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. 41, No. 10, 1995
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■ Preparations of Tryptamine-4,5-dinones, and Their Diels-Alder and Nucleophilic Addition Reactions
Masanori Somei,* Yoshikazu Fukui, and Masakazu Hasegawa
*Faculty of Pharmaceutical Scicences, Kanazawa University, 13-1 Takara-machi, Kanazawa 920, Japan
Abstract
Syntheses of Nb-acetyltryptamine-4,5-dione and (±)-Nb-acetyltryptophan-4,5-dione methyl ester are reported. They were excellent dienophiles as well as good electrophiles, and produced 6,7-disubstituted indoles in Diels-Alder reaction and various 7-substituted indoles with nucleophiles.
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■ Simple Synthesis of 2,2'-Bisindole from Indigo and Its Application for the Syntheses of Indolo[2,3-a]pyrrolo[3,4-c]carbazole-5,7-(6H)dione and -5-(6H)one Derivatives
Masanori Somei,* Hiroyuki Hayashi, Tohru Izumi, and Shinobu Ohmoto
*Faculty of Pharmaceutical Scicences, Kanazawa University, 13-1 Takara-machi, Kanazawa 920, Japan
Abstract
Indiogo was converted to 2,2’-bisindole, from which 6-substituted indolo[2,3-a]pyrrolo[3,4-c]carbazole-5,7-(6H)dione and -5-(6H)one derivatives were prepared in short steps. Bromination of 6-methylindolo[2,3-a]pyrrolo[3,4-c]carbazole-5,7-(6H)dione is also reported.
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■ New Dibenzofuran Formation from the Reactions of 1-Cyclohexenyloxydibutylboranes with 2,3-Dichloro-5,6-dicyano-p-benzoquinone (DDQ)
Kiyoshi Tanemura,* Koji Yamaguchi, Hideo Arai, Tsuneo Suzuki, and Takaaki Horaguchi*
*School of Dentistry at Niigata, The Nippon Dental University, Hamaura-cho 1-8, Niigata 951, Japan
Abstract
1-Cyclohexenyloxydibutylboranes, generated in situ, reacted with 2,3-dichloro-5,6-dicyano-p-benzoquinone (DDQ) to give dibenzofurans.
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■ Synthesis and Properties of Thienyl and Oligothienyl Substituted Tropylium Ions
Takayasu Nihira, Shinji Tarutani, Kahei Takase, and Kazuko Takahashi*
*Department of Chemistry, Faculty of Science, Tohoku University, Sendai 980-77, Japan
Abstract
2-Thienyl- and 2,2’-bithienyl-5-yltropylium ions, as well as 2,5-thienylenebis(tropylium), 2,2’-bithienyl-5,5’-diylbis(tropylium), and 2,2’:5’,2":5",2’’’-quaterthienyl-5,5’’’-diylbis(tropylium) ions have been synthesized and their electronic structures in the ground and excited states have been clarified.
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■ Synthesis of 5-Oxo-1,2,3,5,6,7-hexahydroimidazo[1,2-a]pyridine-8-carbonitriles,6-Oxo-2,3,4,6,7,8-hexahydro-1H-pyrido[1,2-a]pyrimidine-9-carbonitriles, and 7-Oxo-1,2,3,4,5,7,8,9-octahydropyrido[1,2-a][1,3]diazepine-10-carbonitriles
Pedro Victory, Núria Busquets, José I. Borrell,* Jordi Teixidó, Carlos de Alvaro, Anna Arenas, Angel Alvarez-Larena, and Joan F. Piniella
*Departament de Química Orgànica, CETS Institut Químic de Sarrià , Universitat Ramon Llull, E-08017 Barcelona, Spain
Abstract
A simple method for the synthesis of the title compounds is described. Thus, α,β-unsaturated esters (1) are transformed in the already described 2-methoxy-6-oxo-1,4,5,6-tetrahydropyridine-3-carbonitriles (3) which are treated with NH2(CH2)nNH2 (n = 2, 3, 4) to afford the corresponding bicyclic compounds is determined by an X-ray structure analysis of 4a. A ring opening-ring closure mechanism is proposed for the formation of structures (4 - 6) on the basis of the reaction between 3b and 15N,15N’-ethylenediamine which afforded 15N,15N’-4b.
