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. 75, No. 2, 2008
Published online: 2nd November, 2007
■ Barton-Zard Pyrrole Synthesis and Its Application to Synthesis of Porphyrins, Polypyrroles, and Dipyrromethene Dyes
Noboru Ono
*Department of Chemistry and Biology, Graduate School of Science and Engineering, Ehime University, Matsuyama 790-8577, Japan
Abstract
Pyrroles prepared by the reaction of alkyl isocyanoacetates with nitroalkenes or vinylsulfones (Barton-Zard reaction, BZ reaction) are useful for the synthesis of biologically active pyrroles, porphyrins, polypyrroles, and dipyrromethene dyes. This review covers recent development of the BZ reaction and its application to the field of material science.
Published online: 30th October, 2007
■ Asymmetric Synthesis of Stellettamides A and C
Naoki Yamazaki,* Takeshi Suzuki, Yuta Yoshimura, Chihiro Kibayashi, and Sakae Aoyagi*
*School of Pharmacy, Tokyo University of Pharmacy and Life Sciences, 1432-1 Horinouchi, Hachioji, Tokyo 192-0392, Japan
Abstract
The first synthesis of the marine indolizidine alkaloids, (+)-stellettamide A and (-)-stellettamide C, has been achieved through a coupling reaction with the aminomethylindolizidine fragment and the chiral or achiral trienecarboxylic acid fragment, both of which could be derived from farnesol as a common precursor.
Published online: 23rd October, 2007
■ Synthesis and Antitumor Activity of Combretastatin D-4
Kanako Uno, Takamasa Tanabe, Takahisa Ogamino, Ryoko Okada, Masaya Imoto, and Shigeru Nishiyama*
*Department of Chemistry, Faculty of Science and Technology, Keio University, Hiyoshi 3-14-1, Kohoku-ku, Yokohama 223-8522, Japan
Abstract
Combretastatin D-4 1 was synthesized using electrochemical dimerization of phenols as the key step. Anodic oxidation of bromochloro-phenol 7 provided the corresponding diaryl ether 8. Manipulation of the two hydroxyl groups differenciated, provided the seco-acid, which on Mitsunobu reaction gave the target molecule. Its biological assay showed new potent inhibitory activity against cellular proliferation of human HT-29 colon carcinoma cells.
Published online: 23rd October, 2007
■ One-Pot Synthesis of Indolizine Derivative and Its Application as Multi-Dentate Ligand
Osamu Niyomura,* Yoshimi Yamaguchi, Ryo Sakao, Mao Minoura, and Yoshihisa Okamoto*
*Division of Chemistry, Center for Natural Sciences, College of Liberal Arts and Sciences, Kitasato University, 1-15-1 Kitasato, Sagamihara, Kanagawa 228-8555, Japan
Abstract
1-Cyano-3-(2-pyridinecarboxamido)-2-(2-pyridiyl)indolizine (2) was readily synthesized by the one-pot reaction of 2-(cyanomethyl)pyridine (1a) with selenium dioxide. The reaction of 3- or 4-(cyanomethyl)pyridines (1b,c) under the same reaction conditions gave 2,3-bi(3-pyridyl)-2-butenedinitrile (3b) and 2,3-bi(4-pyridyl)-2-butenedinitrile (3c), respectively. The indolizine 2 (L-H) reacted with Ni(NO3)2·6H2O in ethanol to produce the NiL2 complex (4). The structure was determined by X-ray crystallography.
Published online: 16th October, 2007
■ Mass Spectrometry of Aromatic Cyclic Imides and Amides. Part I: Electron Ionization Induced Decomposition of N-Substituted 2,3-Pyridinedicarboximides
Maria Mercedes Blanco and Isabel Perillo*
*Department of Organic Chemistry, Faculty of Pharmacy and Biochemistry, University of Buenos Aires, Junín 956 (1113), Buenos Aires, Argentina
Abstract
The behaviour of a series of N-substituted 2,3-pyridinedicarboximides (1-14) under electron impact mass spectrometry at 70eV is analyzed. Compounds under study were divided into three groups according to their substitution patterns, namely N-aryl, N-alkyl and N-functionalized alkyl derivatives, which in turn determine the dominant fragmentations. The proposed fragmentation patterns are supported by high resolution, B/E and B2/E linked-scan mass spectrometric data of some selected compounds. Results are compared in some cases to data reported for the related phthalimides.
