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. 12, 1980
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■ Aromatic Substitution Effects in the Aspidospermane-Eburnane Rearrangement of Indole Alkaloids
Guy Lewin, Yves Rolland, and Jacques Poisson*
*Centre d’Etudes Pharmaceutiques, C. N. R. S., E. R.. A. 317, 92290 Châtenay-Marabry, France
Abstract
The influence of substitutions in aromatic part of indole alkaloids with aspidosperma skeleton on their rearrangement into products with eburnane-type structure is studied. Results are applied to vincamine derivatives.
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■ The Formation of 1,2-Diselenol-5-one and 5,6-Dihydro-4H-1,3-selenazin-4-one Derivatives from Diphenylcyclopropenone
Masahiko Takahashi,* Shin-ichi Watanabe, and Tohru Kasai
*Department of Materials Sciences, Faculty of Engineering, Ibaraki University, 4-12-1 Nakanarusawamachi, Hitachi, Ibaraki 316-8511, Japan
Abstract
Reaction of diphenylcyclopropenone (1) with selenoamides or sodium hydrogen selenide afforded 3,4-diphenyl-1,2-diselenol-5-one (3), which was transformed into 4,5-diphenyl-3-hydroxypyrazole (4) on treatment with hydrazine. On the other hand, reaction of 1 with N,N-diphenylselenourea gave 2-(N,N-diphenylamino)-5,6-diphenyl-5,6-dihydro-4H-1,3-selenazin-4-one (6a).
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■ Thermal Rearrangement of 2-Vinylpiperidine and 6-Vinyl-1,2,5,6-tetrahydropyridine N-Oxides: Formation of 1,2-Oxazepine Derivatives
Takashi Tsuchiya* and Haruki Sashida
*School of Pharmacy, Hokuriku University, 3-Ho, Kanagawa machi, Kanazawa 920-1181, Japan
Abstract
The thermolysis of both 2-vinyl piperidine N-oxides (9 and 12) and 1,2,5,6-tetrahydropyridine N-oxides (15) resulted in the Meisenheimer-type [1,2] rearrangement to give the corresponding 1,2-oxazepine derivatives (10, 13, 16, and 17). In the thermolysis, the involvement of [2,3]-sigmatropic rearrangement could not be observed in contrast to the cases of the analogous cyclic amine N-imides (3, 5, and 7).
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■ Hydroborations: New Syntheses of Pseudo-baptigenin, O-Methylpseudo-baptigenin and Carbeuvin
B. Serge Kirkiacharian,* Jean-Daniel Brion, Michel Gomis, and Pierre Reynaud
*Laboratoire de Chimie Therapeutique, Faculte de Pharmacie, Université Paris XI, 5, rue Jean-Baptiste Clément, 92290 Chatenay-Malabry Cedex, France
Abstract
Application of hydroboration followed by chromic acid oxydation to 4-hydroxy 7-methoxy 3-(3’,4’-methylenedioxyphenyl) coumarin and 4-hydroxy 7-benzyloxy 3-(3’,4’-methylenedioxyphenyl) coumarin forms the corresponding isoflavanones which are dehydrogenated into isoflavones.
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■ The Conformation of Chelidonine
Mark Cushman* and T. -C. Choong
*Department of Medicinal Chemistry and Pharmacology, School of Pharmacy and Pharmacal Sciences, Purdue University, 1333 Robert E. Heine Pharmacy Building, West Lafayette IN 47907, Indiana 47907, U.S.A.
Abstract
The 360 MHz proton spectra of (+)-chelidonine and (±)-chelidonine-6,6,11-d3 are not in agreement with the generally accepted B/C half chair-half chair conformation. An envelope (twist half chair) form of ring C is indicated.
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■ A Simple General Method for the Acylation of Ethyl Indole-2-carboxylates
Yasuoki Murakami,* Masanobu Tani, Kenjiro Tanaka, and Yuusaku Yokoyama
*School of Pharmaceutical Sciences, Toho University, 2-2-1, Miyama, Funabashi, Chiba 274-8510, Japan
Abstract
Reaction of ethyl indole-2-carboxylates (1) with carboxylic acids in acetonitrile, using trifluoroacetic anhydride-phosphoric acid gave the ethyl 3-acylindole-2-carboxylates (2) in satisfactory yields. The present method provides a simple general method for acylation of ethyl indole-2-carboxylates.
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■ Hypotensive Constituent, Kuwanon H, a New Flavone Derivative from the Root Bark of the Cultivated Mylberry Tree (Morus alba L.)
Taro Nomura,* Toshio Fukai, and Toshiharu Narita
*School of Pharmaceutical Sciences, Toho University, 2-2-1, Miyama, Funabashi, Chiba 274-8510, Japan
Abstract
A new flavone derivative, containing condensed dihydrochalcone partial structure named kuwanon H, was isolated from the root bark of the cultivated mulberry tree (a variety of Morus alba L.). The structure was shown to be I on the basis of chemical and spectral data. The compound (I) to rabbit (1 mg/Kg, i.v.) produced a significant hypotension.
