HETEROCYCLES
An International Journal for Reviews and Communications in Heterocyclic ChemistryWeb Edition ISSN: 1881-0942
Published online by The Japan Institute of Heterocyclic Chemistry
Special Issue
Tetsuo Nozoe's Special Issues, Vol. 11, No. 1, 1978
Published online:
■ Studies on Ketene and Its Derivatives (XCIII). Reaction of Ketene with Isoquinolinium Methylides
Tetsuzo Kato,* Takuo Chiba, Shigeru Tanaka, and Toshiki Sasaki
*Pharmaceutical Institute, Tohoku University, Aramaki, Aoba-ku, Sendai 980-8578, Japan
Abstract
Reaction of ketene with isoquinolinium cyano(ethoxycarbonyl)methylide (1) gave rise to ethyl 3-cyano-2,3-dihydro-2-oxopyrrolo[2,1-a]isoquinoline-3-carboxylate (6). On the other hand, isoquinolinium bis(ethoxycarbonyl)methylide (2) reacted with ketene to give diethyl 4-methylene-2-oxo-1,2,4,5-tetrahydro-12bH-1,4-oxazepino[5,4-a]isoquinoline-5,5-dicarboxylate (7), which, on amnonolysis, was converted to 2-bis(ethoxycarbonyl)methyl-1,2-dihydroisoquinoline-1-acetamide (8).
Published online:
■ Migratory Aptitude of the Ethyl and the Methyl Groups during Stevens Rearrangement of N,N-Dialkyl-2-arylbenzothiazolinium Salts
Kin-ya Akiba,* Yoshio Ohara, and Naoki Inamoto
*Department of Chemistry, Faculty of Science, University of Tokyo, 7-3-1 Hongo, Bunkyo-ku, Tokyo 113-0033
Abstract
Stereochemical relation between the migrating group on the ammonium nitrogen and the carbanion was investigated on Stevens rearrangement of N,N-dialkylbenzothiazolinium salts to show large migratory aptitude of the ethyl against the methyl group (Et: Me > 20:1), where cyclic ammonium ylide with planar π-type carbanion was proposed to be the intermediate.
Published online:
■ Synthesis of Adamantane Derivatives. 44. Facile Synthesis of Some Homoadamantano[4,5]fused Heterocycles by the 1,3-Dipolar Cycloaddition and the Hoch-Campbell Reaction
Tadashi Sasaki,* Shoji Eguchi, and Soji Hattori
*Faculty of Engineering, Nagoya Institute of Technology, Gokiso-cho, Showa-ku, Nagoya 466-8555, Japan
Abstract
Homoadamantano[4,5]fused heterocycles 2, 3, 5 and 7 were obtained by the 1,3-dipolar cycloadditions of homoadamant-4-ene (1), and 2’-substituted homoadamantano[4,5-b]aziridines 9a-c were obtained by the Hoch-Campbell reaction of homoadamantan-4-one oxime (8).
Published online:
■ A Base-catalyzed Rearrangement of Dibenzotropone Oxide
Takahiro Tezuka,* Miyoshi Shinba, and Yasushi Nagai
*Department of Chemistry, University of Tsukuba, 1-1-1 Ten-nodai, Tsukuba-shi, Ibaraki, 305-8571, Japan
Abstract
Dibenzotropone oxide (1) rearranges to dihydrophenanthrene derivative (4) in reaction catalyzed by a base, while 1 gives methylphenanthrol (6) by thermal reaction. Mechanistic paths of these reactions are discussed.
Published online:
■ Formation of 1,3-Dimethyllumazine-6-aldoxime by a Novel Cyclization Reaction
Herbert Fuchs and Wolfgang Pfleiderer*
*Fachbereich Chemi, Universität Konstanz, Postfach 7733, D-7750 Konstanz, Germany
Abstract
Nitrosation of 6-allylamino-1,3-dimethyluracil (1) in aqueous solution caused a novel ring closure forming 1,3-dimethyllumazine-6-aldoxime (5) whereas the reaction in aprotic solvents led to 8-vinyl-theophylline (11). 1,3-Diphenyl- (2), 1-methyl- (3) and 1-benzyl-6-allylaminouracil (4) react normally with nitrosation at C-5 followed by cyclization on heating to the corresponding 8-vinyl-xanthines 12 - 14.
