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. 4, 2004
Published online: 6th February, 2004
■ Well-divided and pH-Dependent Bimodal Chemiluminescence of 2-Methyl-6-phenyl-8-(4-substituted phenyl)imidazo[1,2-a]pyrazin-3(7H)-ones Induced by Superoxide Anion
Ryota Saito,* Chizuru Inoue, and Akira Katoh
*Department of Applied Chemistry, Seikei University, Musashino, Tokyo 180-8633, Japan
Abstract
An unprecedented pH-dependent bimodal chemiluminescence of 2-methyl-6-phenyl-8-(4-substituted phenyl)imidazo[1,2-a]pyrazin-3(7H)-ones (1a and 1b) initiated by superoxide anion (O2·-) in phosphate buffer solutions is described. The intensity ratio of the bimodal luminescence due to two light-emitting species, the singlet-excited neutral 2-acetamido-5-phenyl-3-(4-substituted phenyl)pyrazine [1(2a)* or 1(2b)*] and its amide anion [1(2a-)* or 1(2b-)*], varied as the pH rose. The percentage of the anionic luminescence intensity [Ianion/(Ineutral+Ianion)] for 1a showed a good linear correlation with the pH value, demonstrating the usefulness of 1a as a pH indicator as well as an O2·- probe.
Published online: 9th February, 2004
■ Anodic Oxidation of Tetrahydro-β-carboline Derivatives: Formal Oxidation of Protonated Tertiary Amines
Loïc Planas, Thierry Martens, Florence Billon-Souquet, and Jacques Royer*
*UMR 8638 (CNRS-University Paris-5), Faculty of Pharmaceutical and Biological Sciences, 4 avenue de l'Observatoire, 75270 Paris cedex 06, France
Abstract
A study of the anodic oxidation of indolic compounds in the tetrahydro-β-carboline series is described. Methoxylation at the α position of the C-3 indole ring was observed furnishing a convenient access to variously substituted products at that position. Nevertheless, this oxidation reaction was not general and very slight structural variation led to different chemical behavior corresponding to a formal oxidation of protonated tertiary amines.
Published online: 9th February, 2004
■ Use of Deoxo-Fluor for Double Cyclization to Bis-thiazolines. Limitations of This Agent for the Synthesis of Oxazolines
Laura Scarone, Diver Sellanes, Eduardo Manta, Peter Wipf, and Gloria Serra*
*Department of Organic Chemistry, Facultad de Química, UDELAR, Av. General Flores 2124, Casilla de Correo 1157, Montevideo, Uruguay
Abstract
Double cyclizations to bis-thiazolines have been performed using the Deoxo-Fluor cyclodehydration agent. Some limitations of the use of Deoxo-Fluor for the synthesis of oxazolines are described.
Published online: 20th February, 2004
■ Synthesis of CMP-sialic Acid Mimics That Have 5-Fluorouracil for Cytosine and the C-Terminal's Peptide Bond for the Phosphate Group: Targeting Inhibitors of Sialyltransferases
Shinji Nakahara, Toru Tanaka, Kazuharu Noguchi, Kenji Nozaki, Shuichi Tsuji, Tsuyoshi Miura, and Tetsuya Kajimoto*
*Department of Biotechnology, Tokyo University of Agriculture and Technology, 2-24-16 Naka-cho, Koganei-shi, Tokyo 184-8588, Japan
Abstract
Novel mimics of cytidine 5'-monophosphate-sialic acid (CMP-sialic acid) were designed and synthesized for targeting inhibitors of sialyltransferases on the basis of the phenomenon that the tautomerization of 5-fluorouracil from the lactam to the lactim form produces a structure similar to that of cytosine, and the C-terminal's peptide bond can be a bioisoster of a phosphate group. Since γ-N1-(5-fluorouracilyl)-β-hydroxy-α-L-amino acid, a key synthetic intermediate, was easily prepared using the enzyme-catalyzed aldol reaction, the synthesis of the mimics of the CMP-sialic acid was attained in a short step.
Published online: 20th February, 2004
■ Synthesis of Microcarpalide, a Microfilament Disrupting Agent
Ken Ishigami and Takeshi Kitahara*
*Department of Applied Biological Chemistry, Graduate School of Agricultural and Life Sciences, The University of Tokyo, 1-1-1 Yayoi, Bunkyo-ku, Tokyo 113-8657, Japan
Abstract
Microcarpalide is a strong microfilament disrupting agent. The convergent and stereoselective synthesis of microcarpalide was succeeded via Julia olefination and macrolactonization.