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■ Nitrogen Bridgehead Compounds. Part 15. Halogenation of 4-Oxo-6,7,8,9-tetrahydropyrido[1,2-a]pyrimidine-3-carboxylic Acids
István Hermecz,* Tibor Breining, Zoltán Mészáros, Gábor Tóth, and István Bitter
*CHINOIN Pharmaceutical and Chemical Works Ltd., P. O. Box 110, H-1325 Budapest, Hungary
Abstract
9-Monochloro- and 9,9-dichloro- and bromo-derivatives (3-6) can be prepared from title compounds. Stereochemistry of the halogenation and the product was studied.
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■ A Convenient Preparation of 2-Hydroxydibenzofuran from 2,2’-Dihydroxy-3,3’,5,5’-tetra-tert-butylbiphenyl in Two Steps
Masashi Tashiro,* Haruo Yoshiya, and Gouki Fukata
*Research Institute of Industrial Science, Faculty of Engineering, Kyushu University, 6-1, Kasuga-koen, Kasuga 816-8580, Japan
Abstract
Bromination of 2,2’-dihydroxy-3,3’,5,5’-tetra-tert-butylbiphenyl (2) with bromine in alcohols such as methanol and ethanol afforded the corresponding 1-bromo-2-alkoxy-4,5,7-tri-tert- butyldibenzofurans (5). The AlCl3 catalyzed reaction of 5a (R = CH3) in boiling toluene gave 2-hydroxydibenzofuran (7) in 79% yield. The mechanism of the formation of 5 from 2 was also discussed.
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■ High-pressure Reactions of Quinazoline and Indoles with Dimethyl Acetylenedicarboxylate
Kiyoshi Matsumoto,* Shun’kichi Nakamura, Takane Uchida, and R. Morrin Acheson
*Graduate School of Human and Environmental Studies, Kyoto University, Yoshida-Nihonmatsu-cho, Sakyo-ku, Kyoto 606-8501, Japan
Abstract
4-Ethoxy8-methylquinazoline, inert at 1 bar, with dimethyl acetylenedicarboxylate at 10 kbar gave tetramethyl 6-ethoxy-10-methyl-4aH-pyrido[1,2-a]quinazoline-2,3,4,4a-tetracarboxylate. 10 kbar pressure gave one new product from this acetylene and indole.
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■ Pyrolysis of Azido-diphenylpyrazines
Akihiro Ohta,* Tokuhiro Watanabe, Junko Nishiyama, Kozue Uehara, and Rei Hirate
*Department of Chemistry, University of Tsukuba, 1-1-1 Ten-nodai, Tsukuba-shi, Ibaraki, 305-8571, Japan
Abstract
The pyrolysis of 2-azido-3,5- (IIa), 2-azido-3,6- (IIb), and 2-azido-5,6-diphenylpyrazines (IIc), prepared from the corresponding 2-chloro-diphenylpyrazines and sodium azide, led respectively to 1-cyano-diphenylimidazoles (IIIa, IIIb, and IIIc) in good yields. The structure elucidation of the products is described.
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■ Facile Synthesis of Carbapenem Antibiotics. The First and Simple Stereoselective Synthesis of Antibiotic PS-5 Benzyl Ester
Tetsuji Kametani,* Toshio Honda, Atsushi Nakayama, and Keiichiro Fukumoto
*Pharmaceutical Institute, Tohoku University, Aobayama, Sendai 980-8578, Japan
Abstract
Antibiotic PS-5 benzyl ester was stereoselectively synthesized by using a new carbon-carbon bond formation reaction at the C4-position of azetidin-2-one, as a key reaction.
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■ Flavone Glycosides from Lawsonia innermis
Muhammad Afzal,* Galib Al-Oriquat, Jassim M. Al-Hassan, and Nazar Muhammad
*Biochemistry Department, Kuwait University, Safat 13060, P.O. Box 5969, Kuwait
Abstract
Four flavone glycosides representing 5,7,4’ and 5,7,3’,4’-substitution have been isolated from Lawsonia innermis.
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■ Oxoanolobine, a New Oxoapphine Alkaloid from Guatteria melosma
Charles H. Phoebe, Jr., Paul L. Schiff, Jr., Joseph E. Knapp, and David J. Slatkin*
*Department of Pharmacognosy, School of Pharmacy, University of Pittsburgh, Pittsburgh, PA 15261, U.S.A.
