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. 26, No. 6, 1987
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■ Alcoholisys of 1,2-Bis(1-Isocynato-1-methylethyl)diazene: Unexpected Formation of 5,5-Dimethyl-1,2,4-triazolin-3-one
Joachim G. Schantl, Hubert Gstach, and Norbert Lanznaster
*Institut für Organische Chemie, Universität Innsbruck, Innrain 52, A-6020 Innsbruck , Austria
Abstract
From the reaction of the bis(isocyanatoalkyl)diazene 1 with alcohols the expected adducts 2 could not be isolated (though there is spectroscopic evidence of their formation). The main product obtained was the triazolin-3-one 3, and in addition, several complementing products 4 - 6 were formed.
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■ Synthetic Studies on Eriolanin: 1,2-Carbonyl Transpositions of cis-Bisyclo[4.2.0]octanone via Enol Thioether Foemation
Takeshi Wakamatsu, Nobuhide Miyachi, Fumihiro Ozaki, and Yoshio Ban
*Faculty of Pharmaceutical Sciences, Hokkaido University, Kita 12 Nishi 6, Kita-ku, Sapporo, Hokkaido 060-0812, Japan
Abstract
1,2-Carbonyl transposition of cis-fused cyclobutanone is demonstrated by means of two procedures(method A and method B). This relatively short sequence(method B) provides a new and convenient method for conversion of carbonyl group in the entitled rlng system.
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■ Synthesis and Study of the Stability of 3b,4,4a,5-Tetrahydrothieno[2‘,3‘:5,4]cyclopenta[2,3-b]aziridine Derivatives
Patrick Dallemagne, Sylvain Rault, Daniel Maume, and Max Robba
*Laboratorie de Chimie Thérapeutique, U.F.R. des Sciences Pharmaceutiques, Centre d‘Etudes et de Recherch sur le Medicament de Normandie, 1, rue Vaubénard, 14032 Caen Cedex, France
Abstract
The synthesisof 3b,4,4a,5-tetrahydrothieno[2’,3’:5,4]cyclopenta[2,3-b]-aziridine derivatives is described. Their stability is studied.
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■ Studies on the Active Principles from Aconitum flavum Hand-Mazz. The Structures of Five New Deterpenoid Alkaloids
Zhi-gang Chen, Ai-na Lao, Hong-chemg Wang, and Shan-hai Hong
*Shanghai Institute of Material Media, Chinese Academy of Science, 319, Yue-yang Road, Shanghai, 200031, China
Abstract
Reinvestigation of Aconitum flavum Hand-Mazz resulted in the isolation of five new diterpenoid alkaloids, i.e., dehydronapelline (1), 12-acetyllucidusculine (2), 1-epi-napelline (3), 12-epi-napelline (4), and 1-demethylhypaconitine (9), along with napelline, lucidusculine, aconitine, 3-acetylaconitine, deoxyaconitine, flavaconitine, benzoylaconine. and neoline. The structures of these new compounds were determined based on spectral data and chemical transformations. The pharmacological tests showed that 12-acetyllucidusculine (2) has a strong effect of lowering of heart rate in Langendorff’s guinea pig hearts.
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■ Ring Expansion of 4-Benzoyl-β-lactams
Benito Alcaide, Gema Domíngues, Angel Martín-Domenech, Joaquín Plumet, Angeles Monge, and Virginia Pérez-García
*Departamento de Química Orgánica, Facultad de Química, Universidad Complutense de Madridas, Ciudad Universitaria, E-28040 Madrid, Spain
Abstract
Diastereomerically pure 4-benzoyl-β-lactams react with NaH/DMF in the presence of an alkyl halide to give 5-alkoxy-γ-lactams.
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■ New Methods and Reagents in Organic Synthesis. 68. Reaction of Thioketones with Lithium Trimethylsilyldiazomethane
Takayuki Shioiri, Yuji Iwamoto, and Toyohiko Aoyama
*Faculty of Pharmaceutical Sciences, Nagoya City University, Tanabe-dori, Mizuho-ku, Nagoya 467-8603, Japan
Abstract
Reaction of thioketones with lithium trimethylsilyldiazomethane affords alkynes, vinylsilanes. 1,2,3-thiadiarolines, or 1,2,3-thiadiazoles depending upon substrates and reaction solvents.
