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. 12, No. 4, 1979
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■ A Regiospecific Synthessis of 5-Hydroxy-2H,1-benzopyran
Vernon G. S. Box, Basil A. Burke, and Charles McCaw
*Department of Chemistry, Mona Campus, University of the West Indies, Mona, Kingston 7, Jamaica
Abstract
The regiospecific synthesis of 5-hydroxy-2H,1-benzopyran, by the Claisen rearrangement of the arylpropargyl ether (6) is described.
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■ X-Ray Structure Deterimination of a Cycloadduct of 1H-Azepine and Diazacyclopentadienone
Kazunobu Harano, Takashi Ban, and Ken Kanematsu*
*Faculty of Pharmaceutical Sciences, Kyushu University, 3-1-1 Maidashi, Higashi-ku, Fukuoka 812-8582, Japan
Abstract
The cycloaddition reaction of N-ethoxycarbonylazepine with 2,5-diphenyl-3,4-diazacyclopentadienone gave anti endo[4+2]π cycloadduct. The structure was determined by X-ray crystallographic study.
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■ Ring Contraction of 4-Diazo-1-phenyl-5,6-dioxo-1,4,5,6-tetrahydropyridazine in the Solid Stave via “Pyrazolo-lactone”
Branko Stanovnik,* Miha Tisler, Jernej Bradac, Bojan Budic, Bozidar Koren and Bojana Mozetic-Rescic
*Department of Chemistry, University of Ljubljana, 61000 Ljubljana, Slovakia
Abstract
Conversion of 4-diazo-1-phenyl-5,6-dioxo-1,4,5,6-tetrahydropyridazine into “pyrazolo-lactone”, from which different 5-hydroxy-1-phenyl-pyrazoles can be formed in the solid state, is described.
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■ Preparation of 3,4-Dibenzoylthiophenes from Alkyl Phenyl Ketones under the Action of Thionyl Chloride
Kitaro Oka*
*School of Pharmacy, Tokyo University of Pharmacy and Life Science, 1432-1 Horinouchi, Hachioji, Tokyo 192-0392, Japan
Abstract
Preparation of 3,4-dibenzoylthiophenes from alkyl phenyl ketones such as propiophenone by treatment with a slightly excess thionyl chloride is described. This reaction involves two key steps: (a) olefin-formation and (b) cyclic sulfinylation.
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■ The Preparation of 1,4-Diaryl-1,4-bis(diethylphosphonomethyl)azinemethylene and Its Reaction with Aryldehydes
Otohiko Tsuge,* Gouki Fukata, Kiyoshi Kikuchi, and Masashi Tashiro
*Research Institute of Industrial Science, Faculty of Engineering, Kyushu University, 6-1, Kasuga-koen, Kasuga 816-8580, Japan
Abstract
The title compounds, 1,4-diphenyl- (11a) and 1,4-di-p-tolyl-1,4-bis(diethylphosphonomethyl)azinemethylene (11b) were prepared by the reaction of the corresponding 1,4-bis(bromomethyl)-1,4-diphenyl- (10a) and 1,4-bis(bromomethyl)-1,4-di-p-tolylazinemethylene (10b) with triethylphosphate. It was found in the reaction of 11 with arylaldehydes such as benzaldehyde (8a) and p-tolualdehyde (8b) that 1-(1,3-diarylpropen-1-yl)-3,5-diarylpyrazoles (5) were obtained as main product but not expected styryl aryl ketone azines (4).
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■ A Novel Indole Trimer; Diindolo[2,3-a:2’,3’-c]carbazole
Takao Kaneko, Mitsuyoshi Matsuo,* and Yoichi Iitaka
*Tokyo Metropolitan Institute of Gerontology, 35-2 Sakae-cho, Itabashi-ku, Tokyo 173-, Japan
Abstract
The reaction of indole with a mixture of TiCl3 and H2O2 gives a novel indole trimer, diindolo[2,3-a: 2’,3’-c]carbazole (3), whose structure has been determined spectrometrically and confirmed from the structure determination of its acetyl derivative (4a) by X-ray crystallography.
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■ γ-Bromination of Quinoline and Pyridine N-Oxides
Hirohisa Saito and Masatomo Hamana*
*Faculty of Pharmaceutical Sciences, Kyushu University, 3-1-1 Maidashi, Higashi-ku, Fukuoka 812-8582, Japan
Abstract
Treatment of quinoline 1-oxide (1) with bromine (2 equiv.) and thallium triacetate (3 equiv.) in acetic acid at 50° for 29 hr produces 4-bromoquinoline 1-oxide (2) in 65.8 % yield. Similarly, quinaldine and 3-bromoquinoline 1-oxides (5 and 12) give the corresponding γ-bromo derivatives (6 and 13) in good yields. From the reaction of 2-cyanoquinoline 1-oxide (8), 2-cyano-4-bromoquinoline 1-oxide (9) and 2-carbamoyl-4-bromoquinoline 1-oxide (10) are obtained. The reactivity of N-oxides of pyridine series is somewhat lower and pyridine and 2-picoline 1-oxides resist bromination under similar conditions, but 2,6-lutidine, 3-picoline and 3,5-lutidine 1-oxides (14, 16 and 18) afford the corresponding γ-bromo derivatives (15, 17 and 19).
