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. 19, No. 12, 1982
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■ Sulfer Dioxide Insertion into γ-Functional Vinylic Grinard Reagents. A Facile Synthesis of α,β-Unsaturated γ-Sultines and γ-Sultones
Elisabeth Thoumazeau, Bernard Jousseaume, Françoise Tiffon, and Jean-Georges Duboudin
*Ecole Nationale Spérieure de Chimie et Physique, Université de Bordeaux I, 351, cours de la Libération, 33405 Talence Cedex, France
Abstract
α,β-Unsaturated γ-sultines were synthesised by insertion of sulfur dioxide into γ-functional vinylic Grignard reagents generated by addition of aliphatic or aromatic organomagnesium compounds to α-acetylenic alcohols. These products are easily oxidized to the corresponding γ-sultones.
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■ Activated Nitriles in Heterocyclic Synthesis: A Novel Synthesis of Pyrazolo[5,6:3’,4’]pyrano[5,4-b]isoxazoles
Suzan Ibraheim Aziz, Bahia Yahia Riad, Hassan Attia Elfahham, and Mohamed Hilmy Elnagdi
*Chemistry Department, Faculty of Science, Minia University, Minia, Egypt
Abstract
A novel synthesis of pyrano[2,3-c]isoxazoles is reported via reaction of 4-arylidene-2-isoxazolin-5-ones with malononitrile and ethyl cyanoacetate. The synthesised isoxazole derivatives were converted into derivatives of new ring system pyrazolo[5,6:3’,4’]pyrano[5,4-b]isoxazole via reaction with hydrazine hydrate.
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■ Synthesis of Norrufescine
Mary D. Manachery, Michael P. Cava, Keith T. Buck, and William J. Prinz
*Department of Chemistry, University of Pennsylvania, 231 South 34th Street Philadelphia, PA 19104-6323, U.S.A.
Abstract
The phenolic azafluoranthene alkaloid norrufescine 1 has been synthesized. The key step in the synthesis involved the formation of the tetracyclic azafluoranthene nucleus by a novel aprotic thermolysis of a condensed triazine precursor.
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■ Cycloaddition Reactions of Thiazolium N-Dicyanomethylide with Olefinic Dipolarophiles
Otohiko Tsuge, Yoichi Shimizu, Hiroshi Shimoharada, and Shuji Kanemasa
*Research Institute of Industrial Science, Faculty of Engineering, Kyushu University, 6-1, Kasuga-koen, Kasuga 816-8580, Japan
Abstract
The cycloaddition reaction of a stable N-methylide, thiazolium N-dicyanomethylide, with acyclic olefinic dipolarophiles such as dimethyl fumarate, maleate, and trans-1,2-dibenzoylethylene proceeded in a stereoselective manner to give only the corresponding endo-[3 + 2] cycloadducts, all of which were stable in boiling tetrahydrofurn. In the reaction of the methylide with N-substituted maleimides, however, a mixture of endo- and exo-[3 + 2] cycloadducts, whose relative yields changed with the reaction time, was formed. The endo cycloadduct was found to isomerize into the exo cycloadduct in tetrahydrofuran even at room temperature.
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■ Simple Conversion of 8-Alkyl-8,14-cycloberbines to Spirobenzylisoquinolines by Regioselective C-N Bond Cleavage
Miyoji Hanaoka, Shun-ichiro Sakurai, Yuko Sato, and Chisato Mukai
*Faculty of Pharmaceutical Scicences, Kanazawa University, 13-1 Takara-machi, Kanazawa 920-0934, Japan
Abstract
On acidic treatment the 8-alkyl-8,14-cycloberbines (10) were converted easily to the spirobenzylisoquinolines (11, 12, or 13) in good yields. Reduction of 10 gave stereoselectively the diastereoisomeric alcohols (14 or 15) depending on the reagents, NaBH4 or LiA1H (OBUt)3, respectively. The both alcohols afforded also corresponding spirobenzylisoquinolines with acids.