Published online:
■ EPR Evidence for Dimer Formation of Cu(II) Tetra(4-sulfonatophenyl)porphyrin Sodium Salt in Aqueous Solutions
Makoto Chikira and Hideo Kon*
*Laboratory of Chemistry, Metabolism and Digestive Diseases, National Institute of Arthritis, Bethesda, Marylanf 20014, U.S.A.
Abstract
EPR evidence is presented to show, for the first time, that the water soluble meso-aryl-porphyrin Cu(II) complex forms a non-covalent tight dimer. Analysis of the spectrum gave the Cu-Cu distance (4.9A) and the angle between the g axis and the Cu-Cu axis (33°). Mode of interaction of added imidazole with the aggregates is also discussed.
Published online:
■ Condensation of 1,4-Diols to Tetrahydrofurans Induced by N,N-Diethylphosphoramidic Dichloride
Hsing-Jang Liu,* Wing Hong Chan, and Sing Ping Lee
*Department of Chemistry, University of Alberta, Edmonton, Alberta, T6G 2G2, Canada
Abstract
A simple and efficient procedure has been developed for the condensation of 1,4-diols to tetrahydrofurans using N,N-diethylphosphoramidic dichloride as a reagent.
Published online:
■ Seven-membered N-Heterocycles. XIV. Syntheses of 6,7,8,9-Tetrahydro-5H-pyrido[2,3-d]azepines
Hiroshi Yamamoto,* Heizan Kawamoto, Shiro Morosawa, and Akira Yoko
*Department of Chemistry, Faculty of Science, Okayama University, 3-1-1 Tsushima-naka, Okayama 700-8530, Japan
Abstract
A variety of the title pyrido-azepines (5, 6) were synthesized by utilizing diethyl hexahydro-4-oxo-1H-azepine-1,5-dicarboxylate (2d) as the starting material. The structures of these new heterocyclic compounds are established by spectroscopic methods.
Published online:
■ Seven-membered N-Heterocycles. XV. Ethyl 2-Phenyl-7H-pyrimido[4,5-d]azepine-7-carboxylate
Hiroshi Yamamoto,* Takao Komazawa, Kazuyuki Nakaue, and Akira Yokoo
*Department of Chemistry, Faculty of Science, Okayama University, 3-1-1 Tsushima-naka, Okayama 700-8530, Japan
Abstract
The title azepine (6) was derived from the 6,7,8,9-tetrahydro-5H-pyrimido[4,5-d]azepine (2) via 6,7-dihydro-5H-derivative (3a) by the stepwise dehydrogenation. The 8,9-dihydro-7H-pyrimidoazepine (4a) was also prepared. The structures are discussed on the basis of uv, ir, and nmr spectra.
Published online:
■ A New Synthesis of Dihydroisocoumarin Derivatives
Hiroshi Horino and Naoto Inoue*
*Department of Chemistry, College of General Education, Tohoku University
Abstract
Dihydroisocoumarin derivatives including phyllodulcin analogues were synthesized in one step by the reaction of styrenes with o-carboxyphenylpalladium chloride.
Published online:
■ Synthesis of Heptafulvalene and Sesquifulvalene Derivatives Condensed with a Furan Ring
Toyonobu Asao,* Noboru Morita, and Kazuo Kato
*Department of Chemistry, Graduate School of Science, Tohoku University, Aobayama, Sendai 980-8578, Japan
Abstract
Heptafulvalenes (4 and 5) and sesquifulvalenes (8 and 9) condensed with a furan ring have been synthesized by the reaction of cyclic ketenes with furotropones. Physical properties of the fulvalenes were found to be considerably similar to those of the corresponding carbocyclic fulvalenes.
Published online:
■ Syntheses, Photochemical and Thermal Isomerizations of Pyrazolotropilidenes and Pyrazolonorcaradienes
Tsutomu Miyashi, Yoshinori Nishizawa, and Toshio Mukai*
*Department of Chemistry, Faculty of Science, Tohoku University, Aoba-ku, Ssendai 980-8578, Japan
Abstract
Syntheses of several pyrazolotropilidene derivatives (2, 3, 4 and 6) and irradiation of the phenyl derivative (2) were studied to know the effect of the fused pyrazole ring on photochemical and thermal valence isomerizations of pyrazolonorcaradienes (7 and 8).
