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. 23, No. 9, 1985
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■ A New Synthesis of Quinuclidinium Derivatives
Joëlle Mayrargue, Michel Vayssière, and Marcel Miocque*
*Faculté de Pharmacie, UA 496 CNRS, 5 rue J.B. Clément, 92296 Châtenay-Malabry Cedex, France
Abstract
Six membered rings including at the positions 1 and 4 a basic nitrogen and a propargylic chain undergo cyclization by intramolecular nucleophilic attack of nitrogen on triple bond. Quinuclidiniums are isolated as iodides. The reaction is investigated in the field of piperidine, piperazine, and tropane derivatives.
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■ Nitriles in Heterocyclic Synthesis: Novel Syntheses of Benzo[g]imidazo[1,2-c]pyrimidines and Benzo[g]imidazo[1,2-a]pyridine Derivatives
Mohmoud Ahmed Hammad, Galal Abdel Moien Nawwar,* Galal Eldin Hamza Elgemeie, and Mohamed Hilmy Elnagdi
*Natural Products Department, National Research Centre, Dokki, Cairo, Egypt
Abstract
Novel syntheses of benzo[g]imidazo[1,2-c]pyrimidines and benzo[g]imidazo[1,2-a]pyridine derivatives utilising 2-(2-benzimidazolyl)acetonitrile as starting component is reported.
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■ Studies in Cycloaddition Reactions: A Novel Synthesis of 1H,9H-1,2,4-Triazolo[4,3-a]benzimidazoles from 1-Acylbenzimidazoles and Hydrazidoyl Chloride
Eltepu Sayanna, Revannuru Venkatachaliah Venkataratnam,* and Gopalakrishna Thyagarajan
*Regional Research Laboratory, Hyderabad 500 007, India
Abstract
1-Acylbenzimidazoles undergo 1,3-dipolar cycloaddition with nitrileimine to produce derivatives of the 1H,9H-1,2,4-triazolo[4,3-a]benzimidazole system, followed by a rapid in situ substitution at 9a-position by the benzhydrazidoyl moiety. Substituted imidazoles and benzimidazole give 1-benzhydrazidoyl substituted products.
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■ Synthesis and Reactivity of a New Dibenzobicyclic Phosphorane of Unusual High Stability: 1-Phenyl-5-aza-2,8-dioxa-1-phosphaV-dibenzo[c,f]bicyclo[3.3.0]octane
Rosalinda Contreras,* Apolonia Murillo, Guillermo Uribe, and Alain Klaébé
*Centro de Investigación y de Estudios Avanzados, Departmento de Química , I.P.N, Apartado 14-740, México, D.F., 07000, Mexico
Abstract
The title compound was synthesized, and its structure and reactivity were studied. It shows a remarkable stability.
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■ Reissert Compound Studies. LIII. A New Synthesis of Reissert Compounds Using Tri-n-butyltin Cyanide
Frank D. Popp* and Joydeep Kant
*Department of Chemistry, University of Wisconsin-Milwaukee, Milwaukee, Wisconsin 53201, U.S.A.
Abstract
Reissert compounds were prepared by the reaction of the heterocyclic base and acyl halide with tri-n-butyltin cyanide in methylene chloride.
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■ Synthesis of 5-[1-(3-Methoxycarbonyl)-O-methylpseudoureido]uracil: A Novel Method for the Conversion of an N,N‘-Disubstituted Thiourea into an O-Methyl-N,N‘-disubstituted Pseudourea
Ji-Wang Chern, Dean Sylvester Wise, Jr., and Leroy B. Townsend*
*Department of Medicinal Chemistry, College of Pharmacy, University of Minnesota, 308 Harvard St., S. E., Minneapolis, Minnesota 55455, U.S.A.
Abstract
Treatment of 5-[1-(3-methoxycarbonyl)thioureido]uracil with dicyclohexylcarbodiimide in methanol has resulted in the formation of 5-[1-(3-methoxycarbonyl)-O-methylpseudoureido]uracil.
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■ Schönberg Reactions of Adamantanethione S-Methylide
Grzegorz Mloston and Rolf Huisgen*
*Institut für Organische Chemie, Universität München, Karlstrasse 23, D-80333 München, Germany
Abstract
Nitrogen extrusion from 1,3,4-thiadiazoline-2-spiro-2’-adamantane at 40°C generates the thiocarbonyl ylide of the title which is intercepted in situ by dipolarophiles with CS double bond (aromatic and aliphatic thioketones, dithiocarboxylic esters, carbon disulfide, phenyl isothiocyanate). Both cycloaddition directions are used in the 1,3-dithiolane formation; the structural dependence and orientational forces are discussed.