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■ Introduction of a Hydroxy Group onto 5- and 6-Position of Indole Nucleus by Friedel-Crafts Acylation and Subsequent Baeyer-Villiger Oxideation
Shin-ichi Nakatsuka, Osamu Asano, Kazuo Ueda, and Toshio Goto
*Faculty of Agriculture, Gifu University
, 1-1 Yanagito, Gifu, Gifu 501-1193, Japan
Abstract
A hydroxy group was efficiently introduced onto 5-and 6-position of methyl 1-methylindole-3-carboxylate 1, and methyl indole-3-carboxylate 11.
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■ Synthetic Studis on Teleocidin III. Regioselective Introduction of Nitro Group at 4-Position of Substituted Indole Derivatives
Toshiya Masuda, Kazuo Ueda, Osamu Asano, Shin-ichi Nakatsuka, and Toshio Goto
*Faculty of Agriculture, Gifu University, 1-1 Yanagito, Gifu, Gifu 501-1193, Japan
Abstract
Regioselectivities of nitration of substituted indole derivatives were studied and compound 2,containing three substituents similar to teleocidin B (1) was selectively synthesized.
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■ Metal-catalyzed Intramolecular Cyclization of 2-Diazo-4-(4-indolyl)-3-oxobutanoic Acid Esters
Masakatsu Matsumoto, Nobuko Watanabe, and Hisako Kobayashi
*Sagami Central Research Center, 4-4-1 Nishi-Ohnuma, Sagamihara, Kanagawa 229-0012, Japan
Abstract
Rh2(0Ac)4-catalyzed decompositioon of 2-diazo-4-(4-indolyl)-3-oxobutanoic acid esters (1) leads to indoles 3, whereas Pd(OAc)2-catalyzed reaction of 1 gives lndoles 2 with C-ring.
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■ Silicon-mediated Isoquinoine Alkaloid Synthesis: A New Route to the Dibenzopyrrocoline Alkaloid (±)-Cryptaustoline
Seiichi Takano, Shigeki Satoh, and Kunio Ogasawara
*Pharmaceutical Institute, Tohoku University, Aobayama, Sendai 980-8578, Japan
Abstract
A fundamentally new synthesis of the benzopyrrocoline alkaloid (±)-cryptaustoline iodide (12) has been devised by employing the silicon mediated ring closure through a formal 5-Endo-Trigonal process.
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■ Stereochemistry of the Dibenzopyrrocoline Alkaloids Cryptaustoline and Cryptowoline
Seiichi Takano, Shigeki Satoh, Yoshiteru Oshima, and Kunio Ogasawara
*Pharmaceutical Institute, Tohoku University, Aobayama, Sendai 980-8578, Japan
Abstract
Stereochemistry of the dibenzopyrrocoline alkaloids, (-)-cryptaustoline (1) and (-)-cryptowoline (2), isolated from the Australian shrub Cryptocaria bowiei is deduced both as 7R,13S configuration with cis B/C ring structure based on the analysis of proton-nmr spectra of synthetic materials.
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■ A Facile Synthesis of (+)-Tecomanine Using a Chiral Cyclopentane Derivative
Tetsuji Kametani, Yukio Suzuki, Chieko Ban, and Toshio Honda
*Hoshi University, 2-4-41 Ebara, Shinagawa-ku, Tokyo 142-8501, Japan
Abstract
(-)-Carvone was efficiently converted into a chiral cyclopentane derivative (3) . which was utilized as a starting material in the synthesis of (+)-tecomanine (9) successfully.
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■ Reaction of 2,4,6-Trimethylpyrylium Salt with Organocopper Reagents: Selective Synthesis of 4H-Pyrans
Yohsuke Yamamoto, Takashi Kume, and Kin-ya Akiba
*Department of Chemistry, Faculty of Science, Hiroshima University, 1-3-1 Kagamiyama, Higashi-Hiroshima, Hiroshima 739-8526, Japan
Abstract
Various cuprates (R2CuLi or R2CuMgBr) reacted with 2,4,6-trimethylpyrylium tetrafluoroborate (1) at 4-position to give 4H-pyrans with good regioselectivity (4H-:2H-≥7:3) in high total yield (75-90 %). One-pot transformation of 4H-pyrans into cyclohexenones is also described.