Published online:
■ 10-Mesity-9-arsaanthracene
Ruud J. M. Weustink, Pieter J. A. Geurink, and Friedrich Bickelhaupt*
*Scheikundig Laboratorium, Vrije Universiteit, De Boelelaan, 1083 NL-1081 HV Amsterdam, The Netherlands
Abstract
The highly sterically hindered, 10-mesityl-9-arsaanthracene (1c) has been prepared by pyrolysis of the dihydro-precursor (3). Due to steric hindrance at the 10-position, 1c is the most stable of all known derivatives of arsaanthracane; even the Diels-Alder reaction with maleic anhydride is slow and reversible at ambient temperatures, leading to the 9,10-adduct 4. At higher temperatures, an alternative Diels-Alder reaction yields the 1,4-adduct 5, the first known derivative of arsanaphthalene. The carbon analog 6 of 1c gives the corrasponding 1,4-adduct 7.
Published online:
■ Synthetic Studies on β-Lactam Antibiotics 8. A Useful Method for Preparation of Penicillin α-Sulfoxides
Shoichiro Uyeo,* Tsutomu Aoki, and Wataru Nagata
*Shionogi Research Laboratories, Shionogi & Co. Ltd., Fukushima-ku, Osaka 553-0002, Japan
Abstract
A useful method for preparation of 2β-functionalized-methyl penicillin α-sulfoxide 4 is described.
Published online:
■ Syntheses and Reactivity of 1,2,4-Thiazolo[2,3-a]pyridines and Some Related Systems
Bojan Vercek, Branko Stanovnik, and Miha Tisler*
*Department of Chemistry, University of Ljubljana, 61000 Ljubljana, Slovakia
Abstract
Treatment of N-ethoxycarbonylmethyl-N’-(pyridyl-2)thiourea and derivatives (1) with bromine yielded 1,2,4-thiadiazolo[2, 3-a]pyridines (2) in good yield. Other synthetic paths to 6 and the tricyclic compound 11 as well as some other transformations are described.
Published online:
■ The Sensitized Photooxidation of 7,7-Bicycloheptatrienyl: Formation of Double (4+2)π Type Peroxides together with Biphenyl and 7-Phenylcycloheptatriene
Hitoshi Takeshita* and Akira Mori
*Instituete of Advanced Material Study, Kyushu University, 6-1, Kasuga-koen, Kasuga 816-8580, Japan
Abstract
In the presence of Methylene Blue, photooxygenation of the title olefin gave several double (4+2) π-cycloadducts with oxygen. Structures of these products were deduced by analysis of the 1H- and 13C-NMR spectra. In addition, formation of biphenyl, 7-phenylcycloheptatriene and its oxidation products in the reaction invalidated the previously proposed mechanism for the tropone formation.
Published online:
■ Low-temperature Characterization of a Dioxetane Produced in the Sensitized Photooxygenation of a Vinylcyclopropane, 3,10-Dispirocyclopropyltricyclo [5.2.1.02,6] deca-4,8-diene
Hitoshi Takeshita,* Toshihide Hatsui, and Hiroaki Mametsuka
*Instituete of Advanced Material Study, Kyushu University, 6-1, Kasuga-koen, Kasuga 816-8580, Japan
Abstract
The sensitized photooxidation of the title olefin at -80 °C was, contrary to the results of the reaction at room temperature, shown to afford only the dioxetane and its cleavage product, regardless of the sensitizers and the solvent used. Low-temperature characterization of the product by means of 1H- and 13C-NMR as well as some chemical transformations confirmed the occurrence of the (2+2) π-cycloaddition mode in the singlet oxygen oxidation of vinylcyclopropanes.
Published online:
■ A Combined 1,2-Oxygen and 1,4-Carbonyl Group Transposition in Tetralones via Heterocyclic Intermediates
Werner Tochtermann* and Heinke Timm
*Institut für Organische Chemie der Universitat, Karlstraβe 23, D - 8000 München 2, Germany
Abstract
The conversions of the oxanorbornadiene 1 to the hydroxy-tetralones 2 and 3 are described. The sequence 1 → 3 includes a combined 1,2-oxygen and 1,4-carbonyl group transposition.
