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. 29, No. 1, 1989
Published online:
■ Reaction of Glycosylisothiocyanates with 2-Chloroethylamine
M. Avalos Gonzárez, R. Babiano Caballero, P. Cintas Moreno, J. Fuentes Mota, J. L. Jiménez Requejo, and J. C. Palacios Albarrán*
*Department of Organic Chemistry, Facultad de Veterinard, University of Extremadura, 06071-Badajoz, Spain
Abstract
The products formed in the reaction of per-O-acyl-glycosylisothiocyanatea withÅ@ω-haloalkylamines are shown to be glycosylamino- and N,N’-bis-glycosyl-heterocycles.
Published online:
■ Ring Conversion of 2-Amino-4,5-dihydro-3-furancarbonitriles Catalyzed by Halide Ions
Kenji Yamagata, Hiroshi Maruoka, Yoshichika Hashimoto, and Motoyoshi Yamazaki*
*Faculty of Pharmaceutical Sciences, Fukuoka University, 8-19-1 Nanakuma, Jonan-ku, Fukuoka 814-0180, Japan
Abstract
The reaction of 2-amino-4,5-dihydro-3-furancarbonitrile (1a) with methylamine hydrochloride in dimethylformamide gave 1-cyano-N-methylcyclopropanecarboxamide (2). Similarly. 2-amino-4,5-dihydro-4-phenyl(and 5-phenyl)-3-furancarbonitriles [(1b) and (1c)] provided (E)-1-cyano-N-methyl-2-phenylcyclopropanecarboxamide (3). Compound 1b reacted with sodium iodide to give (E)-1-cyano-2-phenylcyclopropanecarboxamide (6). On the other hand, 2-benzamido-4,5-dihydro-3-furancarbonitrile (7a) reacted with sodium iodide to furnish 1-benzoyl-2-oxo-3-pyrrolidinecarbonitrile (8).
Published online:
■ Regioselectivity in the Diels-Alder Reactions of 2-Vinylindoles and Pyrano[3,4-b]indol-3-ones with CC-Dienophiles
Ulf Pindur,* Manfred Eitel, and Erfanian Abdoust-Houshang
*Department of Chemistry and Pharmacy, Institute of Pharmacy, University of Mainz, Saarstrasse 21, D-55122 Mainz, Germany
Abstract
Diels-Alder reactions of 2-vinylindoles 1 and methylated pyrano[5,4-b]indol-3-ones 6 with acceptor-substituted CC-dienophiles (e.g.propynoates, ethyl phenylpropynoate, acrylonitrile, α-chlnroacrylonitrile, methyl acrylate, 1-penten-3-one) proceed with poor to high regioselectivities to furnish functionalized carbazole derivatives. MNDO calculations have been carried out for the 2-vinylindole and pyrano[3,4-b] indol-3-one parent compounds and, in most cases, qualitative FMO analyses correctly predict the major products. The regiochemistries of the products from the reactions of the pyrano[3,4-b]indol-3-ones 6 with ethyl phenylpropynoate can be predicted by the simple charge controlled orientation in the transition states.
Published online:
■ Formation of Novel 1:3 Adduct in the High Pressure Reaction of 2(1H)-Pyridones with Dimethyl Acetylenedicarboxylate: An X-Ray Crystal Structure Determination
Kiyoshi Matsumoto,* Kensaku Hamada, Takane Uchida, and Hiroshi Yoshida
*College of Liberal Arts and Science, Kyoto University, Yoshida, Sakyou-ku, Kyoto 606-8501, Japan
Abstract
The structure of the 1:3 adduct from 1-(5’,5’-dimethylcyclohex-2’-en-1’-on-3’-yl)-2(1H)-pyridone and dimethyl acetylenedicarboxylate was determined, possible mechanism for the reaction being presented.
Published online:
■ Synthesis of 2’,3’-Dideoxy-3’-methylidenethymidine and 2’,3’-Didehydro-2’,3’-dideoxy-3’-methylthymidine: Deoxygenation of the Allylic Alchol System in 3’-Deoxy-3’-methyodene-5-methyluridine
Akira Matsuda,* Hitomi Okajima, and Tohru Ueda
*Faculty of Pharmaceutical Sciences, Hokkaido University, Kita 12 Nishi 6, Kita-ku, Sapporo, Hokkaido 060-0812, Japan
Abstract
Synthesis of 2’,3’-dideoxy-3’-methylidenethymidine (10) was accomplished by palladium calalyzed deoxygenation of 3’-deoxy-3’-methylidene-5-methyluridine derivative (7). 2’,3’-Didehydro-2’,3’-dideoxy-3’-methylthymidine (11) was synthesized by radical deoxygenation of 3’-deoxy-3’-methylidene-5-methyluridine derivatives.
