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. 57, No. 10, 2002
Published online:
■ Bifunctionalized Allenes. Part V. 3-Sulfinyl-2,5-dihydro-1,2λ5-oxaphosphol-2-ones and 3-Phosphoryl-1,2λ4-oxathiol-2(5H)-ones from 1-Sulfinyl-substituted Phosphorylated Allenes
Valerij Ch. Christov* and Boris Prodanov
*Department of Chemistry, University of Shoumen, BG-9700 Shoumen, Bulgaria
Abstract
3-Sulfinyl-2,5-dihydro-1,2λ5-oxaphosphol-2-ones (3) and 3-phosphoryl-1,2λ4-oxathiol-2(5H)-ones (4) were synthesized in good yields via electrophile-induced cyclization reactions of 1-sulfinyl-substituted phosphorylated allenes (1) and (2). Bromination of dimethyl 1-sulfinyl-1,2-alkadiene-1-phosphonates (1) led to formation of 4-bromo-3-sulfinyl-2,5-dihydro-1,2λ5-oxaphosphol-2-ones (3), while the reaction with methyl 1-diphenylphosphoryl-1,2-alkadiene-1-sulfinates (2) afforded 4-bromo-3-diphenylphosphoryl-1,2λ4-oxathiol-2(5H)-ones (4).
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■ Palladium Catalyzed Double Substitution Reactions of Iodophenol and Iodoaniline Derivatives with Homo-conjugated Compounds to Form Cyclic Ether and Cyclic Amines through Homo-conjugated Interaction
Katsuhiro Saito,* Katsuhiko Ono, Makiko Sano, Shingo Kiso, and Toshihumi Takeda
*Department of Applied Chemistry, Nagoya Institute of Technology, Gokiso-cho, Showa-ku, Nagoya 466-8555, Japan
Abstract
Palladium(II) acetate catalyzed double substitution reaction of a bicyclo[2.2.2]octadiene derivative (1) with o-substituted iodobenzenes afforded six membered cyclic compounds (3b and 3c) via a homo-conjugation type interaction accompanied by a five-membered cyclic compound (4a). On the other hand, a similar type of reaction but using a bicyclo[2.2.1]heptadiene derivative (5) formed only the corresponding five-membered cyclic compound (6a).
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■ Two Novel 6-Hydroxyanthocyanins in the Flowers of Alstroemeria ‘Westland’
Fumi Tatsuzawa,* Norio Saito, Naho Murata, Koichi Shinoda, Atsushi Shigihara, and Toshio Honda
*Hokkaido Junior College, Takushoku University, Fukagawa, Hokkaido 074-8585, Japan
Abstract
Two novel 6-hydroxydelphinidin glycosides were isolated from the red-purple flowers of Alstroemeria ‘Westland’ along with ten known anthocyanins. These novel pigments were determined to be 6-hydroxydelphinidin 3-O-β-D-glucoside and 6-hydroxydelphinidin 3-O-[6-O-(malonyl)-β-D-glucoside] by spectral and chemical methods. The ten known pigments were also identified as cyanidin 3-glucoside, delphinidin 3-glucoside, 6-hydroxycyanidin 3-glucoside, cyanidin 3-rutinoside, delphinidin 3-rutinoside, 6-hydroxycyanidin 3-rutinoside, 6-hydroxydelphinidin 3-rutinoside, cyanidin 3-malonylglucoside, delphinidin 3-malonylglucoside, and 6-hydroxycyanidin 3-malonylglucoside, respectively.
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■ Syntheses of (4R, 5S)- and (4S, 5R)-Muricatacins, and (4S, 5R)-Aza-Muricatacin, Unnatural Analogues of the Annonaceous Acetogenin
Hiroyuki Konno,* Naoki Hiura, and Moegi Yanaru
*Department of Biological Science and Technology, Faculty of Engineering, University of Tokushima, Minamijosanjima-cho, Tokushima 770-0814, Japan
Abstract
(4R, 5S)- and (4S, 5R)-Muricatacins, and (4S, 5R)-aza-muricatacin, unnatural analogues of the Annonaceous acetogenin, were prepared from (-)-muricatacin via Mitsunobu inversion or Weinreb amidation as the key step.
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■ N-Arylation by Aryl Isocyanates as a General Reaction: Useful Route to Disubstituted S,N-Diarylisothioureas
Alan R. Katritzky,* Xiaohong Cai, Vladimir Y. Vvedensky, Boris V. Rogovoy, Behrouz Forood, and Normand Hebert
*Center for Heterocyclic Compounds, Department of Chemistry, University of Florida, Gainesville, FL 32611-7200, U.S.A.
Abstract
N-Arylation of guanidines, isoureas and isothioureas by aryl isocyanates is demonstrated to have generality. Novel N′-arylations of S-arylisothioureas (16) with aryl isocyanates provide a new general route to biologically active S,N′-diarylisothioureas (13). Formation of (13) is explained as [2+2] cycloaddition of isoureas (16) to isocyanates followed by elimination of HNCO.
