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. 14, No. 4, 1980
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■ Convenient Method for the Preparation of 2-Phenacylpyridines
Takeo Konakahara* and Yukio Takagi
*Department of Industrial Chemistry, Faculty of Science and Technology, Science University of Tokyo, 2641 Yamazaki, Noda, Chiba 278-8510, Japan
Abstract
2-Phenacylpyridines (3) were prepared from 2-(trimethylsilylmethyl)pyridine (1) and p-substituted benzonitriles (2) (X = H, Cl, CH3, OCH3) in high yields (70 ~ 99%) under a mild condition (LDA/THF, -75°C) . The method was compared with a reaction of α-picoline with (2) under the same condition. The keto-enol tautomerism of (3) were also discussed by means of the nmr spectra.
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■ New Prenylflavanones from Hernandia nymphaefolia (Presl) Kubitzki
Kenichi Yakushijin, Kenichi Shibayama, Hiroyuki Murata, and Hiroshi Furukawa*
*Faculty of Pharmacy, Meijo University, 150 Yagotoyama, Tenpaku, Nagoya 468-8503, Japan
Abstract
Three new prenylflavanones, nymphaeol-A, -B and -C were isolated from Hernandia nymphaefolia (presl) Kubitzki, and the structures were assigned as I, II and III, respectively.
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■ An Improved Synthesis of an Intermediate for Thienamycin Synthesis
Tetsuji Kametani,* Takayasu Nagahara, Yukio Suzuki, Shuichi Yokohama, Shyh-Pyng Huang, and Masataka Ihara
*Pharmaceutical Institute, Tohoku University, Aobayama, Sendai 980-8578, Japan
Abstract
Methyl 3-amino-5-hydroxy-1,1-dimethoxyhexane-4-carboxylate (2) was converted into trans- and cis-azetidinones (3 and 10) by sequential trimethylsilylation, cyclisation with Grignard reagent, and deblocking. The corresponding tert-butyl ester (15), prepared via the isoxazoline derivative (13), was selectively transformed into the trans-β-lactam (3), a synthetic intermediate of thienamycin, by the same reaction sequence.
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■ A Novel Synthesis of Pyrido[2,3-d]pyrimidines by Reaction of Uracils with 6-Aminouracils via Pyrimidine-to-Pyridine Transformation
Kosaku Hirota, Yukio Kitade, and Shigeo Senda*
*Gifu Pharmaceutical University, 6-1 Mitahora-higashi 5-chome, Gifu 502-8585, Japan
Abstract
Reaction of 1,3-dimethyluracils with 1,3-dialkyl-6-aminouracils in basic media caused the pyrimidine-to-pyridine transformation to afford new pyrido[2,3-d]pyrimidine derivatives. A plausible mechanism for the ring transformation is offered.
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■ Synthesis of Some Isotype Analogs of Vincamine, Eburnamonine and Eburnamine, and an Alternative Approach to Ethyl Apovincaminate
Keiichi Ono, Hajime Kawakami, and Junki Katsube*
*Sumitomo Pharmaceuticals Research Center, 1-98, Kasugadenaka 3-chome, Konohana-ku, Osaka 554-0022, Japan
Abstract
New synthetic analogs of Vinca minor alkaloids were described, together with a new total synthesis of ethyl apovincaminate.
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■ The Reaction of o-Benzenedithiol with Hexachlorobutadiene
Masao Mizuno and Michael P. Cava*
*Department of Chemistry, University of Pennsylvania, 231 South 34th Street Philadelphia, PA 19104-6323, U.S.A.
Abstract
The reaction of o-benzenedithiol with hexachlorobutadiene in the presence of triethylamine affords four products, in ratios dependent upon the experimental conditions employed. These products are assigned the structures of the tetrachloride 2, the isomeric dichlorides 4 and 5, and the fully substituted benzodithiine 3. Dichloride 4 is resistant to zinc reduction, whereas its isomer 5 is reduced by zinc to the corresponding dithiine derivative 7.
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■ Facile Formation of the Basic Skeletons of Naturally Occurring Terpenoidal Lactones
Tetsuji Kametani,* Toshio Honda, and Keiichiro Fukumoto
*Pharmaceutical Institute, Tohoku University, Aobayama, Sendai 980-8578, Japan
Abstract
Three lactones which should be important intermediates in the synthesis of the corresponding natural terpenoidal lactones have been synthesized via thermolysis of benzocyclobutenes. Heating the benzocyclobutenes (7), (8) and (13) afforded the cyclized products (9), (10) and (14) respectively, in reasonable yields.