Published online:
■ Asymmetric Electrophilic α-Amidoalkylation 6: Syntheses of Tetrahydroisoquinolines of High Enantiomeric Purity
Klaus Th. Wanner* and Ilona Praschak
*Institut für Pharmazie, Universität München, Sophienstraße 10, D-80333 München, Germany
Abstract
Syntheses of 1-substituted tetrahydroisoquinolines of high enantiomeric purity are described. As key step a diastereoselective trapping reaction of a chiral acyliminium ion with silyl enol ethers is involved. The starting acyliminium ion can be prepared by hydride abstraction with triphenylcarbonium tetrafluoroborate.
Published online:
■ (4+2)type Cycloaddition of Chromones with α,β-Unsaturated Ketones Mediated by t-Butyldimethylsilyl Triflate: One-pot Preparation of Xanthone Derivatives
Yong-gyun Lee, Hideharu Iwasaki, Yosuke Yamamoto, Katsuo Ohtaka, and Kin-ya Akiba*
*Department of Chemistry, Faculty of Science, Hiroshima University, 1-3-1 Kagamiyama, Higashi-Hiroshima, Hiroshima 739-8526, Japan
Abstract
4-t-Butyldimethylsiloxy-1-benzopyrylium salt (2a,b) reacted with various α,β-unsaturated ketones (3a-g) in the Presence of t-BuMe2SiOTf and 2,6-lutidine to afford the corresponding (4+2) type cycloadducts (4a-i) in high yield. The ring fusion of the adduct was determined to be cis geometry on the basis of the 1H nmr spectral features.
Published online:
■ Litophytolides A and B, Two New Lipid Metabolites of a Soft Coral Litophyton sp.
Masamitsu Ochi,* Kensuke Futatsugi, Yasuhiro Kume, Hiyosizo Kotsuki, Kazuhuko Asao, and Kozo Shibata*
*Department of Material Science, Faculty of Science, Kochi University, 2-5-1, Akebono-cho, Kochi 780-8520, Japan
Abstract
The structures of litophytolides A and B, two new branchedchain lipids containing a γ-lactone ring isolated from a soft coral Litophyton sp., have been established as 1 and 2 on the basis of spectral and chemical evidence.
Published online:
■ The Chemistry of the 6β-Diacylaminopenicillins
Ronald G. Micetich, Rajeshwar Singh, Chen C. Shaw, Samarandra N. Maiti, Maya P. Singh, and Paul Spevak
*SynPhar Laboratories Inc., 4290-91A Street, Edmonton, Alberta, T6E 5V2, Canada
Abstract
A comparison of the chemical reactions of 6β-amidopenicillins, 6β-phthalimidopenicillins and 6β-diacylaminopenicillins with trimethyl phosphite and with benzyl and heteroaryl thiols is reported. The reaction of the unsym-azetidinone disulfides, obtained from the reaction of penicillin sulfoxides with 2-mercaptobenzothiazole, with halogenating agents is also discussed.
Published online:
■ A New Synthetic Route to Heterocyclic Quinones
Abdulla J. Hamdan and Harold W. Moore
*Department of Chemistry, University of California, Irvine, Irvine, California 92697, U.S.A.
Abstract
The synthesis of a variety of heterocyclic quinones is described. This involves a series of unusual transformations of azidoquinones having an active methylene group in conjugation with the azide moiety. Generation of the conjugate base induces nitrogen loss and subsequent heterocyclic ring formation.
Published online:
■ Preparation of New Benzimidazole Derivatives from N-[(Methylthio)thiocarbonylmethyl]azinium Salts
An M. Cuadro, Julio Alvarez-Builla*, and Juan J. Vaquero
*Departamento de Química Orgánica, Universidad de Alcalá de Henares, 28871 Alcalá de Henares (Madrid), Spain
Abstract
A series of new N-[(methylthio)thiocarbonylmethyl] azinium salts has been synthesized by reaction of carbon disulphide and methyl iodide with the corresponding phenacylazinium salt in a two-phase system followed by acid treatment of the ylide thus obtained. Condensation of dithioster derivatives with o-phenylenediamines gave N-(benzimidazolylmethyl) azinium salts in good yields.
Published online:
■ A Novel Mehtod for the Synthesis of 2-Haloalkyl-3(2H)-pyridazinones by O→N-Alkyl Rearrangement
Péter Mátyus,* Nándor Makk, Endre Kasztreiner, and Gyula Jerkovich
*Institute for Drug Research Ltd., H-1325 Budapest, POB 82, Hungary
Abstract
The reaction of (6-substituted 3-pyridazinyloxy)alkanols 2a-d, 3a-d and 14a-c with thionyl chloride is described. The 2-chloroalkylpyridazinones 5b-d, 6b-d and 15a-c were formed from 2b-d, 3b-d and 14a-c, respectively, while the 3-chloroalkoxypyridazines, 7a and 8a were isolated from the reaction of 2a and 3a, respectively. It was shown by chemical and spectroscopic evidences that the rearrangement reaction followed an intramolecular process through bicyclic intermediates.