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■ A New Total Synthesis of Oxyterihanine
Miyoji Hanaoka, Nobuyuki Kobayashi, and Chisato Mukai
*Faculty of Pharmaceutical Scicences, Kanazawa University, 13-1 Takara-machi, Kanazawa 920-0934, Japan
Abstract
Oxyterihanine (1), a phenolic benzo[c]phenanthridine alkaloid, was efficiently synthesized from the corresponding protoberberine 4 through C6-N bond cleavage and subsequent cyclization via the acetal (12).
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■ Heterocycles. 11. Sulfer Analogs of 3-(3-Hydroxyphenyl)-N-n-propylpiperidine
Philip M. Weintraub, Frank P. Miller, and Norbert L. Weich
*Merrell Dow Research Institute, 2110 East Galbraith Road, Cincinnati, Ohio 45215, U.S.A.
Abstract
Analogs of 3-(3-hydroxypheny1)-N-n-propylpiperidine (3-PPP) and 3-(3- hydroxypheny1)-N-(2-phenylethy1)piperidine (phenethyl 3-PP) in which carbon 4 was replaced by sulfur were synthesized and tested for dopamine autoreceptor activity.
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■ Condensation of 2-Pheny-2-oxazolin-5-one with o-Hydroxyacetophenoneimines
Pradeep K. Tripathy and Arya K. Mukerjee
*Department of Chemistry, Faculty of Science, Banaras Hindu University, Varanasi - 221005, India
Abstract
Condensation of 2-phenyl-2-oxazolin-5-one (1) with N-aryl-o-hydroxyacetophenoneimines (2a,b) gave - the corresponding dihydrocoumarins (2). On the other hand, the reaction of 1 with-2 (Y = C6H11N or n-BuN) afforded 3-N-benzoylamino-4-methylcoumarin (6) which underwent hydrolysis to give 3-amino-4-methylcoumarin (9) or 3-hydroxy-4-methylcoumarin (10), depending on the acidic or basic condition and the reaction temperature.
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■ Phenyl Isothiocynate-mediated Condensation of Aceturic/2-acetylaminocinnamic Acid with Aromatic Aldehydes
Archana Jain and Arya K. Mukerjee
*Department of Chemistry, Faculty of Science, Banaras Hindu University, Varanasi - 221005, India
Abstract
One-flask synthesis of 4-arylmethylene-1-phenyl-2-styryl-2-imidazolin-5-ones (3) was achieved by the phenyl isothiocyanate-mediated condensation of aceturic/2-acetylaminocinnamic acid (1) with aromatic aldehydes (2). In the presence of salicylaldehyde (2d), the reaction of 1a and 5 led to the formation of 3-acetylaminocoumarin (4).
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■ Novel One Pot Convenient Synthesis of 3-Benzylidene-2-phenyl-2,3-dihydro-4H-1-benzopyran-4-ones
H. Mohindra Chawla and S. Kumar Sharma
*Department of Chemistry, Indian Institute of Technology, Hauz Khas, New Delhi-110016, India
Abstract
A novel one pot good yield synthesis of 3-benzylidene-2-phenyl-2,3- dihydro-4H-1-benzopyran-4-ones by the condensatm of o- hydroxyacetophenones with aromatlc aldehydes has been described and the new compounds were identified by their chemical, analytical and spectroscopic data.
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■ A New Condensed Triheterocyclic System: 6-Aza-8H-indeno[2,1-b]thiophene
Florence Heude, Michel Cugnon de Sevricourt, Sylvain Rault, and Max Robba
*Laboratorie de Chimie Thérapeutique, U.F.R. des Sciences Pharmaceutiques, Centre d’Etudes et de Recherch sur le Medicament de Normandie, 1, rue Vaubénard, 14032 Caen Cedex, France
Abstract
Cyclization of 2,6-dimethyl-4-(3-thienyl)pyridine-3,5-dicarboxylic acid resulted in the formation of 5,7-dimethyl-δ-oxo-6-aza-8H-indeno[2,1-b]thiophene derivatives.