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■ Reactions of Strained 1,2,5-Oxadiazoles of Thianorbornane Series with Olefins and Unsymmetrical Acetylenes
Otohiko Tsuge* and Toshiaki Takata
*Research Institute of Industrial Science, Faculty of Engineering, Kyushu University, 6-1, Kasuga-koen, Kasuga 816-8580, Japan
Abstract
The strained 1,2,5-oxadiazoles of thianorbornane series, which were obtained from diphenylthieno[3,4-c]-1,2,5-oxadiazole containing tetravalent sulfur and N-phenylmaleimide, reacted with olefins and unsymmetrical acetylenes in refluxing xylene to give the corresponding isoxazoline and isoxazole derivatives arising from cycloadditions of olefins and acetylenes to the nitrile oxide moieties generated from the strained oxadiazoles.
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■ CD Study of Guaianolide Sesquiterpenes Having 8-Fused Lactone; The Absolute Configuration of Helenium Lactone and Pleniradin
Fumio Hamada, Tomihisa Ohta, and Shigeo Nozoe*
*Pharmaceutical Institute, Tohoku University, Aobayama, Sendai 980-8578, Japan
Abstract
9,10-Saturated and unsaturated guaianolide sesquiterpenes having cis- and trans-8-fused α-methylene-γ-lactone were prepared and those CD’s have been studied to complement the rule by Geissman et al.
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■ A Synthetic Approach to Ervitsine — A General Synthesis of 2-Indolypyridine Derivatives
Toshio Suzuki, Estuko Sato, Kozo Goto, Katsuo Unno, and Tetsuji Kametani*
*Pharmaceutical Institute, Tohoku University, Aobayama, Sendai 980-8578, Japan
Abstract
Reactions of indolylmagnesium bromide and lithium diindolylcuprate with several pyridine N-oxides are described.
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■ A Synthetic Approach to Important Intermediates of Reserpine and Yohimbine — Synthesis of Non-tryptamine Components from Furfural
Toshio Suzuki, Akiko Tominio, Katsuo Unno, and Tetsuji Kametani*
*Pharmaceutical Institute, Tohoku University, Aobayama, Sendai 980-8578, Japan
Abstract
A general method for the stereoselective synthesis of the non-tryptamine components of reserpine and yohimbine via the same compound (4) is described. This common intermediate was readily obtained by Diels-Alder reaction of the furfural derivative (10) with maleic anhydride.
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■ Useful Intermediates for the Synthesis of Ergot Alkaloids
Mitsutaka Natsume* and Hideaki Muratake
*Research Foundation Itsuu Laboratory, 2-28-10 Tamagawa, Setagaya-ku, Tokyo 158, Japan
Abstract
6-Substituted 8-oxo-6,7-secoergoline and 8-oxo-10β-6,7-secoergoline derivatives, 17 and 18, were synthesized as useful intermediates for the ergot alkaloid synthesis, starting from the readily available compound, 1-methoxycarbonyl-4-(3-oxo-1-butyl) indole (7).
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■ Novel Type of Analgesic — Synthesis and Analgesic Activity
Tetsuji Kametani,* Kazuo Kigasawa, Mineharu Hiiragi, Haruhide Ishimaru, Nagatoshi Wagatsuma, Toshitaka Kohagisawa, and Toshihisa Nakamura
*Pharmaceutical Institute, Tohoku University, Aobayama, Sendai 980-8578, Japan
Abstract
Two 4a-(3-hydroxyphenyl)decahydrocinnolines (7 and 9) have been synthesised from 2-(3-benzyloxyphenyl)-2-hydroxycarbonylmethylcyclohexanone (1), and both showed stronger analgesic activity than morphine.
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■ An Approach to the Synthesis of the Non-tryptamine Moiety of Reserpine by Diels-Alder Reaction
Seiichi Takano,* Fumitaka Ito, and Kunio Ogasawara
*Pharmaceutical Institute, Tohoku University, Aobayama, Sendai 980-8578, Japan
Abstract
Diels-Alder adduct 2 between furfural ethylene acetal 1 and maleic anhydride has been converted into the tricyclic acetal 10b which would be a promising intermediate for the construction of the non-tryptamine moiety of the Rauwolfia alkaloids, such as reserpine (13).