Abstract
Oxoanolobine (1) , a new alkaloid from an alcoholic extract of Guatteria melosma Diels (Anonaceae), was characterized as 1,2-methylenedioxy-9-hydroxyoxoaporphine (10-hydroxy-8H-benzo[g]-1,3-benzodioxolo[6,5,4-de]quinolin-8-one) by physicochemical data and conversion to lanuginosine (2).
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■ Aurapin, a New Dihydroflavonol Glycoside and Other Flavonoids from Acinos alpinus
Pietro Venturella,* Aurora Bellino, Maria Luisa Marino, and Marco Sorrentino
*Dipartimento di Chimica Organica, Università digli Studi di Palermo, Via Archirafi 20 90123 Palermo, Italy
Abstract
A new dihydroflavonol glycoside has been isolated from Acinos alpinus and identified as 3-O-rhamnosyl-5-hydroxy-7,4’-dimethoxyflavanone on the basis of chemical and spectroscopic evidence.
Three known flavonoids (naringenin, taxifolin and neoponcirin) were additionally isolated from same source.
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■ Benzonorphan Related Compounds. XV. A Versatile Method for the Synthesis of Heteromorphans
Joan Bosch,* Josep Bonjoch, and Isabel Serret
*Laboratory of Organic Chemistry, Faculty of Pharmacy, University of Barcelona, Av. de Joan XXIII, s/n, 08028 Barcelona, Spain
Abstract
From 2-benzoyl-5-methyl-6-oxo-2-azabicyclo[3.3.1]nonane-7-carboxylate the preparation of 5-methyl substituted pyrazolo[3,4-f]-, pyrido[2,3-f]-, and indolo[2,3-f]morphans is described.
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■ The Nitration of Phenylpyrimidines
David Adams, Mohinder Dosanjh, and Derek T. Hurst*
*School of Analytical and Biological Chemistry, Kingston Polytechnic, Kingston-on-Thames, KT1 2EE, U.K.
Abstract
The nitration of 4-phenylpyrimidine using nitric acid/sulphuric acid at 0° has been shown to give 4-o-nitrophenylpyrimidine and 4-m-nitrophenylpyrimidine in the ratio of 4:6. Under similar conditions 5-bromo-2-phenylpyrimidine has given 5-bromo-2-o-nitrophenyl and 5-bromo-2-m-nitrophenylpyrimidine in the ratio of 3:7 and 5-chloro-2-phenylpyrimidine has given the 2-o-nitrophenyl and the 2-m-nitrophenyl isomers in the ratio of 3.5:6.5.
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■ Studies on Tocopherols. II. Convenient Synthesis of Tocopherols
M. Kajiwara,* O. Sakamoto, and S. Ohta
*Shiseido Laboratories, 1050 Nippa-cho, Kohoku-ku, Yokohama 223, Japan
Abstract
A convenient synthesis of tocopherols from methylbenzoquinone and isoprenyl alcohol in high yield is described.
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■ Synthesis of 2-(Phenylthiomethylene)oxapenam Derivatives
Sadao Oida,* Akira Yoshida, and Eiji Ohki
*Exploratory Chemistry Research Laboratories, Sankyo Co., Ltd., 1-2-58 Hiromachi, Shinagawa-ku, Tokyo 140-8710, Japan
Abstract
Copper-catalysed decomposition of azetidinone diazoketones 3a and 3c, resulted in the formation of 2-(phenylthiomethylene)oxapenams, 7a and 11, respectively. Similarly, decomposition of diazoketone 21b gave a mixture of 19 and 22 whose carboxylation afforded an oxapenam-3-carboxylic acid 23a, a novel clavulanic acid analog.
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■ Equilibrium Constants for Heterocyclic Cation. Pseudobase Equilibration
John W. Bunting*
*Department of Chemistry, University of Toronto, Tronto, Ontario, Canada
Abstract
A tabular compilation of pKR+ values is presented for cation-pseudobase equilibration by both heteroaromatic cations and non-aromatic heterocyclic cations in both aqueous and alcoholic solution. Acid dissociation constants (pKR-) are also given for alkoxide ion formation by heterocyclic pseudobases in aqueous solution.
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■ The Chemistry of the Acridizinium Ion
Sayeed-Din Saraf*
*Biochemistry Department, Kuwait University, Safat 13060, P.O. Box 5969, Kuwait
Abstract
This paper reviews the various methods for the preparation of the acridizinium ion. One of the most successful method involved the use of cyclic acetal 2-(1,3-dioxolan-2-yl)pyridine (9), since the resulting intermediate obtained on treatment with benzyl bromide or substituted benzyl bromides are well suited for cyclisation in hot polyphosphoric acid. Acridizinium benzologs have also been prepared by replacement of the benzyl halides by naphthyl or phenanthrylmethyl halides or the pyridine carboxaldehyde by isoquinoline 1- or 3-carboxaldehydes. The properties, such as, oxidation, reduction, reaction with bases and electrophilic reagents are all discussed in detail.