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. 63, No. 10, 2004
Published online: 17th August, 2004
■ Novel 3-Aminothieno[2,3-b]pyridine Synthesis via a Silicon-directed Anionic Cyclization
Jason S. Parnes* and Mercedes Delgado
*Department of Medicinal Chemistry, Signal Pharmaceuticals, LLC, 4550 Towne Center Ct., San Diego, CA 92121, U.S.A.
Abstract
A novel strategy yielding a 3-aminothiophene is described herein. This specifically relies upon an α-thiomethylsilane directing deprotonation, thereafter cyclization of the resultant anion into a pendant nitrile forms the necessary 3-aminothiophene ring.
Published online: 20th August, 2004
■ Alkatrienyl Sulfoxides and Sulfones. Part. VI. Cheletropic Addition of Sulfur Dioxide to 1- and 3-Vinylallenyl Sulfoxides and Sulfones
Valerij Ch. Christov* and Ivaylo K. Ivanov
*Department of Chemistry, University of Shumen, BG-9700 Shumen, Bulgaria
Abstract
The reaction of 1- and 3-vinylallenyl sulfoxides and sulfones with sulfur dioxide in 1,2-dichloroethane at reflux proceeds as a cheletropic addition leading to the formation of 2-isopropylidene-3-sulfinyl(sulfonyl)- or 2-sulfinyl- (sulfonyl)methylidene-substituted 2,5-dihydrothiophene 1,1-dioxides in very good yields.
Published online: 17th August, 2004
■ Synthesis and Properties of Pyrazino[2,3-g]quinoxaline Derivatives: Blue and Green Fluorescent Materials with Electron Affinity
Katsuhiko Ono,* Yutaka Okazaki, Masakazu Ohkita, Katsuhiro Saito,* and Yoshiro Yamashita
*Department of Life and Material Engineering, Nagoya Institute of Technology, Gokiso, Showa, Nagoya 466-8555, Japan
Abstract
The title compounds have been synthesized and their optical and electronic properties were surveyed in comparison to those of [1,2,5]thiadiazolo[3,4-g]quinoxaline and benzo[1,2-c:4,5-c’]bis([1,2,5]thiadiazole) derivatives. They are blue or green fluorophores with electron affinity due to the fused pyrazine rings. Substitution of the fused pyrazine ring for the fused 1,2,5-thiadiazole one led to red shifts of ca. 50 nm in the fluorescence spectra. The substitution also resulted in an increase of electron affinity in the 14π-electron systems. Using a series of these compounds, red-green-blue (RGB) fluorescent emission was achieved.
Published online: 23rd August, 2004
■ Absolute Stereostructures of Acylated Khellactone-Type Coumarins from Angelica furcijuga
Toshio Morikawa, Hisashi Matsuda, Teruki Ohgushi, Norihisa Nishida, Tomoko Ishiwada, and Masayuki Yoshikawa
*Kyoto Pharmaceutical University, Misasagi, Yamashina-ku, Kyoto 607-8412, Japan
Abstract
Two new acylated khellactone-type coumarin hyuganoside I (1) and hyuganin F (2) were isolated from the leaves of Angelica furcijuga. Their absolute stereostructures were determined on the basis of chemical and physicochemical evidence. Furthermore, the absolute stereostructures of the acyl moieties in hyuganins A (3) and C (4) and isoepoxypteryxin (5) were elucidated.
Published online: 7th September, 2004
■ 1,3-Dipolar Cycloaddition Reactions to Galanthamine Nitrone: An Entry to 4a,5,9,10-Tetrahydro-6H,14aH-benzofuro[3a,3,2-ef]isoxazolo[3,2-a][2]benzazepines
Margit Hemetsberger, Matthias Treu, Christian Hametner, Ulrich Jordis, Kurt Mereiter, and Johannes Fröhlich*
*Institute of Applied Synthetic Chemistry, Vienna University of Technology, Getreidemarkt 9, A-1060 Vienna, Austria
Abstract
Starting with galanthamine nitrone as the 1,3-dipole derivatives of the novel 4a,5,9,10-tetrahydro-6H,14aH-benzofuro[3a,3,2-ef]isoxazolo[3,2-a][2]benzaz-epi-ne ring system have been prepared by cycloaddition.
Published online: 17th August, 2004
■ Three Component Synthesis of Some γ-Spiroiminolactones under Microwave-assisted Solvent-free Conditions
Javad Azizian,* Ali R. Karimi, Ali A. Mohammadi, and Mohammad R. Mohammadizadeh
*Department of Chemistry, Faculty of Science, Shahid Beheshti University, P. O. Box 19395-4716, Tehran, Iran
Abstract
Series of some γ-spiroiminolactone derivatives were synthesized through microwave-assisted, three component reaction of isocyanides, dialkyl acetylenedicarboxylates and indenoquinoxalin-11-ones in DMF or in a solvent-less operation on solid support montmorillonite K10.