Published online:
■ High-Pressure Diels-Alder Reactions of 1-Methoxycarbonyl-3-Methylthio- and -3-phenylthiopyrrole. An efficient Entry to 7-Azabicyclo[2.2.1]heptanes
Jan Keijsers, Benno Hams, Chris Kruse,* and Hans Scheeren*
*Department of Chemistry, Duphar Research Laboratories, PO Box 2, 1380 AA Weesp, The Netherlands
Abstract
The high pressure Diels-Alder reaction of new 3-thiosubstituted N-carbonylpyrrole derivatives 5 with electron-poor akenes afforded 2-thiosubstituted 7-azabicyclo[2.2.1]hept-2-enes 9, 10 and 11 regiospecifically in high over-all yields.
Published online:
■ Tetranortriterpemoids from Azadirachta Indica A, Juss (Meliaceae)
Salimuzzaman Siddiqui,* Bina Shaheen Siddiqui, Tariq Mahmood, and Shaheen Faizi
*H. E. J. Postgraduate Institute of Chemistry, University of Karachi, Karachi-75270, Pakistan
Abstract
Nimbocinolide, a new tetranortriterpenoid has been isolated from the acidic fraction of fresh, undried leaves of A.indica (neem) and its structure was established as 21, ,23-epoxy-1,14,20-apoeul (apotirucalla)-trien-3,21-dione-7α,11α,12α,23x-tetraol-11-(2’-hydroxy-2’-methyl) propio-nate-7-acetate (I), through chemical and spectral studies.
Published online:
■ Synthesis of 4-Unsubstituted Isothiazoles
Francesco Lucchesini, Nevio Picci, Marco Pocci, Angela De Munno,* and Vincenzo Bertini
*Dipartimento di Chimica e Chimica Industriale, Università di Pisa, Via Risorgnimento 35, I-56126 Pisa, Italy
Abstract
A new method for the synthesis of 4-unsubstituted isothiazoles starting from α-acetylenic aldehydes or ketones, hydroxylamine-O-sulphonic acid and sodium hydrosulfide in buffered aqueous solution by one-pot procedure, is described.
Published online:
■ Flash-Vacuum Pyrolysis of 1,2,4-Triazolides: A New Synthesis of Functionalized Oxazoles
André Maquestiau, Robert Flammang, and Fouad-Bachir Ben Adbelouahab
*Organic Chemistry Labratory, State University of Mons, B-7000 Mons, Belgium
Abstract
Tandem mass spectrometry (MS/NS) has been applied. to investigate the behaviour of 1,2,4-triazolides upon flash-vacuum pyrolysis (FVP) conditions. Monosubstituted (position 5) oxazoles (loss of nitrogen) and in some cases oxygenated cumulenes (loss of 1,2,4-triazole) are the most important pyrolysis products. Pyrolysis at a preparative scale indicates moreover the interest of the technique as the synthetized oxazoles were usually unknown or very difficult to prepare owing the conventional procedures.
Published online:
■ Photosensitized Dehydrogenation of Flavanones to Flavones Using 2,4,6-Triphenylpyrylium Tetrafluoroborate (TPT)
María J. Climent, Hermenegildo García, Sara Iborra, Miguel A. Miranda,* and Jamie Primo
*Departamento de Química Oránica, Facultad de Farmacia, Av. Blasco Ibañez 13, 46010 Valencia, Spain
Abstract
Irradiation of flavanones 1a-c,e using TPT as photosensitizer leads to the corresponding flavones 2a-c,e in yields ranging between 50 and 69%. 4-Nitroflavanone (1d) remains unchanged under the same conditions. These results are consistent. with a single electron-transfer (SET) occurring from the flavanone B ring to the excited pyrylium salt to give the radical cation intermediate 3.
Published online:
■ Alkylation and Arylation of Pyrazines by Organotin Compounds
Tokuhiro Watanabe, Kazuhiro Hayashi, Jun Sakurada, Michiyo Ohki, Noriko Takamatsu, Harumi Hirohata, Keiko Takeuchi, Kayo Yuasa, and Akihiro Ohta*
*Tokyo University of Pharmacy and Life Science, 1432-1 Horinouchi, Hachioji, Tokyo 192-0392, Japan
Abstract
The palladium-catalyzed cross-coupling reactions of chloropyrazines and tetrabutyltin gave butylpyrazines in good yields. By reactions of chloropyrazines with organotin compounds prepared in situ from the Grignard reagents, alkyl and aryl groups were satisfactorily introduced into the pyrazine ring.