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■ Synthesis of 3-(1’,1’-Dimethylallyl)coumarins: Gravelliferone, Chalepin and Rutamarin
Guillermo M. Massanet, Enrique Pando, Francisco Rodríguez-Luis, and Javier Salvá
*Departamento de Química Orgánica, Facultad de Ciencias, Universidad de Cádiz, Apartado 40, Puerto Real (Cádiz), Spain
Abstract
The 3-(1’,1’-dimethylallyl)coumarins chalepin (2), rutamarin (3) and gravelliferone (4) have been synthesized from umbelliferon (7) via Claisen and Cope rearrangements of 3’,3’-dimethylallyl ethers of 6-(3’,3’-dimethylallyl)umbelliferon with and without an iodine atom as blocking group at C-8.
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■ Pyridindolol Analogues. Synthesis of 3-Hydroxymethyl-1-(polyhydroxyalkyl)-β-carbolines
Nico P. Willard, Erwin Dorland, and Upendra K. Pandit
*Organic Chemistry Department, University of Amsterdam, Nieuwe Achtergracht 129, 1018 WS Amsterdam, The Netherlands
Abstract
Peracetylated (D)-glucose, (D)-galactose, (D)-ribose, (L)-ardbinose and (D)-xylose have been subjected to a Pictet-Spengler cycllsation with methyl tryptophanate to give β-carboline derivatives which have been converted to a series of pyridindolol analogues.
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■ Synthesis of (±)-Deplancheine
Sukhendu B. Mandal and Satyesh C. Pakrashi*
*Indian Institute of Chemical Biology, Calcutta-700 032, India
Abstract
The indole alkaloid (±)deplancheine (1) has been synthesized utilizing the intermediate 3-acatyl-1,2,6,7,12,12b-hexahydroindolo[2,3-a]quinolizine (6) prepared in two synthetic steps from readily available startlng materials.
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■ Studies on the Chemical Constituents of the Seeds of Peganum harmala — Isolation and Structure of a New β-Carboline Alkaloid — Harmalicine
Salimuzzaman Siddiqui, Obaid Yusuf Khan, Shaheen Faizi, and Bina S. Siddiqui
*H. E. J. Postgraduate Institute of Chemistry, University of Karachi, Karachi-75270, Pakistan
Abstract
A new β-carboline alkaloid named as harmalicine has been iso-lated from the aqueous fraction of the methanolic extract of the uncrushed seeds of Peganum harmala and its structure established as I through chemical and spectral studies.
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■ The Synthesis of 5- and 6-Formyl-1-ethoxy-1,2,3-benzotriazole
Dale Evans, M. Paul Serve, Balsubramaniam Ramalingam, Lisa Barna, and William Feld
*Department of Chemistry, Wright State Univerity, Dayton, OH 45435, U.S.A.
Abstract
The bromination of 5- and 6-methyl-l-ethoxy-1,2,3-benzotriazole with NBS provided 5- and 6-bromomethyl-1-ethoxy-1,2,3-benzotriazole which were, by way of the Sommelet reaction, converted t o 5- and 6-formyl-1-ethoxy-1,2,3- benzotriazole.
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■ Fischer Indolization of the Phenylhydrazones from 3-Ethyl- and 3-(2-Methylpropyl)-substituted 1,3,4,6,7,11b-Hexahydroxy-9,10-dimethoxy-2H-benzo[a]quinolizin-2-one. Identification of the indole[1’,2’:3,4]pyrimido[6,1-a]isoquinoline Skeleton
Jonathan B. Ball. John B. Bremner, and Elaine J. Browne
*Department of Chemistry, University of Tasmania, GPO Box 252C Hobart, Tasmania, 7001, Australia
Abstract
A Fischer idolization of the phenylhydrazone (2a) derived from 3-ethyl-1,3,4,6,7, 11b-hexahydro-9,10-dimethoxy-2H-benzo[a]quinolizin-2-one (1a) gave the three products (3a), (4a) and (5a). The identity of (3a) and (4a) as diastereomeric benz[a]indolo[2,3-h]quinolizine derivatives was confirmed, but the third product, previously assigned the benz[a]indolo[3,2-g]quinolizine structure (6a), was identified as the indolo[1’,2’ :3,4]pyrimido[6,1-a]isquinoline derivative (5a), a representative of a new ring system. Similar results were obtained from the 3-(2-methylpropyl)- analogue (1b) (“Tetrabenazine”) of the ketone (1a); indolization of its phenylhydrazone (2b) gave rise to (3b), (4b) ard (5b).