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■ Stereoselective Synthesis of C-6 Substituted Pipecolic Acid Derivatives. Formal Synthesis of (+)-Indolizidine 167B and (+)-Indolizidine 209D
Sylvie Carbonnel and Yves Troin*
*Laboratoire de Chimie des Hétérocycles et des Glucides, EA 987, Ecole Nationale Supérieure de Chimie de Clermont-Ferrand, Université Blaise Pascal, BP187, 63174 Aubiére Cedex, France
Abstract
C-6 Substituted pipecolic acid derivatives were synthesized through two different pathways. The synthetic potential of each route was demonstrated by the formal synthesis of indolizidine Dendrobates alkaloids.
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■ Synthesis of Some Thiophene-fused Azepino[5,4,3-cd]indoles
Basem A. Moosa, Kayed A. Abu Safieh, and Mustafa M. El-Abadelah*
*Chemistry Department, Faculty of Science, University of Jordan, Amman 11942, Jordan
Abstract
Interaction of indolylzinc chloride with 2-chloro-3-nitrothiophene gave 3-(3-nitrothien-2-yl)indole (7) which was converted, via reduction followed by acylation, into 3-(3-acylaminothien-2-yl)indoles (9a-c). Cyclization of 9a-c induced by phosphorus oxy-chloride under Bischler-Napieralski reaction conditions, took place regioselectively at the indolic C-4 locus to furnish the respective thieno[2’,3’ : 6,7]azepino[5,4,3-cd]indoles (3a-c).
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■ Regioselective Preparation of Pterin 6-Triflate and Its Application to 6-Substituted Pterin Synthesis
Masato Kujime, Kazunari Kudoh, and Shizuaki Murata*
*Graduate School of Environmental Studies, Nagoya University, Chikusa, Nagoya, Aichi 464-8601, Japan
Abstract
4-Butoxypteridine 6-triflate is prepared selectively from 4-butoxypteridine 8-oxide by a reaction with trifluoromethanesulfonic anhydride, and the triflate group can be replaced by various nucleophiles with functional groups.
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■ About the Factors Which Govern the Ring-Opening of α-Lactams with Primary Amines: II. The Relative Basicity of the Amine
Victor Cesare,* Tony Taldone, and István Lengyel
*Department of Chemistry, St. John’s University, 8000 Utopia Parkway, Jamaica, New York 11439, U.S.A.
Abstract
The ring-opening reaction of four stable α-lactams, 1-(1-adamantyl)-3,3-di-methylaziridinone (1a), 3-(1-adamantyl)-1-triphenylmethyl-aziridinone (1d), 3-tert-butyl-1-triphenylmethylaziridinone (1e), and 1-(1-adamantyl)-3-tert-butylaziridinone (1g) with some substituted benzylamines and other selected primary amines is described. It emerges from the experimental results that the relative basicity of the amine is a decisive factor in determining regioselectivity in the ring-opening.
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■ 1H NMR Evidence of C–H---O, C–H---N and C–H---Cl Hydrogen Bonds in New Thiazole Derivatives
Francisco Sánchez-Viesca* and Martha Berros
*Faculty of Chemistry, Postgrade Division, National Autonomous University, University City, 04510, Mexico, D.F.
Abstract
A comparative study of the chemical shift differences observed in the 1H NMR spectra of a series of fifteen new polysubstituted 4-aryl- and 2,4-diaryl thiazoles permitted us to establish two groups of rotamers. Some present paramagnetic shifts due to intramolecular weak hydrogen bonding and this was confirmed by experiments “at infinite dilution”, single crystal X-Ray studies, NOESY and HMBC experiments.
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■ Improved Synthesis of N-Substituted 2,3-Pyridinedicarboximides with Microwave Irradiation
María M. Blanco, Gustavo J. Levin, Celia B. Schapira, and Isabel A. Perillo*
*Departamento de Química Orgánica, Facultad de Farmacia y Bioquímica, Universidad de Buenos Aires, Junín 956 (1113) Buenos Aires, Argentina
Abstract
The microwave-induced synthesis of N-substituted 2,3-pyridinedicarboximides (1) by means of two different approaches is presented. One involves direct N-alkylation of quinolinimide (2) (Method A) and the other, dehydrative condensation of quinolinic anhydride (4) and amines (Method B). Reactions resulted highly accelerated, with improved yields in relation to those obtained by conventional heating. The scope and limitations of each method and its variants are discussed.