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■ IAC Reactions in the Indole Series: Total Synthesis of Clavicipitic Acid
Alan P. Kozikowski and Michael N. Greco
*Department of Chemistry, University of Pittsburgh, Parkman Avenue & University Drive, Pittsburgh, PA 15260 , U.S.A.
Abstract
The first total synthesis of clavicipitic acid (1), a derailment product of ergoline biosynthesis, has been accomplished through an intramolecular azide cycloaddition reaction. The 3,4-disubstituted indole required for this work was assembled from indole-4-carboxaldehyde. The single imine generated from the [3+2] cycloaddition reaction was subjected to bromination, dehydrobromination, reduction and hydrolysis to afford clavicipitic acid (~1:1 mixture of the cis and trans-isomers).
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■ Photochemical Ring Opening Rreactions of 3-Alkoxyisocoumarin and 3-Halo-1-isoquinolone
Chikara Kaneko, Toshihiko Naito, and Chiemi Miwa
*Pharmaceutical Institute, Tohoku University, Aobayama, Sendai 980-8578, Japan
Abstract
Irradiation of 3-methoxyisocoumarin (1) in an alcohol afforded two kinds of diester of homophthalic acid (3 and 4) and the mechanism including novel 1,5-sigmatropic methoxy rearrangement from initially formed ketene (5) to the isomeric ketene (6) was proposed. Similar photochemical ring opening reaction of 3-chloro- and -bromo-1-isoquinolones (8 and 9) as well as their novel photoalkoxylation reaction is also described.
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■ A New Synthesis of (±)-Lysergic Acid
Toshiko Kiguchi, Chiyomi Hashimoto, Takeaki Naito, and Ichiya Ninomiya
*Kobe Women’s College of Pharmacy, Motoyamakita, Higashinad, kobe, Hyogo 658, Japan
Abstract
Reductive photocyclization of the enamide (2) followed by the ring opening of the resulting dihydrofuran derivative (4) completed a new total synthesis of (±)-lysergic acid.
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■ An Improved Conversion of 1,4,6-Trisubatituted 2(1H)-Pyrimidinones into the Corresponding Thiones
Akira Katoh, Choji Kashima, and Yoshimori Omote
*Department of Chemistry, University of Tsukubaa, 1-1-1 Ten-nodai, Tsukuba-shi, Ibaraki, 305-8571, Japan
Abstract
1,4,6-Trisubstituted 2(1H)-pyrimidinones (2a-j) are easily converted into the corresponding thiones (3a-j) in high yields by reacting with 2,4-bis(p-methoxyphenyl)-1,3,2,4-dithiadiphosphetane-2,4-disulfide (1). Further, other diazines, e.g., 2-methyl-6-phenyl-3(2H)-pyridazinone (4) and 1-methyl-5,6-diphenyl-2(1H)-pyrazinone (6) are also converted into the corresponding thiones 5 and 7 in 99 and 91% yield, respectively.
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■ The Revised Structure of Paniculine
Orland Muñoz and Mariano Castillo
*Departamento de Química, Facultad de Ciencias, Unversidad de Chile, Casilla 653, Santiago, Chile
Abstract
The original structure of paniculine has been revised based upon additional physical data.
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■ A Facile Conversion of the 1-Methyl Group to the 1-Amino Group of Xanthine Derivatives
Taisei Ueda, Noriichi Oda, Jinsaku Sakakibara, and Kazumi Takeya
*Faculty of Pharmaceutical Sciences, Nagoya City University, Tanabe-dori, Mizuho-ku, Nagoya 467-8603, Japan
Abstract
A facile conversion of the 1-methyl group to the 1-amino group of caffeine and its analogues was carried out by the reaction with hydrazine hydrate: Refluxing of caffeine(Ia) with a large amount of hydrazine hydrate (30 eq. mole) without any other solvents gave 1-amino-3,7-dimethylxanthine(IIa) in 40% yield. Similarly the reaction of 7-substituted 1,3-dimethylxanthines(Ib,Id-f) with hydrazine hydrate gave 7-substituted 1-amino-3-methylxanthines(IIb,IId-f) in 28-42% yield. Deamination of these 7-substituted 1-amino-3-methylxanthines (IIa-b, IId-f) gave the corresponding theobromine derivatives (IVa-b,IVd-f) in 90-96% yield.
