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. 20, No. 3, 1983
Published online:
■ The Synthesis of Diphenyl Ethers Having Tyrosine Moiety
Tsutomu Inoue, Kenji Naitoh, Seiji Kosemura, Isao Umezawa, Thoru Sonobe, Nobuaki Serizawa, Noboru Mori, and Hideji Itokawa
*Tokyo University of Pharmacy and Life Science, 1432-1 Horinouchi, Hachioji, Tokyo 192-0392, Japan
Abstract
Dienone mono-epoxides (13) and (14) were readily reacted with potassium phenoxides to give intermediates (17) and (18) which were subjected to methylation followed by reduction with Zn/AcOH to give the desired diphenyl ethers (15a)-(15f) in good yield.
Published online:
■ A New Synthesis of (±)-Lupinine, (±)-Epilupinine, and the Related Heterocycles by Application of Anodic Oxidation
Makoto Okita, Takeshi Wakamatsu, and Yoshio Ban
*Faculty of Pharmaceutical Sciences, Hokkaido University, Kita 12 Nishi 6, Kita-ku, Sapporo, Hokkaido 060-0812, Japan
Abstract
A new synthesis of (±)-lupinine, (±)-epilupinine, and the related heterocycles has been achieved by utilization of anodic oxidation of lactams bearing the malonate group at the terminal position of N-primary alkyl side chain.
Published online:
■ A Stereoselective Synthesis of 3-Alkyl-6-methoxy-2,5-piperazinedione Derivatives
Chung-gi Shin, Yasuchika Yonezawa, Yoshiaki Sato, Toshitaka Nakano, and Juji Yoshimura
*Departmnet of Applied Chemistry, Faculty of Engineering, Kanagawa University, 3-27-1 Rokkakubashi, Kanagawa-ku, Yokohama 221-8686, Japan
Abstract
A stereoselective formation of 3-alkyl-6-methoxy-2,5-piperazinedione derivatives by the addition of methanol in the presence of NBS to 3-alkyl-6-alkylidene-2,5-piperazinediones is described.
Published online:
■ 18-Methoxygadesine, a New Diterpenoid Alkaloid
Antonio G. González, Gabriel de la Fuente, and Obdulia Munguía
*Instituto Universitario de Química Orgánica, Universidad de La Laguna, Tenerife, Canary Islands, Spain
Abstract
The structure of 18-methoxygadesine has been determined on the basis of its spectral data and chemical correlation with delcosine.
Published online:
■ Unusual Hetisine Rearrangement Products
S. William Pelletier, Jan A. Glinski, Kottayil I. Varughese, Joseph Maddry, and Naresh V. Mody
*Department of Chemistry, Institute for Natural Products Research, The University of Georgia, Chemistry Building, Athens, Georgia 30602-2556, U.S.A.
Abstract
Re-examination of an acid-catalysed hetisine rearrangement gave two, previously undetected products, whose structures were determined by X-ray crystallography. A mechanism for the formation of these products, involving an unusual epimerization of the two hydroxy qroups at C(11) and C(13). is proposed.
Published online:
■ Silicon-Mediated Berbine Synthesis: Synthesis of 11,12-Methylenedioxy-2,3-dimethoxy-7,8,13,14-tetrahydroprotoberberine
Seiichi Takano, Hirotoshi Numata, and Kunio Ogasawara
*Pharmaceutical Institute, Tohoku University, Aobayama, Sendai 980-8578, Japan
Abstract
Silicon-mediated synthesis of 11,12-methylenedioxy-2,3-dimethoxy-7,8,13,14-tetrahydroprotoberberine (8) is described.
Published online:
■ Photo-oxygenation of Indole-3-acetic Acids and Indole-3-acetaldehydes: Biomimetic Conversion of indoles into Quinolines via N1-C2 Fission
Masataka Ihara, Kazuharu Noguchi, Keiichiro Fukumoto, and Tetsuji Kametani
*Institute of Medicinal Chemistry, Hoshi University, 2-4-41 Ebara, Shinagawa-ku, Tokyo 142-8501, Japan
Abstract
New conversion of indoles to quinolines via the N1-C2 fission using singlet oxygen reaction was investigated starting from indole-3-acetic acids and indole-3-acetaldehydes. Dye-induced photo-oxidation of indole-3-acetaldehyde derivatives (17 and 18) followed by treatments with dimethyl sulfide and then acetic acid produced 4-fomyl- and 4-acetylquinolines (19 and 20), respectively.
