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. 3, 1982
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■ A Novel Synthesis of 5-Alkyl-6-cyano-2,3-dihydro-4H-1,4-thiazines
Z. Tanee Fomum, J. Tanyi Mbafor, Stephen R. Landor, and Phyllis D. Landor
*Department of Chemistry, Mona Campus, , University of the West Indies, Mona, Kingston 7, Jamaica
Abstract
4,4-Dialkylallenyl nitriles react with 2-aminoethanethiol in the presence of 2 equivalents of base to give 5-alkyl-6-cyano-2,3-dihydro-4H-1,4-thiazines and not 2-alkylthiazolines previously isolated with catalytic base.
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■ Synthesis of 32-Crown-8 Tetraester Compound: Model of Macrotetrolid Antibiotics
André Samat, Mohammed El Malouli Bibout, and José Elguéro
*Laboratoire de Chimie Moléculaire et Péttoléochimie, associé au C. N. R. S., Université d’Aix-Marseille II, rue H. Poincaré, 13397 Marseille Cedex 13, France
Abstract
A simple synthesis of a new thirty two membered macrocycle including height oxygen atoms (four ether, four esters) is described. This campound is a structural model of macrotetrolid nactins (ionophorous natural antibiotics)
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■ Mannich Cyclization Involcing the α-Position of Ketals: Synthesis of 2-Arly-4-piperidonesnand 2-Aryl-3-acylpyrrolidines
Joan Bosch, Mario Rubiralta, and Montserrat Moral
*Laboratory of Organic Chemistry, Faculty of Pharmacy, University of Barcelona, Av. de Joan XXIII, s/n, 08028 Barcelona, Spain
Abstract
A new method for the preparation of 2-aryl-4-piperidones and 2-aryl-3-acylpyrrolidines based on the acid-induced intramolecular cyclization between an iminium salt and the α-position of a ketal group is reported.
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■ Regioselective Reductions of Vinylogous Imides
Thomas A. Bryson and Ronald B. Gammill
*Department of Chemistry, University of South Carolina , Columbia, South Carolina 29208, U.S.A.
Abstract
The regiospecific reduction of unsymmetrical vinylogous imides was investigated. Controlled selective reduction was realized via employing neighboring group participation to effect reduction of the less reactive carbonyl group.
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■ 2-(2,6-Dimethylpiperidino)acetonitrile as an Acyl Carbanion Equivalent
Takeshi Wakamatsu, Junichi Kondo, Satoshi Hobara, and Yoshio Ban
*Faculty of Pharmaceutical Sciences, Hokkaido University, Kita 12 Nishi 6, Kita-ku, Sapporo, Hokkaido 060-0812, Japan
Abstract
Reaction of lithio 2-(2,6-dimethylpiperidino)acetonitrile with alkyl halides affords monoalkylation products which are easily hydrolyzed under mild conditions to give the homogeneous aldehyde or its acetal in moderate yield. In the case of alkyl halides having an electron donating group on aromatic ring the cyclization products are obtained.
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■ Synthesis of Optically Active 6-Hydroxyethyl Penems
Maurizio Foglio, Carlo Battistini, Franco Zarini, and Giovanni Franceschi
*Ricerca&Sviluppo Chimico, Farmitalia Carlo Erba SpA, Via dei Gracchi 35, 20146 Milano, Italy
Abstract
The synthesis of optically active 6-hydroxyethyl penems introducing the side chain by an aldol condensation on methyl penicillanate S-oxide is described.
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■ Cycloaddition Reactions of 1,3-Benzothiazines II. Reactions of 6,7-Dimethoxy-2H-1,3-Benzothiazine with Dimethyl Acetylenedicarboxylate and Other Dipolarophiles
Lajos Fodor, János Szabó, Gábor Bernáth, and Pál Sohár
*Institute of Pharmaceutical Chemistry, University Medical School, Szeged, Hungary
Abstract
New heterocyclic ring systems containing sulfur and nitrogen (3-6) have been synthesized by the reactions of 6,7-dimethoxy-2H-1,3-benzothiazine with dimethyl acetylenedicarboxylate and other dipolarophiles.
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■ The Crystal and Molecular Structure of 4,6,6-Trimethyl-2-phenyl-1,6-dihydropyrimidine
Alexander L. Weis and Felix Frolow
*Department of Organic Chemistry, Weizmann Institute of Science, Rehovot 76100, Israel
Abstract
An X-ray crystallographic study of dihydropyrimidine (III) has shown that in the solid state it exists in the 1,6-dihydro form (IIIb). Both tautomers IIIa and IIIb were detected by an NMR study of III in a DMSO-d6 solutions.