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■ 1,3-Cycloadditions of 2,2,4,4-Tetramethylcyclobutane-1-one-3-thione S-Methylide
Rolf Huisgen,* Grzegorz Mloston, and Claudia Fulka
*Institut für Organische Chemie, Universität München, Karlstrasse 23, D-80333 München, Germany
Abstract
The 1,3,4-thiadiazoline 2, prepared from 2,2,4,4-tetramethylcyclobutane-1-one-3-thione and diazomethane, loses N2 at 40°C; the thiocarbonyl ylide 5 is a transient intermediate which in situ undergoes 1,3-dipolar cycloadditions to electron-deficient dipolarophiles with C=C, C=C, C=S, C=O, and N=N bonds. Structures and mechanism are discussed.
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■ Chemistry of Metallo-ketene-S,N-acetals. New Synthesis of Azacycloalka[2,3-d]pyrimidines
Hiroki Takahata, Toshiaki Suzuki, and Takao Yamazaki*
*Faculty of Pharmaceutical Sciences, Toyama Medical and Pharmaceutical University, 2630 Sugitani, Toyama, Toyama 930-0194, Japan
Abstract
Bis-lithio-ketene-S,N-acetals, generated from thiolactams by treatment with n-BuLi, react with aryl isothiocyanates to give dithioamides. Bismethylation of the dithioamides followed by condensation with benzamidine affords the azacycloalka[2,3-d]pyrimidines.
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■ Synthesis and Cyclization of 3-Hydroxalkylidene-2,5-piperazinediones (PDO) to the Corresponding 3-Spiro- and 3,6-Bridged PDO Derivatives
Chung-gi Shin,* Yoshiharu Nakajima, and Yoshiaki Sato
*Departmnet of Applied Chemistry, Faculty of Engineering, Kanagawa University, 3-27-1 Rokkakubashi, Kanagawa-ku, Yokohama 221-8686, Japan
Abstract
Synthesis and cyclization of α-dehydroaspartate derivatives gave 3-hydroxyalkylidene-2,5-piperazinediones (PDO), which were then hydrogenated to give 3-hydroxyalkyl-PDO derivatives. Further cyclization of the two PDOs gave 3-spiro- and 3,6-bridged PDO derivatives.
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■ Reaction of 3-Acylindoles with Diethyl Phosphorocyanidate. A Facile Synthesis of 2-Cyano-3-indoleacetonitriles
Takushi Kurihara,* Mitsuko Hayakawa, Takeo Wakita, and Shinya Harusawa
*Faculty of Pharmaceutical Science, Osaka University of Pharmaceutical Sciences, 4-20-1 Nasahara, Takatsuki, Osaka 569-1094, Japan
Abstract
3-Acylindoles (1,7a-7d) were easily converted into 2-cyano-3-indoleacetonitriles (5,9a-9d) by treatment with diethyl phosphorocyanidate in the presence of lithium cyanide in excellent yields. Treatment of 9a with acetylenic esters in the presence of sodium hydride in tetrahydrofuran afforded 1-amino-4-cyanocarbazoles (10a and 10b). The compound 9a also reacted with benzyne in the presence of lithium di-isopropylamide to give 6-amino-11-cyano-5-methylbenzo[b]carbazole (11) in 64% yield, together with a small amount of 6,11-o-benzenobenzo[b]carbazole (12).
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■ On the Possibility of Chlorotropy in Aromatic Azoles: The Case of 1,2,3-Triazoles and Benzotriazoles
Javier Cañada, Rosa Ma. Claramunt, Javier De Mendoza, and José Elguero*
*Centro de Química Orgánica ‘Manuel Lora-Tamayo‘, Instituto de Química Médica, C. S. I. C., Calle Juan de Cierva, 3, E-28006 Madrid, Spain
Abstract
A 13C n.m.r. study of N-chloro derivatives of 4,5-diphenyl-1,2,3-triazole and 5,6-dichloro-4,7-dimethylbenzotriazole reveals that neither a rapid chlorotropy nor a slow chlorine equilibration takes place. For the first time, a derivative of 2-chlorobenzotriazole has been characterized.