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■ Fluorinated Heterocyclic Compounds. Synthesis of 5-Amino-, 5-N-Alkylamino-, and 5-N,N-Dialkylamino-3-perfluoroheptyl-1,2,4-oxadiazoles
Silvestre Buscemi,* Andrea Pace, Ivana Pibiri, and Nicolò Vivona
*Dipartimento di Chimica Organica, Università degli Studi di Palermo, Viale delle Scienze-Parco d’Orleans II, I-90128 Palermo, Italy
Abstract
The synthesis of 5-amino-, 5-N-alkylamino-, and 5-N,N-dialkylamino-3-perfluoroheptyl-1,2,4-oxadiazoles has been realized with very good yields by ammonolysis or aminolysis of the 3-perfluoroheptyl-5-trichloromethyl-1,2,4-oxadiazole with ammonia, primary or secondary aliphatic amine. Some comments on the absorption spectra of fluorinated aminooxadiazoles are reported.
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■ A Photochemical Route to Dibenzonaphthyrones
Yvette A. Jackson* and Karla-Sue C. Marriott
*Department of Chemistry, University of the West Indies, Mona, Kingston 7, Jamaica, West Indies
Abstract
Irradiation of 2-methyl 3-phenyl 5,6-dimethoxy-1-benzofuran-2,3-dicarboxylate (5) gave 2,3-dimethoxybenzopyrano[4,3-c]benzopyran-5,11-dione (1b).
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■ Prenylated Isoflavones from Derris scandens
Mayuree Chuankamnerdkarn,* Somyote Sutthivaiyakit, Nopporn Thasana, and Somchai Pisutjaroenpong
*Department of Chemistry, Faculty of Science, Ramkhamhaeng University, Bangkok 10240, Thailand
Abstract
3′-Formylalpinumisoflavone (1), and 2-(1-hydroxy-1-methylethyl)-3-hydroxy-2,3-dihydrofuranoalpinumisoflavone (2) were isolated from the stem of Derris scandens along with five known isoflavones. The two new compounds were characterised by extensive use of high resolution NMR spectroscopy. Senegalensin (3) was reported here for the first time in D. scandens.
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■ Synthesis of Dihydrothiophene Derivatives as Metabolites of Esonarimod
Toshiya Noguchi,* Akira Onodera, Kazuyuki Tomisawa, and Sadakazu Yokomori
*Process Chemistry Latoratory, Medicinal Research Laboratories, Taisho Pharmaceutical Co., Ltd., 1-403 Yoshino-Cho, Saitama-city, Saitama 330-8530, Japan
Abstract
Three compounds with a dihydrothiophene ring were synthesized as authentic samples to analyze human metabolites of Esonarimod, which has been developed as a new antirheumatic drug.
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■ A New Route to Benzo[b]xanthene-6,11,12-trione Derivatives Based on the Photoinduced o-Hydroxybenzoylation of 1,4-Naphthoquinone
Kazuhiro Kobayashi,* Akihiro Matsunaga, Masaaki Mano, Osamu Morikawa, and Hisatoshi Konishi
*Department of Materials Science, Faculty of Engineering, Tottori University, 4-101 Koyama-minami, Tottori 680-8552, Japan
Abstract
A two-step procedure for the synthesis of the title xanthenequinone derivatives is described. The procedure involves the photoinduced acylation of 1,4- naphthoquinone with 2-hydroxybenzaldehydes, followed by treatment with Ag2O.
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■ Synthesis of Heteromacrocycles Containing 2-Imino-5-mercapto-2,3-dihydro-1,3,4-thiadiazoles as a Subunit
Nam Sook Cho,* Jin Gap Oh, Hye Jeong Hwang, Jin-Guy Kim, and Il-hwan Suh
*Department of Chemistry, College of Natural Sciences, Chungnam National University, Taejon 305-764, Korea
Abstract
Macrocycles containing two 2-imino-5-mercapto-2,3-dihydro-1,3,4-thiadiazole subunits linked to the 3- and 5-positions of the heterocycle unit were prepared by regiospecific alkylation of 5-amino-2,3-dihydro-1,3,4-thiadizole-2-thione and 2-acetylamino-5-alkylthio-1,3,4-thiadizoles, respectively. The structures of the macrocycles were established from 1H and 13C NMR, IR, MS spectrometries and elemental analyses. Moreover, the structure of the macrocycle 1,5-[5,5’-(1,3-phenylenedimethylenedithio)bis(2,3-dihydro-2-acetylimino-1,3,4-thiadiazol-2-yl)]-3-oxapentane (4b) was supported by X-Ray crystallography.
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■ Synthesis of p-Phenylene-Vinylene-Thienylene Oligomers
Cuihua Xue and Fen-Tair Luo*
*Institutue of Chemistry, Academia Sinica, Academia Sinica, Nankang, Taipei,11529, Taiwan, R.O.C.
Abstract
The preparation of alkoxylated phenylene-vinylene-thienylene oligomers with and without cyano substituents at the olefin moieties and their spectroscopic measurements are presented. Both thiophene ring and cyano groups may induce red shift in their absorption spectra.