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■ Formation of Novel 1:3 Molar Adducts in the High Pressure Reaction of 2(1H)-Pyridones with Dimethyl Acetylenedicarboxylate
Kiyoshi Matsumoto, Yukio Ikemi, 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
The high pressure (10-15 kbar) reaction of N-substituted 2(1H)-pyridones possessing bulky groups such as cyclohexenyl, isopropyl, and phenyl with dimethyl acetylenedicarboxylate each yielded only one isomer of a 1: 3 molar adduct along with a 1: 1 adduct while N-methyl- and N-benzyl-2(1H)-pyridones each gave isomeric mixtures of 1: 3 molar adducts together with a 1: 1 molar adduct. The formation of these 1: 3 molar adducts is discussed.
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■ 3-Hydroperoxy-3-methyl-2-phenyl-3H-indole Thermal Decomposition and Chemiluminescence
Masako Nakagawa, Masakazu Sato, Yasuji Watanabe, Tohru Hino, Yasumaru Hatanaka, and Yuichi Kanaoka
*Faculty of Pharmaceutical Sciences, Chiba University, 1-33 Yayoi-cho, Inage-ku, Chiba 263-8522, Japan
Abstract
Thermolysis of 3-hydroperoxy-3-methyl-2-phenyl-3H-indole 1 in dimethyl sulfoxide showed chemiluminescence and 3-hydroxy-3-methyl-2-phenyl-3H-indole 2 was obtained whereas in methanol 1 was converted to o-benzamidacetophenone. Deoxygenation occurred to give 2-phenylskatole on the termolysis of 1 in benzene.
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■ Synthesis of Dutadrupine
François Tillequin, Geneviève Baudouin, and Michel Koch
*Laboratoire de Pharmacognosie, URA au CNRS n1310, Faculté des Sciences Pharmaceutiques et Biologiques, Université René Descartes, 4, Avenue de l’Observatoire, F-75006 Paris, France
Abstract
Dutadrupine (3) was synthetized by Claisen rearrangement of 7-(1,1-dimethylpropyn-1-oxy)-4-methoxyfuro[2,3b]quinoline (2) obtained by condensation of 7-hydroxy-4-methoxyfuro[2,3b]quinoline (1) with 3-chloro-3-methylbutyne.
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■ Alternative Total Synthesis of Elaeocarpus Alkaloids
Hirotaka Otomasu, Noriyuki Takatsu, Toshio Honda, and Tetsuji Kametani
*Hoshi University, 2-4-41 Ebara, Shinagawa-ku, Tokyo 142-8501, Japan
Abstract
An alternative synthesis of Elaeocarpus alkaloids using 1,3-dipolar cycloaddition of Δ1-pyrrolin-1-oxide with the enone to give the isoxazolidine as a key intermediate is described.
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■ Meldrum’s Acid in Organic Synthesis 3. Synthesis of 2-Substituted Indoles from Phenylhydroxylamine
Kunihiko Mohri, Yuji Oikawa, Ken-ichi Hirao, and Osamu Yonemitsu
*Faculty of Pharmaceutical Sciences, Hokkaido University, Kita 12 Nishi 6, Kita-ku, Sapporo, Hokkaido 060-0812, Japan
Abstract
Treatment of phenylhydroxylamine oxalate with acyl Meldrum’s acids in boiling acetonitrile readily gave N-acylacetylphenylhydroxylamines, which were converted to 2-substituted indoles by another treatment with acyl Meldrum’s acids in refluxing toluene. N-Benzoyl, N-acetyl, and N-benzyloxycarbonyl derivatives of phenylhydroxylamine were treated with phenylacetyl Meldrum’s acid in boiling benzene, followed by treatment with hydrochloric acid in ethanol to give the corresponding N-acyl-2-benzylindoles.
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■ Meldrum’s Acid in Organic Synthesis 4. Synthesis of 5-Substituted 2-Phenylisoxazolin-3-one from N-Acylacetylphenylhydroxylamines
Kunihiko Mohri, Yuji Oikawa, Ken-ichi Hirao, and Osamu Yonemitsu
*Faculty of Pharmaceutical Sciences, Hokkaido University, Kita 12 Nishi 6, Kita-ku, Sapporo, Hokkaido 060-0812, Japan
Abstract
When N-acylacetylphenylhydroxylamines, readily prepared from phenylhydroxylamine and acyl Meldrum’s acids (5-acyl-2,2-dimethyl-1,3-dioxane-4,6-diones) were refluxed in benzene in the presence of a catalytic amount of p-toluenesulfonic acid, an acid-catalyzed dehydrative cyclization occurred smoothly to afford 5-substituted 2-phenylisoxazolin-3-ones in high yields.
