koichiro Yamada, Nobuo Itoh, and Shigehiko Sugasawa
*Organic Chemistry Research Laboratory, Tanabe Seiyaku Co.Ltd., 2-2-50, Kawagishi, Toddda, Saitama 335-8505, Japan
Abstract
There has been described a new one-pot synthesis of 1-arylmethyl-1,2,3,4-tetrahydroisoquinoline derivatives by the Barbier reaction of the quaternary salt (4) with various arylmethyl halides followed by reduction with sodium monoacetoxyborohydride.
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■ Synthesis and Chemiluminescence of 2-(Indol-3-yl)-3-phenyldihydro-1,4-dioxin 2,3-Epidioxide, a Dioxetane Having Unsubstituted Indole Group Similar to the Intermediate Proposed in Cynpridina Bioluminescence
Hideshi Nakamura and Toshio Goto*
*Faculty of Agricultures, Nagoya University, Chikusa, Nagoya, Aichi 464-8601, Japan
Abstract
From 2-(indol-3-yl)-3-phenyl-1,4-dioxene was synthesized the title dioxetane, which gave strong chemiluminescence in aprotic solvents.
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■ Chemical Ionization Mass Spectrometry of Macrolide Antibiotics II. Platenomycin and Related Compounds
Makoto Suzuki,* Ken-ichi Harada, Naohito Takeda, and Akira Tatematsu
*Faculty of Pharmacy, Meijo University, 150 Yagoto, Tempaku-ku, Nagoya, Aichi 468-8503, Japan
Abstract
The chemical ionization (CI) mass spectra of four intact 16-membered ring macrolide antibiotics have been examined using i-C4H10 and NH3 as the reagent gases. All CI mass spectra show the abundant protonated molecular ions (MH+) and the aglycone and sugar derived ions arised from the cleavage of the glycosidic linkages. The fruitful information available from above ion species increases the capabilities of chemical ionization mass spectrometry (CIMS) in the structural characteriziation of this class of compounds.
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■ Cycloadditions of 1-Substituted cis- and trans-2,3-Diphenylaziridines via Azomethine Ylides
Rolf Huisgen,* Kiyoshi Matsumoto, and Carl Heinz Ross
*Institute of Organic Chemistry, University of Munich, Karlstrasse 23, D-80333, München, Germany
Abstract
1-Benzyl-cis- and -trans-2,3-diphenylaziridines combine at 110°C with olefinic dipolarophiles to produce pyrrolidine derivatives in high yields. Stereospecific conrotation for the ring opening of the aziridines to azomethine ylides was deduced from the structure of the cycloadducts. The rate constants of adduct formation with diethyl fumarate do not depend on the concentration of the dipolarophile. In contrast, ethyl cis- and trans-2,3-diphenylaziridine-1-corboxylate produce with dimethyl fumarate at 145°C the same mixture of diastereomeric pyrrolidines both of which are derived from the exo,endo- diphenyl substituted azomethine ylide.
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■ Calafatimine, a New Imino Bisbenzylisoquinoline Alkaloid
Victor Fajardo,* Margarita Garrido, and Bruce K. Cassels
*Petróleo y Petroquímica, Departmento de Química, Universidad Técnica del Estado, Punta Arenas, Chile
Abstract
A new bisbenzylisoquinoline alkaloid from Berberis buxifolia was chemically correlated with calafatine. On this basis, and using spectrometric evidence, structure 1 is proposed for calafatimine. The stereochemistry of calafatine is discussed using its specific rotation and that of calafatimine.
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■ Biosynthesis of Cycloheximide,Stereospecific Incorporation of [1,2,3-13C3]Malonate
Hisao Shimada, Hiroshi Noguchi, Yoichi Iitaka, and Ushio Sankawa*
*Faculty of Pharmaceutical Sciences, University of Tokyo, Hongo, Bunkyo-ku, Tokyo 113, Japan
Abstract
The stereochemical course of the incorporation of an intact malonate unit into the glutarimide ring of cycloheximide was investigated by using [1,2,3-13C3] malonate as a precursor. The labelled patterns of enriched cycloheximide and its derivatives revealed that the incorporation of an intact malonate unit was completely stereospecific. The pro-S acetate unit and methine carbons(C-4,5,6) of cycloheximide were shown to be labelled by intact [1,2,3-13C3] malonate.