Published online: 30th January, 2004
■ A Simple and Efficient Synthesis of New 6-Arylimino-6H-indolo[2,1-b]quinazolin-12-ones under Microwave Irradiation
Javad Azizian,* Ali A. Mohammadi, F. Ardakani, Ali R. Karimi, and Mohammad R. Mohammadizadeh
*Department of Chemistry, Faculty of Science, Shahid Beheshti University, P.O. Box 19395-4716, Tehran, Iran
Abstract
A ring opening and selective reaction of isatoic anhydride with isatin-3-imine in the presence of catalytic amount of KF-Al2O3, a reusable catalyst, to yield a novel series of 6-arylimino-6H-indolo[2,1-b]quinazolin-12-one under microwave irradiation, is described.
Published online: 6th February, 2004
■ An Interaction of 2-Thiazoleacetonitriles with N-(2-Chloroacetyl)anthranilic Acid Ester
Elizaveta V. Resnyanska, Anton V. Tverdokhlebov,* Andrey A. Tolmachev, Yulian M. Volovenko, and Tatyana V. Shokol
*'Enamine Ltd.' Co., I. Kudri str. 31, apt. 17, 02042, Kiev, Ukranie
Abstract
The title ester was found to react with 2-benzothiazoleacetonitrile yielding 3-(2-benzothiazolyl)-2,4-dihydropyrrolo[1,2-a]quinazoline-1,5-dione. At the same time 4-aryl-2-thiazoleacetonitriles gave 3,4-dihydro-β,4-dioxo- α,δ-bis(4-aryl-2-thiazolyl)-2-quinazolinepentanenitriles potassium salts under identical conditions. These results were explained in terms of different solubility of the intermediate compounds. Upon acidification the obtained salts were shown to undergo intramolecular Thorpe addition leading to the 3-amino-2,4-bis(4-aryl-2-thiazolyl)-4-[4(3H)-oxo-2-quinazolinyl]-2-cyclopenten-1-ones. Above mentioned pyrrolo[1,2-a]quinazoline derivative was treated with benzylamines and active methylene nitriles to yield β-(2-benzothiazolyl)-N-arylmethyl-3,4-dihydro-4-oxo-2-quinazolinepropanamides and 2-substituted 3-amino-4-(2-benzothiazolyl)-4-[4(3H)-oxo-2-quinazolinyl]-2-cyclopenten-1-ones, respectively.
Published online: 30th January, 2004
■ Some Reactions of 3-Phenyl-8-triphenylphosphoimino-1-azaazulene
Noritaka Abe,* Kentaro Nagamatsu, Kenji Tahara, and Hiroyuki Fujii
*Department of Chemistry, Faculty of Science, Yamaguchi University, Yoshida, Yamaguchi 753-8512, Japan
Abstract
Reaction of 3-phenyl-8-triphenylphosphoimino-1-azaazulene (1) with arylaldehyde gave 2-aryl-4-phenyl-3H-1,2a-diazacyclopent[cd]azulenes. Reaction of 1 with trans-cinnamaldehyde gave 3-benzyl-1-pheny-2a,5-diazabenz[cd]azulene as cyclization product. Cycloaddition reaction of 1 with dimethyl acetylenedicarboxylate gave tetramethyl 4-phenyl-9,9b-diazaindeno[4,3a,3,2-bcd]azulene-1,2,3,9a-tetracarboxylate and hexamethyl 6-phenyl-3aH-10c-azaacephenanthryene-1,2,3,3a,4,5-hexacarboxylate.
Published online: 9th February, 2004
■ Synthesis of 2,3,8-Trisubstituted 7H-Isoindolo[5,6-g]quinoxaline-5,7,9,11(8H)-tetraones
Heesoon Lee,* Sungmoon Cho, Byeonggil Choi, Kwon Namgoong, and Jae-Kyung Jung
*College of Pharmacy, Chungbuk National University, Cheongju 361-763, Korea
Abstract
Oxidation of 3-methyl- or 7,8-dimethylbenzo[g]quinoxalinedione produced the unusual product, dihydroxybenezo[g]quinoxaline-5,10-dione- carboxylic acid or dicarboxylic acid. This process was used for the synthesis of a series of 2,3,8-trisubstituted isoindolo[5,6-g]quinoxalinetetraone derivatives.