Published online: 30th October, 2007
■ A Novel Synthesis of 1,4-Bis(thiopyrano[2,3-d]thiazolyl)benzene Derivatives
Nadia Hanafy Metwally
*Department of Chemistry, Faculty of Science, University of Cairo, Giza, Egypt
Abstract
The novel 5-(4-formylphenyl)methylene-thiazolidine-2,4-dithione 3 and 1,4-bis[(4-thioxo-thiazolidinyl)methylene]benzene derivatives 4a,b were synthesized by condensation of each of 4-thioxo-thiazolidin-2-one (1a) and thiazolidine-2,4-dithione (1b) with terephthalaldehyde (2), in good yields depending on the molar ratio of 1 to 2. The cycloaddition of the newly synthesized compounds to N-arylmaleimides, ethyl acrylate, ω-nitrostyrene and malononitrile was studied. The structures of the synthesized compounds were established by elemental analyses and spectral data.
Published online: 9th November, 2007
■ First Example of Diels-Alder Reaction of 4-(1-Ethenylsubstituted)-3-methylisoxazoles with Acetylenedicarboxylates
Stefano Chimichi,* Barbara Cosimelli,* Marco Boccalini, Alessandra Matteucci, and Abdelatif Messaoudi
*Dipartimento di Chimica Organica ”U. Schiff” and Laboratorio di Progettazione, Sintesi e Studio di Eterocicli Biologicamente Attivi (HeteroBioLab), Via della Lastruccia n. 13, I-50019 Sesto F.no, Italy
Abstract
The first example of a [4+2] cycloaddition reaction of 4-(1-ethenylsubstituted)isoxazoles with acetylenedicarboxylates is reported, while the corresponding 5-substituted isomers do not react with the same dienophile; density functional theory (DFT) calculation indicate the electronic origin of the different behaviour.
Published online: 23rd October, 2007
■ Synthesis of in vivo Metabolites of the New Adenosine A3 Receptor PET-Radiotracer [18F]FE@SUPPY
Karem Shanab,* Wolfgang Wadsak, Leonhard-Key Mien, Markus Mitterhauser, Wolfgang Holzer, Victoria Polster, Helmut Viernstein, and Helmut Spreitzer*
*Department of Drug and Natural Product Synthesis, University of Vienna, Althanstrasse 14, 1090, Vienna, Austria
Abstract
The synthesis of three expected metabolites of the new adenosine A3 receptor PET-radiotracer [18F]FE@SUPPY is described. The target compounds - all pentasubstituted pyridines - were obtained via Hantzsch type synthesis of appropriate 1,4-dihydropyridines, followed by oxidation to the corresponding pyridines and subsequent modifications of the ester moieties.
Published online: 9th November, 2007
■ Oligomers Containing Ethynylpyridazine Moieties: Synthesis, Fluorescence and Liquid Crystalline Properties. Diazines 50
Sylvain Achelle, Nelly Plé,* David Kreher, Fabrice Mathevet, Alain Turck, and André-Jean Attias
*L. C. O. F. H. Laboratory, UMR 6014 IRCOF-INSA, BP. 08. 76131, Mont-Saint-Aignan Cedex, France
Abstract
Conjugated oligomers with ethynylpyridazine units have been synthetized by Sonogashira and Suzuki cross-coupling reactions. Some of them present interesting liquid crystals properties investigated by differential scanning calorimetry (DSC) and polarized light microscopy. Some of these oligomers are fluorescent.
Published online: 2nd November, 2007
■ Facile Synthesis of a Series of 2-(4-Alkyloxyphenyl)-5-cyanopyridine Liquid Crystalline Compounds
Win-Long Chia* and Yu Wei Cheng
*Department of Chemistry, Fu Jen Catholic University,Taipei, Taiwan, R.O.C.
Abstract
This study describes the facile synthesis of a homologous series of pyridine-containing liquid crystalline 2-(4-alkyloxyphenyl)-5-cyanopyridines (nOPPyCN, n = 3-7). The subject liquid crystals were prepared in a short two-step reaction. First, 4-alkyloxyphenylmagnesium bromides were added to N-phenyloxycarbonyl-3- cyanopyridinium chloride, affording a 1,2-dihydropyridine, which was then oxidized by o-chloronil. The resulting products, 2-(4-alkyloxyphenyl)-5-cyanopyridines, were obtained in good yields (72%-83%). Thermotropic behaviors of these liquid crystals were investigated using differential scanning calorimetry (dsc) and polarized optical microscopy (pom).
Published online: 2nd November, 2007
■ Synthesis of 1,3-Di(2-thiazolyl)azulene and Its Selective Chromogenic Response to Mercury(II) Ion
Shigeharu Wakabayashi,* Ryoko Uriu, Tomoko Asakura, Chiharu Akamatsu, and Yoshikazu Sugihara
*Department of Clinical Nutrition, Faculty of Health Science, Suzuka University of Medical Science, Suzuka, Mie 510-0293, Japan
Abstract
Azulene derivatives bearing heteroaryl groups in the 1,3-positions were synthesized, and the color and spectral changes occurring upon the addition of metal ions were examined. Of the compounds tested, title compound 4 appears to exhibit the most selective chromogenic behavior toward Hg2+ ion.