Published online:
■ Chenabine and Jhelumine: Secobisbenzylisoquinolines or Simple Isoquinoline-Benzylisoquinoline Dimers?
John E. Leet, Varadaraj S. Elango, S. Fazal Hussain, and Maurice Shamma
*Department of Chemistry, The Pennsylvania State University, York Campus, P1031 Edgecomb Avenue, York, Pennsylvania 17403, U.S.A.
Abstract
(+)-Chenabine (6) and (+)-jhelumine (7) are the first dimeric alkaloids incorporating a benzylisoquinoline bonded through a diaryl ether bridge to a simple isoquinoline. They may be formed in vivo either through cleavage of a bisbenzylisoquinoline precursor, or by oxidative coupling of the simple isoquinoline corypalline (11) with an analog of the new alkaloid (+)-karakoramine (4).
Published online:
■ Mesoionic Six-membered Heterocycles. VI. Reactions of 6-Oxo-6H-1,3-oxazin-3-ium-4-olates with Carbodiimides
Willy Friedrichsen and Martha Schildberg
*Institut für Organische Chemie, Universität Kiel, Olshausenstrasse. 40, D-24098 Kiel, Germany
Abstract
6-Oxo-6H-1,3-oxazin-3-ium-4-olates (1,2) react with carbodiimides (3) to give 2,3-dihydro-2-imino-4-oxo-1,3-oxazin derivatives (4).
Published online:
■ Synthesis of 2-Carboxylcephem Derivative from 6-Aminopenicillanic Acid
Tetsuji Kametani, Naoaki Kanaya, Tomoko Mochizuki, and Toshio Honda
*Institute of Medicinal Chemistry, Hoshi University, 2-4-41 Ebara, Shinagawa-ku, Tokyo 142-8501, Japan
Abstract
6-Aminopenicillanic acid (6-APA) has been converted into 2α-carboxycephem derivative by a carbene insertion reaction, followed by Michael reaction.
Published online:
■ Synthesis of Substituted 4-(Methoxyphenyl)-3,4-Dihydrocoumarins
Jacques Chenault and Jean-François E. Dupin
*Instiut de Chimie Organique et Analytique, U. F. R. de Sciences, Université d’Orléans, BP 6759, Rue de Chartres, 45067 Orleans Cedex 2, France
Abstract
In polyphosphoric acid (PPA), 2- and 4-methoxycinnamic acids react with various dimethylphenols to give 4-phenyl-3,4-dihydrocoumarins by direct cycloaddition, whereas 3-methoxycinnamic acid, in the same conditions, also gives a flavanone formed by Fries rearrangement from a hydroxychalcone. These results are discussed in terms of electronic effects due to the methoxy substituents on the cinnamic acids.
Published online:
■ Studies on 4-Quinazolinones. Part IX. Raney Nickel Desulphurisation of 4-Thioquinazolines: Aluminia Catalysed Hydration of 1,4- and 3,4-Dihydroquinazolines
Manas Chakrabarty, Ajit K. Chakravarty, and Satyesh C. Pakrashi
*Indian Institute of Chemical Biology, Calcutta-700 032, India
Abstract
A number of 2-substituted 3,4-dihydroquinazolines and 1,2-disubstituted 1,4-dihydroquinazolines but not the 3-mono or 2,3-disubstituted derivatives, prepared by Raney nickel desulphurisation of the corresponding 4-thioquinazolines (IV), underwent unusual alumina catalysed hydration across the C=N bond followed by ring opening through ring-chain tautomerism leading to substituted acetamide derivatives (III). A plausible mechanism has been put forward.
Published online:
■ Synthesis of 7,7-Dimethylaporphine Alkaloids
Hassan A. Ammar, Paul L. Schiff, Jr., and David J. Slatkin
*Department of Pharmacognosy, School of Pharmacy, University of Pittsburgh, Pittsburgh, PA 15261, U.S.A.