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■ N-Vinyl-2-ethoxypyrrolidinimium Tetrafluoborate: A Novel Enophile and Synthetic Equivalent for N-Vinylpyrrolidiniminium
Michael B. Smith* and Hitesh N. Shroff
*Department of Chemistry, U-60, Rm.151, 215 Glenbrok Rd., University of Connecticut, Storrs, CT 06269-3060, U.S.A.
Abstract
Cycloaddition of N-vinyl-2-ethoxypyrrolidiniminium tetrafluoborate, 3, with alkenes, followed by hydride reduction, yields the 8-alkyloctahydroindolizines, 7 and 8 which would be derived from N-vinylpyrrolidiniminium, 2. This cycloaddition-reductive elimination sequence offers a new route to indolizidine type alkaloids.
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■ A New Synthesis of 2-Oxazolones
Pen-Chung Wang*
*Designed Latexes and Resins research, Michigan Division, 1604 Building, The Dow Chemical Company, Midland, MI 48640, U.S.A.
Abstract
2-Oxazolones were synthesized from 2-oxazolidinones utilizing anodic oxidation as the key step.
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■ Mulberroside B, a New C-Glucosylcoumarin from the Cultivated Mulberry Tree (Morus lhou Koidz.)
Kazuhiro Hirakura, Isamu Saida, Toshio Fukai, and Taro Nomura*
*Faculty of Pharmaceutical Sciences, Toho University, 2-2-1, Miyama, Funabashi, Chiba 274-8510, Japan
Abstract
A new C-glucosylcoumarin, mulberroside B, was isolated from the acetone extract of the root bark of cultivated mulberry tree, and identified as 5,7-dihydroxycoumarin-6-C-β-glucopyranoside on the basis of spectral evidence.
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■ Studies on Indenopyridine Derivatives and Related Compounds. V. A Facile Synthesis of Ethyl 9,9-Dimethyl-1,2,3,9a-tetrahydro-9H-indeno[2,1-b]pyridine-3-carboxylate
Ryuji Yoneda, Tatsuya Terada, Shigeyo Satoda, and Takushi Kurihara*
*Faculty of Pharmaceutical Science, Osaka University of Pharmaceutical Sciences, 4-20-1 Nasahara, Takatsuki, Osaka 569-1094, Japan
Abstract
New synthetic methods for 1,2,3,9a-tetrahydro-9H-indeno[2,1-b]pyridine (1) are described. These methods involve the acidic de-t-butoxycarbonylation followed by base treatment of the diene (13) and mesylate (14).
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■ On the Mechanism of the One-pot Conbersion of 4-Carbomethoxy-5-hydroxyimidazoles into 5-Amino-4-carbamoylimidazoles
Ramachandra S. Hosmane* and Benjamin B. Lim
*Labratorl for Chamical Dynamics, Department of Chemistry, University of Maryland Baltimore County, Catonsville, Maryland 21228, U.S.A.
Abstract
A mechanism is proposed for the one-pot conversion of 4-carbomethoxy-5-hydroxyimidazoles into the corresponding 5-amino-4-carbamoylimidazoles.
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■ The Syntheses of 2-Methyl-3-(p-tolylazo)-pyrimido[1,2-a]benzimidazole-4-one, 7-Hydroxy-5-methyl-6-(p-tolylazo)-[1,2,4]triazolo[1,5-a]pyrimidine, 2-Methylpyrazolo[1,5-a]pyridine-5,7(4H,6H)-dione and Arylazothiopyrimidines
Mohmed Abbas Metwally,* Mamoun Y. Yousif, Andel-Kader M. Ismaiel, and Hassan A. Etman
*Department of Medical Chemistry, Faculty of Pharmacy, University of Mansoura, Mansoura, Egypt
Abstract
Condensation of 2-aminobenzimidazole (1) with ethyl α-(p-tolylazo)-β-oxobutyrate (2) in absolute EtOH (molar ratio) afforded 2-methyl-3-(p-tolylazo)-pyrimido[1,2-a]benzimidazole-4-one (4). The reaction of 3-amino-1,2,4-triazole (5) with (2) in the same reaction medium for 16 h gave 7-hydroxy-5-methyl-6-(p-tolylazo)-[1,2,4]triazolo[1,5-a]pyrimidine (6). 2-Methylpyrazolo[1,5-a]pyridine-5,7(4H,6H)-dione (9) was obtained by the fusion of 3-methyl-2-pyrazolin-5-one (8) with ethyl acetoacetate at 120 °C for 6 h. The condensation of ethyl α-(arylazo)-β-oxobutyrate (2a-e) with thiourea in methanolic sodium methoxide afforded the arylazothiopyrimidines (11a-e) in quantitative yield.