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■ Photolysis of Some Quinoxalin-2-one 4-Oxides
Makhluf J. Haddadin* and Amal A. Hawi
*Department of Chemistry, American University of Beirut, Beirut, Lebanon
Abstract
Upon photolysis, 3-phenylquinoxalin-2-one 4-oxides rearranged to 3-(o-hydroxyphenyl)-quinoxalin-2(1H)-one whereas 1-hydroxyquinoxalin-2-one 4-oxides yielded o-nitrosoaniline and o-nitroaniline.
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■ 3-Cyanopyridine Derivatives from Arylidenemalononitriles and N-Monosubstituted Arylacetamidines
Stefan K. Robev*
*Department of Pharmacology, Faculty of Medicine, Sofia 1431, Bulgaria
Abstract
A new synthesis of some polysubstituted nicotinonitrile derivatives of type (III) and (IV) from N-monosubstituted arylacetamidines (I) and arylidenemalononitriles (II) is reported.
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■ Acid Catalyzed Isomerization of 2-(2-Furfurylidene)acetyl-quinoxaline and Its 3-Methyl Derivatives
Katsuhide Matoba,* Kenichi Itoh, Masanori Nagata, and Takao Yamazaki
*Faculty of Pharmaceutical Sciences, Toyama Medical and Pharmaceutical University, 2630 Sugitani, Toyama, Toyama 930-0194, Japan
Abstract
2-(2-Furfurylidene)acetyl-quinoxaline (1a) and its 3-methyl derivative (1b) gave quantitatively 1-furfuryl-pyrrolo[1,2-a]quinoxalin-3-ol (2a) and its 4-methyl analogue (2c), respectively, by treating with hydrochloric acid in ethanol. 2c was treated with bromine in carbon tetrachloride to give dibromide (3a). 2d(methyl ether of 2c) and 2e(enol acetate of 2c) afforded 1 to 2 adducts with dimethyl acetylenedicarboxylate.
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■ A Convenient Synthesis of Monocyclic β-Lactams
Hiroki Takahata, Yoshinori Ohnishi, and Takao Yamazaki*
*Faculty of Pharmaceutical Sciences, Toyama Medical and Pharmaceutical University, 2630 Sugitani, Toyama, Toyama 930-0194, Japan
Abstract
The intramolecular N-alkylation of β-bromopropionamide (1) under phase transfer conditions gave monocyclic β-lactams (2) in high yields.
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■ Characterization and Antimalarial Activity of Four Acetylated Pyrimethamines
Nancy Acton, Arnold Brossi,* David E. Davidson, Jr., and Thomas R. Sweeney
*Medical Chemistry Section, Laboratory of Chemistry, NIDDK, National Institute of Health, Bethesda, MD 20892, U.S.A.
Abstract
Acetylation of the antimalarial drug pyrimethamine afforded four different N-acetyl derivatives which were characterized. These Derivatives do not show sustained release activity but they are active antimalarials per se.
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■ Naturally Occurring Pyrazines and Their Mass Spectrometric Characterisation
J. J. Brophy* and G. W. K. Cavill
*School of Chemistry, The University of New South Wales, Sydney 2052, Australia
Abstract
The occurrence of pyrazines in plants and animals - terrestrial and marine - is reviewed. Pyrazines detected in raw and cooked foods are also listed. Aspects of the biosynthesis and biogenesis of the pyrazines are considered, and attention is drawn to the role of various groups of pyrazines in food chemistry, as insect pheromones and in luminescence processes in marine organisms. Pyrazines occur in trace proportions, so their chemical characterisation by mass spectrometry is considered in detail. Salient features of the mass spectra of the various classes of naturally occurring pyrazines are reviewed.
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■ Synthesis of 2-Azabicyclo[3.3.1]nonanes
Joan Bosch* and Josep Bonjoch
*Laboratory of Organic Chemistry, Faculty of Pharmacy, University of Barcelona, Av. de Joan XXIII, s/n, 08028 Barcelona, Spain
Abstract
All methods for the synthesis of 2-azabicyclo[3.3.1]nonanes paying special attention to those which lead to functionalized systems are reviewed. This system, present in several alkaloids, is synthetically and theoretically interesting. The synthetic routes are classified according to the method used for the final cyclization to the morphan system.