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■ Formation of Dihydroaza-azulanones Possessing Spirocyclic Moieties: [8+2] Type Cycloaddition Reactions of Iminotropones to an Exocyclic Double Bond of 8-Oxoheptafulvene
Yuka Saito, Masayuki Tomita, Hiroshi Taniguchi, Hirofumi Okabayashi, and Katsuhiro Saito*
*Department of Applied Chemistry, Nagoya Institute of Technology, Gokiso-cho, Showa-ku, Nagoya 466, Japan
Abstract
Reactions of N-(p-substituted phenyl) iminotropones with 8-oxoheptafulvene proceeded through [8+2] type cycloadditions to form dihydroaza-azulanones possessing spirocyclic and norcaradiene moieties. Reactions of 8-oxoheptafulvene with phenyl- or tosylhydrazones of tropone gave the same type of dihydroazaazulanones. Analogous reactions with N-alkyliminotropone N-oxides also gave the same type of adducts via the corresponding N-alkyliminotropones, which were derived from reactions of the iminotropone N-oxides with 8-oxoheptafulvene.
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■ Selective Beckmann Rearrangements. Preparation of Isomeric 2,6- and 3,6-Diazepinoisoquinolines and -pyridoindoles
Pál Scheiber* and Péter Nemes
*Department of Chemistry, University of Veterinary Science, H- 1400 Budapest, P.O.Box 2, Hungary
Abstract
Z and E oximes (2, 3, 6, 7) of some benzoquinolizidones (1) and indoloquinolizidone were converted into isomeric diazepinoisoquinolines (4, 5) and diazepinopyridoindoles (8, 9), respectively, via Beckmann ring enlargement. The 1-isopropyl-1,3,4,6,7,11b-hexahydro-2H-benzo[a]quinolizin-2-one (1c) exhibits a cis "b" B/C ring junction.
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■ Studies on Azinethiones: A Novel Synthesis of Bis(azinyl) Trithiocarbonates and Multi-fused Thienoazines
Ayman W. Erian* and Sherif M. Sherif
*Department of Chemistry, Faculty of Science, University of Cairo, Giza, A. R. Egypt
Abstract
A study of the reactivity of azinethione series toward carbon disulphide has been carried out which resulted in a synthesis of bis(azinyl)trithiocarbonates. Reaction of 4-methylazinethiones with N-bromosuccinimide affords in one pot reaction unexpected multifused heterocyclic compounds.
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■ 6- Fluoro-7-(1-piperazinyl)quinoxaline 1,4-Dioxide. Part I. 2-(N-2-Hydroxyalkylcarbamoyl) Derivatives
Mustafa M. El- Abadelah,* Musa Z. Nazer, Naser S. El-Abadla, and Herbert Meier*
*Johannes Gutenberg-Universität Mainz, Institut für Organische Chemie, D-55099 Mainz, Germany
Abstract
A series of N-[6-fluoro-7-(4-methyl-1-piperazinyl)-3-methyl-2-quinoxaloyl]-β-aminoalkanol 1,4-dioxides (12a-h) have been synthesized for bioassay via the Beirut reaction of 5(6)-fluoro-6(5)-(4-methyl-1-piperazinyl)benzofuroxan (9) with the appropriate N-acetoacetyl-β-aminoalkanol in the presence of triethylamine. Preliminary in vitro investigations have indicated that none of the title compounds exhibits any significant antibacterial potency at concentrations ≤ 200 μg / ml.
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■ Studies on Nitrogen-containing Heterocyclic Compounds. Syntheses and Reactions of Benzo[g]quinoline
Isao Takeuchi, Makoto Ushida, Yoshiki Hamada,* Tomoaki Yuzuri, Hiroko Suezawa, and Minoru Hirota
*Faculty of Pharmacy, Meijo University, 150 Yagotoyama, Tempaku-ku, Nagoya 468, Japan
Abstract
The authors devised a new convinient synthesis of benzo[g]quinoline (2) through the condensation of β-naphthylamine with malondialdehyde (MDA) followed by cyclization in polyphosphoric acid. The reactivity of 2 toward N-oxidation, Reissert reaction and methylation with methylsulfinylmethyl carbanion was investigated.