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■ Studies on Heterocyclic Quaternary Nitrogen Bases: Kinetics of Tranfsalkylation of Primary Amines by N-Substituted 5,6-Dihydro-2,4-diphenylnaphtho[1,2-b]pyridinium Cations
Sayed Mohmoud M. Elshafie
*Chemistry Department, Faculty of Science, Minia University, Minia, Egypt
Abstract
N-substituents in 5,6-dihydro-2,4-diphenylnaphtho[1,2-b]pyridiniums are transferred to piperidine by unimolecular and / or bimolecular processes in chlorobenzene solution. The kinetics of this reaction at variable temperatures were studied. It has been shown that the reaction follows either SN1 or SN2 mechanisms dependant on the nature of N-substituent.
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■ Synthesis of Some 5,5-Disubstituted 2-Thiohydantoin Derivatives
Hung-Cheh Chiang and Jin-Ren Ko
*Department of Chemistry, National Taiwan Normal University, 88, Sec. 4, Tingchow Road, Taipei, 116, Taiwan, R.O.C.
Abstract
Treatment of 5,5-diphenyl-2-thiohydantoin (2a) with allyl bromide in basic alcohol solution gave 5,5-diphenyl-2-allylthiohydantoin (3a) in 78.5% yield, whose derivatives (3b), (3f), (4a-c), and (6) were also prepared in a similar fashion.
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■ A Novel Synthesis of Pyrido[1,2-a]1,3,5-triazine-2,4-dithiones
C. P. Joshua and Saramma K. Thomas
*Department of Chemistry, University of Kerala, Trivandrum 695581, India
Abstract
A convenient one step synthesis of pyrido[1,2-a]1,3,5-triazine-2,4-dithiones from the interaction of aryl isothiocyanates and 1-(2-pyridyl)-3-substituted thioureas is being reported.
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■ Studies on the Syntheses of Heterocyclic and Natural Products. Part 968. Racemization Reaction in Bischler-Napieralski Cyclization: Synthesis of β-Carboline and Isoquinoline Nuclei from L-Tryptophan and L-Phenylalanine Derivatives
Tetsuji Kametani, Nanami Takagi, Naoaki Kanaya, and Toshio Honda
*Hoshi University, 2-4-41 Ebara, Shinagawa-ku, Tokyo 142-8501, Japan
Abstract
The Bischler-Napieralski type of cyclization of L-N-acetyltryptophan methyl ester and L-N-acetyl-3,4-dimethoxyphenylalanine methyl ester in order to obtain 3,4-dihydro-9H-pyrido[3,4-b]indole and 3,4-dihydroisoquinoline derivatives has been investigated.
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■ Carbon-13 NMR Spectra of Some Furanoid Diterpenes from Teucrium Species
Eszter Gács-Baitz, Márton Kajtár, Georgi Y. Papanov, and Peter Y. Malakov
*NMR Laboratory, Central Research Institute of Chemistry, H-1525, Budapest, Hungary
Abstract
By carbon-13 and 1H NMR methods, the proposed constitution of eleven newly isolated furanoid diterpenes and some of their transformation products are confirmed and relative stereochemistries are established. CD spectra provide the absolute stereochemistry for teucrin A, 6-ketoteuscordin, teuscordinon and montanin D.
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■ 2,3-Dihydrobenzo-γ-pyrone Oximes. Part VII. A Simple Method of Differentiation of Isomeric Derivatives of Δ2-Isoxazoline and Flavanone Oximes. A Correction of Some Structures
Zbigniew Witczak
*Faculty of Pharmacy, School of Medicine, Department of Organic Chemistry, Institute of Chemical Sciences, 90-145 Lodz, Narutowicza 120a, Poland
Abstract
The simple method of differentiation of isomeric derivatives i.e. (E)-2,3-dihydro-2-(4-ethoxyphenyl)-4H-benzopyran-4-one oxime (2) and
corresponding Δ2-isoxazoline (3) on the basis of their UV and 1H NMR data, allows us to establish that the 2,3-dihydro-4H-benzopyran-4-one derivatives (4a-4d) in the reaction with hydroxylamine give oximes (5a-5d) instead of isomeric Δ2-isoxazolines as previously described12. The isomeric Δ2-isoxazoline derivatives (6b-6d) were obtained by trifluoroacetic acid-catalyzed rearrangement of obtained oximes (5b-5d).
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■ Chemistry of Heterocyclic Diazo Compounds
Mohamed Hilmy Elnagdi, Ezzat Mohamed Zayed, and Sadek Abdou
*Department of Chemistry, Faculty of Science, , University of Cairo, Giza, Egypt
Abstract
The preparation, chemical properties and synthetic utility of nitrogen heterocyclic diazo compounds are reviewed.