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■ 2-(Heteroatom-substituted)methyl Penems. I. Sulphur Derivatives
Marco Alpegiani, Angelo Bedeschi, Ettore Perrone,* Franco Zarini, and Giovanni Franceschi
*Ricerca&Sviluppo Chimico, Farmitalia Carlo Erba SpA, Via dei Gracchi 35, 20146 Milano, Italy
Abstract
Chemical strategies for the synthesis of “2-CH2X” penems wherein X is a (substituted) alkylthio or heterocyclylthio radical are reviewed. The rationale at the basis of the programme is checked against the obtained microbiological data.
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■ The Threo and Erythro Products of the Catalytic Hydrogenation of 1-(2-Pyridyl)-1,2,3,4-tetrahydro-β-carboline
Stanislaw Misztal* and Magorzata Dukat
*Department of Organic Chemistry, Institute of Pharmacology, Polish Acadeamy of Sciences, 12 Smetna Street, 31-343 Kraków, Poland
Abstract
The catalytic reduction of 1-(2-pyridyl)-1,2,3,4-tetrahydro-β-carboline to threo- and erythro-1-(2-piperidyl)-1,2,3,4-tetrahydro-β-carbolines is described.
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■ Synthetic Studies on Carbapenem Anitibiotics from Penicillins. VI. Syntheses of Optically Active O-Methylcarpetimycin and O-Methyl-6-Epicarpetimycin
Hideo Hirai, Kozo Sawada, Akira Yamada, Matsuhiko Aratani, and Masashi Hashimoto*
*Fujisawa Pharmaceutical Co. Ltd., 5-2-3 Tokodai, Tsukuba, Ibaragi 300-2635, Japan
Abstract
The syntheses of the optically active O-methylcarpetimycin 2a and O-methyl-6-epicarpetimycin 2b were achieved by a route involving one-pot syntheses of 5a and 5b from 3.
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■ Nitrogen Bridgehead Compounds Part 57. Synthesi of New 1-Thia-2a,5a-diazaacenaphthenes
István Bitter,* Gábor Tóth, Béle Pete, Atila Almásy, István Hermecz, and Zoltán Mészáros
*Department of Organic Chemical Technology, Technical University of Budapest, H-1521 Budapest, Gellért tér 4, Hungary
Abstract
The first representatives of a new ring system, the 1-thia-2a,5a-diazaacenaphthenes are prepared by the reaction of 9-bromo-6,7,8,9-tetrahydro-4H-pyrido[1,2-d]pyrimidin-4-ones with alkali thiocyanates.
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■ Facile Synthesis of 5H-[1]Benzopyrano[2,3-b]-1,2,3,4-tetrahydropyridin-5-ones
Franco M. Pasutto,* Syrd Abuzar, and Srinivasmurthy Satymurthy
*Faculty of Pharmacy , University of Alberta, Edmonton, Alberta T6G, 2N8, Canada
Abstract
A facile synthesis of 7-substituted-5H-[1]benzopyrano[2,3-b]-1,2,3,4-tetrahydropyridin-5-ones is described. Catalytic hydrogenation of 7-substituted 5H-[1]benzopyrano[2,3-b]pyridin-5-ones affords the title compounds in greater than 90% yields. Facile, high yield, N1-acetylation is achieved by reaction with acetic anhydride.
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■ Preparation and Structure Elucidation of Some N-Alkylpyrazinium Salts and Their N-Oxides
Misa V. Jovanovic*
*Department of Chemistry, Southern Methodist University, P.O. Box 750314, Dallas, TX 75275-0314, U.S.A.
Abstract
Several N4-alkylpyrazinium N-oxide salts were prepared in high yields by heating the corresponding pyrazine N1-oxides in the presence of alkylating reagent and solvent. The proton nmr data point to the quinoidal nature of these compounds. Pyrarine di-N-oxides deoxygenated rapidly under same reaction conditions to yield a mixture of N-alkylpyrazinium and N-alkylpyrazinium mono-N-oxide salts. Mechanism is proposed to account for these reductive deoxygenations of the pyrazine nucleus.