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■ Versatile Syntheses of Heterocyclic[n,3,4]propellanes
Shiro Morita, Sunao Fukushima, and Ken Kanematsu*
*Faculty of Pharmaceutical Sciences, Kyushu University, 3-1-1 Maidashi, Higashi-ku, Fukuoka 812-8582, Japan
Abstract
Pericyclic reactions of N-phenyl p-benzoquinone-2,3-dicarboxylic imide(PBI) with homo-diene and conjugated medium-ring polyenes have been examined. The high peri- and stereospecificity observed with dienes is explained using the frontier orbital model where the diene HOMO-PBI LUMO interaction predominates.
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■ Synthesis and Reactions of 3-Methylthioisotyhiazolo[3,4-d]pyrimidine-4,6(5H,7H)-diones
Hiroto Okuda, Yoshinori Tominaga, Yoshiro Matsuda, and Goro Kobayashi*
*Faculty of Pharmaceutical Sciences, Nagasaki University, 1-14, Bunkyo-machi, Nagasaki 852-8521, Japan
Abstract
3-Methylthioisothiazolo[3,4-d]pyrimidine-4,6-(5H,7H)-diones (IIIa, b) were synthesized by treatment of methyl 6-aminouracil-5-dithiocarboxylates, which were prepared by the reaction of 6-aminouracil with carbon disulfide and dimethyl sulfate in the presence of alkali, with iodine in dimethyl sulfoxide in good yields. The reaction of IIIa, b with amines, amides, and active methylene compounds gave the corresponding substituted products of methylthio group in III in good yields.
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■ A Facile Synthesis of 4-Phenylcarbostyrils and 4-Phenylisocarbostyril Involving Photocyclization of Benzo[b]thiophene-2-carboxanilidines and 2-Benzoylamino-3-chlorobenzo[b]thiophene
Shinzo Kano,* Toshihiko Ozaki, and Satoshi Hibino
*School of Pharmacy, Tokyo University of Pharmacy and Life Science, 1432-1 Horinouchi, Hachioji, Tokyo 192-0392, Japan
Abstract
Photocyclization of 3-chlorobenzo[b]thiophene-2-carboxanilide afforded 1-benzothiophene[2,3-c]quinolin-6-one, which upon desulfurization gave 4-phenylcarbostyril (3a). In this way, 4-phenyl-6-substituted-carbostyrils (3b), (3c), (3d) and (3f) and 8-substituted analogues (6a), (6b) and (6c) were also obtained. This approach to 4-phenylcarbostyrils was applied to a synthesis of 4-phenylisocarbostyril (12) through photocyclization of 2-benzoylamino-3-chlorobenzo[b]thiophene.
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■ Synthesis of New Fundamental Heterocycles IX. Synthesis of 2H-Pyrano[3,2-b]pyridine
Henri Sliwa* and Klaus Peter Krings
*Laboratoire de Chimie Organique et Environnement, Université des Sciences et Technologies de Lille, Bat. C4 -2eme Etage, 59655 Villeneuve d‘ Ascq Cedex, France
Abstract
Reductive ring opening of 5-aza-2-chromanol hydrochloride (6) followed by ring closure afforded 5-azachroman (9) which has been converted to the fundamental parent heterocycle (3) through acetoxylation of its N-oxide and subsequent pyrolysis.
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■ A New Synthesis of (±)-Canadaline
Miyoji Hanaoka,* Kazuyoshi Nagami, and Takeshi Imanishi
*Faculty of Pharmaceutical Scicences, Kanazawa University, 13-1 Takara-machi, Kanazawa 920-0934, Japan
Abstract
(±)-Canadaline was synthesized using a regioselective N-C8 bond cleavage of tetrahydroberberine with ethyl chloroformate.
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■ An Asymmetric Reduction of Prochiral Ketones with a Chiral Hydride Reagent Prepared from Lithium Aluminium Hydride and (S)-2-(2,6-Xylidinomethyl)pyrrolidine
Masatoshi Asami and Teruaki Mukaiyama*
*Faculty of Science, cience University of Tokyo, 2641 Yamazaki, Noda, Chiba 278-8510, Japan
Abstract
An asymmetric reduction of aromatic ketones with a chiral hydride reagent, prepared from lithium aluminium hydride and (S)-2-(2,6-xylidinomethyl)pyrrolidine, affords optically active secondary alcohols with excellent optical purities having S-configurations.
