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. 2, No. 4, 1974
Published online:
■ Photo-Fries Rearrangement of Heteroaromatic Acid Phenyl Esters
Yuichi Kanaoka* and Yasumaru Hatanaka
*Faculty of Pharmaceutical Sciences, Hokkaido University, Sapporo 060-0812, Japan
Abstract
Photolysis of the phenyl esters of pyridine-carbaxylic acids 1a-b and furan-2-4a, thiophene-2-4b, and N-methylpyrrole-2-carboxylic acids 4c afforded the correspanding o- and p-hydroxyketones 2, 3, 5, 6.
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■ Three New Bridged Isoquinoline Alkaloids
Maurice Shamma* and Jerome L. Moniot
*Department of Chemistry, The Pennsylvania State University, University Park, Pennsylvania 16802, U.S.A.
Abstract
Bisnorthalphenine (1), thaliglucine methochloride (4), and thaliglucinone methochloride (6), have been obtained from Thalictrum polygamum Muhl. (Ranunculaceae).
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■ Abnormal Hofmann Degradation of Tetrahydroprotoberberinium Salts
Tetsuji Kametani,* Makoto Takemura, Keiichiro Fukumoto, Tsunekazu Terui, and Atsuko Kozuka
*Pharmaceutical Institute, Tohoku University, Aobayama, Sendai 980-8578, Japan
Abstract
Hofmann degradation of 7,8,13,13a-tetrahydro-9-hydroxy-2,3,10-trimethoxy-7-methylprotoberberinium iodide (2) with methanolic potassium hydroxide gave 1,2,3,4-tetrahydro-1-(3-hydroxy-4-methoxy-2-methoxymethylbenzyl)-6,7-dimethoxy-2-methylisoquinoline (13) in addition to the normal methine base (7). Abnormal Hofmann degradation was observed with nandinine methiodide (4) and its isomer (5). Moreover, this communication discusses the reaction mchanism of the abnormal Hofmann degradation and the biogenesis of the protoberberine alkaloid mecambridine (19).
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■ A New Type of Purine Cyclonucleoside: 5’-O-Trityl-3’,6-anhydro-7-α-D-arabinofuranosylhypoxanthine
Yoshihisa Mizuno,* Yoshibumi Watanabe, Kazuyoshi Ikeda, and James A. McCloskey
*Faculty of Pharmaceutical Sciences, Hokkaido University, Sapporo 060-0812, Japan
Abstract
A new type of purine cyclonucleoside, 5’-O-trityl-3,6-anhydro-7-α-D-arabinofuranosylhypoxanthine (I) was synthesized. This nucleoside was unusual in that VI was quite stable toward aqueous base and acid and absorbed ultraviolet light at a longer wavelength than the corresponding “parent” nucleoside.
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■ Reaction of N-Arylhydroxylamines with Ethyl Acetoacetate
Seitaro Saeki, Mitsuo Hayashida, Takayuki Sukamoto, and Masatomo Hamana*
*Faculty of Pharmaceutical Sciences, Kyushu University, 3-1-1 Maidashi, Higashi-ku, Fukuoka 812-8582, Japan
Abstract
Reaction of N-p-tolylhydroxylamine (Ia) with ethyl acetoacetate (II) at room temperature for 30 days or in boiling ether for 5 h affords 2,5-dimethyl-3-ethoxycarbonylindole (IIIa), N-p-tolyl-2,4-dimethyl-3,5-diethoxycarbonylpyrrole (IVa) and azoxy-p-touene (Va). Some other N-arylhydroxylamines also undergo similar reaction.
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■ A Novel Synthesis of Pyrimidines. I. Cyclization of Cyanoacetylcynamides and Their Derivatives
Tadamasa Hirayama,* Masahiro Kamada, Hideaki Tsurumi, and Masataka Mimura
*Central Research Laboratoeies, Daiichi Pharmaceutical Co., Ltd., 16-13, Kitakasai 1-chome, Edsogawa-ku, Tokyo 134, Japan
Abstract
Cyclization reaction of cyanoacetylcyanamides (III) and their derivatives (V) has been found to give three types of halogeno- and alkoxy-pyrimidines (IV,VI,VII).
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■ A Novel Synthesis of Pyrimidines. II. Cyclization of N-Cyano-cyanoacetamidines
Tadamasa Hirayama,* Masahiro Kamada, and Masataka Mimura
*Central Research Laboratoeies, Daiichi Pharmaceutical Co., Ltd., 16-13, Kitakasai 1-chome, Edsogawa-ku, Tokyo 134, Japan
Abstract
Cyclization reaction of N-cyano-cyanoacetamidines (III) with hydrogen chloride and bromide has been found to give 4,6-diamino-2-halogenopyrimidines (IV), but with hydrogen iodide to give an unexpected 4-amino-6-iodopyrimidine (V).
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■ A Novel Synthesis of Pyrimidines III. Cyclization of Alkyl N-Cyano-cyanoacetimidates
Tadamasa Hirayama,* Masahiro Kamada, Masataka Mimura, and Hideaki Tsurumi
*Central Research Laboratoeies, Daiichi Pharmaceutical Co., Ltd., 16-13, Kitakasai 1-chome, Edsogawa-ku, Tokyo 134, Japan
Abstract
Cyclization reaction of N-cyano-cyanoacetimidates (III) with hydrogen halides has been found to give a mixture of 4-alkoxy-6-amino-2-halogenopyrimidines (IV) and 4-alkoxy-2-amino-6-halogenopyrimidines (V). In the presence of a Lewis acid with hydrogen chloride, this reaction proceeded in one specific direction to give IV.
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■ Reaction of Carbenes with 1,3-Disubstituted Uracil Derivatives
Herman P. M. Thiellier, Alida M. van den Burg, Gerrit-Jan Koomen, and Upendra K. Pandit*
*Organic Chemistry Laboratory, University of Amsterdam, Nieuwe Achtergracht 129,1018 WS Amsterdam, The Netherlands
Abstract
A general approach for the synthesis of 7-substituted 5,6-methano-5,6-dihydrouridine (1) derivatives is described.
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■ Recent Progress in the Mass Spectrometry of Heterocyclic Compounds
Tarozaemon Nishiwaki*
*Department of Chemistry, Faculty of Science, Yamaguchi University, 1677-1 Yoshida, Yamaguchi 753-8512, Japan
Abstract
Mass spectrometry of heterocyclic compounds is reviewed with respect to (1) hydrogen scramblings and skeletal rearrangements, (2) ion structures, and (3) fragmentations. The fragmentations reviewed here are those of azoles, pyridine-carboxylic acids, polyazaindenes and related compounds, seven- and eight-membered heterocyclic rings, chromene derivatives, and heterocyclic rings containing the Group IV and V elements as a heteroatom.
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■ On the Reaction of Azolium Ylides with Dialkyl Acylphosphonate; A New Synthesis for Heterocyclic Compounds
Akira Takamizawa,* Hiroshi Harada, Hisao Sato, and Yoshio Hamashima
*Shionogi Research Laboratories, Shionogi & Co. Ltd., Fukushima-ku, Osaka 553-0002, Japan
Abstract
Azolium ylides react with dialkyl acylphosphonate to form generally six membered azine derivatives by ring expansion of the azolium heterocycle. This article gives a survey of the reaction with thiazolium, thiadiazolium, oxazolium, oxadiazolium, and imidazolium, and also discusses the relationship of the nature of 4’-substituents to the stability and reactivity of thiamine and its analogues in this novel reaction.