Published online:
■ Synthesis of New Racemic Bicyclic γ- and δ-Lactams Based on Two-fold Intramolecular Cyclization
Eddie ViPing Tao,* John Brennan, Kohn Keith Swartzendruber, and Jack Billie Deeter
*Lilly Reserach Laboratories, Lilly Corporate Center, Eli Lilly & Company, Indianapolis, IN 46285-4813, U.S.A.
Abstract
Syntheses of new raccmic γ - and δ -lactams have been achicved via a novel two-fold intramolceular cyclization.
Published online:
■ Annelation of Quinoxaline by Sulfur Stabilized Carbanions
Jean-Michel Vierfond, Lucien Legendre, Jacqueline Mahuteau, and Marcel Miocque*
*Faculté de Pharmacie, UA 496 CNRS, 5 rue J.B. Clément, 92296 Châtenay-Malabry Cedex, France
Abstract
Thieno[3,4-b]quinoxaline derivatives were prepared by nucleophilic addition of carbanions of sulfones, sulfoxides and sulfides on quinoxaline. The use of dissymmetric sulfones or sulfoxides gave diastereoisomers which mre isolated and characterized.
Published online:
■ Witting Reactions of 1-Alkoxycarbonyl-2-hydroxypyrrolidines and -piperidines: Syntheses of (±)-Hygrine and (±)-2-Epilasubine II
Tatsuo Nagasaka,* Hiroto Yamamoto, Hideki Hayashi, Mariko Watanabe, and Fumiko Hamaguchi
*School of Pharmacy, Tokyo University of Pharmacy and Life Science, 1432-1 Horinouchi, Hachioji, Tokyo 192-0392, Japan
Abstract
One-pot reactions of l-alkoxycarbonyl-2-hydroxypyrrolidines and -piperidines with Wittig reagents stabilized by carbonyl groups give α-alkylated pyrrolidines and piperidines in good yields. The syntheses of (±)-hygrine and (±)-2-epilasubine II using the Wittig products are described.
Published online:
■ Tautomerism of Bis(2-bensothiazolyl)arylmethanes
M. Teresa Ramos, Carmen Avendaño,* José Elguero, M. Luisa Jimeno, Juana Bellanato, Feliciana Florencío, and Julia Sanz-Aparicio
*Departamento de Química Orgánica y Farmacéutica, Facultad de Farmacia, Universidad Complutense de Madrid, Ciudad Universitaria, 28040 Madrid, Spain
Abstract
Tautomerism of some bis(2-benzothiazoly1)methanes has been studied by 1H nuclear magnetic resonance, ultraviolet, and infrared spectroscopies using C-methyl and N-methyl derivatives as model compounds of the “CH” and “NH” fixed forms. X-Ray diffraction analysis of compound 6 shows that it corresponds to the Z-sE isomer b2. The presence of two 2-benzothiazolyl groups is necessary for the “NH” tautomer to be stable.
Published online:
■ New Total Synthesis of Patulin
Julio A. Seijas, M. Pilar Vázquez Tato, Ramón Estévez, Luis Castedo, and Ricardo Riguera*
*Departamento de Química Orgánica, Sección de Alcaloides del C.S.I.C, Facultad de Química, Universidad de Santiago, 15706 Santiago de Compostela, Spain
Abstract
The total synthesis of the mycotoxin patulin from L-arabinose is described.
Published online:
■ Mass Spectometric Fragmentation of the Protonated Sydnones under Chemical Ionization
Ling-ling Tien, Shaw-Tao Lin,* and Hui-Jean Chiang
*Department of Applied Chemistry, Providence University, 200 Chungchi Road, Sha-Lu, Taichung Hsien, 433, Taiwan, R.O.C.
Abstract
The chemical ionization spectra of twenty protonated sydnones were measured by using methane a s a reagent gas. The intense fragmentation reaction takes place from the rupture of the sydnone ring by losing of HNO and CO molecules except for 3-benzylsydnones. The benzylsydnones yield the benzylic (tropylium) cations as the base peak. The NH+4 protonated 3-phenylsydnone results in [M+1]+[M+H+NH3]+ and [M+H+2NH3]+ as the principal peaks without any significant fragmentations.
Published online:
■ On the Structure of Sanggenon Q, A New Diels-Alder Type Adduct from Morus mongolica Schneider
Jin Yun Sun, Yoshio Hano, and Taro Nomura*
*Faculty of Pharmaceutical Sciences, Toho University, 2-2-1, Miyama, Funabashi, Chiba 274-8510, Japan
Abstract
A novel Diels-Alder type adduct, sanggenon Q (1), was isolated f from Morus mongolica Schneider (Moraceae) along with fourteen kinds of known phenolic compounds. Structure of sanggenon Q was shown to be 1 on the basis of spectral evidence. Sanggenon Q (1) is regarded biogenetically as a variation of a Diels-Alder type adduct, such as sanggenon C (2).