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■ A Convenient Synthesis of 6-Methylellipticine and 6-Methylolivacine
Martin J. Wanner, Gerrit-Jan Koomen, and Upendra K. Pandit
*Organic Chemistry Laboratory, University of Amsterdam, Nieuwe Achtergracht 129, 1018 WS Amsterdam, The Netherlands
Abstract
Readily accessible 11-ketopyrido[4,3-b]carbazole derivatives 3a,b have been used as central intermediates for the synthesis of 6-methylellipticine and 6-methylolivacine.
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■ Demethylprotoemetinols from Alangium lamarckii
Esahak Ali, Radhika R. Sinha, Basudeb Achari, and Satyesh C. Pakrashi
*Indian Institute of Chemical Biology, Calcutta-700 032, India
Abstract
Structures of two new isomeric alkaloids isolated from the seeds of Alangium lamarckii have been established as 10-demethylprotoemetinol (10) and 9-demethylprotoemetinol (11).
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■ Syntheses of (—)-9-Demethylprotoemethinol and (±)- and (—)-10-demethylprotoemetinols
Tozo Fujii, Masashi Ohba, Hitoshi Suzuki, Satyesh C. Pakrashi, and Esahak Ali
*Faculty of Pharmaceutical Scicences, Kanazawa University, 13-1 Takara-machi, Kanazawa 920-0934, Japan
Abstract
The synthesis of (—)-9-demethylprotoemetinol (X) was achieved by LiAlH4 reduction of the (—)-tricyclic ester XIV followed by catalytic hydrogenolysis of the resulting (—)-tricyclic alcohol XI. Acetylation of (—)-X yielded the (—)-diacetate XVII. Parallel synthetic routes starting with the isomeric (±)- and (—)-tricyclic esters XV gave (±)- and (—)-10-demethylprotoemetinols (XII) and the corresponding diacetates [(±)- and (—)-XVIII] through the (±)- and (—)-tricyclic alcohols XIII, respectively.
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■ Double Ring-transformation of Uracils to Pyrazolones via Hydantoin Ring System
Kosaku Hirota, Yoshihiro Yamada, Jun-ichi Haruta, and Shigeo Senda
*Labolatory of Medicinal Chemistry, Gifu Pharmaceutical University, 6-1 Mitahora-higashi 5-chome, Gifu 502-8585, Japan
Abstract
Hydrazinolysis of 3-alkyl-1-aryl-5-bromo-6-methyluracil derivatives (1) causes a novel double ring-transformation to pyrazolones (2) via hydantoin ring system.
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■ Heterocyclic Quinones with Potential Antitumor Activity. A Convenient Synthesis of 5,6-Dimethyl-4,7-benzimidazolediones
Ippolito Antonini, Gloria Cristalli, Palmarisa Franchetti, Mario Grifantini, and Sante Martelli
*Department of Chemical Sciences, University of Camerino, Italy
Abstract
Simple syntheses of 1-substituted 5,6-dimethyl-4,7-benzimidazolediones (Ia-c) are described. The commercially available 5,6-dimethylbenzimidazole was alkylated and nitrated. The corresponding 4,7-dinitro derivatives were reduced to diamines and subsequently oxidized to quinones.
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■ A New Synthesis of γ-Ylidene-α,β-butenolides from 2-Nitro-5-furancarbaldehyde and Pyrazoles
Maria de Bernadi, Giovanni Vidari, and Paola Vita Finzi
*Dipartamento di Chimica Organica, Università di Pavia, V. le Taramelli 10, 27100 Pavia, Italy
Abstract
A new and rapid synthesis of 5-pyrazolylmethylene-2(5H)furanones by the reaction of 2-nitro-5-furancarbaldehyde (I) with different substituted pyrazoles (IIa-f) in acetic acid-acetic anhydride is described.