Abstract
The synthesis of N,O,O-trimethyltetrahydromelosmine (1,2,3,9-tetramethoxy-7,7-dimethylaporphine) (3) is described. The amide derivative (9), prepared from the appropriate acid (8) and amine (6) by condensation, was cyclized by a Bischler-Napieralski reaction to afford the 3,4-dihydroisoquinoline derivative (10). The N-methyltetrahydrobenzylisoquinoline (12) from the reduction of 10 and subsequent N-methylation, was cyclized with thalium trifluoroacetate/trifluoroacetic acid and boron trifluoride etherate to the target compound (3).
Published online:
■ Studies on the S1-C2 Bond Cleavage Reaction of Penicillins by Carbene Reaction: Synthesis of Penicillin Derivative
Tetsuji Kametani, Naoaki Kanaya, Tomoko Mochizuki, and Toshio Honda
*Institute of Medicinal Chemistry, Hoshi University, 2-4-41 Ebara, Shinagawa-ku, Tokyo 142-8501, Japan
Abstract
Treatment of α-diazomalonate (5) with penicillin derivative (1 - 4) in the presence of a catalytic amount of rhodium acetate brought about the facile S1-C2 bond cleavage reactions in moderate yields. 2-Dicarboxylated penicillin derivative was synthesized by employing the above reaction as a key step.
Published online:
■ Preparation of Substituted 5-Pyrimidinecarbonitriles and 1,3,5-Triazines from Alkyl N-Cyanoimidates
Miguel A. Pérez and José L. Soto
*Departamento de Química Orgánica, Facultad de Química, Universidad Complutense de Madridas, Ciudad Universitaria, E-28040 Madrid, Spain
Abstract
Sodium methoxide induced the cyclization of alkyl N-cyanoimidates 1 with propanedinitrile affording the 5-pyrimidinecarbonitriles 2. The reaction of 1 with methyl cyanoacetate led to the methyl 3-[(aminocarbonyl)amino]propenoates 7 and the 2,4-dioxo-5-pyrimidinecarbonitrile 8. An analogous cyclization of 1 with cyanamide yielded the 1,3,5-triazines 10.
Published online:
■ Reactions with Indole Derivatives, XLVIII. A Simple Synthesis of the Staurosporine Aglycon
Burkhard Sarstedt and Ekkehard Winterfeldt
*Institut für Organische Chemie, Universität Hannover, Schneiderberg 1b, D-30167 Hannover, Germany
Abstract
The staurosporine aglycon is prepared from tryptamine and β-indole acetic acid in two consecutive cyclization reactions.
Published online:
■ Thienopyrrolizines: New Condensed Triheterocyclic Systems
Sylvain Rault, Jean-Charles Lancelot, Yamien Effi, and Max Robba
*Laboratoire de Chimie Thérapeutique, U. F. R. des Sciences Pharmaceutiques, Université de Caen, 1, rue Vaubénard, 14032 Caen Cedex, France
Abstract
Cyclisation of amide derivatives of 2-(3)-(1-pyrrolyl)-3-(2)-thienylcarboxylic acids resulted in the formation of thieno[2,3(3,2)-b]pyrrolizin-4-ones whose reduction gave the corresponding 4H pyrrolizines.
Published online:
■ Synthesis of meta-Substituted 9-Phenylxanthenes
John L. Hinds, Shirish N. Rajadhyaksha, and Joseph D. Wander
*Department of Chemsitry, The University of Georgia, Athens, Georgia 30602, U.S.A.
Abstract
Construction of the dibenzopyran ring of 9-(3-methoxyphenyl)xanthene (2) by an aluminum chloride-catalyzed, geminal dialkylation reaction between 3-methoxybenzal chloride and phenyl ether was accomplished, but in poor yield; however, a satisfactory preparation of 2 was attained by the grignard reaction of 3-methoxyphenylmagnesium iodide with xanthone, and subsequent reduction; demethylation of 2 was effected by treatment with trimethylsilyl iodide in hot quinoline.
Published online:
■ Reactions of 2,1-Benzisothiazoles with Acetylenic Esters
Martin R. Bryce, R. Morrin Acheson, and Anthony J. Rees
*Department of Chemistry, University of Durham, South Road, Durham DH1 3LE, U.K.