Published online: 30th January, 2004
■ Investigation of Intramolecular Pauson-Khand Reaction of 2-Aryl-1,6- and 1-Methyl-1,7-enynes (exo-Olefins) and 1-Phenyl-1-octen-7-yne (endo-Olefin)
Miyuki Ishizaki,* Hiroshi Satoh, Osamu Hoshino, Kiyoshi Nishitani, and Hiroshi Hara*
*Faculty of Pharmaceutical Sciences, Tokyo University of Science, 2641 Yamazaki, Noda-shi, Chiba 278-8510, Japan
Abstract
The intramolecular Pauson-Khand reaction of various 2-aryl-1-hepten-6-ynes and its aza-derivatives (exo-olefins) efficiently produced aryl-bicyclo[3.3.0]octenones and azaoctenone bearing quaternary carbon centers at angular positions in good yields. Although a similar reaction of 2-phenyl-1-octen-7-yne (exo-olefin), which is a homologue of 2-phenyl-1-hepten-6-yne, did not take place, the reaction of the methyl derivatives smoothly proceeded. However, the reaction of regioisomeric 1-phenyl-1-octen-7-yne (endo-olefin) afforded the desired product in moderate yields.
Published online: 6th February, 2004
■ Conodusarine, a New Biologically Active Bisindole Alkaloid from Tabernaemontana divaricata
Toh-Seok Kam* and Huey-Shen Pang
*Department of Chemistry, University of Malaya, 50603 Kuala Lumpur, Malaysia
Abstract
A new bisindole alkaloid of the vobasine-iboga type, conodusarine, was isolated from the stem-bark extract of Tabernaemontana divaricata and the structure established by spectroscopic analysis.
Published online: 30th January, 2004
■ Sequential Bromination-Rearrangement of Push-pull Thiazolidines Induced by Pyridinium Hydrobromide Perbromide under Homogenous Reaction Conditions
Rade Markovic,* Marija Baranac, and Zdravko Dzambaski
*Faculty of Chemistry, University of Belgrade, Studentski trg 16, P.O.Box 158, 11001 Belgrade, Serbia and Montenegro
Abstract
Regiospecific bromination-rearrangement of the 5-substituted 2-alkylidene-4-oxothiazolidine derivatives induced by pyridinium hydrobromide perbromide (PHBP) provides a new synthetic approach to the corresponding push-pull thiazolidines with two exocyclic double bonds. In comparison to a heterogenous alternative, this conversion, taking place in acetonitrile under homogenous reaction conditions, has the advantage of almost quantitative yields and a substantial rate enhancement.
Published online: 20th February, 2004
■ A New Tricyclic 6-7-5-Ring Diterpene from Pliocene Fossil Tsuga dumosa
You-Xing Zhao, Cheng-Sen Li, Xiao-Dong Luo, and Jun Zhou*
*State Key Laboratory of Phytochemistry and Plant Resources in West China, Kunming Institute of Botany, Chinese Academy of Sciences, Kunming 650204, Yunnan, China
Abstract
A new diterpene named (+)-parryin-15,16-O-isopropylidene (1) and three known isopimara analogues (2-4) were isolated from the Pliocene lignified wood of Tsuga dumosa collected in Changning coalmine, Yunnan, China. Their structures were elucidated by spectroscopic analysis.
Published online: 20th February, 2004
■ A Convenient Oxidation Method of the Benzylic 10-Position in 4,5-Epoxymorphinan
Hiromasa Horikiri and Kuniaki Kawamura*
*Pharmaceutical Research Laboratories, Toray Industries, Inc., 111 Tebiro, Kamakura, Kanagawa, 248-8555, Japan
Abstract
A convenient oxidation method of the benzylic 10-position in 4,5-epoxymorphinan to obtain its 10-oxo derivatives is described. The reaction by using potassium permanganate proceeds in good yield and can be performed in large scale.