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■ Synthesis of Pyrimido[4,5-d]pyrimidines
Yoshinori Tominaga, Hiroto Okuda, Yoshiro Mitsutomi, Yoshiro Matsuda, Goro Kobayashi,* and Kanro Sakemi
*Faculty of Pharmaceutical Sciences, Nagasaki University, 1-14, Bunkyo-machi, Nagasaki 852-8521, Japan
Abstract
5-Aminopyrimido[4,5-d]pyrimidine-2,4 (1H,3H)-diones were synthesized by the reaction of 6-aminouracil with dimethyl cyanoimidodithiocarbonate in the presence of potassium carbonate in dimethylformamide in good yields.
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■ The Synthesis and Characterisations of Retinoidal 3(2H)-Furanones
Masayoshi Ito,* Masako Ohno, Etsuko Takano, Yôko Oda, and Kiyoshi Tsukida
*Kobe Pharmaceutical University, Motoyamakita, Higashinada, Kobe 658-8558, Japan
Abstract
Retinoidal 3(2H)-furanones [(4) and (4’)] have been synthesised via a Claisen type condensation between the polyene ester (1) and the α-hydroxy methyl ketone (2) and their spectral characterisations have been reported.
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■ Synthesis of the 8H-Isoquino[2,1-b][2]benzazocine System via 1,3-Dipolar Cycloaddition of 8-Methoxyberberinephenolbetaine
Miyoji Hanaoka,* Akimori Wada, Shingo Yasuda, Chisato Mukai, and Takeshi Imanishi
*Faculty of Pharmaceutical Scicences, Kanazawa University, 13-1 Takara-machi, Kanazawa 920-0934, Japan
Abstract
Reaction of 8-methoxyberberinephenolbetaine with various acetylenic compounds afforded the 1,3-dipolar cycloadducts, which were heated subsequently in ethanol to provide the 8H-isoquino[2,1-b][2]benzazocines in excellent yields.
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■ Effective Catalytic Asymmetric Synthesis of S-(—)-3-Methoxycarbonyl-4-(3,4-methylenedioxyphenyl)butanoic Acid. A Simple and Effective Route to Chiral Lignans
Kazuo Achiwa*
*Schol of Pharmaceutical Sciences, University of Shizuoka, 52-1 Yada, Shizuoka 422-8526, Japan
Abstract
Effective catalytic asymmetric synthesis of s-2, a key intermediate for the synthesis of chiral lignans, was described. Thus, BPPM-Rh+ in the presence of triethylamine gave s-2 in 78% optical yield.
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■ Synthesis of Perhydro-1,5,2-dioxazines. A Novel Type of Heterocyclic Compounds
Detlef Geffken*
*Institut für Phaemazeutische Chemie, Technische Universität , D-38106 Brauschweig, Germany
Abstract
Derivatives of perhydro-1,5,2-dioxazine have been prepared by the reaction of N-substituted 2-hydroxycarbohydroxamic acids with the dimethyl acetals of aromatic aldehydes.
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■ Synthetic Studies on β-Lactam Antibiotics II. Condensation of β-Lactams with Active Methylene Groups
Tetsuji Kametani,* Shoji Hirata, Hideo Nemoto, Masataka Ihara, and Keiichiro Fukumoto
*Pharmaceutical Institute, Tohoku University, Aobayama, Sendai 980-8578, Japan
Abstract
β-Lactams (3), (6), and (14) were not condensed with 2-methylthiazoline anion. 4-Acetoxy-2-azetidinone (5) reacted at the 4-position with diethyl bromomalonate, but in the case of diethyl malonate, N1-C4 cleavage occurred after C4-condensation, and the product (16) was obtained.
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■ Polyazaphenanthrenes
Wanda Sliwa* and Henri Zamarlik
*Institute of Organic and Physical Chemistry, Politechnical University, 30-370 Wroclaw, Poland
Abstract
Diazaphenanthrenes (DAP), including 1) DAP with two N atoms in outer rings (phenanthrolines) and in adjacent rings (benzo[h]naphthyridines), 2) DAP with two N atoms in the outer ring and 3) DAP with two N atoms in the middle ring, i.e. benzo[c]cinnoline, and also triaza- and tetrazaphenanthrenes are of interest as well for their chemistry as for their pharmacological potential.
In this paper the literature has been reviewed with respect to the synthesis and properties of these ring systems. Since the literature on 1,10-phenanthroline and its complexes is very extensive, this subject requires rather an independent treatment and will not be included here.