Published online: 23rd October, 2007
■ N-Bromosuccinimide (NBS) as Promoter for Acylation of Sydnones in the Presence Acetic Anhydride under Neutral Conditions
Hassan Ghasemnejad-Bosra,* Mina Haghdadi, and Issa Gholampour-Azizi
*Islamic Azad University-Babol Branch, School of Science, P.O. Box 755, Babol, Iran
Abstract
Various 4 - acetyl sydnones (2) can be prepared by reaction of the corresponding 3-aryl sydnones (1) with acetic anhydride at ~110 °C promoted by N-Bromosuccinimide (NBS) as an effective reagent for acylation of sydnones under neutral conditions in satisfactory yields.
Published online: 30th October, 2007
■ An Improved Quinoline Synthesis in the Presence of Nickel Chloride
Minoo Dabiri,* Mostafa Baghbanzadeh, and Elham Arzroomchilar
*Department of Chemistry, Faculty of Science, Shahid Beheshti University, Postal Code 1983963113, Evin, Tehran, Iran
Abstract
NiCl2·6H2O has been used as an efficient catalyst for the synthesis of quinolines by the reaction of 2-aminoaryl ketones and α-methyleneketones under the solvent-free conditions. The clean, mild acidity conditions and quantitative yields of products are attractive features of this reaction which build a suitable method for sensitive substrates, particularly in drug synthesis.
Published online: 16th October, 2007
■ A New Rotenoid from Derris malaccensis
Ruchira Wangteeraprasert and Kittisak Likhitwitayawuid*
*Department of Pharmacognosy, Faculty of Pharmaceutical Sciences, Chulalongkorn University, Bangkok 10330, Thailand
Abstract
A new rotenoid named 6-oxo-dehydroelliptone (2) was isolated from the roots of Derris malaccensis Prain, along with six known compounds. The isolation of dehydroelliptone (1) from a natural source and its unequivocal 1H and 13C NMR assignments were reported for the first time.
Published online: 2nd November, 2007
■ Constituents of Green and Ripened Fruit of Garcinia subelliptica
Kenji Terashima, Tomoko Ishida, Tadashi Furukawa, Yoshiaki Takaya, and Masatake Niwa*
*Faculty of Pharmacy, Meijo University, Tempaku, Nagoya 468-8503, Japan
Abstract
The structure of one new C-3/C-8′′-biflavonoid from Garcinia subelliptica fruit, (+)-4′′′-O-methylfukugetin, and the comparison of the constituents from green and ripened G. subelliptica fruit are described.
Published online: 13th November, 2007
■ Improved Convenient and Environmentally Benign Synthesis of Biological Active Benzimidazoles Using Activated Carbon and Molecular Oxygen
Yoshinobu Tagawa,* Kenji Yamagata, and Kunihiro Sumoto
*Faculty of Pharmaceutical Sciences, Fukuoka University, Nanakuma 8-19-1, Jonan-ku, Fukuoka 814-0180, Japan
Abstract
The reaction of 1,2-phenylenediamine with a variety of aromatic aldehydes in xylenes gave the corresponding benzimidazole derivatives in good to excellent yields (82-93%) in the presence of dry activated carbon and bubbling molecular oxygen. The present reaction involves the simple procedure, easy workup and environmentally benign materials such as molecular oxygen and reusable activated carbon.
Published online: 9th November, 2007
■ Three New Flavonol Glycosides from the Aerial Parts of Tetragonia tetragonoides
Kyu Ha Lee, Ki Myun Park, Kyung Ran Kim, Jongki Hong, Hak Cheol Kwon, and Kang Ro Lee*
*Natural Products Laboratory, College of Pharmacy, Sungkyunkwan University, Suwon 440-746, Korea
Abstract
Three new flavonol glycosides (1-3) and three known lignan amides (4-6) were isolated from the MeOH extract of the aerial parts of Tetragonia tetragonoides. The chemical structures of the new compounds (1-3) were determined to be 6-methoxykaemferol-3-O-β-D-glucosyl (1’’’→2")-β-D- glucopyranosyl-(6""-(E)-caffeoyl)-7-O-β-D-glucopyranoside (1), 6,4’-dimethoxy kaemferol-3-O-β-D-glucosyl (1’"→2")-β-D-glucopyranosyl-(6""-(E)-caffeoyl)-7- O-β-D-glucopyranoside (2), 4’-methoxypatuletin-3-O-β-D-glucosyl (1’"→2") -β-D- glucopyranosyl-(6""-(E)-caffeoyl)-7-O-β-D-glucopyranoside (3) on the basis of extensive spectroscopic analyses (FAB-MS/MS, 1D and 2D NMR experiments).