Published online: 20th August, 2004
■ Kinetics of the Thermal Decomposition of Substituted Cyclic Organic Peroxides in Toluene Solution: Substituent Effects on the Reaction Rates and the Activation Parameters of the Unimolecular Reactions
Adriana I. Cañizo,* Gladys N. Eyler, Carmen M. Mateo, Elida E. Alvarez, and Rosa K. Nesprías
*Department of Chemistry Engineering, Engineering Faculty, National University of the Center of Buenos Aires Province, del Valle Avenue N° 5737 (B7400JWI) Olavarria, Buenos Aires, Argentine
Abstract
Thermal decomposition reactions of substituted cyclic organic di- and triperoxides have been carried out in toluene solution in order to investigate substituent effects on homolytic scission of the O-O bond in those compounds. A comparative analysis of the reactivities at 145 °C and the activation parameters for unimolecular reactions of molecules of this type were interpreted in terms of substituent effects and ring size. An isokinetic relationship was established to validate the existence of a genuine substituent effect for the unimolecular homolysis reaction of the substances considered. Cyclic organic peroxides of very high reactivity and sterically hindered deviated from correlation’s. It appears to be possible to determine whether a peroxy group is part of a six or nine membered ring on the basis of the activation parameters values.
Published online: 7th September, 2004
■ Synthesis, Oxidation and Dehydrogenation of Cyclic N,O- and N,S-Acetals. Part 1. Transformation of N,S-Acetals: 3-Acyl-1,3,4-thiadiazolines
László Somogyi
*Department of Organic Chemistry, University of Debrecen, P.O.Box 20, H-4010 Debrecen, Hungary
Abstract
Aldehyde and ketone thiosemicarbazones are synthesized and cyclized into 3-acyl-1,3,4-thiadiazolines under acylating conditions. Reactions of the 2-monosubstituted heterocycles with oxidizing and dehydrogenating agents (KMnO4 or for the first time with CAN, DDQ, IBDA) lead to the formation of thiadiazoles. CAN oxidation of 2,2-disubstituted 3-acyl-1,3,4-thiadiazolines regenerates the parent ketones efficiently.
Published online: 27th August, 2004
■ 2-(1,3,5-Dithiazinan-5-yl)ethanol Heterocycles, Structure and Reactivity
Juan Carlos Gálvez-Ruiz, Javier C. Jean-Gaspar, Indira G. Castellanos-Arzola, Rosalinda Contreras, and Angelina Flores-Parra*
*Chemistry Department , Centro de Investigación y de Estudios Avanzados del I.P.N., A.P. 14-740, C.P. 07000 México, D.F., Mexico
Abstract
Treatment of 2-(1,3,5-dithiazinan-5-yl)ethanol (1), 2-(1,3,5-dithiazinan-5-yl)-1-phenylethanol (2), 2-(1,3,5-dithiazinan-5-yl)-1-methylethanol (3) and 2-(1,3,5-dithiazinan-5-yl)-2-methyl-1-phenylethanol (4) with TsCl and NEt3 in CH2Cl2 afforded the corresponding 3-tosyl-1,3-oxazolidine derivatives (5-8), whereas tosylation of 1-4 in the presence of NHMe3Cl gave the corresponding O-tosyl-2-(1,3,5-dithiazinan-5-yl)ethanol derivatives (11-14). The direct preparation of 5 and 7 from formaldehyde and N-tosylethanolamine (9) or N-tosyl-2-propanolamine was not successful. Reactions of 1 or 3 with benzylamine furnish 1,3,5-tribenzyl-1,3,5-triazinane. Heating of 1 and 2 affords the corresponding 1,3,5-tri(2-hydroxyethyl)-1,3,5-triazinanes. X-Ray diffraction studies of compounds (1-9 and 11) are reported.
Published online: 20th August, 2004
■ New Preparative Route to Hetaryldienes and Azadienes
Ildikó Nagy, György Hajós,* and Zsuzsanna Riedl
*Chemical Research Center, Hungarian Academy of Sciences, H-1525 Budpest, P.O. Box 17, Hungary
Abstract
Tetrazolylacroleins easily available via a four step pathway from 2-aminopyridines proved to be suitable starting compounds for preparation of new tetrazolyldiene systems. Reaction with reagents containing active methylene group gave a series of new dienes, whereas hydroxylamines yielded nitrones. The new dienes underwent cyclizations with electron withdrawn dienophiles to yield tetrazolyl substituted new polycycles, and the nitrones gave fused isoxazolines. The electron demand of the tetrazolyldienes in cycloadditions was interpreted by calculation of frontier orbital energy levels.