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■ Synthesis and Stereochemistry of Chiral 1,3-Dioxanic Compounds Obtained from α-Alkylated β-Ketoesters
Ion Grosu* , Sorin Mager, Gérard Plé, Roberto Martinez, Luminita Muntean, and Eugen Mesaros
*Instituto de Química, Universidad Nacional Autónama de México, Ciudad Universitaria, Circuito Exterior, Mexico D.F., 04510, Mexico
Abstract
1,3-Dioxanic compounds were obtained by the ketalisation reaction of some α-alkylated β-ketoesters. The conformational analysis by means of 1H- and 13C-nmr investigations showed the anancomeric structure of the compounds. The axial or the equatorial position of the groups was inferred by N.O.E. experiments. The influence of the chiral carbon atom of the esteric group located at C2 was studied using the diastereotopicity of the protons and of the carbon atoms recorded in high field nmr spectra.
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■ Garcinianin, a Novel Biflavonoid from the Roots of Garcinia kola
Kenji Terashima, Muhd Aqil, and Masatake Niwa*
*Faculty of Pharmacy, Meijo University, Tempaku, Nagoya 468, Japan
Abstract
A novel biflavonoid named garcinianin was isolated from the roots of Garcinia kola (Guttiferae) and the structure was characterized as a C-3/C-8"-naringenin/kaempferol dimer by spectroscopic methods. Garcinianin is present as a mixture of two atropisomers (relative ratio; 1:1.2) at 25 °C. Garcinianin is the first example of a flavanone-flavonol biflavonoid.
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■ Polycyclic N-Heterocyclic Compounds. 47 Synthesis and Evaluation of Anti-Platelet Aggregation Activity of 11,13,15-Triazasteroid and Related Compounds
Kenji Sasaki, Tomohiro Funabashi, Hiromi Ohtomo, Taiji Nakayama, and Takashi Hirota*
*Faculty of Pharmaceutical Science, Okayama University, 1-1-1 Tsushima-Naka, Okayama 700, Japan
Abstract
Synthesis and separation of cis- and trans-1,2,4,5,5a,6,7,8,9,9a-decahydrobenz[h]imidazo[1,2-c]quinazolines and its precursors are described. Inhibitory activity against collagen-induced platelet aggregation for rabbit blood of these compounds and their benzologues at A ring is also evaluated.
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■ Synthesis of 2-Substituted 2,3-Dihydro-1,4-benzothiazine-3-thiones via Iminophosphoranes
Masahiko Takahashi* and Masaru Ohba
*Department of Materials Science, Faculty of Engineering, Ibaraki University, Hitachi, Ibaraki 316, Japan
Abstract
2-(Substituted methylsulfanyl)anilines (5) were treated with triphenylphosphine dibromide to yield iminophosphoranes (6), whose aza-Wittig reaction with carbon disulfide gave 2-(substituted methylsulfanyl)phenyl isothiocyanates (8). Cyclization of 8 by strong bases afforded 2-substituted 2,3-dihydro-1,4-benzothiazine-3-thiones (10).
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■ A Formal Total Synthesis of (+)-Galactostatin via a Tetrahydroxynorleucine Derivative
Mitsunori Kirihata,* Yoshinobu Nakao, Masahiro Mori, and Itsuo Ichimoto
*Department of Applied Biochemistry, College of Agriculture, University of Osaka Prefecture, 1-1 Gakuencho, Sakai, Osaka 593, Japan
Abstract
(2S,3S,4S,5R)-2,3:4,6-Bis(isopropylidenedioxy)-5-[[(p-methoxybenzyloxy)carbonyl]amino]hexan-1-ol (14), a synthetic intermediate for (+)-galactostatin (1), has been synthesized starting from (+)-diethyl tartarate using the aldol-type condensation of methyl isocyanoacetate (2) with 4-O-benzyl-2,3-O-isopropyliden-L-threose (4) via a 3,4,5,6-tetrahydroxynorleucine derivative (8) as a key reaction.
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■ A New Synthesis of 3-Substituted Indolines and Indoles
Masaru Kihara,* Yasumasa Iwai, and Yoshimitsu Nagao
*Faculty of Pharmaceutical Sciences, University of Tokushima, Sho-machi, Tokushima 770, Japan
Abstract
3-Phenyl- and 3-alkyl-3-hydroxyindolines were synthesized by intramolecular Barbier reaction of phenyl and alkyl N-(2-iodophenyl)-N-methylaminomethyl ketones with n-BuLi, which were easily prepared from N-methyl-2-iodoaniline and bromomethyl ketones. The treatment of the indolines with acid gave the corresponding indoles in quantitative yields.