Abstract
2,1-Benzisothiazole and the 3-methyl derivative react with dimethyl acetylenedicarboxylate (DMAD) under forcing conditions by addition across the heterodiene and loss of sulphur to afford dimethyl quinoline-2,3-dicarboxylate and the corresponding 4-methyl derivative, respectively. Diethyl acetylenedicarboxylate and methyl propiolate react similarly but in very low yield. These reactions could involve initial Michael-type attack of the acetylenic ester on the heterocyclic nitrogen or concerted cycloaddition. 3-Amino-2,1-benzisothiazole and DMAD react differently to yield dimethyl 2-cyanoanilinofumarate; a possible mechanism is presented.
Published online:
■ The Preparation of N’-Alkylnicotinium Salts
Makoto Shibagaki, Hajime Matsushita, and Hajime Kaneko
*Life Science Research Laboratory, Japan Tobacco Inc., 6-2, Umegaoka, Midori-ku, Yokohama, Kanagawa 227-8512, Japan
Abstract
Treatment of N-benzyl-N’-alkylnicotinium dihalides with triphenylphosphine provided a synthetic route to N’-alkylnicotinium salts.
Published online:
■ Studies on Isomeric Pyridylisoxazoles
Elena Belgodere, Ricardo Bossio, Francesco De Sio, Stefano Marcaccini, and Roberto Pepino
*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
Data concerning the reaction between hydroxylamine hydrochloride and 1-(2-pyridyl)-3-phenyl- (Ia) and 1-(2-thienyl)-3-phenyl-1,3-propanedione (I1) disagree with those previously reported in literature. The same reaction was also studied employing a series of 1,3-diketones-1-(pyridyl)-substituted I b-i. The direction of enolization of 1,3-diketones accounted for the isomeric isoxazoles formation.
Published online:
■ Synthetic Studsies on Carbapenem Antibiotics: Synthesis of 6-Phenoxyacetyloxy-1-carbapen-2-em o-Nitrobenzyl Ester
Tetsuji Kametani, Shyh-Pyng Huang, Shih-Der Chu, and Toshio Honda
*Institute of Medicinal Chemistry, Hoshi University, 2-4-41 Ebara, Shinagawa-ku, Tokyo 142-8501, Japan
Abstract
6-Phenoxyacetyloxy-1-carbapen-2-em o-nitrobenzyl ester (11) was synthesized from the readily available azetidinone (1), efficiently.
Published online:
■ Beckmann Fragmentation in the Wolff-Kishner Reduction of 6-Aryl-3-hydroxyimino-4-piperidones
Joan Bosch, Montserrat Moral, and Mario Rubiralta
*Laboratory of Organic Chemistry, Faculty of Pharmacy, University of Barcelona, Av. de Joan XXIII, s/n, 08028 Barcelona, Spain
Abstract
Treatment of 6-aryl-3-hydroxyimino-4-piperidones under Wolff-Kishner conditions afforded 5-aryl-2-pyrrolidones by a process that involves a Beckmann fragmentation.
Published online:
■ Synthesis and Rearrangement of Cycloadducts from Trimethylsilanecarbonitrile Oxide
Francesco De Sarlo, Alberto Brandi, Andrea Goti, Antonio Guarna, and Paolo Rovero
*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 cycloadducts from trimethylsilanecarbonitrile oxide and ethylenic or acetylenic compounds easily rearrange to open-chain intermediates, which, in turn, are hydrolysed respectively to β-hydroxynitriles and β-oxonitriles. The cycloadducts of the same nitrile oxide with sulfur dioxide and sulfinylamines are unstable, too, leading respectively to trimethylsilylisocyanate and trimethylsilylcarbodiimides. All these reactions are of preparative interest, in comparison with previous methods.
Published online:
■ Utility of α,β-Unsaturated Nitrirles in Heterocyclic Synthesis
Mohamed Hilmy Elnagdi, Hassan Attia Elfahham, and Galal Eldin Hamza Elgemeie
*Department of Chemistry, Faculty of Science, University of Cairo, Giza, Egypt
Abstract
New approaches for synthesis of different mono and polyheterocyclic derivatives utilising α,β-unsaturated nitriles are surveyed. The scope and limitation of the most important of these approaches are demonstrated.