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■ A New Contraction of Pteridine 5-Oxides to Purines and a 7-Deazapurine by the 1,3-Dipolar Cycloaddition Reaction
Misuzu Ichiba, Hashime Kanazawa, Zenzo Tamura, and Keitaro Senga*
*Pharmaceutical Institute, School of Medicine, Keio University, Shinanomachi 35, Shinjuku, Tokyo 160-0016, Japan
Abstract
The 1,3-dipolar cycloaddition reaction of pteridine 5-oxides with dimethyl acetylenedicarboxylate resulted in a new ring contraction of the pyrazine moiety to give purines and a 7-deazapurine.
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■ Azadirachtanin, a New Limonoid from the Leaves of Azadirachta indicca
Gurudas Podder and Shashi B. Mohato*
*Indian Institute of Chemical Biology, Calcutta-700 032, India
Abstract
Azadirachtanin, a new limonoid of the Δ14-meliacan skeleton has been isolated from the leaves of Azadirachta indica A. Juss and its structure has been deduced from its spectral data coupled with chemical evidence.
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■ Palladium-catalyzed Coupling Reaction of Chloropyrazines with Indole
Yasuo Akita, Akira Inoue, Keiko Yamamoto, Akihiro Ohta,* Teruo Kurihara, and Mitsuru Shimizu
*Tokyo University of Pharmacy and Life Science, 1432-1 Horinouchi, Hachioji, Tokyo 192-0392, Japan
Abstract
The palladium-catalyzed cross-coupling reaction of 2-chloropyrazines with indole was shown to proceed in moderate to good yields, giving 2-(pyrazin-2-yl)indoles. The structure determination of the products was made on the basis of the X-Ray diffraction and 13C-NMR spectroscopic analyses.
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■ On Reaction of 3-(9’β-Acetyl-des-A,B-cholestan-8’α-yl)-propionic Acis with Ethanolamine
Michal Chodynski, Bozena Grzeszczyk-Morzycka, Jacek W. Morzycki,* Zbigniew Boncza-Tomaszewski, and Wladyslaw J. Rodewald
*Department of Chemistry, University of Warsaw, Pasteura St.1, 02-093 Warsaw, Poland
Abstract
Two procedures for the synthesis of A-oxazolidine compound 4 from keto-ester 1b have been elaborated. The two-step method involving kera-amide 2 preparation and its reaction with LiH seems to be superior to the direct synthesis from 1b and ethanolamine in the presence of KOH followed by Ac2O/Py promoted cyclization.
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■ Pyrolytic Products of N-Alkyl-N‘-(4-methyl-2-thiazolyl)-S-methylisothioureas
Reiko Yoda,* Yuichi Yamamoto, Tomoko Okada, and Yoshikazu Matsushima
*Faculty of Pharmaceutical Sciences, Kyoritsu College of Pharmacy, 1-5-30, Shiba-koen, Minato-ku, Tokyo 105-8512, Japan
Abstract
N-Methyl-N’-(4-methyl-2-thiazolyl)-S-methylisothiourea (1a) was pyrolyzed at 155°C, for 14 h. N-Methyl-N’,N”-bis(4-methyl-2-thiazolyl)guanidine (2a) was identified as the product. 3-Methyl-thiazolyl compounds such as N-methyl-N’-(3,4-dimethyl-2(3H)thiazolylidene)thiourea (3a) and N-methyl-N’-(3,4-dimethyl-2-thiazolyl)-N”-(4-methyl-2-thiazolyl)guanidine (6a) were not obtained in the pyrolysis, in contrast to the previous finding that a main pyrolytic product of N,N-dimethyl-N’-(4-methyl-2-thiazolyl)-S-methylisothiourea was N,N-dimethyl-N’-(3,4-dimethyl-2(3H)thiazolylidene)thiourea.
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■ A Simple and Practical Procedure for the Conversion of (S)-4-Hydroxymethyl-4-butanolide into Its (R)-Enantiomer
Masahide Tanaka, Kiyoshi Tomioka, and Kenji Koga*
*Faculty of Pharmaceutical Sciences, University of Tokyo, Hongo, Bunkyo-ku, Tokyo 113, Japan
Abstract
A practical procedure for the conversion of (S)-4-hydroxymethyl-4-butanolide into its (R)-enantiomer is described.