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. 6, No. 5, 1977
Published online:
■ Studies on Pyrimidine Derivatives. IV. Synthesis of Hydroxymethylpyrimidines by Means of the Homolytic Hydroxymethylation
Takao Sakamoto, Kazuko Konno, Takayasu Ono, and Hiroshi Yamanaka*
*Pharmaceutical Institute, Tohoku University, Aobayama, Sendai 980-8578, Japan
Abstract
2-Hydroxymethyl- and 4-hydroxymethyl-pyrimidines were synthesized in yield ranging from 28 to 93% by the reactions of some simple pyrimidine derivatives with the hydroxymethyl radical generated from methanol and ammonium peroxydisulfate.
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■ A Facile Synthesis of 1-(2-Tetrahydrofuryl)-5-fluorouracil (Ftorafur)
Tetsuji Kametani,* Kazuo Kigasawa, Mineharu Hiiragi, Kikuo Wakisaka, Osamu Kusama, Hideo Sugi, and Kumeo Kawasaki
*Pharmaceutical Institute, Tohoku University, Aobayama, Sendai 980-8578, Japan
Abstract
1- (2-Tetrahydrofuryl)-5-fluorouracil (1), a potent anti-tumor agent, was conveniently synthesized by the the condensation of 5-fluorouracil (2) with various 2-alkoxy-2,3,4,5-tetrahydrofurans (3a-j), and the best yield of 1 by this method was obtained in the reaction of 2-t-butoxy analog (3h).
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■ Studies on the Reactivity of Isoquinoline and Related Compounds. IV. Addition Reaction of Active Methylene Compounds with Isoquinline
Takayuki Shiraishi and Hiroshi Yamanaka*
*Pharmaceutical Institute, Tohoku University, Aobayama, Sendai 980-8578, Japan
Abstract
In connection with addition reaction of acetic anhydride to the isoquinoline nucleus, reaction of active methylene compounds with isoquinoline (I) in acetic anhydride was investigated. Thus, the N-acetyl-1,2-dihydroisoquinoline derivatives such as 1-acetonyl- (IV), 1-phenacyl-2-acetyl-1,2-dihydroisoquinoline (X), diethyl 2-acetyl-1,2-dihydro-1-isoquinolylmalonate (XII), and α-(2-acetyl-1,2-dihydro-1-isoquinolyl)phenylacetic acid (XIII) were obtained.
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■ Preparation and Some Reactions of o-Nitrosoaniline
Musa Z. Nazer, Makhluf J. Haddadin, Joanna P. Petridou, and Costas H. Issidorides*
*Department of Chemistry, American University of Beirut, Beirut, Lebanon
Abstract
Treatment of o-nitrosoaniline with benzofuran-3(2H)-ones in base gives the corresponding 3-(o-hydroxyphenyl)quinoxaline 1-oxides in good yield. The reaction of o-nitrosoaniline with benzoin gives a mixture of the mono- and di-N-oxides of 2,3-diphenylquinoxaline. o-Nitrosoaniline reacts readily with benzaldehyde to give 1-hydroxy-2-phenylbenzimidazole.
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■ Convenient Synthesis of Nicotinamide Derivatives
Takushi Kurihara* and Toshiko Uno
*Faculty of Pharmaceutical Science, Osaka University of Pharmaceutical Sciences, 4-20-1 Nasahara, Takatsuki, Osaka 569-1094, Japan
Abstract
A one-step synthesis of 5-acetyl-4-ethoxycarbonyl-2-methylnicotinamide (IV) by the reaction of ethyl 3-ethoxymethylene-2,4-dioxovalerate (I) with β-aminocrotonamide (II) was described, and this was easily converted to nicotinamide derivatives (VI, VII, and VIII).
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■ Lactonalkaloide aus Amaryllidaceen
Werner Döpke*
*Fachbereich Chemie, Humboldt-Universität Berlin, Hessische Strasse 1-2, D-10115 Berlin, Germany
Abstract
In dem folgenden Artikel wird elne kurze Übersicht übsr die zur Zeit bekannten Lacton- Lactol- Alkaloide aus der Familie der Amaryllidaceen gegeben. Es werden die wich-tigsten Strukturableitungen von Basen, die nahe mit dem Clivonin verwandt sind abgehandelt. Schließlich werden die wichtigsten Fragmentierungen im Massenspektrometer sowie die mÜgliche Biosynthese diskutiert.
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■ Rearrangementws of t-Amine Oxides
Shigeru Oae* and Kenji Ogino
*Department of Chemistry, University of Tsukuba, 1-1-1 Ten-nodai, Tsukuba-shi, Ibaraki, 305-8571, Japan
Abstract
Heteroaromatic N-oxides and related tertiary amine oxides react with acylating agents and undergo various reactions depending upon the nature of the amine oxides, acylating agents,etc. These reactions are broadly divided into the following five basic types of reactions: 1) deoxygenative reduction, 2) rearrangement to ring carbon, 3) rearrangement to side chain carbon, 4) other heteroaromatic rearrangements, 5) rearrangements of open-chain N-oxides.
Each of these five representative reactions are illustrated by numerous examples, including many of our mechanistic investigations, hoping eventually to serve as nice guides to new synthetic inventions and innovations. The contents of this review are the following:
1. Introduction
2. Deoxygenative Reduction of N-oxides
3. Reactions with acylating agents : Rearrangements to heteroaromatic ring
4. Reactions with acylating agents : Rearrangements to alkyl side-chain
5. Other related rearrangements of heteroaromatic N-oxides
6. Reactions of non-heteroaromatic N-oxides with acylating agents : Aliphatic t-amine
oxides, nitrones and azoxybenzenes
7. Acknowledgement