Published online:
■ Synthesis and Cycloaddition Reactions of Di- and Trisubstituted 1,3-Oxazepine Derivatives
Takashi Toda,* Takeo Takase, Toshio Mukai, and Yoshizo Suzuki
*Department of Chemistry, Faculty of Science, Tohoku University, Aoba-ku, Ssendai 980-8578, Japan
Abstract
The reactions of pyrylium salts and sodium azide are proven to be a general synthetic method for di- to pentaphenyl-1,3-oxazepines. Cycloadditions of mono-, di-, and triphenyl-1,3-oxazepines with cyclopentadienone and triazoline derivatives were also investigated.
Published online:
■ 13C-NMR Spectra of Aromatic N-Oxides
Harald Günther* and Angela Gronenborn
*Institute of Organic Chemistry, University of Cologne, Greinstrasse 4, D-50939 Köln, Germany
Abstract
The 13C-NMR spectra of six aromatic N-oxides have been measured and assigned. Empirical substituent effects on carbon chemical shifts in α-, β-, and γ-positions to the NO-group are derived. A strong shielding effect for carbons in peri-position is found.
Published online:
■ Preferential Cleavage of the Methoxyl Group Adjacent to a Phenolic Function in Polymethoxylated Isoquinolines
Jay P. O’Brien* and Sidney Teitel
*Chemical Research Department, Hoffmann - La Roche Inc., Nutley, New Jersey 07110, U.S.A.
Abstract
Boron trichloride selectively O-demethylated the methoxyl group adjacent to a phenolic function in various polymethoxylated isoquinolines to afford the corresponding catechol in excellent yield. While the carhoxylic ester in (9) was unaffected by the reaction conditions, the methylenedioxy moiety in (11) was more labile than the methoxyl ortho to the phenol. The utility of the method was demonstrated by the facile synthesis of the alkaloid dicentrine (16).
Published online:
■ Novel Oxidative Cyclization of Bridged Secondary Alcohols with Ceric Ammonium Nitrate
Yutaka Fujise,* Etsuko Kobayashi, Hisatoshi Tsuchida, and Sho Ito
*Department of Chemistry, Tohoku University, Aoba-ku, Ssendai 980-8578, Japan
Abstract
The formation of 5-membered ring ether, on unprecedented reaction of ceric ammonium nitrate on secondary alcohols, has been observed in five cases. Possible mechanisms were proposed.
Published online:
■ Concerning the Inhibition of Singlet Oxygen Attack on Compounds Containig Urazole Rings
Guy Kretschmer and Leo A. Paquette*
*Evans Chemical Laboratories, The Ohio State University, 120 W. 18th Avenue, Columbus, Ohio 43210, U.S.A.
Abstract
The urazole ring is shown not to be an efficient quencher of singlet oxygen; however, electrophilic attack by 1O2, on a double bond situated in a urazole-containing molecule may be entirely suppressed or retarded depending upon distance because of the powerful electron-withdrawing inductive effect of this heterocyclic unit.
Published online:
■ Macrocycles from Bifunctional 1,2-Bis(stryl)benzenes and Some Aza Analogues
Peter Skrabal and Heinrich Zollinger*
*Laboratorium für Organische, Eidgenössischen Technischen Hochschule, Universitatstrasse 16,8092 Zürich, Switzerland
Abstract
The diamines 1 - 3 and the dialdehyde 4 have been synthesized. From these compounds the macrocycles 6, 7, 9, 10, 14 and 15 have been obtained. Fundamental aspects of cyclisation reactions of this type are discussed.
Published online:
■ A Preliminary Study on Phase-tranfer Catalyzed Reaction of Aromatic N-Oxide Derivatives. Reaction of 4-Chloroquinoline 1-Oxide with Carbanions
Masatomo Hamana,* Fuminori Sato, Yoshio Kimura, Makoto Nishikawa, and Hiroshi Noda
*Faculty of Pharmaceutical Sciences, Kyushu University, 3-1-1 Maidashi, Higashi-ku, Fukuoka 812-8582, Japan
Abstract
A solution of 4-chloroquinoline 1-oxide (1) and α-phenylpropionitrile in benzene was treated with 50% sodium hydroxide and a catalytic amount of tetrabutyl-ammonium bromide at 50° for 8 hr with vigorous stirring to produce 4-(α-cyano-α-phenyl)ethylquinoline 1-oxide in 72% yield. Reactions of 1 with butyl vinyl ether adducts of some aromatic aldehyde cyanohydrins under the same conditions gave, after hydrolysis with hot 10% hydrochloric acid, 4-aroylquinoline 1-oxides.