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■ Structure and Basicity of 2-Guanidiobenzimidazoles
Carmen Acerete, Javier Catalán, Fernando Fabero, Marta Sánchez-Cabezudo, Rosa María Claramunt, and José Elguero
*Departamento de Química Orgánica, Facultad de Ciencias, Universidad Autónoma de Madrid, Cantoblanco, 28049-Madrid, Spain
Abstract
A theoretical and experimental study of the basicity of three 2-guanidinobenzimidazoles has been carried out. The most abundant tautomer, the structure of the protonated molecule, and the reason of the relatively low pKa 1 are discussed. In addition, a careful 1H and 13C nmr study provides information about the influence of intramolecular hydrogen bonds on annular tautomeric rates.
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■ Vinyl Monomers Containing 1,2-Thia-, -Selena- and -Tellurazole Systems, Their Polymers and Copolymers
Francesco Lucchesini, Vincenzo Bertini, Angela De Munno, Marco Pocci, Nevio Picci, and Michele Liguori
*Dipartimento di Chimica e Chimica Industriale, Università di Pisa, Via Risorgnimento 35, I-56126 Pisa, Italy
Abstract
3-Methyl-5-vinyl-1,2-tellurazole, -selenazole, and-thiazole have been prepared by one pot reaction from 5-hexen-3-yn-2-one, hydroxylamine-0-sulphonic acid and the proper alkaline chalcogenide. Their radical homopolymerization and copolymerization with styrene have been investigated.
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■ 1-Oxotetrahydro-2-benzazepines from 1-Methyl-3,4-dihydro-5H-2-benzazepines: Synthesis of N-Methyl-7,8,9-trimethoxy-2,3,4,5-tetrahydro-1H-2-benzazepine
Ricardo Alonso, Kimio Takahashi, Bernhard Schönenberger, and Arnold Brossi
*Section of Medical Chemistry, Laboratory of Analytical Chemistry, NIDDK, National Institute of Health, Bethesda, MD 20982, U.S.A.
Abstract
A new approach to 1-oxo-2,3,4,5-tetrahydro-1H-2-benzazepines is described, the key step being the rutheniun catalyzed oxidative cleavage of 1-methylene-2-benzazepine 5 obtained by N-acetylation of the Bischler-Napieralski cyclization product of N-acetyl-3-(3’,4’.5’-trimethoxyphenyl)-propylamine (3). Aromatic bromination instead of benzylic oxidation took place upon irradiation of the 1-oxo-2-benzazepine 8 with visible light in the presence of CaCO3 and NBS.
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■ The Synthesis of 4-Substituted Isoquinoline Derivatives from Diethyl(4-isoquinolyl)borane
Minoru Ishikura, Izumi Oda, and Masanao Terashima
*Faculty of Pharmaceutical Scicences, Higashinihonngakuen University, 1757 Kanazawa, Toubetu-cho, Ishikari-gun, Hokkaodo 061-0212, Japan
Abstract
Syntheses of 4-substituted isoquinolines by the palladiumcatalyzed cross-coupling reactions of diethyl(4-isoquinoly1)borane with organic halides are described.
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■ Photoisomerization of 4-t-Butyl-2-piridones and Chemical Properties of the Resulting 2-Azabicyclo[2.2.0]hex-5-en-3-one and the Hexan-3-one Systems
Eisuke Sato, Yoshiya Ikeda, Yuichi Kanaoka, and Haruo Okajima
*Faculty of Pharmaceutical Sciences, Hokkaido University, Kita 12 Nishi 6, Kita-ku, Sapporo, Hokkaido 060-0812, Japan
Abstract
Irradiation of 4-t-butyl-2-pyridones 1a,b gave their valence isomers 2a,b in good yields. Treatment of bicyclic photoproducts 2a and 3a with acid gave the products due to C-C bond cleavage - of the 4-membered rings.