Published online: 23rd August, 2004
■ An Efficient Synthesis of Benzene Fused Six-, Seven- and Eight-membered Rings Containing Nitrogen and Sulfur by Benzyne Ring Closure Reaction
Chandrani Mukherjee and Ed Biehl*
*Department of Chemistry, Southern Methodist University, Dallas, TX 75275, U.S.A.
Abstract
3,4-Dihydro-2-H-benzo[1,4]thiazines (3a—c), 2,3,4,5-tetrahydro[b]-[1,4]thiazapines (3d—f) and 2,3,4,5-tetrahydro-2H-benzo[b][1,4]thiazocines (3g—i) were prepared by the cyclization of the respective 2-bromophenylsulfanyl derivatives of ethylamine (1a—c), propylamine (2d—f) and butylamine (2g—i).
Published online: 7th September, 2004
■ A New Synthesis of Thiazole Derivatives via Ring Transformation of 6-Imino-6H-1,3-thiazine Hydroperchlorates
Detlef Briel
*Institut für Pharmazie, Pharmazeutische Chemie, der Universität Leipzig, Brüderstr. 34, D-04103 Leipzig, Germany
Abstract
2-Arylthiazoles (8) with a cyanoacetate moiety in position 4 were synthesized by a new ring transformation reaction. Therefore 2-aryl-6-imino-6H-1,3-thiazinecarboxylic ester hydroperchlorates (3) were converted into 2-arylthiazoles (8) by reaction with acceptor substituted halomethanes (e.g. chloroacetonitrile, chloroacetic acid ester or phenacyl bromide). Using 2-(2-hydroxyphenyl)-6H-1,3-thiazinecarboxylicacid ester hydroperchlorate (3c) as the starting compound the benzoxazine (11a) was obtained. Starting from 2-(4-chlorophenyl)-6H-1,3-thiazinecarboxylicacid ester hydroperchlorate (3b) the thiazolo[5,4-c]pyridine (9e) was the final product.
Published online: 23rd August, 2004
■ Synthesis of 1-Methyl-3-methylthio- and 1-Methyl-3-methylsulfinyl-4-substituted 2-(1H)-Quinolinones
Elwira Chrobak and Andrzej Maslankiewicz*
*Department of Organic Chemistry, The Medical University of Silesia, Jagiellonska 4, 41-200 Sosnowiec, Poland
Abstract
Treatment of 4-substituted (X=Cl, OCH3, SCH3) quinolinium salts (2) in aqueous-DMSO solution with K3[Fe(CN)6] / NaOH system led to the respective 2-quinolinones (3) (60-69 %) which were accompanied by 1-methyl-
3-methylthio-4-quinolinone (8) (ca. 20%). 3-Methylthio substituent in quinolines (1), 4-quinolinethione (5) and 2-quinolinones (3) underwent S-oxidation to a sulfinyl group when the compounds (1), (3) and (5) were treated with nitrating mixture (-5 °C, 1 mol. eqv. of HNO3), but with an excess of nitric acid 2-quinolinones (3) were transformed to the respective 3-methylsulfinyl-6-nitro derivatives (7). The reaction of 4-chloroquinolines (1a), (3a) (at 140-160 °C) and (4a) (at 0 °C) with dimethylamine gave high yield of the 4-dimethylamino derivatives (1d), (3d) and (4d), respectively.
Published online: 31st August, 2004
■ Synthesis of 2-Chloro-8-(2-pyridyl)-1-azaazulene and Its Metal Complexes
Noritaka Abe,* Eri Hashimoto, Hiroyuki Fujii, Yoshiko Murakami, Shoji Tagashira, and Akikazu Kakehi
*Department of Chemistry, Faculty of Science, Yamaguchi University, Yamaguchi 753-8512, Japan
Abstract
Reaction of 2-chloro-1-azaazulenes with 2-pyridyllithium followed by dehydrogenation by chloranil gave 8-(2-pyridyl) -1-azaazulene (2). Formation of metal complexes (M = Cu, Fe, Pd) of 2 was achieved. The reaction of 2 with Cu(I) gave 1:1-complex (3) and 2:1-complex (4). Complex (3) was deduced to have a polymeric chain structure with the copper center is +1. The ESR spectrum study of 4 showed that the copper center is +2. The structure of 4 was decided by X-Ray structural analysis and it is shown that the complex takes a trigonal bi-pyramidal structure.