Published online: 6th February, 2004
■ Two Lignan Glycosides from Vitis thunbergii
Yue-Hua He, De-Qiang Dou, Kenji Terashima, Yoshiaki Takaya, and Masatake Niwa*
*Faculty of Pharmacy, Meijo University, Tempaku, Nagoya 468-8503, Japan
Abstract
Two new isolariciresinol-type lignan glycosides were isolated from Vitis thunbergii (Vitaceae) along with some oligostilbenes. Their structures were elucidated as (+)-3α-O-α-L-rhamnopyranosyl-5-methoxyisolariciresinol and (—)-3α-O-β-D-xylopyranosyl-6-O-β-D-glucopyranosylisolariciresinol, respectively, on the basis of the spectral evidence
Published online: 6th February, 2004
■ A New Pterocarpan from Erythrina fusca
Pranorm Khaomek, Nijsiri Ruangrungsi,* Ekarin Saifah, Nongluksna Sriubolmas, Chikara Ichino, Hiroaki Kiyohara, and Haruki Yamada
*Faculty of Pharmaceutical Sciences, Chulalonghorn University, Bangkok 10330, Thailand
Abstract
A new pterocarpan, 3-hydroxy-10-(3-hydroxy-3-methylbutyl)-9-methoxypterocarpan (1), together with seven known compounds, sandwicensin (2), erythrisenegalone (3), citflavanone (4), liquiritigenin (5), lonchocarpol A (6), lupinifolin (7) and 8-prenyldaidzein (8), were isolated from the stem bark of Erythrina fusca. The structure of 1 was determined on the basis of spectroscopic analyses. Among these compounds, lonchocarpol A (6) exhibited strongly antibacterial activities in vitro against Staphylococcus aureus, Bacillus subtilis and Enterococcus faecalis. Compounds (2, 3, 6 and 7) exhibited weakly antimycobacterial activity with minimum concentrations (MICs) of 100, 50, 50 and 25 μg/mL, respectively.
Published online: 6th February, 2004
■ Synthesis of the ABCD Ring System of Azaspiracid, a Marine Poison from Mytilus edulis
Yuichi Ishikawa 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 the ABCD ring system of azaspiracid (1) was accomplished. The bridge system between the B and C rings using a sulfur atom, supported the spiroacetal-construction at the C13 position in the natural form. The stereochemistry was confirmed by the NOE experiments, along with conversion under acidic conditions into the unnatural derivative (12).
Published online: 20th February, 2004
■ Briaexcavatolide W, a New Diterpenoid from Briareum excavatum
Shwu-Li Wu, Ping-Jyun Sung, Jui-Hsin Su, Guey-Horng Wang, and Jyh-Horng Sheu*
*Department of Marine Resources, National Sun-Yat Sen University, Kaohsiung, 804, Taiwan, R.O.C.
Abstract
A new briarane-type diterpenoid, briaexcavatolide W (1), has been isolated from the gorgonian coral Briareum excavatum. The structure was elucidated by spectroscopic methods.
Published online: 20th February, 2004
■ (Delphinidin 3-Gentiobiosyl) (Luteorin 7-Glucosyl) Malonate from the Flowers of Eichhornia crassipes
Kenjiro Toki, Norio Saito, Shinya Tsutsumi, Chihiro Tamura, Atsushi Shigihara, and Toshio Honda*
*Faculty of Pharmaceutical Sciences, Hoshi University, Shinagawa, Tokyo, Japan
Abstract
An additional new pigment exhibiting anthocyanin and flavone disubstituted malonate structure, was isolated from the blue-purple flowers of Eichhornia crassipes as a minor anthocyanin. This pigment was identified as (6'''-O-(delphinidin 3-O-(6''-O-(β-D-glucopyranosyl)-β-D-glucopyranosyl))) (6''-O-(luteolin 7-O-( β-D-glucopyranosyl))) malonate by chemical and spectroscopic methods. The λmax of this pigment is 547 nm in 0.1% HCl-MeOH, where the negative cotton effect is also observed as similar to that of Eichhornia anthocyanin A, (delphinidin 3-gentiobiosyl) (apigenin 7-glucosyl) malonate previously isolated from the same flowers. This result supports that the new pigment also takes a folding conformation between delphinidin (chromophore) and luteorin (co-pigmnet).
Published online: 30th January, 2004
■ Syntheses of Heterocyclic Compounds under Microwave Irradiation
Yu Xu and Qing-Xiang Guo*
*Department of Chemistry, University of Science and Technology of China, Hefei 230026, China
Abstract
Microwave technique has been applied extensively in organic syntheses. In this paper, syntheses of different kinds of heterocyclic compounds under microwave irradiation were reviewed.