Published online:
■ Flash Vacuum Pyrolysis of 3,5-Disubstituted β-Phenethylsulfonyl Azides
Rudolph A. Abramovitch* and Shigeo Wake
*Department of Chemistry, University of Alabama, Box 870336, University, Tuscaloosa, Alabama 35478-0336, U.S.A.
Abstract
Flash vacuum pyrolysis of 3,5-dimethyl-β-phenethylsulfonyl azide at 650° gives appreciable quantities of the normal nitrene cyclization products as well as some 2-cyclopropyl-3,5-dimethylpyridine. 3-Chloro-(5H)- and (7H)-pyrindine are obtained from 3,5-dichloro-β-phenethylsulfonyl azide. Possible mechanisms are proposed to account for the results.
Published online:
■ Thiabenzenes. XI. the Reaction between Thioxanthylium and Phenylmercaptide Ions
Charles C. Price* and Joanne Follweiler
*Department of Chemistry, University of Pennsylvania, 231 South 34th Street Philadelphia, PA 19104-6323, U.S.A.
Abstract
The main products of the titled reaction are thioxanthenone and thioxanthene. By chromatography, a small amount (0.5-1.5%) of a purple solid was obtained which had properties consistent with those expected for 10-phenylthio-10-thiaanthracene.
Published online:
■ Synthesis, Structure and Properties of Methyl-azuleno[1,8-cd]pyridazines
Klaus Hafner,* Hans Jörg Lindner, and Werner Wassem
*Institut für Organische Chemie, Technische Hochschule Darmstadt, Petersenstrasse. 22 D-6100 Darmstadt, Germany
Abstract
N-Substituted 2H-cyclopenta[d]pyridazines (6) possessing methyl groups in 1- and/or 4-positions are easily deprotonated by strong bases to anions of type (7) which react with derivatives of β-dicarbonyl compounds to the substitution products (11) and (17). Cyclization of these in the presence of acids afford 1,3,5-trimethyl- and 1,3-dimethylazuleno[l,8-cd]pyridazine (12) and (18). The structure of the novel heterocyclic azulenes was determined by spectroscopic methods as well as by an X-ray analysis of (12).
Published online:
■ Cycloaddition of Azepine Derivatives with Methoxycarbonyl-2-pyrones
Shigenori Iida,* Toshio Mukai, and Katsuhiro Saito
*Department of Chemistry, Faculty of Science, Tohoku University, Aoba-ku, Ssendai 980-8578, Japan
Abstract
Cycloaddition reactions of 5- or 3-methoxycarbonyl-2-pyrone with 1-ethoxycarbonyl-1H-azepine and 1-ethoxycarbonyl-1H-1,2-diazepine were investigated. The (4+2) and (4+6) type adducts such as 6, 7 and 10 were obtained in addition to the corresponding benzazepine derivatives, 3 and 4, which derived from the (4+2) type adducts.
Published online:
■ Stable 1H- and 2H-Isoindoles with Methyl Groups at the Carbocyclic System
Richard Kreher* and Karl Josef Herd
*Institut für Organische Chemie, Technische Hochschule Darmstadt, Petersenstrasse. 22 D-6100 Darmstadt, Germany
Abstract
4,5,6,7-Tetramethyl-2H-isoindole and 4,7- and 5,6-dimethyl-2H-isoindole are stable and isolable 10π-hetarenes, which can be prepared through a general and efficient route. The key step of the reaction sequence is the introduction of a cyclic carbon-nitrogen double bond via elimination of methanesulfinic acid. The spectroscopic properties of the tautomeric 2H- and 1H-isoindoles in solution and the chemical reactivity of the o-quinoid system towards dienophiles with an activated CC-double bond have been investigated and elucidated.