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■ Reactions of 2-Alkylamino- and 2-Dialkylamino-1-azaazulenes with Diphenylcyclopropenone
Noritaka Abe,* Toshihiro Murafuji, Yoshikazu Sugihara, and Akikazu Kakehi
*Department of Chemistry, Faculty of Science, Yamaguchi University, Yamaguchi 753, Japan
Abstract
Reaction of 2-alkylamino-1-azaazulenes with DPP gave 1,2-diphenyl-3H-9-azacyclopent[a]azulen-3-one and N-alkyl-N-(1-azaazulen-2-yl)-2,3-diphenyl-2-propenamides. Reaction of 2-dialkylamino-1-azaazulenes with DPP gave 2-dialkylamino-4,5-diphenyl-7H-1-azacyclopent[e]azulen-7-ones 2-dialkylamino-3,4-diphenyl-5H-1-azabenz[cd]azulen-5-ones. Some structures of the products were determined by single-crystal X-ray structure analyses.
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■ Fused [1]Benzazepines. Pentacyclic [1]Benzazepines by Reaction of 1H-[1]Benzazepine-2,5(3H,4H)-dione with Aldehydes
Conrad Kunick*
*Institut für Pharmazie, Universität Hamburg, 20146 Humburg, Germany
Abstract
Condensation reaction of 1H-[1]benzazepine-2,5(3H,4H)-dione (1) with the aromatic aldehydes (2a-e) in the presence of piperidine furnished 4-benzylidene-1H-[1]benzazepine-2,5(3H,4H)-diones (3a-e), whereas in the presence of potassium hydroxide the 7a,8,15a,15b-tetrahydro-15b-hydroxy-5H-[1]benzazepino[4’,5’:4,5]cyclopenta[1,2-c][1]benzazepine-6,9,15(7H,8aH,14H)-triones (4a-e) were formed. The reaction of 1 with formaldehyde yielded the spiro compound (7) as the product of a Diels-Alder dimerization.
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■ Formations of Organic Semiconductors: Bistropylium Ions Linked by Heterocyclic Moieties as Components of Charge Transfer Complex
Kazuaki Ito and Katsuhiro Saito*
*Department of Applied Chemistry, Nagoya Institute of Technology, Gokiso-cho, Showa-ku, Nagoya 466, Japan
Abstract
Bistropylium ions linked by heterocyclic moieties were synthesized to measure their reduction potentials of -0.47 ~ -0.42 V vs. SCE. Charge transfer complexes between these bistropylium ions and radical anion of TCNQ showed conductivities of 7.7 X 10-4 ~ 7.7 X 10-5 Scm-1, indicating that they can be classified as semiconductors.
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■ Paratocarpins F - L, Seven New Isoprenoid-substituted Flavonoids from Paratocarpus venenosa Zoll
Yoshio Hano, Naoyuki Itoh, Akio Hanaoka, and Taro Nomura*
*Faculty of Pharmaceutical Sciences, Toho University, 2-2-1, Miyama, Funabashi, Chiba 274, Japan
Abstract
Two new isoprenoid substituted chalcones, paratocarpins F (1) and G (2), along with five new isoprenoid substituted flavanones, paratocarpins H (3), I (4), J (5), K (6), and L (7), were isolated from the Indonesian moraceous plant, Paratocarpus (= Artocarpus) venenosa Zoll. The structures of paratocarpins F, G, H, I, J, K, and L were shown to be 1, 2, 3, 4, 5, 6, and 7, respectively, on the basis of spectroscopic and chemical evidence.
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■ Heterocyclic Saturated Compounds as Derivatives or Precursors of Chloromycetine and of Some Related Structures
Mircea Darabantu, Sorin Mager, Gérard Plé, and Camelia Puscas*
*University Babes-Bolyai Cluj-Napoca, Department of Organic Chemistry, 11 Arany Ianos str., 3400 Cluj-Napoca, Romania
Abstract
The review summarizes the diastereoselective synthesis of chloromycetine, of its cyclic acetals or ketals and related structures via 1,3-dioxanes, oxazolidines and 1,2-epoxides.
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■ Heterocycles from Intramolecular Wittig, Horner and Wadsworth-Emmons Reactions
B. Mark Heron*
*Department of Chemistry, University of Central Lancashire, Preston, Lancashire, PR1 2HE, England
Abstract
The synthesis of a range of heterocyclic systems based on intramolecular reactions of phosphorus ylides and phosphinoxy and phosphonate carbanions is reviewed.