Published online: 27th August, 2004
■ Synthesis of (-)-Tuliparin B Utilizing 2-Bromo-1-alkenes Conveniently Synthesized from the 3-O-Substituted 1,2-Dibromoalkane System by Regioselective Elimination
Tadaaki Ohgiya and Shigeru Nishiyama*
*Department of Chemistry, Faculty of Science and Technology, Keio University, Hiyoshi 3-14-1, Kohoku-ku, Yokohama 223-8522, Japan
Abstract
Synthesis of (—)-tulipalin B with a variety of biological properties including cutaneous allergenic activity, was accomplished by using the 2-bromo-1-alkenes synthesized by the regioselective HBr elimination reaction of 3-acyloxy-1,2-dibromoalkanes.
Published online: 27th August, 2004
■ Synthesis of Cribrostatin 6
Shinsuke Nakahara* and Akinori Kubo
*Meiji Pharmaceutical University, 2-552-1, Noshio, Kiyose, Tokyo 204-8588, Japan
Abstract
The first synthesis of cribrostatin 6 (1), a dark blue cancer cell growth inhibiter was achieved in ten-steps from 2,4-diethoxy-3-methylphenol (8), utilizing a catalytic hydrogenation which induces an intramolecular transfer reaction.
Published online: 27th August, 2004
■ Two New C19-Diterpenoid Alkaloids from Aconitum nagarum var. lasiandrum
Hong Ji, Dong-Lin Chen, and Feng-Peng Wang*
*Department of Chemistry of Medicinal Natural Products, West China College of Pharmacy, Sichuan University, No. 17, Duan 3, Remin Nan Road, Chengdu 610041, China
Abstract
Further investigation on the phytochemistry of the plant Aconitum nagarum var. lasiandrum led to isolate two C19-diterpenoid alkaloids, francheline (1) and lasianine (3). Their structures were established on the basis of the spectral data.
Published online: 27th August, 2004
■ Effect of Sodium Naphthalenide, a Key Set Reagent, on 3-Substituted Indoles
Avijit Banerji*, Debasish Bandyopadhyay, and Bidyut Basak
*Centre of Advanced Studies on Natural Products, Department of Chemistry, Calcutta University, 92, A. P. C Road, Kolkata 700009, India
Abstract
Action of the single electron transfer (SET) reagent sodium naphthalenide on 3-substituted indoles revealed that indoles with electron-donating substituents do not respond whereas indoles with electron-withdrawing substituents easily react, yielding several products depending upon the substituent.
Published online: 17th August, 2004
■ Formation of Unnatural Cyclic Amino Acid Equivalent from the Simple Cyclic Hydrazine
Duk Keun An, Hye-Min Kim, Min Sung Kim, Seung Kyu Kang, Jae Du Ha, Sung Soo Kim, Joong-Kwon Choi, and Jin Hee Ahn*
*Medicinal Science Division, Korea Research Institute of Chemical Technology, Daejeon 305-600, Korea
Abstract
An alternative method for the synthesis of unnatural cyclic amino acid equivalent from the simple cyclic hydrazine via oxidation and cyanation was developed.
Published online: 20th August, 2004
■ Enantioselective Synthesis of (S)-3-(4-Thiazolyl)-2-tert-butoxycarbonylaminopropionic Acid: A Chiral Building Block for Renin Inhibitor
Yoshifumi Yuasa, Haruki Tsuruta, and Yoko Yuasa*
*School of Pharmacy, Tokyo University of Pharmacy and Life Science, 1432-1 Horinouchi, Hachioji, 192-0392, Tokyo, Japan
Abstract
(S)-3-(4-Thiazolyl)-2-tert-butoxycarbonylaminopropionic acid (6), an important structural constituent of the renin inhibitor, has been synthesized from (Z)-3-(4-thiazolyl)-2-benzoylaminoprop-2-enoic acid (4b) by enantioselective hydrogenation using the Ru-(S)-p-tolyl-BINAP complex as the key step, and then followed by acid hydrolysis and tert-butoxycarbonylation.
Published online: 30th July, 2004
■ Transition Metal Complexes in Organic Synthesis, Part 73. Synthetic Routes to Naturally Occurring Furocarbazoles
Wolfgang Fröhner, Micha P. Krahl, Kethiri R. Reddy, and Hans-Joachim Knölker*
*Institut of Organic Chemistry, Technical University Dresden, Bergstrasse 66, 01069 Dresden, Germany
Abstract
The isolation and the development of total syntheses of naturally occurring furocarbazole alkaloids are described. The diverse synthetic strategies which were elaborated by different research groups are discussed and compared.