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■ Regioselective Functionalisation of the Δα,β-Butenolide Ring via Group IV-B Organometallics
Mariella Fiorenza, Alfredo Ricci, M. Novella Romanelli, Maurizio Taddei, Pasquale Dembech, and Giancarlo Seconi
*CNR, Centro di Studio Sulla Chimica e la Struttura dei Composti Eterociclici e lolo Applicazioni, c/o Dipartimento di Chimica Organica “Ugo Schiff”, Università di Firenze, Via Gino Capponi 9, I-50121 Firenze, Italy
Abstract
The Δα,β-butenolide ring reacts with amino- and thiosilanes to give 4-substituted γ-butyrolactone and siloxyfuran. The latter undergoes regiospecific functionalisation at the 5 position with benzaldehyde under F- catalysis.
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■ A Study of the Structure of 4-Arylazo Derivatives of 2-Phenyl-5-oxazolone
Ahmad S. Shawali, Abdou O. Abdelhamid, Nada F. Ahmad, and Cyril Párkányi
*Department of Chemistry, Faculty of Science, University of Cairo, Giza, Egypt
Abstract
Spectroscopic methods (1H NMR and IR) were used to determine the structure of the 4-arylazo derivatives of 2-phenyl-5-oxazolone. The data indicate that such compounds exist in the chelated hydrazone form 1A(z). The 15N isotopomer of compound 1a confirms the hydrazone structure. Also, the HMO method has been used to study tautomerism in such compounds. The results are in full agreement with the spectral data, the hydrazone form 1A(z) being most stable. It is further shown that both the intermolecular and intramolecular hydrogen bonding and electron-withdrawing substituents favor the hydrazone tautomer.
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■ Selective Preparation. 39. Preparation of Some Chlorodibenzofurans from 1-Hydroxy- and 2-Hydroxydibenzofuran
Masashi Tashiro and Haruo Yoshiya
*Research Institute of Industrial Science, Faculty of Engineering, Kyushu University, 6-1, Kasuga-koen, Kasuga 816-8580, Japan
Abstract
Some chlorodibenzofurans such as 1-chloro-, 2-chloro-, 1,2,4-trichloro- and 1,2,3-trichlorodibenzofurans were prepared from 1-hydroxy- and 2-hydroxydibenzofuran.
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■ Preparative Electrochemistry I. A Novel Electrochemical Oxodation of a 1,2,3,4-Tetrahydrocarbazole to a Carbazole Derivative
Gilbert Reymond, Janis Vasilevskis, and Voldemar Toome
*Roche Research Center, Hoffman-La Roghe Inc., Nutley, New Jersey 07110, U.S.A.
Abstract
Diethyl(6-chloro-1,2,3,4-tetrahydro-2-carbazolyl)methyl malonate can be oxidized via a four electron process at a platinum electrode in 0.1 M tetraethylammonium p-toluenesulfonate in methylene chloride to diethyl(6-chloro-2-carbazolyl)methyl malonate in 15% yield.
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■ Deterimination of Structures of Tri- and Tetrabromodibenzofurans Formed in Bromination of Dibenzofuran
Masashi Tashiro and Haruo Yoshiya
*Research Institute of Industrial Science, Faculty of Engineering, Kyushu University, 6-1, Kasuga-koen, Kasuga 816-8580, Japan
Abstract
Dibenzofuran reacted with bromine in the presence of Fe powder to afford tri- and tetrabromodibenzofurans and their structures were determined.
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■ Sindamine, Punjabine, and Gilgitine: Three New Secobisbenzylisoquinoline Alkaloids
John E. Leet, S. Fazal Hussain, Robert D. Minard, and Maurice Shamma
*Department of Chemistry, The Pennsylvania State University, York Campus, P1031 Edgecomb Avenue, York, Pennsylvania 17403, U.S.A.
Abstract
Three new secobisbenzylisoquinolines found in Berberis lycium Royle (Berberidaceae) are (+)-sindamine (3). (—)-punjabine (4) and (—)-gilgitine (5). Alkaloids 4 and 5 are the first seco dimeric alkaloids derived from in vivo oxidation of a bisbenzylisoquinoline precursor incorporating three diaryl ether bridges.