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■ C-13 Spin-Lattice Relaxation Times of Quercetin and Rutin
Yoshito Takeuchi*
*Department of Chemistry, The College of Arts & Sciences, The University of Tokyo, Komaba, Meguro-ku, Tokyo 153, Japan
Abstract
C-13 Spin-lattice relaxation times(T1) of quercetin and rutin were determined. The assignment of C-13 signals based on T1’s removed any ambiguity left in the previous assignments based on a combination of chemical shift correlation and carbon-proton spin-spin coupling.
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■ Design and Syntheses of Paracyclophanes Having Charged Side Chains That Are Soluble in Neutral Aqueous Solution
Kazunori Odashima and Kenji Koga*
*Faculty of Pharmaceutical Sciences, University of Tokyo, Hongo, Bunkyo-ku, Tokyo 113, Japan
Abstract
A series of water-soluble paracyclophanes having charged side chains (2a,b,3a,b) were synthesized, and their complexation properties toward organic guest molecules in neutral aqueous solution were examined.
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■ Bond Switch with Participation of π -Bonded SIV from Isothiazole to Thiadiazole Ring System
Kin-ya Akiba,* Akiko Noda, Katsuo Ohkata, Takahiko Akiyama, Yutaka Murata, and Yohsuke Yamamoto
*Department of Chemistry, Faculty of Science, Hiroshima University, 1-3-1 Kagamiyama, Higashi-Hiroshima, Hiroshima 739-8526, Japan
Abstract
5-Amino-3-methylisothiazole (3) gave 1: 1 adduct with aromatic nitriles and ethyl acetimidate and the structure of the adduct was shown to be 3-substituted 5-(2-amino-2-methylvinyl)-1, 2, 4-thiadiazole (2), where ring transformation took place from isothiazole to 1, 2, 4-thiadiazole.
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■ Selective Reduction of the Carbonyl Group of Chromone and Thiochromone to the Methylene Group
Hiroshi Yamaoka, Tatsushi Hakucho, and Kin-ya Akiba*
*Department of Chemistry, Faculty of Science, Hiroshima University, 1-3-1 Kagamiyama, Higashi-Hiroshima, Hiroshima 739-8526, Japan
Abstract
2-Methyl and 2,3-dimethylthiochromones were reduced selectively to the corresponding thiochromenes with NaBH4 in the presence of CeCl3-7H2O in methanol in good yields. 2,3-Dimethylchromone was reduced to the corresponding chromene with sodium bis(2-methoxyethoxy)aluminum hydride in benzene in a moderate yield.
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■ Antimicrobial Agents from an East African Medicinal Plant Erythrina abyssinica
Vinayak S. Kamat , Frances Y. Chuo, Isao Kubo,* and Koji Nakanishi*
*Department of Chemistry, Columbia University, 3000 Broadway, Mail Code 3114, New York, New York 10027, U.S.A.
Abstract
Two pterocarpans, five flavanones and a chalcone, all new natural products have been isolated from an East African folk medicinal plant. They exhibit antimicrobial activity or inhibition of platelet aggregation.
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■ Synthesis of Three Stereoisomeric Forms of 2,8-Dimethyl-1,7-dioxaspiro[5.5]undecane, the Main Component of the Cephalic Secretion of Andrena wilkella
Kenji Mori* and Kaichi Tanida
*Faculty of Science, cience University of Tokyo, 2641 Yamazaki, Noda, Chiba 278-8510, Japan
Abstract
Three stereoisomers of 2,8-dimethyl-1,7-dioxaspiro[5.5]undecane with defined stereochemistry at C-2 and C-8 were synthesized utilizing yeast reduction and dianion alkylation of ethyl acetoacetate.
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■ The Synthesis of Condensed Quinolizinium Systems
Alan R. Katritzky,* Kevin Burgess, and Ranjan C. Patel
*Center for Heterocyclic Compounds, Department of Chemistry, University of Florida, P. O. Box 117200, Gainesville, FL 32611-7200, U.S.A.
Abstract
Dimethyl β-aminoethylacetal reacts with pyryliums (1-3a) to yield pyridiniums (1-3b) which are cyclised to fused benzoquinoliziniums (4-6).